JPS6244764B2 - - Google Patents
Info
- Publication number
- JPS6244764B2 JPS6244764B2 JP58145214A JP14521483A JPS6244764B2 JP S6244764 B2 JPS6244764 B2 JP S6244764B2 JP 58145214 A JP58145214 A JP 58145214A JP 14521483 A JP14521483 A JP 14521483A JP S6244764 B2 JPS6244764 B2 JP S6244764B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- particulate polymer
- organic liquid
- aqueous organic
- dispersion stabilizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920000642 polymer Polymers 0.000 claims description 113
- 239000006185 dispersion Substances 0.000 claims description 80
- 239000003381 stabilizer Substances 0.000 claims description 72
- 239000007788 liquid Substances 0.000 claims description 57
- 239000002253 acid Substances 0.000 claims description 44
- 239000005056 polyisocyanate Substances 0.000 claims description 41
- 229920001228 polyisocyanate Polymers 0.000 claims description 41
- 238000004519 manufacturing process Methods 0.000 claims description 24
- -1 alicyclic hydrocarbon Chemical class 0.000 claims description 18
- 125000004018 acid anhydride group Chemical group 0.000 claims description 17
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 16
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 4
- HENCHDCLZDQGIQ-UHFFFAOYSA-N 3-[3,5-bis(2-carboxyethyl)-2,4,6-trioxo-1,3,5-triazinan-1-yl]propanoic acid Chemical compound OC(=O)CCN1C(=O)N(CCC(O)=O)C(=O)N(CCC(O)=O)C1=O HENCHDCLZDQGIQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 229920005604 random copolymer Polymers 0.000 claims description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000002245 particle Substances 0.000 description 41
- 239000000243 solution Substances 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 39
- 230000015572 biosynthetic process Effects 0.000 description 31
- 238000003786 synthesis reaction Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 22
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 20
- 239000004342 Benzoyl peroxide Substances 0.000 description 20
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 20
- 238000010521 absorption reaction Methods 0.000 description 20
