US20230295370A1 - Filled polyurethane or polyisocyanurate foam and method of making same - Google Patents
Filled polyurethane or polyisocyanurate foam and method of making same Download PDFInfo
- Publication number
- US20230295370A1 US20230295370A1 US18/305,122 US202318305122A US2023295370A1 US 20230295370 A1 US20230295370 A1 US 20230295370A1 US 202318305122 A US202318305122 A US 202318305122A US 2023295370 A1 US2023295370 A1 US 2023295370A1
- Authority
- US
- United States
- Prior art keywords
- fibers
- less
- foam
- mixture
- polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000006260 foam Substances 0.000 title claims abstract description 234
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 86
- 239000004814 polyurethane Substances 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 229920000582 polyisocyanurate Polymers 0.000 title claims description 71
- 239000011495 polyisocyanurate Substances 0.000 title claims description 71
- 229920005862 polyol Polymers 0.000 claims abstract description 133
- 150000003077 polyols Chemical class 0.000 claims abstract description 130
- 239000000203 mixture Substances 0.000 claims abstract description 129
- 239000000945 filler Substances 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 59
- 239000012948 isocyanate Substances 0.000 claims abstract description 46
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 45
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 12
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 12
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 8
- 239000000835 fiber Substances 0.000 claims description 156
- 239000003365 glass fiber Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000006071 cream Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 8
- 229920000297 Rayon Polymers 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 239000002964 rayon Substances 0.000 claims description 5
- 229920003043 Cellulose fiber Polymers 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000002557 mineral fiber Substances 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920001281 polyalkylene Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920006306 polyurethane fiber Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 40
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 description 80
- 230000002787 reinforcement Effects 0.000 description 57
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 42
- 239000010881 fly ash Substances 0.000 description 41
- 239000000843 powder Substances 0.000 description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 33
- 239000012190 activator Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 27
- 239000002245 particle Substances 0.000 description 25
- -1 polymethylene Polymers 0.000 description 22
- 229920000768 polyamine Polymers 0.000 description 17
- 239000004568 cement Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- 239000004721 Polyphenylene oxide Substances 0.000 description 13
- 239000004088 foaming agent Substances 0.000 description 13
- 229920000570 polyether Polymers 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- 239000002657 fibrous material Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229920005830 Polyurethane Foam Polymers 0.000 description 11
- 125000002947 alkylene group Chemical group 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 239000011496 polyurethane foam Substances 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000011398 Portland cement Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 229920000592 inorganic polymer Polymers 0.000 description 9
- 239000002893 slag Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 206010052904 Musculoskeletal stiffness Diseases 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 7
- 229930006000 Sucrose Natural products 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 239000007822 coupling agent Substances 0.000 description 7
- 238000005187 foaming Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000010348 incorporation Methods 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000005720 sucrose Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000004971 Cross linker Substances 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- 239000004604 Blowing Agent Substances 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 5
- 229940043237 diethanolamine Drugs 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 239000000123 paper Substances 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 235000006708 antioxidants Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002956 ash Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001860 citric acid derivatives Chemical class 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical class 0.000 description 3
- 125000004209 (C1-C8) alkyl group Chemical class 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 239000004599 antimicrobial Substances 0.000 description 3
- 230000001680 brushing effect Effects 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000010883 coal ash Substances 0.000 description 3
- 238000007766 curtain coating Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000007761 roller coating Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 150000003512 tertiary amines Chemical group 0.000 description 3
- 229960004418 trolamine Drugs 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 2
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- ZHZFKLKREFECML-UHFFFAOYSA-L calcium;sulfate;hydrate Chemical compound O.[Ca+2].[O-]S([O-])(=O)=O ZHZFKLKREFECML-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 230000009970 fire resistant effect Effects 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000010451 perlite Substances 0.000 description 2
- 235000019362 perlite Nutrition 0.000 description 2
- ULSIYEODSMZIPX-UHFFFAOYSA-N phenylethanolamine Chemical compound NCC(O)C1=CC=CC=C1 ULSIYEODSMZIPX-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 150000003335 secondary amines Chemical group 0.000 description 2
- 239000010454 slate Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- ATHGHQPFGPMSJY-UHFFFAOYSA-N spermidine Chemical compound NCCCCNCCCN ATHGHQPFGPMSJY-UHFFFAOYSA-N 0.000 description 2
- PFNFFQXMRSDOHW-UHFFFAOYSA-N spermine Chemical compound NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 150000003892 tartrate salts Chemical class 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- GBAXGHVGQJHFQL-UHFFFAOYSA-N 1-(2-hydroxyethylamino)propan-2-ol Chemical compound CC(O)CNCCO GBAXGHVGQJHFQL-UHFFFAOYSA-N 0.000 description 1
- RDTCWQXQLWFJGY-UHFFFAOYSA-N 1-(methylamino)butan-2-ol Chemical compound CCC(O)CNC RDTCWQXQLWFJGY-UHFFFAOYSA-N 0.000 description 1
- HHKUQCFQGCCLGA-UHFFFAOYSA-N 1-[2-hydroxyethyl(2-hydroxypropyl)amino]propan-2-ol Chemical compound CC(O)CN(CCO)CC(C)O HHKUQCFQGCCLGA-UHFFFAOYSA-N 0.000 description 1
- BFIAIMMAHAIVFT-UHFFFAOYSA-N 1-[bis(2-hydroxybutyl)amino]butan-2-ol Chemical compound CCC(O)CN(CC(O)CC)CC(O)CC BFIAIMMAHAIVFT-UHFFFAOYSA-N 0.000 description 1
- ZFECCYLNALETDE-UHFFFAOYSA-N 1-[bis(2-hydroxyethyl)amino]propan-2-ol Chemical compound CC(O)CN(CCO)CCO ZFECCYLNALETDE-UHFFFAOYSA-N 0.000 description 1
- NZIGXAQHXJFYEW-UHFFFAOYSA-N 1-aminobutan-2-ol;ethanol Chemical compound CCO.CCC(O)CN NZIGXAQHXJFYEW-UHFFFAOYSA-N 0.000 description 1
- KYTMHUXSDFKSEO-UHFFFAOYSA-N 1-aminobutan-2-ol;propan-2-ol Chemical compound CC(C)O.CCC(O)CN KYTMHUXSDFKSEO-UHFFFAOYSA-N 0.000 description 1
- WHJWHBMJEOQRPH-UHFFFAOYSA-N 1-aminohexan-2-ol;ethanol Chemical compound CCO.CCCCC(O)CN WHJWHBMJEOQRPH-UHFFFAOYSA-N 0.000 description 1
- CEVWBJCREUNMRI-UHFFFAOYSA-N 1-aminohexan-2-ol;propan-2-ol Chemical compound CC(C)O.CCCCC(O)CN CEVWBJCREUNMRI-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- BQBWUVWMUXGILF-UHFFFAOYSA-N 2-anthrol Chemical compound C1=CC=CC2=CC3=CC(O)=CC=C3C=C21 BQBWUVWMUXGILF-UHFFFAOYSA-N 0.000 description 1
- WRVIGSXNYQECJV-UHFFFAOYSA-N 2-bromo-6-cyclohexylphenol Chemical compound OC1=C(Br)C=CC=C1C1CCCCC1 WRVIGSXNYQECJV-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- AQDKZPFDOWHRDZ-UHFFFAOYSA-N 2-methyl-6-nitrophenol Chemical compound CC1=CC=CC([N+]([O-])=O)=C1O AQDKZPFDOWHRDZ-UHFFFAOYSA-N 0.000 description 1
- IIBOYMCHHLZIKC-UHFFFAOYSA-N 2-nitro-6-phenylphenol Chemical compound C1=CC=C([N+]([O-])=O)C(O)=C1C1=CC=CC=C1 IIBOYMCHHLZIKC-UHFFFAOYSA-N 0.000 description 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- IYUVNGUJOOMKHQ-UHFFFAOYSA-N 3-[2-hydroxyethyl(3-hydroxypropyl)amino]propan-1-ol Chemical compound OCCCN(CCO)CCCO IYUVNGUJOOMKHQ-UHFFFAOYSA-N 0.000 description 1
- BIHLHMHULOMJLI-UHFFFAOYSA-N 3-[bis(2-hydroxyethyl)amino]propan-1-ol Chemical compound OCCCN(CCO)CCO BIHLHMHULOMJLI-UHFFFAOYSA-N 0.000 description 1
- NHIRIMBKJDSLBY-UHFFFAOYSA-N 3-[bis(3-hydroxypropyl)amino]propan-1-ol Chemical compound OCCCN(CCCO)CCCO NHIRIMBKJDSLBY-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- HESBSZDDIGGELX-UHFFFAOYSA-N 4-[4-hydroxybutyl(2-hydroxyethyl)amino]butan-1-ol Chemical compound OCCCCN(CCO)CCCCO HESBSZDDIGGELX-UHFFFAOYSA-N 0.000 description 1
- HMRLYSGDNOUYEO-UHFFFAOYSA-N 4-[bis(3-hydroxypropyl)amino]butan-1-ol Chemical compound OCCCCN(CCCO)CCCO HMRLYSGDNOUYEO-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
- 239000010754 BS 2869 Class F Substances 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000009261 D 400 Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 240000000907 Musa textilis Species 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- SGBDRKZSMKKNHE-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C Chemical compound N=C=O.N=C=O.N=C=O.C SGBDRKZSMKKNHE-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241001520808 Panicum virgatum Species 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 244000273256 Phragmites communis Species 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 235000005018 Pinus echinata Nutrition 0.000 description 1
- 241001236219 Pinus echinata Species 0.000 description 1
- 235000017339 Pinus palustris Nutrition 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 241001625808 Trona Species 0.000 description 1
- 239000013036 UV Light Stabilizer Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000010882 bottom ash Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000011411 calcium sulfoaluminate cement Substances 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- IQYKECCCHDLEPX-UHFFFAOYSA-N chloro hypochlorite;magnesium Chemical compound [Mg].ClOCl IQYKECCCHDLEPX-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- NOAAMORLQWOAEL-UHFFFAOYSA-N ethoxy-n,n-di(propan-2-yl)phosphonamidous acid Chemical compound CCOP(O)N(C(C)C)C(C)C NOAAMORLQWOAEL-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical class O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- UPRXAOPZPSAYHF-UHFFFAOYSA-N lithium;cyclohexyl(propan-2-yl)azanide Chemical compound CC(C)N([Li])C1CCCCC1 UPRXAOPZPSAYHF-UHFFFAOYSA-N 0.000 description 1
- 150000002672 m-cresols Chemical class 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NJTGANWAUPEOAX-UHFFFAOYSA-N molport-023-220-454 Chemical compound OCC(O)CO.OCC(O)CO NJTGANWAUPEOAX-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000002883 o-cresols Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000002931 p-cresols Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229950006768 phenylethanolamine Drugs 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003473 refuse derived fuel Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 102220051014 rs141837529 Human genes 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940057950 sodium laureth sulfate Drugs 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- HLPHHOLZSKWDAK-UHFFFAOYSA-M sodium;formaldehyde;naphthalene-1-sulfonate Chemical compound [Na+].O=C.C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HLPHHOLZSKWDAK-UHFFFAOYSA-M 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229960002920 sorbitol Drugs 0.000 description 1
- 229940063673 spermidine Drugs 0.000 description 1
- 229940063675 spermine Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000008030 superplasticizer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010435 syenite Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 229940113165 trimethylolpropane Drugs 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/06—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Definitions
- This disclosure relates generally to polyurethane or polyisocyanurate foams, more particularly, to highly filled polyurethane or polyisacyanurare foams.
- Polymeric composites that contain organic and/or inorganic filler materials have become desirable for a variety of uses because of their excellent mechanical properties and weathering stability.
- the superior properties of the organic-inorganic composites are achieved through use of the organic as a matrix material that acts as a glue with enhanced flexural properties or as a fibrous component providing reinforcement and improved tensile properties.
- the inorganic material imparts various properties of rigidity, toughness, hardness, optical appearance, interaction with electromagnetic radiation, density, and many other physical and chemical attributes.
- polyurethane compositions have grown due to their superior tensile strength, impact resistance, and abrasion resistance compared to, for example, unsaturated polyester and vinyl ester-based composites.
- Processes for preparing polyurethane foamed compositions are known and have significant commercial success.
- certain problems that often limit application of the polyurethane foams are known to those in the industry. For example, die processes to prepare these compositions may experience difficulties. Additionally, the foams may be brittle, or suffer from poor adhesion to substrates due to the relatively high urea concentration that often forms on the surface of these foams.
- the foams may also be dimensionally unstable, due to a relatively high diffusion coefficient of the carbon dioxide through the cell walls, and demolding may be poor due to the relatively high exothermic nature of the water-blown reactions.
- demolding may be poor due to the relatively high exothermic nature of the water-blown reactions.
- the foam stock can include (a) a polyurethane or polyisocyanurate formed by the reaction of (i) one or more isocyanates selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, and (ii) one or more polyols, and (b) a filler in an amount of from greater than 50% to 90% by weight, based on the total weight of the polyurethane composite, wherein during formation of the foam stock, the reaction mixture of the one or more isocyanates and one or more polyols is allowed to rise freely (eg. in a mold).
- the density of the foam stock can be at least 10 lb/ft 3 . In some cases, the density of the foam stock can be from 10 lb/ft 3 to 35 lb/ft 3 , from 10 lb/ft 3 to 30 lb/ft 3 or from 15 lb/ft 3 to 25 lb/ft 3
- the flexural strength of the foam stock can be at least 100 psi. In some cases, the flexural strength of the foam slock can be from 100 psi to 700 psi.
- the amount of polyorethane or polyisocyanurate in the foam stock can be from 100% to 50% by weight, for example, 15% to 45% by weight, based on the total weight of the foam stock
- the one or more polyols can have an average hydroxyl number of from 100 to 700 mg KOH/g, from 100 to 500 mg KOH/g, or from 200 to 400 mg KOH/g.
- the one or more polyols can have an average molecular weight of from 250 to 1500 g/mol from 500 to 1000 g/mol.
- the average functionality of the one or more polyols can be from 2.5 to 5.5. from 3 to 5.5, or from 3 to 4.
- the one or more first polyols can have an average viscosity of 150 to 5000 cPs or from 150 to 2500 cPs at 25° C.
- a blend of the one or more polyols and the one or more isocyanates used in the foams can have an average viscosity of from 100 to 6000 cPs, from 100 to 2500 cPs, or from 100 to 1400 cPs at 25° C.
- the polyurethane or polyisocyanurate foam stock can include a filler,
- the filler can include a particulate filler and/or a plurality of fibers.
- the particulate filler in the foam stock can include coal ash such as fly ash.
- the amount of particulate filler in the foam stock can be from 50 to 90% by weight, based on the total weight of the foam stock
- the particulate filler can be present in an amount from 50% to 85% or from 60% to 80% by weight, based on the total weight of the foam stock.
- the plurality of fibers can be present in the foam stock can be from 0.25% to 10%by weight, based on the total weight of the foam stock. In some examples, the fibers can be present in an amount from 0.25% to 8%, from 0 25% to 6% from 0.5% to 6% or from 0.5% to 5% by weight, based on the total weight of the foam stock.
- the foam stock can include a plurality of glass fibers, polyalkylene fibers, polyester fibers, polyamide fibers, phenol-fornmldehyde fibers, polyvinyl chloride fibers, polyacrylic fibers, acrylic polyester fibers, polyurethane fibers, polyacrylonitrile fibers, rayon fibers, cellulose fibers, carbon fibers, metal and metal-coated fibers, mineral fibers, or combinations thereof in some embodiments, the foam stock comprises a plurality of glass fibers.
- the glass fibers can have an average length of 1 mm or greater. In some examples, the glass fibers can have an average length of from 1.5 mm to 30 mm In some embodiments, the foam stock is free of fibers.
- the average thickness of the polyurethane or polyisocyanurate foam stock can be 2 inches or greater or 2 feet or greater. In some embodiments, the average thickness of the polyurethane or polyisocyanurate foam stock can be from 1 inch to 4 feet, from 3 inches to 4 feet, or from 2 feet to 4 feet.
- the method can include mixing the (i) one or more isocyanates selected from the group consisting of drisocyanates, polyisocyanales, and mixtures thereof, (ii) one or more polyols, and (iii) filler to form a mixture.
- the mixture may further comprise a catalyst
- the mixture can include the catalyst at 0.05 to 0.5 part per hundred pans of polyol.
- the method can include allowing the one or more isocyanates and the one or more polyols to react in the presence of the particulate filler.
- the polyurethane or polyisocyanurate foam stock can be formed in a mold.
- the mold can be a flexible, disposable container which can be removed from the foam by cutting through the container
- the mold can be a cardboard box.
- the method can include applying the mixture to a mold at a viscosity of from 5,000 to 100,000 cPs or from 20,000 to 100,000 cPs at the temperature of the mixture
- the mixture can be applied to the mold using a nozzle traversing the mold.
- the mixture applied to the mold can have a tack free time of from 90 seconds to 7 minutes or from 2 to 7 minutes.
- the mixture can also have a cream time of from 20 to 120 seconds, from 40 to 120 seconds or from 80 to 120 seconds
- the method of making the polyurethane or polyisocyanurate foam stock can include allowing the mixture to react and expand to form the polyurethane or polyisocyanurate foam.
- the mixture can be allowed to rise freely during foaming in the mold.
- the foam does not reach a hardness of 20 shore D in less than 5 minutes or in less than 10 minutes.
- the method can further include cutting the resulting foam.
- Foam stocks including poly urethane or polyisocyanurate and methods of preparing the foam stocks are described herein.
- the term “foam stock” as used herein, may also be referred to as a “foam,” “bun,” “bun stock.” or “foam bun stock.”
- the foam stock can comprise a polyurethane or polyisocyanurate formed using reactive systems including reactive isocyanates and reactive polyols
- Isocyanates suitable for use in the foam stock described herein include one or more monomeric or oligomeric poly- or di-isocyanates
- the monomeric or oligomeric poly- or diisocyanate include aromatic diisocyanates and polyisocy anates.
- the isocyanates can also be blocked isocy anates or pre-polymer isocyanates.
- the particular isocyanate used in the foam stock can be selected based on the desired viscosity of the mixture used to form the foam stock.
- a low viscosity is desirable for ease of handling
- Other factors that influence the particular isocyanate can include the overall properties of the foam stock, such as the amount of foaming, strength of bonding to the filler, wetting of the inorganic particulates in the reaction mixture, strength of the resulting foam, stillness (elastic modulus), and reactivity
- Suitable isocyanate compositions for forming the foam stock include those having viscosities ranging front 25 to 700 cPs at 2° C.
- useful diisocyanate is methylene diphenyl diisocyanate (MDI).
- Useful MDl include MDI monomers. MDI oligomers, and mixtures thereof.
- Further examples of useful isocyanates include those having NCO (i e., the reactive group of an isocyanate) contents ranging from about 25% to about 35% by weight. Examples of useful isocy anates are found, for example, in Polyurethane Handbook: Chemistry, Raw Materials. Processing Application. Properties . 2 nd Edition. Ed Gunter Oertel; Hanser/Gardner Publications, Inc, Cincinnati. OH.
- aromatic polyisocyanates include 2,4- or 2,6-toluene diisocyanate, including mixtures thereof; p-phenylene diisocyanate, tetramethylene and hexamethylene diisocyanates, 4,4-dicyclohexylmethane diisocytate; isophorone diisocyanate, 4,4-phenylmethane diisocyanate; polymethylene polyphenylisocyanate; and mixtures thereof.
- triisocyanates may be used, for example, 4,4,4-triphertyl methane triisocyanate; 1,2,4-benzene triisocyanate; polymethylene polyphenyl polyisocyanate, methylene polyphenyl polyisocyanate, and mixtures thereof.
- Suitable blocked isocyanates are formed by the treatment of the isocyanates described herein with a blocking agent (e.g.. diethyl malonate, 3,5-dimethylpyrazole, methylethylketoxime, and caprolactarn).
- Isocyanates are commercially available, for example, from Bayer Corporation (Pittsburgh, PA) under the trademarks MONDUR and DESMODUR.
- isocyanates include MONDUR MR Light (Bayer Corporation. Pittsburgh, PA), PAPI 27 (Dow Chemical Company: Midland. MI), Lupranate M20 (BASF Corporation: Florham Park, NJ), Lupranate M70L (BASF Corporation, Florham Park, NJ). Rubinate M (Huntsman Polyurethanes; Geismar. LA). Econate 31 (Ecopur Industries), and derivatives thereof.
- the average functionality of isocyanates useful with the foam stocks described herein can be from 1.5 to 5. Further, examples of useful isocyanates include isocyanates with an average functionality of 2 to 4.5, 2.2 to 4, 2.4 to 3.7, 2.6 to 3.4, and 2.8 to 3.2.
- the poly urethane or polyisocyanurate foam stock includes one or more polyols It is generally desirable to use polyols in liquid form, and generally in low viscosity liquid form available, as these can be more easily mixed.
- Suitable polyol compositions for forming the foam stock include those having viscosities of 5000 cPs or less at 25° C.
- the polyol composition can include those having viscosities of 4500 cPs or less, 4000 cPs or less, 3500 cPs or less, 3000 cPs or less, 2500 cPs or less, or 2000 cPs or less at 25° C.
- the polyolcomposition can include those having viscosities of 150 cPs or greater. 250 cPs or greater, 500 cPs or greater. 750 cPs or greater. 1000 cPs or greater, or 1500 cPs or greater. In certain embodiments, the polyol composition can include those having viscosities of from 150 to 5000 cPs or from 150 to 2500 cPs at 25° C.
- a blend of the one or more polyols and the one or more isocyanates used in the foams can have a viscosity of from 100 to 6000 cPs, from 100 to 2500 cPs, from 100 to 1400 cPs, from 100 to 1200 cPs or from 100 to 1000 cPs at 25° C.
- the one or more polyols can have an average equivalent weight of 150 g/eq or greater (eg., 175 g/eq or greater, 200 g/eq or greater, 210 g/eq or greater, 220 g/eq or greater, 225 g/eq or greater, or 230 g/eq or greater) .
- the one or more polyols have an average equivalent weight of 700 g/eq or less (eg., 550 g/eq or less, 500 g/eq or less, 450 g/eq or less, 400 g/eq or less, 350 g/eq or less, 300 g/eq or less, 275 g/eq or less, 250 g/eq or less, or 235 g/eq or less).
- the one or more polyols have an average equivalent weight of from 150 g/eq to 700 g/eq, from 175 g/eq to 700 g/eq, from 200 g/eq to 700 g/eq, from 150 g/eq to 500 g/eq, from 1 50 g/eq to 400 g/eq, or from 150 g/eq to 300 g/eq.
- the one or more polyols do not include any polyols having an equivalent weight of 750 g/eq or greater.
- the one or more polyols in the polyurethane or polyisocyanurate foam stock can include a less reactive polyol.
- the less reactive polyol can have lower numbers of primary hydroxyl groups, lower primary hydroxyl numbers, higher numbers of secondary hydroxyl groups, and higher cream times and tack-free times in a poly urethane or polyisocyanurate mixture, than a highly reactive polyol.
- the one or more polyols can be capped with an alkylene oxide group, such as ethylene oxide, propylene oxide, butylene oxide, and combinations thereof, to provide the polyols with the desired reactivity.
