CN106543426A - 一种含硅阻燃型松香基多元醇及其制备方法和应用 - Google Patents
一种含硅阻燃型松香基多元醇及其制备方法和应用 Download PDFInfo
- Publication number
- CN106543426A CN106543426A CN201610956966.1A CN201610956966A CN106543426A CN 106543426 A CN106543426 A CN 106543426A CN 201610956966 A CN201610956966 A CN 201610956966A CN 106543426 A CN106543426 A CN 106543426A
- Authority
- CN
- China
- Prior art keywords
- rosin
- flame retardant
- retardant type
- based polyol
- parts
- 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
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 106
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 106
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000003063 flame retardant Substances 0.000 title claims abstract description 97
- 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 77
- 150000003077 polyols Chemical class 0.000 title claims abstract description 54
- 229920005862 polyol Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 25
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 25
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000019253 formic acid Nutrition 0.000 claims abstract description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 10
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 10
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 8
- 239000001294 propane Substances 0.000 claims abstract description 7
- -1 hydride group Chemical group 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000012948 isocyanate Substances 0.000 claims description 18
- 150000005846 sugar alcohols Polymers 0.000 claims description 17
- 150000002513 isocyanates Chemical class 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000006260 foam Substances 0.000 claims description 14
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 239000004814 polyurethane Substances 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000004088 foaming agent Substances 0.000 claims description 7
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 claims description 3