- 235000019400 benzoyl peroxide Nutrition 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000000862 absorption spectrum Methods 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000004962 Polyamide-imide Substances 0.000 description 13
- 229910001873 dinitrogen Inorganic materials 0.000 description 13
- 229920002312 polyamide-imide Polymers 0.000 description 13
- 239000000376 reactant Substances 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000013638 trimer Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 239000012456 homogeneous solution Substances 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 230000002940 repellent Effects 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- IWTIBPIVCKUAHK-UHFFFAOYSA-N 3-[bis(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCC(O)=O IWTIBPIVCKUAHK-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical class O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- ADOQBZAVKYCFOI-HWKANZROSA-N (E)-2-dodecene Chemical compound CCCCCCCCC\C=C\C ADOQBZAVKYCFOI-HWKANZROSA-N 0.000 description 1
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- BDBDSYCJVGJQNK-NSCUHMNNSA-N (E)-non-7-en-1-ol Chemical compound C\C=C\CCCCCCO BDBDSYCJVGJQNK-NSCUHMNNSA-N 0.000 description 1
- ZUHYIBBOAOBYDJ-NSCUHMNNSA-N (e)-hept-5-en-1-ol Chemical compound C\C=C\CCCCO ZUHYIBBOAOBYDJ-NSCUHMNNSA-N 0.000 description 1
- GCWAFWMUTOXMIT-HWKANZROSA-N (e)-heptadec-2-ene Chemical compound CCCCCCCCCCCCCC\C=C\C GCWAFWMUTOXMIT-HWKANZROSA-N 0.000 description 1
- YITMLDIGEJSENC-HWKANZROSA-N (e)-hexadec-2-ene Chemical compound CCCCCCCCCCCCC\C=C\C YITMLDIGEJSENC-HWKANZROSA-N 0.000 description 1
- IICQZTQZQSBHBY-HWKANZROSA-N (e)-non-2-ene Chemical compound CCCCCC\C=C\C IICQZTQZQSBHBY-HWKANZROSA-N 0.000 description 1
- FSUXYWPILZJGCC-NSCUHMNNSA-N (e)-pent-3-en-1-ol Chemical compound C\C=C\CCO FSUXYWPILZJGCC-NSCUHMNNSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 1
- HLMACKQLXSEXIY-UHFFFAOYSA-N 2-methyldec-1-ene Chemical compound CCCCCCCCC(C)=C HLMACKQLXSEXIY-UHFFFAOYSA-N 0.000 description 1
- PWRBDKMPAZFCSV-UHFFFAOYSA-N 2-methyldodec-1-ene Chemical compound CCCCCCCCCCC(C)=C PWRBDKMPAZFCSV-UHFFFAOYSA-N 0.000 description 1
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- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
