CN104130368A - 一种阻燃聚氨酯浇注硬质泡沫塑料板材 - Google Patents
一种阻燃聚氨酯浇注硬质泡沫塑料板材 Download PDFInfo
- Publication number
- CN104130368A CN104130368A CN201410347900.3A CN201410347900A CN104130368A CN 104130368 A CN104130368 A CN 104130368A CN 201410347900 A CN201410347900 A CN 201410347900A CN 104130368 A CN104130368 A CN 104130368A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- glycol
- polyol component
- component
- polyol
- 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.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 62
- 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 51
- 239000004814 polyurethane Substances 0.000 title claims abstract description 35
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 35
- 239000002985 plastic film Substances 0.000 title abstract 3
- 239000000463 material Substances 0.000 claims abstract description 65
- 229920005862 polyol Polymers 0.000 claims abstract description 51
- 150000003077 polyols Chemical class 0.000 claims abstract description 51
- 239000012948 isocyanate Substances 0.000 claims abstract description 42
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 42
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 19
- 239000010954 inorganic particle Substances 0.000 claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- 239000006260 foam Substances 0.000 claims description 33
- -1 catalyzer Substances 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 15
- 229920001228 polyisocyanate Polymers 0.000 claims description 13
- 239000005056 polyisocyanate Substances 0.000 claims description 13
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 101100136616 Arabidopsis thaliana PHT1-4 gene Proteins 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 101100243924 Pseudomonas putida pht4 gene Proteins 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 4
- 229940051250 hexylene glycol Drugs 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 125000002524 organometallic group Chemical group 0.000 claims description 4
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- VLJVXFIVDXQSNJ-UHFFFAOYSA-N 1,1,1,2-tetrafluorobutane Chemical compound CCC(F)C(F)(F)F VLJVXFIVDXQSNJ-UHFFFAOYSA-N 0.000 claims description 2
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical compound CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 claims description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 2
- FDIPWBUDOCPIMH-UHFFFAOYSA-N 2-decylphenol Chemical compound CCCCCCCCCCC1=CC=CC=C1O FDIPWBUDOCPIMH-UHFFFAOYSA-N 0.000 claims description 2