- the one or more polyols can include a poly(propylene oxide) polyol which contain terminal secondary hydroxyl groups and are end-capped with ethylene oxide to provide polyols with primary hydroxyl groups
- the one or more polyols have about 40% or less primary hydroxyl groups, about 35% or less primary hydroxyl groups, about 30% or less primary hydroxyl groups, about 25% or less primary hydroxyl groups, about 20% or less primary hydroxyl groups, about 15% or less primary hydroxyl groups, or even about 10% or less primary hydroxyl groups.
- the one or more polyols can have primary hydroxyl numbers (as measured in units of mg KOH/g) of less than about 220, less than about 200, less than about 180. less than about 160, less than about 140, less than about 120, less than about 100, less than about 80, less than about 60, less than about 40, or even less than about 20.
- the number of primary hydroxyl groups can be determined using fluorine NMR spectroscopy as described in ASTM D4273.
- the one or more polyols can have hydroxyl numbers (as measured in units of mg KOH/g) of 1000 or less, 900 or less, 800 or less, 700 or less. 650 or less, 600 or less, 550 or less, 500 or less, 450 or less. 400 or less, 350 or less, 300 or less, 250 or less, 200 or less, or 150 or less,
- the one or more polyols can have hydroxyl numbers (as measured in units of mg KOH/g) of 50 or more, 100 or more, 150 or more, 200 or more, 250 or more, 300 or more 350 or more, 400 or more. 450 or more, or 500 or more.
- the average hydroxyl number is 700 or less, 650 or less, 600 or less, 550 or less, 500 or less, 450 or less, 400 or less. 350 or less, 300 or less, or 250 or less, and/or is 100 or more. 150 or more. 200 or more. 250 or more, 300 or more. 350 or more, 400 or more. 450 or more, or 500 or more.
- the average hydroxyl number can be from 100-700, 100-500, 150-450, or 200-400.
- the one or more polyols include two or more polyols. For example, there can be a blend of 75% of a polyol having a hydroxyl number of 400 and 25% of a polyol having a hydroxyl number of 100 to produce an average hydroxyl number of 325.
- the polyurethane or polyisocyanurate foam stock can include one or more polyols that can provide a delay in the cream time and tack free time of the polyurethane or polyisocyanurate mixture during foaming
- the foam stock can include polyols containing glycerine and/or amine groups which can delay the cream time and/or tack free time of the poly urethane or polyisocyanurate mixture
- the one or more polyols can increase the cream time of the polyurethane or polyisocyanurate mixture to 40 seconds or greater such as from 40 seconds to 120 seconds.
- the one or more polyols can increase the tack-free time of the poly urethane or polyisocyanurate mixture to 90 seconds or greater such as from 90 seconds to 7 minutes.
- the one or more poly ols can include amine groups, such as primary amine groups, secondary amine groups, tertiary amine groups, or combinations thereof
- the total amine value i.e., a measure of the concentration of tertiary, secondary, and primary amine groups as measured in units of mg KOH/g
- the one or more polyols can have a total amine value (as measured in units of mg KOH/g) of from 0 to 50, from greater than 0 to 50, or from greater than 0 to 45.
- the functionality of the one or more polyols useful with the foam stocks described herein can be 7 or less, 6.5 or less, 6 or less, 5.5 or less, 5 or less, 4.5 or less, 4 or less. 3.5 or less, 3.25 or less, 3 or less, 2.75 or less, 2.5 or less, or 2.25 or less, In some embodiments, the functionality of the one or more polyols can be 2 or greater, 2.25 or greater, 2.5 or greater, 2.75 or greater, 3 or greater, 3.25 or greater, 3.5 or greater, 3.75 or greater, or 4 or greater, The average functionality of the one or more polyols useful with the foam described herein can be 5.5 or less, for example, 5 or less, 4.5 or less, 4 or less, 3.5 or less, 3.25 or less, 3 or less, 2.75 or less, 2 5 or less, or 2.25 or less, In some embodiments, the average functionality of the one or more first polyols can be 2 or greater, 2.25 or greater, 2.5 or greater, 2.75 or greater, 3 or greater
- examples of useful first polyols include polyols with an average functionality of from 2.0 to 5.5, from 3 to 5.5, from 3 to 5, from 3 to 4.5, from 2.5 to 4, from 2.5 to 3.5, or from 3 to 4.
- the one or more polyols can have an average molecular weight of 250 g/mol or greater (e.g., 300 g/mol or greater, 350 g/mol or greater, 400 g/mol or greater, 450 g/mol or greater, 500 g/mol or greater, 550 g/mol or greater, 600 g/mol or greater, 650 g/mol or greater, 700 g/mol or greater, 750 g/mol or greater, 800 g/mol or greater, 900 g/mol or greater. 1000 g/mol or greater, 1200 g/mol or greater, or 1400 g/mol or greater). In some cases, the one or more polyols have an average molecular weight of 1500 g/mol or less (e g.
- the one or more polyols have an average molecular weight of from 250 g/mol to 1500 g/mol. from 250 g/mol to 1000 g/mol or from 500 g/mol to 1000 g/mol. In some embodiments, the one or more polyols do not include any polyols having a molecular weight of 1000 g/mol or greater.
- Table 1 provides a description of exemplary polyols (Polyols A-C) that can be used in the the poly urethane and polyisocsanurate foam stock.
- the one or more poly ols can include polyester polyols. a polyether polyols, or combinations thereof. Suitable polyols include polyether polyols such as those sold under the Carpol® trademark or under the Jeffol® trademark. In some examples, the polyether polyol can include a glycerin-based polyol and derivatives thereof commercially available from Carpenter Co. (e.g., Carpol® GP-240; Carpol® GP-725, Carpol® GP-700; Carpol® GP-1000; Carpol® GP-1500;).
- the polyether polyol can include a polypropylene-based polyol and derivatives thereof commercially available from Huntsman International (e.g., Jeffol® FX31-240; Jeffol® G30-650; Jeffol® FX31-167; Jeffol® A-630; Jeffol® AD-310).
- Suitable polyols include polyester polyols available from Huntsman International (e.g., XO 13001).
- the polyols can include a sucrose and/or amine-based polyol.
- Tire sucrose and/or amine-based polyol can include, for example, a polyether polyol (including for example ethylene oxide, propylene oxide, butylene oxide, and combinations thereof) which is initiated by a sucrose and/or amine group.
- Sucrose and/or amine-based polyols are known in the art, and include, for example, sucrose/amine initiated polyether polyol sold under the trade name CARPOL® SPA-357 or CARPOL® SPA-530 (Carpenter Co., Richmond, VA) and triethanol amine initiated polyether poly ol sold under the trade name CARPOL® TEAP-265 (Carpenter Co., Richmond. VA).
- the polyurethane or polyisocyanurate foam stock can include one or more additional polyols.
- the one or more additional polyols include aromatic polyols such as aromatic polyester polyols, aromatic polyether polyols, or combinations thereof, such as those sold under the TEROL® trademark (e.g., TEROL® 198 and TEROL® 250).
- the aromatic polyol can have an aromaticity of 35% or greater, such as 38% or greater, 40% or greater, 45% or greater, 50% or greater, or 55% or greater and/or an aromaticity of 80% or less, 75% or less. 70% or less, 65% or less, 60% or less, 55% or less, 50% or less. 45% or less, 50% or less, 45% or less, or 40% or less.
- the one or more additional polyols can include polyols having a large number of primary hydroxyl groups (e.g., 75% or more) based on the total number of hydroxyl groups in the polyol
- the high primary hydroxyl group polyols can include 80% or more, 85% or more, 90% or more, 95% or more, or 100% of primary hydroxyl groups.
- the one or more additional polyols can include a Mannich polyol.
- Mannich polyols are the condensation product of a substituted or unsubstituted phenol, an alkanolamine, and formaldehyde.
- Mannich polyols can be prepared using methods known in the art. For example, Mannich poly ols can be prepared by premixing the phenolic compound with a desired amount of the alkanolamine, and then slowly adding formaldehyde to the mixture at a temperature below the temperature of Novolak formation. At the end of the reaction, water is stripped from the reaction mixture to provide a Mannich base. See, for example, U.S. Pat. No. 4,883,826, which is incorporated herein by reference in its entirety. The Mannich base can then be alkoxylated to provide a Mannich polyol.
- the substituted or unsubstituted phenol can include one or more phenolic hydroxyl groups.
- the substituted or unsubstituted phenol includes a single hydroxyl group bound to a carbon in an aromatic ring
- the phenol can be substituted with substituents which do not undesirably react under the conditions of the Mannich condensation reaction, a subsequent alkoxylation reaction (if performed), or the preparation of polyurethanes from the final product.
- suitable substituents include alkyl (e.g., a C 1 -C 18 alkyl, or a C 1 -C 12 alkyl), aryl, alkoxy, phenoxy, halogen, and nitro groups
- Suitable substituted or unsubstituted phenols that can be used to form Mannich polyols include phenol, o-, p-, or m-cresols, ethylphenol, nonylphenol, dodecylphenol, p-phenylphenol, various bisphenols including 2,2-bis(4-bydroxyphenyl)propane (bisphenol A), ⁇ -naphthol, ⁇ -hydroxyanthracene, p-chlorophenol, o-bromophenol, 2,6-dichlorophenol, p-nitrophenol, 4- or 2-nitro-6-phenylphenol, 2-nitro-6- or 4-methylphenol, 3,5-dimethylphenol, p-isopropylphenol, 2-bromo-6-cyclohexylphenol, and combinations thereof.
- bisphenol A 2,2-bis(4-bydroxyphenyl)propane
- bisphenol A 2,2-bis(4-bydroxyphenyl)propane
- the Mannich polyol is derived from phenol or a monoalkyl phenols (e.g., a para-alkyl phenols). In some embodiments, the Mannich polyol is derived from a substituted or unsubstituted phenol selected from the group consisting of phenol, para-n-nonylphenol, and combinations thereof.
- the alkanolamine used to produce the Mannich polyol can include a monoalkanolamine, a dialkanolamine, a trialkanolamine, a tetraalkanolamine, or combinations thereof.
- suitable monoalkanolamines include methylethanolamine, ethylethanolamine, methyhsopropanolamine, ethylisopropanolamine, methyl-2-hydroxybutylamine, phenylethanolamine, ethanolanime, isopropanolamine, and combinations thereof.
- Suitable dialkanolamines include dialkanolamines which include two hydroxy-substituted C 1 C- 12 alkyl groups (e.g., two hydroxy-substituted C 1 -C 8 alkyl groups, or two hydroxy-substituted C 1 -C 6 alkyl groups).
- the two hydroxy-substituted alkyl groups can be branched or linear, and can be of identical or different chemical composition.
- dialkanolamines examples include diethanolamine, diisopropanolamine, ethanolisopropanolamine, ethanol-2-hydroxybutylamine, isopropanol-2-hydroxybutylamine, isopropanol-2-hydroxyhexylamine, ethanol-2-hydroxyhexylamine, and combinations thereof.
- Suitable trialkanolamines include trialkanolamines which include three hydroxy-substituted C 1 -C 12 alkyl groups (e.g., three hydroxy-substituted C 1 -C 8 alkyl groups, or three hydroxy-substituted C 1 -C 6 alkyl groups).
- the three hydroxy-substituted alkyl groups can be branched or linear, and can be of identical or different chemical composition.
- suitable trialkanolamines include triisopropanoiamine (TIPA), triethanolamine, N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine (DEIPA), N,N-bis(2-hydroxypropyl)-N-(hydroxyethyl)amine (EDIPA), tris(2-hydroxybutyl)amine, hydroxyethyl di(hydroxypropyl)amine, hydroxypropyl di(hydroxyethyl)amine, tri(hydroxypropyl)amine, hydroxyethyl di(hydroxy-n-butyl)amine, hydroxybutyl di(hydroxypropyl)amine, and combinations thereof.
- TIPA triisopropanoiamine
- DEIPA N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine
- EDIPA N,N-bis(2-hydroxypropyl)
- Exemplary tetraalkanolamines include four hydroxy-substituted C 1 -C 1 2 alkyl groups (e.g. four hydroxy-substituted C 1 -C 8 alkyl groups, or four hydroxy-substituted C 1 -C 6 alkyl groups).
- the alkanolamine is selected from the group consisting of diethanolamine, diisopropanolamine, and combinations thereof.
- the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and combinations thereof.
- the Mannich polyol is alkoxylated with from 100% to about 80% propylene oxide and from 0 to about 20 wt% ethylene oxide.
- Mannich polyols are known in the art, and include, for example, ethylene and propylene oxide-capped Mannich polyols sold under the trade names CARPOL® MX-425 and CARPOL® MX-470 (Carpenter Co., Richmond, VA).
- the reaction mixture can include one or more additional isocyanate-reactive monomers such as one or more polyamines.
- Suitable polyamines can correspond to the polyols described herein (for example, a polyester polyol or a polyether polyol), with the exception that the terminal hydroxy groups are converted to amino groups, for example by amination or by reacting the hydroxy groups with a diisocyanate and subsequently hydrolyzing the terminal isocyanate group to an amino group
- the polyamine can be polyether polyamine, such as poly oxyalkylene diamine or polyoxyalkylene triamine.
- Polyether polyamines are known in the art, and can be prepared by methods including those described in U.S. Pat.
- Exemplary polyoxyalkylene diamines are commercially available, for example, from Huntsman Corporation under the trade names Jeffamine® D-230, Jeffamine® D-400 and Jeffamine® D-2000
- Exemplary polyoxyalkylene triamines are commercially available, for example, from Huntsman Corporation under the trade names Jeffamine® T-403, Jeffamine® T-3000, and Jeffamine® T-5000.
- the reaction mixture can include an alkoxylated polyamine (ie., alkylene oxide-capped polyamines) derived from a polyamine and an alkylene oxide.
- Alkoxylated polyamines can be formed by reacting a suitable polyamine with a desired number of moles of an alkylene oxide.
- Suitable polyamines include monomeric, oligomeric, and polymeric polyamines.
- the polyamines has a molecular weight of less than 1000 g/mol (eg., less than 800 g/mol, less than 750 g/mol, less than 500 g/mol, less than 250 g/mol, or less than 200 less than 200 g/mol).
- suitable poly amines that can be used to form alkoxylated polyamines include ethylenediamine, 1,3-diaminopropane, putrescine, cadaverine, hexamethylenediamine, 1,2-diaminopropane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, spermidine, spermine, nonspermidine, toluene diamine, 1,2-propane-diamine, diethylenetriamine, triethylenetetramine, tetraethylene-pentamine (TEPA), pentaethylenehexamine (PEHA), and combinations thereof.
- TEPA tetraethylene-pentamine
- PEHA pentaethylenehexamine
- alkylene oxide or combination of alkylene oxides can be used to cap the polyamine.
- the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and combinations thereof.
- Alkylene oxide-capped polyamines are known in the art, and include, for example, propylene oxide-capped ethylene diamine sold under the trade name CARPOL® EDAP-770 (Carpenter Co., Richmond, VA) and ethylene and propylene oxide-capped ethylene diamine sold under the trade name CARPOL® EDAP-800 (Carpenter Co., Richmond. VA)
- the additional isocyanate-reactive monomer (when used) can be present in varying amounts relative the one or more polyols used to form the foam stock. In some embodiments, the additional isocyanate-reactive monomer can be present in an amount of 30% or less, 25% or less, 20% or less. 15% or less, 10% or less, or 5% or less by weight based on the weight of the one or more polyols
- the ratio of isocyanate groups to the total isocyanate reactive groups is in the range of about 0.5:1 to about 1.5:1, which when multiplied by 100 produces an isocyanate index between 50 and 150.
- the isocyanate index can be from about 80 to about 120, from about 90 to about 120, from about 100 to about 115, or from about 105 to about 110.
- the isocyanate index can be from 180 to 380, for example, from 180 to 350, from 200 to 350, or from 200 to 270.
- an isocyanate may be selected to provide a reduced isocyanate index, which can be reduced without compromising the chemical or mechanical properties of the foam stock
- One or more catalysis can be added to facilitate curing and can be used to control the curing time of the polyurethane or poly isocyanimate matrix.
- useful catalysts include amine-containing catalysts (including tertiary amines such as DABCO and tetramethylbutanediamine, and diethanolamine) and tin-, mercury-, and bismuth-containing catalysts.
- the catalyst includes a delayed-action tin catalyst.
- 0.01 wt% to 2 wt% catalyst or catalyst system e.g., 0.025 wt% to 1 wt% 0.05 wt% to 0.5 wt %, or 0.1 wt% to about 0.25 wt% can be used based on the weight of the polyurethane or polyisocyanurate In some embodiments, 0.05 to 0.5 parts catatyst or catalyst system per hundred parts of polyol can be used.
- the polyurethane or polyisocyanurate can be present in the foam stock in amounts from 10% to 50% based on the weight of the foam stack.
- the polyurethane or polyisocyanurate can be included in an amount from 14% to 50% or 20% to 50% by weight, based on the weight of the foam stock.
- the polyurethane or polyisocyanurate can be present in an amount of 10% or greater, 15% or greater, 20% or greater. 25% or greater, 30% or greater. 35% or greater, 40% or greater, or 45% or greater by weight based on the weight of the foam stock.
- the polyurethane or polyisocyanurate can be present in an amount of 50% or less, 45% or less, 40% or less. 35% or less, 30% or less. 25% or less, 20% or less, or 15% or less by weight, based on the weight of foam stock.
- the polyurethane or polyisocyanurate foam stock can include a filler.
- the filler can be described by its aspect ratio.
- the filler in the foam can have an average aspect ratio of length to diameter of from 1:1 to 6000:1.
- the filler can have an average aspect ratio of from 11 to 5000:1, 1:1 to 4000:1, 1:1 to 3000:1, 1:1 to 2000:1, 1:1 to 1000:1, 1:1 to 700:1, 1.1 to 500:1, 1:1 to 250:1, 1.05:1 to 400:1, 1.1:1 to 300:1, 1.15:1 to 250:1, or 1.2:1 to 200:1.
- the filler can have an average aspect ratio of length to diameter of 200:1 or less, 150:1 or less, 100:1 or less, 75:1 or less, 50:1 or less, 40:1 or less. 30:1 or less, 20:1 or less, 10:1 or less, or 5:1 or less, and from 1:1 or more (e.g.. 1.05:1 or more, 1.1.1 or more, 1.15:1 or more, or 1.2:1 or more).
- the filler can include a particulate filler and particularly an inorganic particulate filler Suitable examples of particulate fillers can be an ash, ground, recycled glass (eg., window or bottle glass); milled glass, glass spheres; glass flakes; activated carbon; calcium carbonate; aluminum trihydrate (ATH); silica; sand: ground sand: silica fume; slate dust; crusher fines; red mud; amorphous carbon (e.g., carbon black); days (e.g., kaolin); mica: talc; wollastonite; alumina; feldspar, bentonite; quartz, garnet; saponite; beidellite; granite; slag: calcium oxide, calcium hydroxide; antimony trioxide; barium sulfate, magnesium oxide: titanium dioxide: zinc carbonate; zinc oxide: nepheline syenite; perlite; diatomite; pyrophillite; flue gas desulfurization (FGD) material;
- the particulate filler can have a median particle size diameter of from 0.2 micron to 100 microns
- the particulate filler can have a median particle size diameter of 100 microns or less, 95 microns or less, 90 microns or less, 85 microns or less, 80 microns or less, 75 microns or less, 70 microns or less. 65 microns or less, 60 microns or less, 55 microns or less, 50 microns or less, 45 microns or less, 40 microns or less, 35 microns or less, 30 microns or less, or 25 microns or less, In some embodiments, the particulate filler can have a median particle size diameter of 0.2 microns or more. 0.3 microns or more.
- the particulate filler can have a median particle size diameter of from 0.2 microns to 100 microns, 0.2 microns to 90 microns, or 0.3 microns to 80 microns, 1 to 50 microns. 1 to 25 microns, or 5 to 15 microns.
- the particulate filler includes an ash.
- the ash can be a coal ash or another type of ash such as those produced by firing fuels including industrial gases, petroleum coke, petroleum products, municipal solid waste, paper sludge, wood, sawdust, refuse derived fuels, switchgrass or other biomass material.
- the coal ash can be fly ash, bottom ash, or combinations thereof.
- the particulate filler mdudes fly ash Fly ash is produced from the combustion of pulverized coal in electrical power generating plants.
- the fly ash useful with the foam stock described herein can be Class C fly ash. Class F fly ash, or a mixture thereof. Fly ash produced by coal-fueled power plants is suitable for incorporation in the foam stocks descnbed herein
- the particulate filler consists of or consists essentially of fly ash.
- the fly ash can have a particle size distribution with at least two modes.
- the panicle size distribution of the fly ash can be three, four, five, or more modes.
- the fly ash can be blended with another fly ash to modify the properties of the fly ash to produce a fly ash having a particle size distribution with at least three modes.
- the fly ash can include a first mode having a median particle diameter of 2.0 microns or less.
- the median particle size of the first mode can be 0.3 microns to 1.5 microns, 0.4 microns to 1 microns, or 0.5 microns to 0.8 microns (e.g., 0.7 microns)
- the fly ash can include a second mode having a median particle diameter of from 3 microns to less than 40 microns in some examples, the median particle size of the second mode can be from 5 microns to 35 microns. 10 microns to 30 microns, or 10 microns to 25 microns.
- the fly ash can include a third mode having a median particle diameter of 40 microns or greater.
- the median particle size of the third mode can be from 40 microns to less than 100 microns, for example from 40 microns to 90 microns. 40 microns to 80 microns, or from 40 microns to 75 microns.
- the fly ash can include a first mode having a median particle diameter of from 0.3 microns to 1.0 micron, a second mode having a median particle diameter of from 10 microns to 25 microns, and a third mode having a median particle diameter of from 40 microns to 80 microns.
- the fly ash can also include an additional ultrafine mode with a median particle diameter of from 0.05 microns to 0.2 microns.
- the particle size distribution can include 11-35% of the particles by volume in the first mode, 65-89% of the particles by volume in the second mode In some embodiments, the particle size distribution can include 11-17% of the particles by volume in the first mode. 56-74% of the particles by volume m the second mode, and 12-31% of the particles by volume in the third mode.
- the ratio of the volume of particles in the second mode to the volume of particles in the first mode can be from 4.5 to 7.5
- the particulate filler can be present in the foam stock described herein in amounts from 35% to 90% by weight
- Examples of the amount of particulate filler present in the foam stock described herein include 35%. 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%.
- the particulate filler for example fly ash
- the particulate filler can be present in amounts from 50% to 80% by weight such as from 55% to 80% by weight or from 60% to 75% by weight
- the particulate filler can include fly ash and calcium carbonate.
- the amount of calcium carbonate in the foam stock can be from 0.1% to 15% by weight, based on the weight of the foam stock.
- the foam stock can include 15% or less, 14% or less, 12% or less, 10% or less, or 8% or less by weight calcium carbonate.
- the foam stock can include 0.1% or greater, 0.5% or greater, 1% or greater, 2% or greater, 3% or greater, or 5% or greater by weight calcium carbonate
- the foam stock when used with fly ash, can include 1% to 15%, 1% to 10%, or 1% to 8% by weight calcium carbonate.
- the particulate filler can include an organic filler, such as a recycled polymeric material. Suitable examples include pulverized polymeric foam or recycled rubber material.
- the filler can include a plurality of fibers.
- the fibers can be any natural or synthetic fiber, based on inorganic or organic materials.
- Inorganic and organic fibers suitable for use with the foam stock can include glass fibers, basali fibers, alumina silica fibers, aluminum oxide fibers, silica fibers, carbon fibers, metal fibers, metal and metal-coated fibers, mineral fibers (such as stone wool, slag wool, or ceramic fiber wool), polyalkylene fibers, polyester fibers, polyamide fibers, phenol-formaldehyde fibers, polyvinyl chloride fibers, polyacrylic fibers, acrylic polyester fibers, polyurethane fibers, polyacrylonitrile fibers, rayon fibers, cellulose fibers, carbon fibers, or combinations thereof.
- the fiber material can include hemp fibers, sisal fibers, cotton fibers, straw, reeds, or other grasses, jute, bagasse fibers, bamboo fibers, abaca fibers, flax, southern pine fibers, wood fibers, cellulose, saw dust, wood shavings, lint, vicose, leather fibers, rayon, and mixtures thereof.
- Other suitable fibers include synthetic fibers such as, Kevlar, viscose fibers, Dralon® fibers, polyethylene fibers, polyethylene terephthalate fibers, polyethylene naphthalate fibers, polypropylene fibers, polyvinyl alcohol fibers, aramid fibers, or combinations thereof.
- the fiber material can include glass fibers.
- Glass fibers can include fibrous glass such as E-glass, C-glass, S-glass, and AR-glass fibers,
- fire resistant or retardant glass fibers can be included to impart fire resistance or retarding properties to the foam stock.
- the foam stock can include a combination of fibers that break and fibers that do not break when the foam stock is being formed using processing machinery and/or fractured by external stress.
- the fibers can be dispersed within the foam stock.
- the fibers in the foam stock can be present in the form of individual fibers, chopped fibers, bundles, strings such as yarns, fabrics, papers, rovings, mats, or tows.
- the foam stock can include a plurality of glass fibers. The average length of the glass fibers in the foam stock can be 1 mm or greater, 1.5 mm or greater, 2 mm or greater, 3 mm or greater, 4 mm or greater, 5 mm or greater, or 6 mm or greater.
- the average length of the glass fibers can be 50 mm or less, 40 mm or less, 30 mm or less, 20 mm or less, 15 mm or less, 12 mm or less, or 10 mm or less
- the glass fibers can be from 1 mm to 50 mm in average length.
- the glass fibers can be from 1.5 mm to 30 mm, from 2 mm to 30 mm, from 3 mm to 30 mm, or from 3 mm to 15 mm in average length.
- the glass fibers in the foam stock can have any dimension of from 1 ⁇ m to 30 ⁇ m in average diameter.
- the average diameter of the glass fibers can be 1.5 ⁇ m to 30 ⁇ m, 3 ⁇ m to 20 ⁇ m, 4 ⁇ m to 18 ⁇ m, or 5 ⁇ m to 15 ⁇ m in average diameter.
- the glass fibers can be provided in provided in the foam stock in a random orientation or can be axially oriented.
- the fibers in the foam stock can have an average aspect ratio of length to diameter of from 8:1 to 4000:1.
- the fibers can have an average aspect ratio of from 5:1 to 2000:1, 5:1 to 1500:1, 5:1 to 1000:1, 5:1 to 750.1, 1.5:1 to 500:1, 1.5:1 to 400:1, 15:1 to 300:1, 1.5:1 to 250:1, 2:1 to 200:1, 2.5:1 to 150:1, 3:1 to 100.1, 3.5:1 to 75:1. 4:1 to 50:1, 5:1 to 25:1, 5:1 to 20:1, or 5:1 to 10:1.
- the fibers can have an average aspect ratio of length to diameter of 1.5:1 or greater, 2:1 or greater, 3:1 or greater. 4:1 or greater, 5:1 or greater. 7.5:1 or greater, 10:1 or greater, 15:1 or greater, 20:1 or greater, 25:1 or greater, 30:1 or greater, or 40:1 or greater. In some embodiments, the fiber can have an average aspect ratio of length to diameter of 200.1 or less, 150:1 or less, 100:1 or less, 75:1 or less, 50:1 or less, 40:1 or less, 30:1 or less, 20:1 or less, 10:1 or less, or 5:1 or less.
- the fibers can be present in the foam stock in amounts of 15% or less by weight, based on the weight of foam stock.
- the fibers can be present in amounts from 0.25% to 15%, 0.5% to 15%, 1% to 15%, 0.25% to 10%, 0.5% to 10%, 1% to 10%, 0.25% to 8%, 0.25% to 6%, or 0.25% to 4% by weight, based on the weight of the foam stock.
- the foam stock is free of fibers dispersed within the foam stock.
- the foam stock described herein can comprise additional materials.
- the additional materials useful with the foam stock can include foaming agents, blowing agents, surfactants, chain-extenders, crosslinkers, coupling agents, UV stabilizers, fire retardants, antimicrobials, anti-oxidants, and pigments. Though the use of such components is well known to those of skill in the art, some of these additional additives are further described herein
- Chemical foaming agents include azodicarbonamides (eg., Celogen manufactured by Lion Copolymer Geismar), and other materials that react at the reaction temperature to form gases such as carbon dioxide.
- azodicarbonamides eg., Celogen manufactured by Lion Copolymer Geismar
- water is an exemplary foaming agent that reacts with isocyanate to yield carbon dioxide.
- the presence of water as an added component or in the filler also can result in the formation of polyurea bonds through the reaction of the water and isocyanate.
- water may be present in the mixture used to produce the foam stock in an amount of from greater than 0% to 5% by weight or less, based on the weight of the mixture.
- water can be present in a range of 0.02% to 4%, 0.05% to 3%, 0.1 % to 2%, or 0.2% to 1% by weight, based on the weight of the mixture.
- the mixture used to produce the foam stock includes less than 0.5% by weight water.
- no chemical foaming agents are used.
- water is the only foaming agent used.
- Surfactants can be used as wetting agents and to assist in mixing and dispersing the materials in a foam. Surfactants can also stabilize and control the size of bubbles formed during the foaming event and the resultant cell structure. Surfactants can be used, for example, m amounts below about 0.5 wt% based on the total weight of the mixture.
- surfactants useful with the polyurethanes described herein include anionic, non-ionic and cationic surfactants
- silicone surfactants such as Tegostab B-8870, DC-197 and DC-193 (Air Products, Allentown, PA) can be used.
- Chain-extenders are difunctional molecules, such as diols or diamines, that can polymerize to lengthen the urethane polymer chains
- chain-extenders include ethylene glycol. 1,4-butanediol, ethylene diamine, 4,4′-methylenebis(2-chloroaniline), (MBOCA), diethylioluene diamine (DETDA): and aromatic diamines such as Unilink 4200 (commercially available from UOP).
- Crosslinkers are tri- or greater functional molecules that can integrate into a polymer chain through two functionalities and provide one or more further functionalities (i.e.. linkage sites) to crosslink to additional polymer chains.
- crosslinkers include glycerin, trimethylolpropane, sorbitol, diethanolamine, and triethanolamine.
- a crosslinker or chain-extender may be used to replace at least a portion of the one or more polyols in the foam stock.
- the polyurethane or polyisocyanurate can be formed by the reaction of an isocyanate, a polyol, and a crosslinker
- Coupling agents and other surface treatments such as viscosity reducers, flow control agents, or dispersing agents can be added directly to the filler or fiber, or incorporated prior to, during, and/or after the mixing and reaction of the foam stock Coupling agents may also reduce the viscosity of the foam stock mixture
- Coupling agents can also allow higher filler loadings of the particulate filler such as fly ash, and/or fiber material, and may be used in small quantities
- the foam stock may comprise about 0.01 wt% to about 0.5 wt% of a coupling agent
- Examples of coupling agents useful with the foam stock described herein include Ken-React LICA 38 and KEN-React KR 55 (Kenrich Petrochemicals; Bayonne, NJ).
- dispersing agents useful with the foam stock described herein include JEFFSPERSE X3202, JEFFSPERSE X3202RF, and JEFFSPERSE X3204 (Huntsman Polyurethanes; Gisemar, LA)
- UV light stabilizers such as UV absorbers
- UV light stabilizers include hindered amine type stabilizers and opaque pigments like carbon black powder.
- Fire retardants can be included to increase the flame or fire resistance of the foam stock.
- Antimicrobials can be used to limit the growth of mildew and other organisms on the surface of the composite.
- Antioxidants such as phenolic antioxidants, can also be added. Antioxidants provide increased UV protection, as well as thermal oxidation protection.
- Pigments or dyes can optionally be added to the foam stock described herein.
- An example of a pigment is iron oxide, which can be added in amounts ranging from about 2 wt% to about 7 wt%, based on the total weight of the foam stock
- the polyurethane or polyisocyanurate foam stock can have a thickness (z direction) of 1 inch to 4 feet
- the foam stock can have a thickness of from 3 inches to 4 feet.
- the foam stock can have an average thickness of 3 inches or greater, 4 inches or greater, 6 inches or greater, 1 foot or greater. 2 feet or greater, 2.5 feet or greater, 3 feet or greater, 3.5 feet or greater, or 4 feet or greater,
- the foam stock can have an average thickness of from 3 inches to 4 feet, 3 inches to 6 inches, 1 foot to 4 feet, or 2 feet to 3 feet.
- the polyurethane or polyisocyanurate foam stock can have a length and width (x and y direction) of 2 feet or greater and from 2 feet to 4 feet respectively.
- the polyurethane or polyisocyanurate foam stock can have a length of 2 feet or greater, 5 feet or greater, 10 feet or greater, or it can be produced with a continuous length.
- the polyurethane or polyisocyanurate foam stock can have a width of 2 feet to 4 feet, or from 2 to 3 feet.
- the polyurethane or polyisocyanurate foam stock can comprise a high filler loading, such as from 50% to 90% by weight of the foam stock, which can result in an increase in the density of the foam stock.
- a high filler loading such as from 50% to 90% by weight of the foam stock
- the amount of fibers and/or particulate filler can be present in the composite mixture in amounts to produce a foam stock having a density of 35 lb/ft 3 or less
- the density of the foam stock can be 10 lb/ft 3 to 35 lb/ft 3 ,15 lb/ft 3 to 35 lb/ft 3 , 15 lb/ft 3 to 25 lb/ft 3 , 10 lb/ft 3 to 30 lb/ft 3 , 10 lb/ft 3 to 25 lb/ft 3 , or 20 lb/ft 3 to 30 lb/ft 3 .
- the density of the foam stock is at least 10 lb/ft 3 .
- Incorporation of the fibers and/or particulate filler in a high filler loading can increase the flexural strength of the foam stock, compared to a foam stock without the fibers and/or high particulate filler. It is desirable to provide polyurethane and polyisocyanurate foams that are relatively lightweight and strong enough to be used in various applications such as by itself as a structural material or in place of composite boards or the like.
- the flexural strength of the polyurethane or polyisocyanurate foam stock can be increased by at least 10%, for example, 15% or greater, 20% or greater, 25% or greater, 30% or greater, 35% or greater, 50% or greater, 75% or greater, or even 100% or greater, compared to a foam stock without fibers and/or particulate filler.
- the flexural strength of the foam stock described herein can be 100 psi or greater,
- the flexural strength of the foam stock can be 200 psi or greater, 300 psi or greater, 400 psi or greater, 500 psi or greater, 600 psi or greater, or 700 psi or greater
- the flexural strength of the foam stock can be from 100 to 700 psi.
- the flexural strength can be determined by the load required to fracture a rectangular prism loaded in the three point bend test as described in ASTM C1185-08 (2012).
- the foam stock can exhibit a ratio of flexural strength (in psi) to density (in lb/ft 3 ) of from 10:1 to 200:1. In some embodiments, the foam stock can exhibit a ratio of flexural strength (in psi) to density (in lb/ft 3 ) of from 10:1 to 100:1 or from 20:1 to 100:1.
- the modulus of elasticity (stiffness) of the foam stock can be 10 ksi or greater, 15 ksi or greater, 20 ksi or greater, 25 ksi or greater, or 30 ksi or greater.
- the modulus of elasticity can be front 15 to 30 ksi, from 20 to 30 ksi, or from 22 to 28 ksi.
- the modulus of elasticity can be determined as described m ASTM C947-03.
- the foam stock can exhibit a ratio of modulus of elasticity (in ksi) to density (in lb/ft 3 ) of from 1:2 to 2:1. In some embodiments, the foam stock can exhibit a ratio of modulus of elasticity (in ksi) to density (in lb/ft 3 ) of 1:1.5 to 1.5:1 or from 1:1.2 to 1.2:1.
- the compressive strength of the foam stock can be 100 psi or greater.
- the compressive strength can be from 100 to 300 psi, from 150 to 250 psi or from 175 to 240 psi.
- the compressive strength can be determined as descnbed in ASTM D1621.
- the foam stock can exhibit a ratio of compressive strength (in psi) to density (in lb/ft 3 ) of from 7:1 to 25:1. In some embodiments, the foam stock can exhibit a ratio of compressive strength (in psi) to density (in lb/ft 3 ) of from 8:1 to 15:1.
- the composite panel can include a first fiber reinforcement; a polyurethane or polyisocyanurate foam stock having a first surface and a second surface opposite the first surface, wherein the first surface is in contact with the first fiber reinforcement, and a cementitious material adjacent the first fiber reinforcement opposite the foam stock.
- the fiber reinforcement can include any of the fiber materials as described herein and can include a blend of different fibers (either type or size).
- the fiber reinforcement can include glass fibers.
- the fibrous glass is a low alkalinity fiber such as an E-glass fiber.
- the fiber reinforcement can be woven or non-woven.
- the fiber reinforcement can be present in the form of individual fibers, chopped fibers, bundles, strings such as yarns, fabrics, scrims, papers, rovings, mats, or tows.
- the fibers in the reinforcement can have an average diameter of 100 microns or less.
- the fibers in the fiber reinforcement can have an average diameter of 1 ⁇ m or greater, 2 ⁇ m or greater, 3 ⁇ m or greater, 4 ⁇ m or greater, 5 ⁇ m or greater, 10 ⁇ m or greater, 15 ⁇ m or greater, 20 ⁇ m or greater, 25 ⁇ m or greater, 30 ⁇ m or greater, 40 ⁇ m or greater, 50 ⁇ m or greater, 60 ⁇ m or greater, 70 ⁇ m or greater, 80 ⁇ m or greater, 90 ⁇ m or greater, or 100 ⁇ m or greater.
- the fibers in the fiber reinforcement can have an average diameter of 90 ⁇ m or less, 80 ⁇ m or less.
- the fibers in the fiber reinforcement can have an average diameter of from 1 ⁇ m to 100 ⁇ m, 1 ⁇ m to 70 ⁇ m, 1 ⁇ m to 50 ⁇ m, 1 ⁇ m to 25 ⁇ m, 5 ⁇ m to 100 ⁇ m, 5 ⁇ m to 50 ⁇ m, 5 ⁇ m to 25 ⁇ m, or 5 ⁇ m to 20 ⁇ m.
- the thickness of the fiber reinforcement on the foam stock can be any suitable thickness to reinforce the foam stock.
- the average thickness of the fiber reinforcement can be 0.1 inch or less.
- the fiber reinforcement can have an average thickness of 0.07 inch or less, 0.05 inch or less, 0.03 inch or less. 0.01 inch or less, 0.005 inch or less, or 0.001 inch or less.
- the fiber reinforcement can have an average thickness of 0.001 inch or greater, 0.005 inch or greater, 0.01 inch or greater, 0.03 inch or greater, 0.05 inch or greater, or 0.07 inch or greater.
- the fiber reinforcement can have an average thickness of from 0.001 inch to 0.1 inch or from 0.001 inch to 0.05 inch.
- the fiber reinforcement can have a basis weight of 50 g/ft 2 or less. In some embodiments, the fiber reinforcement can have a basis weight of 40 g/ft 2 or less, 30 g/ft 2 or less. 20 g/ft 2 or less. 17 g/ft 2 or less. 15 g/ft 2 or less. 12 g/ft 2 or less, 10 g/ft 2 or less, 9 g/ft 2 or less, 8 g/ft 2 or less, 7 g/ft 2 or less, 6 g/ft 2 or less, or 5 g/ft 2 or less.
- the fiber reinforcement can have a basis weight of 0.5 g/ft 2 or greater, 1 g/ft 2 or greater, 2 g/ft 2 or greater, 3 g/ft 2 or greater, 4 g/ft 2 or greater, 5 g/ft 2 or greater, 7 g/ft 2 or greater, 10 g/ft 2 or greater, 15 g/ft 2 or greater, or 20 g/ft 2 or greater.
- the fiber reinforcement can have a basis weight of from 0.5 g/ft 2 to 50 g/ft 2 , from 0.5 g/ft 2 to 25 g/ft 2 , from 0.5 g/ft 2 to 20 g/ft 2 , from 1 g/ft 2 to 10 g/ft 2 , or from 1.5 g/ft 2 to 10 g/ft 2 .
- the composite panel can include a cementitious material.
- the cementitious material can form a layer adjacent the first fiber reinforcement, opposite the foam stock
- the cementitious material can include any suitable material for forming a cementitious layer with the desirable properties.
- the cementitious material includes a rapid set cement.
- the rapid set cement can include calcium aluminate cement (CAC), calcium phosphate cement, calcium sulfate hydrate, calcium sulfoaluminate (CSA) cement, magnesium oxychloride cement, magnesium oxysulfate cement, magnesium phosphate cement, or combinations thereof.
- the cementitious material can include Portland cement.
- the rapid set cement and/or the Portland cement can be present in an amount of 50% or greater by weight, e.g., 60% or greater, 70% or greater. 80% or greater, or 90% or greater by w eight, based on the total weight of the cementitious material.
- the cementitious material does not include gypsum (calcium sulfate hydrate).
- the cementitious material can include an inorganic polymer formed by reading a reactive powder and an activator in the presence of water. Suitable inorganic polymers are described in U.S. Pat. Publication No. 2014/0349104, which is herein incorporated by reference, in some embodiments, the reactive powder for use in the cementitious material includes fly ash In some examples, the majority of the fly ash present is Class C fly ash (i.e., greater than 50% of the fly ash present is Class C fly ash).
- the fly ash is the principal component of the reactive powder and can be present in an amount of greater than 50% by weight. 65% by weight or greater. 75% by weight or greater, or 85% by weight or greater of the reactive powder. In some examples, the fly ash is present in an amount of 90% by weight or greater of the reactive powder or 95% by weight or greater of the reactive powder For example, the fly ash can be present in an amount of 85% by weight or greater, 86% by weight or greater. 87% by weight or greater, 88% by weight or greater. 89% by weight or greater. 90% by weight or greater. 91 % by weight or greater. 92% by weight or greater, 93% by weight or greater. 94% by weight or greater, 95% by weight or greater. 96% by weight or greater, 97% by weight or greater. 98% by weight or greater, or 99% by weight or greater based on the weight of the reactive powder In some embodiments, the reactive powder consists of or consists essentially of fly ash.
- the reactive powder for use as a reactant to form the inorganic polymer compositions can further include other cementitious components.
- the reactive powder can include a rapid set cement as described herein,
- the reactive powder can include Portland cement.
- the reactive powder further includes slag.
- the reactive powder further includes sand.
- the reactive powder includes Portland cement, calcium aluminate cement calcium sulfoaluminate cement, and/or slag
- the reactive powder can include 10% or less by weight of the other cementitious material. In some examples, the reactive powder includes 5% by weight or less.
- the reactive powder can include the other cementitious material cement in an amount of 10% or less by weight 9% or less by weight. 8% or less by weight 7% or less by weight. 6% or less by weight. 5% or less by weight, 4% or less by weight. 3% or less by weight, 2% or less by weight. 1% or less by weight or 0.5% or less by weight.
- the reactive powder is substantially free from other cementitious material.
- the reactive powder can include less than 0.1% by weight, less than 0.01% by weight, or less than 0.001%by weight of Portland cement based on the weight of the reactive powder.
- the reactive powder includes no Portland cement.
- the reactive powder can also include a ground slag such as blast furnace slag in an amount of 10% or less by weight.
- a ground slag such as blast furnace slag in an amount of 10% or less by weight.
- the reactive powder can include slag in an amount of 10% or less, 9% or less. 8% or less. 7% or less. 6% or less. 5% or less. 4% or less, 3% or less. 2% or less, or 1% or less by weight.
- An activator is a further reactant used to form the inorganic polymer compositions described herein.
- the activator allows for rapid setting of the inorganic poly mer compositions and also imparts compressive strength to the compositions.
- the activator can include one or more of acidic, basic, and/or salt components
- the activator can include citrates, hydroxides, metasilicates, carbonates, aluminates, sulfates, and/or tartrates
- the activator can also include other multifunctional acids that are capable of complexing or chelating calcium ions (e.g., EDTA)
- suitable citrates for use as activators include citric acid and its salts, including, for example, sodium citrate and potassium citrate.
- suitable tartrates include tartaric acid and its salts (eg. sodium tartrate and potassium tartrate).
- the activator can include alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide.
- suitable activators include metasilicates (e.g., sodium metasilicate and potassium metasilicate): carbonates (e.g.. sodium carbonate and potassium carbonate); aluminates (e.g., sodium aluminate and potassium aluminate); and sulfates (e.g., sodium sulfate and potassium sulfate).
- the activator includes citric acid, tartaric acid, or mixtures thereof In some examples, the activator includes sodium hydroxide In some examples, the activator includes a mixture of citric acid and sodium hydroxide In examples including a mixture of citric acid and sodium hydroxide, the weight ratio of citric acid present in the mixture to sodium hydroxide present in the mixture is from 0.4:1 to 2.0:1, 0.6:1 to 1.9:1, 0.8:1 to 1.8:1, 0.9:1 to 1.7:1, or 1.0.1 to 1.6:1.
- the activator components can be pre-mixed prior to being added to the other reactive components in the inorganic polymer or added separately to the other reactive components.
- citric acid and sodium hydroxide could be combined to produce sodium citrate and the mixture can include possibly one or more of citric acid and sodium hydroxide in stoichiometric excess.
- the activator includes a stoichiometric excess of sodium hydroxide
- the total amount of activators can include less than 95% by weight of citrate salts.
- the total amount of activator can include from 25-85%, 30-75%, or 35-65% citrate salts by weight
- the mixture in solution and the mixture when combined with the reactive powder can have a pH of from 12 to 13.5 or about 13.
- the activator can be present as a reactant in an amount of from 1.5% to 8.5% dry weight based on the weight of the reactive powder.
- the activator can be present in an amount of from 2% to 8%, from 3% to 7%, or from 4% to 6%.
- the activator can be present in an amount of 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4 5%, 5%, 5.5% 6%, 6.5%, 7%, 7.5%, 8% or 8.5% dry weight based on the weight of the reactive powder.
- the amount of sodium hydroxide used in the activator solution can be from 0.3 to 15.6, 0.5 to 10, 0.75 to 7.5, or 1 to 5 dry pans by weight based on the weight of reactive powder and the amount of citric acid used in the activator solution can be from 0.25 to 8.5, 0.5 to 0.7, 0.75 to 0.6, or 1 to 4.5 dry parts by weight based on the weight of reactive powder
- the resulting activator solution can include sodium citrate and optionally one or more of citnc acid or sodium hydroxide.
- the activator can be provided, for example, as a solution.