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- 239000003365 glass fiber Substances 0.000 description 1
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- 239000002648 laminated material Substances 0.000 description 1
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Landscapes
- Polyurethanes Or Polyureas (AREA)
Description
本発明は粒子状重合体の製造法に関し、さらに
詳しくは主にシート、成形モールド品、接着剤、
塗料、複合材料などに適用しうる耐熱性のすぐれ
た粒子状重合体の製造法に関する。
ポリイソシアネートと酸無水物基を有するポリ
カルボン酸とをＮ−メチルピロリドン、ジメチル
フオルムアミド、ジメチルアセトアミドなどの高
価な溶媒中で溶液状で反応させて、イミド基を有
する重合体溶液、例えばポリアミドイミド溶液、
ポリイミド溶液などを得ることが知られている。
しかしながら、かかる重合体溶液から固体重合体
を得るためには極めて不経済なプロセスによる溶
媒の除去又は回収操作が必要であり、工業的規模
の製造においてコスト的に大きな問題がある。固
体重合体を得るための有力な一つの製法は溶媒を
必要としない塊状重合法である。しかしながら、
イミド基を有する重合体は一般に剛直で高極性の
分子構造をもち、高いガラス転移温度によつて特
徴づけられる。従つて、塊状重合法の適用にあた
つては、一般に高温、高圧の過酷な条件下で反応
を進める必要があるため、反応の制御、副反応の
抑制などが困難であり、未だ実用化に成功した例
は見当らない。
又、ポリアミド樹脂の中では芳香族ポリアミド
が非常に耐熱性が良いと知られているが一般的に
芳香族ジカルボン酸と芳香族ジアミンとの反応性
は充分でない。
６・６−ナイロンや６−ナイロンのような高分
子量の重合体を得るためには、遊離のカルボン酸
より反応性に富む芳香族ジカルボン酸二塩化物と
芳香族ジアミンの重合反応が用いられる。しか
し、芳香族ジアミンと芳香族ジカルボン酸二塩化
物の反応では塩酸が副生し、好ましくないアミン
塩酸塩が生成するなどの副反応を起こすので塩酸
を除去する必要があり、工業的規模の製造では問
題を残している。
本発明者らは、耐熱性のすぐれた粒子状重合体
の安価な製造法についての検討を重ねた結果、非
水有機液体中に分散させた粒子状重合体の製造法
を完成するに至つた。
本発明は、生成する粒子状重合体に対して不溶
性である第一の非水有機液体、第一の非水有機液
体に可溶な分散安定剤及び生成する粒子状重合体
に対して可溶性又は膨潤性であり、第一の非水有
機液体とは本質上非混和性である第二の非水有機
液体の存在下で、ポリイソシアネート（）と酸
無水物基を有するポリカルボン酸（）及び／又
はポリカルボン酸（）とを反応させて、第一の
非水有機液体中に分散された粒子状重合体とする
粒子状重合体の製造法において、該分散安定剤と
して炭素数６以上の炭化水素基からなる側鎖を有
するエチレン性不飽和単量体(A)とヒドロキシル基
を有するエチレン性不飽和単量体(B)をモル比で
(A)／(B)を１／１から５／１の範囲として反応させ
て得られる数平均分子量6000以上のヒドロキシル
基含有ビニル重合体を、第二の非水有機液体、ポ
リイソシアネート、酸無水物基を有するポリカル
ボン酸及び／又はポリカルボン酸に対して0.5重
量％以上用いることを特徴とする粒子状重合体の
製造法に関する。
本発明の製造法によれば、粒子状重合体は、第
一の非水有機液体中で比較的小さな粒子の分散体
として得られるためろ過操作によつて容易に分散
体から回収できる。また、特に本発明になる製造
法では第一の非水有機液体として生成する粒子状
重合体に対して不溶性である安価な汎用溶媒を用
いることができる。重合体の溶媒に対する不溶性
によつて高固形分化に限界がある溶液重合法と違
つて、本発明によれば非水有機液体中で50重量％
以上の高固形分を得ることができる。
また、本発明における粒子状重合体への単量体
の転換率は溶液重合法における反応温度領域で十
分に高めることができ、比較的温和な条件下で反
応を完結できるため副反応などによる純度の低下
をきたさない。
本発明における第一の非水有機液体としては、
生成する粒子状重合体に対して不溶性であつて、
重合反応を阻害しない不活性な性質を有する非水
有機液体が用いられる。
例えばｎ−ヘキサン、オクタン、ドデカン、流
動パラフイン、ISOPAR−Ｅ、ISOPAR−Ｈ、
ISOPAR−Ｋ（以上、エツソ・スタンダード石油
社製商品名。沸点範囲が40〜300℃程度の石油系
飽和脂肪族又は脂環族炭化水素）等の脂肪族又は
脂環族炭化水素類などが用いられる。反応温度を
考慮すると沸点が80℃以上のものが好ましい。こ
れらは単独で又は二種以上を用いることができ
る。
本発明における第一の非水有機液体とは本質上
非混和性である第二の非水有機液体は、重合反応
を阻害しない不活性な性質を有する非水有機液体
であり、反応剤（上記（）、（）及び／又は
（））の少なくとも１種に対して可溶性又は膨潤
性であつて、重合反応過程において末端基間の反
応を接触化し、生成する重合体の高分子量化を達
成するための溶媒として作用するものが用いられ
る。ここで、第一の非水有機液体とは本質上非混
和性とは第一の非水有機液体に対して完全に不溶
性なものに加えて、完全に不溶性ではないが、あ
る混合比において二液が相分離する程度に非混和
性である非水有機液体をも含むという意味であ
る。かかる第二の非水有機液体は極性液体であつ
て、第一の非水有機液体よりも分散相に含まれる
生成する重合体又は反応剤に対して大きな親和性
を持つものが好ましい。このような第二の非水有
機液体としては、例えばＮ−メチルピロリドン、
Ｎ−ビニルピロリドン、ジメチルフオルムアミ
ド、ジメチルアセトアミド、γ−ブチロラクト
ン、フエノール、クレゾールなどが用いられる。
これらは単独で又は二種以上が用いられる。好ま
しくは、第一の非水有機液体として脂肪族又は脂
環族炭化水素とＮ−メチルピロリドンとの組み合
わせが用いられる。
本発明において分散安定剤の製造に用いられる
炭素数６以上の炭化水素基からなる側鎖を有する
エチレン性不飽和単量体としては、例えば１−オ
クテン、１−又は２−ノネン、１−又は２−デセ
ン、１−又は２−ドデセン、１−又は２−ヘキサ
デセン、１−又は２−ヘプタデセン、２−メチル
−１−ノネン、２−メチル−１−デセン、２−メ
チル−１−ドデセン、２−メチル−１−ヘキサデ
セン、２−メチル−１−ヘプタデセンなどのビニ
ル、プロペニル又はイソプロペニル基含有脂肪族
直鎖型不飽和炭化水素、アクリル酸又はメタクリ
ル酸と２−エチルヘキシルアルコール、ヘキシル
アルコール等の炭素数６以上の脂肪族アルコール
又はシクロヘキサノール、ノルボナノール、アダ
マンタノール等の炭素数６以上の脂環族アルコー
ルとのエステルなどが用いられる。
本発明で用いられるヒドロキシル基を有するエ
チレン性不飽和単量体としては、アリルアルコー
ル、３−ブテン−１−オール、４−又は３−ペン
テン−１−オール、５−又は４−ヘキセン−１−
オール、６−又は５−ヘプテン−１−オール、７
−又は６−オクテン−１−オール、８−又は７−
ノネン−１−オール、２−メチルアリルアルコー
ル、３−メチル−３−ブテン−１−オール、４−
メチル−４−ペンテン−１−オール、５−メチル
−５−ヘキセン−１−オール、６−メチル−６−
ヘプテン−１−オール、７−メチル−７−オクテ
ン−１−オール、８−メチル−８−ノネン−１−
オールなどの脂肪族不飽和アルコール、アクリル
酸又はメタクリル酸とエチレングリコール、１・
２−又は１・３−プロパンジオール、１・３−又
は１・４−ブタンジオールとのモノエステルなど
が用いられる。これらの炭素数６以上の炭化水素
基からなる側鎖を有するエチレン性不飽和単量体
とヒドロキシル基を有するエチレン性不飽和単量
体はランダム共重合体、ブロツク共重合体又はグ
ラフト共重合体として得られ、分散安定剤として
機能する。
共重合体としてはラウリルメタクリレート、ス
テアリルメタクリレート、ラウリルアクリレート
又はステアリルアクリレートとアクリル酸又はメ
タクリル酸−２−ヒドロキシエチルとのランダム
共重合体が好ましい。
分散安定剤を得る重合法には特に制限はなく、
反応開始剤としてラジカル開始剤を用いる通常の
エチレン性単量体の重合法などが利用できる。
即ち、分散安定剤の炭素数６以上の炭化水素基
からなる側鎖部分は、第一の非水有機液体に可溶
な部分であり、共重合体の第一の非水有機液体へ
の溶解性を保持する。更に該部分は分散粒子同士
の融合を防ぐ分散粒子表面をおおう反撥層を形成
する。
又、ヒドロキシル基は第一の非水有機液体には
本質的に不溶な部分であり、むしろ第二の非水有
機液体に溶解性がある。
さらに、粒子状重合体を構成するポリイソシア
ネートとヒドロキシル基が、化学的に結合するこ
とにより分散剤が分散粒子表面に固定され、個々
の分散粒子に安定な反撥層を形成させ得る。
従つて、以上の二種の異なる機能の兼ね合いが
分散安定剤の効果を決定する。炭素数６以上の炭
化水素基からなる側鎖を有するエチレン性不飽和
単量体(A)とヒドロキシル基を有するエチレン性不
飽和単量体(B)のモル比(A)／(B)が５／１を越えると
分散粒子への親和性より第一の非水有機液体への
溶解性が大きいため、分散安定剤の効果が充分発
揮されない。１／１未満では、分散安定剤として
の効果が発揮できないほど第一の非水有機液体へ
の溶解性が低下する。
一方、分散粒子表面をおおう反撥層を形成し分
散粒子同士の融合を防ぐ、即ち分散安定剤として
の効果を発揮するには、共重合体の数平均分子量
が6000以上であることが必要である。数平均分子
量が6000未満では反撥層の形成が不充分で、分散
粒子同子の融合する割合が多くなるため、分散粒
子が凝集しやすくなり安定な粒子状重合体の合成
が困難となる。通常の重合法で得た数平均分子量
の大きな共重合体を分散安定剤として用いること
については特に制限はない。又、一定条件下で粒
子状重合体を合成すると得られた粒径と共重合体
の数平均分子量には関連がある。例えば数平均分
子量6000の共重合体を分散安定剤として用いると
主粒子径は50〜500μであつたが、数平均分子量
60000の共重合体では主粒子径は20〜40μで数平
均分子量300000では主粒子径は５〜20μであつ
た。これは特別な製造装置を使用せずに数平均分
子量の異つた共重合体を分散安定剤として用いる
だけで得られる粒子状重合体の粒径調節ができる
という工業的に有効な技術であることを示してい
る。
しかし、数平均分子量を300000より大きくする
と当然粘度が上昇し、取り扱いにくくなり、更に
微細な粒子を得る目的には数平均分子量の大きな
分散剤を使用するよりも乳化器（ホモミキサー）
を用いるなど合成装置を改良した方が有利であ
る。
以上のことから分散安定剤としては共重合体の
数平均分子量は6000以上が必要で、数平均分子量
6000から300000の範囲が好ましいとされる。数平
均分子量は、分子量既知のポリスチレンを検量線
とするゲルパーミエーシヨンクロマトグラフイ法
から求められる。
分散安定剤の数平均分子量は、その製造の際
の、反応温度と触媒量によつて調節される。
分散安定剤の使用量は分散粒子（第二の非水有
機液体、ポリイソシアネート、酸無水物基を有す
るポリカルボン酸及び／又はポリカルボン酸）の
重量に対して0.5重量％以上とされる。
分散安定剤の使用量は耐熱性と経済性を考慮す
れば、２〜20重量％の範囲が好ましい。
分散安定剤は、通常溶液の形で製造され、溶液
の形で使用されるがその使用量は例えば170℃で
２時間乾燥後の溶液中の不揮発分の重量により計
算される。
本発明に用いられるポリイソシアネートとして
は、例えばトリレンジイソシアネート、キシリレ
ンジイソシアネート、４・4′−ジフエニルエーテ
ルジイソシアネート、ナフタレン−１・５−ジイ
ソシアネート、４・4′−ジフエニルメタンジイソ
シアネート等の芳香族ジイソシアネート、エチレ
ンジイソシアネート、１・４−テトラメチレンジ
イソシアネート、１・６−ヘキサメチレンジイソ
シアネート、１・12−ドデカンジイソシアネート
等の脂肪族ジイソシアネート、シクロブテン１・
３−ジイソシアネート、シクロヘキサン１・３−
および１・４−ジイソシアネート、イソフオロン
ジイソシアネート等の脂環式ジイソシアネート、
トリフエニルメタン−４・4′・4″−トリイソシア
ネート、ポリフエニルメチルポリイソシアネー
ト、例えばアニリンとフオルムアルデヒドとの縮
合物をフオスゲン化したもの等のポリイソシアネ
ート、これらのポリイソシアネートの三量化反応
によつて得られるイソシアヌレート環含有ポリイ
ソシアネートが使用される。耐熱性、コスト面等
を考慮すると、好適にはトリレンジイソシアネー
ト、４・4′−ジフエニルメタンジイソシアネー
ト、４・4′−ジフエニルエーテルジイソシアネー
ト、トリフエニルメタン−４・4′・4″−トリイソ
シアネートなどの芳香族ポリイソシアネート及び
これらのうちの芳香族ジイソシアネートの三量化
反応によつて得られるイソシアヌレート環を有す
るポリイソシアネートを用いることが好ましい。
好適なイソシアヌレート環含有ポリイソシアネー
トの製造法は特公昭56−34209号公報に示されて
いる。イソシアヌレート環含有ポリイソシアネー
トは分岐成分として使用され、そのイソシアヌレ
ート環骨核はすぐれた耐熱性を付与する。実質的
に線状であつて熱可塑性である粒子状重合体の合
成には二官能性のポリイソシアネートが使用され
る。また、分岐した熱硬化性の粒子状重合体の合
成には三官能性以上のポリイソシアネートが使用
される。これらポリイソシアネートは目的に応じ
て単独で又は二種以上が用いられる。ポリイソシ
アネートは重縮合反応過程での反応速度を制御
し、安定な粒子状重合体を得るためにメタノー
ル、ｎ−ブタノール、ベンジルアルコール、ε−
カプロラクタム、メチルエチルケトンオキシム、
フエノール、クレゾールなどの活性水素を分子内
に１個有する適当なブロツク剤で一部分又は全部
を安定化したものを使用してもよい。
酸無水物基を有するポリカルボン酸としては、
例えばトリメリツト酸無水物、１・２・４−ブタ
ントリカルボン酸−１・２−無水物、３・４・
4′−ベンゾフエノントリカルボン酸−３・4′−無
水物等のトリカルボン酸無水物、１・２・３・４
−ブタンテトラカルボン酸、シクロペンタンテト
ラカルボン酸、エチレンテトラカルボン酸、ビシ
クロ−〔２・２・２〕−オクト−(7)−エン−２：
３、５：６−テトラカルボン酸等の脂肪族系およ
び脂環族系四塩基酸、ピロメリツト酸、３・3′・
４・4′−ベンゾフエノンテトラカルボン酸、ビス
（３・４−ジカルボキシフエニル）エーテル、
２・３・６・７−ナフタレンテトラカルボン酸、
１・２・５・６−ナフタレンテトラカルボン酸、
エチレングリコールビストリメリテート、２・
