CN114656602B - Prepolymer for polymer polyol and preparation method thereof - Google Patents
Prepolymer for polymer polyol and preparation method thereof Download PDFInfo
- Publication number
- CN114656602B CN114656602B CN202210140107.0A CN202210140107A CN114656602B CN 114656602 B CN114656602 B CN 114656602B CN 202210140107 A CN202210140107 A CN 202210140107A CN 114656602 B CN114656602 B CN 114656602B
- Authority
- CN
- China
- Prior art keywords
- prepolymer
- compound
- monomer
- initiator
- macromer
- 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.)
- Active
Links
- 150000003077 polyols Chemical class 0.000 title claims abstract description 54
- 229920005862 polyol Polymers 0.000 title claims abstract description 51
- 229920000642 polymer Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004917 polyol method Methods 0.000 title description 2
- 239000002245 particle Substances 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 238000009826 distribution Methods 0.000 claims abstract description 8
- 230000002902 bimodal effect Effects 0.000 claims abstract description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 29
- 229920000570 polyether Polymers 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- -1 oxazolidine compound Chemical class 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 150000003254 radicals Chemical class 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- RSJWKIDVVZWYTD-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-2-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1C(C)(C)N=C=O RSJWKIDVVZWYTD-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- KNHJIEOCVVIBIV-UHFFFAOYSA-N 2,3-dimethylphenyl isocyanate Chemical compound CC1=CC=CC(N=C=O)=C1C KNHJIEOCVVIBIV-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 10
- 230000008021 deposition Effects 0.000 abstract description 3
- 125000000160 oxazolidinyl group Chemical group 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 150000002978 peroxides Chemical group 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 description 1
- DWMPZBNVQGVLIJ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC(C)(C)CC DWMPZBNVQGVLIJ-UHFFFAOYSA-N 0.000 description 1
- BWOITHKYQUJGSB-UHFFFAOYSA-N 2-methylbutan-2-ylperoxycyclohexane Chemical compound CCC(C)(C)OOC1CCCCC1 BWOITHKYQUJGSB-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N n-butyl mercaptan Natural products CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KQYLUTYUZIVHND-UHFFFAOYSA-N tert-butyl 2,2-dimethyloctaneperoxoate Chemical compound CCCCCCC(C)(C)C(=O)OOC(C)(C)C KQYLUTYUZIVHND-UHFFFAOYSA-N 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GSECCTDWEGTEBD-UHFFFAOYSA-N tert-butylperoxycyclohexane Chemical compound CC(C)(C)OOC1CCCCC1 GSECCTDWEGTEBD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a prepolymer for preparing polymer polyol, which improves the storage stability of the prepolymer with bimodal distribution by introducing a compound with an oxazolidine structure, and solves the problems of particle size increase or prepolymer deposition caused by too long storage time after standing for 48 hours, thereby reducing the content of filter residues in the POP preparation process.
Description
Technical Field
The invention belongs to the technical field of polymer polyol, in particular relates to a prepolymer synthesis process for preparing polymer polyol, and more particularly relates to a synthesis process for preparing polymer polyol prepolymer capable of being stored stably.
Background
Polymer polyols (also known as graft polyether polyols or filled polyols) are dispersions of polymer particles in polyether polyols. Depending on the type of polymer particles, styrene-acrylonitrile copolymer polyols (POPs) and polyurea polymer Polyols (PHDs) have been commercially available, the former being widely used, POPs having stringent requirements for the polymer particles when applied, otherwise blocking the blowing heads of the foaming machines. Therefore, in the preparation or packaging process, the POP reaction solution or the product must be filtered, for example, a 100-150 mesh filter screen is used, and the generation of filter residues under the filtration is greatly influenced by the prepolymer. The filter cleaning also brings the reduction of production efficiency and the increase of dangerous waste, and prolongs the inspection and maintenance time of the equipment.
In order to reduce the amount of filter residues in the POP synthesis process, a prepolymer Process (PFS) is generally used for synthesis, that is, monomer, base polyether polyol, initiator and prepolymer are reacted, and the prepolymer is a polymer dispersion with a lower solid content, such as 3-15%, and is obtained by initiating polymerization of a macromer and monomer by the initiator in the presence of a solvent. The macromers are linear or branched polyether polyols containing polymerizable double bonds, in particular prepolymers of suitable particle size distribution.
However, since small particle size tends to agglomerate, the prepolymer is inferior in storage performance, and agglomeration and increase and even sedimentation delamination are liable to occur during storage. If the residual prepolymer in the storage tank or the reactor is lack of stirring during equipment maintenance or stopping, quality degradation appears in the standing process, large particles larger than 4000nm appear, sedimentation layering appears in serious cases, if the prepolymer is adopted for synthesizing POP, filter residues in the product are increased, and the fluidity of the product is difficult. The complete replacement and rejection can cause a great deal of organic liquid waste, and the labor intensity is increased.
In order to solve the problem, the invention provides a prepolymer, which can improve the storage time of the prepolymer, solve the problem of particle size increase or prepolymer deposition caused by too long storage time, and further reduce the content of filter residues in the POP preparation process.
Disclosure of Invention
In order to solve the problem that the particle size of a prepolymer used for producing polymer polyol is increased in the storage process, so that the content of filter residues in the POP preparation process is increased, the invention provides a preparation process of the prepolymer, which can improve the storage time of the prepolymer, solve the problem of the increase of the particle size or the deposition of the prepolymer caused by the too long storage time, and further reduce the content of the filter residues in the POP preparation process.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, there is provided a prepolymer for use in the preparation of a polymer polyol having an at least bimodal distribution with one peak at 50 to 120nm and the other peak at 300 to 750nm, the ratio of small particle size to large particle size volume being 10/90 to 40/60; after the prepolymer is kept stand for 48 hours, the particle ratio of particles larger than 4000nm is within 4 percent.
In a second aspect of the present invention, there is provided a prepolymer synthesis process for preparing a polymer polyol as described above, comprising:
at a certain reaction temperature, the mixture of the monomer, the macromer, the oxazolidine compound and the solvent is polymerized in the presence of a free radical initiator.
In the present invention, the monomer used in the synthesis process for preparing the prepolymer is selected from one or more of vinyl aromatic compounds, unsaturated carboxylic acids and esters thereof, unsaturated nitriles or amides, vinyl esters or vinyl halides, such as styrene, methyl acrylate, ethyl acrylate, acrylamide, acrylonitrile, methylstyrene, chlorostyrene, etc., with styrene and acrylonitrile being particularly preferred. When the monomers are a mixture, it is preferable to use a mixture of two monomers, for example, styrene and acrylonitrile, in a mass ratio of usually 80/20 to 20/80 (styrene/acrylonitrile), particularly preferably 60/40 to 40/60 (styrene/acrylonitrile). Suitable total monomer masses are from 7 to 25% based on the total weight of the prepolymer (i.e., the sum of the masses of macromer, monomer, free radical initiator, oxazolidine compound, and solvent).
In the invention, the free radical initiator used in the synthesis process of the prepolymer is a peroxide initiator or azo initiator, such as didecanoyl peroxide, di (3, 5-trimethylhexanoyl) peroxide, dilauroyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 1-di (t-butylperoxy) cyclohexane, 1-di (t-amyl peroxy) cyclohexane, 1, 3-tetramethylbutyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate (TBPEH), and tert-butyl perpivalate, tert-amyl peroctoate, tert-amyl peroxypivalate, 2, 5-dimethylhexane-2, 5-dipenta-2-ethylhexanoate, tert-butyl perneodecanoate, tert-butyl perbenzoate, 1-dimethyl-3-hydroxybutyl peroxy-2-ethylhexanoate, azobisisobutyronitrile, azobisisovaleronitrile, dimethyl azobisisobutyrate. Suitable free radical initiators are used in amounts of from 0.05 to 0.5% based on the total weight of the prepolymer.
In the present invention, the solvent used in the synthesis process for preparing the prepolymer is one or more selected from benzene, toluene, ethylbenzene, xylene, hexane, isopropyl alcohol, n-butanol, 2-butanol, ethyl acetate, butyl acetate and mercaptan, preferably isopropyl alcohol. Suitable solvents are used in amounts of 35 to 60% based on the total weight of the prepolymer.
In the invention, the macromer used in the prepolymer synthesis process is composed of a compound I and a compound II, wherein the compound I is a macromer obtained by reacting a non-terminal alkenyl structure double bond compound with polyether polyol, and the compound II is a macromer obtained by reacting a compound containing a terminal alkenyl structure double bond with polyether polyol; the mass ratio of the compound I to the compound II is 2/8-8/2; the amount of the macromer is 15 to 40 percent based on the total weight of the prepolymer;
preferably, the non-terminal alkenyl structure double bond compound for preparing the compound I is maleic acid or fumaric acid or itaconic acid and derivatives thereof;
as an example, compound I is a macromer containing maleic acid diester or fumaric acid diester or maleimide groups, as shown below by way of illustration:
particularly preferred is the structure of hydroxyethyl fumaric acid diester:
the double bond compound containing terminal alkenyl structure for preparing the compound II can be selected from one or more of isopropenyl dimethylbenzyl isocyanate (TMI), glycidyl methacrylate, (methyl) acrylic acid, dimethyl phenyl isocyanate and hydroxyethyl methacrylate, and the preferable structure of the compound II is shown as the following by way of illustration:
particularly preferred are compounds containing isopropenyldimethylbenzyl isocyanate (TMI), glycidyl methacrylate residues:
wherein Y1 and Y2 represent polyether polyol residues; the polyether polyol is prepared by taking polyol with functionalities of 3-7 such as glycerol, trimethylolpropane, sorbitol, pentaerythritol and the like as an initiator and carrying out ring-opening reaction with propylene oxide and ethylene oxide, wherein the hydroxyl value of the polyether polyol is controlled to be 20-48 mgKOH/g, preferably 24-38 mgKOH/g, and the proportion of the ethylene oxide to the total mass of the epoxy compound is controlled to be 3-20%, preferably 7-15%; the polyether polyols may be prepared by any of the existing processes well known in the art and are not described in detail herein (see, for example, encyclopedia of chemical industry (volume 9), first edition 1997, chemical industry Press P165-181).
The synthesis steps of the compounds are described in patents CN03811632.4, CN200410094080.8, CN200710129225.7, CN201480012226.1, CN200510116277.1 and CN 96112759.7.
In the invention, in the synthesis process of the prepolymer, the structural formula of the oxazolidine compound is shown as follows:
wherein X is-CH 2- (-O-CH 2-CHR-) n -OH, n is an integer between 0 and 9 (e.g. 1, 2, 3,4, 5, 6, 7, 8, 9), R is a hydrogen atom or a methyl group;
in the present invention, the oxazolidine compound is suitably used in an amount of 0.5 to 3% based on the total weight of the prepolymer during the synthesis of the prepolymer.
The prepolymer synthesis process is prepared by adopting a continuous process, preferably a two-stage continuous reaction system is used, and the oxazolidine is preferably added in a second-stage reactor;
in the present invention, the synthesis temperature of the prepolymer is preferably 85 to 140℃and the pressure is preferably 2 to 5bar.
The invention also relates to a method for preparing polymer polyol by using the prepolymer and application thereof. Firstly, carrying out polymerization reaction on a prepolymer, a monomer and an initiator in the presence of basic polyether; then, the unreacted monomers and the solvent in the prepolymer are removed by vacuum distillation, and the polymer polyol product is obtained.
In the invention, the mass fraction of the prepolymer is 10-20%, the mass fraction of the monomer is 35-55%, the mass fraction of the initiator is 0.05-0.6%, and the mass fraction of the base polyether is 25-50%, calculated by 100% of the total mass of the prepolymer, the monomer, the initiator and the base polyether.
The basic polyether used in the invention is the short name of polyoxyalkylene polyether polyol, the molecular weight (number average molecular weight, the same applies below) is 500-14000, and the hydroxyl functionality is 2-6; the weight content of ethylene oxide in the polyoxyalkylene polyether polyol is preferably 2 to 9.9wt%; as one embodiment, the polyether polyol is obtained by ring-opening polymerization with a bimetallic catalyst using glycerol as an initiator.
In the process for preparing polymer polyols, as initiators for free-radical polymerization, organic peroxides and/or azo-based compounds, such as benzoyl peroxide, tert-amyl 2-ethylhexanoate, lauroyl peroxide, butyl peroctoate, di-tert-butyl cyclohexylperoxide, di-tert-amyl cyclohexylperoxide, dimethyl azotetramethylsuccinate, azobisisobutyronitrile (AIBN) and Azobisisobutyronitrile (AMBN), may be used as known.
In the process for preparing polymer polyols according to the invention, the monomers are ethylenically unsaturated monomers selected from aromatic olefins, such as styrene, methylstyrene, chlorostyrene, etc., or unsaturated nitriles, such as acrylonitrile, methacrylonitrile, or acrylic and methacrylic esters, such as methyl (meth) acrylate, ethyl (meth) acrylate, nonyl (meth) acrylate, etc. As an ideal solution, styrene and acrylonitrile are generally chosen by the person skilled in the art. The two monomers can be combined according to the respective formula and in any proportion, and the preferable scheme is that the mass ratio of the monomer styrene to the monomer acrylonitrile is 20/80-80/20.
In the process for producing a polymer polyol of the present invention, the polymerization temperature is preferably in the range of 90 to 130℃and more preferably in the range of 100 to 110 ℃. Batch, semi-continuous and continuous operation can be carried out, continuous operation is preferred, double-kettle continuous operation is particularly preferred, and the total polymerization residence time of the reaction solution in the polymerization kettle is generally controlled to be 0.5-3 h; after the polymerization is completed, the person skilled in the art generally carries out an ageing treatment for a period of time, the ageing temperature is generally 10-20 ℃ higher than the reaction temperature, and the ageing residence time is generally 0.5-3 h.
In the present invention, the distillation operation is a conventional operation for removing unreacted monomers and solvents from the polymer polyol, which is generally referred to as a single removal operation, and the vacuum distillation treatment process may be selected from common single removal unit operations such as flash evaporation, thin film evaporation, and super gravity evaporation, but is not limited thereto. As a preferred option, the unreacted unsaturated monomers may be removed by inert gas stripping or steam stripping, preferably steam stripping. The operating temperature is generally controlled between 90 and 140℃and the pressure between 0 and 20kpa, preferably between 110 and 140℃and the pressure between 2 and 10kpa.
The invention has the beneficial effects that:
the oxazolidine has remarkable stabilizing effect on prepolymer particles, especially small particle size, can solve the problems of standing aggregation and layering of the prepolymer with bimodal distribution, further reduces the amount of filter residues in the subsequent POP production process, reduces the cleaning frequency of filter bags, ensures the stable quality of start-stop products and reduces the operation strength.
Drawings
FIG. 1 is a particle size distribution diagram of a prepolymer of an example
FIG. 2 is a graph showing the particle size distribution of a prepolymer obtained in example one after being left for 48 hours;
FIG. 3 is a graph showing the particle size distribution of a comparative example two prepolymer after being left for 48 hours;
wherein the abscissa represents the particle size (nm) and the ordinate represents the scattered light intensity;
FIG. 4 is a photograph of a residue obtained after filtration of a polymer polyol product of example four
FIG. 5 is a photograph of the residue of the comparative polymer polyol product after filtration.
Detailed Description
The present invention will be described in detail with reference to specific examples. The scope of the invention is not limited by the specific embodiments.
Molecular weight measurement: gel Permeation Chromatography (GPC) was determined using DIN55672-1, using chloroform as eluent, mixed bed column (Agilent PL Gel; SDVB), infrared refractive index detector, polyethylene glycol standard calibration.
Viscosity in millipascal seconds (mPas) was measured using an Anton Paar SVM3000 viscometer at 25 ℃.
Particle size: the malvern nanoparticle tester ZS90, polystyrene test cell was diluted 1 ten thousand times with ethanol at 25 ℃.
Filtration performance and filter residue content: a 500 mesh nylon screen, pressurized to 0.5bar gauge, heated the polymer polyol to 50 ℃, and recorded the passage time of 1L of polymer polyol in seconds(s); after filtering, washing a filter screen by using ethanol, drying, weighing the quality of filter residues on the filter screen, and calculating the content of the filter residues in ppm;
residue photograph: gaopin GP-300C electron microscope, 150 times magnification;
abbreviations and meanings of the compounds used in the present invention are described below:
compound I: KOH-catalyzed, high resilience, soft foam polyether polyol (hydroxyl value 28.5mgKOH/g, EO content 15%,) prepared by reacting glycerin with propylene oxide and ethylene oxide was reacted with maleic anhydride and then treated with EO cap, viscosity 4100 mPa.s@25 ℃.
Compound II:1200 g of KOH-catalyzed polyether polyol (hydroxyl number 29mgKOH/g, EO content 16%,) prepared by reacting sorbitol with propylene oxide and ethylene oxide were reacted with 0.12mol of isopropenyldimethylbenzyl isocyanate in the presence of 60g of toluene at 90℃and after 3h of catalytic reaction with 300ppm of organotin (T-9) the viscosity 1765 mPa.s@25℃.
Oxazolidine compound: 145g of 1H,3H, 5H-oxazolo [3,4-C ] oxazolo-7A (7H) methanol (6542-37-6) was added with 1.2g of potassium methoxide, heated to 80℃for 30min of vacuum degassing, warmed to 100℃and 264g of ethylene oxide was added, after 3H of reaction, warmed to 120℃for 1H of aging, kept at the temperature for 2H of degassing, test n=6, recorded as OOM.
F3156: a base polyether polyol, a soft foam polyether polyol prepared by reacting glycerin with KOH prepared by reacting propylene oxide and ethylene oxide, wanhua chemical group Co., ltd., hydroxyl value of 56.2mgKOH/g, EO content of 7 to 10%.
Initiator a:1, 3-tetramethylbutyl peroxy-2-ethylhexanoate, available from Nouryon;
initiator B: AMBN, 2' -azobis (2-methylbutyronitrile), purchased from Nouryon.
Preparation of the prepolymer:
a two-stage continuous reaction system was used, the first stage being a continuous stirred tank reactor (300 ml CSTR) and the second stage being a tubular plug flow reactor (300 ml). The reaction raw materials are mixed and then cooled to below 5 ℃, the mixture enters a first-stage reactor through a feed pipe by a advection pump, the reactor is fully mixed and overflows to a second reactor, the temperature of the reaction mixture is controlled to be 120+/-0.5 ℃, the pressure of a reaction system is controlled to be maintained to be 4+/-0.5 bar by the second-stage reactor, then the prepolymer reaction liquid is collected to test the initial particle size, and the particle size is tested again after the mixture is placed for 48 hours.
TABLE 1 raw material ratio for prepolymer synthesis
Preparation of polymer polyol:
a two-stage continuous reaction system was used, both stages being continuous stirred tank reactors (1000 ml CSTR). After the reaction raw materials are mixed (wherein the PFS is used after being placed for 48 hours), the temperature is reduced to below 5 ℃, the mixture enters a first-stage reactor through a feed pipe by a advection pump and overflows to a second-stage reactor, the temperature of the reaction mixture is controlled to be 120+/-0.5 ℃, and prepolymer reaction liquid is collected for standby after passing through the second-stage reactor. Collecting the reaction liquid, vacuum stripping (the operation temperature is 110-140 ℃ and the pressure is 0.01-0.1 kpa) to remove volatile matters, and testing indexes.
TABLE 2 raw material formulation for Polymer polyol Synthesis
The prepolymer and polymer polyol test indexes are shown in tables 3 and 4, respectively:
TABLE 3-1 prepolymer test index
TABLE 3-2 prepolymer test indicators (after 48h of standing)
TABLE 4 Polymer polyol test index
As can be seen from the above graph, after adding a proper amount of OOM, the mixture still has a bimodal particle size after standing for 48 hours, and the large particle size (> 4000 nm) accounts for < 4%; and too much or too little OOM is added, the primary particle size is larger than 4% even if the primary particle size is not larger than the primary particle size, and the primary particle size (> 4000 nm) is larger than 4% after the primary particle size is placed or stored.
The filter residues synthesized by normal PFS are filiform, so that the compactness of the filter cake is effectively reduced, and the speed of flowing through the filter cake is accelerated and the time is shortened. The filter cake of the PFS synthesized POP with more large particles has small particles and needle-shaped scaling, and the formed filter cake is compact and difficult to filter.
Claims (10)
1. A prepolymer for the preparation of a polymer polyol, characterized in that it has an at least bimodal distribution in which one peak is 50 to 120nm and the other peak is 300 to 750nm, the ratio of small particle size to large particle size volume being 10/90 to 40/60; after the prepolymer is kept stand for 48 hours, the particle ratio of particles larger than 4000nm is within 4 percent;
the preparation method of the prepolymer comprises the following steps: polymerizing a mixture of a monomer, a macromer, an oxazolidine compound and a solvent in the presence of a free radical initiator at a certain reaction temperature; wherein, based on the mass sum of the macromer, the monomer, the free radical initiator, the oxazolidine compound and the solvent, the dosage of the monomer is 7-25%, the dosage of the free radical initiator is 0.05-0.5%, the dosage of the solvent is 35-60%, the dosage of the macromer is 15-40%, and the dosage of the oxazolidine compound is 0.5-3%;
the monomer is selected from one or more of vinyl aromatic compounds, unsaturated carboxylic acids and esters thereof, unsaturated nitrile or amide, vinyl ester or vinyl halide;
the structural formula of the oxazolidine compound is shown as follows:
wherein X is-CH 2 -(O-CH 2 -CHR-) n -OH, n is an integer ranging from 0 to 9, R is a hydrogen atom or a methyl group;
the macromer consists of a compound I and a compound II, wherein the compound I is a macromer obtained by reacting a non-terminal alkenyl structure double bond compound with polyether polyol, and the compound II is a macromer obtained by reacting a compound containing a terminal alkenyl structure double bond with polyether polyol; the mass ratio of the compound I to the compound II is 2/8-8/2;
the polyether polyol is prepared by ring-opening reaction of polyol with functionality of 3-7 serving as an initiator, propylene oxide and ethylene oxide, wherein the hydroxyl value is 20-48 mgKOH/g, and the ethylene oxide accounts for 3-20% of the total mass of the epoxy compound.
2. The prepolymer of claim 1, wherein the monomer is selected from one or more of styrene, methyl acrylate, ethyl acrylate, acrylamide, acrylonitrile, methyl styrene, chlorostyrene.
3. The prepolymer of claim 1 wherein the monomer is a mixture of styrene and acrylonitrile in a mass ratio of 80/20 to 20/80.
4. The prepolymer of claim 1, wherein the non-terminal alkenyl structural double bond compound is maleic acid or fumaric acid or itaconic acid and derivatives thereof.
5. The prepolymer of claim 4, wherein compound I has the structure shown below:
y1 represents a polyether polyol residue.
6. The prepolymer according to claim 1, wherein the compound having an alkenyl-terminated double bond is one or more selected from the group consisting of isopropenyldimethylbenzyl isocyanate, glycidyl methacrylate, (meth) acrylic acid, dimethylphenyl isocyanate, and hydroxyethyl methacrylate.
7. The prepolymer of claim 6, wherein compound II has the structure:
y2 represents a polyether polyol residue.
8. The prepolymer of claim 7, wherein compound II has the structure:
9. use of a prepolymer according to any one of claims 1 to 8 in the preparation of a polymer polyol.
10. A polymer polyol, characterized in that it is prepared from monomers, initiator, base polyether, prepolymer according to any one of claims 1-8; the mass fraction of the prepolymer is 10-20%, the mass fraction of the monomer is 35-55%, the mass fraction of the initiator is 0.05-0.6%, and the mass fraction of the base polyether is 25-50%, calculated by 100% of the total mass of the prepolymer, the monomer, the initiator and the base polyether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210140107.0A CN114656602B (en) | 2022-02-16 | 2022-02-16 | Prepolymer for polymer polyol and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210140107.0A CN114656602B (en) | 2022-02-16 | 2022-02-16 | Prepolymer for polymer polyol and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114656602A CN114656602A (en) | 2022-06-24 |
| CN114656602B true CN114656602B (en) | 2023-12-19 |
Family
ID=82026740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210140107.0A Active CN114656602B (en) | 2022-02-16 | 2022-02-16 | Prepolymer for polymer polyol and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114656602B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1656136A (en) * | 2002-03-15 | 2005-08-17 | 巴斯福股份公司 | Graft polyols with a bimodal particle size distribution and method for producing graft polyols of this type, in addition to the use thereof for producing polyurethanes |
| CN1845763A (en) * | 2003-07-25 | 2006-10-11 | 施拖克豪森有限公司 | Powdery, water-absorbent polymers comprising fine particles bonded by means of thermoplastic adhesives |
| JP2008001842A (en) * | 2006-06-23 | 2008-01-10 | Dainichiseika Color & Chem Mfg Co Ltd | Polyurea colloidal solution, its production method and dispersion stabilizer |
| CA2672604A1 (en) * | 2006-12-19 | 2008-06-26 | Dow Global Technologies Inc. | An ultra-high solid content polyurethane dispersion and a continuous process for producing ultra-high solid content polyurethane dispersions |
| CN103408704A (en) * | 2013-05-07 | 2013-11-27 | 江苏长华聚氨酯科技有限公司 | Continuous method for preparing high-stability polymer polyols |
| CN112708037A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Polymer polyol with wide particle size distribution, and preparation method and application thereof |
-
2022
- 2022-02-16 CN CN202210140107.0A patent/CN114656602B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1656136A (en) * | 2002-03-15 | 2005-08-17 | 巴斯福股份公司 | Graft polyols with a bimodal particle size distribution and method for producing graft polyols of this type, in addition to the use thereof for producing polyurethanes |
| CN1845763A (en) * | 2003-07-25 | 2006-10-11 | 施拖克豪森有限公司 | Powdery, water-absorbent polymers comprising fine particles bonded by means of thermoplastic adhesives |
| JP2008001842A (en) * | 2006-06-23 | 2008-01-10 | Dainichiseika Color & Chem Mfg Co Ltd | Polyurea colloidal solution, its production method and dispersion stabilizer |
| CA2672604A1 (en) * | 2006-12-19 | 2008-06-26 | Dow Global Technologies Inc. | An ultra-high solid content polyurethane dispersion and a continuous process for producing ultra-high solid content polyurethane dispersions |
| CN103408704A (en) * | 2013-05-07 | 2013-11-27 | 江苏长华聚氨酯科技有限公司 | Continuous method for preparing high-stability polymer polyols |
| CN112708037A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Polymer polyol with wide particle size distribution, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 基于二次乳化的多粒径高固含芳香族水性聚氨酯的制备;陈新;吴锦京;李季衡;;广州化工(第23期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114656602A (en) | 2022-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5527920B2 (en) | Low viscosity polymer polyol characterized by high hydroxyl number | |
| JP6372861B2 (en) | Preformed stabilizers and polymer polyols useful for the production of polymer polyols | |
| CA2187125A1 (en) | Continuous process for the preparation of highly stable, finely divided, low viscosity polymer polyols of small average particle size | |
| CN101010344A (en) | Method for preparing adhesive acrylic ester polymer syrup | |
| US8987396B2 (en) | Active polymer polyols and a process for their production | |
| CN109689695B (en) | Improved polymer polyol quality | |
| JP6366074B2 (en) | Polymer polyol with improved quality | |
| WO2020132940A1 (en) | Macromonomeric stabilizer, preparation method thereof, and method for preparing polymeric polyol | |
| DE2812109A1 (en) | METHOD FOR MANUFACTURING GRAFT POLYMERISATES AND THEIR USE | |
| CN114656602B (en) | Prepolymer for polymer polyol and preparation method thereof | |
| CN111363133A (en) | Macromolecular monomer stabilizer, preparation method thereof and method for preparing copolymer polyol by using macromolecular monomer stabilizer | |
| KR100908177B1 (en) | Method of Preparation of Copolymer | |
| US11945775B2 (en) | Stable dispersant and application thereof in preparing copolymer polyols | |
| CN114644733A (en) | Preparation method of polymer polyol | |
| CN109705305B (en) | Isocyanate biuret containing polyunsaturated group and preparation and application thereof | |
| WO2020132944A1 (en) | Modified polyether polyol and use thereof in polyurethane foam materials | |
| JP2009040946A (en) | Method for manufacturing polymer polyol | |
| CN110078911A (en) | Phosphoric acid ester macromonomer and preparation method thereof, polymer polyatomic alcohol and preparation method thereof | |
| WO2023033997A1 (en) | Filled polyol compositions that include a triazole | |
| EP2473546A1 (en) | Process for preparing a polymer polyol | |
| CN109796588B (en) | Modified polyether polyol and application thereof in polyurethane foam material | |
| CN109836538B (en) | Polymer polyol and method for producing the same | |
| EP4146708B1 (en) | Process for preparing low molecular weight polyacrylates and products thereof | |
| US6362297B1 (en) | Preparation of allylic copolymers of broad molecular weight distributions | |
| CA2227346A1 (en) | Low-viscosity polymer polyols, a process for their production and their use for producing polyurethane 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 |