- FIWYWGLEPWBBQU-UHFFFAOYSA-N 2-heptylphenol Chemical compound CCCCCCCC1=CC=CC=C1O FIWYWGLEPWBBQU-UHFFFAOYSA-N 0.000 claims description 2
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- LZQVWQSVPXJPHC-UHFFFAOYSA-N C(CC)C1=C(C(=C(C=C1)O)CCCC)OC1=CC=CC=C1 Chemical compound C(CC)C1=C(C(=C(C=C1)O)CCCC)OC1=CC=CC=C1 LZQVWQSVPXJPHC-UHFFFAOYSA-N 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical group 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 2
- 229940096992 potassium oleate Drugs 0.000 claims description 2
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 10
- 238000003756 stirring Methods 0.000 abstract description 9
- 238000005266 casting Methods 0.000 abstract description 6
- 238000000465 moulding Methods 0.000 abstract description 4
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 239000004566 building material Substances 0.000 abstract 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000010276 construction Methods 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000009413 insulation Methods 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 229920005830 Polyurethane Foam Polymers 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000011496 polyurethane foam Substances 0.000 description 5
- 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 4
- 229930006000 Sucrose Natural products 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000005720 sucrose Substances 0.000 description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 2
- 239000011491 glass wool Substances 0.000 description 2
- 239000011490 mineral wool Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 1
- ANHAEBWRQNIPEV-UHFFFAOYSA-N 2-chloroethyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCCl ANHAEBWRQNIPEV-UHFFFAOYSA-N 0.000 description 1
- LLUIQISTLAXOHC-UHFFFAOYSA-N 2-chloropropyl dihydrogen phosphate Chemical compound CC(Cl)COP(O)(O)=O LLUIQISTLAXOHC-UHFFFAOYSA-N 0.000 description 1
- 241000024287 Areas Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000283984 Rodentia Species 0.000 description 1
- 229920006328 Styrofoam Polymers 0.000 description 1
- HOHPOKYCMNKQJS-UHFFFAOYSA-N [P].[Br] Chemical compound [P].[Br] HOHPOKYCMNKQJS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000008261 styrofoam Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 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
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
- C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4027—Mixtures of compounds of group C08G18/54 with other macromolecular compounds
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
-
- 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
-
- 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
- C08G18/54—Polycondensates of aldehydes
- C08G18/544—Polycondensates of aldehydes with nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及一种阻燃聚氨酯浇注硬质泡沫塑料板材，属于聚氨酯硬质泡沫塑料板材领域。该板材由异氰酸酯组分与多元醇组分聚合而成，异氰酸酯组分与多元醇组分质量比为(140-200):100。多元醇组分包括聚酯多元醇、反应型阻燃剂、无机微粒以及助剂，四者分别占多元醇组分总重量的10-40％、5-40％、10-30％、22-52％。其可以使用聚氨酯浇注机或者电动、气动搅拌等设备把异氰酸酯组分和多元醇组分均匀混合后浇注成型，该板材具有优异的阻燃性能，可以满足国标GB8624-2012《建筑材料及制品燃烧性能分级》平板状建筑材料及制品的燃烧性能等级和分级判据中难燃材料B级要求。
Description
技术领域
本发明涉及一种阻燃聚氨酯浇注硬质泡沫塑料板材。
背景技术
聚氨酯硬质泡沫塑料(硬泡)是由硬泡聚醚多元醇(聚氨酯硬泡组合聚醚又称白料)，与聚合MDI(又称黑料)反应制备的。主要用于制备硬质聚氨酯泡沫塑料，广泛应用于冰箱、冷库、喷涂、太阳能、热力管线、建筑等领域。
聚氨酯硬质泡沫塑料具有优异的的物理与隔热保温性能：
1、导热系数低于岩棉、玻璃棉、聚苯板、挤塑板等建筑保温隔热材料，节电效率高；
2、重量轻，降低载荷；
3、具优良的防水性能，保温、防水合二为一；
4、设计简单、效率高、进度快、质量好、寿命长；
5、聚氨酯是惰性材料,与酸和碱都不发生反应,且不是虫类以及啮齿类动物的食物源,可保持材料性质及保温性能恒定。
聚氨酯硬泡的成型工艺一般分为喷涂和浇注两种；喷涂是使用聚氨酯喷涂机将聚氨酯双组份原料直接以细小的雾状液滴形式喷出，涂布在物体表面上，物料快速发泡膨胀并固化，形成与基体形状一致的聚氨酯硬泡保温层。最突出的特点是对于各种形状的基材，不论是平面、立面还是顶面都可以直接实施浇注发泡，不需模具。
浇注是使用聚氨酯浇注机或者是电动、气动搅拌等设备把异氰酸酯组分和多元醇组分均匀混合后浇注到模具中，经过在模具中保温保压一段时间后取出得到硬泡制品。对比喷涂有以下主要优点：
1、可以工厂连续化生产，产品质量容易控制；
2、生产不受温度、风力等气候影响，一年四季均可进行；
3、相比喷涂，材料飞溅损耗少，对施工环境污染少；
4、可以生产需要较厚结皮、形状复杂的各种板材或线条；
5、异氰酸酯组分和多元醇组分混合比例可以调整范围比较灵活。
但是聚氨酯硬泡毕竟属于有机物，其本身的阻燃性能相对于岩棉、玻璃棉、膨胀珍珠岩等无机材料还有很大差距，随着有机保温材料火灾事故的多次发生，人们对其阻燃指标要求也越来越严格。
国标GB8624-2012《建筑材料及制品燃烧性能分级》中对平板状建筑材料及制品的燃烧性能等级和分级判据中难燃材料B级要求：
目前B级阻燃还很少有人达到，特别是其中GB/T20284单体燃烧试验要求：燃烧增长速率指数小于120W/s的要求几乎没有人能够达到。
发明内容
本发明的目的在于：解决聚氨酯浇注硬泡板材在阻燃方面的不足之处，提供一种满足国标GB8624-2012《建筑材料及制品燃烧性能分级》平板状建筑材料及制品的燃烧性能等级和分级判据中难燃材料B级要求的阻燃聚氨酯浇注硬质泡沫塑料板材。
本发明的技术解决方案是:
一种阻燃聚氨酯浇注硬质泡沫塑料板材，由异氰酸酯组分与多元醇组分聚合而成，其特殊之处在于：
所述异氰酸酯组分与多元醇组分质量比为(140-200):100；所述多元醇组分包括聚酯多元醇、带羟基的反应型阻燃剂、无机微粒和助剂；所述反应型阻燃剂占多元醇组分总重量的10-40％；所述聚酯多元醇占多元醇组分总重量的5-40％；所述无机微粒占多元醇组分总重量的10-30％；所述助剂占多元醇组分总重量的22-52％。
一种阻燃聚氨酯浇注硬质泡沫塑料板材的另一种配方：异氰酸酯组分与多元醇组分质量比为(140-200):100；多元醇组分包括聚酯多元醇、带羟基的反应型阻燃剂、助剂，这些原料占多元醇组分总质量的百分比为：聚酯多元醇6-57％，带羟基的反应型阻燃剂12-57％，助剂22-52％；异氰酸酯组分包括多亚甲基多苯基多异氰酸酯以及无机微粒，占异氰酸酯组分总重量的百分比为，多亚甲基多苯基多异氰酸酯70-90％，无机微粒10-30％。
上述聚酯多元醇是由苯酐、苯二甲酸中的至少一种与乙二醇、丙二醇、丁二醇、戊二醇、己二醇、一缩二乙二醇、一缩二丙二醇、丙三醇、己三醇、三羟甲基丙烷、六羟甲基三聚氰胺中的至少一种缩聚得到的聚酯多元醇。例如南京金陵斯泰潘化学有限公司生产的牌号为PS-3152的聚酯多元醇,江苏富盛新材料有限公司生产的牌号为CF-6255的聚酯多元醇。本发明选用高苯环含量的聚酯多元醇，没有使用常规的二甘醇或者甘油与蔗糖或者乙二胺与蔗糖加环氧乙烷和/或环氧丙烷聚合而成的聚醚多元醇，其原理是减少硬泡中易燃-CH2-链段的含量，增加苯环含量，苯环在燃烧中容易形成碳化保护层，有保护泡沫内部免受火焰攻击的作用。而且我们实验中发现，硬泡中易燃-CH2-链段含量越少，苯环含量越高，越有利于碳化保护层的形成，阻燃效果越好。