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- XADCESSVHJOZHK-UHFFFAOYSA-N Meperidine Chemical compound C=1C=CC=CC=1C1(C(=O)OCC)CCN(C)CC1 XADCESSVHJOZHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 239000012974 tin catalyst Chemical group 0.000 claims description 3
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-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
- 239000002253 acid 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
- 239000004872 foam stabilizing agent Substances 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims 1
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 claims 1
- 101710130081 Aspergillopepsin-1 Proteins 0.000 claims 1
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 229940102253 isopropanolamine Drugs 0.000 claims 1
- 150000002924 oxiranes Chemical group 0.000 claims 1
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 9
- 239000004593 Epoxy Substances 0.000 abstract description 7
- 229920001296 polysiloxane Polymers 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000077 silane Inorganic materials 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 3
- 239000000779 smoke Substances 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 7
- 238000005292 vacuum distillation Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 5
- 235000011613 Pinus brutia Nutrition 0.000 description 5
- 241000018646 Pinus brutia Species 0.000 description 5
- 229920005610 lignin Polymers 0.000 description 5
- 239000002304 perfume Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006049 ring expansion reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- 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
- C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
-
- 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
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- 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
- C08J2203/10—Water or water-releasing 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
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
一种含硅阻燃型松香基多元醇及其制备方法和应用,含硅阻燃型松香基多元醇由松香经双氧水、甲酸环氧化制备环氧化松香,再与含有活泼氢的硅烷阻燃剂3‑氨基丙基三乙氧基硅烷反应制得阻燃型松香衍生物单体,然后通入环氧乙烷或丙烷进行开环聚合反应制备含硅阻燃型松香基多元醇。利用环氧开环反应把阻燃硅烷基团引入到松香结构中,合成了含硅阻燃型松香基多元醇,降低了阻燃成本,其多元醇结构中含有可调控的酯键和醚键,和市售聚酯、聚醚多元醇混溶性较好;且反应活性较高,硅含量高达5.5 %;用其制备的阻燃型聚氨酯泡沫,氧指数可达到22~26%,具有燃烧时制品不滴液,保持形状,烟密度小等优点。
Description
技术领域
本发明属于阻燃型高分子材料技术领域,主要涉及含硅阻燃型松香基多元醇及其合成方法及其在阻燃型硬质聚氨酯泡沫中的应用。
背景技术
聚氨酯泡沫保温材料是目前国际上性能最好的保温材料。硬质聚氨酯泡沫具有质量轻、导热系数低、耐热性好、容易与其它基材粘结、燃烧不产生熔滴等优异性能。未经阻燃处理的聚氨酯泡沫材料是可燃物,燃烧时产生大量有毒烟雾,不仅给灭火带来困难,还会影响到人们的身体健康和生命安全。因此对于硬质聚氨酯泡沫的耐热性、阻燃型、无毒性的要求越来越高。各国家和地区出台了大量的法规,特别是欧洲国家,规定聚氨酯泡沫材料的阻燃性能必须达到一定的标准才能生产,各种法规的出现大大推进了聚氨酯阻燃技术的发展。随着石油化石原料的大量消耗,伴随着环境的日益恶化,生物质资源的开发利用越来越受到研究人员的关注。
有关生物质基阻燃型聚氨酯泡沫塑料的专利特别是含硅阻燃型聚氨酯泡沫塑料不多,主要为以生物质制备多元醇,然后在配方中加入阻燃剂制备阻燃型聚氨酯泡沫塑料CN1543478A中公开了利用木质素制备聚氨酯的方法,该方法包括使以溶解状态含有木质素磺酸或其部分中和盐的多醇溶液与多异氰酸酯发生缩聚反应,由于木质素成分不能在聚氨酯中起到大分子多官能度交联核的作用,造成木质素成分与聚氨酯的结合性能较差,且制备的聚氨酯的阻燃性能一般。CN 102585143 A公开了一种生物质基阻燃聚氨酯泡沫及其制备方法,包括利用木质素改性物和其他原料一起制备阻燃型聚氨酯泡沫塑料,合成工艺较复杂。
有机硅氧烷具有良好的热稳定性和阻燃性能,它使材料的防火性能集中于聚合物表面并保留材料的本体性能。由于含硅氧烷阻燃剂的聚合物在燃烧过程中形成硅和炭质保护层,这个硅炭层阻碍并限制聚合物和火焰之间的物质转移和热传递,减缓了聚合物燃烧释放生成气体的速度。3-氨基丙基三乙氧基硅烷阻燃剂常温下是液态,流动性好,利用方便,结构中含有活性氢与多元醇相容性较好,且具有较高的热稳定性,阻燃性能持久。不仅可以应用在聚氨酯泡沫保温材料中,还可用于线性聚酯、聚酰胺、环氧树脂、聚氨酯等多种高分子材料阻燃处理。国外已广泛用于电子设备用塑料、铜衬里压层、电路板等材料的阻燃。
本专利公开的一种含硅阻燃型松香基多元醇,和市售聚酯、聚醚多元醇及发泡剂环戊烷混溶性较好、不分层。
发明内容
解决的技术问题:为了提高聚氨酯泡沫的阻燃性和阻燃持久性,本发明提供了一种含硅阻燃型松香基多元醇及其制备方法和应用,利用环氧开环反应将含硅阻燃剂3-氨基丙基三乙氧基硅烷引入到松香结构中,减少了添加阻燃剂的成本;制备的阻燃型聚氨酯泡沫氧指数可达到22~26%,燃烧时具有不滴液,保持形状,烟密度小等优点;其多元醇结构中含有可调控的酯键和醚键,和市售聚酯、聚醚多元醇、环戊烷发泡剂混溶性较好,不分层;且反应活性较高。
技术方案:一种制备含硅阻燃型松香基多元醇的方法及产物应用,由松香、双氧水、甲酸、3-氨基丙基三乙氧基硅烷、环氧乙烷或环氧丙烷反应得到,其结构式如下:
制备所述的用于阻燃型硬质聚氨酯泡沫的含硅阻燃松香基多元醇的方法,利用环氧开环反应将3-氨基丙基三乙氧基硅烷阻燃基团引入到松香结构中所得到,反应方程式为:
含硅阻燃型松香基多元醇的制备步骤为:以松香、双氧水和甲酸为原料,通过环氧化反应得到环氧化松香,反应温度为60-90℃,反应时间为3-6h;然后环氧化松香再与3-氨基丙基三乙氧基硅烷,以甲苯作溶剂进行开环得到阻燃型松香衍生物单体,反应温度为60-110℃,反应时间为4-8h;最后除去溶剂,在耐压釜中通入环氧乙烷或丙烷进行开环聚合得到阻燃型松香基多元醇。
含硅阻燃型松香基多元醇在阻燃型硬质聚氨酯泡沫中的应用,先把阻燃型松香基多元醇和市售聚酯、聚醚多元醇混合配制成组合多元醇,再与助剂快速搅拌混合均匀,然后与异氰酸酯混合高速搅拌10~20s,发泡时,按NCO/OH的摩尔比为1.2~2.5的比例配制,倒入模具中,熟化48h;各原料以质量份计为:组合多元醇100份,异氰酸酯100~250份,泡沫稳定剂1~2份,催化剂1~2份,水1~2份,发泡剂10~30份;其制备配方、性能测定结果见附表。
(1)含硅阻燃型松香基多元醇50-100份;
(2)市售聚酯、聚醚多元醇0-50份(羟值250~450mgKOH/g),优选苯酐聚酯多元醇PS-3152和聚醚多元醇4110;
(3)催化剂0.1-0.6份,可以是胺类催化剂或胺类催化剂和锡类催化剂的混合物。其中,胺类催化剂选自:N,N,-二甲基环己胺、三亚乙基二胺、二甲基苄胺、三乙醇胺、异丙醇胺、季胺盐或类似的催化剂,可以是上述物质之一,也可以两种以上以任意比例的混合物。锡类催化剂选自:二月桂酸二正丁基锡及类似的催化剂。