- the activator can be provided in water as an aqueous solution in a concentration of from 10% to 50% or from 20% to 40% based on the weight of the solution
- concentration of the activator in the aqueous solution can be from 25% to 35% or from 28% to 32% based on the weight of the solution.
- suitable concentrations for the activator in the aqueous solution include 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% based on the weight of the solution.
- the inorganic polymer compositions described herein are prepared in the presence of aerating agents, including blowing agents and foaming agents.
- suitable blowing agents include aluminum powder, perborates (eg., sodium perborate), peroxides (e.g., H 2 O 2 or an organic peroxide), and chloride dioxide.
- the blowing agent can be present in an amount of from 0.1% to 10% by weight of the reactive powder.
- the aerating agents described herein can also include foaming agents
- the foaming agent can be an air-entraining agent
- Foaming agents can be used to help the system maintain air or other gases, e.g., from the mixing process.
- the foaming agents can include non-ionic surfactants, anion surfactants, and/or cationic surfactants
- suitable foaming agents include sodium alkyl ether sulfate, ammonium alkyl ether sulfate, sodium alpha olefin sulfonate, sodium deceth sulfate, ammonium deceth sulfate, sodium laureth sulfate, and sodium dodecylbenzene sulfonate
- the foaming agents can be provided in an amount of 0.1% or less based on the weight of the reactive powder. In some examples, the foaming agents can be included in the compositions in an amount of from 0.001% by weight to 0.1% by weight or from 0.005% by weight to 0.05% by weight (e.g., 0.01% by weight).
- the reactants to form the inorganic polymer compositions are reacted in the presence of water.
- the water can be provided in the reactive mixture by providing the activator in solution and/or by adding water directly to the reactive mixture.
- the solution to binder or solution to reactive powder weight ratio i.e., the ratio of the solution including activator to reactive powder
- the reactants used to form the inorganic polymer compositions can further include a retardant.
- Retardants are optionally included to prevent the composition from stiffening too rapidly, which can result in a reduction of strength in the structure
- suitable retardants for inclusion as reactants include borax, boric acid, gypsum, phosphates, gluconates, or a mixture of these.
- the retardant is present in an amount of from 0.4% to 7.5% based on the weight of the reactive powder.
- the cementitious material can include a filler, such as those described herein.
- the cementitious material can include a rapid set cement, Portland cement, and a filler such as fly ash, slag, sand, or combinations thereof.
- the cementitious material can include a rapid set cement and a filler such as fly ash, slag, or sand.
- the cementitious material can include Portland cement and a filler.
- the cementitious material consists or consists essentially of a rapid set cement, a filler in an amount of 30% or less by weight (e.g., 25% or less by weight, or 20% or less by weight), based on the total weight of the cementitious material, and optionally Portland cement
- the filler e.g., fly ash, slag, sand, or combinations thereof
- the filler can be present in an amount of from 5% to 30% by weight, based on the total weight of the cementitious material.
- the filler can include a lightweight filter.
- a cementitious material can include a fiber material, e.g., to provide increased strength, stiffness or toughness.
- fire resistant or retardant glass fibers can be included to impart fire resistance or retarding properties to the cementitious material Suitable fiber materials useful with the cementitious material are described herein. The fibers can be included in an amount of 0.1% to 6% based on the weight of the cementitious material
- Additional components useful with the cementitious material described herein include air entraining agents, water reducers, plasticizers, pigments, anti-efflorescence agents, ultraviolet light stabilizers, retardants including fire retardants, antimicrobials, and antioxidants.
- Air entraining agents can be used to entrain air in the cementitious material thereby reducing the density of the cementitious material
- Water reducers can be included in the compositions described herein to reduce the amount of water in the composition while maintaining the workability, fluidity, and/or plasticity of the composition
- the water reducer is a high-range water reducer, such as, for example, a superplasticizer admixture.
- water reducers examples include lignin, naphthalene, melamine, polycarboxylates, lignosulfates and formaldehyde condensates (e g., sodium naphthalene sulfonate formaldehyde condensate).
- Water reducers can be provided in an amount of from greater than 0 to 1% by weight based on the weight of the cementitious material
- the cementitious material can further include a photocatalyst Photocatalysts are optionally included for the reduction of nitrogen oxides (NOx) and self-cleaning.
- the cementitious material can include titanium dioxide
- Example of stumble photocatalyst includes titanium dioxide.
- the photocatalyst can be dispersed within the cementitious material,
- the photocatalyst can be present as a coating on the cementitious material,
- the titanium dioxide can be provided as a coating on the cementitious material and is present in an amount of from 1% to 10% based on the weight of the coating on the cementitious material,
- the cementitious material can be any suitable thickness to confer a desirable property to the composite panel, e.g.. to provide increased strength, handleability, stiffness or toughness .
- the thickness of the cementitious material can be 0.5 inch or less.
- the cementitious material can have an average thickness of 0.4 inch or less. 0.3 inch or less, 0.25 inch or less, 0.20 inch or less, or 0.15 inch or less.
- the cementiuous material can have an average thickness of 0.005 inch or greater, 0.01 inch or greater, 0.05 inch or greater, or 0.1 inch or greater.
- the cementitious layer can have an average thickness of from 0.005 inch to 0.25 inch or from 0.005 inch to 0.20 inch.
- the fiber material (including the fiber reinforcement), the cementitious material, and/or the particulate filler such as fly ash can be coated with a composition to modify their reactivity .
- the fiber material, the cementitious material, and/or the particulate filler can be coated with a sizing agent such as a coupling agent (compatibilizer).
- the fiber material, the cementitious material, and or the particulate filler can be coated with a composition for promoting adhesion.
- U.S Pat. No. 5,064,876 to Hamada er al. and U.S. Pat. No. 5,082,738 to Swofford disclose compositions for promoting adhesion.
- the fiber material, the cementitious material, and/or the paniculate filler are surface coated with a composition comprising a silane compound such as aminosilane
- the fiber material, the cementitious material, and/or the particulate filler are surface coated with a composition comprising an oil, starch, or a combination thereof.
- the composite panel can include a first fiber reinforcement on a first surface of the foam stock and a second fiber reinforcement on a second surface, opposite the first surface, of the foam stock.
- the composite panel can include a first fiber reinforcement on a first surface of the foam stock and a material, other than a fiber reinforcement, on a second surface of the foam stock.
- the material can include a cementitious layer, a paper sheet, a metal sheet, a polymeric layer, or a combination thereof
- Suitable materials that can be included on the second surface of the foam stock include an aluminum sheet, an aluminum-plated sheet, a zinc sheet, a zinc-plated sheet, an aluminum zinc alloy sheet, an aluninum zinc alloy-plated sheet, a stainless steel sheet, craft paper, a polymeric surfacing film, or a combination thereof.
- the foam stocks can be produced using a batch, semi-batch, or continuous process
- the method can include forming a poly urethane or poly anwate mixture.
- the poly urethane or polyisocyanurate mixture can be produced by mixing the one or more isocyanates, the one at more polyols, and the filler in a mixing apparatus.
- the materials can be added in any suitable order.
- the mixing stage of the method used to prepare the foam stock can include: (1) mixing the polyol and filler; (2) mixing the isocyanate with the polyol, and filler, and optionally (3) mixing the catalyst with the isocyanate, the polyol, and the filler.
- the polyurethane or polyisocyanurate mixture can be blended in any suitable manner to obtain a homogeneous or heterogeneous blend of the one or more isocyanate, the one or more polyols, the filler, and the catalyst.
- mixing can be conducted in a high speed mixer or an extruder
- the method can include applying shear to the mixture to disperse the filler in the mixture.
- An ultrasonic device can be used for enhanced mixing and/or wetting of the various components of the composite, The ultrasonic device produces an ultrasound of a certain frequency that can be varied during the mixing and/or extrusion process.
- the ultrasonic device useful in the preparation of composite panels described herein can be attached to or adjacent to the extruder and/or mixer.
- the ultrasonic device can be attached to a die or nozzle or to the port of the extruder or mixer.
- An ultrasonic device may provide de-aeration of undesired gas bubbles and better mixing for the other components, such as blowing agents, surfactants, and catalysts.
- the method of making the foam stock can include allowing the one or more isocyanates and the one or more polyols to react in the presence of the filler to form a polyurethane or polyisocyanurate foam having a first surface and a second surface opposite the first surface.
- the curing stage of the method used to prepare the foam stock can be carried out in a mold cavity of a mold, the mold cavity formed by at least an intenor mold surface.
- the mold can include individual batch molds such as a cardboard box.
- the cardboard box can work as a protective material during handling of the mold in the plant.
- a molded article can then be formed prior to the additional method steps in forming the composite panel
- the polyurethane or polyisocyanurate mixture can be applied to the mold using a nozzle traversing the mold.
- the one or more polyols, one or more isocyanates, or a mixture thereof, and the filler can be included in amounts, which result in a workable viscosity (initial viscosity) of 100,000 cPs or less for the polyurethane or polyisocyanurate mixture, and thus improves the processability of such materials and products.
- the mixture can be applied to the mold at a viscosity of from 5,000 to 100,000 cPs or from 20,000 to 100,000 cPs at the temperature of the mixture, The viscosity of the composite mixture can be measured using a Brookfield Viscometer.
- the polyurethane or polyisocyanurate mixture can be foamed
- the method of making the polyurethane or polyisocyanurate foams can include allowing the mixture to expand via a gas phase to form a foam having a first surface and a second surface opposite the first surface.
- the gas phase can be generated in situ from reaction of water with the one or more isocyanates.
- the gas can be introduced into the polyurethane mixture Suitable gases are known in the art.
- the gas can be captured after gelation (i.e., formation) of the foam
- the foaming action of the polyurethane or polyisocyanurate foams can be described as having a “cream time,” during which foaming is initiated and the mixture reaches a consistency of a soft creamy foam, a “firm time” at which the foam sets up and hardens, and a “tack free time” at which time surface no longer feels sticky.
- the cream time of the polyisocyanurate or polyurethane can be 20 seconds or longer. 40 seconds or longer. 60 seconds or longer, or 80 seconds or longer
- the cream time of the polyisocyanurate or polyurethane can be from 20 seconds to 120 seconds, from 40 seconds to 120 seconds, from 60 seconds to 120 seconds or from 80 seconds to 120 seconds.
- the tack free time of the polyisocyanurate or polyurethane can be 90 seconds or longer, 2 minutes or longer, 3 minutes or longer, 4 minutes or longer, or 5 minutes or longer and/or 7 minutes or less, 6 minutes or less, 5 minutes or less, or 4 minutes or less.
- the tack free time of the polyisocyanurate or polyurethane can be from 90 seconds to 7 minutes, from 2 minutes to 7 minutes or from 3 minutes to 6 minutes
- the polyisocyanurate or polyurethane foam reaches a hardness of 20 shore D at no less than 5 minutes.
- the polyisocyanurate or polyurethane foam does not reach a hardness of 20 shore D in less than 5 minutes.
- the polyurethane foam does not reach a hardness of 20 shore D in less than 7.5 minutes, less than 10 minutes, less than 12.5 minutes, less than 15 minutes, less than 17.5 minutes, or less than 20 minutes.
- the Shore D hardness can be determined using a durometer as described in ASTM D2240.
- the mixture can be allowed to rise freely during foaming in the mold.
- the method can include removing the foam stock from the mold.
- the mold can be a flexible, disposable container.
- the method can include cutting through the container to remove the foam stock from the mold
- the foam stock can be trimmed to remove the bottom skin from the mold and the crown of the foam stock or bun that forms from the free rise of the foam
- the foam stock can be cut using a horizontal blade into a plurality of polyurethane or polyisocyanurate foam units having predetermined thicknesses.
- the polyurethane or polyisocyanurate foam thickness can be from 0.1 inch to 6 inches
- the polyurethane or polyisocyanurate foam can have a thickness of 0.1 inch to 4 inches, 0.1 inch to 3 inches, 0.1 inch to 2 inches, or 0.125 inch to 1 inch.
- Composite panels can be produced from the cut polyurethane or polyisocyanurate foam units.
- the method can include applying a first fiber reinforcement to a surface of the foam
- the fiber reinforcement can be applied to the foam before it has completely cured, such that at least a portion of the fiber reinforcement becomes embedded in the foam.
- the fiber reinforcement can be applied to the polyurethane or polyisocyanurate mixture after the mixture is fed to the mold.
- the fiber reinforcement can be applied to the mold prior to the mixture being fed into the mold and can become embedded prior to the full curing of the mixture.
- the fiber reinforcement can be applied to the foam after the polyurethane or polyisocyanurate has been cured.
- an adhesive can be applied to bond the fiber reinforcement to the foam.
- the adhesive can be applied by spray coating, curtain coating, brushing, roller coating, dip coating, spin coating, or flow coating.
- Suitable adhesives include an adhesive derived from ethylene vinyl acetate, acrylic, urethane, epoxy, starch, gum, resin (such as gum arabic, gum tragacanth, rubber or shellac), or combinations thereof.
- the method can further include applying a cementitious material to the fiber reinforcement.
- the cementitious material can be in the form of a cementitious slurry.
- the cementitious slurry can be applied by roller coating, curtain coating, dip coating, brushing, with a trowel, or spraying.
- the application of the cementitious material can be vacuum assisted.
- the method can include applying the cementitious slurry to the fiber reinforcement, after applying the fiber reinforcement to the foam.
- the cementitious material and the fiber reinforcement can be applied to the foam simultaneously.
- the method can include applying a cementitious slurry to the fiber reinforcement prior to applying the fiber reinforcement to the foam. In this example, at least a portion of the fiber reinforcement becomes embedded in the cementitious material
- the method can include applying the cementitious slurry to the foam, prior to applying the fiber reinforcement to the foam
- the method of making the composite panels can include applying an adhesive to the fiber reinforcement or the foam prior to applying the cementitious material to facilitate bonding of the cementitious material.
- the adhesive can be applied by spray coating, curtain coating, brushing, roller coating, dip coating, spin coating, or flow coating Suitable adhesives are described herein.
- the method can include applying a water and/or water vapor barrier prior to applying the cementitious material
- the adhesive can produce a water and/or water vapor barrier.
- a water and/or water vapor barrier film or other material can be applied prior to applying the cementitious material.
- the cementitious material, the first fiber reinforcement and the foam are directly adhered without the use of an adhesive layer.
- the cementitious slurry and the first fiber reinforcement are directly bonded to a fly ash-filled foam, it has been discovered that the cementitious slurry forms mechanical bonds with the fly ash present in the foam thereby enhancing the bonding of the cementitous slurry and the first fiber reinforcement to the foam.
- the method can include apply ing a liquid to a surface of the foam to activate the cementitious slurry.
- the liquid can be an aqueous solution having a pH of 5 or greater or 6.5 or greater
- the liquid optionally includes an activator. Suitable activators are described herein.
- incorporation of the fiber reinforcement and/or the cementitious layer onto the filled foam can maintain similar or improved physical properties and mechanical performance such as flexural strength, hardness, stiffness, flame resistance and handleability of such material, when the fiber reinforcement and/or the cementitous layer is excluded from or included in minor amounts in the foam
- the optimization of various properties of the composite panels, such as hardness, stiffness, flexural strength, handleability, and flame resistance of the foams allows their use in building materials and other structural applications.
- the composite panels can be formed into shaped articles and used in building materials Suitable building materials include building panels, tile backer board, sheathing, roofing products, siding materials, sheets, sound barrier/insulation, thermal barriers, insulation, decking materials, fencing materials, dadding, or other shaped articles.
- Examples of shaped articles made using the composite panels described herein include roof tiles such as roof tile shingles, roof cover boards, slate panels, shake panels, cast molded products, moldings, sills, stone, masonry, brick products, posts, signs, guard rails, retaining walls, park benches, tables, slats, corner arches, columns, wall boards, ceiling tiles, ceiling boards, soffits, or railroad ties.
- roof tiles such as roof tile shingles, roof cover boards, slate panels, shake panels, cast molded products, moldings, sills, stone, masonry, brick products, posts, signs, guard rails, retaining walls, park benches, tables, slats, corner arches, columns, wall boards, ceiling tiles, ceiling boards, soffits, or railroad ties.
- incorporation of the fiber reinforcement on the filled foam to form the composite panels can increase the flexural strength of the foam, compared to a foam without the fiber reinforcement
- the flexural strength of the foam can be increased by at least 10%, for example. 15% or greater, 20% or greater, 25% or greater, 30% or greater, 35% or greater, 50% or greater, 75% or greater, or even 100% or greater, compared to a foam without the fiber reinforcement
- the flexural strength of the composite panels described herein can be 200 psi or greater (e.g., up to 1600 psi).
- the flex ural strength of the composite panels can be 300 psi or greater, 500 psi or greater, 700 psi or greater, 900 psi or greater, 1000 psi or greater, 1100 psi or greater, 1200 psi or greater, 1300 psi or greater, 1400 psi or greater, or 1500 psi or greater.
- the flexural strength can be determined by the load required to fracture a rectangular prism loaded in the three point bend test as described in ASTM C1185-08 (2012).
- incorporation of die fiber reinforcement and the cementitious layer on the filled polyurethane foam can increase the hardness of the foam, compared to a composite without the fiber reinforcement and the cementitious layer.
- the Shore D hardness of the composite panels described herein can be 50 or greater (eg., up to 90).
- the Shore D hardness of the composite panels can be 55 or greater, 60 or greater, 65 or greater, 75 or greater, or 80 or greater.
- the Shore D hardness can be determined using a durometer as described in ASTM D2240.
- incorporation of the fiber reinforcement and the cementitious lay er on the foam can increase the sti ffness of the composite, compared to a composite without the fiber reinforcement and the cementitious layer.
- themodulus of elasticity (stiffness) of the composite panel can be 10 ksi or greater, 50 ksi or greater or 100 ksi or greater.
- the modulus of elasticity can be from 10 to 500 ksi or from 50 to 500 ksi
- the modulus of elasticity can be determined as described in ASTM C947-03.
- incorporation of the fiber reinforcement and the cementitious layer on the filled foam can increase the flame resistance of the composite, compared to a composite without the fiber reinforcement and the cementitious layer.
- the composite panels can be qualified as a Class A material in the ASTM E84 tunnel test.
- the composite panels have a flame spread rating of 25 or less and a smoke development rating of 450 or less. The flame spread and smoke development ratings can be determined as described in the ASTM E84 test.
- Polyurethane foams were prepared using three different polyols labeled as Polyol A, a petroleum-derived polypropylene based polyol having a hydroxyl number of 240 mg KOH/g, a functionality of 3, and a viscosity of 250 mPa.s; Polyol B, a glycerin initiated polyether polyol having a hydroxyl number of 240 mg KOH/g, a functionality of 3, and a viscosity of 250 mPa.s at 25° C.; and Polyol C, a sucrose/amine initiated polyether polyol having a hydroxyl number of 350 mg KOH/g, a functionality of 5.5, and a viscosity of 2,500 mPa.s at 25° C.
- Polyol A a petroleum-derived polypropylene based polyol having a hydroxyl number of 240 mg KOH/g, a functionality of 3, and a viscosity of 250 mPa.s
- the composites were prepared by wetting fly ash and 1 ⁇ 8′′ chopped fiber glass in an extruder with concurrent streams of polyol (about 12% by weight of the foam) and methylene diphenyl diisocyanate (about 13% by weight of the foam) and optionally a catalyst and simultaneously stirring began.
- the mixture was extruded into a cardboard box and allowed to freely rise and cure.
- the physical properties of the composites including flexural strength, density, handleability, extension, and modulus were determined.
- the handleabdity is a measure of the ability of the material to be flexed during use and is calculated as 0.5 ⁇ breaking load ⁇ ultimate deflection/thickness of the test specimen.
- the extension is a measure of the deflection of a sample during the three point bend test as defined in ASTM C947-03.
- the modulus is calculated from the stress/strain curve of the three point bend test, Normalized flexural strength is the ratio of flexural strength divided by the density
- the polyurethane foams prepared using Polyols A-C produced foams having suitable density, modulus, flexural strength, extension, and handleability.
- the cream time for the three samples was 41 seconds up to 115 seconds.
- the tack-free time was from 140 seconds up to 375 seconds
- compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Polyurethane or polyisocyanate form stock and methods of manufacturing are described herein. The foam stock can include (a) a polyurethane or polyisocyanate formed by the reaction of (i) one or more isocyanates selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, and (ii) one or more polyols; and (b) a filler present in an amount from greater than 50% to 90% by weight, based on the total weight of the foam stock. The density of the foam stock can be from 10 lb/ft3 to 35 lb/ ft3. The flexural strength of the foam stock can be at least 100 psi. The resulting foam stock can be used to produce polyurethane or polyisocyanate foam to be used in composite panels.
Description
- This disclosure relates generally to polyurethane or polyisocyanurate foams, more particularly, to highly filled polyurethane or polyisacyanurare foams.
- Polymeric composites that contain organic and/or inorganic filler materials have become desirable for a variety of uses because of their excellent mechanical properties and weathering stability. In general, the superior properties of the organic-inorganic composites are achieved through use of the organic as a matrix material that acts as a glue with enhanced flexural properties or as a fibrous component providing reinforcement and improved tensile properties. The inorganic material imparts various properties of rigidity, toughness, hardness, optical appearance, interaction with electromagnetic radiation, density, and many other physical and chemical attributes.
- The use of polyurethane compositions has grown due to their superior tensile strength, impact resistance, and abrasion resistance compared to, for example, unsaturated polyester and vinyl ester-based composites. Processes for preparing polyurethane foamed compositions are known and have significant commercial success. However, certain problems that often limit application of the polyurethane foams are known to those in the industry. For example, die processes to prepare these compositions may experience difficulties. Additionally, the foams may be brittle, or suffer from poor adhesion to substrates due to the relatively high urea concentration that often forms on the surface of these foams. The foams may also be dimensionally unstable, due to a relatively high diffusion coefficient of the carbon dioxide through the cell walls, and demolding may be poor due to the relatively high exothermic nature of the water-blown reactions. Thus, there is a need for alternate polyurethane foams with desirable mechanical properties The compositions and methods described herein address these and other needs.
- Polyurethane or poiyisocyanurate foam stock and methods of manufacturing are described herein. In some embodiments, the foam stock can include (a) a polyurethane or polyisocyanurate formed by the reaction of (i) one or more isocyanates selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, and (ii) one or more polyols, and (b) a filler in an amount of from greater than 50% to 90% by weight, based on the total weight of the polyurethane composite, wherein during formation of the foam stock, the reaction mixture of the one or more isocyanates and one or more polyols is allowed to rise freely (eg. in a mold). The density of the foam stock can be at least 10 lb/ft3. In some cases, the density of the foam stock can be from 10 lb/ft3 to 35 lb/ft3, from 10 lb/ft3 to 30 lb/ft3 or from 15 lb/ft3 to 25 lb/ft3 The flexural strength of the foam stock can be at least 100 psi. In some cases, the flexural strength of the foam slock can be from 100 psi to 700 psi.
- The amount of polyorethane or polyisocyanurate in the foam stock can be from 100% to 50% by weight, for example, 15% to 45% by weight, based on the total weight of the foam stock In some embodiments, the one or more polyols can have an average hydroxyl number of from 100 to 700 mg KOH/g, from 100 to 500 mg KOH/g, or from 200 to 400 mg KOH/g. The one or more polyols can have an average molecular weight of from 250 to 1500 g/mol from 500 to 1000 g/mol. The average functionality of the one or more polyols can be from 2.5 to 5.5. from 3 to 5.5, or from 3 to 4. The one or more first polyols can have an average viscosity of 150 to 5000 cPs or from 150 to 2500 cPs at 25° C. In some cases, a blend of the one or more polyols and the one or more isocyanates used in the foams can have an average viscosity of from 100 to 6000 cPs, from 100 to 2500 cPs, or from 100 to 1400 cPs at 25° C.
- As described above, the polyurethane or polyisocyanurate foam stock can include a filler, The filler can include a particulate filler and/or a plurality of fibers. The particulate filler in the foam stock can include coal ash such as fly ash. The amount of particulate filler in the foam stock can be from 50 to 90% by weight, based on the total weight of the foam stock For example, the particulate filler can be present in an amount from 50% to 85% or from 60% to 80% by weight, based on the total weight of the foam stock.
- The plurality of fibers can be present in the foam stock can be from 0.25% to 10%by weight, based on the total weight of the foam stock. In some examples, the fibers can be present in an amount from 0.25% to 8%, from 0 25% to 6% from 0.5% to 6% or from 0.5% to 5% by weight, based on the total weight of the foam stock. Examples of fibers useful in the foam stock can include a plurality of glass fibers, polyalkylene fibers, polyester fibers, polyamide fibers, phenol-fornmldehyde fibers, polyvinyl chloride fibers, polyacrylic fibers, acrylic polyester fibers, polyurethane fibers, polyacrylonitrile fibers, rayon fibers, cellulose fibers, carbon fibers, metal and metal-coated fibers, mineral fibers, or combinations thereof in some embodiments, the foam stock comprises a plurality of glass fibers. The glass fibers can have an average length of 1 mm or greater. In some examples, the glass fibers can have an average length of from 1.5 mm to 30 mm In some embodiments, the foam stock is free of fibers.
- The average thickness of the polyurethane or polyisocyanurate foam stock can be 2 inches or greater or 2 feet or greater. In some embodiments, the average thickness of the polyurethane or polyisocyanurate foam stock can be from 1 inch to 4 feet, from 3 inches to 4 feet, or from 2 feet to 4 feet.
- Methods of making the polyurethane or polyisocyanurate foam stock are also described herein. The method can include mixing the (i) one or more isocyanates selected from the group consisting of drisocyanates, polyisocyanales, and mixtures thereof, (ii) one or more polyols, and (iii) filler to form a mixture. The mixture may further comprise a catalyst The mixture can include the catalyst at 0.05 to 0.5 part per hundred pans of polyol. The method can include allowing the one or more isocyanates and the one or more polyols to react in the presence of the particulate filler.
- The polyurethane or polyisocyanurate foam stock can be formed in a mold. The mold can be a flexible, disposable container which can be removed from the foam by cutting through the container For example, the mold can be a cardboard box. The method can include applying the mixture to a mold at a viscosity of from 5,000 to 100,000 cPs or from 20,000 to 100,000 cPs at the temperature of the mixture The mixture can be applied to the mold using a nozzle traversing the mold. The mixture applied to the mold can have a tack free time of from 90 seconds to 7 minutes or from 2 to 7 minutes. The mixture can also have a cream time of from 20 to 120 seconds, from 40 to 120 seconds or from 80 to 120 seconds
- The method of making the polyurethane or polyisocyanurate foam stock can include allowing the mixture to react and expand to form the polyurethane or polyisocyanurate foam. The mixture can be allowed to rise freely during foaming in the mold. In some embodiments, the foam does not reach a hardness of 20 shore D in less than 5 minutes or in less than 10 minutes. The method can further include cutting the resulting foam.
- Foam stocks including poly urethane or polyisocyanurate and methods of preparing the foam stocks are described herein. The term “foam stock” as used herein, may also be referred to as a “foam,” “bun,” “bun stock.” or “foam bun stock.” The foam stock can comprise a polyurethane or polyisocyanurate formed using reactive systems including reactive isocyanates and reactive polyols
- Isocyanates suitable for use in the foam stock described herein include one or more monomeric or oligomeric poly- or di-isocyanates The monomeric or oligomeric poly- or diisocyanate include aromatic diisocyanates and polyisocy anates. The isocyanates can also be blocked isocy anates or pre-polymer isocyanates. The particular isocyanate used in the foam stock can be selected based on the desired viscosity of the mixture used to form the foam stock. A low viscosity is desirable for ease of handling Other factors that influence the particular isocyanate can include the overall properties of the foam stock, such as the amount of foaming, strength of bonding to the filler, wetting of the inorganic particulates in the reaction mixture, strength of the resulting foam, stillness (elastic modulus), and reactivity Suitable isocyanate compositions for forming the foam stock include those having viscosities ranging front 25 to 700 cPs at 2° C.
- An example of a useful diisocyanate is methylene diphenyl diisocyanate (MDI). Useful MDl’s include MDI monomers. MDI oligomers, and mixtures thereof. Further examples of useful isocyanates include those having NCO (i e., the reactive group of an isocyanate) contents ranging from about 25% to about 35% by weight. Examples of useful isocy anates are found, for example, in Polyurethane Handbook: Chemistry, Raw Materials. Processing Application. Properties. 2nd Edition. Ed Gunter Oertel; Hanser/Gardner Publications, Inc, Cincinnati. OH. which is herein incorporated by reference Suitable examples of aromatic polyisocyanates include 2,4- or 2,6-toluene diisocyanate, including mixtures thereof; p-phenylene diisocyanate, tetramethylene and hexamethylene diisocyanates, 4,4-dicyclohexylmethane diisocytate; isophorone diisocyanate, 4,4-phenylmethane diisocyanate; polymethylene polyphenylisocyanate; and mixtures thereof. In addition, triisocyanates may be used, for example, 4,4,4-triphertyl methane triisocyanate; 1,2,4-benzene triisocyanate; polymethylene polyphenyl polyisocyanate, methylene polyphenyl polyisocyanate, and mixtures thereof. Suitable blocked isocyanates are formed by the treatment of the isocyanates described herein with a blocking agent (e.g.. diethyl malonate, 3,5-dimethylpyrazole, methylethylketoxime, and caprolactarn). Isocyanates are commercially available, for example, from Bayer Corporation (Pittsburgh, PA) under the trademarks MONDUR and DESMODUR. Other examples of suitable isocyanates include MONDUR MR Light (Bayer Corporation. Pittsburgh, PA), PAPI 27 (Dow Chemical Company: Midland. MI), Lupranate M20 (BASF Corporation: Florham Park, NJ), Lupranate M70L (BASF Corporation, Florham Park, NJ). Rubinate M (Huntsman Polyurethanes; Geismar. LA). Econate 31 (Ecopur Industries), and derivatives thereof.
- The average functionality of isocyanates useful with the foam stocks described herein can be from 1.5 to 5. Further, examples of useful isocyanates include isocyanates with an average functionality of 2 to 4.5, 2.2 to 4, 2.4 to 3.7, 2.6 to 3.4, and 2.8 to 3.2.
- As indicated herein, the poly urethane or polyisocyanurate foam stock includes one or more polyols It is generally desirable to use polyols in liquid form, and generally in low viscosity liquid form available, as these can be more easily mixed. Suitable polyol compositions for forming the foam stock include those having viscosities of 5000 cPs or less at 25° C. In certain embodiments, the polyol composition can include those having viscosities of 4500 cPs or less, 4000 cPs or less, 3500 cPs or less, 3000 cPs or less, 2500 cPs or less, or 2000 cPs or less at 25° C. In certain embodiments, the polyolcomposition can include those having viscosities of 150 cPs or greater. 250 cPs or greater, 500 cPs or greater. 750 cPs or greater. 1000 cPs or greater, or 1500 cPs or greater. In certain embodiments, the polyol composition can include those having viscosities of from 150 to 5000 cPs or from 150 to 2500 cPs at 25° C. In some embodiments, a blend of the one or more polyols and the one or more isocyanates used in the foams can have a viscosity of from 100 to 6000 cPs, from 100 to 2500 cPs, from 100 to 1400 cPs, from 100 to 1200 cPs or from 100 to 1000 cPs at 25° C.
- The one or more polyols can have an average equivalent weight of 150 g/eq or greater (eg., 175 g/eq or greater, 200 g/eq or greater, 210 g/eq or greater, 220 g/eq or greater, 225 g/eq or greater, or 230 g/eq or greater) .In some cases, the one or more polyols have an average equivalent weight of 700 g/eq or less (eg., 550 g/eq or less, 500 g/eq or less, 450 g/eq or less, 400 g/eq or less, 350 g/eq or less, 300 g/eq or less, 275 g/eq or less, 250 g/eq or less, or 235 g/eq or less). In some cases, the one or more polyols have an average equivalent weight of from 150 g/eq to 700 g/eq, from 175 g/eq to 700 g/eq, from 200 g/eq to 700 g/eq, from 150 g/eq to 500 g/eq, from 1 50 g/eq to 400 g/eq, or from 150 g/eq to 300 g/eq. In some embodiments, the one or more polyols do not include any polyols having an equivalent weight of 750 g/eq or greater.
- In some embodiments2 the one or more polyols in the polyurethane or polyisocyanurate foam stock can include a less reactive polyol. The less reactive polyol can have lower numbers of primary hydroxyl groups, lower primary hydroxyl numbers, higher numbers of secondary hydroxyl groups, and higher cream times and tack-free times in a poly urethane or polyisocyanurate mixture, than a highly reactive polyol. In some embodiments, the one or more polyols can be capped with an alkylene oxide group, such as ethylene oxide, propylene oxide, butylene oxide, and combinations thereof, to provide the polyols with the desired reactivity. In some examples, the one or more polyols can include a poly(propylene oxide) polyol which contain terminal secondary hydroxyl groups and are end-capped with ethylene oxide to provide polyols with primary hydroxyl groups
- In some embodiments, the one or more polyols have about 40% or less primary hydroxyl groups, about 35% or less primary hydroxyl groups, about 30% or less primary hydroxyl groups, about 25% or less primary hydroxyl groups, about 20% or less primary hydroxyl groups, about 15% or less primary hydroxyl groups, or even about 10% or less primary hydroxyl groups. The one or more polyols can have primary hydroxyl numbers (as measured in units of mg KOH/g) of less than about 220, less than about 200, less than about 180. less than about 160, less than about 140, less than about 120, less than about 100, less than about 80, less than about 60, less than about 40, or even less than about 20. The number of primary hydroxyl groups can be determined using fluorine NMR spectroscopy as described in ASTM D4273.
- The one or more polyols can have hydroxyl numbers (as measured in units of mg KOH/g) of 1000 or less, 900 or less, 800 or less, 700 or less. 650 or less, 600 or less, 550 or less, 500 or less, 450 or less. 400 or less, 350 or less, 300 or less, 250 or less, 200 or less, or 150 or less, The one or more polyols can have hydroxyl numbers (as measured in units of mg KOH/g) of 50 or more, 100 or more, 150 or more, 200 or more, 250 or more, 300 or more 350 or more, 400 or more. 450 or more, or 500 or more. In some embodiments, the average hydroxyl number is 700 or less, 650 or less, 600 or less, 550 or less, 500 or less, 450 or less, 400 or less. 350 or less, 300 or less, or 250 or less, and/or is 100 or more. 150 or more. 200 or more. 250 or more, 300 or more. 350 or more, 400 or more. 450 or more, or 500 or more. For example, the average hydroxyl number can be from 100-700, 100-500, 150-450, or 200-400. In some embodiments, the one or more polyols include two or more polyols. For example, there can be a blend of 75% of a polyol having a hydroxyl number of 400 and 25% of a polyol having a hydroxyl number of 100 to produce an average hydroxyl number of 325.
- The polyurethane or polyisocyanurate foam stock can include one or more polyols that can provide a delay in the cream time and tack free time of the polyurethane or polyisocyanurate mixture during foaming For example, the foam stock can include polyols containing glycerine and/or amine groups which can delay the cream time and/or tack free time of the poly urethane or polyisocyanurate mixture In some embodiments, the one or more polyols can increase the cream time of the polyurethane or polyisocyanurate mixture to 40 seconds or greater such as from 40 seconds to 120 seconds. In some embodiments, the one or more polyols can increase the tack-free time of the poly urethane or polyisocyanurate mixture to 90 seconds or greater such as from 90 seconds to 7 minutes.
- The one or more poly ols can include amine groups, such as primary amine groups, secondary amine groups, tertiary amine groups, or combinations thereof In some embodiments, the total amine value (i.e., a measure of the concentration of tertiary, secondary, and primary amine groups as measured in units of mg KOH/g) is 50 or less, 45 or less, 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less, The one or more polyols can have a total amine value (as measured in units of mg KOH/g) of from 0 to 50, from greater than 0 to 50, or from greater than 0 to 45.
- The functionality of the one or more polyols useful with the foam stocks described herein can be 7 or less, 6.5 or less, 6 or less, 5.5 or less, 5 or less, 4.5 or less, 4 or less. 3.5 or less, 3.25 or less, 3 or less, 2.75 or less, 2.5 or less, or 2.25 or less, In some embodiments, the functionality of the one or more polyols can be 2 or greater, 2.25 or greater, 2.5 or greater, 2.75 or greater, 3 or greater, 3.25 or greater, 3.5 or greater, 3.75 or greater, or 4 or greater, The average functionality of the one or more polyols useful with the foam described herein can be 5.5 or less, for example, 5 or less, 4.5 or less, 4 or less, 3.5 or less, 3.25 or less, 3 or less, 2.75 or less, 2 5 or less, or 2.25 or less, In some embodiments, the average functionality of the one or more first polyols can be 2 or greater, 2.25 or greater, 2.5 or greater, 2.75 or greater, 3 or greater, 3.25 or greater, 3.5 or greater. 3.75 or greater, or 4 or greater Further, examples of useful first polyols include polyols with an average functionality of from 2.0 to 5.5, from 3 to 5.5, from 3 to 5, from 3 to 4.5, from 2.5 to 4, from 2.5 to 3.5, or from 3 to 4.
- The one or more polyols can have an average molecular weight of 250 g/mol or greater (e.g., 300 g/mol or greater, 350 g/mol or greater, 400 g/mol or greater, 450 g/mol or greater, 500 g/mol or greater, 550 g/mol or greater, 600 g/mol or greater, 650 g/mol or greater, 700 g/mol or greater, 750 g/mol or greater, 800 g/mol or greater, 900 g/mol or greater. 1000 g/mol or greater, 1200 g/mol or greater, or 1400 g/mol or greater). In some cases, the one or more polyols have an average molecular weight of 1500 g/mol or less (e g. 1400 g/mol or less, 1300 g/mol or less, 1200 g/mol or less, 1100 g/mol or less, 1000 g/mol or less, 900 g/mol or less, 800 g/mol or less, 750 g/mol or less. 700 g/mol or less. 650 g/mol or less, 600 g/mol or less, 550 g/mol or less, 500 g/mol or less, 450 g/mol or less, 400 g/mol or less, or 300 g/mol or less). In some cases, the one or more polyols have an average molecular weight of from 250 g/mol to 1500 g/mol. from 250 g/mol to 1000 g/mol or from 500 g/mol to 1000 g/mol. In some embodiments, the one or more polyols do not include any polyols having a molecular weight of 1000 g/mol or greater.
- Table 1 provides a description of exemplary polyols (Polyols A-C) that can be used in the the poly urethane and polyisocsanurate foam stock.
-
TABLE 1 Properties of Polyols A-C. Properties Polyol A Polyol B Polyol C Description Glycerine Glycerine, propylene oxide Sucrose, diethanol amine, propylene oxide Equivalent wt, g/eq 234 234 154-167 OH # (mg KOH/g) 240 240 335-365 Functionality 3 3 5.5 Ethylene oxide cap (EOC, %) 8 25 Total amine value (TAV, mg KOH/g) 49 Vise (cPs @ 25° C.) 250 250 2500 Cream time (s) 115 85 41 Tack-free Time (s) 240 140 375 - The one or more poly ols can include polyester polyols. a polyether polyols, or combinations thereof. Suitable polyols include polyether polyols such as those sold under the Carpol® trademark or under the Jeffol® trademark. In some examples, the polyether polyol can include a glycerin-based polyol and derivatives thereof commercially available from Carpenter Co. (e.g., Carpol® GP-240; Carpol® GP-725, Carpol® GP-700; Carpol® GP-1000; Carpol® GP-1500;). In some examples, the polyether polyol can include a polypropylene-based polyol and derivatives thereof commercially available from Huntsman International (e.g., Jeffol® FX31-240; Jeffol® G30-650; Jeffol® FX31-167; Jeffol® A-630; Jeffol® AD-310). Suitable polyols include polyester polyols available from Huntsman International (e.g., XO 13001). In some embodiments, the polyols can include a sucrose and/or amine-based polyol. Tire sucrose and/or amine-based polyol can include, for example, a polyether polyol (including for example ethylene oxide, propylene oxide, butylene oxide, and combinations thereof) which is initiated by a sucrose and/or amine group. Sucrose and/or amine-based polyols are known in the art, and include, for example, sucrose/amine initiated polyether polyol sold under the trade name CARPOL® SPA-357 or CARPOL® SPA-530 (Carpenter Co., Richmond, VA) and triethanol amine initiated polyether poly ol sold under the trade name CARPOL® TEAP-265 (Carpenter Co., Richmond. VA).
- The polyurethane or polyisocyanurate foam stock can include one or more additional polyols. In some examples, the one or more additional polyols include aromatic polyols such as aromatic polyester polyols, aromatic polyether polyols, or combinations thereof, such as those sold under the TEROL® trademark (e.g., TEROL® 198 and TEROL® 250). The aromatic polyol can have an aromaticity of 35% or greater, such as 38% or greater, 40% or greater, 45% or greater, 50% or greater, or 55% or greater and/or an aromaticity of 80% or less, 75% or less. 70% or less, 65% or less, 60% or less, 55% or less, 50% or less. 45% or less, 50% or less, 45% or less, or 40% or less.
- In some embodiments, the one or more additional polyols can include polyols having a large number of primary hydroxyl groups (e.g., 75% or more) based on the total number of hydroxyl groups in the polyol For example, the high primary hydroxyl group polyols can include 80% or more, 85% or more, 90% or more, 95% or more, or 100% of primary hydroxyl groups.
- In some embodiments, the one or more additional polyols can include a Mannich polyol. Mannich polyols are the condensation product of a substituted or unsubstituted phenol, an alkanolamine, and formaldehyde. Mannich polyols can be prepared using methods known in the art. For example, Mannich poly ols can be prepared by premixing the phenolic compound with a desired amount of the alkanolamine, and then slowly adding formaldehyde to the mixture at a temperature below the temperature of Novolak formation. At the end of the reaction, water is stripped from the reaction mixture to provide a Mannich base. See, for example, U.S. Pat. No. 4,883,826, which is incorporated herein by reference in its entirety. The Mannich base can then be alkoxylated to provide a Mannich polyol.
- The substituted or unsubstituted phenol can include one or more phenolic hydroxyl groups. In certain embodiments, the substituted or unsubstituted phenol includes a single hydroxyl group bound to a carbon in an aromatic ring The phenol can be substituted with substituents which do not undesirably react under the conditions of the Mannich condensation reaction, a subsequent alkoxylation reaction (if performed), or the preparation of polyurethanes from the final product. Examples of suitable substituents include alkyl (e.g., a C1-C18 alkyl, or a C1-C12 alkyl), aryl, alkoxy, phenoxy, halogen, and nitro groups
- Examples of suitable substituted or unsubstituted phenols that can be used to form Mannich polyols include phenol, o-, p-, or m-cresols, ethylphenol, nonylphenol, dodecylphenol, p-phenylphenol, various bisphenols including 2,2-bis(4-bydroxyphenyl)propane (bisphenol A), β-naphthol, β-hydroxyanthracene, p-chlorophenol, o-bromophenol, 2,6-dichlorophenol, p-nitrophenol, 4- or 2-nitro-6-phenylphenol, 2-nitro-6- or 4-methylphenol, 3,5-dimethylphenol, p-isopropylphenol, 2-bromo-6-cyclohexylphenol, and combinations thereof. In some embodiments, the Mannich polyol is derived from phenol or a monoalkyl phenols (e.g., a para-alkyl phenols). In some embodiments, the Mannich polyol is derived from a substituted or unsubstituted phenol selected from the group consisting of phenol, para-n-nonylphenol, and combinations thereof.
- The alkanolamine used to produce the Mannich polyol can include a monoalkanolamine, a dialkanolamine, a trialkanolamine, a tetraalkanolamine, or combinations thereof. Examples of suitable monoalkanolamines include methylethanolamine, ethylethanolamine, methyhsopropanolamine, ethylisopropanolamine, methyl-2-hydroxybutylamine, phenylethanolamine, ethanolanime, isopropanolamine, and combinations thereof. Suitable dialkanolamines include dialkanolamines which include two hydroxy-substituted C1C-12 alkyl groups (e.g., two hydroxy-substituted C1-C8 alkyl groups, or two hydroxy-substituted C1-C6 alkyl groups). The two hydroxy-substituted alkyl groups can be branched or linear, and can be of identical or different chemical composition. Examples of suitable dialkanolamines include diethanolamine, diisopropanolamine, ethanolisopropanolamine, ethanol-2-hydroxybutylamine, isopropanol-2-hydroxybutylamine, isopropanol-2-hydroxyhexylamine, ethanol-2-hydroxyhexylamine, and combinations thereof. Suitable trialkanolamines include trialkanolamines which include three hydroxy-substituted C1-C12 alkyl groups (e.g., three hydroxy-substituted C1-C8 alkyl groups, or three hydroxy-substituted C1-C6 alkyl groups). The three hydroxy-substituted alkyl groups can be branched or linear, and can be of identical or different chemical composition. Examples of suitable trialkanolamines include triisopropanoiamine (TIPA), triethanolamine, N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine (DEIPA), N,N-bis(2-hydroxypropyl)-N-(hydroxyethyl)amine (EDIPA), tris(2-hydroxybutyl)amine, hydroxyethyl di(hydroxypropyl)amine, hydroxypropyl di(hydroxyethyl)amine, tri(hydroxypropyl)amine, hydroxyethyl di(hydroxy-n-butyl)amine, hydroxybutyl di(hydroxypropyl)amine, and combinations thereof. Exemplary tetraalkanolamines include four hydroxy-substituted C1-C1 2 alkyl groups (e.g. four hydroxy-substituted C1-C8 alkyl groups, or four hydroxy-substituted C1-C6 alkyl groups). In certain embodiments, the alkanolamine is selected from the group consisting of diethanolamine, diisopropanolamine, and combinations thereof.
- Any suitable alkylene oxide or combination of alkylene oxides can be used to form the Mannich polyol In some embodiments, the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and combinations thereof. In certain embodiments, the Mannich polyol is alkoxylated with from 100% to about 80% propylene oxide and from 0 to about 20 wt% ethylene oxide.
- Mannich polyols are known in the art, and include, for example, ethylene and propylene oxide-capped Mannich polyols sold under the trade names CARPOL® MX-425 and CARPOL® MX-470 (Carpenter Co., Richmond, VA).
- In some embodiments, the reaction mixture can include one or more additional isocyanate-reactive monomers such as one or more polyamines. Suitable polyamines can correspond to the polyols described herein (for example, a polyester polyol or a polyether polyol), with the exception that the terminal hydroxy groups are converted to amino groups, for example by amination or by reacting the hydroxy groups with a diisocyanate and subsequently hydrolyzing the terminal isocyanate group to an amino group By was of example, the polyamine can be polyether polyamine, such as poly oxyalkylene diamine or polyoxyalkylene triamine. Polyether polyamines are known in the art, and can be prepared by methods including those described in U.S. Pat. 3,236,895 to Lee and Winfrey. Exemplary polyoxyalkylene diamines are commercially available, for example, from Huntsman Corporation under the trade names Jeffamine® D-230, Jeffamine® D-400 and Jeffamine® D-2000 Exemplary polyoxyalkylene triamines are commercially available, for example, from Huntsman Corporation under the trade names Jeffamine® T-403, Jeffamine® T-3000, and Jeffamine® T-5000.
- In some embodiments, the reaction mixture can include an alkoxylated polyamine (ie., alkylene oxide-capped polyamines) derived from a polyamine and an alkylene oxide. Alkoxylated polyamines can be formed by reacting a suitable polyamine with a desired number of moles of an alkylene oxide. Suitable polyamines include monomeric, oligomeric, and polymeric polyamines. In some cases, the polyamines has a molecular weight of less than 1000 g/mol (eg., less than 800 g/mol, less than 750 g/mol, less than 500 g/mol, less than 250 g/mol, or less than 200 less than 200 g/mol). Examples of suitable poly amines that can be used to form alkoxylated polyamines include ethylenediamine, 1,3-diaminopropane, putrescine, cadaverine, hexamethylenediamine, 1,2-diaminopropane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, spermidine, spermine, nonspermidine, toluene diamine, 1,2-propane-diamine, diethylenetriamine, triethylenetetramine, tetraethylene-pentamine (TEPA), pentaethylenehexamine (PEHA), and combinations thereof. Any suitable alkylene oxide or combination of alkylene oxides can be used to cap the polyamine. In some embodiments, the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and combinations thereof. Alkylene oxide-capped polyamines are known in the art, and include, for example, propylene oxide-capped ethylene diamine sold under the trade name CARPOL® EDAP-770 (Carpenter Co., Richmond, VA) and ethylene and propylene oxide-capped ethylene diamine sold under the trade name CARPOL® EDAP-800 (Carpenter Co., Richmond. VA)
- The additional isocyanate-reactive monomer (when used) can be present in varying amounts relative the one or more polyols used to form the foam stock. In some embodiments, the additional isocyanate-reactive monomer can be present in an amount of 30% or less, 25% or less, 20% or less. 15% or less, 10% or less, or 5% or less by weight based on the weight of the one or more polyols
- As indicated herein, in the poly urethane or polyisocyanurate foams, one or more isocyanates are reacted with the one or more polyols (and any additional isocyanate-reactive monomers) to produce the polyurethane or polyisocyanurate formulation In general, with regards to the poly urethane formulation, the ratio of isocyanate groups to the total isocyanate reactive groups, such as hydroxyl groups, water and amine groups, is in the range of about 0.5:1 to about 1.5:1, which when multiplied by 100 produces an isocyanate index between 50 and 150. Additionally, the isocyanate index can be from about 80 to about 120, from about 90 to about 120, from about 100 to about 115, or from about 105 to about 110. With regards to the polyisocyanurate formulation, the isocyanate index can be from 180 to 380, for example, from 180 to 350, from 200 to 350, or from 200 to 270. As used herein, an isocyanate may be selected to provide a reduced isocyanate index, which can be reduced without compromising the chemical or mechanical properties of the foam stock
- One or more catalysis can be added to facilitate curing and can be used to control the curing time of the polyurethane or poly isocyanimate matrix. Examples of useful catalysts include amine-containing catalysts (including tertiary amines such as DABCO and tetramethylbutanediamine, and diethanolamine) and tin-, mercury-, and bismuth-containing catalysts. In some embodiments, the catalyst includes a delayed-action tin catalyst. In some embodiments, 0.01 wt% to 2 wt% catalyst or catalyst system (e.g., 0.025 wt% to 1 wt% 0.05 wt% to 0.5 wt %, or 0.1 wt% to about 0.25 wt%) can be used based on the weight of the polyurethane or polyisocyanurate In some embodiments, 0.05 to 0.5 parts catatyst or catalyst system per hundred parts of polyol can be used.
- The polyurethane or polyisocyanurate can be present in the foam stock in amounts from 10% to 50% based on the weight of the foam stack. For example, the polyurethane or polyisocyanurate can be included in an amount from 14% to 50% or 20% to 50% by weight, based on the weight of the foam stock. In some embodiments, the polyurethane or polyisocyanurate can be present in an amount of 10% or greater, 15% or greater, 20% or greater. 25% or greater, 30% or greater. 35% or greater, 40% or greater, or 45% or greater by weight based on the weight of the foam stock. In some embodiments, the polyurethane or polyisocyanurate can be present in an amount of 50% or less, 45% or less, 40% or less. 35% or less, 30% or less. 25% or less, 20% or less, or 15% or less by weight, based on the weight of foam stock.
- The polyurethane or polyisocyanurate foam stock can include a filler. The filler can be described by its aspect ratio. In some embodiments, the filler in the foam can have an average aspect ratio of length to diameter of from 1:1 to 6000:1. For example, the filler can have an average aspect ratio of from 11 to 5000:1, 1:1 to 4000:1, 1:1 to 3000:1, 1:1 to 2000:1, 1:1 to 1000:1, 1:1 to 700:1, 1.1 to 500:1, 1:1 to 250:1, 1.05:1 to 400:1, 1.1:1 to 300:1, 1.15:1 to 250:1, or 1.2:1 to 200:1. In some embodiments, the filler can have an average aspect ratio of length to diameter of 200:1 or less, 150:1 or less, 100:1 or less, 75:1 or less, 50:1 or less, 40:1 or less. 30:1 or less, 20:1 or less, 10:1 or less, or 5:1 or less, and from 1:1 or more (e.g.. 1.05:1 or more, 1.1.1 or more, 1.15:1 or more, or 1.2:1 or more).
- The filler can include a particulate filler and particularly an inorganic particulate filler Suitable examples of particulate fillers can be an ash, ground, recycled glass (eg., window or bottle glass); milled glass, glass spheres; glass flakes; activated carbon; calcium carbonate; aluminum trihydrate (ATH); silica; sand: ground sand: silica fume; slate dust; crusher fines; red mud; amorphous carbon (e.g., carbon black); days (e.g., kaolin); mica: talc; wollastonite; alumina; feldspar, bentonite; quartz, garnet; saponite; beidellite; granite; slag: calcium oxide, calcium hydroxide; antimony trioxide; barium sulfate, magnesium oxide: titanium dioxide: zinc carbonate; zinc oxide: nepheline syenite; perlite; diatomite; pyrophillite; flue gas desulfurization (FGD) material; soda ash; trona; expanded clay, expanded shale; expanded perlite; vermiculite; volcanic tuff; pumice; hollow ceramic spheres; hollow plastic spheres, expanded plastic beads (e.g., polystyrene beads): ground tire rubber: and mixtures thereof
- The particulate filler can have a median particle size diameter of from 0.2 micron to 100 microns For example, the particulate filler can have a median particle size diameter of 100 microns or less, 95 microns or less, 90 microns or less, 85 microns or less, 80 microns or less, 75 microns or less, 70 microns or less. 65 microns or less, 60 microns or less, 55 microns or less, 50 microns or less, 45 microns or less, 40 microns or less, 35 microns or less, 30 microns or less, or 25 microns or less, In some embodiments, the particulate filler can have a median particle size diameter of 0.2 microns or more. 0.3 microns or more. 0.4 microns or more. 0.5 microns or more, 0.7 microns or more. 1 micron or more, 2 microns or more, 5 microns or more, 10 microns or more. 15 microns or more, 20 microns or more, 25 microns or more, 30 microns or more, 35 microns or more. 40 microns or more, or 45 microns or more. In some examples, the particulate filler can have a median particle size diameter of from 0.2 microns to 100 microns, 0.2 microns to 90 microns, or 0.3 microns to 80 microns, 1 to 50 microns. 1 to 25 microns, or 5 to 15 microns.
- In some embodiments, the particulate filler includes an ash. The ash can be a coal ash or another type of ash such as those produced by firing fuels including industrial gases, petroleum coke, petroleum products, municipal solid waste, paper sludge, wood, sawdust, refuse derived fuels, switchgrass or other biomass material. The coal ash can be fly ash, bottom ash, or combinations thereof In some examples, the particulate filler mdudes fly ash Fly ash is produced from the combustion of pulverized coal in electrical power generating plants. The fly ash useful with the foam stock described herein can be Class C fly ash. Class F fly ash, or a mixture thereof. Fly ash produced by coal-fueled power plants is suitable for incorporation in the foam stocks descnbed herein In some embodiments, the particulate filler consists of or consists essentially of fly ash.
- The fly ash can have a particle size distribution with at least two modes. For example, the panicle size distribution of the fly ash can be three, four, five, or more modes. Alternatively, the fly ash can be blended with another fly ash to modify the properties of the fly ash to produce a fly ash having a particle size distribution with at least three modes.
- In some embodiments, the fly ash can include a first mode having a median particle diameter of 2.0 microns or less. In some examples, the median particle size of the first mode can be 0.3 microns to 1.5 microns, 0.4 microns to 1 microns, or 0.5 microns to 0.8 microns (e.g., 0.7 microns) The fly ash can include a second mode having a median particle diameter of from 3 microns to less than 40 microns in some examples, the median particle size of the second mode can be from 5 microns to 35 microns. 10 microns to 30 microns, or 10 microns to 25 microns. The fly ash can include a third mode having a median particle diameter of 40 microns or greater. In some examples, the median particle size of the third mode can be from 40 microns to less than 100 microns, for example from 40 microns to 90 microns. 40 microns to 80 microns, or from 40 microns to 75 microns. In some embodiments, the fly ash can include a first mode having a median particle diameter of from 0.3 microns to 1.0 micron, a second mode having a median particle diameter of from 10 microns to 25 microns, and a third mode having a median particle diameter of from 40 microns to 80 microns. In some examples, the fly ash can also include an additional ultrafine mode with a median particle diameter of from 0.05 microns to 0.2 microns.
- In some embodiments, the particle size distribution can include 11-35% of the particles by volume in the first mode, 65-89% of the particles by volume in the second mode In some embodiments, the particle size distribution can include 11-17% of the particles by volume in the first mode. 56-74% of the particles by volume m the second mode, and 12-31% of the particles by volume in the third mode. The ratio of the volume of particles in the second mode to the volume of particles in the first mode can be from 4.5 to 7.5
- The particulate filler can be present in the foam stock described herein in amounts from 35% to 90% by weight Examples of the amount of particulate filler present in the foam stock described herein include 35%. 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%. 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90% by weight. In some embodiments, the particulate filler, for example fly ash, can be present in amounts from 50% to 80% by weight such as from 55% to 80% by weight or from 60% to 75% by weight
- In some embodiments, the particulate filler can include fly ash and calcium carbonate. When used with fly ash, the amount of calcium carbonate in the foam stock can be from 0.1% to 15% by weight, based on the weight of the foam stock. In some embodiments, the foam stock can include 15% or less, 14% or less, 12% or less, 10% or less, or 8% or less by weight calcium carbonate. In some embodiments, the foam stock can include 0.1% or greater, 0.5% or greater, 1% or greater, 2% or greater, 3% or greater, or 5% or greater by weight calcium carbonate In some embodiments, when used with fly ash, the foam stock can include 1% to 15%, 1% to 10%, or 1% to 8% by weight calcium carbonate.
- In some embodiments, the particulate filler can include an organic filler, such as a recycled polymeric material. Suitable examples include pulverized polymeric foam or recycled rubber material.
- The filler can include a plurality of fibers. The fibers can be any natural or synthetic fiber, based on inorganic or organic materials. Inorganic and organic fibers suitable for use with the foam stock can include glass fibers, basali fibers, alumina silica fibers, aluminum oxide fibers, silica fibers, carbon fibers, metal fibers, metal and metal-coated fibers, mineral fibers (such as stone wool, slag wool, or ceramic fiber wool), polyalkylene fibers, polyester fibers, polyamide fibers, phenol-formaldehyde fibers, polyvinyl chloride fibers, polyacrylic fibers, acrylic polyester fibers, polyurethane fibers, polyacrylonitrile fibers, rayon fibers, cellulose fibers, carbon fibers, or combinations thereof. In certain embodiments, the fiber material can include hemp fibers, sisal fibers, cotton fibers, straw, reeds, or other grasses, jute, bagasse fibers, bamboo fibers, abaca fibers, flax, southern pine fibers, wood fibers, cellulose, saw dust, wood shavings, lint, vicose, leather fibers, rayon, and mixtures thereof. Other suitable fibers include synthetic fibers such as, Kevlar, viscose fibers, Dralon® fibers, polyethylene fibers, polyethylene terephthalate fibers, polyethylene naphthalate fibers, polypropylene fibers, polyvinyl alcohol fibers, aramid fibers, or combinations thereof. In some embodiments, the fiber material can include glass fibers. Glass fibers can include fibrous glass such as E-glass, C-glass, S-glass, and AR-glass fibers, In some examples, fire resistant or retardant glass fibers can be included to impart fire resistance or retarding properties to the foam stock. In some embodiments, the foam stock can include a combination of fibers that break and fibers that do not break when the foam stock is being formed using processing machinery and/or fractured by external stress.
- In some embodiments, the fibers can be dispersed within the foam stock. The fibers in the foam stock can be present in the form of individual fibers, chopped fibers, bundles, strings such as yarns, fabrics, papers, rovings, mats, or tows. In some embodiments, the foam stock can include a plurality of glass fibers. The average length of the glass fibers in the foam stock can be 1 mm or greater, 1.5 mm or greater, 2 mm or greater, 3 mm or greater, 4 mm or greater, 5 mm or greater, or 6 mm or greater. In some embodiments, the average length of the glass fibers can be 50 mm or less, 40 mm or less, 30 mm or less, 20 mm or less, 15 mm or less, 12 mm or less, or 10 mm or less In some examples, the glass fibers can be from 1 mm to 50 mm in average length. For example, the glass fibers can be from 1.5 mm to 30 mm, from 2 mm to 30 mm, from 3 mm to 30 mm, or from 3 mm to 15 mm in average length. The glass fibers in the foam stock can have any dimension of from 1 µm to 30 µm in average diameter. For example, the average diameter of the glass fibers can be 1.5 µm to 30 µm, 3 µm to 20 µm, 4 µm to 18 µm, or 5 µm to 15 µm in average diameter. The glass fibers can be provided in provided in the foam stock in a random orientation or can be axially oriented.
- The fibers can also be described by its aspect ratio. In some embodiments, the fibers in the foam stock can have an average aspect ratio of length to diameter of from 8:1 to 4000:1. For example, the fibers can have an average aspect ratio of from 5:1 to 2000:1, 5:1 to 1500:1, 5:1 to 1000:1, 5:1 to 750.1, 1.5:1 to 500:1, 1.5:1 to 400:1, 15:1 to 300:1, 1.5:1 to 250:1, 2:1 to 200:1, 2.5:1 to 150:1, 3:1 to 100.1, 3.5:1 to 75:1. 4:1 to 50:1, 5:1 to 25:1, 5:1 to 20:1, or 5:1 to 10:1. In some embodiments, the fibers can have an average aspect ratio of length to diameter of 1.5:1 or greater, 2:1 or greater, 3:1 or greater. 4:1 or greater, 5:1 or greater. 7.5:1 or greater, 10:1 or greater, 15:1 or greater, 20:1 or greater, 25:1 or greater, 30:1 or greater, or 40:1 or greater. In some embodiments, the fiber can have an average aspect ratio of length to diameter of 200.1 or less, 150:1 or less, 100:1 or less, 75:1 or less, 50:1 or less, 40:1 or less, 30:1 or less, 20:1 or less, 10:1 or less, or 5:1 or less.
- The fibers (when used) can be present in the foam stock in amounts of 15% or less by weight, based on the weight of foam stock. For example, the fibers can be present in amounts from 0.25% to 15%, 0.5% to 15%, 1% to 15%, 0.25% to 10%, 0.5% to 10%, 1% to 10%, 0.25% to 8%, 0.25% to 6%, or 0.25% to 4% by weight, based on the weight of the foam stock. In some embodiments, the foam stock is free of fibers dispersed within the foam stock.
- The foam stock described herein can comprise additional materials. The additional materials useful with the foam stock can include foaming agents, blowing agents, surfactants, chain-extenders, crosslinkers, coupling agents, UV stabilizers, fire retardants, antimicrobials, anti-oxidants, and pigments. Though the use of such components is well known to those of skill in the art, some of these additional additives are further described herein
- Chemical foaming agents include azodicarbonamides (eg., Celogen manufactured by Lion Copolymer Geismar), and other materials that react at the reaction temperature to form gases such as carbon dioxide. In the case of polyurethane and polyisocyamurate foam, water is an exemplary foaming agent that reacts with isocyanate to yield carbon dioxide. The presence of water as an added component or in the filler also can result in the formation of polyurea bonds through the reaction of the water and isocyanate. ln some embodiments, water may be present in the mixture used to produce the foam stock in an amount of from greater than 0% to 5% by weight or less, based on the weight of the mixture. In some embodiments, water can be present in a range of 0.02% to 4%, 0.05% to 3%, 0.1 % to 2%, or 0.2% to 1% by weight, based on the weight of the mixture. In some embodiments, the mixture used to produce the foam stock includes less than 0.5% by weight water. In some embodiments, no chemical foaming agents are used. In some embodiments, water is the only foaming agent used.
- Surfactants can be used as wetting agents and to assist in mixing and dispersing the materials in a foam. Surfactants can also stabilize and control the size of bubbles formed during the foaming event and the resultant cell structure. Surfactants can be used, for example, m amounts below about 0.5 wt% based on the total weight of the mixture. Examples of surfactants useful with the polyurethanes described herein include anionic, non-ionic and cationic surfactants For example, silicone surfactants such as Tegostab B-8870, DC-197 and DC-193 (Air Products, Allentown, PA) can be used.
- Low molecular weight reactants such as chain-extenders and/or crosslinkers can be included in the foam stock described herein. These reactants help the foam stock to distribute and contain the fiber material and/or particulate filler within the composite. Chain-extenders are difunctional molecules, such as diols or diamines, that can polymerize to lengthen the urethane polymer chains Examples of chain-extenders include ethylene glycol. 1,4-butanediol, ethylene diamine, 4,4′-methylenebis(2-chloroaniline), (MBOCA), diethylioluene diamine (DETDA): and aromatic diamines such as Unilink 4200 (commercially available from UOP). Crosslinkers are tri- or greater functional molecules that can integrate into a polymer chain through two functionalities and provide one or more further functionalities (i.e.. linkage sites) to crosslink to additional polymer chains. Examples of crosslinkers include glycerin, trimethylolpropane, sorbitol, diethanolamine, and triethanolamine. In some foam stock, a crosslinker or chain-extender may be used to replace at least a portion of the one or more polyols in the foam stock. For example, the polyurethane or polyisocyanurate can be formed by the reaction of an isocyanate, a polyol, and a crosslinker
- Coupling agents and other surface treatments such as viscosity reducers, flow control agents, or dispersing agents can be added directly to the filler or fiber, or incorporated prior to, during, and/or after the mixing and reaction of the foam stock Coupling agents may also reduce the viscosity of the foam stock mixture Coupling agents can also allow higher filler loadings of the particulate filler such as fly ash, and/or fiber material, and may be used in small quantities For example, the foam stock may comprise about 0.01 wt% to about 0.5 wt% of a coupling agent Examples of coupling agents useful with the foam stock described herein include Ken-React LICA 38 and KEN-React KR 55 (Kenrich Petrochemicals; Bayonne, NJ). Examples of dispersing agents useful with the foam stock described herein include JEFFSPERSE X3202, JEFFSPERSE X3202RF, and JEFFSPERSE X3204 (Huntsman Polyurethanes; Gisemar, LA)
- Ultraviolet light stabilizers, such as UV absorbers, can be added to the foam stock described herein. Examples of UV light stabilizers include hindered amine type stabilizers and opaque pigments like carbon black powder. Fire retardants can be included to increase the flame or fire resistance of the foam stock. Antimicrobials can be used to limit the growth of mildew and other organisms on the surface of the composite. Antioxidants, such as phenolic antioxidants, can also be added. Antioxidants provide increased UV protection, as well as thermal oxidation protection.
- Pigments or dyes can optionally be added to the foam stock described herein. An example of a pigment is iron oxide, which can be added in amounts ranging from about 2 wt% to about 7 wt%, based on the total weight of the foam stock
- The polyurethane or polyisocyanurate foam stock can have a thickness (z direction) of 1 inch to 4 feet For example, for foam stock that can be further subdivided into units having thicknesses of 2 inches or less (e.g., ¼ inch to 1 inch), the foam stock can have a thickness of from 3 inches to 4 feet. For example, the foam stock can have an average thickness of 3 inches or greater, 4 inches or greater, 6 inches or greater, 1 foot or greater. 2 feet or greater, 2.5 feet or greater, 3 feet or greater, 3.5 feet or greater, or 4 feet or greater, In some embodiments, the foam stock can have an average thickness of from 3 inches to 4 feet, 3 inches to 6 inches, 1 foot to 4 feet, or 2 feet to 3 feet.
- The polyurethane or polyisocyanurate foam stock can have a length and width (x and y direction) of 2 feet or greater and from 2 feet to 4 feet respectively. For example, the polyurethane or polyisocyanurate foam stock can have a length of 2 feet or greater, 5 feet or greater, 10 feet or greater, or it can be produced with a continuous length. The polyurethane or polyisocyanurate foam stock can have a width of 2 feet to 4 feet, or from 2 to 3 feet.
- As described herein, the polyurethane or polyisocyanurate foam stock can comprise a high filler loading, such as from 50% to 90% by weight of the foam stock, which can result in an increase in the density of the foam stock. In some embodiments, it is desirable that the foam stock has a density below a particular threshold at the desired loadings so it remains relatively lightweight and/or can be effectively processed. In some embodiments, the amount of fibers and/or particulate filler can be present in the composite mixture in amounts to produce a foam stock having a density of 35 lb/ft3 or less For example, the density of the foam stock can be 10 lb/ft3 to 35 lb/ft3,15 lb/ft3 to 35 lb/ft3, 15 lb/ft3 to 25 lb/ft3, 10 lb/ft3 to 30 lb/ft3, 10 lb/ft3 to 25 lb/ft3, or 20 lb/ft3 to 30 lb/ft3. In some embodiments, the density of the foam stock is at least 10 lb/ft3.
- Incorporation of the fibers and/or particulate filler in a high filler loading can increase the flexural strength of the foam stock, compared to a foam stock without the fibers and/or high particulate filler. It is desirable to provide polyurethane and polyisocyanurate foams that are relatively lightweight and strong enough to be used in various applications such as by itself as a structural material or in place of composite boards or the like. In some embodiments, the flexural strength of the polyurethane or polyisocyanurate foam stock can be increased by at least 10%, for example, 15% or greater, 20% or greater, 25% or greater, 30% or greater, 35% or greater, 50% or greater, 75% or greater, or even 100% or greater, compared to a foam stock without fibers and/or particulate filler. The flexural strength of the foam stock described herein can be 100 psi or greater, For example, the flexural strength of the foam stock can be 200 psi or greater, 300 psi or greater, 400 psi or greater, 500 psi or greater, 600 psi or greater, or 700 psi or greater In some embodiments, the flexural strength of the foam stock can be from 100 to 700 psi. The flexural strength can be determined by the load required to fracture a rectangular prism loaded in the three point bend test as described in ASTM C1185-08 (2012).
- The foam stock can exhibit a ratio of flexural strength (in psi) to density (in lb/ft3) of from 10:1 to 200:1. In some embodiments, the foam stock can exhibit a ratio of flexural strength (in psi) to density (in lb/ft3) of from 10:1 to 100:1 or from 20:1 to 100:1.
- The modulus of elasticity (stiffness) of the foam stock can be 10 ksi or greater, 15 ksi or greater, 20 ksi or greater, 25 ksi or greater, or 30 ksi or greater. For example, the modulus of elasticity can be front 15 to 30 ksi, from 20 to 30 ksi, or from 22 to 28 ksi. The modulus of elasticity can be determined as described m ASTM C947-03.
- The foam stock can exhibit a ratio of modulus of elasticity (in ksi) to density (in lb/ft3) of from 1:2 to 2:1. In some embodiments, the foam stock can exhibit a ratio of modulus of elasticity (in ksi) to density (in lb/ft3) of 1:1.5 to 1.5:1 or from 1:1.2 to 1.2:1.
- The compressive strength of the foam stock can be 100 psi or greater. For example, the compressive strength can be from 100 to 300 psi, from 150 to 250 psi or from 175 to 240 psi. The compressive strength can be determined as descnbed in ASTM D1621. The foam stock can exhibit a ratio of compressive strength (in psi) to density (in lb/ft3) of from 7:1 to 25:1. In some embodiments, the foam stock can exhibit a ratio of compressive strength (in psi) to density (in lb/ft3) of from 8:1 to 15:1.
- Composite panels comprising the polyurethane and polyisocyanurate foam stock are described herein. In some embodiments, the composite panel can include a first fiber reinforcement; a polyurethane or polyisocyanurate foam stock having a first surface and a second surface opposite the first surface, wherein the first surface is in contact with the first fiber reinforcement, and a cementitious material adjacent the first fiber reinforcement opposite the foam stock.
- The fiber reinforcement can include any of the fiber materials as described herein and can include a blend of different fibers (either type or size). In some embodiments, the fiber reinforcement can include glass fibers. In some embodiments, the fibrous glass is a low alkalinity fiber such as an E-glass fiber. The fiber reinforcement can be woven or non-woven. In some embodiments, the fiber reinforcement can be present in the form of individual fibers, chopped fibers, bundles, strings such as yarns, fabrics, scrims, papers, rovings, mats, or tows.
- The fibers in the reinforcement can have an average diameter of 100 microns or less. For example, the fibers in the fiber reinforcement can have an average diameter of 1 µm or greater, 2 µm or greater, 3 µm or greater, 4 µm or greater, 5 µm or greater, 10 µm or greater, 15 µm or greater, 20 µm or greater, 25 µm or greater, 30 µm or greater, 40 µm or greater, 50 µm or greater, 60 µm or greater, 70 µm or greater, 80 µm or greater, 90 µm or greater, or 100 µm or greater. In some embodiments, the fibers in the fiber reinforcement can have an average diameter of 90 µm or less, 80 µm or less. 70 µm or less, 60 µm or less, 50 µm or less. 40 µm or less, 30 µm or less, 25 µm or less, or 20 µm or less. In certain embodiments, the fibers in the fiber reinforcement can have an average diameter of from 1 µm to 100 µm, 1 µm to 70 µm, 1 µm to 50 µm, 1 µm to 25 µm, 5 µm to 100 µm, 5 µm to 50 µm, 5 µm to 25 µm, or 5 µm to 20 µm.
- The thickness of the fiber reinforcement on the foam stock can be any suitable thickness to reinforce the foam stock. In some embodiments, the average thickness of the fiber reinforcement can be 0.1 inch or less. For example, the fiber reinforcement can have an average thickness of 0.07 inch or less, 0.05 inch or less, 0.03 inch or less. 0.01 inch or less, 0.005 inch or less, or 0.001 inch or less. In some embodiments, the fiber reinforcement can have an average thickness of 0.001 inch or greater, 0.005 inch or greater, 0.01 inch or greater, 0.03 inch or greater, 0.05 inch or greater, or 0.07 inch or greater. In some embodiments, the fiber reinforcement can have an average thickness of from 0.001 inch to 0.1 inch or from 0.001 inch to 0.05 inch.
- The fiber reinforcement can have a basis weight of 50 g/ft2 or less. In some embodiments, the fiber reinforcement can have a basis weight of 40 g/ft2 or less, 30 g/ft2 or less. 20 g/ft2 or less. 17 g/ft2 or less. 15 g/ft2 or less. 12 g/ft2 or less, 10 g/ft2 or less, 9 g/ft2 or less, 8 g/ft2 or less, 7 g/ft2 or less, 6 g/ft2 or less, or 5 g/ft2 or less. In some embodiments, the fiber reinforcement can have a basis weight of 0.5 g/ft2 or greater, 1 g/ft2 or greater, 2 g/ft2 or greater, 3 g/ft2 or greater, 4 g/ft2 or greater, 5 g/ft2 or greater, 7 g/ft2 or greater, 10 g/ft2 or greater, 15 g/ft2 or greater, or 20 g/ft2 or greater. In some embodiments, the fiber reinforcement can have a basis weight of from 0.5 g/ft2 to 50 g/ft2, from 0.5 g/ft2 to 25 g/ft2, from 0.5 g/ft2 to 20 g/ft2, from 1 g/ft2 to 10 g/ft2, or from 1.5 g/ft2 to 10 g/ft2.
- As described herein, the composite panel can include a cementitious material. In some embodiments, the cementitious material can form a layer adjacent the first fiber reinforcement, opposite the foam stock The cementitious material can include any suitable material for forming a cementitious layer with the desirable properties. In some embodiments, the cementitious material includes a rapid set cement. The rapid set cement can include calcium aluminate cement (CAC), calcium phosphate cement, calcium sulfate hydrate, calcium sulfoaluminate (CSA) cement, magnesium oxychloride cement, magnesium oxysulfate cement, magnesium phosphate cement, or combinations thereof. In some embodiments, the cementitious material can include Portland cement. The rapid set cement and/or the Portland cement can be present in an amount of 50% or greater by weight, e.g., 60% or greater, 70% or greater. 80% or greater, or 90% or greater by w eight, based on the total weight of the cementitious material. In some embodiments, the cementitious material does not include gypsum (calcium sulfate hydrate).
- In some embodiments, the cementitious material can include an inorganic polymer formed by reading a reactive powder and an activator in the presence of water. Suitable inorganic polymers are described in U.S. Pat. Publication No. 2014/0349104, which is herein incorporated by reference, in some embodiments, the reactive powder for use in the cementitious material includes fly ash In some examples, the majority of the fly ash present is Class C fly ash (i.e., greater than 50% of the fly ash present is Class C fly ash).
- The fly ash is the principal component of the reactive powder and can be present in an amount of greater than 50% by weight. 65% by weight or greater. 75% by weight or greater, or 85% by weight or greater of the reactive powder. In some examples, the fly ash is present in an amount of 90% by weight or greater of the reactive powder or 95% by weight or greater of the reactive powder For example, the fly ash can be present in an amount of 85% by weight or greater, 86% by weight or greater. 87% by weight or greater, 88% by weight or greater. 89% by weight or greater. 90% by weight or greater. 91 % by weight or greater. 92% by weight or greater, 93% by weight or greater. 94% by weight or greater, 95% by weight or greater. 96% by weight or greater, 97% by weight or greater. 98% by weight or greater, or 99% by weight or greater based on the weight of the reactive powder In some embodiments, the reactive powder consists of or consists essentially of fly ash.
- The reactive powder for use as a reactant to form the inorganic polymer compositions can further include other cementitious components. In some embodiments, the reactive powder can include a rapid set cement as described herein, In some embodiments, the reactive powder can include Portland cement. In some embodiments, the reactive powder further includes slag. In some embodiments, the reactive powder further includes sand. In some embodiments, the reactive powder includes Portland cement, calcium aluminate cement calcium sulfoaluminate cement, and/or slag In these examples, the reactive powder can include 10% or less by weight of the other cementitious material. In some examples, the reactive powder includes 5% by weight or less. 3% by weight or less, or 1 % by weight or less of other cemenutrous material For example, the reactive powder can include the other cementitious material cement in an amount of 10% or less by weight 9% or less by weight. 8% or less by weight 7% or less by weight. 6% or less by weight. 5% or less by weight, 4% or less by weight. 3% or less by weight, 2% or less by weight. 1% or less by weight or 0.5% or less by weight. In some examples, the reactive powder is substantially free from other cementitious material. For example, the reactive powder can include less than 0.1% by weight, less than 0.01% by weight, or less than 0.001%by weight of Portland cement based on the weight of the reactive powder. In some embodiments, the reactive powder includes no Portland cement.
- The reactive powder can also include a ground slag such as blast furnace slag in an amount of 10% or less by weight. For example, the reactive powder can include slag in an amount of 10% or less, 9% or less. 8% or less. 7% or less. 6% or less. 5% or less. 4% or less, 3% or less. 2% or less, or 1% or less by weight.
- An activator is a further reactant used to form the inorganic polymer compositions described herein. The activator allows for rapid setting of the inorganic poly mer compositions and also imparts compressive strength to the compositions. The activator can include one or more of acidic, basic, and/or salt components For example, the activator can include citrates, hydroxides, metasilicates, carbonates, aluminates, sulfates, and/or tartrates The activator can also include other multifunctional acids that are capable of complexing or chelating calcium ions (e.g., EDTA) Specific examples of suitable citrates for use as activators include citric acid and its salts, including, for example, sodium citrate and potassium citrate. Specific examples of suitable tartrates include tartaric acid and its salts (eg. sodium tartrate and potassium tartrate). In some examples, the activator can include alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide. Further examples of suitable activators include metasilicates (e.g., sodium metasilicate and potassium metasilicate): carbonates (e.g.. sodium carbonate and potassium carbonate); aluminates (e.g., sodium aluminate and potassium aluminate); and sulfates (e.g., sodium sulfate and potassium sulfate). In some examples, the activator includes citric acid, tartaric acid, or mixtures thereof In some examples, the activator includes sodium hydroxide In some examples, the activator includes a mixture of citric acid and sodium hydroxide In examples including a mixture of citric acid and sodium hydroxide, the weight ratio of citric acid present in the mixture to sodium hydroxide present in the mixture is from 0.4:1 to 2.0:1, 0.6:1 to 1.9:1, 0.8:1 to 1.8:1, 0.9:1 to 1.7:1, or 1.0.1 to 1.6:1. The activator components can be pre-mixed prior to being added to the other reactive components in the inorganic polymer or added separately to the other reactive components. For example, citric acid and sodium hydroxide could be combined to produce sodium citrate and the mixture can include possibly one or more of citric acid and sodium hydroxide in stoichiometric excess. In some embodiments, the activator includes a stoichiometric excess of sodium hydroxide The total amount of activators can include less than 95% by weight of citrate salts. For example, the total amount of activator can include from 25-85%, 30-75%, or 35-65% citrate salts by weight The mixture in solution and the mixture when combined with the reactive powder can have a pH of from 12 to 13.5 or about 13.
- The activator can be present as a reactant in an amount of from 1.5% to 8.5% dry weight based on the weight of the reactive powder. For example, the activator can be present in an amount of from 2% to 8%, from 3% to 7%, or from 4% to 6%. In some examples, the activator can be present in an amount of 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4 5%, 5%, 5.5% 6%, 6.5%, 7%, 7.5%, 8% or 8.5% dry weight based on the weight of the reactive powder. For example, when sodium hydroxide and citric acid are used as the activators, the amount of sodium hydroxide used in the activator solution can be from 0.3 to 15.6, 0.5 to 10, 0.75 to 7.5, or 1 to 5 dry pans by weight based on the weight of reactive powder and the amount of citric acid used in the activator solution can be from 0.25 to 8.5, 0.5 to 0.7, 0.75 to 0.6, or 1 to 4.5 dry parts by weight based on the weight of reactive powder The resulting activator solution can include sodium citrate and optionally one or more of citnc acid or sodium hydroxide.
- The activator can be provided, for example, as a solution. In some examples, the activator can be provided in water as an aqueous solution in a concentration of from 10% to 50% or from 20% to 40% based on the weight of the solution For example, the concentration of the activator in the aqueous solution can be from 25% to 35% or from 28% to 32% based on the weight of the solution. Examples of suitable concentrations for the activator in the aqueous solution include 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% based on the weight of the solution.
- The inorganic polymer compositions described herein are prepared in the presence of aerating agents, including blowing agents and foaming agents, Examples of suitable blowing agents include aluminum powder, perborates (eg., sodium perborate), peroxides (e.g., H2O2 or an organic peroxide), and chloride dioxide. The blowing agent can be present in an amount of from 0.1% to 10% by weight of the reactive powder. The aerating agents described herein can also include foaming agents In some examples, the foaming agent can be an air-entraining agent Foaming agents can be used to help the system maintain air or other gases, e.g., from the mixing process. The foaming agents can include non-ionic surfactants, anion surfactants, and/or cationic surfactants Examples of suitable foaming agents include sodium alkyl ether sulfate, ammonium alkyl ether sulfate, sodium alpha olefin sulfonate, sodium deceth sulfate, ammonium deceth sulfate, sodium laureth sulfate, and sodium dodecylbenzene sulfonate The foaming agents can be provided in an amount of 0.1% or less based on the weight of the reactive powder. In some examples, the foaming agents can be included in the compositions in an amount of from 0.001% by weight to 0.1% by weight or from 0.005% by weight to 0.05% by weight (e.g., 0.01% by weight).
- The reactants to form the inorganic polymer compositions are reacted in the presence of water. The water can be provided in the reactive mixture by providing the activator in solution and/or by adding water directly to the reactive mixture. The solution to binder or solution to reactive powder weight ratio (i.e., the ratio of the solution including activator to reactive powder) can be from 0.09:1 to 0.5:1, depending on the product being made and the process being used for producing the product.
- The reactants used to form the inorganic polymer compositions can further include a retardant. Retardants are optionally included to prevent the composition from stiffening too rapidly, which can result in a reduction of strength in the structure Examples of suitable retardants for inclusion as reactants include borax, boric acid, gypsum, phosphates, gluconates, or a mixture of these. In some examples, the retardant is present in an amount of from 0.4% to 7.5% based on the weight of the reactive powder.
- The cementitious material can include a filler, such as those described herein. In some examples, the cementitious material can include a rapid set cement, Portland cement, and a filler such as fly ash, slag, sand, or combinations thereof. In some embodiments, the cementitious material can include a rapid set cement and a filler such as fly ash, slag, or sand. In some examples, the cementitious material can include Portland cement and a filler. In some examples, the cementitious material consists or consists essentially of a rapid set cement, a filler in an amount of 30% or less by weight (e.g., 25% or less by weight, or 20% or less by weight), based on the total weight of the cementitious material, and optionally Portland cement In some examples, the filler (e.g., fly ash, slag, sand, or combinations thereof) can be present in an amount of from 5% to 30% by weight, based on the total weight of the cementitious material. In some examples, the filler can include a lightweight filter.
- In some embodiments, a cementitious material can include a fiber material, e.g., to provide increased strength, stiffness or toughness. In some examples, fire resistant or retardant glass fibers can be included to impart fire resistance or retarding properties to the cementitious material Suitable fiber materials useful with the cementitious material are described herein. The fibers can be included in an amount of 0.1% to 6% based on the weight of the cementitious material
- Additional components useful with the cementitious material described herein include air entraining agents, water reducers, plasticizers, pigments, anti-efflorescence agents, ultraviolet light stabilizers, retardants including fire retardants, antimicrobials, and antioxidants. Air entraining agents can be used to entrain air in the cementitious material thereby reducing the density of the cementitious material, Water reducers can be included in the compositions described herein to reduce the amount of water in the composition while maintaining the workability, fluidity, and/or plasticity of the composition In some examples, the water reducer is a high-range water reducer, such as, for example, a superplasticizer admixture. Examples of suitable water reducers include lignin, naphthalene, melamine, polycarboxylates, lignosulfates and formaldehyde condensates (e g., sodium naphthalene sulfonate formaldehyde condensate). Water reducers can be provided in an amount of from greater than 0 to 1% by weight based on the weight of the cementitious material
- The cementitious material can further include a photocatalyst Photocatalysts are optionally included for the reduction of nitrogen oxides (NOx) and self-cleaning. In some embodiments, the cementitious material can include titanium dioxide Example of stumble photocatalyst includes titanium dioxide. In some embodiments, the photocatalyst can be dispersed within the cementitious material, In some embodiments, the photocatalyst can be present as a coating on the cementitious material, In some examples, the titanium dioxide can be provided as a coating on the cementitious material and is present in an amount of from 1% to 10% based on the weight of the coating on the cementitious material,
- The cementitious material can be any suitable thickness to confer a desirable property to the composite panel, e.g.. to provide increased strength, handleability, stiffness or toughness . In some embodiments, the thickness of the cementitious material can be 0.5 inch or less. For example, the cementitious material can have an average thickness of 0.4 inch or less. 0.3 inch or less, 0.25 inch or less, 0.20 inch or less, or 0.15 inch or less. In some embodiments, the cementiuous material can have an average thickness of 0.005 inch or greater, 0.01 inch or greater, 0.05 inch or greater, or 0.1 inch or greater. In some embodiments, the cementitious layer can have an average thickness of from 0.005 inch to 0.25 inch or from 0.005 inch to 0.20 inch.
- In some embodiments, the fiber material (including the fiber reinforcement), the cementitious material, and/or the particulate filler such as fly ash can be coated with a composition to modify their reactivity . For example, the fiber material, the cementitious material, and/or the particulate filler can be coated with a sizing agent such as a coupling agent (compatibilizer). In some embodiments, the fiber material, the cementitious material, and or the particulate filler can be coated with a composition for promoting adhesion. U.S Pat. No. 5,064,876 to Hamada er al. and U.S. Pat. No. 5,082,738 to Swofford, for example, disclose compositions for promoting adhesion. U.S. Pat. No. 4,062,999 to Kondo et al. and U.S Pat. No 6,602,379 to Li et al. describe suitable ammosilane compounds for coming fibers. In some embodiments, the fiber material, the cementitious material, and/or the paniculate filler are surface coated with a composition comprising a silane compound such as aminosilane In some embodiments, the fiber material, the cementitious material, and/or the particulate filler are surface coated with a composition comprising an oil, starch, or a combination thereof.
- As described herein, the composite panel can include a first fiber reinforcement on a first surface of the foam stock and a second fiber reinforcement on a second surface, opposite the first surface, of the foam stock. In some embodiments, the composite panel can include a first fiber reinforcement on a first surface of the foam stock and a material, other than a fiber reinforcement, on a second surface of the foam stock. In some embodiments, the material can include a cementitious layer, a paper sheet, a metal sheet, a polymeric layer, or a combination thereof Suitable materials that can be included on the second surface of the foam stock include an aluminum sheet, an aluminum-plated sheet, a zinc sheet, a zinc-plated sheet, an aluminum zinc alloy sheet, an aluninum zinc alloy-plated sheet, a stainless steel sheet, craft paper, a polymeric surfacing film, or a combination thereof.
- Methods of preparing the poly urethane or polyisocyanurate foam stocks are described herein. Methods of preparing the composite panels are also described herein. The foam stocks can be produced using a batch, semi-batch, or continuous process In some embodiments, the method can include forming a poly urethane or poly anwate mixture. The poly urethane or polyisocyanurate mixture can be produced by mixing the one or more isocyanates, the one at more polyols, and the filler in a mixing apparatus. The materials can be added in any suitable order. For example, in some embodiments, the mixing stage of the method used to prepare the foam stock can include: (1) mixing the polyol and filler; (2) mixing the isocyanate with the polyol, and filler, and optionally (3) mixing the catalyst with the isocyanate, the polyol, and the filler.
- The polyurethane or polyisocyanurate mixture can be blended in any suitable manner to obtain a homogeneous or heterogeneous blend of the one or more isocyanate, the one or more polyols, the filler, and the catalyst. In some embodiments, mixing can be conducted in a high speed mixer or an extruder The method can include applying shear to the mixture to disperse the filler in the mixture. An ultrasonic device can be used for enhanced mixing and/or wetting of the various components of the composite, The ultrasonic device produces an ultrasound of a certain frequency that can be varied during the mixing and/or extrusion process. The ultrasonic device useful in the preparation of composite panels described herein can be attached to or adjacent to the extruder and/or mixer. For example, the ultrasonic device can be attached to a die or nozzle or to the port of the extruder or mixer. An ultrasonic device may provide de-aeration of undesired gas bubbles and better mixing for the other components, such as blowing agents, surfactants, and catalysts.
- The method of making the foam stock can include allowing the one or more isocyanates and the one or more polyols to react in the presence of the filler to form a polyurethane or polyisocyanurate foam having a first surface and a second surface opposite the first surface. The curing stage of the method used to prepare the foam stock can be carried out in a mold cavity of a mold, the mold cavity formed by at least an intenor mold surface. The mold can include individual batch molds such as a cardboard box. The cardboard box can work as a protective material during handling of the mold in the plant. In some embodiments, a molded article can then be formed prior to the additional method steps in forming the composite panel
- The polyurethane or polyisocyanurate mixture can be applied to the mold using a nozzle traversing the mold. In some embodiments, the one or more polyols, one or more isocyanates, or a mixture thereof, and the filler can be included in amounts, which result in a workable viscosity (initial viscosity) of 100,000 cPs or less for the polyurethane or polyisocyanurate mixture, and thus improves the processability of such materials and products. In some embodiments, the mixture can be applied to the mold at a viscosity of from 5,000 to 100,000 cPs or from 20,000 to 100,000 cPs at the temperature of the mixture, The viscosity of the composite mixture can be measured using a Brookfield Viscometer.
- In some embodiments, the polyurethane or polyisocyanurate mixture can be foamed The method of making the polyurethane or polyisocyanurate foams can include allowing the mixture to expand via a gas phase to form a foam having a first surface and a second surface opposite the first surface. The gas phase can be generated in situ from reaction of water with the one or more isocyanates. The gas can be introduced into the polyurethane mixture Suitable gases are known in the art. In some embodiments, the gas can be captured after gelation (i.e., formation) of the foam
- The foaming action of the polyurethane or polyisocyanurate foams can be described as having a “cream time,” during which foaming is initiated and the mixture reaches a consistency of a soft creamy foam, a “firm time” at which the foam sets up and hardens, and a “tack free time” at which time surface no longer feels sticky. The cream time of the polyisocyanurate or polyurethane can be 20 seconds or longer. 40 seconds or longer. 60 seconds or longer, or 80 seconds or longer For example, the cream time of the polyisocyanurate or polyurethane can be from 20 seconds to 120 seconds, from 40 seconds to 120 seconds, from 60 seconds to 120 seconds or from 80 seconds to 120 seconds. The tack free time of the polyisocyanurate or polyurethane can be 90 seconds or longer, 2 minutes or longer, 3 minutes or longer, 4 minutes or longer, or 5 minutes or longer and/or 7 minutes or less, 6 minutes or less, 5 minutes or less, or 4 minutes or less. For example, the tack free time of the polyisocyanurate or polyurethane can be from 90 seconds to 7 minutes, from 2 minutes to 7 minutes or from 3 minutes to 6 minutes In some embodiments, the polyisocyanurate or polyurethane foam reaches a hardness of 20 shore D at no less than 5 minutes. For example, the polyisocyanurate or polyurethane foam does not reach a hardness of 20 shore D in less than 5 minutes. For example, the polyurethane foam does not reach a hardness of 20 shore D in less than 7.5 minutes, less than 10 minutes, less than 12.5 minutes, less than 15 minutes, less than 17.5 minutes, or less than 20 minutes. The Shore D hardness can be determined using a durometer as described in ASTM D2240.
- In some cases, the mixture can be allowed to rise freely during foaming in the mold. After the polyurethane or polyisocyanurate foam is formed, the method can include removing the foam stock from the mold. As described herein, the mold can be a flexible, disposable container. In some embodiments, the method can include cutting through the container to remove the foam stock from the mold
- Once the foam stock is removed from the mold, it can be trimmed to remove the bottom skin from the mold and the crown of the foam stock or bun that forms from the free rise of the foam For example, the foam stock can be cut using a horizontal blade into a plurality of polyurethane or polyisocyanurate foam units having predetermined thicknesses. The polyurethane or polyisocyanurate foam thickness can be from 0.1 inch to 6 inches For example, the polyurethane or polyisocyanurate foam can have a thickness of 0.1 inch to 4 inches, 0.1 inch to 3 inches, 0.1 inch to 2 inches, or 0.125 inch to 1 inch.
- Composite panels can be produced from the cut polyurethane or polyisocyanurate foam units. The method can include applying a first fiber reinforcement to a surface of the foam In some embodiments, the fiber reinforcement can be applied to the foam before it has completely cured, such that at least a portion of the fiber reinforcement becomes embedded in the foam. For example, the fiber reinforcement can be applied to the polyurethane or polyisocyanurate mixture after the mixture is fed to the mold. In some embodiments, the fiber reinforcement can be applied to the mold prior to the mixture being fed into the mold and can become embedded prior to the full curing of the mixture. In some embodiments, the fiber reinforcement can be applied to the foam after the polyurethane or polyisocyanurate has been cured. For example, an adhesive can be applied to bond the fiber reinforcement to the foam. The adhesive can be applied by spray coating, curtain coating, brushing, roller coating, dip coating, spin coating, or flow coating. Suitable adhesives include an adhesive derived from ethylene vinyl acetate, acrylic, urethane, epoxy, starch, gum, resin (such as gum arabic, gum tragacanth, rubber or shellac), or combinations thereof.
- The method can further include applying a cementitious material to the fiber reinforcement. The cementitious material can be in the form of a cementitious slurry. The cementitious slurry can be applied by roller coating, curtain coating, dip coating, brushing, with a trowel, or spraying. In some embodiments, the application of the cementitious material can be vacuum assisted. In some embodiments, the method can include applying the cementitious slurry to the fiber reinforcement, after applying the fiber reinforcement to the foam. In some embodiments, the cementitious material and the fiber reinforcement can be applied to the foam simultaneously. For example, the method can include applying a cementitious slurry to the fiber reinforcement prior to applying the fiber reinforcement to the foam. In this example, at least a portion of the fiber reinforcement becomes embedded in the cementitious material
- In some embodiments, the method can include applying the cementitious slurry to the foam, prior to applying the fiber reinforcement to the foam
- The method of making the composite panels can include applying an adhesive to the fiber reinforcement or the foam prior to applying the cementitious material to facilitate bonding of the cementitious material. The adhesive can be applied by spray coating, curtain coating, brushing, roller coating, dip coating, spin coating, or flow coating Suitable adhesives are described herein.
- In some embodiments, the method can include applying a water and/or water vapor barrier prior to applying the cementitious material For example, the adhesive can produce a water and/or water vapor barrier. Alternatively, a water and/or water vapor barrier film or other material can be applied prior to applying the cementitious material.
- In some embodiments, the cementitious material, the first fiber reinforcement and the foam are directly adhered without the use of an adhesive layer. In embodiments wherein the cementitious slurry and the first fiber reinforcement are directly bonded to a fly ash-filled foam, it has been discovered that the cementitious slurry forms mechanical bonds with the fly ash present in the foam thereby enhancing the bonding of the cementitous slurry and the first fiber reinforcement to the foam.
- In some embodiments, the method can include apply ing a liquid to a surface of the foam to activate the cementitious slurry. In certain embodiments, the liquid can be an aqueous solution having a pH of 5 or greater or 6.5 or greater The liquid optionally includes an activator. Suitable activators are described herein.
- In some embodiments, incorporation of the fiber reinforcement and/or the cementitious layer onto the filled foam can maintain similar or improved physical properties and mechanical performance such as flexural strength, hardness, stiffness, flame resistance and handleability of such material, when the fiber reinforcement and/or the cementitous layer is excluded from or included in minor amounts in the foam The optimization of various properties of the composite panels, such as hardness, stiffness, flexural strength, handleability, and flame resistance of the foams allows their use in building materials and other structural applications. For example, the composite panels can be formed into shaped articles and used in building materials Suitable building materials include building panels, tile backer board, sheathing, roofing products, siding materials, sheets, sound barrier/insulation, thermal barriers, insulation, decking materials, fencing materials, dadding, or other shaped articles. Examples of shaped articles made using the composite panels described herein include roof tiles such as roof tile shingles, roof cover boards, slate panels, shake panels, cast molded products, moldings, sills, stone, masonry, brick products, posts, signs, guard rails, retaining walls, park benches, tables, slats, corner arches, columns, wall boards, ceiling tiles, ceiling boards, soffits, or railroad ties.
- In some embodiments, incorporation of the fiber reinforcement on the filled foam to form the composite panels can increase the flexural strength of the foam, compared to a foam without the fiber reinforcement In some embodiments, the flexural strength of the foam can be increased by at least 10%, for example. 15% or greater, 20% or greater, 25% or greater, 30% or greater, 35% or greater, 50% or greater, 75% or greater, or even 100% or greater, compared to a foam without the fiber reinforcement The flexural strength of the composite panels described herein can be 200 psi or greater (e.g., up to 1600 psi). For example, the flex ural strength of the composite panels can be 300 psi or greater, 500 psi or greater, 700 psi or greater, 900 psi or greater, 1000 psi or greater, 1100 psi or greater, 1200 psi or greater, 1300 psi or greater, 1400 psi or greater, or 1500 psi or greater. The flexural strength can be determined by the load required to fracture a rectangular prism loaded in the three point bend test as described in ASTM C1185-08 (2012).
- In some embodiments, incorporation of die fiber reinforcement and the cementitious layer on the filled polyurethane foam can increase the hardness of the foam, compared to a composite without the fiber reinforcement and the cementitious layer. In some embodiments, the Shore D hardness of the composite panels described herein can be 50 or greater (eg., up to 90). For example, the Shore D hardness of the composite panels can be 55 or greater, 60 or greater, 65 or greater, 75 or greater, or 80 or greater. The Shore D hardness can be determined using a durometer as described in ASTM D2240.
- In some embodiments, incorporation of the fiber reinforcement and the cementitious lay er on the foam can increase the sti ffness of the composite, compared to a composite without the fiber reinforcement and the cementitious layer. In some embodiments, themodulus of elasticity (stiffness) of the composite panel can be 10 ksi or greater, 50 ksi or greater or 100 ksi or greater. For example, the modulus of elasticity can be from 10 to 500 ksi or from 50 to 500 ksi The modulus of elasticity can be determined as described in ASTM C947-03.
- In some embodiments, incorporation of the fiber reinforcement and the cementitious layer on the filled foam can increase the flame resistance of the composite, compared to a composite without the fiber reinforcement and the cementitious layer. In some embodiments, the composite panels can be qualified as a Class A material in the ASTM E84 tunnel test. In some embodiments, the composite panels have a flame spread rating of 25 or less and a smoke development rating of 450 or less. The flame spread and smoke development ratings can be determined as described in the ASTM E84 test.
- The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices and/or methods claimed herein are made and evaluated, and are intended to be purely exemplary and are not intended to limit the scope of the disclosure. Unless indicated otherwise, parts and percentages are on a weight basis, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric.
- Polyurethane foams were prepared using three different polyols labeled as Polyol A, a petroleum-derived polypropylene based polyol having a hydroxyl number of 240 mg KOH/g, a functionality of 3, and a viscosity of 250 mPa.s; Polyol B, a glycerin initiated polyether polyol having a hydroxyl number of 240 mg KOH/g, a functionality of 3, and a viscosity of 250 mPa.s at 25° C.; and Polyol C, a sucrose/amine initiated polyether polyol having a hydroxyl number of 350 mg KOH/g, a functionality of 5.5, and a viscosity of 2,500 mPa.s at 25° C.
- The composites were prepared by wetting fly ash and ⅛″ chopped fiber glass in an extruder with concurrent streams of polyol (about 12% by weight of the foam) and methylene diphenyl diisocyanate (about 13% by weight of the foam) and optionally a catalyst and simultaneously stirring began. The mixture was extruded into a cardboard box and allowed to freely rise and cure. The physical properties of the composites, including flexural strength, density, handleability, extension, and modulus were determined. The handleabdity is a measure of the ability of the material to be flexed during use and is calculated as 0.5 × breaking load × ultimate deflection/thickness of the test specimen. The extension is a measure of the deflection of a sample during the three point bend test as defined in ASTM C947-03. The modulus is calculated from the stress/strain curve of the three point bend test, Normalized flexural strength is the ratio of flexural strength divided by the density
-
TABLE 2 Components and mechanical properties of filled polyurethane foams Foam #1 Foam #2 Foam #3 Polyol Polyol A Polyol B Polyol C Polyol conc. (wt%) 17% 19% 14% isocyanate conc. (wt%) 13% 14% 13.4% Surfactant Silicocone-based Surfactant conc. (wt%) 0.16% Fiber glass conc. (wt%) 1% 4% 5% Filler conc. (wt%) 69% 66% 68% Catalyst conc. (pphp) 0.2 0.1 Water conc. (wt%) 0.17% 0.31% 0.11% Viscosity (cPs) 7590 (77° F.) 35000 (80° F.) 72300 (85° F.) Cream time (sec) 115 85 41 Tack-free time (sec) 240 140 375 Density (pcf) 21.7 17.0 22.6 Modulus (ksi) 31.6 15.0 26.5 Flexural strength (psi) 413 352 271 Extension (in.) 0.041 0.089 0.611 Handleability 4.02 7.69 7.43 - Summary: As shown in Table 2, the polyurethane foams prepared using Polyols A-C produced foams having suitable density, modulus, flexural strength, extension, and handleability. The cream time for the three samples was 41 seconds up to 115 seconds. The tack-free time was from 140 seconds up to 375 seconds
- The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative materials and method steps disclosed herein are specifically described, other combinations of the materials and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein; however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated The term “comprising” and variations thereof as used herein is used synonymously with the term “including” and variations thereof and are open, non-limning terms. Although the terms “comprising” and “including” have been used herein to describe various embodiments, the terms “consisting essentially of” and “consisting of” can be used in place of “comprising” and “including” to provide for more specific embodiments and are also disclosed As used in this disclosure and in the appended claims, the singular forms “a”, “an”, “the”, include plural referents unless the context clearly dictates otherwise
Claims (20)
1-57. (canceled)
58. A method of making a polyurethane or polyisocyanurate foam, the method comprising:
mixing one or more isocyanates selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof; one or more polyols; and a filler to produce a mixture, wherein the filler is present in an amount from greater than 50% to 90% by weight, based on the total weight of the mixture;
applying the mixture to a mold at a viscosity of 20,000 cPs to 100,000 cPs at the temperature of the mixture; and
allowing the mixture to react and expand to form the polyurethane or polyisocyanurate foam;
wherein the foam does not reach a hardness of 20 shore D in less than 5 minutes.
59. The method of claim 58 , wherein the foam has a flexural strength of from 100 psi to 700 psi.
60. The method of claim 58 , wherein filler includes a particulate filler, a plurality of fibers, or a combination thereof.
61. The method of claim 58 , wherein the filler comprises glass fibers, polyalkylene fibers, polyester fibers, polyamide fibers, phenol-formaldehyde fibers, polyvinyl chloride fibers, polyacrylic fibers, acrylic polyester fibers, polyurethane fibers, polyacrylonitrile fibers, rayon fibers, cellulose fibers, carbon fibers, metal and metal-coated fibers, mineral fibers, or combinations thereof.
62. The method of claim 58 , wherein the foam has a density of 10 lb/ft3 to 35 lb/ft3.
63. The method of claim 58 , wherein the mixture further comprises a catalyst.
64. The method of claim 58 , wherein the mixture applied to the mold has a tack free time of from 90 seconds to 7 minutes.
65. The method of claim 58 , wherein the mixture applied to the mold has a cream time of from 20 seconds to 120 seconds.
66. The method of claim 58 , wherein the foam has a thickness from 0.1 inch to 6 inches.
67. A method of making a polyurethane or polyisocyanurate foam, the method comprising:
mixing one or more isocyanates selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof; one or more polyols; and a filler to produce a mixture, wherein the filler is present in an amount from greater than 50% to 90% by weight, based on the total weight of the mixture;
applying the mixture to a mold; and
allowing the mixture to react and expand to form the polyurethane or polyisocyanurate foam,
wherein the mixture applied to the mold has a tack free time of from 90 seconds to 7 minutes and
wherein the resulting polyurethane or polyisocyanurate foam has a density of 10 lb/ft3 or greater.
68. The method of claim 67 , wherein the foam has a flexural strength of from 100 psi to 700 psi.
69. The method of claim 67 , wherein the foam has a compressive strength from 100 psi to 300 psi.
70. The method of claim 67 , wherein the filler comprises an inorganic particulate filler and a plurality of fibers.
71. The method of claim 70 , wherein the plurality of fibers comprises glass fibers, polyalkylene fibers, polyester fibers, polyamide fibers, phenol-formaldehyde fibers, polyvinyl chloride fibers, polyacrylic fibers, acrylic polyester fibers, polyurethane fibers, polyacrylonitrile fibers, rayon fibers, cellulose fibers, carbon fibers, metal and metal-coated fibers, mineral fibers, or combinations thereof.
72. The method of claim 67 , wherein the mixture has a viscosity of 20,000 cPs to 100,000 cPs when applied to the mold.
73. The method of claim 67 , wherein the mixture applied to the mold has a cream time of from 80 seconds to 120 seconds.
74. The method of claim 67 , wherein the foam does not reach a hardness of 20 shore D in less than 5 minutes.
75. A method of making a polyurethane or polyisocyanurate foam, the method comprising:
mixing one or more isocyanates selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof; one or more polyols; and a filler to produce a mixture, wherein the filler is present in an amount from greater than 50% to 90% by weight, based on the total weight of the mixture;
applying the mixture to a mold; and
allowing the mixture to react and expand to form the polyurethane or polyisocyanurate foam,
wherein the mixture applied to the mold has a cream time of from 80 seconds to 120 seconds.
76. The method of claim 75 , wherein the foam has a flexural strength of from 100 psi to 700 psi.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18/305,122 US20230295370A1 (en) | 2016-05-23 | 2023-04-21 | Filled polyurethane or polyisocyanurate foam and method of making same |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2016/033734 WO2017204778A1 (en) | 2016-05-23 | 2016-05-23 | Filled polyurethane or polyisocyanurate foam and method of making same |
US201816301996A | 2018-11-15 | 2018-11-15 | |
US18/305,122 US20230295370A1 (en) | 2016-05-23 | 2023-04-21 | Filled polyurethane or polyisocyanurate foam and method of making same |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/301,996 Continuation US11661472B2 (en) | 2016-05-23 | 2016-05-23 | Filled polyurethane or polyisocyanurate foam and method of making same |
PCT/US2016/033734 Continuation WO2017204778A1 (en) | 2016-05-23 | 2016-05-23 | Filled polyurethane or polyisocyanurate foam and method of making same |
Publications (1)
Publication Number | Publication Date |
---|---|
US20230295370A1 true US20230295370A1 (en) | 2023-09-21 |
Family
ID=60411525
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/301,996 Active 2039-06-19 US11661472B2 (en) | 2016-05-23 | 2016-05-23 | Filled polyurethane or polyisocyanurate foam and method of making same |
US18/305,122 Pending US20230295370A1 (en) | 2016-05-23 | 2023-04-21 | Filled polyurethane or polyisocyanurate foam and method of making same |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/301,996 Active 2039-06-19 US11661472B2 (en) | 2016-05-23 | 2016-05-23 | Filled polyurethane or polyisocyanurate foam and method of making same |
Country Status (2)
Country | Link |
---|---|
US (2) | US11661472B2 (en) |
WO (1) | WO2017204778A1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017204778A1 (en) * | 2016-05-23 | 2017-11-30 | Boral Ip Holdings (Australia) Pty Limited | Filled polyurethane or polyisocyanurate foam and method of making same |
WO2020005270A1 (en) | 2018-06-29 | 2020-01-02 | Boral Ip Holdings (Australia) Pty Limited | Foam composites and methods of preparation thereof |
CN109627638A (en) * | 2018-12-26 | 2019-04-16 | 浙江维派管业有限公司 | A kind of mute drainage pipe hard polyvinyl chloride composition and preparation method thereof |
US20220195182A1 (en) * | 2020-12-18 | 2022-06-23 | Evoco Ltd. | Plasticizer lignin compositions |
CA3211169A1 (en) * | 2021-02-24 | 2022-09-01 | Soft-Tex Group, Inc. | Composition of foam, cushions, and related methods of manufacture |
AU2022226563A1 (en) * | 2021-02-26 | 2023-09-07 | Soft-Tex Group, Inc. | Composition of foam and cushions that include digesters, and related methods of manufacture |
CA3160844A1 (en) * | 2021-05-28 | 2022-11-28 | Westlake Royal Building Products Inc. | Insulation panels and methods of preparation thereof |
CN117043246A (en) * | 2021-08-20 | 2023-11-10 | 优势全球创新公司 | Method and system for recycling polyurethane |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1070095B1 (en) * | 1998-04-03 | 2003-10-08 | Huntsman International Llc | fibre reinforced structural reaction injection molded polyisocyanurate foams |
US7259207B2 (en) * | 2000-05-23 | 2007-08-21 | Henkel Kommanditgesellschaft Auf Aktien | Single-component polyurethane adhesive |
US20090023525A1 (en) * | 2007-07-20 | 2009-01-22 | Invista North America S.A.R.L. | Manufacture of polyurethane foam ball |
US11661472B2 (en) * | 2016-05-23 | 2023-05-30 | Westlake Royal Building Products Inc. | Filled polyurethane or polyisocyanurate foam and method of making same |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4062999A (en) | 1974-02-12 | 1977-12-13 | Teijin Limited | Synthetic organic fibers coated with an amino silane and an epoxy siloxane containing treating agent |
JP2657249B2 (en) | 1986-11-25 | 1997-09-24 | 東レ・ダウコーニング・シリコーン株式会社 | Adhesion improver |
US5082738A (en) | 1988-06-15 | 1992-01-21 | Hoechst Celanese Corporation | Polyester film primed with an aminofunctional silane, and film laminates thereof |
US4883826A (en) | 1988-07-27 | 1989-11-28 | The Dow Chemical Company | Tertiary amine-containing polyols prepared in a mannich condensation reaction using a mixture of alkanolamines |
US6046262A (en) | 1998-03-09 | 2000-04-04 | Milliken & Company | Composition for promoting adhesion between rubber and textiles |
US6881764B2 (en) * | 2001-12-04 | 2005-04-19 | Textile Rubber & Chemical Company, Inc. | Polyurethane composition with glass cullet filler and method of making same |
BRPI0510894A (en) * | 2004-06-17 | 2007-11-27 | Dow Global Technologies Inc | Method for incorporating a glass filler into a storage stable polyurethane article, polyurethane article, carpet and dispersion |
CA2534237A1 (en) | 2005-03-04 | 2006-09-04 | Gaz Transport Et Technigaz | Polyurethane/polyisocyanurate foam reinforced with glass fibres |
EP2681039B1 (en) | 2011-11-22 | 2016-02-03 | Kordsa Global Endustriyel Iplik ve Kord Bezi Sanayi ve Ticaret Anonim Sirketi | Production method of a composite material |
CN103709367B (en) | 2012-09-29 | 2018-09-04 | 科思创聚合物(中国)有限公司 | The method for maintaining of urethane composition and polyurethane ballast railway roadbed |
-
2016
- 2016-05-23 WO PCT/US2016/033734 patent/WO2017204778A1/en active Application Filing
- 2016-05-23 US US16/301,996 patent/US11661472B2/en active Active
-
2023
- 2023-04-21 US US18/305,122 patent/US20230295370A1/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1070095B1 (en) * | 1998-04-03 | 2003-10-08 | Huntsman International Llc | fibre reinforced structural reaction injection molded polyisocyanurate foams |
US7259207B2 (en) * | 2000-05-23 | 2007-08-21 | Henkel Kommanditgesellschaft Auf Aktien | Single-component polyurethane adhesive |
US20090023525A1 (en) * | 2007-07-20 | 2009-01-22 | Invista North America S.A.R.L. | Manufacture of polyurethane foam ball |
US11661472B2 (en) * | 2016-05-23 | 2023-05-30 | Westlake Royal Building Products Inc. | Filled polyurethane or polyisocyanurate foam and method of making same |
Also Published As
Publication number | Publication date |
---|---|
US20220259371A1 (en) | 2022-08-18 |
WO2017204778A1 (en) | 2017-11-30 |
US11661472B2 (en) | 2023-05-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20240001661A1 (en) | Highly-filled polyurethane composites with fiber reinforcement | |
US10030126B2 (en) | Filled polyurethane composites with lightweight fillers | |
US11661472B2 (en) | Filled polyurethane or polyisocyanurate foam and method of making same | |
US9944063B1 (en) | Method of producing reinforced substrate | |
US10472281B2 (en) | Polyurethane composites with fillers | |
US10377868B2 (en) | Filled polyurethane composites with organic and inorganic fibers | |
US20220177637A1 (en) | Surfactant-free filled polyurethane foam and method of making same | |
US20230086412A1 (en) | Panel for attachment to a mounting surface of a building structure and method of making the same | |
WO2016118141A1 (en) | Highly filled polyurethane composites | |
US9752015B2 (en) | Filled polymeric composites including short length fibers | |
US11174372B2 (en) | Highly-filled polyurethane composites with non-silane treated glass fibers | |
US20210146655A1 (en) | Composites comprising cementitious coatings including fibers | |
US10941292B2 (en) | Filled composites comprising glass and polyester fibers | |
US20230069660A1 (en) | Polymeric materials with improved environmental durability | |
WO2019117952A1 (en) | Fatty acid modified polyurethane composites with improved dimensional stability | |
US10737508B2 (en) | Building materials comprising composites with printed images | |
AU2016408342B2 (en) | Filled polyurethane foam having tailored microstructures | |
US10377065B1 (en) | Method for producing building panels by making coated foam in situ in a mold |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |