CN1142980C - Polymer polyol composition, process for producing the same, and process for producing polyurethane resin - Google Patents
Polymer polyol composition, process for producing the same, and process for producing polyurethane resin Download PDFInfo
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- CN1142980C CN1142980C CNB008021112A CN00802111A CN1142980C CN 1142980 C CN1142980 C CN 1142980C CN B008021112 A CNB008021112 A CN B008021112A CN 00802111 A CN00802111 A CN 00802111A CN 1142980 C CN1142980 C CN 1142980C
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- polymer
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- polyol composition
- compound
- monomer
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- 229920000642 polymer Polymers 0.000 title claims abstract description 292
- 239000000203 mixture Substances 0.000 title claims abstract description 133
- 229920005862 polyol Polymers 0.000 title claims abstract description 101
- 150000003077 polyols Chemical class 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 95
- 229920005749 polyurethane resin Polymers 0.000 title abstract description 7
- 230000008569 process Effects 0.000 title abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 115
- 239000002245 particle Substances 0.000 claims abstract description 84
- 239000006185 dispersion Substances 0.000 claims abstract description 81
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 20
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 198
- -1 alkyl olefin Chemical class 0.000 claims description 137
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 82
- 239000000178 monomer Substances 0.000 claims description 79
- 229920002554 vinyl polymer Polymers 0.000 claims description 77
- 238000004519 manufacturing process Methods 0.000 claims description 74
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 65
- 238000006116 polymerization reaction Methods 0.000 claims description 62
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 61
- 239000003795 chemical substances by application Substances 0.000 claims description 47
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 35
- 150000002148 esters Chemical class 0.000 claims description 33
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 24
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 claims description 24
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 18
- 150000002825 nitriles Chemical class 0.000 claims description 18
- 239000000376 reactant Substances 0.000 claims description 18
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 17
- 238000005187 foaming Methods 0.000 claims description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 15
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 15
- 239000011737 fluorine Substances 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 15
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 15
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 14
- 150000002334 glycols Chemical class 0.000 claims description 14
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 12
- 239000002612 dispersion medium Substances 0.000 claims description 12
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- 239000001530 fumaric acid Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 239000006260 foam Substances 0.000 abstract description 47
- 230000006835 compression Effects 0.000 abstract description 10
- 238000007906 compression Methods 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000004615 ingredient Substances 0.000 abstract 3
- 239000004604 Blowing Agent Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 description 62
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 52
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 31
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000002253 acid Substances 0.000 description 22
- VGEREEWJJVICBM-UHFFFAOYSA-N phloretin Chemical compound C1=CC(O)=CC=C1CCC(=O)C1=C(O)C=C(O)C=C1O VGEREEWJJVICBM-UHFFFAOYSA-N 0.000 description 22
- 239000002994 raw material Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 19
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 18
- 125000002947 alkylene group Chemical group 0.000 description 18
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 16
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 238000009835 boiling Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 229920006305 unsaturated polyester Polymers 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 14
- 229920000728 polyester Polymers 0.000 description 14
- 150000001412 amines Chemical class 0.000 description 13
- 229910021529 ammonia Inorganic materials 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 239000012948 isocyanate Substances 0.000 description 13
- 125000001118 alkylidene group Chemical group 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 125000003368 amide group Chemical group 0.000 description 11
- 239000004202 carbamide Substances 0.000 description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 11
- 229920001451 polypropylene glycol Polymers 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- 150000008065 acid anhydrides Chemical class 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 10
- 230000006641 stabilisation Effects 0.000 description 10
- 238000011105 stabilization Methods 0.000 description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 9
- 235000011187 glycerol Nutrition 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 6
- 150000004985 diamines Chemical class 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 150000005826 halohydrocarbons Chemical class 0.000 description 6
- 150000002596 lactones Chemical class 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- 238000009423 ventilation Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- 229940051250 hexylene glycol Drugs 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 150000008442 polyphenolic compounds Chemical class 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 4
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- 101800000863 Galanin message-associated peptide Proteins 0.000 description 4
- 102100028501 Galanin peptides Human genes 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 229920000891 common polymer Polymers 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 229940059574 pentaerithrityl Drugs 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 229920000223 polyglycerol Polymers 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 4
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 3
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- RSJKGSCJYJTIGS-UHFFFAOYSA-N N-undecane Natural products CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 3
- 150000001718 carbodiimides Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
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- 238000013019 agitation Methods 0.000 description 1
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- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
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- 125000005263 alkylenediamine group Chemical group 0.000 description 1
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
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- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
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- 239000001273 butane Substances 0.000 description 1
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 description 1
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- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
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- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- JNWGOCSTXJQFEP-UHFFFAOYSA-N hexane-1,1,1,2-tetracarboxylic acid Chemical compound CCCCC(C(O)=O)C(C(O)=O)(C(O)=O)C(O)=O JNWGOCSTXJQFEP-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000004941 influx Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
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- 229960004232 linoleic acid Drugs 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- HOVAGTYPODGVJG-UHFFFAOYSA-N methyl beta-galactoside Natural products COC1OC(CO)C(O)C(O)C1O HOVAGTYPODGVJG-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000013518 molded foam Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 125000005574 norbornylene group Chemical group 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
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- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229940038597 peroxide anti-acne preparations for topical use Drugs 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N xylylenediamine group Chemical group C=1(C(=CC=CC1)CN)CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- 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
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- 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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a polymer polyol composition and preparation method thereof. The polymer polyol composition comprises a polyol (A) and, dispersed in (A), polymer particles (B) formed by polymerizing an ethylenically unsaturated compound (b) in a polyol, wherein the content of (B) is 35 to 75 wt.% based on (I) and the amount of a soluble polymer (P) which is dissolving in (A) is up to 5 wt.% based on (A); and a process for producing a foamed or unfoamed polyurethane resin which comprises reacting a polyol ingredient with a polyisocyanate ingredient in the presence or absence of a blowing agent, wherein the polymer polyol composition is used as at least part of the polyol ingredient. The polymer polyol composition has a low viscosity and excellent dispersion stability even when having a heightened polymer particle concentration. It is useful for efficiently producing a polyurethane resin excellent in 25% ILD (hardness) and compression set or a foam thereof.
Description
Technical field
The present invention relates to make polymer polyol composition and manufacture method thereof that urethane resin uses and the manufacture method of using urethane resin or its foams of resulting polymer polyatomic alcohol.
Background technology
In polyvalent alcohol, polymer composition that the ethene unsaturated polymerizable compound obtains and mixture generally are called polymer polyatomic alcohol, are widely used as the raw material of the urethane resin of urethane foam and polyurethane elastomer etc.
People are known, in order to produce the polymer polyatomic alcohol that to give urethane high rigidity, high elastic coefficient, polymer particle content in the polymer polyatomic alcohol is improved more, as the means of making such polymer polyatomic alcohol, be to make a part and coupler (silicon-containing compound, four alkoxyl group ortho-formiates, tri-alkoxy alkane chain hydrocarbon, the dialkoxy paraffinic hydrocarbons etc.) reaction of polyvalent alcohol and make the modified polyalcohol of polymer quantification exist following, make vinyl monomer polymeric method (for example, international open WO85/04891 communique); Containing in the presence of the macromonomer of ammonia ester bond, making vinyl monomer polymeric method (for example, Japanese kokai publication sho 61-115919 communique) etc.
But, problem is that the dispersion stabilization of resulting polymer polyol composition is poor, perhaps, when the urethane resin moulding, poor with the mixed performance of isocyanic ester, be difficult to handle etc., even polymer particle content height still is difficult to obtain the good polymer polyol composition of dispersion stabilization.
The inventor is in order to address the above problem, and that inquires into keen determination found that, below the specified quantitative, can obtain high quality urethane can be provided at certain by making oligomer, and low viscous polymer polyol composition is so finished the present invention.In addition, find also in the presence of specific dispersion agent that the polymer polyatomic alcohol that monomer polymerization is become is disperseed this polymer polyatomic alcohol with machinery, or is pulverized, and can obtain same polymer polyol composition, so finished the present invention.
Even the purpose of this invention is to provide a kind of raising polymer particle concentration, remain fabulous polymer polyatomic alcohol of low viscosity and dispersion stabilization and manufacture method thereof.Another purpose of the present invention provides a kind of, make the manufacture method of urethane resin or its foams with these polymer polyol compositions, with the production efficiency height, the polyurethane resin that 2 5% ILD (hardness) and compression set are good or the manufacture method of its foams.
Brief summary of the invention
That is to say that the present invention is as described below:
[the 1st invention] a kind of polymer polyol composition, said composition contain number-average molecular weight be more than 500 polyvalent alcohol (A) and in (A) dispersive polymer particle (B), and be in polyvalent alcohol, to make ethene unsaturated compound (b) polymerization form the polymer polyol composition (I) that (B) constituted, wherein, (b) be the ethene unsaturated compound (b1) more than a kind more than 500 by being selected from number-average molecular weight, aromatic hydrocarbons monomer (b2-1), unsaturated nitrile (b2-2), (methyl) esters of acrylic acid (b2-3), the monomer (b2-5) that contains polyfunctional vinyl, (methyl) acrylamide, the carboxylic acid and the derivative thereof that contain vinyl, the aliphatic hydrocarbon monomer, fluorine-containing vinyl monomer, nitrogenous vinyl monomer, the vinyl modified siloxane, the ethene unsaturated compound more than a kind of alkyl olefin(e) compound and cyclic olefin compound constitutes, and (b1) be selected from the ester of unsaturated carboxylic acid (p) and glycols (q) and the ester of unsaturated alcohol (r) and carboxylic acid (s)
(B) content is that benchmark is 35～75 quality % with the quality of (I), and the amount of dissolved soluble polymer (P) is that benchmark is below the 5 quality % in the quality of (A) in (A).
The polymer polyol composition of record in [the 2nd invention] the 1st invention, contain number-average molecular weight and be the polyvalent alcohol (A) or (A) and the dispersion medium that constitutes of thinner (C) more than 500, and in this dispersion medium dispersive polymer particle (B), wherein, (I) the viscosity V that is mPas at 25 ℃ of units that record with Brookfield type viscometer down is in the scope of following formula (1)
V≤(Va-Va×C/10)^〔e^x〕 (1)
In the formula, x=0.0010354 * Bp^1.5;
Va:(A) be the viscosity of mPas at 25 ℃ of units that record with Brookfield type viscometer;
C: the content of (C) among (I) that represents with quality %;
Bp: the content of (B) among (I) that represents with quality %;
^: expression power exponent;
E: the end of natural logarithm.
The polymer polyol composition of record in [the 3rd invention] the 1st invention or the 2nd invention, wherein, (I) content of in (B) is 45～75 quality %.
The polymer polyol composition of any one record in [the 4th invention] the 1st invention or the 2nd invention wherein, in (A), in the presence of dispersion agent (D) and/or the thinner (C) or not, is polymerized (b) that contain more than (b1) 5 quality %.
[the 5th invention] a kind of polymer polyol composition, said composition contain number-average molecular weight be more than 500 polyvalent alcohol (A) and in (A) dispersive polymer particle (B), and be in polyvalent alcohol, to make ethene unsaturated compound (b) polymerization form the polymer polyol composition (II) that (B) constitutes, wherein, (b) be the ethene unsaturated compound (b1) more than a kind more than 500 by being selected from number-average molecular weight, aromatic hydrocarbons monomer (b2-1), unsaturated nitrile (b2-2), (methyl) esters of acrylic acid (b2-3), (methyl) acrylamide, the carboxylic acid and the derivative thereof that contain vinyl, the aliphatic hydrocarbon monomer, fluorine-containing vinyl monomer, nitrogenous vinyl monomer, the vinyl modified siloxane, the ethene unsaturated compound more than a kind of alkyl olefin(e) compound and cyclic olefin compound constitutes, and (b1) be selected from the ester of unsaturated carboxylic acid (p) and glycols (q) and the ester of unsaturated alcohol (r) and carboxylic acid (s)
In (A), in the presence of dispersion agent (D),, (b) that contain more than (b1) 5 quality % is polymerized in thinner (C) existence or not.
The polymer polyol composition of record in [the 6th invention] the 4th invention, wherein, the molecular weight (X) of the two keys of (b1) each is below 1200.
The polymer polyol composition of record in [the 7th invention] the 1st invention, wherein, unsaturated carboxylic acid (p) is the carboxylic acid of selecting from toxilic acid, fumaric acid and methylene-succinic acid more than a kind.
The polymer polyol composition of any one record in [the 8th invention] the 1st invention or the 2nd invention, the polymer particle of separating from the polymer polyol composition that (b) polymerization is formed (B) is carried out mechanical dispersion form in (A), and the quality that (A) does not contain in (A) is the soluble polymer that benchmark surpasses 5 quality %.
[the 9th invention] a kind of polymer polyol composition (III), contain number-average molecular weight and be more than 500 polyvalent alcohol (A) and in (A) dispersive polymer particle (B), wherein, (B) be that ethene unsaturated compound (b) is in the dispersion medium that contains (A), the polymer particle that carries out the polymerization formation in the presence of dispersion agent (D ') carries out the polymer particle that mechanical dispersion or pulverizing form again, and, said dispersion agent (D ') has and the difference of (A) solubility parameter SPa is solubility parameter SPd below 0.8, (b) by being selected from aromatic hydrocarbons monomer (b2-1), unsaturated nitrile (b2-2), (methyl) esters of acrylic acid (b2-3), the monomer (b2-5) that contains polyfunctional vinyl, (methyl) acrylamide, the carboxylic acid and the derivative thereof that contain vinyl, the aliphatic hydrocarbon monomer, fluorine-containing vinyl monomer, nitrogenous vinyl monomer, the vinyl modified siloxane, the ethene unsaturated compound more than a kind of alkyl olefin(e) compound and cyclic olefin compound constitutes.
The manufacture method of [the 10th invention] a kind of polymer polyol composition, be in number-average molecular weight is polyvalent alcohol (A) more than 500, dispersion agent (D) and/or thinner (C) exist or not in the presence of, make the manufacture method of ethene unsaturated compound (b) polymeric polymer polyol composition, (b) be the ethene unsaturated compound (b1) more than a kind more than 500 by being selected from number-average molecular weight, aromatic hydrocarbons monomer (b2-1), unsaturated nitrile (b2-2), (methyl) esters of acrylic acid (b2-3), (methyl) acrylamide, the carboxylic acid and the derivative thereof that contain vinyl, the aliphatic hydrocarbon monomer, fluorine-containing vinyl monomer, nitrogenous vinyl monomer, the vinyl modified siloxane, the ethene unsaturated compound more than a kind of alkyl olefin(e) compound and cyclic olefin compound constitutes, and (b1) be selected from the ester of unsaturated carboxylic acid (p) and glycols (q) and the ester of unsaturated alcohol (r) and carboxylic acid (s)
Comprising, adopt (b) that contain 5 quality % (b1) at least, obtain the 1st invention described polymer polyol composition (I).
The manufacture method of [the 11st invention] a kind of polymer polyol composition, be in number-average molecular weight is polyvalent alcohol (A) more than 500, dispersion agent (D) and/or thinner (C) exist or not in the presence of, make the manufacture method of ethene unsaturated compound (b) polymeric polymer polyol composition, (b) be the ethene unsaturated compound (b1) more than a kind more than 500 by being selected from number-average molecular weight, aromatic hydrocarbons monomer (b2-1), unsaturated nitrile (b2-2), (methyl) esters of acrylic acid (b2-3), (methyl) acrylamide, the carboxylic acid and the derivative thereof that contain vinyl, the aliphatic hydrocarbon monomer, fluorine-containing vinyl monomer, nitrogenous vinyl monomer, the vinyl modified siloxane, the ethene unsaturated compound more than a kind of alkyl olefin(e) compound and cyclic olefin compound constitutes, and (b1) be selected from the ester of unsaturated carboxylic acid (p) and glycols (q) and the ester of unsaturated alcohol (r) and carboxylic acid (s)
Comprising, adopt (b) that contain 5 quality % (b1) at least, obtain the 5th invention described polymer polyol composition (II).
The manufacture method of the polymer polyol composition (I) of record in [the 12nd invention] a kind of the 1st invention, be contain number-average molecular weight be more than 500 polyvalent alcohol (A) and in (A) manufacture method of the polymer polyol composition of dispersive polymer particle (B), comprising, isolated polymer particle (B) from make the polymer polyol composition that ethene unsaturated compound (b) polymerization obtains polyvalent alcohol is carried out mechanical dispersion in (A), and the quality that (A) does not contain in (A) is the soluble polymer that benchmark surpasses 5 quality %, (b) by being selected from aromatic hydrocarbons monomer (b2-1), unsaturated nitrile (b2-2), (methyl) esters of acrylic acid (b2-3), the monomer (b2-5) that contains polyfunctional vinyl, (methyl) acrylamide, the carboxylic acid and the derivative thereof that contain vinyl, the aliphatic hydrocarbon monomer, fluorine-containing vinyl monomer, nitrogenous vinyl monomer, the vinyl modified siloxane, the ethene unsaturated compound more than a kind of alkyl olefin(e) compound and cyclic olefin compound constitutes.
The manufacture method of the polymer polyol composition (III) of record in [the 13rd invention] a kind of the 9th invention, comprising, in containing the dispersion medium that number-average molecular weight is the polyvalent alcohol (A) more than 500, in the presence of dispersion agent (D '), make the polymer particle in the polymer polyatomic alcohol that ethene unsaturated compound (b) is polymerized carry out mechanical dispersion or pulverizing again, and, said dispersion agent (D ') has and the difference of (A) solubility parameter SPa is solubility parameter SPd below 0.8, (b) by being selected from aromatic hydrocarbons monomer (b2-1), unsaturated nitrile (b2-2), (methyl) esters of acrylic acid (b2-3), the monomer (b2-5) that contains polyfunctional vinyl, (methyl) acrylamide, the carboxylic acid and the derivative thereof that contain vinyl, the aliphatic hydrocarbon monomer, fluorine-containing vinyl monomer, nitrogenous vinyl monomer, the vinyl modified siloxane, the ethene unsaturated compound more than a kind of alkyl olefin(e) compound and cyclic olefin compound constitutes.
The manufacture method of [the 14th invention] a kind of urethane resin, this method is that polyhydroxy reactant and polyisocyanates composition are being reacted in the presence of the whipping agent or not, the method of the urethane resin of making foaming or not foaming, comprising, adopt the polymer polyol composition of record in the 1st invention at least a portion as polyhydroxy reactant.
The manufacture method of [the 15th invention] a kind of urethane resin, this method is that polyhydroxy reactant and polyisocyanates composition are being reacted in the presence of the whipping agent or not, the method of the urethane resin of making foaming or not foaming, comprising, adopt the polymer polyol composition of record in the 5th invention at least a portion as polyhydroxy reactant.
The manufacture method of [the 16th invention] a kind of urethane resin, this method is that polyhydroxy reactant and polyisocyanates composition are being reacted in the presence of the whipping agent or not, the method of the urethane resin of making foaming or not foaming, comprising, adopt the polymer polyol composition of record in the 10th invention at least a portion as polyhydroxy reactant.
That invents is open in detail
In the 1st invention of the present invention, the content of dispersive polymer particle (B) is generally 35～75% (quality) among (A) in polymer polyol composition (I), and ideal is 45～75% (quality).When (B) content was less than 35% (quality), the occasion making urethane foam can not get sufficient foams compressive hardness.In addition, when surpassing 75% (quality), polymer particle cohesion, sedimentation, difficult treatment.
In addition, in this 1st invention, be dissolved in the amount of the soluble polymer (P) in the polyvalent alcohol (A) in (I), be as the criterion, below 5% (quality), it is desirable to below 3% (quality) with the quality of (A).When the amount of (P) surpassed 5% (quality), the viscosity of polymer polyol composition raise, difficult treatment, or produce the shortcoming of the hardness reduction etc. of the urethane foam that makes foaming.
Here, the so-called soluble polymer (P) that is dissolved in the polyvalent alcohol (A), being meant and removing the polymer particle (B) that is insoluble in (A) and (A) (comprise a spot of low molecular weight by-products) in addition material from polymer polyol composition (I), is than the high compound of common polyvalent alcohol (A) molecular weight.
The mensuration of soluble polymer (P) amount is undertaken by laxative remedy.
In 5g (I), add methyl alcohol 20g, put into the stainless steel tube of 100ml,, carry out centrifugation, make (B) aggegation, obtain the clarifying clear solution in upper strata with 18000rpm * 60 minute kind in 20 ℃ of temperature.After removing methyl alcohol with the drying under reduced pressure machine from this solution, isolate polyvalent alcohol (A) (containing a spot of low molecular weight by-products) and dissolve in the polymkeric substance (P) of (A) that [molecular weight is more than 4000 with the preparation liquid chromatography, in general chromatography, its peak appears at than the high side of (A) peak molecular weight], obtain from its mass ratio.(P) weight-average molecular weight (use gel permeation chromatography, be called for short GPC below) is generally 6000～30000, still, also comprise more high-molecular weight those.
Also have, soluble polymer (P) when can not be with the preparation liquid chromatography with itself and polyvalent alcohol (A) when separating (molecular weight eclipsed occasion), carries out centrifugation equally and makes (B) aggegation with above-mentioned, obtains the clarifying clear solution in upper strata.Use the drying under reduced pressure machine, remove methyl alcohol from this solution after, add ether, it is in addition dry to leach throw out, can isolate soluble polymer (P) from (A).
In the 2nd invention of the present invention, the content of the polymer particle (B) in the polymer polyol composition (I) is generally 35～75% (quality), and ideal is 45～75% (quality).When (B) content is less than 35% (quality), when making urethane foam, can not get sufficient foams compressive hardness.In addition, when greater than 75% (weight), operational difficulty is handled in polymer particle aggegation, sedimentation.
In addition, in this 2nd invention, polymer polyol composition (I), in 25 ℃, viscosity V (mPas) with Brookfield type viscometer records in the scope of following formula (1), it is desirable to satisfy following formula (2) and (3) two sides' the interior polymer polyol composition of scope usually.
V≤(Va-Va×C/10)^〔e^x〕 (1)
V≤(Va-Va×C/10)^〔e^y〕 (2)
V≥0.5×(Va-Va×C/10)^〔e^y〕 (3)
In the formula, x=0.0010354 * Bp^1.5
y＝0.0009514×Bp^1.5
Va:(A) at 25 ℃, the viscosity that records with Brookfield type viscometer
(mPa·s)；
C:(I) (C) content (quality %) in;
Bp:(I) (B) content (quality %) in;
^: expression power exponent;
E: the end of natural logarithm.In the formula, the mensuration of V and Va is undertaken by following condition.
Below the 1500mPas; Rotor NO.3,60rpm
1500～3000mPas; Rotor NO.3,30rpm
3000～8000mPas; Rotor NO.3,12rpm
8000～16000mPas; Rotor NO.3,6rpm
16000～40000mPas; Rotor NO.4,12rpm
40000～100000mPas; Rotor NO.4,6rpm
By satisfying the scope of following formula (1), the Combination that can be made into polymer polyol composition (I) and other raw materials is good, the polymer polyol composition that operability is also good.
In this 2nd invention, also available as required thinner (C) transfers to the viscosity of polymer polyol composition lower.As (C), can enumerate the internal olefin of 5～30 of carbonatomss such as hexene, octene, decene; The fire retardant of low viscosity (below 100mPas/25 ℃), for example, three (chloroethyl) phosphoric acid ester, three (chloropropyl) phosphoric acid ester etc.; And solvent, for example, toluene, aromatic solvents such as dimethylbenzene; Deng.
(I) (C) content in it is desirable to below 3% (quality), and better is below 2% (quality), it is desirable to especially below 1% (quality).
Preparation method as this 1st invention and/or the 2nd polymer polyol composition of inventing (I) for example, can enumerate, and following method (i) reaches (ii).
(i) [this 5th invention] is in polyvalent alcohol (A), dispersion agent (D) and/or thinner (C) exist or not in the presence of, make ethene unsaturated compound (b) polymerization, preparation is during polymer polyol composition, use be that to contain the ethene unsaturated compound (b1) of number-average molecular weight 500 or more be (b) more than 5% (quality).
(ii) [this 6th invention] is the polymer particle of separating in the polymer polyol composition that obtains from polymerization polyvalent alcohol (b) (B), in (A), carry out mechanical dispersion, and the amount of soluble polymer is no more than 5% (quality) of (A) quality (A), makes to contain polyvalent alcohol (A) and the polymer polyol composition of dispersive polymer particle (B) in (A).
Wherein, method (i) is an ideal.
The 3rd invention of the present invention is in the method for above-mentioned the 5th invention, dispersion agent (D) be as must with the polymer polyol composition (II) made of composition.As the content of soluble polymer (P), be as the criterion with the quality of (A), be ideal below 5% (quality), yet, also can be below 10% (quality).
Used polyvalent alcohol (A) in this 1st～the 3rd invention can use in the common polymer polyatomic alcohol manufacturing used.For example, can enumerate, at the compound (polyvalent alcohol, polyphenol, amine, poly carboxylic acid, phosphoric acid etc.) that contains 2 (it is desirable to 2～8) reactive hydrogen atoms at least compound (A1) and their mixture of alkylene oxide structure of having gone up addition.
Wherein, the compound of alkylene oxide that it is desirable on polyvalent alcohol addition.
As polyvalent alcohol, can enumerate 2 yuan of alcohol that carbonatoms is 2～12 (for example, ethylene glycol, glycol ether, propylene glycol, 1,3-or 1,4 one butyleneglycol, 1,6 one hexylene glycol, neopentyl glycol and cyclohexandiol); 3 yuan of alcohol that carbonatoms is 3～12 (for example, glycerine, TriMethylolPropane(TMP), trimethylolethane, triol and trolamine); 4～8 yuan of 5～18 of carbonatomss or high-grade alcohol (for example, tetramethylolmethane, methyl glucoside, sorbitan, Glycerol dimer, dipentaerythritol, Sorbitol Powder, mannitol, glucose, seminose, fructose and sucrose) more.
As polyphenol, can enumerate the monocycle polyhydroxy phenol, as pyrogallol, quinhydrones and Phloroglucinol monomethyl ether etc.; Bisphenols, for example dihydroxyphenyl propane, Bisphenol F and bisphenol sulphone etc.; Phenol, aldehyde polycondensate (novolak) etc.
As amine, can enumerate ammonia; As fatty amine, the alkanolamine that carbonatoms is 2～18 (for example, monoethanolamine, diethanolamine, Yi Bingchunan and amino ethyl ethanolamine), the alkyl amine of 1～20 of carbonatoms (for example, n-Butyl Amine 99 and octylame), the Alkylenediamine of 2～6 of carbonatomss (for example, quadrol, propylene diamine and hexamethylene-diamine), the polyalkylenepolyamines class (carbonatoms of alkylidene group from two alkylene triamine of 2～6 carbon atoms to six alkylidene groups, seven amine, for example, diethylenetriamine and Triethylenetetramine (TETA)).
In addition, aromatic series list that carbonatoms is 6～20 or polyamines class (for example, aniline, phenylenediamine, first phenylene diamines, xylylene diamines, methylene dianiline (MDA) and phenyl ether diamines); The ester ring type amine that carbonatoms is 4～15 (isophorone diamine, cyclohexylidene diamines and dicyclohexyl methyl hydride diamines); The heterocyclic amine that carbonatoms is 4～15 (for example, aminoethylpiperazine) etc.
As poly carboxylic acid, can enumerate aromatic multi-carboxy acid's (terephthalic acid, m-phthalic acid etc.) and their two or more mixtures of 8～18 of aliphaticpolycarboxylic acid (succsinic acid, hexanodioic acid, sebacic acid, pentanedioic acid and nonane diacid etc.), the carbonatomss of 4～18 of carbonatomss.
As the alkylene oxide that adds on the above-mentioned compound that contains reactive hydrogen, can enumerate, the ethylene oxide that carbonatoms is 2～8 (below be abbreviated as EO), third alkylene oxide (below be abbreviated as PO), fourth alkylene oxide (below be abbreviated as BO), styrene oxide (below be abbreviated as SO) etc., and their use (block addition and/or random addition) simultaneously more than 2 kinds.It is desirable to PO, or use (EO content is that 25% (quality) is following) PO and EO the time.
Object lesson as above-mentioned polyvalent alcohol, can enumerate, PO adds to the product on the above-mentioned compound that contains reactive hydrogen, and, the alkylene oxide of PO and other (below be abbreviated as AO) is the product of addition in the following manner, perhaps the carboxylate of their addition compound and poly carboxylic acid or phosphoric acid etc.
1. with the order block adduct (end capped) of PO-AO
2. with the order block adduct (equilibrated) of PO-AO-PO-AO
3. with the order block adduct of AO-PO-AO
4. with the order block adduct of PO-AO-PO (active two generation product)
5. the random affixture of PO and AO mixing addition
6. the order to put down in writing in No. 4226756 specification sheets of United States Patent (USP), the product of random addition or block addition.
As polyvalent alcohol (A), can use the polyvalent alcohol (A2) of the compound (A1) of addition alkylene oxide structure on the above-mentioned compound that contains reactive hydrogen with other.In this occasion, usage ratio (A1)/(A2) is generally 100/0～80/20 by its mass ratio.
As other polyvalent alcohol (A2), can enumerate the macromolecule polyols such as polyvalent alcohol of polyester polyol, modification, and, their mixture.
Can enumerate above-mentioned polyvalent alcohol (ethylene glycol, glycol ether, propylene glycol, 1 as polyester polyol, 3-or 1,4-butyleneglycol, 1, dibasic alcohol such as 6-hexylene glycol, neopentyl glycol or, the mixture of they and the alcohol more than 3 yuan or 3 yuan such as glycerine, TriMethylolPropane(TMP)) can form the condensation reaction thing of the derivative (for example, hexanodioic acid, sebacic acid, maleic anhydride, anhydride phthalic acid, dimethyl terephthalate (DMT) etc.) of ester with above-mentioned poly carboxylic acid or its acid anhydrides, lower member ester etc.; Its alkylene oxide (EO, PO etc.) addition reaction; The product that lactone (6-caprolactone etc.) ring-opening polymerization obtains etc.
As modified polyalcohol, can enumerate polydiene polyvalent alcohols such as polybutadiene polyol; The ethene polymers of hydroxyls such as acrylic acid or the like polyvalent alcohol; Castor-oil plant wet goods natural oils polyvalent alcohol; The modified product of natural oils polyvalent alcohol etc.
These macromolecule polyols normally have 2～8, it is desirable to 3～8 hydroxyls and have 200～4000 usually, it is desirable to 400～3000 hydroxyl equivalent.
The number-average molecular weight of polyvalent alcohol (A) (measure with GPC, following number-average molecular weight is also measured with this method), common more than 500, ideal is 500～20000, and special ideal is 1200～15000, and optimal is 2000～9000.When number-average molecular weight 500 was above, urethane foam was difficult for becoming fragile.In addition, when 20000 when following, viscosity is low, consider from the processing aspect of polymer polyatomic alcohol, and be ideal.
In this 6th invention, used polyvalent alcohol when making (b) polymerization make polymer particle (B) is also identical with the polyvalent alcohol of enumerating above (A).This polyvalent alcohol and (A) both can be identical also can be different.
As this 3rd invention and the used dispersion agent (D) of the 5th invention, be not particularly limited, can use the used general dispersion agent of polymer polyatomic alcohol.Can enumerate, for example, 1. contain the polyvalent alcohol of polyether glycol (for example, with reference to Japanese kokai publication hei 08-333508 communique) etc. of the modification of ethene unsaturated group and the macromole type dispersion agent of ethene unsaturated compound reaction; 2. the graft type dispersion agent that is combined to of polyvalent alcohol and oligopolymer, polyvalent alcohol wherein is to be that 2 above segments of the polyvalent alcohol affinity below 1.0 are as side chain with the difference with the solubility parameter of polyvalent alcohol, and with difference from the solubility parameter of the polymkeric substance of vinyl monomer be the segment of the polymer affinity below 2.0 as the polyvalent alcohol of the graft type polymkeric substance (for example, with reference to Japanese kokai publication hei 05-059134 communique) of main chain etc.; 3. high molecular weight polyols type dispersion agent, it is at least a portion and the methylene halide that makes in the polyvalent alcohol hydroxyl, and/or the reaction of dihalo-ethane, generates high-molecular weight modified polyalcohol (for example, with reference to Japanese kokai publication hei 07-196749 communique); 4. oligomeric dispersion agent, it is to use weight-average molecular weight 1000-30000, wherein at least a portion is the low polymer of ethylene that dissolves in the polyvalent alcohol, and (for example, with reference to the Japanese kokai publication hei 09-77968 communiques) such as dispersion agents such as polyether glycols that use the above-mentioned modification that contains the ethene unsaturated group 1..Wherein, it is desirable to 1. reach 4. type.In either case, number-average molecular weight (GPC method mensuration), 1000～10000 be ideal.
In addition, consumption (D) according to (b) quality, it is desirable to below 10% (quality), and better is below 5% (quality), it is desirable to 0.1～3% (quality) especially.
At the polymer polyol composition (I) that is used to prepare this 1st invention and/or the 2nd invention, and, in the method (i) of the polymer polyol composition (II) of the 3rd invention [this 5th invention], as ethene unsaturated compound (b), can use number-average molecular weight more than 500 ethene unsaturated compound (b1) and polymer polyol composition when making used usually number-average molecular weight less than 500 ethene unsaturated compound (b2), as (b2), can enumerate, aromatic hydrocarbon monomer ((b2-1), unsaturated nitrile ((b2-2), (methyl) esters of acrylic acid (b2-3), other ethene unsaturated compound (b2-4) and their mixtures more than 2 kinds.
The number-average molecular weight of the rare property of second unsaturated compound (b1) normally more than 500, it is desirable to more than 550, it is desirable to 800～10000 especially, it would be desirable 1000～10000.Because number-average molecular weight is more than 500, the soluble oligopolymer amount of polyvalent alcohol in the polymer polyatomic alcohol that uses their manufacturings is the least possible, is ideal.
Also have, the double key number of ethene unsaturated compound (b1) is at least on average getting final product more than 1.It is desirable to 1～500, better is 1～70.Because double key number on average more than 1, then can make the solvable composition of polyvalent alcohol few, can prevent that resulting polymer polyatomic alcohol viscosity from increasing.Therefore, the decline of the physical properties of the urethane resin of manufacturing in the time of can preventing to use them is ideal.
In addition, when 2 of double key numbers were above, the compound of unconjugated double bond was an ideal.
In addition, the molecular weight (X) of each (b1) two key normally below 1200, it is desirable to below 1150, and better is 100～1050.When being 1200 when following, use the minimizing effect of the polyvalent alcohol solubility oligopolymer in the polymer polyatomic alcohol of their manufacturings obvious, be ideal.
Here, the molecular weight (X) of the two keys of (b1) each defines according to following formula.
X＝1000/N
N: the degree of unsaturation of (b1) that the measuring method of stipulating among the employing JIS K-1557 records
Ethene unsaturated compound (b1), the compound that has ester bond, amido linkage, ammonia ester bond, urea bond and/or imide bond etc. in the molecule is an ideal.Wherein, it is desirable to ester bond/amido linkage and/or ammonia ester bond, it is desirable to ester bond especially, also have, also can mix existence at the above-mentioned 2 kinds of keys of same intramolecularly.
Ester bond can and contain the compound or the alkylene oxide reaction of hydroxyl by 1. carboxylic acid or acid anhydrides, perhaps, 2. can generate by the lactone ring-opening reaction; Amido linkage, 1. by carboxylic acid or acid anhydrides with contain amino compound reaction, or the 2. ring-opening reaction of lactone, or 3. the polycondensation of aminocarboxylic acid generates; Imide bond can form polyamic acid by the reaction of acid and diamines, then, generates with dehydration reaction.Ammonia ester bond or urea bond can generate by isocyanate compound and the compound reaction that reactive hydrogen is arranged.
As the example of the carboxylic acid that can generate ester bond and amido linkage, can enumerate, the unsaturated aliphatic monocarboxylic acid that carbonatoms is 3～24, for example, vinylformic acid, methacrylic acid, oleic acid and linolic acid; The unsaturated aliphatic dicarboxylic acid that carbonatoms is 4～24, for example, toxilic acid, fumaric acid, methylene-succinic acid and citraconic acid; The representative examples of saturated aliphatic poly carboxylic acid that carbonatoms is 2～24, for example, oxalic acid, propanedioic acid, succsinic acid, L-glutamic acid, hexanodioic acid, sebacic acid, hexane tricarboxylic acid and hexane tetracarboxylic acid; The aromatic multi-carboxy acid that carbonatoms is 8～24, for example, m-phthalic acid, terephthalic acid; The alicyclic ring shape dicarboxylic acid that carbonatoms is 7～24, for example, 1,4-cyclohexane diacid and tetrahydro-phthalein diacid; Unsaturated carboxylic acid (being total to) polymkeric substance [number-average molecular weight 1000～10000], for example, multipolymer, (methyl) vinylformic acid and the cinnamic multipolymer etc. of poly-(methyl) vinylformic acid, poly-methylene-succinic acid, (methyl) vinylformic acid and toxilic acid.The what is called here " (methyl) vinylformic acid ... ", mean " vinylformic acid ... " and/or " methacrylic acid ... "
As the acid anhydrides that can generate ester bond and amido linkage, can enumerate aliphatic carboxylic acid acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; Aromatic anhydrides such as anhydride phthalic acid.
As the compound of the hydroxyl that can generate ester bond, can enumerate, above-mentioned (A1) reaches (A2); Be shown in polyvalent alcohol and polyphenol in the compound that contains reactive hydrogen of polyvalent alcohol (A) in illustrating; The unsaturated alcohol that carbonatoms is 3～24 (r), for example, vinyl carbinol and vinylcarbinol; (gathering) oxyalkylene ether (2～8 of carbonatomss of alkylidene group of unsaturated alcohol (3～24 of carbonatomss), the polymerization degree: n=1～30, the polymerization degree n here, expression (gathering) oxyalkylene segmental polymerization degree), for example, (gathering) oxygen propylidene (n=1～30) monoallyl ether, and, the single propylene ether of (gathering) oxygen butylidene (n=1～20); Polyvinyl alcohol polyhydric alcohol polymers such as (saponification value 70～100, number-average molecular weights 1000～10000).As above-mentioned alkylene oxide, can enumerate the alkylene oxide of 2～8 of carbonatomss, for example, ethylene oxide, third alkylene oxide, fourth alkylene oxide and styrene oxide (below be abbreviated as SO) and their mixtures (block addition and/or random addition) more than 2 kinds etc.
Also have,, can enumerate the lactone of carbonatoms 5～12 as the example of the lactone that can generate ester bond, for example, caprolactone, oenantholacton, lauryl lactone and undecane lactone etc.
As the example of the compound that contains reactive hydrogen that can generate amido linkage, can enumerate at the amine in the active hydrogen compounds of containing shown in the explanation of polyvalent alcohol (A).
As the example of the lactan that can generate amido linkage, can enumerate hexanolactam, oenantholactam, laurolactam and the undecane lactan etc. of 5～12 of carbonatomss.
Example as the aminocarboxylic acid that can generate amido linkage, can enumerate the aminocarboxylic acid of 2～18 of carbonatomss, for example, amino acid, omega-amino-caproic acids such as glycine, L-Ala, Xie Ansuan, leucine, Isoleucine and phenylalanine, omega-amino-enanthic acid, omega-amino-are sad, omega-amino-n-nonanoic acid, omega-amino-capric acid, the amino undecanoic acid of 11-and 12 amino dodecanoic acid etc.
As the acid and the diamines that are used to generate imide bond, can use synthetic general used known acid and the diamines of polyimide resin.For example,, can use 3,4,3 ', 4 '-xenyl tetracarboxylic acid, 2,3, the aromatic tetracarboxylic acid that carbonatomss such as 3 ', 4 '-xenyl tetracarboxylic acid and pyromellitic acid are 10～20, the acid anhydrides that these are sour and these sour ester cpds as acid.Also have, as diamines, can enumerate 4,4 '-diamino-diphenyl ether, P-pHENYLENE dI AMINE, m-phenylenediamine and 4, the aromatic diamine that carbonatomss such as 4 '-diaminodiphenyl-methane are 6～18 etc.
Be used to generate the isocyanate compound of ammonia ester bond or urea bond, can use the synthetic general used known isocyanate compound of urethane resin.For example, 2,4-or 2,6-tolylene diisocyanate (TDI), thick product TDI, 2,4 '-or 4,4 '-diphenylmethanediisocyanate (MDI) and the thick thick product diaminodiphenyl-methane (condensation product of formaldehyde and aromatic amine, aniline or its mixture of product MDI{; The mixture of the polyamines that 3 functional groups of diaminodiphenyl-methane and a small amount of (for example, 5～20% (quality)) are above) phosgenation thing; Polyenoid propyl group polyisocyanates (PAPI) } etc. the aromatic polyisocyanate of 6～20 of carbonatomss (except the carbon atom in the NCO base, too) to following isocyanic ester; The aliphatic polyisocyante that carbonatoms such as hexamethylene diisocyanate and lysinediisocyanate is 2～18; Carbonatoms such as isophorone diisocyanate and dicyclohexyl methane diisocyanate 4-15 ester ring type polyisocyanates; The aromatic-aliphatic polyisocyanates that carbonatomss such as penylene dimethyl vulcabond are 8～15; The modifier of these polyisocyanates (containing modifier of urethano, carbodiimide-based, allophanate group, urea base, biuret groups, uretdion (ウ レ ト シ オ Application base), urea ketimide base (ウ レ ト Application ィ ミ Application base), isocyanuric acid ester group and/or oxazoline ketone group etc.); More than their mixtures more than 2 kinds.
Be used to generate the compound that contains reactive hydrogen of ammonia ester bond or urea bond, can use above-mentioned (A1), (A2) and polyvalent alcohol (A) compound that contains reactive hydrogen shown in illustrating.
In manufacture method of the present invention used (b1), ester bond, amido linkage, ammonia ester bond, urea bond or imide bond can obtain by known esterification, amidate action, ammonia esterification, urea reaction or the imidization reaction of common enforcement.
For example, ester bond or amido linkage are that carboxylic acid or acid anhydrides and the compound that contains reactive hydrogen are packed in the reactive tank with specified amount, generate by dehydration reaction in 50～250 ℃.Also have, also can be, add to depress and carry out dehydration reaction at decompression, normal pressure.In addition, also can make by the addition reaction of carboxylic acid or acid anhydrides and alkylene oxide.
The ratio [equivalence ratio] of the carbonyl of carboxylic acid or acid anhydrides and the active hydrogen atom of the compound that contains reactive hydrogen is generally 0.01/1～0.98/1, it is desirable to 0.1/1～0.8/1.
In above-mentioned esterification, amidate action, can use known esterifying catalyst.As this catalyzer, can enumerate antimony class catalyzer such as ANTIMONY TRIOXIDE SB 203 99.8 PCT; Tin class catalyzer such as Mono-n-butyltin; Titanium class catalyzer such as tetrabutyl titanate ester; Zirconium class catalyzer such as tetrabutyl zirconate; Acetic acid metallic salt catalyzer such as acetic acid zirconium and zinc acetate; The mixture of these catalyzer more than 2 kinds.Catalyst consumption, the compound that is generally carboxylic acid and contains reactive hydrogen adds up to 0.1～5% (quality) of quality.
Also have, amido linkage also can generate with the method beyond above-mentioned, promptly the specified amount of lactan is packed in the reactive tank, passes through ring-opening reaction in 50～250 ℃, or the specified amount of the aminocarboxylic acid reactive tank of packing into, generates by polycondensation in 50～250 ℃.
Imide bond, can be by adopting organic polar solvents such as N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N, N-dimethyl sulfoxide (DMSO), in 60～130 ℃, make acid and diamine reactant, synthesizing amide acid, then, it in 60～400 ℃ of dehydrations, is generated imide bond.In order to promote imidization reaction, can add catalyzer.As the object lesson of catalyzer, can enumerate basic cpds such as triethylamine and glyoxal ethyline etc.The amount of catalyzer is generally 0.01～5% (quality) that acid and diamines add up to quality
Ammonia ester bond or urea bond isocyanate compound and have the specified amount of the compound of reactive hydrogen to put into reactive tank, make its reaction in 25～150 ℃.Isocyanate index [equivalence ratio * 100 of (NCO base/contain the base of reactive hydrogen atom)] is generally 80～140, it is desirable to 85～120, and special ideal is 95～115.
When carrying out the ammonia esterification,, can use normally used catalyzer in the polyurethane reaction in order to promote reaction.For example, can enumerate amines catalysts such as triethylenediamine, N-ethylmorpholine; Tin class catalyzer such as stannous octoate, dibutyl tin two lauryls; Other metal catalysts such as lead octoate 36.The amount of catalyzer is generally 0.001～5% (quality) of isocyanate compound and active hydrogen compounds quality.
In manufacture method of the present invention, the object lesson of ethene unsaturated compound (b1) is as follows.
The example that has 1 two key as intramolecularly, can enumerate, unsaturated aliphatic dicarboxylic acid (4～24 of the carbonatomss) diester of Fatty Alcohol(C12-C14 and C12-C18) (1～24 of carbonatoms) (gathering) oxyalkylene (2～8 of the carbonatomss of alkylidene group) ether, for example, the maleic acid diester of polyoxytrimethylene (n=4～30) monomethyl ether, the methylene-succinic acid diester of the dimethyl ester of polyoxytrimethylene (n=3～30) single-butyl ether and the random affixture of butanols polyoxybutylene (n=2～20) polyoxyethylene (n=2～10); Fatty Alcohol(C12-C14 and C12-C18) (1～24 of carbonatoms) polyoxy alkylidene (2～8 of the carbonatomss of alkylidene group) ether (methyl) acrylate, for example, polyoxytrimethylene [n=8 (7)～30] monomethyl ether methacrylic ester (in the formula, the numerical value when the interior numerical value of () of n is methacrylic ester.Below same).Polyoxybutylene [n=6 (5)～20] single-butyl ether (methyl) acrylate and polyoxytrimethylene (n=5～30) single bay ethers (methyl) acrylate; Polyoxy alkylidene (2～8 of the carbonatomss of the alkylidene group) ether of unsaturated alcohol (3～24 of carbonatomss), for example, the single oleyl ether of polyoxytrimethylene (n=4～30), polyoxytrimethylene (n=8～30) mono allyl ether; Unsaturated aliphatic monocarboxylic acid (3～24 of carbonatomss) polyoxy alkylidene (2～8 of alkylidene group carbonatomss) ester, for example, the random affixture of oleic acid oxidation propylene (n=2～30) ethylene oxide (n=2～10) of number-average molecular weight more than 500 etc.
The example that has 2 two keys as intramolecularly, can enumerate polyalkylene (2～8 of the carbonatomss of alkylidene group) ethylene glycol bisthioglycolate (methyl) acrylate, for example, polypropylene glycol [n=7 (6)～30] two (methyl) acrylate and polytetramethylene glycol [n=6 (5)～20] two (methyl) acrylate; Aliphatic carboxylic acid (2～24 of the carbonatomss) diester of unsaturated alcohol (3～24 of carbonatomss), for example, the succinic diester of polyoxytrimethylene (n=3～30) mono allyl ether, the succinic diester of the di adipate of polyoxytrimethylene (n=3～30) mono allyl ether, the single propylene ether of polyoxytrimethylene (n=3～30) etc.
The example that 3 two keys are arranged as intramolecularly, can enumerate unsaturated fatty acids (3～24 of carbonatomss) three esters of 3 yuan of alcohol of 3～12 of carbonatomss, for example, three (methyl) acrylate of glycerol polyoxytrimethylene [n=5 (4)～30] ether, three (methyl) acrylate of TriMethylolPropane(TMP) polyoxytrimethylene [n=4 (3)～30] ether, three (methyl) acrylate of tetramethylolmethane polyoxytrimethylene [n=4 (3)～30] ether, three (methyl) acrylate of two glycerol polyoxytrimethylenes (n=3～30) ether and sorbitan polyoxybutylene [n=3 (2)～20] three (methyl) acrylate; Aliphatic carboxylic acid (3～24 of carbonatomss) three esters of unsaturated alcohol (3～24 of carbonatomss), for example, hexane tricarboxylic acid three esters of vinyl carbinol (gathering) propylene oxide (n=1～30) ether; The ether compound that contains unsaturated alkyl, for example, three allyl ethers of glycerol polyoxytrimethylene (n=5～30) ether etc.
The example that two keys more than 4 are arranged as intramolecularly, can enumerate polynary (4～8 yuan, or more polynary) pure unsaturated fatty acids (3～24 of carbonatomss) polyester, for example, poly-(methyl) acrylate of the polyglycerol (n=3～4) of number-average molecular weight more than 500, the polyglycerol (n=2～4) of number-average molecular weight more than 500 gathers oleic acid ester, the Dipentaerythritol of number-average molecular weight more than 500 gathers (methyl) acrylate, polyglycerol (n=2～4) (gather) propylene oxide (n=1～30) of number-average molecular weight more than 500 gathers (methyl) acrylate, four (methyl) acrylate of tetramethylolmethane polyoxytrimethylene [n=3 (2)～30] ether, four (methyl) acrylate of sorbitan polyoxybutylene (n=2～20) ether; Polyvinyl alcohol (saponification value 70～100, number-average molecular weight 1000～10000) (methyl) acrylate; The polycarboxylate (number-average molecular weight 1000～10000) of unsaturated alcohol (3～24 of carbonatomss), the polyester (number-average molecular weight 1000～10000) of hexane tetracarboxylic ester, (methyl) acrylate copolymer and the vinyl carbinol of vinyl carbinol (gathering) propylene oxide (n=1～30) ether for example, the polyester of toxilic acid polymkeric substance and allyl alcohol (number-average molecular weight 1000～10000); The ether compound that contains unsaturated alkyl, for example, the four glycerol polyallyl ethers of number-average molecular weight more than 500, the polyallyl ether of polyglycerol (n=2～4) (gather) propylene oxide (n=1～30) ether of number-average molecular weight more than 500; The polyester (number-average molecular weight 500～10000) of unsaturated carboxylic acid (carbonatoms 4～22) and glycols, for example, the polyester of toxilic acid and ethylene glycol (number-average molecular weight 500～10000), the polyester of toxilic acid and glycol ether (number-average molecular weight 500～10000), the polyester of toxilic acid and propylene glycol (number-average molecular weight 500～10000), toxilic acid and 1,3-or 1, the polyester of 4-butyleneglycol (number-average molecular weight 500～10000), the polyester of methylene-succinic acid and ethylene glycol (number-average molecular weight 500～10000), the polyester of methylene-succinic acid and glycol ether (number-average molecular weight 500～10000), the polyester (number-average molecular weight 500～10000) of toxilic acid and polyoxy propylene glycol (n=1～30), the polyester (number-average molecular weight 500～10000) of the polyester (number-average molecular weight 500～10000) of methylene-succinic acid and polyoxy propylene glycol (n=1～30) and fumaric acid and polyoxy butyleneglycol (n=1～20); Deng.
Wherein, by the ester cpds of unsaturated carboxylic acid (p) and glycols (q) formation and/or the ester cpds that is made of unsaturated alcohol (r) and carboxylic acid (s) is ideal, and the free-radical polymerised compound that is made of unsaturated carboxylic acid (p) and glycols (q) is special ideal.Unsaturated carboxylic acid (p) is that intramolecularly has two keys (when two key is arranged more than 2, be unconjugated double bond) the carboxylic acid or derivatives thereof, for example, the carboxylic acid of 3～24 of carbonatomss such as vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, pyrocitric acid and oleic acid; Acid anhydrides such as maleic anhydride, itaconic anhydride and pyrocitric acid acid anhydride etc.It is desirable to the carboxylic acid or derivatives thereof of selection more than a kind from toxilic acid, fumaric acid and methylene-succinic acid.
Except that above-mentioned, as required, also can and use with other carboxylic acids.As other carboxylic acids, can enumerate, for example the aliphatic carboxylic acid of 2～24 of carbonatomss such as acetic acid, propionic acid, caproic acid, stearic acid, oxalic acid, propanedioic acid, succsinic acid, L-glutamic acid, hexanodioic acid and sebacic acid; The aromatic carboxylic acid that carbonatoms such as m-phthalic acid and terephthalic acid is 7～18; 1, the alicyclic ring shape carboxylic acid that carbonatomss such as 4-cyclohexane dicarboxylic acid and tetrahydrochysene phthalandione are 6～20 etc.
As glycols (q), can use polyvalent alcohol and polyphenol in the compound that contains reactive hydrogen that above-mentioned polyvalent alcohol (A) provides in illustrating, and, the alkylene oxide that above-mentioned carbonatoms is 2～8.It is desirable to ethylene glycol, glycol ether, polyoxyethylene glycol, propylene glycol, polyoxy propylene glycol, 1,3-or 1,4-butyleneglycol, 1, aklylene glycol and alkylene oxides such as EO, PO, BO and SO such as 6-hexylene glycol, neopentyl glycol, better is ethylene glycol, glycol ether, 1,4-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, EO and PO.
As above-mentioned aromatic hydrocarbons monomer (b2-1), can enumerate vinylbenzene, alpha-methyl styrene, hydroxy styrenes, chlorostyrene etc.
(b2-2) can enumerate vinyl cyanide, methacrylonitrile etc. as unsaturated nitrile.
((b2-3) can enumerate (methyl) methyl acrylate as (methyl) esters of acrylic acid, (methyl) butyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) vinylformic acid undecane ester, (methyl) vinylformic acid dodecane ester, (methyl) vinylformic acid tridecane ester, (methyl) vinylformic acid tetradecane ester, (methyl) vinylformic acid pentadecane ester, (methyl) vinylformic acid n-Hexadecane ester, (methyl) vinylformic acid octadecane ester, (methyl) alkyl-acrylates (1～24 of the carbonatoms of alkyl) such as (methyl) vinylformic acid eicosane ester and (methyl) vinylformic acid docosane ester; Hydroxyl polyoxy alkylidene list (methyl) esters of acrylic acid etc.
As other ethene unsaturated compound (b2-4), can enumerate (methyl) acrylamide; (methyl) vinylformic acid etc. contains the carboxylic acid and the derivative thereof of vinyl; Aliphatic hydrocarbon such as ethene, propylene monomer; Fluorine-containing vinyl monomers such as perfluoro capryl ethyl-methyl acrylate, perfluoro capryl ethyl propylene acid esters; Nitrogenous vinyl monomers such as diamino ethyl methacrylic ester, morpholino ethyl-methyl acrylate; The siloxanes of ethene modification; Alkyl olefin(e) compounds such as alpha-olefin, β-alkene, polyisobutene; Cyclic olefin compounds such as norbornylene, cyclopentadiene, norbornadiene etc.
Wherein, (b2-1) reaching (b2-2) is ideal, and vinylbenzene and/or vinyl cyanide are better.
As in order to obtain the manufacture method of (I), adopting under the situation of above-mentioned (i) method, (b1) is more than 5% (quality) of total consumption of (b) usually, it is desirable to more than 10% (quality), special ideal is 15～99% (quality), and optimal is 20～80% (quality).
By (b1) consumption is reached more than 5% (quality), can prevent that the viscosity of resulting polymer polyatomic alcohol from raising, be ideal.
In the manufacturing of this 1st invention or the 2nd polymer polyol composition of inventing, as used ethene unsaturated compound (b) in the additive method beyond basis the 5th invention of above-mentioned (i), has 1 energy polymeric vinyl at least, when polymer polyol composition was made, normally used had above-mentioned (b2-1), (b2-2), (b2-3), (b2-4), and their mixtures more than 2 kinds.
Wherein, (b2-1), and (b2-2) be ideal, vinylbenzene and/or vinyl cyanide are better.
In the additive method beyond (i) method in the used ethene unsaturated compound, aromatic hydrocarbon monomer (b2-1), unsaturated nitrile (b2-2), (methyl) esters of acrylic acid (b2-3) and other ethene unsaturated compounds (b2-4), mass ratio to (b) total consumption, can be according to the physical properties change of desired urethane, be not particularly limited, shown in one is for example following.
(b2-1): be generally 0～100% (quality), ideal is 20～80% (quality)
(b2-2): be generally 0～95% (quality), ideal is 20～80% (quality)
(b2-3): be generally 0～50% (quality), ideal is 0～20% (quality)
(b2-4): be generally 0～10% (quality), ideal is 0～5% (quality)
Also have, with the method beyond this 5th invention, in the occasion of making polymer polyatomic alcohol (I), contain the monomer (b2-5) of the polyfunctional group vinyl that (it is desirable to 2～8 functional groups) more than 2 functional groups as at least a portion (ideal is 0.05～1% (quality)) of (b) by use, can improve polymer strength more.As the monomer that contains the polyfunctional group vinyl, can enumerate Vinylstyrene, ethylene glycol bisthioglycolate (methyl) acrylate, polyalkylene (2～8 of the carbonatomss of alkylidene group) glycol two (methyl) acrylate, pentaerythritol triallyl ether, trimethylolpropane tris (methyl) acrylate etc.
As the polymerization process of (b), can enumerate radical polymerization, coordinated anionic polymerization, metathesis polymerization, diels-alder (Dieles-Alder) polymerization etc., yet radical polymerization is ideal.
The polymerization of free-radical polymerised compound can similarly be carried out with the polymerization in original polymer polyatomic alcohol.For example, can adopt in the polyvalent alcohol that contains dispersion agent (D) (A), in the presence of polymerization starter, make ethene unsaturated compound (b) carry out polymeric method (method of record among No. 3383351 specification sheets of United States Patent (USP) etc.).
The also available continous way of the both available intermittent type of polymerization is carried out, can be under normal pressure, add depress or reduce pressure under carry out polymerization.As required, can use solvent and chain-transfer agent.
As radical polymerization initiator, can adopt the initiator that can generate free radical and initiated polymerization, for example, 2,2 '-azobisisobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (cyclohexyl-1-ア Le ボ nitrile), 2,2 '-azo two (2,4,4-trimethylpentane), dimethyl 2,2 '-azo two (2 Methylpropionic acid ester), 2,2 '-azo two [2-(methylol) propionitrile] and 1,1 '-azo two azo-compounds such as (1-acetoxyl groups-1-diphenylphosphino ethane); Organo-peroxides such as dibenzoyl superoxide, dicumyl peroxide, two (4-tert-butylcyclohexyl) peroxy dicarbonate, benzoyl peroxide, lauroyl superoxide and mistake succsinic acid; Inorganic peroxide such as persulphate and perborate etc.Also have, these can use more than 2 kinds together.
The consumption of radical polymerization initiator is generally 0.05～20% (quality) of (b) consumption, and ideal is 0.1～15% (quality), and special ideal is 0.2～10% (quality).The consumption of polymerization starter is in 0.05～20% (quality) scope the time, and (b) percent polymerization in the polymer polyatomic alcohol reaches very high, also has, molecular weight also becomes greatly, so, when urethane foam is made, can obtain sufficient foams compressive hardness, be good.
As solvent, can enumerate toluene, dimethylbenzene, acetonitrile, vinyl acetic monomer, hexane, heptane, octene, nonene, decene, diox, N, dinethylformamide, N,N-dimethylacetamide, Virahol and propyl carbinol etc.The amount of solvent is generally 0～50% (quality) of (b) consumption.
As chain-transfer agent, can enumerate, for example alkyl sulfide such as lauryl mercaptan and mercaptoethanol alcohols; Alcohols such as Virahol, methyl alcohol, 2-butanols and vinyl carbinol; Halohydrocarbon such as tetracol phenixin, carbon tetrabromide and chloroform etc.
The consumption of chain-transfer agent is generally 0～2% (quality) of (b) consumption.
In the non-free radical polymerization, as the example of polymerization starter, can enumerate, in coordinated anionic polymerization, can enumerate initiator by periodictable I, II, III family various metal Organoalkyl compound and the IV～VII family metal-salt constitutes.In addition, in metathesis polymerization, adopt by WCl
6And MoCl
5The initiator that constitutes with organoaluminum.
In order to obtain polymer polyol composition (I), isolated polymer particle (B) from polyvalent alcohol, make the resulting polymer polyol composition of (b) polymerization, the aforesaid method of mechanical dispersion (ii) in [this 6th invention] in addition in not containing (A) of soluble polymer, polymer particle (B), it is ethene polymers, the perhaps polymer particle that makes with polycondensation, addition reaction is generally the particle of 0.1～50 μ m.Use is from polyvalent alcohol, in the presence of polymerization starter, make in the common polymer polyatomic alcohol of ethene unsaturated compound (b) polymerization formation, as required, add solvent, make its settlement separate polymeric microsphere that obtains as polymer particle (B) with centrifuge separator.In addition, also can use letex polymerization and the produced polymer particles of suspension polymerization by the known polymer particle manufacture method of people.
As (B), from process operations this some consideration easily, the particle that (b) polymerization is made is an ideal.
In the method for (11) [this 6th invention],, can enumerate, for example varsols such as toluene, dimethylbenzene, hexane, heptane, octene, nonene, decene as the solvent that uses as required; Alcoholic solvents such as methyl alcohol, Virahol, propyl carbinol; Diox, acetonitrile, N, non-proton property polar solvents such as dinethylformamide, N,N-dimethylacetamide.
As the polymer polyatomic alcohol after the polyreaction, can add solvent as required, carry out polymkeric substance that centrifugation obtains and in polyvalent alcohol (A), carry out the device of mechanical redispersion, so long as utilize the principle of impacting, shaking, cutting off, dispersion or broken device all can be adopted, and no matter its mechanism, structure and material.
One of dispersion machine that uses as the present invention or crusher example can adopt the liquid pressurization, by the impact to metallic walls (shell), makes that liquid is pulverized, dispersive dispersion machine (homogenizing device, A.P.V.GAURIN society makes).
The 4th invention of the present invention is polymer polyol composition (III), and, the 7th invention is the manufacture method of above-mentioned (III), said composition is to contain polyvalent alcohol (A) and dispersive polymer particle (B) constitutes in (A) polymer polyol composition, wherein, (B) be in the dispersion medium that contains (A) formation, have with the difference of (A) solubility parameter SPa in the presence of the dispersion agent of the solubility parameter SPd below 0.8 (D '), make polymer particle that ethene unsaturated compound (b) polymerization the obtains particle that forms of mechanical dispersion or pulverizing in addition again.
In this 4th invention, as dispersion medium, both can use above-mentioned polyvalent alcohol (A) separately, also can be that (A) and organic solvent use together.
As used organic solvent, can enumerate those identical solvents with the illustrated use that goes out of above-mentioned the 6th invention.
Organic solvent content in the dispersion medium is arbitrarily, yet normally 0～80% (quality) it is desirable to 1～50% (quality).
As the used dispersion agent of this 4th invention (D '), the absolute value of difference of solubility parameter SPa that must select to have solubility parameter SPd and polyvalent alcohol it is desirable to the dispersion agent below 0.6 usually below 0.8.Become below 0.8 by the absolute value that makes the solubility parameter difference, then the dispersion stabilization of polymer polyatomic alcohol improves, and can prevent the cohesion and the sedimentation of polymer particle, is ideal.
Here said solubility parameter can be represented with the following square root that condenses the ratio of energy density and molecular volume.
[solubility parameter]=(Δ E/V)
1/2
The Δ B here represents that cohesion can density, represents molecular volume with V, and this value is calculated by people (Robert FFedoors) such as Robert Ai Fufei Dares, is published in " polymer engineering and science " the 14th volume, on 151～154 pages.Enumerate representational dissolving resin degree parameter below, as the value of polyvinyls be: polystyrene=10.6, polyacrylonitrile=14.4, polymethylmethacrylate=9.9; Value as polyethers: polyoxyethylene glycol=9.4, polypropylene glycol=8.7; As polyolefinic value: polyethylene=8.6, polypropylene=8.0; Value as polyester: polyethylene terephthalate=12.4, polybutylene terephthalate=11.7; Value as polymeric amide: nylon-6=11.9, nylon 66=11.9.Other resin also can calculate by the value of each chemical bond of putting down in writing in the combination table.For example, the value of polyimide, from 1,2,4,5-pyromellitic acid and 1 when the 4-diaminobenzene calculates, is 19.6; The value of urethane from 1, when 4-butyleneglycol and diphenylmethanediisocyanate calculate, is 12.3.But because the difference or the resin end-group structure of microtexture, actual value may have more or less different with calculated value.
As dispersion agent of the present invention (D '), as long as can satisfy the condition of above-mentioned SP value, also can with the identical material of above-mentioned dispersion agent (D).
As one of dispersion agent (D ') example, the compound that polypropylene glycol and glycidyl methacrylate reaction obtain, the solubility parameter SPd of the compound of above-mentioned record is 8.8, the difference of the SPa with polyethers (A) during for polypropylene glycol is 0.1.
As the ethene unsaturated compound (b) in this 4th invention, can be taken to rare 1 energy polymeric vinyl, when polymer polyatomic alcohol is made used known ethene unsaturated compound.Concrete can enumerate (b2-1), (b2-2), (b2-3), (b2-4) and the mixture more than 2 kinds in them.
Wherein, (b2-1) reaching (b2-2) is ideal, and vinylbenzene and/or vinyl cyanide are better.
They can be according to the changes such as physical properties of desired urethane to the mass ratio of (b) total amount, and there is no particular limitation, yet, shown in one is for example following.
(b2-1): be generally 0～100% (quality), ideal is 20～80% (quality)
(b2-2): be generally 0～95% (quality), ideal is 20～80% (quality)
(b2-3): be generally 0～50% (quality), ideal is 0～20% (quality)
(b2-4): be generally 0～10% (quality), ideal is 0～5% (quality)
Also have, by adopting the above-mentioned polyfunctional group vinyl monomer (b2-5) that contains (ideal is 2～8 functional groups) of 2 above functional groups that contains some (ideal is 0.05～1% (quality)) in (b) at least, can further improve polymer strength.
The polymer polyatomic alcohol of this 4th invention, even the polymer particle content height in the polymer polyatomic alcohol also remains low viscosity, this is its characteristics, and common polymer particle content is 30～75% (quality), ideal is 40～70% (quality), and ideal is 45-60% (quality) more.If polymer particle content reaches 30% (quality) when above, can obtain sufficient foams compressive hardness, be ideal.In addition, becoming below 75% (quality) by making polymer particle content, then can prevent cohesion, the sedimentation of polymer particle, can obtain the good polymer polyatomic alcohol of processing characteristics, is ideal.
In this 4th invention, the polymer polyatomic alcohol polymerization is in the presence of dispersion agent (D '), similarly carries out polymerization with the polymerization process of above-mentioned common polymer polyatomic alcohol.
In this 4th invention,, can adopt above-mentioned radical polymerization initiator used in the 1st invention and the 2nd invention etc. as the used polymerization starter of polymer polyatomic alcohol polymerization.
The consumption of above-mentioned radical polymerization initiator is generally 0.05～10% (quality) of ethene unsaturated compound (b) quality, and ideal is 0.1～5% (quality), and better is 0.2～2.5% (quality).Reach more than 0.05% (quality) by the consumption that makes polymerization starter, can prevent the decline of (b) percent polymerization, the polymer particle content that is made of (b) in the polymer polyatomic alcohol can reach enough height.In addition, when its content reaches (quality) below 10%, can prevent that the molecular weight of polymer particle from reducing, can obtain having the urethane foam of sufficient foams compressive hardness, be ideal.
In addition, as required, can be at chain-transfer agent, alkyl sulfide such as lauryl mercaptan, mercaptoethanol alcohols for example; Alcohols such as Virahol, methyl alcohol, 2-butanols, vinyl carbinol; Halohydrocarbon such as tetracol phenixin, carbon tetrabromide, chloroform carry out polymerization under existing.
In this 4th invention, polymer polyatomic alcohol (III), be in the polymer polyatomic alcohol that polymerization is obtained the dispersive polymer particle in addition the mechanical dispersion or the mechanical disintegration of physics obtain.Under this occasion, polymkeric substance (B) particle is not separated from polymer polyatomic alcohol, and the polymer particle that contains in the polymer polyatomic alcohol (B) is remained untouched, and uses mechanical means that polymer particle (B) is disperseed again.For example, 1. polymer polyatomic alcohol is delivered to dispersion machine or crusher from reactive tank.2. after delivering to the interim storage groove from polymerization tank, deliver to the method for dispersion machine or crusher again.
Disperse, broken principle is to utilize to impact and vibrations, or shearing action utilizes these principles to disperse or the device pulverized gets final product so long as adopt, and regardless of its mechanism, structure and material.One of dispersion machine that uses among the present invention or crusher example can be enumerated by to liquid pressurization, impacts housing, makes that liquid is torn, dispersive dispersion machine (homogenizer; A.P.V.GAURIN society makes).
The particle diameter of the polymer particle (B) in the polymerization terminated polymer polyatomic alcohol, normally below the 3 μ m, it is desirable to below the 2 μ m, yet, the polymer polyatomic alcohol that contains this polymer particle (B) is dropped into dispersion machine or crusher, force to disperse, pulverize, make polymer particle (B) miniaturization, then obtain polymer polyatomic alcohol (III).The particle diameter of the polymer particle after dispersion, the fragmentation normally below the 1 μ m, it is desirable to 0.5 μ m following [mensuration of particle diameter adopts scattering of light formula size-grade distribution meter, LA-700 (the hole field makes manufacturing)].
Temperature after dispersion, the fragmentation is in 0 ℃～100 ℃ scope, and ideal is 5 ℃～50 ℃.In addition, when making polymer particle (B) in the polymer polyatomic alcohol carry out mechanical dispersion or Mechanical Crushing, as required, also useable solvents dilution.As solvent, can use in above-mentioned dispersion medium, can use as the illustrative material of solvent with (A).The mechanical dispersion of polymer polyatomic alcohol or the number of times of break process are generally 1～20 time, and ideal is 2～10 times.Also have the solvent after the dispersion treatment, the removal of can reducing pressure.
Remove condition, (for example, under the decompression degree 20～30mmHg), carry out for 60～100 ℃ in temperature, residual quantity of solvent is with respect to polymer polyatomic alcohol, and ideal is below the 50ppm in normal pressure or decompression.
The 4th invention is, polymer particle content in the polymer polyatomic alcohol is generally 30～75% (quality), the viscosity of the polymer polyatomic alcohol that polyreaction obtains is 2000～100000mPas (25 ℃), and, after the polyreaction, because carry out the mechanical dispersion or the mechanical disintegration of physics, the result makes gained viscosity reach 500～20000mPas (25 ℃).
In the 4th invention, the viscosity of polymer polyatomic alcohol (III), also the content according to polymer particle changes, but is generally 500～20000mPas (25 ℃), and ideal is 700～15000mPas (25 ℃).The viscosity of polymer polyatomic alcohol (III) is when 20000mPas (25 ℃) is following, can obtain the good polymer polyatomic alcohol of processing property, and the viscosity of polymer polyatomic alcohol (III) reaches 500mPas (25 ℃) when above, can obtain the good urethane foam of foams compressive hardness, be ideal.
In the manufacture method of the 5th invention, the 6th invention and the 7th invention, the 5th invention and the 6th invention are ideal, and the manufacture method of the 5th invention is an ideal more.
The 8th invention of the present invention is to adopt any polymer polyol composition of the 1st invention～the 4 invention to make the manufacture method of urethane resin as at least a portion of polyhydroxy reactant.
Polyhydroxy reactant and isocyanate prepolymer composition, its reaction is made in the method for urethane resin, at this moment, except that the polymer polyol composition that adopts method for making of the present invention to obtain, can also use together with other the known compound that contains reactive hydrogen atom as required.As other the compound that contains reactive hydrogen atom, other macromolecule polyols (T) of common usefulness in the time of can using urethane to make, contain the low molecular compound (U) of reactive hydrogen atom.
Macromolecule polyol (T) as other can use polyether glycol, polyester polyol, modified polyalcohol; And their mixture.
As polyether glycol, can enumerate with above-mentioned polyvalent alcohol (A1) a joint in the same polyether glycol enumerated.
As polyester polyol, can enumerate above-mentioned polyvalent alcohol (ethylene glycol, glycol ether, propylene glycol, 1,3-or 1,4-butyleneglycol, 1, dibasic alcohol such as 6-hexylene glycol, neopentyl glycol, perhaps 3 yuan of they and glycerol, TriMethylolPropane(TMP)s etc. or more the mixture of polybasic alcohol and above-mentioned polyprotonic acid or its acid anhydrides, lower member ester etc. can form the condensation reaction thing of the derivative (for example, hexanodioic acid, sebacic acid, maleic anhydride, anhydride phthalic acid, dimethyl terephthalate (DMT) etc.) of ester; Its alkylene oxide (EO, PO etc.) addition reaction; The product that lactone (6-caprolactone etc.) ring-opening polymerization obtains etc.
As the polyvalent alcohol of modification, also can use the polyvalent alcohol of polydiene polyvalent alcohol (polybutadiene polyol etc.), acrylic acid or the like polyvalent alcohol and castor-oil plant wet goods natural oils polyvalent alcohol, its modification etc.
These other polyvalent alcohol has 2～8 usually, 3～8 hydroxyls of ideal and have 200～4000 usually, the hydroxyl equivalent of ideal 400～3000.
It is desirable to polyether glycol especially.
The compound (U) that contains the activity hydrogen atom as low molecule, can enumerate (2～3 of the ideal that have 2 at least, 2 of special ideal) reactive hydrogen atom (hydroxyl, amino, sulfydryl etc., it is desirable to hydroxyl) the compound of molecular weight (ideal is 60～400) below 500, for example, low molecular polylol, amino alcohol.
As low molecular polylol, can enumerate ethylene glycol, glycol ether, propylene glycol, dipropylene glycol, 1,2 yuan of alcohol such as 4-butyleneglycol, neopentyl glycol, hexylene glycol; 3～8 yuan of glycerol, TriMethylolPropane(TMP), tetramethylolmethane, Glycerol dimer, α-Jia Jiputanggan, Sorbitol Powder, Xylitol, mannitol, dipentaerythritol, glucose, fructose and sucrose etc. or polybasic polyvalent alcohol more; The polyvalent alcohol alkylene oxide affixture (polyoxyethylene glycol, polypropylene glycol etc.) of lower molecular weight (for example, molecular weight 200～400); Low-molecular-weight diol class with ring texture, for example, the propylene oxide adduct of dihydroxyphenyl propane etc.
As amino alcohol, can enumerate single or double-stranded alkanol amine (monoethanolamine, diethanolamine, single Propanolamine etc.).
Wherein, it is desirable to low molecular polylol, 2 yuan of alcohol particularly, concrete is ethylene glycol, 1,4-butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, and their mixtures more than 2 kinds.
Polyhydroxy reactant in urethane manufacture method of this 8th invention all (Z) [polymer polyol composition (I), (II), (III) and, as required, the amount of the polymer polyol composition (T) and/or (U)], ideal is more than 5% (quality), better is more than 10% (quality), and special ideal is more than 20% (quality).When the amount of polymer polyol composition is 5% (quality) when above, the compressive hardness of the foams during as urethane foam is easy to obtain.The content of (B) in the polyhydroxy reactant all (Z), ideal is 5～75% (quality), better is 7～55% (quality).
In addition, content (T) it is desirable to 0～95% (quality), and better is 0～80% (quality).When (T) content is 95% (quality) when following, be easy to obtain the compressive hardness of foams.
And content (U) it is desirable to 0～30% (quality), and better is 0～10% (quality).When the content of (U) when 30% (quality) is following, the heating temp during reaction can be not too high, therefore, do not worry scorching can take place.
When making urethane resin, as used organic multiple isocyanate, can use making so far always use in the urethane resin known those.As such polyisocyanates, can enumerate, the aromatic polyisocyanate that carbonatoms (except the carbon atom in the NCO base) is 6～20 (for example, 2,4-and/or 2,6-toluene support vulcabond (TDI)), thick TDI, 2,4 ' and/or 4,4 '-diphenylmethanediisocyanate (MDI), the diaminodiphenyl-methane that thick MDI[is thick formaldehyde and aromatic amine (aniline) or with the condensation product of its mixture: the mixture of the polyamines that 3 functional groups of diaminodiphenyl-methane and a small amount of (for example 5～20% (quality)) are above } the phosgenation product: polyene propyl group polyisocyanates (PAPI) etc.]; The aliphatic polyisocyante that carbonatoms is 2～18 (for example, hexamethylene diisocyanate, lysinediisocyanate etc.); The ester ring type polyisocyanates that carbonatoms is 4～15 (for example, isophorone diisocyanate, dicyclohexyl methane diisocyanate); The aromatic-aliphatic polyisocyanates that carbonatoms is 8～15 (for example, xylylene vulcabond etc.); And, the modifier of these polyisocyanates (containing urethano, carbodiimide-based, allophanate group, urea base, biuret groups, uretdion, uride imide, isocyanuric acid ester group or oxazolidine ketone group etc.); And, their mixtures more than 2 kinds.
Wherein, it is desirable to 2,4-and 2,6-TDI, their mixture of isomers, thick TDI; 4,4 '-and 2,4 '-MDI, their mixture of isomers, PAPI; And, contain urethano, carbodiimide-based, allophanate group, urea base, biuret groups, contain the modified polyisocyanate class of isocyanuric acid ester group from these polyisocyanates deutero-.
When making urethane resin, isocyanate index [equivalence ratio * 100 of (NCO/ contains the group of reactive hydrogen atom)] is generally 80～140, and ideal is 85～120, and special ideal is 95～115.In addition, significantly improve (for example, 300～1000) from above-mentioned scope, also can in urethane, import many tricarbimides ester group for making isocyanate index.
When making urethane resin,, also can use normally used catalyzer in the polyurethane reaction in order to promote reaction.For example can enumerate amines catalyst (3 grades of amine such as Triethylene Diamine, N-ethylmorpholine), tin class catalyzer (stannous octoate, dibutyltin dilaurate etc.), other metal catalysts (lead octoate 36 etc.).Wherein, amines catalyst and/or tin class catalyzer are ideal.The amount of catalyzer, according to the quality of reaction mixture, ideal is 0.001～5% (quality).
Adopt the method for this 8th invention, as required, can in the presence of whipping agent, react.
As whipping agent, at least a kind that can select among the halohydrocarbon of hydrogen atoms, water, low boiling hydrocarbon, the Liquid carbon dioxide etc. as whipping agent.
As the object lesson of the halohydrocarbon of hydrogen atoms, can enumerate:
HCFC (hydrochlorofluorocarazeotropic) type (for example, HCFC-123, HCFC-141b, HCFC-22 and HCFC-142b);
HFC (hydrogen fluorine carbon) type (for example, HFC-134a, HFC-152a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa and HFC-365mcf) etc.
Wherein it is desirable to HCFC-141b, HFC-134a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, HFC-365mcf and their mixtures more than 2 kinds.
Low boiling hydrocarbon can be enumerated the hydrocarbon that boiling point is generally-5～70 ℃, and its object lesson has butane, pentane, pentamethylene and their mixture.
When employing contained the halogenated hydrocarbon compound of hydrogen atom, its consumption was no more than 50 parts (quality) usually to polyhydroxy reactant all (Z) 100 parts (quality), and ideal is 5～45 parts (quality).
When adopting low boiling hydrocarbon, its consumption is no more than 45 parts (quality) usually to (Z) 100 parts (quality), and ideal is 5～40 parts (quality).
When adopting liquefied carbon dioxide, its consumption is no more than 30 parts (quality) usually to (Z) 100 parts (quality), and ideal is 5～25 parts (quality).
When the halohydrocarbon of hydrogen atoms and water use together, the halohydrocarbon consumption of hydrogen atoms is to (Z) 100 parts (quality), usually be no more than 45 parts (quality), ideal is 5～40 parts (quality), the consumption of water is to (Z) 100 parts (quality), usually be no more than 10 parts (quality), ideal is 0.5～8 part (quality).
The occasion of using together at low boiling hydrocarbon and water, the consumption of low boiling hydrocarbon is to (Z) 100 parts (quality), usually be no more than 40 parts (quality), ideal is 2～35 parts (quality), the consumption of water is to (Z) 100 parts (quality), usually be no more than 10 parts (quality), ideal is 0.5～8 part (quality).
Occasion in liquefied carbon dioxide and water and usefulness, the amount of liquefied carbon dioxide be per 100 parts (quality) (Z), usually be no more than 25 parts (quality), preferably 01～20 part (quality), the consumption of water be per 100 parts (quality) (Z), usually be no more than 10 parts (quality), preferably 0.5～8 part (quality).
The occasion of only independent water in whipping agent, the consumption of water is generally 0.1～30 part (quality) to (Z) 100 parts (quality), and ideal is 1～20 part (quality).
In the method for this 8th invention, as required, can also use following foams stablizer and other additives, also can in the presence of it, react.
For example, foams stablizer (dimethyl silica alkanes, polyether-modified dimethyl silica alkanes etc.), tinting material (dyestuff, pigment, carbon black etc.), softening agent (phthalate, adipic acid ester etc.), organic filler (synthetic staple, hollow bead that constitutes by thermoplasticity or thermosetting resin etc.), fire retardant (phosphoric acid ester, the halogenated phosphate class, the melamine class, phosphazene derivative class etc.), antiaging agent (connects triazole species, benzophenone etc.), antioxidant (Hinered phenols, hindered amines etc.), internal mold release, under known auxiliary material such as sterilant exists reaction is carried out.
To polyvalent alcohol all (Z) 100 parts (quality), the consumption of these additives that relate to is, foams stablizer, ideal are below 10 parts (quality), and better is 0.5～5 part (quality); Tinting material, ideal is below 1 part (quality).Softening agent, ideal are below 10 parts (quality), and be better below 5 parts (quality); Organic filler, ideal are below 50 parts (quality), and better is below 30 parts (quality); Fire retardant, ideal are below 20 parts (quality), and better is below 5～15 parts (quality); Antiaging agent, ideal are below 1 part (quality), and better is 0.01～0.5 part of (quality) antioxidant, below preferred 1 part (quality), more preferably 0.01～0.5 part (quality).
The manufacturing of urethane resin can adopt usual method to carry out, for example, and a step foaming, semi-prepolymer method [urethane foam method for making], known method such as prepolymer method.
When urethane resin is made, can adopt used manufacturing installation usually.Under solvent-free situation, for example, can adopt devices such as kneader or forcing machine.For example, in closed or open mold, can carry out the manufacturing of the various urethane resins that do not foam or foam.The manufacturing of urethane resin is adopted common low pressure or highly compressed mechanism to make raw material mix to react and is made.And the gases such as air of sneaking into when air that dissolves in (especially before raw material mixes), the raw material before and after raw material mixes or mixing are removed with vacuum method, also can carry out the manufacturing of urethane resin.
The polymer polyatomic alcohol that obtains with manufacture method of the present invention is to making soft molded foam body body and slab foam body body is useful especially.And also be suitable for the moulding of RIM (reaction injection moulding) method.
Embodiment
Be described more specifically the present invention below by embodiment, and the present invention is not limited.Also have, following " part " " % " reaches " ratio " and represents that respectively " mass fraction ", " quality % " reach " mass ratio ".
The raw material that uses in embodiment and the comparative example is formed, shown in symbol etc. are following.
(1) polyvalent alcohol (A)
G50: the average resulting number average molecule of 50 moles of PO of addition on glycerol
The polyvalent alcohol of amount 3000, hydroxyl value 55, its viscosity is 500mPas
(25℃)。
(2) contain the carboxylic acid (p) of reactive unsaturated group
MA: maleic anhydride
IA: itaconic anhydride
(3) saturated carboxylic acid
AA: hexanodioic acid
FA: phthalandione
(4) glycols (q)
EG: ethylene glycol
DEG: glycol ether
PP-200: polyoxypropyleneglycol (number-average molecular weight 200)
PP-400: polyoxypropyleneglycol (number-average molecular weight 400)
PO: propylene oxide (propylene oxide)
(5) other ethene unsaturated compounds (b2)
ACN: vinyl cyanide
St: vinylbenzene
(6) dispersion agent (D)
GMAP: the methacrylic acid of polypropylene glycol (number-average molecular weight 3000) shrinks sweet
The grease affixture
SAN: vinyl cyanide/vinylbenzene=80/20 quality % multipolymer (number-average molecular weight
5000)
(7) polymerization starter
AVN:2,2 '-azo two (2, the 4-methyl pentane nitrile)
(8) organic multiple isocyanate
TDI-80: " ミ リ オ ネ-ト (Millionate) T-80 " [Japan
Polyurethane industrial (strain) is made]
(9) catalyzer
Catalyst A: " ネ オ ス Application (Neostann) U-28 " [(stannous octoate)
Day east changes into (strain) and makes]
Catalyst B: DABCO (Triethylene Diamine) [Japanese emulsifying agent (strain) manufacturing]
Catalyzer C:DABCO33LV (the dipropylene glycol of DABCO 33% (quality)
Solution) [three エ ア プ ロ ダ Network ト (strain) manufacturings altogether]
TBT: tetrabutyl titanate
(10) foams stablizer
" F-242T ": polyether silicone polymkeric substance [SHIN-ETSU HANTOTAI's siloxanes (strain) manufacturing]
In addition, number-average molecular weight, degree of unsaturation, viscosity, polyvalent alcohol soluble polymer, dispersion stabilization are measured by laxative remedy.
＜number-average molecular weight 〉
The instrument type; HLC-8120GPC (liquid chromatograph that eastern ソ-Co., Ltd. makes)
Post: the TSK gel, super, H4000
+ TSK gel, super, H3000
+ tsk gel, super, H2000
(being eastern Application-Co., Ltd. makes)
Column temperature: 40 ℃
Detector: RI (specific refractory power)
Solvent: tetrahydrofuran (THF)
Flow velocity: 0.6ml/ branch
Sample concentration: 0.25% (quality)
Injection rate: 10 μ l
Standard: polystyrene
(eastern ソ-Co., Ltd. makes; The TSK polystyrene standard)
＜degree of unsaturation 〉
Assay method by JIS K-1557 regulation is measured.
＜viscosity 〉
Instrument type: BL type viscometer (manufacturing of TOKIMEC society)
Measure temperature: 25 ℃
Rotor No:No.3 or No.4
Rotation number: the explanation according to viscometric formula (1) decides above-mentioned rotation number
＜polyvalent alcohol soluble polymer 〉
The polyvalent alcohol soluble polymer is measured as stated above.Yet preparation form and aspect chromatogram adopts following condition:
Instrument type: LC-09 (Japanese analytical industry Co., Ltd. make)
Post: JAIGEL-1H
+JAIGEL-2H
+JAIGEL-3H
(be Japanese analytical industry Co., Ltd. make)
Column temperature: 40 ℃
Detector: RI
Solvent: chloroform
Flow velocity: 2.5ml/ branch
Sample concentration: 0.25% (quality)
Injection rate: 4ml * 12 time
＜dispersion stabilization 〉
1. the polymer polyatomic alcohol of putting into 140ml glass encloses container, in 50 ℃ of thermostatic baths, placed 30 days.
2. after placing, the Visual Confirmation dispersion stabilization.
Judgement criteria
Zero no sediment, homodisperse state
△ has sediment, after sample bottle is put upside down 5 times, and even redispersion
* have sediment, sample bottle to put upside down 5 times after, even redispersion
＜Production Example l〉manufacturing-1 of free-radical polymerised compound
In the 1 liter of four-hole boiling flask that has ジ system-ロ ト (Dimroth) prolong and デ ィ-Application ス -Network (Dean-Stark) collector, put into MA:98 part, PP-400:440 part, behind nitrogen replacement, (before the reaction terminating) is warming up to 80 ℃ while stirring in nitrogen atmosphere, keeps 1 hour.Then, be warmed up to 170 ℃, under this temperature, make reaction 6 hours.Then, add 0.02 part of TBT,, obtain the unsaturated polyester (b1 1.) of number-average molecular weight 5400, hydroxyl value 21mgKOH/g, degree of unsaturation 1.86 (X=538) in 170 ℃ of reactions 2 hours.Also have, the definition of X is the same, represents the molecular weight of each two key.
＜Production Example 2〉manufacturing-2 of free-radical polymerised compound
Adopt the same device and method of Production Example 1,, make the unsaturated polyester (b1 2.) of number-average molecular weight 1094, hydroxyl value 103mgKOH/g, degree of unsaturation 2.74 (X=365) with MA:294 part, PEG-200:800 part.
＜Production Example 3〉manufacturing-3 of free-radical polymerised compound
Adopt the same device and method of Production Example 1,, make the unsaturated polyester (b1 3.) of number-average molecular weight 3400, hydroxyl value 33mgKOH/g, degree of unsaturation 2.96 (X=338) with MA:98 part, PP-200:240 part.
＜Production Example 4〉manufacturing-4 of free-radical polymerised compound
Adopt the same device and method of Production Example 1,, make the unsaturated polyester (b1 4.) of number-average molecular weight 5600, hydroxyl value 20mgKOH/g, degree of unsaturation 1.79 (X=559) with IA:118 part, PP-400:440 part.
＜Production Example 5〉manufacturing-5 of free-radical polymerised compound
Put into 0.11 part of MA:98 part, PP-400:400 part, FA:296 part, N-ethylmorpholine in the compressive reaction device of 1.5 liters of capacity, behind nitrogen replacement, (before the reaction terminating) kept 2 hours while stir and be warming up to 120 ℃ in nitrogen atmosphere.Then, in 120 ℃, pressure 0.3mPas injected 232 parts of PO through 6 hours.Then, reacted again 2 hours in 120 ℃.Make the unsaturated polyester (b1 5.) of number-average molecular weight 1100, hydroxyl value 102mgKOH/g, degree of unsaturation 0.98 (X=1020).
＜Production Example 6〉manufacturing-6 of free-radical polymerised compound
Adopt the same device and method of Production Example 1,, make the unsaturated polyester (b1 6.) of number-average molecular weight 1000, hydroxyl value 112mgKOH/g, degree of unsaturation 4.34 (X=230) with MA:280 part, DEG:370 part.
＜Production Example 7〉manufacturing-7 of free-radical polymerised compound
Adopt the same device and method of Production Example 1,, make the unsaturated polyester (b1 7.) of number-average molecular weight 920, hydroxyl value 122mgKOH/g, degree of unsaturation 5.49 (X=182) with MA:390 part, EG:284 part.
＜embodiment 1〉manufacturing-1 of polymer polyatomic alcohol
In the four-hole boiling flask of 1 liter of the capacity that has the Dimroth prolong, put into SAN:10 part and G50:440 part, behind nitrogen replacement, (polymerization stop before) is while stir and be warming up to 130 ℃ in nitrogen atmosphere, then, unsaturated polyester (b1 1.): 250 parts; With, AN:150 part, St:100 part is raw materials mixed in addition in advance, and, the raw material that G50:50 part and AVN:1 part are pre-mixed, drip continuously simultaneously through 1 hour with the dropping liquid pump respectively, make polymerization 2 hours in 130 ℃, make the polymer polyatomic alcohol (F-1) of polymer particle content 50%, hydroxyl value 28mgKOH/g, viscosity 4500mPas (25 ℃).
＜embodiment 2〉manufacturing-2 of polymer polyatomic alcohol
In the four-hole boiling flask of 1 liter of the capacity that has the Dimroth prolong, put into SAN:10 part and G50:390 part, behind nitrogen replacement, (polymerization stops preceding) is warming up to 130 ℃ while stirring in nitrogen atmosphere, then, unsaturated polyester (b1 2.): 200 parts and AN:150 part, St:200 part is raw materials mixed in addition in advance, and, G50:50 part and AVN:1 part raw materials mixed in addition in advance, drip continuously simultaneously through 1 hour with the dropping liquid pump respectively, make polymerization 2 hours in 130 ℃, make polymer particle content 55%, hydroxyl value 25mgKOH/g, the polymer polyatomic alcohol (F-2) of viscosity 4800mPas (25 ℃).
＜embodiment 3〉manufacturing-3 of polymer polyatomic alcohol
Be to put into SAN:10 part and G50:490 part in 1 liter the four-hole boiling flask toward the volume that has the Dimroth prolong, behind nitrogen replacement, (polymerization stops preceding) is warming up to 130 ℃ while stirring in nitrogen atmosphere, then, unsaturated polyester (b 3.): 50 parts and AN:200 part, St:200 part is raw materials mixed in addition in advance, and the raw material that G50:50 part and AVN:1 part are pre-mixed, drip continuously simultaneously through 1 hour with the dropping liquid pump respectively, make polymerization 2 hours in 130 ℃, make polymer particle content 45%, hydroxyl value 31mgKOH/g, the polymer polyatomic alcohol (F-3) of viscosity 4000mPas (25 ℃).
＜embodiment 4〉manufacturing-4 of polymer polyatomic alcohol
In the four-hole boiling flask of 1 liter of the capacity that has the Dimroth prolong, put into SAN:10 part and G50:340 part, behind nitrogen replacement, (polymerization stops preceding) is warming up to 130 ℃ while stirring in nitrogen atmosphere, then, unsaturated polyester (b1 4.): 400 parts and AN:100 part, St:100 part is raw materials mixed in addition in advance, and, the raw material that G50:50 part and AVN:1 part are pre-mixed, drip continuously through 1 hour with the dropping liquid pump simultaneously respectively, make polymerization 2 hours in 130 ℃, make polymer particle content 60%, hydroxyl value 22mgKOH/g, the polymer polyatomic alcohol (F-4) of viscosity 6200mPas (25 ℃).
＜embodiment 5〉manufacturing-5 of polymer polyatomic alcohol
In the four-hole boiling flask of 1 liter of the capacity that has the Dimroth prolong, put into SAN:10 part and G50:440 part, behind nitrogen replacement, (polymerization stops preceding) is warming up to 130 ℃ while stirring in nitrogen atmosphere, then, unsaturated polyester (b1 4.): 250 parts and AN:150 part, St:100 part is raw materials mixed in addition in advance, and, the raw material that G50:50 part and AVN:1 part are pre-mixed, dripped continuously through 1 hour in 130 ℃ with the dropping liquid pump simultaneously respectively and made polymerization 2 hours, make polymer particle content 50%, hydroxyl value 28mg/KOH/g, the polymer polyatomic alcohol (F-5) of viscosity 4700mPas (25 ℃).
＜embodiment 6〉manufacturing-6 of polymer polyatomic alcohol
Be to put into SAN:10 part and G50:440 part in 1 liter the four-hole boiling flask toward the volume that has the Dimroth prolong, behind nitrogen replacement, (polymerization stops preceding) is warming up to 130 ℃ while stirring in nitrogen atmosphere, then, unsaturated polyester (b1 5.): 250 parts and AN:150 part, St:100 part is raw materials mixed in addition in advance, and the raw material that is pre-mixed of G50:50 part and AVN:1 part, drip continuously through 1 hour with the dropping liquid pump simultaneously respectively, in 130 ℃ make the reaction 2 hours, make polymer particle content 50%, hydroxyl value 28mgKOH/g, the polymer polyatomic alcohol (F-6) of viscosity 4900mPas (25 ℃).
＜embodiment 7〉manufacturing-7 of polymer polyatomic alcohol
Be to put into unsaturated polyester (b1 6.) in 1 liter the four-hole boiling flask toward the volume that has the Dimroth prolong: 500 parts, behind nitrogen replacement, (polymerization stops preceding) is warming up to 130 ℃ while stirring in nitrogen atmosphere, the raw material input of blended SAN:50 part and G50:400 part in addition in advance, stirred 3 hours then in 130 ℃.Then with the dropping liquid pump G50:50 part and AVN:1 part in advance in addition raw materials mixed dripped continuously through 1 hour, made polymerization 2 hours in 130 ℃, make polymer particle content 50%, hydroxyl value 28mgKOH/g, the polymer polyatomic alcohol (F-7) of viscosity 5500mPas (25 ℃).
＜embodiment 8〉manufacturing-8 of polymer polyatomic alcohol
With device and method similarly to Example 7, adopt (b1 is 7.) to replace unsaturated polyester (b1 is 6.), make the polymer polyatomic alcohol (F-8) of polymer particle content 50%, hydroxyl value 28mgKOH/g, viscosity 5640mPas (25 ℃).
＜embodiment 9〉manufacturing-9 of polymer polyatomic alcohol
In the four-hole boiling flask of 2 liters of capacity that have thermoswitch, vacuum stirring blade, dropping liquid pump, reliever, Dimroth prolong, nitrogen influx and spout, put into G50:50 part, be heated to 125 ℃ under stirring, then, with the dropping liquid pump St:450 part, ACN:300 part, GMAP:20 part, G50:680 part, AVN:4 part in advance in addition raw materials mixed dripped continuously through 4 hours, make its polymerization.Then, unreacted monomer is removed in decompression.
Make the polymer polyatomic alcohol (F-9) of the relatively usefulness of polymer particle content 50%, hydroxyl value 28, viscosity 20000mPas (25 ℃).
Toward should (F-9) adding 2000 parts of methyl alcohol in 800 parts, with 8000rpm * 60 minute centrifugation 3 times, the polymkeric substance methanol wash after the separation is carried out drying in 30～40 ℃, obtains 350 parts in polymkeric substance.Again this polymkeric substance is pulverized with mortar and add G50:350 part, methyl alcohol makes dispersion liquid for 1400 parts.And device inside has check valve (ホ モ バ Le Block), can change the homogenizer (model 15M-8TA) of A.P.V.GAURIN company manufacturing of the pressurization degree of liquid with ram pump, and this dispersion liquid is carried out dispersion treatment 2 times repeatedly.The dispersion treatment condition is dispersive pressure 700kgf/cm
2, 25 ℃ of processing speed 60kg/hr, treatment temp.
After the dispersion treatment, methyl alcohol is removed in decompression, and the viscosity that has obtained the polymer polyatomic alcohol (F-10) that makes with method for making of the present invention is 5000mPas (25 ℃).
＜embodiment 10〉manufacturing-10 of polymer polyatomic alcohol
The polymer polyatomic alcohol that obtains among the embodiment 9 (F-9) is put into inside have check valve, and can change homogenizer (model 15M-8TA) the device inside of the A.P.V.GAURIN company manufacturing of liquid pressurization degree with ram pump, repeating dispersion is handled 2 times.The dispersion treatment condition is dispersive pressure 700kgf/cm
2, processing speed 60kg/hr, 2 minutes treatment times, 25 ℃ of treatment temps.After the dispersion treatment, the viscosity of resulting polymer polyatomic alcohol (F-11) is 9760mPas (25 ℃).
＜comparative example 1〉the comparison Production Example-1 of polymer polyatomic alcohol
With the product of handling without mechanical dispersion that obtains among the embodiment 9 polymer polyatomic alcohol (F-9) as a comparison.
＜comparative example 2〉the comparison Production Example-2 of polymer polyatomic alcohol
Used same device and method when making (F-9) with embodiment 9, with G50:150 part and St:280 part, AN:120 part, GMAP:8 part, G50:442 part and AVN:1.6 part, make the comparative polymers polyvalent alcohol (F-12) of polymer particle content 40%, hydroxyl value 33mgKOH/g, viscosity 5540mPas (25 ℃).
＜comparative example 3〉the comparison Production Example-3 of polymer polyatomic alcohol
Adopt and make (F-9) same device and method among the embodiment 9, use G50:175 part, St:210 part, AN:90 part, GMAP:6 part, G50:519 part and AVN:1.2 part, make the comparative polymers polyvalent alcohol (F-13) of polymer particle content 30%, hydroxyl value 39mgKOH/g, viscosity 2000mPas (25 ℃).
＜embodiment (1)～(11) and comparative example 1～3〉manufacturing of urethane foam
The polymer polyatomic alcohol of the present invention (F-1～F-8, F-10,11) and the comparative polymers polyvalent alcohol (F-9, F-12,13) that use embodiment 1～10 and comparative example 1～3 to make, proportioning with table 1,2 urethane foams of putting down in writing, foaming formulation below adopting is made urethane foam.
The physical properties evaluation result of these foams is shown in table 1, table 2.
＜foaming formulation 〉
1. polymer polyatomic alcohol and organic multiple isocyanate are adjusted temperature respectively at 25 ± 2 ℃.
2. successively polymer polyatomic alcohol, foams stablizer, water, catalyzer, put into the stainless steel beaker of 1 liter of capacity successively, mix in room temperature (25 ± 2 ℃), add organic multiple isocyanate immediately, with stirrer (homogenizer: special machineization (strain) system, agitation condition: 2000rpm * 6 second), stirred, foamed.
3. stir stop after, materials inside is put into the wooden case of 25 * 25 * 10cm, make urethane foam.
Table 1
| Embodiment | ||||||||
| (1) | (2) | (3) | (4) | (5) | (6) | (7) | (8) | |
| Polymer polyatomic alcohol | F-1 | F-2 | F-3 | F-4 | F-5 | F-6 | F-7 | F-8 |
| Polymer particle concentration [quality %] | 50 | 55 | 45 | 60 | 50 | 50 | 50 | 50 |
| Hydroxyl value [mgKOH/g] | 28 | 25 | 31 | 22 | 28 | 28 | 28 | 28 |
| Viscosity (25 ℃) [mPas] | 4500 | 4800 | 4000 | 6200 | 4700 | 4900 | 5500 | 5640 |
| The viscosity upper limit in the formula (1) (25 ℃) [mPas] | 7800 | 13100 | 4900 | 23300 | 7800 | 7800 | 7800 | 7800 |
| Polyvalent alcohol soluble polymer [quality %] | 2 | 1 | 1 | 2 | 2 | 2 | 5 | 5 |
| Dispersion stabilization | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Urethane foam (proportioning, part) | ||||||||
| Polymer polyatomic alcohol | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Water | 2.7 | 2.7 | 2.7 | 2.7 | 2.7 | 2.7 | 2.7 | 2.7 |
| Catalyst A | 0.04 | 0.04 | 0.04 | 0.04 | 0.04 | 0.04 | 0.04 | 0.04 |
| Catalyst B | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 |
| Catalyzer C | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| F-242T | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| TD1-80 | 31.1 | 30.6 | 31.6 | 30.1 | 31.1 | 32.0 | 32.0 | 32.0 |
| ＜foams physical properties 〉 | ||||||||
| Density [kg/m3] | 33.5 | 33.8 | 33.3 | 33.8 | 33.9 | 33.4 | 33.6 | 33.9 |
| 25％ILD [kgf/314cm2] | 41.8 | 42.7 | 41.6 | 44.3 | 41.4 | 43.3 | 41.5 | 41.0 |
| Tensile strength [kgf/cm 2] | 1.49 | 1.40 | 1.48 | 1.35 | 1.46 | 1.46 | 1.48 | 1.49 |
| Tear strength [kgf/cm] | 0.84 | 0.81 | 0.85 | 0.92 | 0.81 | 0.82 | 0.83 | 0.78 |
| Extension at break degree [%] | 71 | 69 | 70 | 66 | 68 | 70 | 70 | 68 |
| Rebound degree [%] | 31 | 30 | 31 | 27 | 30 | 28 | 26 | 25 |
| Ventilation property [ft 3/ minute] | 2.9 | 3.2 | 2.8 | 2.2 | 3.1 | 2.8 | 2.9 | 3.2 |
| Compression set [%] | 31.4 | 33.0 | 31.3 | 36.0 | 33.0 | 32.5 | 31.4 | 33.0 |
Table 2
| Embodiment | Comparative example | |||||
| (9) | (10) | (11) | (1) | (2) | (3) | |
| Polymer polyatomic alcohol | F-10 | F-11 | F-6 | F-9 | F-12 | F-13 |
| Polymer particle concentration [quality %] | 50 | 50 | 50 | 50 | 40 | 30 |
| Hydroxyl value [mgKOH/g] | 28 | 28 | 28 | 28 | 33 | 39 |
| Viscosity (25 ℃) [mPas] | 5000 | 9760 | 4900 | 20000 | 5540 | 2000 |
| The viscosity upper limit in the formula (1) (25 ℃) [mPa.s] | 7800 | 7800 | 7800 | 7800 | 3200 | 1580 |
| Polyvalent alcohol soluble polymer [quality %] | 0 | 6 | 2 | 10 | 8 | 6 |
| Dispersion stabilization | ○ | ○ | ○ | △ | △ | △ |
| Urethane foam (proportioning, part) | ||||||
| Polymer polyatomic alcohol | 100 | 100 | 100 | 100 | 100 | 100 |
| Water | 2.7 | 2.7 | 2.7 | 2.7 | 2.7 | 2.7 |
| Catalyst A | 0.04 | 0.04 | 0.20 | 0.04 | 0.04 | 0.04 |
| Catalyst B | 0.30 | 0.30 | 0 | 0.30 | 0.30 | 0.30 |
| Catalyzer C | 0 | 0 | 0.30 | 0 | 0 | 0 |
| F-242T | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| TDI-80 | 32.0 | 32.0 | 32.0 | 32.0 | 33.0 | 33.9 |
| ＜foams physical properties 〉 | ||||||
| Density [kg/m 3] | 33.7 | 33.8 | 32.4 | 33.4 | 33.2 | 33.8 |
| 25％ILD [kgf/314cm 2] | 45.7 | 41.7 | 44.5 | 40.3 | 35.7 | 32.4 |
| Tensile strength [kgf/cm 2] | 1.52 | 1.48 | 1.52 | 1.46 | 1.57 | 1.66 |
| Tear strength [kgf/cm] | 0.89 | 0.83 | 0.86 | 0.75 | 0.76 | 0.71 |
| Elongation at break [%] | 70 | 70 | 74 | 65 | 90 | 105 |
| Rebound degree [%] | 30 | 30 | 32 | 24 | 27 | 28 |
| Ventilation property [ft 3/ minute] | 3.9 | 2.9 | 2.2 | 1.3 | 3.0 | 3.7 |
| Compression set [%] | 28.4 | 31.4 | 27.5 | 37.5 | 28.2 | 10.5 |
The evaluation method of the physical properties of foams is as described below in table 1 and the table 2.
Density (kg/m
3): by JIS K6400-1997[project 5] measure
25%ILD (kgf/314cm
2): by JIS K6382-1995[project 5.3] measure
Tensile strength (kgf/cm
2): by JIS K6301-1995[project 3] measure
Tear strength (kgf/cm): by JIS K6301-1995[project 9] measure
Elongation at break (%): by JIS K6301-1995[project 3] measure
Rebound degree (%): by JIS K6400-1997[project 7] measure
Ventilation property (ft
3/ minute): measure (test piece 5cm * 5cm * 2.5cm) with the ダ ウ formula instrument method [manufacturing of AMSCOR company] that flows
Compression set (%): by JIS K6382-1995[project 5.3] measure
Also have common physical properties, density 15～50kg/m as ammonia ester foams
3Be ideal, 25%ILD, tensile strength, tear strength, elongation at break, rebound degree and ventilation property, numerical value is bigger more desirable.In addition, compression set, numerical value is healed little more desirable.
As shown in table 1, the polymer polyatomic alcohol of embodiment 1～10 (F-1～8, F-10,11) compares with the polymer polyatomic alcohol (F-9) of comparative example 1, viscosity is low, and, foams physical properties, particularly 25%ILD (hardness), ventilation property and compression set excellence as urethane foam.In addition, tear strength, tensile strength, elongation at break, rebound resilience are equal or better.Also have, the polymer polyatomic alcohol of comparative example 2,3 (F-12, F-13), because its polymer particle concentration is lacked than the polymer polyatomic alcohol (F-1～F-8, F10,11) of embodiment 1～10 and the comparative polymers polyvalent alcohol (F-9) of comparative example 1, so, viscosity is low, yet the foams physical properties, particularly 25%ILD (hardness) of urethane foam be variation significantly.Also have, generally speaking, when polymer particle reaches high density, tensile strength, elongation at break, rebound resilience, ventilation property reduce, compression set raises, use the urethane foam [embodiment (1), (5)～(10)] of polymer polyatomic alcohol of the present invention, compare, show equal or better foams physical properties with the comparative example 1 of identical polymer particle concentration.
The possibility of industrial utilization
PEPA of the present invention and manufacture method thereof are compared with original polymer polyatomic alcohol, even polymer particle concentration is high, still can obtain the polymer polyatomic alcohol that viscosity is low, dispersion stabilization is fabulous. Therefore, when polyurethane resin is made, operating efficiency is greatly improved.
And, the polyurethane resin of polymer polyatomic alcohol of the present invention as the essential component manufacturing of polyalcohol, when situation about equating with the viscosity of polymer polyatomic alcohol compares, occasion with PEPA of the present invention, compare with original, 25%ILD (hardness) and compression set are fabulous. Also have, compare with the original polymer polyatomic alcohol that uses the same polymer particle concentration, when using polymer polyatomic alcohol of the present invention, 25%ILD, gas permeability and the compression set of ammonia ester resin can significantly improve.
Owing to brought into play above-mentioned effect, the polyurethane resin with polymer polyatomic alcohol of the present invention is made very is suitable for for the built-in material of automobile and the ornament materials of furniture as polyurethane foam.
Claims (16)
1. polymer polyol composition, said composition contain number-average molecular weight be more than 500 polyvalent alcohol (A) and in (A) dispersive polymer particle (B), and be in polyvalent alcohol, to make ethene unsaturated compound (b) polymerization form the polymer polyol composition (I) that (B) constituted, wherein, (b) be the ethene unsaturated compound (b1) more than a kind more than 500 by being selected from number-average molecular weight, aromatic hydrocarbons monomer (b2-1), unsaturated nitrile (b2-2), (methyl) esters of acrylic acid (b2-3), the monomer (b2-5) that contains polyfunctional vinyl, (methyl) acrylamide, the carboxylic acid and the derivative thereof that contain vinyl, the aliphatic hydrocarbon monomer, fluorine-containing vinyl monomer, nitrogenous vinyl monomer, the vinyl modified siloxane, the ethene unsaturated compound more than a kind of alkyl olefin(e) compound and cyclic olefin compound constitutes, and (b1) be selected from the ester of unsaturated carboxylic acid (p) and glycols (q) and the ester of unsaturated alcohol (r) and carboxylic acid (s)
(B) content is that benchmark is 35～75 quality % with the quality of (I), and the amount of dissolved soluble polymer (P) is that benchmark is below the 5 quality % in the quality of (A) in (A).
In the claim 1 record polymer polyol composition, contain number-average molecular weight and be the polyvalent alcohol (A) or (A) and the dispersion medium that constitutes of thinner (C) more than 500, and in this dispersion medium dispersive polymer particle (B), wherein, (I) the viscosity V that is mPas at 25 ℃ of units that record with Brookfield type viscometer down is in the scope of following formula (1)
V≤(Va-Va×C/10)^〔e^x〕 (1)
In the formula, x=0.0010354 * Bp^1.5;
Va:(A) be the viscosity of mPas at 25 ℃ of units that record with Brookfield type viscometer;
C: the content of (C) among (I) that represents with quality %;
Bp: the content of (B) among (I) that represents with quality %;
^: expression power exponent;
E: the end of natural logarithm.
In the claim 1 or 2 record polymer polyol composition, wherein, (I) content of in (B) is 45～75 quality %.
4. the polymer polyol composition of any one record in the claim 1 or 2 wherein, in (A), in the presence of dispersion agent (D) and/or the thinner (C) or not, is polymerized (b) that contain more than (b1) 5 quality %.
5. polymer polyol composition, said composition contain number-average molecular weight be more than 500 polyvalent alcohol (A) and in (A) dispersive polymer particle (B), and be in polyvalent alcohol, to make ethene unsaturated compound (b) polymerization form the polymer polyol composition (II) that (B) constitutes, wherein, (b) be the ethene unsaturated compound (b1) more than a kind more than 500 by being selected from number-average molecular weight, aromatic hydrocarbons monomer (b2-1), unsaturated nitrile (b2-2), (methyl) esters of acrylic acid (b2-3), (methyl) acrylamide, the carboxylic acid and the derivative thereof that contain vinyl, the aliphatic hydrocarbon monomer, fluorine-containing vinyl monomer, nitrogenous vinyl monomer, the vinyl modified siloxane, the ethene unsaturated compound more than a kind of alkyl olefin(e) compound and cyclic olefin compound constitutes, and (b1) be selected from the ester of unsaturated carboxylic acid (p) and glycols (q) and the ester of unsaturated alcohol (r) and carboxylic acid (s)
In (A), in the presence of dispersion agent (D),, (b) that contain more than (b1) 5 quality % is polymerized in thinner (C) existence or not.
6. the polymer polyol composition of record in the claim 4, wherein, the molecular weight (X) of the two keys of (b1) each is below 1200.
In the claim 1 record polymer polyol composition, wherein, unsaturated carboxylic acid (p) is the carboxylic acid of selecting from toxilic acid, fumaric acid and methylene-succinic acid more than a kind.
8. the polymer polyol composition of any one record in the claim 1 or 2, the polymer particle of separating from the polymer polyol composition that (b) polymerization is formed (B) is carried out mechanical dispersion form in (A), and the quality that (A) does not contain in (A) is the soluble polymer that benchmark surpasses 5 quality %.
9. a polymer polyol composition (III), contain number-average molecular weight and be more than 500 polyvalent alcohol (A) and in (A) dispersive polymer particle (B), wherein, (B) be that ethene unsaturated compound (b) is in the dispersion medium that contains (A), the polymer particle that carries out the polymerization formation in the presence of dispersion agent (D ') carries out the polymer particle that mechanical dispersion or pulverizing form again, and, said dispersion agent (D ') has and the difference of (A) solubility parameter SPa is solubility parameter SPd below 0.8, (b) by being selected from aromatic hydrocarbons monomer (b2-1), unsaturated nitrile (b2-2), (methyl) esters of acrylic acid (b2-3), the monomer (b2-5) that contains polyfunctional vinyl, (methyl) acrylamide, the carboxylic acid and the derivative thereof that contain vinyl, the aliphatic hydrocarbon monomer, fluorine-containing vinyl monomer, nitrogenous vinyl monomer, the vinyl modified siloxane, the ethene unsaturated compound more than a kind of alkyl olefin(e) compound and cyclic olefin compound constitutes.
10. the manufacture method of a polymer polyol composition, be in number-average molecular weight is polyvalent alcohol (A) more than 500, dispersion agent (D) and/or thinner (C) exist or not in the presence of, make the manufacture method of ethene unsaturated compound (b) polymeric polymer polyol composition, (b) be the ethene unsaturated compound (b1) more than a kind more than 500 by being selected from number-average molecular weight, aromatic hydrocarbons monomer (b2-1), unsaturated nitrile (b2-2), (methyl) esters of acrylic acid (b2-3), (methyl) acrylamide, the carboxylic acid and the derivative thereof that contain vinyl, the aliphatic hydrocarbon monomer, fluorine-containing vinyl monomer, nitrogenous vinyl monomer, the vinyl modified siloxane, the ethene unsaturated compound more than a kind of alkyl olefin(e) compound and cyclic olefin compound constitutes, and (b1) be selected from the ester of unsaturated carboxylic acid (p) and glycols (q) and the ester of unsaturated alcohol (r) and carboxylic acid (s)
Comprising, adopt (b) that contain 5 quality % (b1) at least, obtain the described polymer polyol composition of claim 1 (I).
11. the manufacture method of a polymer polyol composition, be in number-average molecular weight is polyvalent alcohol (A) more than 500, dispersion agent (D) and/or thinner (C) exist or not in the presence of, make the manufacture method of ethene unsaturated compound (b) polymeric polymer polyol composition, (b) be the ethene unsaturated compound (b1) more than a kind more than 500 by being selected from number-average molecular weight, aromatic hydrocarbons monomer (b2-1), unsaturated nitrile (b2-2), (methyl) esters of acrylic acid (b2-3), (methyl) acrylamide, the carboxylic acid and the derivative thereof that contain vinyl, the aliphatic hydrocarbon monomer, fluorine-containing vinyl monomer, nitrogenous vinyl monomer, the vinyl modified siloxane, the ethene unsaturated compound more than a kind of alkyl olefin(e) compound and cyclic olefin compound constitutes, and (b1) be selected from the ester of unsaturated carboxylic acid (p) and glycols (q) and the ester of unsaturated alcohol (r) and carboxylic acid (s)
Comprising, adopt (b) that contain 5 quality % (b1) at least, obtain the described polymer polyol composition of claim 5 (II).
12. the manufacture method of the polymer polyol composition (I) of record in the claim 1, be contain number-average molecular weight be more than 500 polyvalent alcohol (A) and in (A) manufacture method of the polymer polyol composition of dispersive polymer particle (B), comprising, isolated polymer particle (B) from make the polymer polyol composition that ethene unsaturated compound (b) polymerization obtains polyvalent alcohol is carried out mechanical dispersion in (A), and the quality that (A) does not contain in (A) is the soluble polymer that benchmark surpasses 5 quality %, (b) by being selected from aromatic hydrocarbons monomer (b2-1), unsaturated nitrile (b2-2), (methyl) esters of acrylic acid (b2-3), the monomer (b2-5) that contains polyfunctional vinyl, (methyl) acrylamide, the carboxylic acid and the derivative thereof that contain vinyl, the aliphatic hydrocarbon monomer, fluorine-containing vinyl monomer, nitrogenous vinyl monomer, the vinyl modified siloxane, the ethene unsaturated compound more than a kind of alkyl olefin(e) compound and cyclic olefin compound constitutes.
13. the manufacture method of the polymer polyol composition (III) of record in the claim 9, comprising, in containing the dispersion medium that number-average molecular weight is the polyvalent alcohol (A) more than 500, in the presence of dispersion agent (D '), make the polymer particle in the polymer polyatomic alcohol that ethene unsaturated compound (b) is polymerized carry out mechanical dispersion or pulverizing again, and, said dispersion agent (D ') has and the difference of (A) solubility parameter SPa is solubility parameter SPd below 0.8, (b) by being selected from aromatic hydrocarbons monomer (b2-1), unsaturated nitrile (b2-2), (methyl) esters of acrylic acid (b2-3), the monomer (b2-5) that contains polyfunctional vinyl, (methyl) acrylamide, the carboxylic acid and the derivative thereof that contain vinyl, the aliphatic hydrocarbon monomer, fluorine-containing vinyl monomer, nitrogenous vinyl monomer, the vinyl modified siloxane, the ethene unsaturated compound more than a kind of alkyl olefin(e) compound and cyclic olefin compound constitutes.
14. the manufacture method of a urethane resin, this method is that polyhydroxy reactant and polyisocyanates composition are being reacted in the presence of the whipping agent or not, the method of the urethane resin of making foaming or not foaming, comprising, adopt the polymer polyol composition of record in the claim 1 at least a portion as polyhydroxy reactant.
15. the manufacture method of a urethane resin, this method is that polyhydroxy reactant and polyisocyanates composition are being reacted in the presence of the whipping agent or not, the method of the urethane resin of making foaming or not foaming, comprising, adopt the polymer polyol composition of record in the claim 5 at least a portion as polyhydroxy reactant.
16. the manufacture method of a urethane resin, this method is that polyhydroxy reactant and polyisocyanates composition are being reacted in the presence of the whipping agent or not, the method of the urethane resin of making foaming or not foaming, comprising, adopt the polymer polyol composition of record in the claim 10 at least a portion as polyhydroxy reactant.
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP218171/1999 | 1999-07-30 | ||
| JP21817199 | 1999-07-30 | ||
| JP22411999 | 1999-08-06 | ||
| JP224119/1999 | 1999-08-06 | ||
| JP33923499 | 1999-11-30 | ||
| JP339234/1999 | 1999-11-30 | ||
| JP15109/2000 | 2000-01-24 | ||
| JP2000015109 | 2000-01-24 | ||
| JP2000182351 | 2000-06-16 | ||
| JP182351/2000 | 2000-06-16 |
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|---|---|
| CN1327465A CN1327465A (en) | 2001-12-19 |
| CN1142980C true CN1142980C (en) | 2004-03-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008021112A Expired - Fee Related CN1142980C (en) | 1999-07-30 | 2000-07-26 | Polymer polyol composition, process for producing the same, and process for producing polyurethane resin |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3686372B2 (en) |
| CN (1) | CN1142980C (en) |
| WO (1) | WO2001009242A1 (en) |
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| CN101218299B (en) * | 2005-07-07 | 2012-06-20 | 三洋化成工业株式会社 | Polyol composition containing fine particles dispersed therein, process for production of polymeric polyols, and process for production of polyurethane resins |
| CN100376616C (en) * | 2005-12-21 | 2008-03-26 | 中国科学院山西煤炭化学研究所 | Method for preparing polyester type polymer polyatomic alcohol |
| JP4861972B2 (en) * | 2007-01-10 | 2012-01-25 | 三洋化成工業株式会社 | Polymer polyol, method for producing the same, and method for producing polyurethane |
| EP2194097B1 (en) | 2007-09-28 | 2013-07-03 | Sanyo Chemical Industries, Ltd. | Polymer polyol, method for producing the same, and method for producing polyurethane resin |
| JP4851503B2 (en) | 2007-10-10 | 2012-01-11 | 三洋化成工業株式会社 | Method for producing fine particle dispersed polyol and method for producing polyurethane resin |
| US20160318285A1 (en) * | 2013-12-24 | 2016-11-03 | Sanyo Chemical Industries, Ltd. | Vehicle-interior material and production method therefor |
| JP6928599B2 (en) | 2016-02-22 | 2021-09-01 | 株式会社カネカ | Polyol composition and thermosetting resin |
| CN110462009B (en) | 2017-03-23 | 2021-12-07 | 三洋化成工业株式会社 | Viscosity index improver and lubricating oil composition |
| CN109422910B (en) * | 2017-08-24 | 2021-04-13 | 补天新材料技术有限公司 | Blowing agents comprising orthoformate and carbonate alkanolamine salts and use in polyurethane continuous panel foam materials |
| EP3992271B1 (en) | 2019-06-26 | 2024-08-28 | Sanyo Chemical Industries, Ltd. | Viscosity index-improving composition and lubricating oil composition |
| CN115885026B (en) | 2020-08-20 | 2024-06-21 | 三洋化成工业株式会社 | Viscosity index improver composition and lubricating oil composition |
| US20230323241A1 (en) | 2020-09-14 | 2023-10-12 | Sanyo Chemical Industries, Ltd. | Viscosity index improver and lubricating oil composition |
| CN112225873B (en) * | 2020-09-15 | 2022-04-22 | 万华化学集团股份有限公司 | High-transparency fast-forming degradable thermoplastic polyurethane elastomer and preparation method thereof |
| FR3118630B1 (en) | 2021-01-06 | 2024-04-19 | Total Marketing Services | Lubricating composition having cold stability and improved fuel eco properties |
| FR3126711A1 (en) | 2021-09-03 | 2023-03-10 | Totalenergies Marketing Services | Lubricant composition with improved cold thickening properties |
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| CA1074049A (en) * | 1974-11-13 | 1980-03-18 | Russell Van Cleve | Polymer/polyols and polyurethane derivatives thereof |
| US4198488A (en) * | 1978-06-26 | 1980-04-15 | Union Carbide Corporation | Polymer-polyols and polyurethanes based thereon |
| JPS61115919A (en) * | 1984-11-13 | 1986-06-03 | Asahi Glass Co Ltd | Production of polyol containing polymer dispersed therein |
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- 2000-07-26 WO PCT/JP2000/004999 patent/WO2001009242A1/en active Application Filing
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