CN1749291A - Flame-retardant polyurethane water dispersion and its preparing method - Google Patents
Flame-retardant polyurethane water dispersion and its preparing method Download PDFInfo
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- CN1749291A CN1749291A CN200510030113.7A CN200510030113A CN1749291A CN 1749291 A CN1749291 A CN 1749291A CN 200510030113 A CN200510030113 A CN 200510030113A CN 1749291 A CN1749291 A CN 1749291A
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- Prior art keywords
- flame
- water dispersion
- glycol
- polyurethane water
- retardant
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Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 73
- 239000004814 polyurethane Substances 0.000 title claims abstract description 67
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 66
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000006185 dispersion Substances 0.000 title claims description 48
- 238000000034 method Methods 0.000 title description 2
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- -1 flame retardant polyol Chemical class 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 9
- 229920005862 polyol Polymers 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 28
- 229920000570 polyether Polymers 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 150000002334 glycols Chemical class 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- SLKPORNFSBUSRF-UHFFFAOYSA-N [Cl].[Sb].[P] Chemical compound [Cl].[Sb].[P] SLKPORNFSBUSRF-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 150000002009 diols Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 238000004945 emulsification Methods 0.000 claims description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000004970 Chain extender Substances 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 150000003384 small molecules Chemical group 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 4
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical group CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002924 oxiranes Chemical class 0.000 claims description 4
- 229940059574 pentaerithrityl Drugs 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 4
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 4
- 150000003512 tertiary amines Chemical group 0.000 claims description 4
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 3
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001083 polybutene Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 claims 2
- 239000012948 isocyanate Substances 0.000 claims 1
- 150000002513 isocyanates Chemical group 0.000 claims 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000006386 neutralization reaction Methods 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000007859 condensation product Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 235000013336 milk Nutrition 0.000 description 5
- 239000008267 milk Substances 0.000 description 5
- 210000004080 milk Anatomy 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 229920003009 polyurethane dispersion Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011527 polyurethane coating Substances 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910021331 inorganic silicon compound Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- ZENRLIAXIHXUFB-UHFFFAOYSA-N n,n-diethylethanamine;3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid Chemical compound CC[NH+](CC)CC.OCC(C)(CO)C([O-])=O ZENRLIAXIHXUFB-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- JYFPFWCWXLBYDY-UHFFFAOYSA-N n,n-diethylethanamine;propanoic acid Chemical compound CCC(O)=O.CCN(CC)CC JYFPFWCWXLBYDY-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
The water dispersed flame retardant polyurethane consists of: diisocyanate 14-53wt%, flame retardant polyol 6-78 wt%, non-flame retardant polyol 0-52.5wt%, compound with active hydrogen and capable of forming hydrophilic radical 4-8 wt%, neutralizing agent 1.5-5wt%, and small molecular weight chain expander 1-18.5wt%. Its preparation process includes the steps of: pre-polymerizing diisocyanate, flame retardant polyol, non-flame retardant polyol and compound with active hydrogen and capable of forming hydrophilic radical to form pre-polymre I; neutralizing the hydrophilic radical with neutralizing agent to prepare -NCO radical ended pre-polymre II; dispersing pre-polymre II into deionized water and expanding chain with the small molecular weight chain expander to prepare the water dispersed flame retardant polyurethane. The present invention endows the product with internal flame retardant performance and expands the application range of water dispersed polyurethane.
Description
Technical field
What the present invention relates to is dispersion of a kind of chemical technology field and preparation method thereof, is specifically related to a kind of Fire-retardant waterborne polyurethane dispersion and its preparation method.
Background technology
Urethane (being called for short PU) is meant and contains a carbamate (NHCOO-) family macromolecule polymkeric substance of structure in the molecular chain.Because the variety of raw material of preparation urethane is various, it is varied to fill a prescription, and variable range is very big, and the laudatory title of " cutting " superpolymer is arranged, and its goods comprise polyurethane foam, polyurethane elastomer, polyurethane coating and polyurethane adhesive etc.Polyurethane aqueous dispersions is an important kind in the urethane family various in style, it is on the basis that has kept the polyurethane elastomer excellent properties, with the alternative organic solvent of the water of cheapness is dispersion medium, have safe in utilization, nontoxic, do not fire, can not cause advantages such as environmental pollution, now become one of important kind of aqueous high molecular material, and industry such as widespread use and light textile, printing and dyeing, leather processing, papermaking.Along with the expansion of polyurethane synthetic material application surface, each industrial sector is more and more higher to the requirement of the flame retardant properties of its goods.Especially furniture industry, paper industry and building industry wishes that not only polyurethane product is fire-retardant, the low toxicity but also the amount of smoke that requires it to decomposite under flame interaction is few.At present, the preparation of relevant flame retardant polyurethane both at home and abroad is mainly aspect flame retarded polyurethane-foam, and the preparation of flame-retardant polyurethane water dispersion rarely has report.
Find through literature search prior art, Chinese patent application number is 200310117505.8 patent, this patent adopts in the high molecular synthesis or in the emulsifying water chain extension process silicoorganic compound is incorporated in the urethane, in emulsion, add the further chain extension-crosslinking reaction of a certain amount of inorganic silicon compound again, prepared the stabilized aqueous polyaminoester emulsion, it is filmed and has water-tolerant, gloss, soft durometer and application performance require advantages such as suitable, compare with unmodified aqueous polyurethane coating, each basic mechanical design feature all is significantly improved, organic and the composite modified aqueous polyurethane coating of inorganic silicon compound that can be used for wood lacquer etc., but it also proposes relevant fire-retardant problem.Chinese patent application number is 200410067408.7 patent, and this patent is mixed the organic silicon acrylic ester resin with the HDI tripolymer, obtain a kind of high-gloss and high temperature resistant silicon-acrylic polyurethane paint.This coating has higher surface luster, and good thermotolerance and good weathering resistance can be at 150 ℃ of following life-time service.But as organic solvent, environmental hazard is bigger with toluene for it, does not meet the developing direction of environmental-friendly aqueousization of polyurethane material.In further retrieving, find as yet and the identical or similar bibliographical information of theme of the present invention " Fire-retardant waterborne polyurethane dispersion and its preparation method ".
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of Fire-retardant waterborne polyurethane dispersion and its preparation method is provided.Make it pass through " molecular designing ", on the polyurethane molecular main chain, introduce flame retarding construction, give the interior flame retardant resistance that aqueous dispersion is filmed, satisfying the raising to fire-retardant requirement such as furniture industry, paper industry and building industry, and enlarge the range of application of aqueous polyurethane.
The present invention is achieved by the following technical solutions, flame-retardant polyurethane water dispersion of the present invention, and its component and weight percent are:
Vulcabond 14～53%
Flame retardant resistance polyvalent alcohol 6～78%
Non-flame retardant resistance polyvalent alcohol 0～52.5%
What can form hydrophilic radical has a compound bearing active hydrogen 4～8%
Neutralizing agent 1.5～5%
Small molecule chain extender 1～18.5%
The preparation method of the flame-retardant polyurethane water dispersion that the present invention is above-mentioned comprises the steps:
(1) earlier vulcabond, flame retardant resistance polyvalent alcohol, non-flame retardant resistance polyvalent alcohol and the compound bearing active hydrogen that has that can form hydrophilic radical are carried out the prepolymer hybrid reaction earlier (NCO) content obtains prepolymer I to the isocyanate group of setting;
(2) with above-mentioned prepolymer I with in the neutralizing agent and hydrophilic radical, make-negatively charged ion or the cation type polyurethane performed polymer II of NCO group end capping;
(3) above-mentioned performed polymer II is added deionized water in emulsify at a high speed equipment and carry out emulsification, and promptly get anionic or cationic polyurethane aqueous dispersions with anti-flaming function with the small molecule chain extender chain extension.
Described vulcabond is selected from tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), naphthalene-1,5-vulcabond (NDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2, the sour methyl esters of 6-vulcabond (LDI), 4,4 '-methylene radical-dicyclohexyl vulcabond (H
12MDI), xylylene diisocyanate (XDI), 1,12-dodecyl vulcabond (C
12DDI) etc. a kind of in common aromatic series and the aliphatic diisocyanate.
That described flame retardant resistance polyvalent alcohol is selected from is phosphorous, the polyvalent alcohol with anti-flaming function of one or more elements in the antimony, halogen, as one or more the mixture in phosphoric acid ester polyether glycol, phosphorus antimony chlorine ternary phosphoric acid ester polyether glycol, halogenated polyether polyvalent alcohol, dibromoneopentyl glycol, the tetrabromo-bisphenol.Wherein:
Described phosphoric acid ester polyether glycol is for being phosphide with in phosphorus trichloride, phosphoric acid or five phosphorus oxide one or more, in glycerine, TriMethylolPropane(TMP), propylene glycol, sorbyl alcohol, the tetramethylolmethane one or more are polyol, ethylene oxide, propylene oxide, epoxy chloropropane, butylene oxide ring, 1,1,1-three chloro-3, one or more in the 4-butylene oxide ring are the phosphor-containing flame-proof dibasic alcohol of feedstock production gained for epoxide;
Described phosphorus antimony chlorine ternary phosphoric acid ester polyether glycol is for being phosphide with in phosphorus trichloride, phosphoric acid or five phosphorus oxide one or more, in glycerine, TriMethylolPropane(TMP), propylene glycol, sorbyl alcohol, the tetramethylolmethane one or more are polyol, ethylene oxide, propylene oxide, epoxy chloropropane, butylene oxide ring, 1-three chloro-3, in the 4-butylene oxide ring one or more are epoxide, and butter of antimony is phosphorous, the antimony of feedstock production gained, the dibasic alcohol of three kinds of ignition-proof elements of chlorine;
Described halogenated polyether polyvalent alcohol is 4,4,4-three chloro-1, and 2-butylene oxide ring or 4,4,4-three bromo-1, the 2-butylene oxide ring is a raw material, lewis' acid is a catalyzer, the various halogenated polyether dibasic alcohol that reaction makes.
Described non-flame retardant resistance polyvalent alcohol is selected from polyether Glycols commonly used, polyester diol, polycarbonate diol, polybutadiene diol, polybutene glycol, acrylate polyvalent alcohol, polycaprolactone glycol, the mixture of one or more in the PTMG.
The described compound bearing active hydrogen that has that forms hydrophilic radical is selected from dibasic alcohol such as the methyldiethanolamine that contains the tertiary amine structure, contains dibasic alcohol such as dimethylol propionic acid, the tartrate of carboxyl structure and contains one or more mixture in the dibasic alcohol of sulfonic acid structure.
Described neutralizing agent be selected from one or more or the energy in the suitable acid such as can make quaternary ammoniated compound of tertiary amine such as methyl iodide alkylating reagent, acetate, hydrochloric acid etc. and mineral alkalis such as tertiary amines organic bases, sodium hydroxide, ammoniacal liquor such as the compound of carboxylic acid and sulfonic acid such as triethylamine in one or more mixture.
Described small molecule chain extender is selected from micromolecular diamine, dibasic alcohol or polyamine, polyvalent alcohol such as quadrol, hexanediamine, diethylenetriamine, hydrazine hydrate, ethylene glycol, 1, the 4-butyleneglycol, glycol ether, TriMethylolPropane(TMP), thanomin, trolamine, the mixture of one or more in the neopentyl glycol.
The present invention adopts the molecular designing means, with vulcabond and flame retardant resistance polyol reaction, introduces flame retarding construction on polyurethane backbone, and the preparation method according to traditional polyurethane aqueous dispersions makes flame-retardant polyurethane water dispersion then.The present invention can give these polyurethane aqueous dispersions goods good interior flame retardant effect by kind, the content of group of band anti-flaming function is regulated.The preparation condition and the equipment of the preparation condition of flame-retardant polyurethane water dispersion of the present invention and equipment and existing polyurethane aqueous dispersions are basic identical.
The flame-retardant polyurethane water dispersion of the present invention's preparation is compared with existing polyurethane aqueous dispersions has following advantage: (1) the present invention guides on the polyurethane backbone by the chemical structure that " molecular designing " means will have anti-flaming function; (2) chemical structure of band anti-flaming function gives flame retardant polyurethane aqueous dispersion goods certain interior flame retardant effect, and has avoided adding fire retardant to the polyurethane aqueous dispersions Effect on Performance.
Embodiment
Below by embodiment embodiment of the present invention are described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
Flame-retardant polyurethane water dispersion prescription one:
| Raw material | Weight | Weight percent |
| Tolylene diisocyanate (TDI) phosphorus antimony chlorine ternary phosphoric acid ester polyether Glycols (hydroxyl value 50mgKOH/g) dimethylol propionic acid triethylamine quadrol | 17400g 95724g 5452g 3493g 1000g | 14％ 78％ 4.5％ 2.5％ 1％ |
In the reactor that stirring arm, thermometer and condenser are housed, add tolylene diisocyanate, hydroxyl value is the phosphorus antimony chlorine ternary phosphoric acid ester polyether Glycols of 50mgKOH/g, dimethylol propionic acid, be warming up to 60 ℃, insulation reaction 0.5 hour is warming up to 75 ℃ of reactions to-NCO content again and reaches prescribed value.Be cooled to 30～60 ℃, add the triethylamine neutralization, make-the anion polyurethane performed polymer of NCO group end capping.Above-mentioned performed polymer is added deionized water carry out emulsification in emulsify at a high speed equipment, and adding quadrol stirring reaction promptly got the polyurethane aqueous dispersions that anionic has anti-flaming function in 20～30 minutes.In the prescription of the present invention, NCO/OH (mol ratio) is 1.2, and-COOH mass content is 1.5%, and neutralization ratio is 85%.The flame-retardant polyurethane water dispersion of the present invention preparation be translucent, do not have mechanical impurity, no condensation product milk sap.The flame-retardant polyurethane water dispersion of the present invention that takes a morsel preparation is measured according to GB GB12441-1998 " finishing fire retardant paint general technical specifications ", its anti-combustion time 〉=20min, ratio≤30 are relayed in the fire combustion, reach secondary domestic enterprise production fire resistance.
Embodiment 2
Flame-retardant polyurethane water dispersion prescription two:
| Raw material | Weight | Weight percent |
| Isophorone diisocyanate (IPDI) phosphoric acid ester polyether Glycols (hydroxyl value 200mgKOH/g) dibromoneopentyl glycol tartrate NaOH hexanediamine | 22200g 6626g 2907g 1682g 628g 7731g | 53％ 16％ 7％ 4％ 1.5％ 18.5％ |
In the reactor that stirring arm, thermometer and condenser are housed, add isophorone diisocyanate, the phosphoric acid ester polyether Glycols, dibromoneopentyl glycol, tartrate is warming up to 60 ℃, insulation reaction 0.5 hour is warming up to 80 ℃ of reactions to-NCO content again and reaches prescribed value.Be cooled to 30～40 ℃, add the NaOH neutralization, make-the anion polyurethane performed polymer of NCO group end capping.Above-mentioned performed polymer is added deionized water carry out emulsification in emulsify at a high speed equipment, and adding hexanediamine stirring reaction promptly got the polyurethane aqueous dispersions that anionic has anti-flaming function in 20～30 minutes.In the prescription of the present invention, NCO/OH (mol ratio) is 3.0, and-COOH mass content is 3.0%, and neutralization ratio is 70%.The flame-retardant polyurethane water dispersion of the present invention preparation be transparent, colourless, do not have mechanical impurity, no condensation product milk sap.The flame-retardant polyurethane water dispersion of the present invention that takes a morsel preparation is measured according to GB GB12441-1998 " finishing fire retardant paint general technical specifications ", its anti-combustion time 〉=10min, ratio≤45 are relayed in the fire combustion, reach three grades of domestic enterprise's production fire resistances.
Embodiment 3
Flame-retardant polyurethane water dispersion prescription three:
| Raw material | Weight | Weight percent |
| Hexamethylene diisocyanate (HDI) phosphorus antimony chlorine ternary phosphoric acid ester polyether Glycols (hydroxyl value 200mgKOH/g) Polyoxypropylene diol (mean molecule quantity 1000) methyl diethanolamine acetic acid butanediol | 16800g 4058g 33272g 3110g 1568g 4500g | 27％ 6％ 52.5％ 5％ 2.5％ 7％ |
In the reactor that stirring arm, thermometer and condenser are housed, add hexamethylene diisocyanate, phosphorus antimony chlorine ternary phosphoric acid ester polyether Glycols, the polyoxytrimethylene dibasic alcohol, methyldiethanolamine is warming up to 60 ℃, insulation reaction 1 hour, being warming up to 90 ℃ of reactions to-NCO content again reaches prescribed value, adds chain expansion of succinic acid again.Be cooled to 30～40 ℃, add the acetate neutralization, obtain positively charged ion flame-retardant polyurethane performed polymer.Above-mentioned performed polymer is added deionized water in emulsify at a high speed equipment carry out emulsification and promptly get cationic polyurethane aqueous dispersions with anti-flaming function.In the prescription of the present invention, NCO/OH (mol ratio) is 2.0, and-COOH mass content is 2.0%, and neutralization ratio is 100%.The flame-retardant polyurethane water dispersion of the present invention preparation be transparent, colourless, do not have mechanical impurity, no condensation product milk sap.The flame-retardant polyurethane water dispersion of the present invention that takes a morsel preparation is coated on 2～3 150mm * 150mm glued board, by the situation brushing of practice of construction, waits to parch, with the flame inspection of spirit lamp.About flame height 40mm, apply the time 20min of flame, the only a small amount of black smoke of its burning, remove and to put out certainly.
Embodiment 4
Flame-retardant polyurethane water dispersion prescription four:
| Raw material | Weight | Weight percent |
| 4,4 '-diphenylmethanediisocyanate (MDI) phosphoric acid ester polyether Glycols (hydroxyl value 150mgKOH/g) chloro polyether Glycols (hydroxyl value 100mgKOH/g) dimethylol propionic acid triethylamine | 25000g 6904g 10355g 4169g 2671g | 48％ 13.5％ 20％ 8％ 5％ |
| Diethylenetriamine | 2829g | 5.5％ |
In the reactor that stirring arm, thermometer and condenser are housed, add 4,4 '-diphenylmethanediisocyanate, phosphoric acid ester polyether Glycols, the chloro polyether Glycols, dimethylol propionic acid is warming up to 60 ℃, insulation reaction 1 hour, be warming up to 85 ℃ of reactions to-NCO content again and reach prescribed value, be cooled to 30～40 ℃, add the triethylamine neutralization, obtain negatively charged ion flame-retardant polyurethane performed polymer.Above-mentioned performed polymer is added deionized water carry out emulsification in emulsify at a high speed equipment, and added the diethylenetriamine stirring reaction 20～30 minutes, promptly get the polyurethane aqueous dispersions that anionic has anti-flaming function.In the prescription of the present invention, NCO/OH (mol ratio) is 1.7, and-COOH mass content is 2.5%, and neutralization ratio is 85%.The flame-retardant polyurethane water dispersion of the present invention preparation be transparent, colourless, do not have mechanical impurity, no condensation product milk sap.The flame-retardant polyurethane water dispersion of the present invention that takes a morsel preparation is measured according to GB GB12441-1998 " finishing fire retardant paint general technical specifications ", its anti-combustion time 〉=10min, ratio≤40 are relayed in the fire combustion, reach three grades of domestic enterprise's production fire resistances.
Embodiment 5
Flame-retardant polyurethane water dispersion prescription five:
| Raw material | Weight | Weight percent |
| 4,4 '-methylene radical-dicyclohexyl vulcabond (H 12MDI) phosphorus antimony chlorine ternary phosphoric acid ester polyether Glycols (hydroxyl value 112mgKOH/g) Polyoxypropylene diol (mean molecule quantity 2000) PTMG (mean molecule quantity 1000) dihydromethyl propionic acid triethylamine hexamethylene diamine | 26200g 14917g 9945g 4972g 4113g 2635g 5155g | 38.5％ 22％ 15％ 7％ 6％ 3.5％ 8％ |
In the reactor that stirring arm, thermometer and condenser are housed, add 4,4 '-methylene radical-dicyclohexyl vulcabond, phosphorus antimony chlorine ternary phosphoric acid ester polyether Glycols, the polyoxytrimethylene dibasic alcohol, PTMG, dimethylol propionic acid, be warming up to 60 ℃, insulation reaction 1.5 hours is warming up to 75～90 ℃ of reactions to-NCO content again and reaches prescribed value, be cooled to 30～60 ℃, add the triethylamine neutralization, obtain negatively charged ion flame-retardant polyurethane performed polymer.Above-mentioned performed polymer is added deionized water carry out emulsification in emulsify at a high speed equipment, and added the hexanediamine stirring reaction 20～30 minutes, promptly get the polyurethane aqueous dispersions that anionic has anti-flaming function.In the prescription of the present invention, NCO/OH (mol ratio) is 1.8, and-COOH mass content is 2.2%, and neutralization ratio is 85%.The flame-retardant polyurethane water dispersion of the present invention preparation be transparent, colourless, do not have mechanical impurity, no condensation product milk sap.The flame-retardant polyurethane water dispersion of the present invention that takes a morsel preparation is measured according to GB GB12441-1998 " finishing fire retardant paint general technical specifications ", its anti-combustion time 〉=10min, ratio≤55 are relayed in the fire combustion, reach three grades of domestic enterprise's production fire resistances.
Claims (10)
1, a kind of flame-retardant polyurethane water dispersion is characterized in that, component and weight percent are:
Vulcabond 14～53%
Flame retardant resistance polyvalent alcohol 6～78%
Non-flame retardant resistance polyvalent alcohol 0～52.5%
What can form hydrophilic radical has a compound bearing active hydrogen 4～8%
Neutralizing agent 1.5～5%
Small molecule chain extender 1～18.5%.
2, flame-retardant polyurethane water dispersion according to claim 1, it is characterized in that, described vulcabond is selected from tolylene diisocyanate TDI, diphenylmethanediisocyanate MDI, naphthalene-1,5-vulcabond NDI, hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, 2,6-vulcabond methyl caproate LDI, 4,4 '-methylene radical-dicyclohexyl vulcabond H12MDI, xylylene diisocyanate XDI, 1, a kind of among the 12-dodecyl vulcabond C12DDI.
3, flame-retardant polyurethane water dispersion according to claim 1, it is characterized in that described flame retardant resistance polyvalent alcohol is selected from one or more the mixture in phosphoric acid ester polyether glycol, phosphorus antimony chlorine ternary phosphoric acid ester polyether glycol, halogenated polyether polyvalent alcohol, dibromoneopentyl glycol, the tetrabromo-bisphenol.
4, flame-retardant polyurethane water dispersion according to claim 3, it is characterized in that, described phosphoric acid ester polyether glycol is for being phosphide with in phosphorus trichloride, phosphoric acid or five phosphorus oxide one or more, in glycerine, TriMethylolPropane(TMP), propylene glycol, sorbyl alcohol, the tetramethylolmethane one or more are polyol, ethylene oxide, propylene oxide, epoxy chloropropane, butylene oxide ring, 1,1,1-three chloro-3, one or more in the 4-butylene oxide ring are the phosphor-containing flame-proof dibasic alcohol of feedstock production gained for epoxide.
5, flame-retardant polyurethane water dispersion according to claim 3, it is characterized in that, described phosphorus antimony chlorine ternary phosphoric acid ester polyether glycol is with phosphorus trichloride, in phosphoric acid or five phosphorus oxide one or more are phosphide, glycerine, TriMethylolPropane(TMP), propylene glycol, sorbyl alcohol, in the tetramethylolmethane one or more are polyol, ethylene oxide, propylene oxide, epoxy chloropropane, butylene oxide ring, 1-three chloro-3, in the 4-butylene oxide ring one or more are epoxide, and butter of antimony is the phosphorous of feedstock production gained, antimony, the dibasic alcohol of three kinds of ignition-proof elements of chlorine;
Described halogenated polyether polyvalent alcohol is 4,4,4-three chloro-1, and 2-butylene oxide ring or 4,4,4-three bromo-1, the 2-butylene oxide ring is a raw material, lewis' acid is a catalyzer, the various halogenated polyether dibasic alcohol that reaction makes.
6, flame-retardant polyurethane water dispersion according to claim 1, it is characterized in that, described non-flame retardant resistance polyvalent alcohol is selected from polyether Glycols, polyester diol, polycarbonate diol, polybutadiene diol, the polybutene glycol, the acrylate polyvalent alcohol, polycaprolactone glycol, the mixture of one or more in the PTMG.
7, flame-retardant polyurethane water dispersion according to claim 1, it is characterized in that, the described compound bearing active hydrogen that has that forms hydrophilic radical is selected from dibasic alcohol such as the methyldiethanolamine that contains the tertiary amine structure, contains dibasic alcohol such as dimethylol propionic acid, the tartrate of carboxyl structure and contains one or more mixture in the dibasic alcohol of sulfonic acid structure.
8, flame-retardant polyurethane water dispersion according to claim 1, it is characterized in that, described neutralizing agent is selected from and can makes the quaternary ammoniated compound of tertiary amine, for in one or more or the energy in methyl iodide, acetate, the hydrochloric acid and the compound of carboxylic acid and sulfonic acid, perhaps be one or more the mixture in triethylamine, tri-n-butylamine, sodium hydroxide, the ammoniacal liquor.
9, flame-retardant polyurethane water dispersion according to claim 1, it is characterized in that, described small molecule chain extender is selected from quadrol, hexanediamine, diethylenetriamine, hydrazine hydrate, ethylene glycol, 1, the 4-butyleneglycol, glycol ether, TriMethylolPropane(TMP), thanomin, trolamine, the mixture of one or more in the neopentyl glycol.
10, a kind of preparation method of flame-retardant polyurethane water dispersion as claimed in claim 1 is characterized in that, comprises the steps:
(1) earlier vulcabond, flame retardant resistance polyvalent alcohol, non-flame retardant resistance polyvalent alcohol and the compound bearing active hydrogen that has that can form hydrophilic radical are carried out the prepolymer hybrid reaction earlier to isocyanate group-NCO content of setting, obtain prepolymer I;
(2) with above-mentioned prepolymer I with in the neutralizing agent and anhydrating property of parent group, make-negatively charged ion or the cation polyurethane performed polymer II of NCO group end capping;
(3) above-mentioned performed polymer II is added deionized water in emulsify at a high speed equipment and carry out emulsification, and promptly get anionic or cationic polyurethane aqueous dispersions with anti-flaming function with the small molecule chain extender chain extension.
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