(4)泡沫稳定剂0.5-5份,主要是硅-氧或硅-炭型表面活性剂,德美世创公司产泡沫稳定剂AK8805、AK8815、AK8812、AK8809等;德国德国萨公司:B8460、B8481、B8474、B8471、B8476、B8481等。泡沫稳定剂可以是上述之一也可以是两种或两种以上任意比例混合使用。(5)发泡剂10-30份:HCFC-141b、环戊烷、异戊烷、HFC-245fa、HFC-365mfc、等任选一种或多种以任意比例的混合物;水0.01-5份。
有益效果:1、含硅阻燃型松香基多元醇利用环氧开环反应将3-氨基丙基三乙氧基硅烷的阻燃基团引入到松香结构中,合成的含硅阻燃型松香基多元醇;同时含有酯键和醚键,刚性三元菲环和柔性长链,因此和市售聚酯、醚多元醇具有较好的相容性,提高了组合料的储存稳定性。
2、含硅阻燃型松香基多元醇应用到阻燃型硬质聚氨酯泡沫中,由于分子结构中含有硅烷阻燃基团,提高了泡沫的热稳定性和阻燃性能。
3、把硅烷阻燃基团通过环氧开环反应引入到松香基多元醇结构中,降低了添加阻燃剂成本,本发明的含硅阻燃型松香基多元醇,因阻燃硅烷基团存在于多元醇的分子结构中,具有抗迁移性能,制备的阻燃型聚氨酯泡沫具有较高的阻燃性和阻燃的持久性;氧指数可达到22~26%。
附图说明
图1为含硅阻燃型松香基多元醇的红外光谱图
从图1中可知:3460m-1处为-OH的振动吸收峰;2962cm-1、2858cm-1处分别是甲基、亚甲基的伸缩振动吸收峰;1744cm-1是松香结构中的酯C=O伸缩振动吸收峰;1457cm-1、1374cm-1、为松香环异丙基上谐二甲基的特征吸收峰;1260cm-1为酯键C-O伸展或OH变形振动;1096cm-1和1027cm-1为硅氧烷峰分裂成两个强度几乎相等的峰;同时,1090cm-1左右为多元醇中C-O-C的强伸缩振动峰,说明经过环氧乙烷开环聚合后松香基多元醇结构的制备。
具体实施方式
下面以具体实施例作进一步说明:本发明中所有原料皆为市售,以下实施例中若无特别指明,皆为质量份。
本发明对松香进行一系列的改性得到含硅阻燃型松香基多元醇。所制得含硅阻燃型松香基多元醇与市售多元醇、异氰酸酯以及其它助剂,通过一步发泡法制得阻燃型硬质聚氨酯泡沫;主要方案包括以下两方面的内容:
一、制备上述含硅阻燃型松香基多元醇的方法
通过分子设计,利用环氧开环反应将3-氨基丙基三乙氧基硅烷的阻燃基团引入到松香结构中,合成的含硅阻燃型松香基多元醇含有可调控的酯键、醚键和多个活性羟基,反应方程式为:
具体的制法为:以质量份计,取100份的松香加入装有恒压漏斗和温度计的250ml三口烧瓶中,升温至60~90℃,在1小时之内逐滴加入45份双氧水和90份甲酸的混合物,滴加完毕之后反应3~6小时,然后用wt.5%的NaHCO3溶液和水洗涤至中性,减压蒸馏1h,即可得到环氧化松香。取60份环氧化松香于250ml三口烧瓶中,加入100ml甲苯作溶剂,然后用恒压滴液漏斗在1h之内滴加80质量份的3-氨基丙基三乙氧基硅烷,升温到60~110℃,反应4~8h可得到阻燃型松香衍生物单体;在耐压釜中加入60份阻燃型松香衍生物单体,然后通入环氧乙烷或丙烷进行开环聚合得到含硅阻燃型松香基多元醇。
二、松香基阻燃型硬质聚氨酯泡沫的组成与制备:
1、组合多元醇的组成,按质量份计:
(1)50-100份的含硅阻燃型松香基多元醇,0-50份的市售聚酯多元醇PS-3152或聚醚多元醇4110。
(2)胺类催化剂1份,如N,N-二甲基环己胺及类似的催化剂。
(3)水1~2份。
(4)泡沫稳定剂1~2份,主要是硅型泡沫稳定剂,德美世创公司生产的泡沫稳定剂AK8805、AK8815、AK8812、AK8809等;德国萨公司:B8464、B8481、B8474、B8471、B8481等。泡沫稳定剂可以是上述之一,也可以是两种或两种以上的任意复配。
(5)发泡剂10~30份:HCFC-141b、环戊烷、异戊烷、HFC-245fa、HFC-365mfc等任选一种或多种以任意比例的混合物。
2、松香基阻燃型硬质聚氨酯泡沫的配方与制备:
松香基阻燃型硬质聚氨酯泡沫的制备配方、性能测试结果见附表1、2。以组合多元醇和异氰酸酯为主要原料,发泡时,按NCO/OH的摩尔比为1.2~2.5的比例配制得到。具体操作如下:把组合多元醇和助剂快速搅拌混合均匀,然后再与异氰酸酯高速搅拌混合10~20s,转速2000~3000r/min,倒入模具中,熟化48h。
异氰酸酯的选择:甲苯二异氰酸酯、二甲苯二异氰酸酯、多次甲基多苯基多异氰酸酯(PAPI),优选PAPI,商品牌号为烟台万华聚氨酯股份有限公司的PM-200。
实施例1
取100份松香加入装有恒压漏斗的250ml三口烧瓶中,升温至80℃,在1小时之内逐滴加入45份双氧水和90份甲酸的混合物,滴加完毕之后反应5小时,然后用5wt.%的NaHCO3溶液和水洗涤至中性,减压蒸馏除水,得到环氧化松香。取60份环氧化松香于250ml三口烧瓶中,加入100ml甲苯作溶剂,然后在1h之内滴加80份的3-氨基丙基三乙氧基硅烷,升温到60℃,反应8h得到阻燃型松香衍生物单体。在耐压釜中加入60份阻燃型松香衍生物单体,然后通入22份环氧乙烷进行开环聚合得到阻燃型松香基多元醇。其性能指标如下:羟值为287mg/g KOH,水分0.04%,粘度13600mPa·s(25℃)。根据表1所示的配方,把含硅阻燃型松香基多元醇、市售多元醇与助剂快速搅拌混合均匀,再与异氰酸酯混合高速搅拌10~20s,转速2000~3000r/min,倒入模具中,熟化48h。
实施例2
取100份松香加入装有恒压漏斗的250ml三口烧瓶中,升温至90℃,在1小时之内逐滴加入45份双氧水和90份甲酸的混合物,滴加完毕之后反应3小时,然后用5wt.%的NaHCO3溶液和水洗涤至中性,减压蒸馏除水,得到环氧化松香。取60份环氧化松香于250ml三口烧瓶中,加入100ml甲苯作溶剂,然后在1h之内滴加75份的3-氨基丙基三乙氧基硅烷,升温到75℃,反应7h得到阻燃型松香衍生物单体。在耐压釜中加入60份阻燃型松香衍生物单体,然后通入45份环氧乙烷进行开环聚合得到阻燃型松香基多元醇。其性能指标如下:羟值为262mg/g KOH,水分0.06%,粘度8500mPa·s(25℃)。根据表1所示的配方,把含硅阻燃型松香基多元醇、市售多元醇与助剂快速搅拌混合均匀,再与异氰酸酯混合高速搅拌10~20s,转速2000~3000r/min,倒入模具中,熟化48h。
实施例3
取100份松香加入装有恒压漏斗的250ml三口烧瓶中,升温至70℃,在1小时之内逐滴加入50份双氧水和90份甲酸的混合物,滴加完毕之后反应5小时,然后用5wt.%的NaHCO3溶液和水洗涤至中性,减压蒸馏除水,得到环氧化松香。取60份环氧化松香于250ml三口烧瓶中,加入100ml甲苯作溶剂,然后在1h之内滴加80份的3-氨基丙基三乙氧基硅烷,升温到90℃,反应6h得到阻燃型松香衍生物单体。在耐压釜中加入60份阻燃型松香衍生物单体,然后通入56份环氧丙烷进行开环聚合得到阻燃型松香基多元醇。其性能指标如下:羟值为275mg/g KOH,水分0.04%,粘度11200mPa·s(25℃)。根据表1所示的配方,把含硅阻燃型松香基多元醇、市售多元醇与助剂快速搅拌混合均匀,再与异氰酸酯混合高速搅拌10~20s,转速2000~3000r/min,倒入模具中,熟化48h。
实施例4
取100份松香加入装有恒压漏斗的250ml三口烧瓶中,升温至65℃,在1小时之内逐滴加入50份双氧水和95份甲酸的混合物,滴加完毕之后反应6小时,然后用5wt.%的NaHCO3溶液和水洗涤至中性,减压蒸馏除水,得到环氧化松香。取60份环氧化松香于250ml三口烧瓶中,加入100ml甲苯作溶剂,然后在1h之内滴加85份的3-氨基丙基三乙氧基硅烷,升温到100℃,反应5h得到阻燃型松香衍生物单体。在耐压釜中加入60份阻燃型松香衍生物单体,然后通入76份环氧丙烷进行开环聚合得到阻燃型松香基多元醇。其性能指标如下:羟值为235mg/g KOH,水分0.05%,粘度9400mPa·s(25℃)。根据表1所示的配方,把含硅阻燃型松香基多元醇、市售多元醇与助剂快速搅拌混合均匀,再与异氰酸酯混合高速搅拌10~20s,转速2000~3000r/min,倒入模具中,熟化48h。
实施例5
取100份松香加入装有恒压漏斗的250ml三口烧瓶中,升温至60℃,在1小时之内逐滴加入55份双氧水和95份甲酸的混合物,滴加完毕之后反应6小时,然后用5wt.%的NaHCO3溶液和水洗涤至中性,减压蒸馏除水,得到环氧化松香。取60份环氧化松香于250ml三口烧瓶中,加入100ml甲苯作溶剂,然后在1h之内滴加80份的3-氨基丙基三乙氧基硅烷,升温到110℃,反应4h得到阻燃型松香衍生物单体。在耐压釜中加入60份阻燃型松香衍生物单体,然后通入65份环氧乙烷进行开环聚合得到阻燃型松香基多元醇。其性能指标如下:羟值为227mg/g KOH,水分0.06%,粘度6600mPa·s(25℃)。根据表1所示的配方,把含硅阻燃型松香基多元醇、市售多元醇与助剂快速搅拌混合均匀,再与异氰酸酯混合高速搅拌10~20s,转速2000~3000r/min,倒入模具中,熟化48h。
实施例6
取100份松香加入装有恒压漏斗的250ml三口烧瓶中,升温至75℃,在1小时之内逐滴加入50份双氧水和90份甲酸的混合物,滴加完毕之后反应4.5小时,然后用5wt.%的NaHCO3溶液和水洗涤至中性,减压蒸馏除水,得到环氧化松香。取60份环氧化松香于250ml三口烧瓶中,加入100ml甲苯作溶剂,然后在1h之内滴加85份的3-氨基丙基三乙氧基硅烷,升温到95℃,反应5.5h得到阻燃型松香衍生物单体。在耐压釜中加入60份阻燃型松香衍生物单体,然后通入75份环氧乙烷进行开环聚合得到阻燃型松香基多元醇。其性能指标如下:羟值为212mg/g KOH,水分0.05%,粘度5800mPa·s(25℃)。根据表1所示的配方,把含硅阻燃型松香基多元醇、市售多元醇与助剂快速搅拌混合均匀,再与异氰酸酯混合高速搅拌10~20s,转速2000~3000r/min,倒入模具中,熟化48h。
表1 含硅阻燃型松香基硬质聚氨酯泡沫的配方(质量份)
表2 含硅阻燃型松香基硬质聚氨酯泡沫的产品性能(测试方法参照国家标准)
各项分析测试结果表明:利用环氧开环反应把阻燃硅氧烷基团引入到松香结构中,合成了阻燃型松香基多元醇,降低了阻燃的成本,其多元醇结构中含有可调控的酯键和醚键,和市售聚酯、聚醚多元醇混溶性较好;且反应活性较高,硅含量高达5.5%;用其制备的阻燃型聚氨酯泡沫,氧指数可达到22~26%,具有燃烧时制品不滴液,保持形状,烟密度小等优点,在建筑保温、管道运输等一些特殊的场合具有广泛的应用前景。
Claims (9)
1.一种含硅阻燃型松香基多元醇的制备方法,其特征在于由松香经环氧化反应之后再与3-氨基丙基三乙氧基硅烷开环得到阻燃松香衍生物单体、最后和环氧乙烷或丙烷开环聚合反应制得含硅阻燃型松香基多元醇,并作为多元醇组分在阻燃型聚氨酯泡沫塑料中的应用。
2.根据权利要求1所述的制备方法,其特征在于所述含硅阻燃松香衍生物单体结构式如下:
3.根据权利要求1所述的制备方法,其特征在于所述含硅阻燃型松香基多元醇结构式如下所示:
4.根据权利要求1所述的制备方法,其特征在于:将松香、双氧水和甲酸通过环氧化反应得到环氧化松香,其中松香、双氧水和甲酸得摩尔比为1:2:2,所述环氧化反应的反应温度为60-90℃,反应时间为3-6h,再除去体系中的双氧水、水和酸;环氧化松香再与3-氨基丙基三乙氧基硅烷在甲苯作溶剂条件下开环反应,其中环氧化松香与3-氨基丙基三乙氧基硅烷的摩尔比为1:2,甲苯的使用量为环氧化松香与3-氨基丙基三乙氧基硅烷总质量的60-80%,反应温度为60-110℃,反应时间为4-8h,再除去溶剂得到阻燃型松香衍生物单体,然后进一步在耐压釜中按通入环氧乙烷或丙烷进行开环聚合制得,其中阻燃型松香衍生物单体上的活性羟基和环氧基团摩尔比为1:1~1:10。
5.权利要求1~4任一所述方法制备得到的含硅阻燃型松香基多元醇。
6.权利要求5所述含硅阻燃型松香基多元醇在硬质聚氨酯泡沫中的应用。
7.根据权利要求6所述的应用,其特征在于:先把含硅阻燃型松香基多元醇和聚酯多元醇或聚醚多元醇混合配制成组合多元醇,再与助剂搅拌混合均匀,所述助剂为泡沫稳定剂、催化剂、发泡剂和水,然后与异氰酸酯按NCO/OH的摩尔比为1.2~2.5的比例配制并搅拌10~20s,倒入模具中,熟化48h;各原料以质量份计为:(1)含硅阻燃型松香基多元醇50-100份;(2)羟值250~450mgKOH/g的聚酯多元醇或聚醚多元醇0-50份,优选苯酐聚酯多元醇PS-3152和聚醚多元醇4110;(3)催化剂0.1-0.6份,具体为胺类催化剂或胺类催化剂和锡类催化剂的混合物,其中,胺类催化剂选自:N,N,-二甲基环己胺、三亚乙基二胺、二甲基苄胺、三乙醇胺、异丙醇胺或季胺盐中的至少一种;锡类催化剂选自:二月桂酸二正丁基锡;(4)泡沫稳定剂0.5-5份,所述泡沫稳定剂为硅-氧或硅-炭型表面活性剂中的至少一种;(5)发泡剂10-30份,所述发泡剂为HCFC-141b、环戊烷、异戊烷、HFC-245fa、HFC-365mfc中的至少一种;(6)水0.01-5份;(7)异氰酸酯100~250份。
8.根据权利要求7所述的应用,其特征在于所述泡沫稳定剂为德美世创公司产泡沫稳定剂AK8805、AK8815、AK8812、AK8809;德国德国萨公司:B8460、B8481、B8474、B8471、B8476、B8481。
9.根据权利要求7所述的应用,其特征在于所述异氰酸酯为甲苯二异氰酸酯、二甲苯二异氰酸酯、多次甲基多苯基多异氰酸酯(PAPI),优选PAPI,商品牌号为烟台万华聚氨酯股份有限公司的PM-200。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610956966.1A CN106543426B (zh) | 2016-10-27 | 2016-10-27 | 一种含硅阻燃型松香基多元醇及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610956966.1A CN106543426B (zh) | 2016-10-27 | 2016-10-27 | 一种含硅阻燃型松香基多元醇及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106543426A true CN106543426A (zh) | 2017-03-29 |
CN106543426B CN106543426B (zh) | 2018-12-18 |
Family
ID=58393655
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610956966.1A Active CN106543426B (zh) | 2016-10-27 | 2016-10-27 | 一种含硅阻燃型松香基多元醇及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106543426B (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107312033A (zh) * | 2017-07-27 | 2017-11-03 | 中国林业科学研究院林业新技术研究所 | 一种阻燃型脂肪族曼尼希碱的制备方法 |
CN108774259A (zh) * | 2018-07-20 | 2018-11-09 | 中国林业科学研究院林产化学工业研究所 | 一种二苯基硅二醇改性桐油基多元醇及其制备方法和应用 |
CN108948067A (zh) * | 2018-06-26 | 2018-12-07 | 中国林业科学研究院林产化学工业研究所 | 一种含硅阻燃型桐油基多元醇及其制备方法和应用 |
CN109897384A (zh) * | 2019-03-01 | 2019-06-18 | 史雪芳 | 一种具有良好耐热老化性的硅胶烤垫 |
CN112341495A (zh) * | 2020-10-27 | 2021-02-09 | 中国林业科学研究院林产化学工业研究所 | 一种松香基硅磷协同阻燃剂、其制备方法及由其制备的氨酯泡沫 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101891883A (zh) * | 2010-06-25 | 2010-11-24 | 中国林业科学研究院林产化学工业研究所 | 用于阻燃型硬质聚氨酯泡沫塑料的松香聚酯多元醇及制备方法和应用 |
CN103709395A (zh) * | 2013-12-16 | 2014-04-09 | 中国林业科学研究院林产化学工业研究所 | 生物质基结构阻燃型多元醇及其制备方法和应用 |
CN105669936A (zh) * | 2016-03-29 | 2016-06-15 | 中国林业科学研究院林产化学工业研究所 | 一种含磷腰果酚基聚氨酯预聚体改性酚醛泡沫塑料及其制备方法 |
-
2016
- 2016-10-27 CN CN201610956966.1A patent/CN106543426B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101891883A (zh) * | 2010-06-25 | 2010-11-24 | 中国林业科学研究院林产化学工业研究所 | 用于阻燃型硬质聚氨酯泡沫塑料的松香聚酯多元醇及制备方法和应用 |
CN103709395A (zh) * | 2013-12-16 | 2014-04-09 | 中国林业科学研究院林产化学工业研究所 | 生物质基结构阻燃型多元醇及其制备方法和应用 |
CN105669936A (zh) * | 2016-03-29 | 2016-06-15 | 中国林业科学研究院林产化学工业研究所 | 一种含磷腰果酚基聚氨酯预聚体改性酚醛泡沫塑料及其制备方法 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107312033A (zh) * | 2017-07-27 | 2017-11-03 | 中国林业科学研究院林业新技术研究所 | 一种阻燃型脂肪族曼尼希碱的制备方法 |
CN108948067A (zh) * | 2018-06-26 | 2018-12-07 | 中国林业科学研究院林产化学工业研究所 | 一种含硅阻燃型桐油基多元醇及其制备方法和应用 |
CN108948067B (zh) * | 2018-06-26 | 2021-02-02 | 中国林业科学研究院林产化学工业研究所 | 一种含硅阻燃型桐油基多元醇及其制备方法和应用 |
CN108774259A (zh) * | 2018-07-20 | 2018-11-09 | 中国林业科学研究院林产化学工业研究所 | 一种二苯基硅二醇改性桐油基多元醇及其制备方法和应用 |
CN108774259B (zh) * | 2018-07-20 | 2020-10-30 | 中国林业科学研究院林产化学工业研究所 | 一种二苯基硅二醇改性桐油基多元醇及其制备方法和应用 |
CN109897384A (zh) * | 2019-03-01 | 2019-06-18 | 史雪芳 | 一种具有良好耐热老化性的硅胶烤垫 |
CN112341495A (zh) * | 2020-10-27 | 2021-02-09 | 中国林业科学研究院林产化学工业研究所 | 一种松香基硅磷协同阻燃剂、其制备方法及由其制备的氨酯泡沫 |
Also Published As
Publication number | Publication date |
---|---|
CN106543426B (zh) | 2018-12-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106543426A (zh) | 一种含硅阻燃型松香基多元醇及其制备方法和应用 | |
CA2762377C (en) | Silicone stabilizers for rigid polyurethane or polyisocyanurate foams | |
ES2635839T3 (es) | Procedimiento para preparar espumas de poliuretano que tienen emisiones reducidas de COV | |
CA2762568C (en) | Silicone stabilizers for rigid polyurethane or polyisocyanurate foams | |
Yang et al. | A novel polyurethane prepolymer as toughening agent: Preparation, characterization, and its influence on mechanical and flame retardant properties of phenolic foam | |
Atta et al. | Porous polyurethane foams based on recycled poly (ethylene terephthalate) for oil sorption | |
CN113166367B (zh) | 硬质聚氨酯泡沫配制物以及由其制备的泡沫 | |
US4713399A (en) | Flexible polyurethane foams prepared from poly(alkylene carbonate) polyols | |
CN105884992A (zh) | 一种阻燃聚氨酯硬质泡沫塑料及其制备方法和应用 | |
CN103391954B (zh) | 耐高温泡沫材料 | |
CA2493102C (en) | Process for preparing closed-cell water-blown rigid polyurethane foams having improved mechanical properties | |
CN107892739B (zh) | 一种阻燃硬质聚氨酯泡沫塑料及其制备方法 | |
CN106167540A (zh) | 连续式生产聚氨酯板材用高阻燃组合聚醚及其制备方法 | |
CN106397475A (zh) | 一种植物油基多元醇及其制备方法和应用 | |
WO1984000373A1 (en) | Modified polyisocyanurate foam and method of preparation | |
CN114395108B (zh) | 一种阻燃生物基聚氨酯泡沫及其制备方法 | |
CN1400229A (zh) | 一种聚氨酯泡沫材料及其制备方法 | |
CN106928442A (zh) | 阻燃多元醇制法及其制备的聚氨酯泡沫和聚氨酯泡沫制法 | |
US20110023989A1 (en) | Syntactic polyurethanes and their utilization for off-shore insulation | |
CN101353408B (zh) | 一种聚氨酯酰亚胺泡沫材料及其制备方法 | |
JP4881139B2 (ja) | 硬質ポリウレタンフォーム用ポリオール組成物及び硬質ポリウレタンフォームの製造方法 | |
CN106519157B (zh) | 用于硬质聚氨酯泡沫的结构阻燃型松香基多元醇及其制备方法和应用 | |
JP2007046043A (ja) | 硬質ポリウレタンフォーム用ポリオール組成物及び硬質ポリウレタンフォームの製造方法 | |
CN105820311A (zh) | 一种脱硫石膏-聚氨酯复合防火保温板及其制备方法 | |
Czupryński et al. | Studies on Effect of Tri (2‐hydroxypropyl), Tri (2‐hydroxybutyl) and Tri (hydroxythiodiethylene) Borates on Thermal and Heat Properties of Rigid Polyurethane‐Polyisocyanurate Foams |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |