CN108659194A - A kind of polyurethane rigid foam plastic composite material and preparation method and purposes - Google Patents
A kind of polyurethane rigid foam plastic composite material and preparation method and purposes Download PDFInfo
- Publication number
- CN108659194A CN108659194A CN201810386183.3A CN201810386183A CN108659194A CN 108659194 A CN108659194 A CN 108659194A CN 201810386183 A CN201810386183 A CN 201810386183A CN 108659194 A CN108659194 A CN 108659194A
- Authority
- CN
- China
- Prior art keywords
- composite material
- coupling agent
- plastic composite
- rigid foam
- foam plastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000006260 foam Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 49
- 239000004814 polyurethane Substances 0.000 title claims abstract description 49
- 229920003023 plastic Polymers 0.000 title claims abstract description 45
- 239000004033 plastic Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 239000007822 coupling agent Substances 0.000 claims abstract description 48
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 33
- 238000005187 foaming Methods 0.000 claims abstract description 18
- 239000012948 isocyanate Substances 0.000 claims abstract description 16
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000004088 foaming agent Substances 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011859 microparticle Substances 0.000 claims abstract description 10
- 150000003077 polyols Chemical class 0.000 claims abstract description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 5
- 229920005862 polyol Polymers 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 103
- 229920000570 polyether Polymers 0.000 claims description 53
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 49
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 47
- 239000003054 catalyst Substances 0.000 claims description 24
- 239000010954 inorganic particle Substances 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- -1 alkane diamines Chemical class 0.000 claims description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 14
- 238000007259 addition reaction Methods 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 7
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- 239000002904 solvent Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005829 trimerization reaction Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 238000009421 internal insulation Methods 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- SXKNYNUXUHCUHX-UHFFFAOYSA-N 1,1,2,3,3,4-hexafluorobut-1-ene Chemical compound FCC(F)(F)C(F)=C(F)F SXKNYNUXUHCUHX-UHFFFAOYSA-N 0.000 claims description 3
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical compound FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 claims description 3
- CYLWXTCHTYMIHB-UHFFFAOYSA-N 1-ethoxyimidazole Chemical class CCON1C=CN=C1 CYLWXTCHTYMIHB-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 3
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 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 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- 229940106691 bisphenol a Drugs 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 238000001879 gelation Methods 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 239000012774 insulation material Substances 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- UPVCRZBVVOXMDA-UHFFFAOYSA-N trimethylazanium;formate Chemical compound OC=O.CN(C)C UPVCRZBVVOXMDA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000811 xylitol Substances 0.000 claims description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 3
- 235000010447 xylitol Nutrition 0.000 claims description 3
- 229960002675 xylitol Drugs 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical compound [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003851 azoles Chemical class 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- LDTMPQQAWUMPKS-UHFFFAOYSA-N 1-chloro-3,3,3-trifluoroprop-1-ene Chemical class FC(F)(F)C=CCl LDTMPQQAWUMPKS-UHFFFAOYSA-N 0.000 claims 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 229920000647 polyepoxide Polymers 0.000 claims 1
- 229920005830 Polyurethane Foam Polymers 0.000 abstract description 24
- 239000011496 polyurethane foam Substances 0.000 abstract description 24
- 230000002708 enhancing effect Effects 0.000 abstract description 5
- 239000002667 nucleating agent Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical class FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 150000002460 imidazoles Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
-
- 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
- C08J9/141—Hydrocarbons
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing 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
- 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
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- 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
-
- 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
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- 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
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- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
Present invention is disclosed a kind of polyurethane rigid foam plastic composite material including coupling agent modified inorganic particulate, inorganic particulate is inorganic nano-particle or inorganic micro particles, and coupling agent includes at least one of silane coupling agent and titanate coupling agent；The composite material is specifically prepared by the foaming feed composition including combination polyalcohol, inorganic particulate, coupling agent, surfactant, foaming agent, isocyanates.The invention also discloses the preparation method of above-mentioned polyurethane rigid foam plastic composite material and the purposes of this composite material.The present invention utilizes the incompatibility of inorganic particulate and raw polyol, in foaming process, foam hole is reduced as heterogeneous nucleation agent, while the structural rigidity and dimensional stability of hard polyurethane foam are improved to the enhancing effect of hard polyurethane foam using inorganic particulate.
Description
Technical field
The present invention relates to polyurethane foam plastics technical fields, and it is compound to specifically provide a kind of polyurethane rigid foam plastic
Material and its preparation method and application.
Background technology
Rigid polyurethane foam great advantage is light, heat-insulation and heat-preservation is good, sound-absorbing and buffering excellent in vibration resistance, tool
There are higher compressive strength and preferable dimensional stability, thus is widely used in the national economy such as national defence, building and traffic neck
Domain.Hard polyurethane foam not only acts as the adiabatic efficiency of heat preservation in system, also acts as the effect of support refrigerator structure, so
It is required that refrigerator is other than with lower thermal coefficient, in addition it is also necessary to more demanding mechanical performance
So far, chlorofluorocarbons has been used as the foaming agent of rigid polyurethane foam, but they are used as foaming
Agent uses the worry that can so that stratospheric ozone layer dilution and global warming cause people to environmental problem.At present in the world
On, limitation is taken to the use of chlorine-containing compound, and its usage degree is gradually decreasing.Therefore, from environmental protection
Angle set out, it has recently been suggested that on foaming agent of the ozone layer without influence, such as pentamethylene.
There is good heat-insulating property using the rigid polyurethane foam that pentamethylene is prepared as foaming agent, therefore extensive
Ground is used as the structural material of the heat-insulating material of refrigerator, building or vehicle.But it is with active dydrogen compounds such as polyalcohol
Compatibility is very poor, and so as to cause the polyol blends containing pentamethylene extended storage stability is poor, gives hard polyaminoester
The preparation of foamed material proposes new challenge.At present when mixing polyalcohol with hydrocarbon blowing agent, pass through addition
Such as the phase stability of polyalcohol is set to be improved as the compound of the surfactant of emulsifier etc.Although when using
Such as conventional surface-active of polyoxyethylene alkyl ether, polyoxyethylene phenol, alkylbenzene sulfonate, nonyl phenol and stearyl alcohol etc
When agent, the compatibility of polyalcohol and hydrocarbon blowing agent is improved, but the mechanical performance of polyurethane foam plastics finished product
But it is damaged.
It would therefore be highly desirable to provide one kind when making foaming agent using pentamethylene, it is desirable that improve the long-term storage of polyol blends
The new polyurethane rigid foam plastic composite material of the thermal conductivity and mechanical strength depositing stability, while keeping heat-insulating material high
And the preparation method that step is more succinct, cost is less expensive.
Invention content
One of the objects of the present invention is to provide a kind of polyurethane rigid foam plastic composite materials, can enhance polyurethane
The structural strength of foam reduces the change in size of polyurethane foam.
The present invention also aims to provide a kind of method preparing above-mentioned polyurethane rigid foam plastic composite material.
The present invention also aims to provide a kind of purposes of above-mentioned polyurethane rigid foam plastic composite material, can make
Obtain has better intensity and better heat-insulating property using this polyurethane rigid foam plastic composite material.
One of embodiments of the present invention are to disclose a kind of polyurethane rigid foam plastic composite material, the composite wood
Material includes coupling agent modified inorganic particulate；The inorganic particulate is inorganic nano-particle or inorganic micro particles；The coupling
Agent includes at least one of silane coupling agent and titanate coupling agent；
The composite material is specifically prepared by following foaming feed composition, the foaming each component of feed composition
Parts by weight are：
As being further improved for present embodiment, the particle size range of the inorganic nano-particle is 40-100nm, described
The particle size range of inorganic micro particles is 10-30 μm.
As being further improved for present embodiment, the dosage of the coupling agent is the inorganic nano-particle weight
0.3-0.4 times, or be 0.1-0.2 times of the inorganic micro particles weight.
As being further improved for present embodiment, the inorganic particulate selects silica, titanium oxide, aluminium oxide, oxidation
Calcium, calcium carbonate, aluminium oxide, zinc oxide, magnesia, aluminium hydroxide, magnesium hydroxide, barium sulfate, calcium sulfate, mica powder, hydrotalcite,
At least one of aluminium-magnesium silicate etc..
As being further improved for present embodiment, the coupling agent selects γ-(2,3- the third oxygen of epoxy) propyl trimethoxy
Base silane (KH560), gamma-aminopropyl-triethoxy-silane (KH550), γ-aminopropyltrimethoxysilane, tetraethoxy-silicane
Alkane, methyltrimethoxysilane are at least one.
As being further improved for present embodiment, the titanate coupling agent selects (the dioctyl phosphoric acid acyl of isopropyl three
Oxygroup) titanate esters, at least one of isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters.
As being further improved for present embodiment, the combination polyalcohol is polyether glycol composition, the polyethers
The parts by weight of each component of glycol composition are：
Polyether glycol I：40-50 parts；
Polyether glycol I I：15-35 parts；
Polyether glycol I II：20-30 parts；
Polyether glycol I V：5-10 parts；
Wherein, the polyether glycol I is to pass through addition reaction as initiator and oxyalkylene using bisphenol-A and polyalcohol
It is prepared；The polyalcohol is one or more in ethylene glycol, propylene glycol, diglycol, triethylene-glycol；Institute
The viscosity for stating polyether glycol I is 200-350mPas, hydroxyl value 160-300mgKOH/g, average functionality 2-3；
The polyether glycol I I is using at least one of glycerine, triethylol propane as initiator and oxyalkylene
It is prepared by addition reaction；The viscosity of the polyether glycol I I is 400-800mPas, hydroxyl value 250-
500mgKOH/g, average functionality 2-3；
The polyether glycol I II is using at least one of alkane diamines, toluenediamine and pentaerythrite as starting
Agent is prepared with oxyalkylene by addition reaction, and the carbon atom number of the alkane diamines is 6-10；The polyethers is more
The viscosity of first alcohol III is 1000-2000mPas, hydroxyl value 350-500mgKOH/g, average functionality 3-5；
The polyether glycol I V be using in xylitol, sucrose one of which and diethylenetriamine as initiator and oxygen
Change alkene to be prepared by addition reaction, the viscosity of polyether glycol I V is 2000-4000mPas, hydroxyl value 350-
600mgKOH/g, average functionality 4-6.
As being further improved for present embodiment, it is chloro- that selected foaming agent is selected from pentamethylene, isopentane, pentafluoropropene, 1-
At least one of 3,3,3- trifluoro propenes, hexafluorobutene；The surfactant is polydimethyl siloxane fluid.
As being further improved for present embodiment, the catalyst includes expansion type catalyst I, gel-type catalyst II
With trimerization type catalyst III；
The expansion type catalyst I is dimethylaminoethoxyethanol；
The gel-type catalyst II is hexamethyl trien, triethylenediamine, triethylamine, N- (3- ammonia third
Base) it is imidazoles, N- (ethoxy) imidazoles, one or more in the gelation catalyst comprising isocyanate reactive group；
The trimerization type catalyst III is (2- hydroxypropyls) trimethyl ammonium formate or pungent quaternary ammonium salt.
As being further improved for present embodiment, the isocyanates is polymethylene multi-phenenyl isocyanate, described
Isocyanate content is 30.5-32.0%, viscosity 150-250mPas.
On the other hand, another embodiment of the present invention is to disclose that a kind of to prepare above-mentioned polyurethane rigid foam plastic multiple
The method of condensation material, the method includes：
S1, polyether glycol composition is mixed by predetermined ratio, obtains the first mixture；
S2, processing is modified to inorganic particulate with coupling agent, modified inorganic particle is made；
S3, modified inorganic particle made from S2 is added to the first mixture, carries out high speed shear, obtains the second mixing
Object；
S4, foaming agent is added in the second mixture, carries out being mixed to get third mixture；
S5, isocyanates is added in third mixture, carries out being mixed to get the 4th mixture；
S6, the 4th mixture is injected to membrane cavity, polyurethane rigid foam plastic composite material is made in foaming curing.
As being further improved for present embodiment, it is described by polyether glycol composition by predetermined ratio carry out mixing and
It is that stirring 2-3 is small under conditions of 20-25 DEG C of temperature, pressure are 1-2bar by the hybrid manipulation of foaming agent and the second mixture
When；It is small that the third mixture stirs under conditions of temperature is 20-25 DEG C, pressure is 120-130bar 2-3 with isocyanates
When.
As being further improved for present embodiment, the specific processing side of processing is modified to inorganic particulate with coupling agent
Method includes：
S201, by the coupling agent of corresponding proportion be added in solvent be uniformly mixed, obtain coupling agent solution；
S202, it inorganic particulate is added in the coupling agent solution being prepared by S201 carries out high speed grinding, until obtaining
Obtain the modified inorganic particle with target grain size；
The modified inorganic particle that S203, baking S202 are obtained removes solvent, the inorganic particle that attrition grinding is handled well.
In another aspect, another embodiment of the present invention is the polyurethane disclosed described in any one of claim 1-10
Rigid foam composite material or the polyurethane rigid foam plastic prepared by claim 11-13 any one of them methods
Purposes of the composite material in household electrical appliances internal insulation material..
The invention has the advantages that：
The embodiment of the present invention is mixed with foamed material in the prior art by the way that inorganic particulate to be modified by coupling agent
It closes, carries out foaming curing, the polyurethane rigid foam plastic composite material for including modified inorganic particle is made；At coupling agent
By the surface grafting and the good organic component of polyalcohol compatibility in inorganic particulate, then the inorganic particulate managed substantially is
It is scattered in polyalcohol with high shear so that inorganic particulate can be uniformly suspended in system, be kept for a period of time not
Sedimentation, makes full use of the incompatibility of inorganic particulate and polyalcohol, in foaming process, inorganic particulate as heterogeneous nucleation agent,
It is easy to make to be nucleated during polyurethane foam, keeps the foam of preparation finer and smoother；Simultaneously using inorganic particulate to rigid polyurethane
The enhancing effect of matter foam improves the structural rigidity and dimensional stability of hard polyurethane foam；And processed inorganic grain
The viscosity influence that son is added in polyalcohol to system is little, is conducive to subsequent foamed material in the indoor mobility of chamber.Therefore,
Inorganic particulate can enhance the structural strength of polyurethane foam, reduce the change in size of polyurethane foam；The rigid polyurethane of preparation
Matter foamy body is high, and thermal coefficient is low；There is better intensity by refrigerator prepared by this hard polyurethane foam, preferably
Heat-insulating property.
Description of the drawings
Attached drawing described herein is used for providing further understanding of the present application, constitutes part of this application, this Shen
Exemplary embodiment and its explanation please does not constitute the improper restriction to the application for explaining the application.Wherein：
Fig. 1 be the present embodiments relate to polyurethane rigid foam plastic composite structure schematic diagram；
Fig. 2 be the present embodiments relate to the refrigerator insulation construction including polyurethane rigid foam plastic composite material show
It is intended to.
Specific implementation mode
To keep the purpose, technical scheme and advantage of the application clearer, below in conjunction with the application specific implementation mode
And technical scheme is clearly and completely described in corresponding attached drawing.Obviously, described embodiment is only this Shen
Please a part of embodiment, rather than whole embodiment.Based on the embodiment in the application, ordinary skill people
The every other embodiment that member is obtained without making creative work, shall fall in the protection scope of this application.
Embodiments of the present invention are described below in detail, the example of the embodiment is shown in the accompanying drawings, wherein from beginning
Same or similar element or element with the same or similar functions are indicated to same or similar label eventually.Below by ginseng
The embodiment for examining attached drawing description is exemplary, and is only used for explaining the present invention, and is not considered as limiting the invention.
One of embodiments of the present invention are to disclose a kind of polyurethane rigid foam plastic composite material, the composite material
Including coupling agent modified inorganic particulate；Wherein, inorganic particulate is inorganic nano-particle or inorganic micro particles；Coupling agent includes
At least one of silane coupling agent and titanate coupling agent；
Above-mentioned composite material is specifically prepared by following foaming feed composition, the weight of each component of foaming feed composition
Measuring number is：
As being further improved for present embodiment, consider from preparation process, effect and cost, more preferable micron model
The inorganic particulate enclosed；Preferably, the particle size range of inorganic nano-particle is 40-100nm, and the particle size range of inorganic micro particles is
10-30μm.Be in micron order, Nano Particle range inert carrier of the inorganic particulate as scion grafting other groups, fully send out
The advantage for the bigger serface that dimensional effect is brought has been waved, it can abundant scion grafting coupling agent；Simultaneously using inorganic particulate to poly- ammonia
The enhancing effect of ester rigid foam improves the structural rigidity and dimensional stability of hard polyurethane foam；And processed nothing
The viscosity influence that machine particle is added in polyalcohol to system is little, is conducive to subsequent foamed material in the indoor mobility of chamber.
As being further improved for present embodiment, the dosage of coupling agent is 0.3-0.4 times of inorganic nano-particle weight,
Or 0.1-0.2 times for inorganic micro particles weight.Coupling agent is anticipated, the presence of coupling agent can prevent very well particle it
Between reunion, improve with the compatibility of polyalcohol, so that inorganic particulate is uniformly suspended in polyalcohol.
As being further improved for present embodiment, inorganic particulate selects silica, titanium oxide, aluminium oxide, calcium oxide, carbon
Sour calcium, aluminium oxide, zinc oxide, magnesia, aluminium hydroxide, magnesium hydroxide, barium sulfate, calcium sulfate, mica powder, hydrotalcite, silicic acid
At least one of magnalium etc..Inert carrier of the inorganic particulate as scion grafting other groups, it is of low cost, it is easily obtained.