上述助剂包括物理发泡剂、泡沫表面活性剂、催化剂、液体有机阻燃剂和水；助剂中各组分的质量用量占多元醇组分总质量的百分比为：
上述反应型阻燃剂为含有羟基的化合物，并且含有卤元素、磷元素、氮元素中的至少一种元素。反应型阻燃剂含有可以与异氰酸酯反应的羟基，和不含羟基的液体有机阻燃剂相比，不仅起到阻燃作用，而且没有增塑作用。含有2个以上羟基的反应型阻燃剂还可以增加硬泡交联度，代替常规的二甘醇或者甘油或者乙二胺与蔗糖加环氧乙烷和/或环氧丙烷聚合而成的聚醚多元醇，不仅得到较高的泡沫强度，还可以减少硬泡中易燃-CH2-链段的含量。
上述反应型阻燃剂为曼尼烯多元醇或者含氮/磷/卤素聚醚多元醇或者四溴苯酐二醇。曼尼烯多元醇为酚类、甲醛、二乙醇胺聚合得到的的多元醇；所述的酚类为苯酚、对苯二酚、丙基酚、丁基酚、戊基酚、庚基酚、辛基酚、壬基酚和癸基酚中的至少一种，如R2470M(万华容威聚氨酯有限公司)；含氮/磷/卤素聚醚多元醇是以含氮/磷/卤素羟基化合物加环氧乙烷和/或环氧丙烷和/或环氧氯丙烷聚合而成的分子中含有氮/磷/卤素的聚醚多元醇，如Fr-130(万华容威聚氨酯有限公司)；四溴苯酐二醇为四溴邻苯二甲酸或四溴苯酐与乙二醇、丙二醇、丁二醇、戊二醇、己二醇、一缩二乙二醇、一缩二丙二醇中的至少一种缩聚得到的聚酯多元醇，如Saytex RB-79(美国雅宝公司Albemarle Corporationin USA)。
上述无机微粒指不燃无机物，比如氢氧化铝、氢氧化镁、碳酸钙、三氧化二锑、硼酸锌微粒中的至少一种，优选氢氧化铝。使用电动、气动搅拌等混合设备时候对无机微粒粒径没有要求，使用低压、高压聚氨酯浇注机等混合设备时候无机微粒小于500目并相应调整原料滤网孔径，优先采用气缸计量泵或齿轮泵或者柱塞计量泵的高压浇注机混合。无机微粒不仅本身具有阻燃作用，而且和含有卤、磷、氮元素的反应型阻燃剂和液体有机阻燃剂具有很好的阻燃协同效应，能够泡沫燃烧中容易形成的碳化保护层一起保护泡沫内部免受火焰攻击。
上述液体有机阻燃剂为不含羟基，为磷酸酯和/或卤代磷酸酯类有机化合物，优选甲基磷酸二甲酯、三(2-氯丙基)磷酸酯、三(2-氯乙基)磷酸酯和乙基磷酸二乙酯中的至少一种。
上述泡沫表面活性剂为硅油，硅油为聚二甲基硅氧烷，硅油可以采用迈图高新材料集团生产的牌号为L6950的硅油或者江苏美思德化学股份有限公司生产的牌号为AK8803的硅油；
上述催化剂为叔胺类催化剂和有机金属盐类催化剂；所述的叔胺类催化剂包括五甲基二乙烯三胺、N,N-二甲基环己胺、三乙烯二胺、三乙胺、1,4-二甲基哌嗪、N,N-二甲基苄胺和双二甲胺基乙基醚中的至少一种，所述的有机金属盐类催化剂包括异辛酸钾、甲酸季铵盐、醋酸钾、二月桂酸二丁基锡、辛酸亚锡、二醋酸二丁基锡和油酸钾中的至少一种；
上述物理发泡剂为1,1-二氯-1-氟乙烷、1,1,1,3,3-五氟丙烷、1,1,1,3,3-五氟丁烷和1,1,1,2-四氟丁烷中的至少一种；
上述异氰酸酯组分为多亚甲基多苯基多异氰酸酯。该多亚甲基多苯基多异氰酸酯优选万华化学集团股份有限公司生产的牌号为PM-200的多亚甲基多苯基多异氰酸酯。
上述无机微粒还可以只添加到异氰酸酯组分中，添加量不超过多元醇组分总质量的30％；所述无机微粒还可以同时添加到异氰酸酯组分中，添加到异氰酸酯组分中时添加量不超过多元醇组分总质量的30％。
上述双组份原料中还可以添加占有多元醇组分总质量0.1-2％的色浆，可以任意添加到异氰酸酯组分或者多元醇组分中。所述色浆可以采用宝美施化工(上海)有限公司生产的牌号为126-3M1665、036-2M1941的色浆，或者采用广州市墨克化工有限公司生产的牌号为P89855、P89750、P89856色浆中的至少一种。
本发明为了增加聚氨酯浇注硬质泡沫塑料的阻燃性，从三方面入手：一方面减少硬泡中易燃-CH2-链段的含量，没有使用常规的二甘醇或者甘油或者乙二胺与蔗糖加环氧乙烷和/或环氧丙烷聚合而成的聚醚多元醇；另一方面使用含有磷溴阻燃元素的反应型阻燃剂与高苯环含量的聚酯多元醇；最后使用不燃物无机微粒，添加到异氰酸酯组分或者多元醇组分中，增加阻燃性能。通过这三方面，我们得到了可以满足国标GB8624-2012《建筑材料及制品燃烧性能分级》中对平板状建筑材料及制品的燃烧性能等级和分级判据中难燃材料B级要求。
本发明的一种阻燃聚氨酯浇注硬质泡沫塑料板材，其最终制品的形状取决于生产中使用模具的形状，可以使用不同的模具生产各种不同花纹、造型、尺寸的阻燃聚氨酯浇注硬质泡沫塑料制品。比如如果使用球型模具，可以得到球型的阻燃聚氨酯浇注硬质泡沫塑料制品。
本发明的制备上述阻燃聚氨酯浇注硬质泡沫塑料板材的生产方法为：使用聚氨酯浇注机或者电动搅拌设备或者气动搅拌设备把异氰酸酯组分和多元醇组分均匀混合后浇注到模具中，在模具中保温保压一段时间后取出得到硬泡制品。
本发明的有益效果是：
(1)本发明的阻燃聚氨酯浇注硬质泡沫塑料板材具有优异的阻燃性能：可以满足国标GB8624-2012《建筑材料及制品燃烧性能分级》平板状建筑材料及制品的燃烧性能等级和分级判据中难燃材料B级要求。
(2)本发明的阻燃聚氨酯浇注硬质泡沫塑料板材适用于对阻燃要求高的建筑墙体、屋面、地面保温等应用领域。
具体实施方式
下面结合实施例进一步说明本发明的实施方案，但是本发明不限于所列出的实施例，还应包括在本发明所要求的权利范围内其它任何公知的改变。
实施例1
异氰酸酯组分与多元醇组分质量比为140:100。
多元醇组分：
异氰酸酯组分选用多亚甲基多苯基多异氰酸酯PM-200(万华化学集团股份有限公司)90wt％，氢氧化铝微粒(320目)10wt％；
生产步骤：
(1)把4*1.2*0.6尺寸块泡模具涂好脱模剂；
(2)将多元醇组分预混合，机械搅拌5min以上；
(3)将步骤(2)所得物与异氰酸酯组分通过箱泡机(河北香河巨龙泡沫机械有限公司)充分混合，浇注140kg到模具中；
(4)合模，等待12小时，块泡充分熟化后取出；
(5)使用平切机把块泡切割成2-20cm厚度板材即可。
所制的板材颜色为均匀灰色，各种性能如下：
达到国标GB8624-2012《建筑材料及制品燃烧性能分级》平板状建筑材料及制品的燃烧性能等级和分级判据中难燃材料B级要求。
实施例2
异氰酸酯组分与多元醇组分质量比为160:100；
多元醇组分：
异氰酸酯组分：多亚甲基多苯基多异氰酸酯PM-200(万华化学集团股份有限公司)82wt％，氢氧化镁微粒(200目)18wt％；
生产步骤：
(1)把1.2*0.6*0.03m尺寸板材模具使用循环水加热到45℃，并且涂好脱模剂；
(2)将多元醇组分预混合，机械搅拌0.5min以上；
(3)将步骤(2)所得物与异氰酸酯组分通过电动、气动搅拌手工搅拌充分混合，浇注1270g到模具中；
(4)立即合上板材模具，等待20min板材充分熟化后取出。
达到国标GB8624-2012《建筑材料及制品燃烧性能分级》平板状建筑材料及制品的燃烧性能等级和分级判据中难燃材料B级要求。
实施例3
异氰酸酯组分与多元醇组分质量比为160:100；
多元醇组分：
异氰酸酯组分：多亚甲基多苯基多异氰酸酯PM-200(万华化学集团股份有限公司)；
生产步骤：
(1)把聚氨酯板材连续生产线压机加热到55℃；
(2)然后把上下两面卷材预热、并引到压机内部；
(3)将多元醇组分预混合，机械搅拌10min以上；
(4)开动压机；
(5)将步骤(3)所得物与异氰酸酯组分通过低压浇注机(镇江奥力聚氨酯机械有限公司)混合，均匀浇注到下卷材面上；
(6)调整压机走速，保持在4-6m/min，连续生产。
所制的板材颜色为均匀淡黄色，各种物理性能如下：
实施例4
异氰酸酯组分与多元醇组分质量比为140:100。
多元醇组分：
异氰酸酯组分选用多亚甲基多苯基多异氰酸酯PM-200(万华化学集团股份有限公司)80wt％，氢氧化铝微粒(320目)20wt％；
生产步骤：
(1)把4*1.2*0.6尺寸块泡模具涂好脱模剂；
(2)将多元醇组分预混合，机械搅拌5min以上；
(3)将步骤(2)所得物与异氰酸酯组分通过箱泡机(河北香河巨龙泡沫机械有限公司)充分混合，浇注140kg到模具中；
(4)合模，等待12小时，块泡充分熟化后取出；
(5)使用平切机把块泡切割成2-20cm厚度板材即可。
所制的板材颜色为均匀灰色，各种性能如下：
达到国标GB8624-2012《建筑材料及制品燃烧性能分级》平板状建筑材料及制品的燃烧性能等级和分级判据中难燃材料B级要求。
实施例5
异氰酸酯组分与多元醇组分质量比为160:100；
多元醇组分：
异氰酸酯组分：多亚甲基多苯基多异氰酸酯PM-200(万华化学集团股份有限公司)70wt％，氢氧化镁微粒(200目)30wt％；
生产步骤：
(1)把1.2*0.6*0.03m尺寸板材模具使用循环水加热到45℃，并且涂好脱模剂；
(2)将多元醇组分预混合，机械搅拌0.5min以上；
(3)将步骤(2)所得物与异氰酸酯组分通过电动、气动搅拌手工搅拌充分混合，浇注1270g到模具中；
(4)立即合上板材模具，等待20min板材充分熟化后取出。
所制的板材颜色为均匀灰色，各种性能如下：
达到国标GB8624-2012《建筑材料及制品燃烧性能分级》平板状建筑材料及制品的燃烧性能等级和分级判据中难燃材料B级要求。
以上实施例的产品具有较高的抗压强度和优异的阻燃性能，阻燃水平达到GB/T8624-2012中B级阻燃要求。此板材可以方便地用于建筑物外墙、屋顶、地面等保温领域的硬质聚氨酯泡沫领域。
Claims (10)
1.一种阻燃聚氨酯浇注硬质泡沫塑料板材，由异氰酸酯组分与多元醇组分聚合而成，其特征在于：
所述异氰酸酯组分与多元醇组分质量比为(140-200):100；
所述多元醇组分包括聚酯多元醇、带羟基的反应型阻燃剂、无机微粒和助剂，这些原料占多元醇组分总质量的百分比为：聚酯多元醇5-40％，带羟基的反应型阻燃剂10-40％，无机微粒10-30％，助剂22-52％。
2.根据权利要求1所述的阻燃聚氨酯浇注硬质泡沫塑料板材，其特征在于：
所述聚酯多元醇是由苯酐、苯二甲酸中的至少一种和乙二醇、丙二醇、丁二醇、戊二醇、己二醇、一缩二乙二醇、一缩二丙二醇、丙三醇、己三醇、三羟甲基丙烷、六羟甲基三聚氰胺中的至少一种缩聚得到的聚酯多元醇。
3.根据权利要求1或2所述的阻燃聚氨酯浇注硬质泡沫塑料板材，其特征在于：
所述助剂包括物理发泡剂、泡沫表面活性剂、催化剂、液体有机阻燃剂和水，助剂中各组分的质量用量占多元醇组分总质量的百分比为：
4.根据权利要求3所述的阻燃聚氨酯浇注硬质泡沫塑料板材，其特征在于：所述带羟基的反应型阻燃剂含有含有卤元素、磷元素、氮元素中的至少一种元素；所述反应型阻燃剂为曼尼烯多元醇或者含氮/磷/卤素聚醚多元醇或者四溴苯酐二醇的任一种；
曼尼烯多元醇为酚类、甲醛、二乙醇胺和环氧丙烷聚合而成的多元醇；所述的酚类为苯酚、对苯二酚、丙基酚、丁基酚、戊基酚、庚基酚、辛基酚、壬基酚和癸基酚中的至少一种；
含氮/磷/卤素聚醚多元醇是以含氮/磷/卤素羟基化合物加环氧乙烷和/或环氧丙烷和/或环氧氯丙烷聚合而成的分子中含有氮/磷/卤素的聚醚多元醇；
四溴苯酐二醇为四溴邻苯二甲酸或四溴苯酐与乙二醇、丙二醇、丁二醇、戊二醇、己二醇、一缩二乙二醇、一缩二丙二醇中的至少一种缩聚得到的聚酯多元醇。
5.根据权利要求4所述的阻燃聚氨酯浇注硬质泡沫塑料板材，其特征在于：所述无机微粒包括氢氧化铝、氢氧化镁、碳酸钙、三氧化二锑、硼酸锌微粒中的至少一种。
6.根据权利要求5所述的阻燃聚氨酯浇注硬质泡沫塑料板材，其特征在于：
所述液体有机阻燃剂不含羟基，为磷酸酯和/或卤代磷酸酯类有机化合物；
所述泡沫表面活性剂为硅油，硅油为聚二甲基硅氧烷；
所述催化剂为叔胺类催化剂和有机金属盐类催化剂；所述的叔胺类催化剂包括五甲基二乙烯三胺、N,N-二甲基环己胺、三乙烯二胺、三乙胺、1,4-二甲基哌嗪、N,N-二甲基苄胺和双二甲胺基乙基醚中的至少一种，所述的有机金属盐类催化剂包括异辛酸钾、甲酸季铵盐、醋酸钾、二月桂酸二丁基锡、辛酸亚锡、二醋酸二丁基锡和油酸钾中的至少一种；
所述物理发泡剂为1,1-二氯-1-氟乙烷、1,1,1,3,3-五氟丙烷、1,1,1,3,3-五氟丁烷和1,1,1,2-四氟丁烷中的至少一种；
所述异氰酸酯组分为多亚甲基多苯基多异氰酸酯。
7.根据权利要求6所述的阻燃聚氨酯浇注硬质泡沫塑料板材，其特征在于：所述无机微粒还可以同时添加到异氰酸酯组分中，添加量不超过多元醇组分总质量的30％。
8.根据权利要求7所述的阻燃聚氨酯浇注硬质泡沫塑料板材，其特征在于：所述多元醇组分或者异氰酸酯组分中还包括占多元醇组分总质量0.1-2％的色浆。
9.一种阻燃聚氨酯浇注硬质泡沫塑料板材，由异氰酸酯组分与多元醇组分聚合而成，其特征在于：
所述异氰酸酯组分与多元醇组分质量比为(140-200):100；
所述多元醇组分包括聚酯多元醇、带羟基的反应型阻燃剂、助剂，这些原料占多元醇组分总质量的百分比为：聚酯多元醇6-57％，带羟基的反应型阻燃剂12-57％，助剂22-52％；
所述异氰酸酯组分包括多亚甲基多苯基多异氰酸酯以及无机微粒，占异氰酸酯组分总重量的百分比为，多亚甲基多苯基多异氰酸酯70-90％，无机微粒10-30％。
10.根据权利要求9所述的阻燃聚氨酯喷涂硬质泡沫塑料，其特征在于：所述带羟基的反应型阻燃剂为曼尼烯多元醇或者含氮/磷/卤素聚醚多元醇或者四溴苯酐二醇中的至少一种。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410347900.3A CN104130368B (zh) | 2014-07-21 | 2014-07-21 | 一种阻燃聚氨酯浇注硬质泡沫塑料板材 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410347900.3A CN104130368B (zh) | 2014-07-21 | 2014-07-21 | 一种阻燃聚氨酯浇注硬质泡沫塑料板材 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104130368A true CN104130368A (zh) | 2014-11-05 |
| CN104130368B CN104130368B (zh) | 2016-09-21 |
Family
ID=51803256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410347900.3A Active CN104130368B (zh) | 2014-07-21 | 2014-07-21 | 一种阻燃聚氨酯浇注硬质泡沫塑料板材 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104130368B (zh) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105696715A (zh) * | 2016-01-30 | 2016-06-22 | 万华节能科技集团股份有限公司 | 一种后置式结构防火保温板及其间歇生产工艺 |
| CN105713165A (zh) * | 2014-12-03 | 2016-06-29 | 南京理工大学常熟研究院有限公司 | 一种用于门窗型材的聚氨酯泡沫隔热材料及其生产工艺 |
| CN106633011A (zh) * | 2016-12-30 | 2017-05-10 | 山东诺威聚氨酯股份有限公司 | 反应型阻燃聚酯多元醇及其制备方法 |
| WO2018023986A1 (zh) * | 2016-08-01 | 2018-02-08 | 常州聚博节能科技有限公司 | 水发泡无机杂化三聚氰胺聚氨酯硬泡材料及其制造方法 |
| CN108047411A (zh) * | 2017-12-21 | 2018-05-18 | 中昊北方涂料工业研究设计院有限公司 | 一种耐温阻燃易降解树脂及其制备方法 |
| CN110524985A (zh) * | 2019-08-06 | 2019-12-03 | 衢州艾科科技有限公司 | 一种三纤维复合增强的环氧地面材料及其制备方法 |
| CN114250947A (zh) * | 2022-01-11 | 2022-03-29 | 万华节能科技(烟台)有限公司 | 高抗压高阻燃喷涂聚氨酯硬泡冷库地坪及其施工工艺 |
| CN115073695A (zh) * | 2022-07-14 | 2022-09-20 | 上海玓墨节能科技有限公司 | 一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1510543A2 (de) * | 2003-08-14 | 2005-03-02 | Basf Ag | Flammgeschützter Polyurethanhartschaumstoff, enthaltend siliconfreie Schaumstabilisatoren |
| CN102585148A (zh) * | 2011-12-28 | 2012-07-18 | 烟台万华聚氨酯股份有限公司 | 制备高阻燃性聚异氰脲酸酯泡沫用组合料 |
| CN103073986A (zh) * | 2012-12-19 | 2013-05-01 | 烟台万华聚氨酯股份有限公司 | 一种高级阻燃聚氨酯喷涂泡沫材料及其制备方法 |
| CN103183806A (zh) * | 2013-04-17 | 2013-07-03 | 北京东方雨虹防水技术股份有限公司 | 一种高阻燃硬质聚氨酯泡沫材料及其制备方法 |
| CN103755915A (zh) * | 2013-12-24 | 2014-04-30 | 南京红宝丽股份有限公司 | 一种聚异氰脲酸酯阻燃泡沫体 |
| CN103923290A (zh) * | 2014-04-25 | 2014-07-16 | 万华节能科技集团股份有限公司 | 一种适用于低温环境的聚氨酯硬泡双组份原料及其施工方法 |
-
2014
- 2014-07-21 CN CN201410347900.3A patent/CN104130368B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1510543A2 (de) * | 2003-08-14 | 2005-03-02 | Basf Ag | Flammgeschützter Polyurethanhartschaumstoff, enthaltend siliconfreie Schaumstabilisatoren |
| CN102585148A (zh) * | 2011-12-28 | 2012-07-18 | 烟台万华聚氨酯股份有限公司 | 制备高阻燃性聚异氰脲酸酯泡沫用组合料 |
| CN103073986A (zh) * | 2012-12-19 | 2013-05-01 | 烟台万华聚氨酯股份有限公司 | 一种高级阻燃聚氨酯喷涂泡沫材料及其制备方法 |
| CN103183806A (zh) * | 2013-04-17 | 2013-07-03 | 北京东方雨虹防水技术股份有限公司 | 一种高阻燃硬质聚氨酯泡沫材料及其制备方法 |
| CN103755915A (zh) * | 2013-12-24 | 2014-04-30 | 南京红宝丽股份有限公司 | 一种聚异氰脲酸酯阻燃泡沫体 |
| CN103923290A (zh) * | 2014-04-25 | 2014-07-16 | 万华节能科技集团股份有限公司 | 一种适用于低温环境的聚氨酯硬泡双组份原料及其施工方法 |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105713165A (zh) * | 2014-12-03 | 2016-06-29 | 南京理工大学常熟研究院有限公司 | 一种用于门窗型材的聚氨酯泡沫隔热材料及其生产工艺 |
| CN105696715A (zh) * | 2016-01-30 | 2016-06-22 | 万华节能科技集团股份有限公司 | 一种后置式结构防火保温板及其间歇生产工艺 |
| CN105696715B (zh) * | 2016-01-30 | 2018-04-10 | 万华节能科技集团股份有限公司 | 一种后置式结构防火保温板及其间歇生产工艺 |
| WO2018023986A1 (zh) * | 2016-08-01 | 2018-02-08 | 常州聚博节能科技有限公司 | 水发泡无机杂化三聚氰胺聚氨酯硬泡材料及其制造方法 |
| CN106633011A (zh) * | 2016-12-30 | 2017-05-10 | 山东诺威聚氨酯股份有限公司 | 反应型阻燃聚酯多元醇及其制备方法 |
| CN108047411A (zh) * | 2017-12-21 | 2018-05-18 | 中昊北方涂料工业研究设计院有限公司 | 一种耐温阻燃易降解树脂及其制备方法 |
| CN108047411B (zh) * | 2017-12-21 | 2020-08-25 | 中昊北方涂料工业研究设计院有限公司 | 一种耐温阻燃易降解树脂及其制备方法 |
| CN110524985A (zh) * | 2019-08-06 | 2019-12-03 | 衢州艾科科技有限公司 | 一种三纤维复合增强的环氧地面材料及其制备方法 |
| CN114250947A (zh) * | 2022-01-11 | 2022-03-29 | 万华节能科技(烟台)有限公司 | 高抗压高阻燃喷涂聚氨酯硬泡冷库地坪及其施工工艺 |
| CN115073695A (zh) * | 2022-07-14 | 2022-09-20 | 上海玓墨节能科技有限公司 | 一种用于集装箱模块化建筑保温的喷涂型环保聚氨酯泡沫 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104130368B (zh) | 2016-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104130368A (zh) | 一种阻燃聚氨酯浇注硬质泡沫塑料板材 | |
| CN102702955B (zh) | 一种建筑防水保温用喷涂型聚氨酯组合料及其使用方法 | |
| CN101735425B (zh) | 冷库用硬泡喷涂聚氨酯组合料的制备方法 | |
| CN105294989B (zh) | 生物基聚氨酯喷涂泡沫塑料及其制备方法 | |
| CN102030977B (zh) | 组合聚醚，聚氨酯原料组合物，聚氨酯泡沫及其用途 | |
| CN103865025B (zh) | 一种本质阻燃硬质聚氨酯泡沫塑料 | |
| CN104987484A (zh) | 一种无机材料杂化硬质三聚氰胺聚氨酯泡沫保温材料及其制备方法和用于其中的组合聚醚 | |
| CN104847026B (zh) | 玄武岩纤维布增强聚氨酯硬质泡沫复合保温板及其制备方法 | |
| CN104481103A (zh) | 一种硬泡聚氨酯防火保温装饰一体板及其生产方法 | |
| CN104628979A (zh) | 一种连续线生产用b1级阻燃聚氨酯硬质泡沫及制备方法和用途 | |
| CN102229697B (zh) | 一种太阳能聚氨酯保温材料 | |
| CN103073986A (zh) | 一种高级阻燃聚氨酯喷涂泡沫材料及其制备方法 | |
| CN102558479A (zh) | 聚异氰脲酸酯泡沫用组合聚醚及使用方法 | |
| CN101735553A (zh) | 一种制造改性酚醛防火保温板的材料 | |
| CN101487299A (zh) | 一种多功能硬泡聚氨酯复合保温板的制作方法 | |
| CN101508763A (zh) | 喷涂聚氨酯硬质泡沫原料以及由其制得的泡沫 | |
| CN100341929C (zh) | 一种常温发泡制备酚醛泡沫保温材料的方法 | |
| CN104119498B (zh) | 一种阻燃聚氨酯喷涂硬质泡沫塑料 | |
| CN104513454A (zh) | 一种阻燃耐高温板材及其生产方法 | |
| CN104448188A (zh) | 组合聚醚、含其组合物、聚氨酯块泡及其制备方法和应用 | |
| CN103923290A (zh) | 一种适用于低温环境的聚氨酯硬泡双组份原料及其施工方法 | |
| CN106117490A (zh) | 一种建筑物聚氨酯泡沫材料 | |
| CN106832204B (zh) | 一种改性聚氨酯屋面保温材料及其制备方法 | |
| CN102153723A (zh) | 喷涂型聚氨酯组合料 | |
| CN104961878A (zh) | 连续法生产聚异氰脲酸酯保温板用组合聚醚及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Flame-retardant polyurethane cast rigid foamed plastic sheet Effective date of registration: 20190104 Granted publication date: 20160921 Pledgee: Bank of Qingdao Co. Yantai branch Pledgor: Wanhua Energy-Saving Technology Group Co.,Ltd. Registration number: 2019370010003 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20200720 Granted publication date: 20160921 Pledgee: Bank of Qingdao Co. Yantai branch Pledgor: WANHUA ENERGY-SAVING TECHNOLOGY GROUP Co.,Ltd. Registration number: 2019370010003 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20141105 Assignee: Yantai Yida Financial Leasing Co.,Ltd. Assignor: WANHUA ENERGY-SAVING TECHNOLOGY GROUP Co.,Ltd. Contract record no.: X2020980009192 Denomination of invention: A rigid polyurethane foam board with flame retardant polyurethane Granted publication date: 20160921 License type: Exclusive License Record date: 20201214 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A rigid polyurethane foam board with flame retardant polyurethane Effective date of registration: 20201218 Granted publication date: 20160921 Pledgee: Yantai Yida Financial Leasing Co.,Ltd. Pledgor: WANHUA ENERGY-SAVING TECHNOLOGY GROUP Co.,Ltd. Registration number: Y2020980009564 |
|
| EC01 | Cancellation of recordation of patent licensing contract | ||
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Yantai Yida Financial Leasing Co.,Ltd. Assignor: WANHUA ENERGY-SAVING TECHNOLOGY GROUP Co.,Ltd. Contract record no.: X2020980009192 Date of cancellation: 20230907 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20230907 Granted publication date: 20160921 Pledgee: Yantai Yida Financial Leasing Co.,Ltd. Pledgor: WANHUA ENERGY-SAVING TECHNOLOGY GROUP Co.,Ltd. Registration number: Y2020980009564 |