As being further improved for present embodiment, silane coupling agent selects γ-(2,3- the third oxygen of epoxy) propyl trimethoxy
Base silane (KH560), gamma-aminopropyl-triethoxy-silane (KH550), γ-aminopropyltrimethoxysilane, tetraethoxy-silicane
Alkane, methyltrimethoxysilane are at least one.Substantially it is by the surface of inorganic particulate using coupling agent treatment inorganic particulate
Grafting and the good organic component of polyalcohol compatibility, are then scattered in high shear in polyalcohol so that inorganic particulate energy
It is enough to be uniformly suspended in system, kept for a period of time do not settle；Then the not phase of inorganic particulate and polyalcohol is made full use of again
Capacitive, in foaming process, inorganic particulate is as heterogeneous nucleation agent, it is easy to make to be nucleated during polyurethane foam, make preparation
Foam it is finer and smoother.
As being further improved for present embodiment, titanate coupling agent selects isopropyl three (dioctyl phosphoric acid acyloxy)
At least one of titanate esters, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters.As the further of present embodiment
It improves, combination polyalcohol is polyether glycol composition, and the parts by weight of the above-mentioned each component of polyether glycol composition are：
Polyether glycol I：40-50 parts；
Polyether glycol I I：15-35 parts；
Polyether glycol I II：20-30 parts；
Polyether glycol I V：5-10 parts；
Wherein, polyether glycol I is to be prepared using bisphenol-A as initiator by addition reaction with oxyalkylene with polyalcohol
It obtains；Polyalcohol is one or more in ethylene glycol, propylene glycol, diglycol, triethylene-glycol；Polyether polyol
The viscosity of I is 200-350mPas, hydroxyl value 160-300mgKOH/g, average functionality 2-3；
Polyether glycol I I is passed through using at least one of glycerine, triethylol propane as initiator and oxyalkylene
Addition reaction is prepared；The viscosity of polyether glycol I I is 400-800mPas, hydroxyl value 250-500mgKOH/g, is averaged
Degree of functionality is 2-3；
Polyether glycol I II be using at least one of alkane diamines, toluenediamine and pentaerythrite as initiator with
Oxyalkylene is prepared by addition reaction, and the carbon atom number of alkane diamines is 6-10；The viscosity of polyether glycol I II
For 1000-2000mPas, hydroxyl value 350-500mgKOH/g, average functionality 3-5；
Polyether glycol I V be using in xylitol, sucrose one of which and diethylenetriamine as initiator and oxyalkylene
Hydrocarbon is prepared by addition reaction, and the viscosity of polyether glycol I V is 2000-4000mPas, hydroxyl value 350-
600mgKOH/g, average functionality 4-6.
As being further improved for present embodiment, foaming agent is selected from pentamethylene, isopentane, pentafluoropropene, 1- chloro- 3,3,
At least one of 3- trifluoro propenes, hexafluorobutene；
Surfactant is polydimethyl siloxane fluid.
As being further improved for present embodiment, catalyst includes expansion type catalyst I, gel-type catalyst II and three
Poly- type catalyst III；
Expansion type catalyst I is dimethylaminoethoxyethanol；
Gel-type catalyst II is hexamethyl trien, triethylenediamine, triethylamine, N- (3- aminopropyls) miaow
It is one or more in azoles, N- (ethoxy) imidazoles, the gelation catalyst comprising isocyanate reactive group；
Trimerization type catalyst III is (2- hydroxypropyls) trimethyl ammonium formate or pungent quaternary ammonium salt.
As being further improved for present embodiment, isocyanates is polymethylene multi-phenenyl isocyanate, isocyanates
Content is 30.5-32.0%, viscosity 150-250mPas.
Further, another embodiment of the present invention is to disclose that a kind of to prepare above-mentioned polyurethane rigid foam plastic multiple
The method of condensation material, method include：
S1, polyether glycol composition is mixed by predetermined ratio, obtains the first mixture；By polyether polyol group
The operating condition that is mixed by predetermined ratio of object is closed to be 1-2bar in 20-25 DEG C of temperature, pressure under stir 2-3 hours；Its
Middle predetermined ratio is that the parts by weight of each component of above-mentioned polyether glycol composition are：Polyether glycol I：40-50 parts；Polyethers
Polyalcohol II：25-40 parts；Polyether glycol I II：20-40 parts；Polyether glycol I V：5-10 parts；
S2, processing is modified to inorganic particulate with coupling agent, modified inorganic particle is made；
Specifically, being further improved as present embodiment is modified inorganic particulate with coupling agent the tool of processing
Body processing method includes：
S201, by the coupling agent of corresponding proportion be added in solvent be uniformly mixed, obtain coupling agent solution；
S202, by inorganic particulate be added in the coupling agent solution being prepared by S201 carry out high speed grind S203, baking
The modified inorganic particle that S202 is obtained is to remove solvent, the inorganic particle that attrition grinding is handled well.
It is modified, is as follows through silane resin acceptor kh-550 with nano-sized magnesium hydroxide：
(1) by nano-sized magnesium hydroxide particle in 110 DEG C of dryings；
(2) 0.3 times of coupling agent that weight is inorganic nano-particle weight is dissolved in the mixed solution of second alcohol and water and being mixed
It is even, coupling agent solution is obtained, is prepared into the KH-550 prehydrolysis solution for later use that mass fraction is 50% in proportion；
(3) inorganic particulate is added in above-mentioned coupling agent solution and carries out high speed grinding；
The modified inorganic particle that S203, baking S202 are obtained
(4) stirred 2 hours under conditions of 20-25 DEG C, it is true at 80 DEG C by the mixture after reaction after filtering alcohol and washing
Sky is dry, removes solvent, and the inorganic particle for the modified Nano magnesium hydroxide that attrition grinding is handled well realizes a nanometer hydrogen-oxygen
Change the surface organo-functionalization of magnesium.
S3, modified inorganic particle made from S2 is added to the first mixture, carries out high speed shear, obtains the second mixing
Object；Modified inorganic particulate is 20-25 DEG C in temperature, high speed shear 2-3 hours under conditions of pressure is 1-2bar.It will foaming
It is that 1-2bar is stirred 2-3 hours that the hybrid manipulation condition of agent and the second mixture, which is in 20-25 DEG C of temperature, pressure,.
Substantially it is good by surface grafting in inorganic particulate and polyalcohol compatibility using coupling agent treatment inorganic particulate
Organic component, be then scattered in polyalcohol with high shear so that inorganic particulate can be uniformly suspended in system,
It is kept for a period of time do not settle, makes full use of the incompatibility of inorganic particulate and polyalcohol, in foaming process, inorganic particulate is made
For heterogeneous nucleation agent, it is easy to make to be nucleated during polyurethane foam, keep the foam of preparation finer and smoother；Inorganic grain is utilized simultaneously
Son improves the structural rigidity and dimensional stability of hard polyurethane foam to the enhancing effect of hard polyurethane foam；And locate
The viscosity influence that the inorganic particulate managed is added in polyalcohol to system is little, and it is indoor in chamber to be conducive to subsequent foamed material
Mobility.S4, foaming agent is added in the second mixture, carries out being mixed to get third mixture；
S5, isocyanates is added in third mixture, carries out being mixed to get the 4th mixture；The third mixture
It is stirred 2-3 hours under conditions of temperature is 20-25 DEG C, pressure is 120-130bar with isocyanates.
S6, the 4th mixture is injected to membrane cavity, polyurethane rigid foam plastic composite material is made in foaming curing.
In another aspect, another embodiment of the present invention is to disclose above-mentioned polyurethane rigid foam plastic composite material
Or purposes of the polyurethane rigid foam plastic composite material of above method preparation in household electrical appliances internal insulation material, specific real
Shi Zhong, polyurethane rigid foam plastic composite material disclosed in this invention can be used for refrigerator, refrigerator, solar energy, gas and hot water
Device and disinfection cabinet household electrical appliances internal insulation.
Specifically, the polyurethane rigid foam plastic composite material being related in the present embodiment prepares raw material and additive
Portion rate specifically see the table below, and include the specific embodiment and in the prior art as a comparison of 8 groups of different materials and proportioning composition altogether
Example；
The polyurethane rigid foam plastic composite material that above-described embodiment is prepared carries out compressive strength, average close
The performance test of degree, thermal coefficient, low-temperature stability, rate of closed hole and aperture size；Through the experimental results showed that, relative to existing skill
Art, the embodiment of the present invention in polyurethane rigid foam plastic composite material by being added modified inorganic particulate, compressive strength
Apparent raising is realized, the compressive strength as embodiment 6 corresponds to the composite material prepared can reach 163kPa, be significantly higher than
147kPa in comparative example；Although mechanical strength significantly increases, each embodiment of thermal coefficient remains basically stable with comparative example, says
The addition of bright modified inorganic particle has no influence for heat conductivility；And the present invention also has the advantages that：
The embodiment of the present invention is mixed with foamed material in the prior art by the way that inorganic particulate to be modified by coupling agent
It closes, carries out foaming curing, the polyurethane rigid foam plastic composite material for including modified inorganic particle is made；At coupling agent
By the surface grafting and the good organic component of polyalcohol compatibility in inorganic particulate, then the inorganic particulate managed substantially is
It is scattered in polyalcohol with high shear so that inorganic particulate can be uniformly suspended in system, be kept for a period of time not
Sedimentation；The incompatibility for making full use of inorganic particulate and polyalcohol, in foaming process, inorganic particulate as heterogeneous nucleation agent,
It is easy to make to be nucleated during polyurethane foam, keeps the foam of preparation finer and smoother；Simultaneously using inorganic particulate to rigid polyurethane
The enhancing effect of matter foam improves the structural rigidity and dimensional stability of hard polyurethane foam；And processed inorganic grain
The viscosity influence that son is added in polyalcohol to system is little, is conducive to subsequent foamed material in the indoor mobility of chamber.Therefore,
Inorganic particulate can enhance the structural strength of polyurethane foam, reduce the change in size of polyurethane foam；The rigid polyurethane of preparation
Matter foamy body is high, and thermal coefficient is low；There is better intensity by refrigerator prepared by this hard polyurethane foam, preferably
Heat-insulating property.
It should be appreciated that although this specification is described in terms of embodiments, but not each embodiment only includes one
A independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should will say
As a whole, the technical solution in each embodiment may also be suitably combined to form those skilled in the art can for bright book
With the other embodiment of understanding.
The series of detailed descriptions listed above only for the present invention feasible embodiment specifically
It is bright, it is all without departing from equivalent implementations made by technical spirit of the present invention or change not to limit the scope of the invention
More it should all be included in the protection scope of the present invention.
Claims (14)
1. a kind of polyurethane rigid foam plastic composite material, which is characterized in that the composite material includes coupling agent modified
Inorganic particulate；The inorganic particulate is inorganic nano-particle or inorganic micro particles；The coupling agent include silane coupling agent and
At least one of titanate coupling agent；
The composite material is specifically prepared by following foaming feed composition, the weight of the foaming each component of feed composition
Number is：
2. polyurethane rigid foam plastic composite material according to claim 1, which is characterized in that the inorganic nano-particle
The particle size range of son includes 40-100nm, and the particle size range of the inorganic micro particles includes 10-30 μm.
3. polyurethane rigid foam plastic composite material according to claim 1, which is characterized in that the use of the coupling agent
Amount is 0.3-0.4 times of the inorganic nano-particle weight or the dosage of the coupling agent is the inorganic micro particles weight
0.1-0.2 times.
4. polyurethane rigid foam plastic composite material according to claim 1, which is characterized in that the inorganic particulate choosing
With silica, titanium oxide, aluminium oxide, calcium oxide, calcium carbonate, aluminium oxide, zinc oxide, magnesia, aluminium hydroxide, magnesium hydroxide,
At least one of barium sulfate, calcium sulfate, mica powder, hydrotalcite, aluminium-magnesium silicate etc..
5. polyurethane rigid foam plastic composite material according to claim 1, which is characterized in that the coupling agent is selected
γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy silicon
At least one of alkane, tetraethoxysilane, methyltrimethoxysilane.
6. polyurethane rigid foam plastic composite material according to claim 1, which is characterized in that the titanate esters coupling
Agent is selected in isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters
It is at least one.
7. polyurethane rigid foam plastic composite material according to claim 1, which is characterized in that the combination polyalcohol
Parts by weight for polyether glycol composition, each component of polyether glycol composition are：
Polyether glycol I：40-50 parts；
Polyether glycol I I：15-35 parts；
Polyether glycol I II：20-30 parts；
Polyether glycol I V：5-10 parts；
The polyether glycol I is to be prepared using bisphenol-A as initiator by addition reaction with oxyalkylene with polyalcohol；
The polyalcohol is one or more in ethylene glycol, propylene glycol, diglycol, triethylene-glycol；The polyethers is more
The viscosity of first alcohol I is 200-350mPas, hydroxyl value 160-300mgKOH/g, average functionality 2-3；
The polyether glycol I I is passed through using at least one of glycerine, triethylol propane as initiator and oxyalkylene
Addition reaction is prepared；The viscosity of the polyether glycol I I be 400-800mPas, hydroxyl value 250-500mgKOH/g,
Average functionality is 2-3；
The polyether glycol I II be using at least one of alkane diamines, toluenediamine and pentaerythrite as initiator with
Oxyalkylene is prepared by addition reaction, and the carbon atom number of the alkane diamines is 6-10；The polyether polyol
The viscosity of III is 1000-2000mPas, hydroxyl value 350-500mgKOH/g, average functionality 3-5；
The polyether glycol I V be using in xylitol, sucrose one of which and diethylenetriamine as initiator and oxyalkylene
Hydrocarbon is prepared by addition reaction, and the viscosity of polyether glycol I V is 2000-4000mPas, hydroxyl value 350-
600mgKOH/g, average functionality 4-6.
8. polyurethane rigid foam plastic composite material according to claim 1, which is characterized in that selected foaming agent is selected from
At least one of the chloro- 3,3,3- trifluoro propenes of pentamethylene, isopentane, pentafluoropropene, 1-, hexafluorobutene；It lives on the surface
Property agent be polydimethyl siloxane fluid.
9. polyurethane rigid foam plastic composite material according to claim 1, which is characterized in that the catalyst includes
Expansion type catalyst I, gel-type catalyst II and trimerization type catalyst III；
The expansion type catalyst I is dimethylaminoethoxyethanol；
The gel-type catalyst II is hexamethyl trien, triethylenediamine, triethylamine, N- (3- aminopropyls) miaow
It is one or more in azoles, N- (ethoxy) imidazoles, the gelation catalyst comprising isocyanate reactive group；
The trimerization type catalyst III is (2- hydroxypropyls) trimethyl ammonium formate or pungent quaternary ammonium salt.
10. polyurethane rigid foam plastic composite material according to claim 1, which is characterized in that the isocyanates
For polymethylene multi-phenenyl isocyanate, the isocyanate content is 30.5-32.0%, viscosity 150-250mPas.
11. a kind of method preparing the polyurethane rigid foam plastic composite material as described in claim 1-10 any one,
It is characterized in that, the method includes：
S1, polyether glycol composition is mixed by predetermined ratio, obtains the first mixture；
S2, processing is modified to inorganic particulate with coupling agent, modified inorganic particle is made；
S3, modified inorganic particle made from S2 is added to the first mixture, carries out high speed shear, obtains the second mixture；
S4, foaming agent is added in the second mixture, carries out being mixed to get third mixture；
S5, isocyanates is added in third mixture, carries out being mixed to get the 4th mixture；
S6, the 4th mixture is injected to membrane cavity, polyurethane rigid foam plastic composite material is made in foaming curing.
12. polyurethane rigid foam plastic composite material and preparation method thereof according to claim 11, which is characterized in that described
Polyether glycol composition is subjected to mixing and by the hybrid manipulation of foaming agent and the second mixture in temperature by predetermined ratio
20-25 DEG C, pressure be 1-2bar under conditions of stir 2-3 hours；The third mixture is 20-25 in temperature with isocyanates
DEG C, pressure be 120-130bar under conditions of stir 2-3 hours.
13. polyurethane rigid foam plastic composite material and preparation method thereof according to claim 11, which is characterized in that with occasionally
Connection agent is modified inorganic particulate the specific processing method of processing and includes：
S201, by the coupling agent of corresponding proportion be added in solvent be uniformly mixed, obtain coupling agent solution；
S202, it inorganic particulate is added in the coupling agent solution being prepared by S201 carries out high speed grinding, until being had
There is the modified inorganic particle of target grain size；
The modified inorganic particle that S203, baking S202 are obtained removes solvent, and inorganic particle is made in attrition grinding.
14. polyurethane rigid foam plastic composite material described in any one of claim 1-10 or by claim 11-13
The purposes of polyurethane rigid foam plastic composite material prepared by any one of them method in household electrical appliances internal insulation material.
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| CN109503794A (en) * | 2018-11-13 | 2019-03-22 | 江苏奥斯佳材料科技股份有限公司 | A kind of polyurethane rigid foam composition and polyurethane rigid foam material and preparation method thereof |
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| CN113698569A (en) * | 2021-07-20 | 2021-11-26 | 佳化化学科技发展（上海）有限公司 | Combined polyether, polyurethane block foam for LNG pipe bracket and preparation method and application of polyurethane block foam |
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