2′−ビス（３・４−ビスカルボキシフエニル）プ
ロパン、２・2′・３・3′−又は３・3′・４・4′−
ビフエニルテトラカルボン酸、ペリレン−３・
４・９・10−テトラカルボン酸、ビス３・４−ジ
カルボキシフエニルスルホン、２・２−ビス〔４
−（３・４−ジカルボキシフエノキシ）フエニ
ル〕プロパン、２・２−ビス〔４−（２・３−ジ
カルボキシフエノキシ）フエニル〕プロパン、４
−（２・３−ジカルボキシフエノキシ）−4′−
（３・４−ジカルボキシフエノキシ）−ジフエニル
−２・２−プロパン等の芳香族四塩基酸、チオフ
エン−２・３・４・５−テトラカルボン酸、ピラ
ジンテトラカルボン酸等の複素環式四塩基酸など
の四塩基酸二無水物又は一無水物などが挙げられ
る。
トリカルボン酸無水物などの誘離のカルボキシ
ル基をもつ酸無水物基を含有するポリカルボン酸
とポリイソシアネートとからポリアミドイミドが
得られる。また、テトラカルボン酸二無水物など
の酸無水物基のみをもつ酸無水物基を有するポリ
カルボン酸とポリイソシアネートとからポリイミ
ドが得られる。一般的には耐熱性、コスト面等を
考慮すればトリメリツト酸無水物、２・２−ビス
〔４−（３・４−ジカルボキシフエノキシ）フエニ
ル〕プロパン二無水物、３・3′・４・4′−ベンゾ
フエノンテトラカルボン酸二無水物又はピロメリ
ツト酸二無水物が好ましい。
ポリカルボン酸としては例えばテレフタル酸、
イソフタル酸、２・６−、２・５−又は３・６−
ジカルボキシトルエン、２・６−ジカルボキシナ
フタレン、３・3′−又は４・4′−ジカルボキシビ
フエニル、ビス（３−又は４−カルボキシフエニ
ル）エーテル、ビス（３−又は４−カルボキシフ
エニル）ケトン、ビス（３−又は４−カルボキシ
フエニル）スルホン、ビス（３−又は４−カルボ
キシフエニル）メタン、ビス（３−又は４−カル
ボキシフエニル）ジメチルメタン、トリメリツト
酸、トリメシン酸、ピロメリツト酸、トリス（２
−カルボキシエチル）イソシアネート、トリカル
バリリツク酸、ニトリロ三酢酸、ニトリロ三プロ
ピオン酸、アジピン酸、セバシン酸、ドデカンジ
カルボン酸などが用いられる。
耐熱性などを考慮すればイソフタル酸又はテレ
フタル酸、トリメシン酸、トリス（２−カルボキ
シエチル）イソシアヌレート又はニトリロ三酢酸
が好ましい。
ポリイソシアネートと酸無水物基を有するポリ
カルボン酸及び／又はポリカルボン酸の使用量
は、ポリイソシアネートの全イソシアネート基に
対して酸無水物基を有するポリカルボン酸及び／
又はポリカルボン酸の全カルボキシル基の当量比
（全カルボキシル基／全イソシアネート基）が0.5
〜2.0の範囲内とすることが好ましい。ここで、
酸無水物基１当量はカルボキシル基１当量として
取り扱う。十分に高分子量であつて高度な耐熱
性、可とう性を有する粒子状重合体が要求される
場合には、イソシアネート基に対するカルボキシ
ル基の当量比が好ましくは0.85〜1.15、より好ま
しくは実質的に当量となるように調整される。
本発明によればゲル化した粒子状重合体も得る
ことができる。ゲル化した粒子状重合体を得るに
は、ゲル化するに充分な３官能以上の架橋成分を
含む樹脂組成で反応をゲル化するまで進めれば良
い。
前記したポリイソシアネートのうち、３官能以
上の架橋成分となりうるものとしては、ジイソシ
アネートを３量化して得られる化合物、例えばト
リレンジイソシアネート、キシリレンジイソシア
ネート、４・4′−ジフエニルエーテルジイソシア
ネート、ナフタレン−１・５−ジイソシアネー
ト、４・4′−ジフエニルメタンジイソシアネート
等の芳香族ジイソシアネートの３量体、エチレン
ジイソシアネート、１・４−テトラメチレンジイ
ソシアネート、１・６−ヘキサメチレンジイソシ
アネート、１・12−ドデカンジイソシアネート等
の脂肪族ジイソシアネートの３量体、シクロブテ
ン１・３−ジイソシアネート、シクロヘキサン
１・３−および１・４−ジイソシアネート、イソ
フオロンジイソシアネート等の脂環式ジイソシア
ネートの３量体、トリイソシアネート化合物、例
えばトリフエニルメタン−４・4′・4″−トリイソ
シアネート、ポリフエニルメチルポリイソシアネ
ート、例えばアニリンとフオルムアルデヒドとの
縮合物とホスゲンを反応させたものなどが用いら
れる。これらの架橋成分となりうるポリイソシア
ネートは、ポリイソシアネート成分の全部又は一
部に用いることができる。
前記した酸無水物基を有するポリカルボン酸及
び／又はポリカルボン酸のうち３官能以上の架橋
成分となり得るものとしては、トリメリツト酸、
トリメシン酸、ピロメリツト酸、トリス（２−カ
ルボキシエチル）イソシアヌレート、トリカルバ
リリツク酸、ニトリロ三酢酸、ニトリロ三プロピ
オン酸などが用いられる。
本発明においては、ポリイソシアネートと反応
される酸無水物基を有するポリカルボン酸及びポ
リカルボン酸は、両者か又はいずれかが用いられ
る。これらの架橋成分となりうるポリカルボン酸
は、酸無水物基を有するポリカルボン酸及び／又
はポリカルボン酸の全部又は一部に用いることが
できる。
以上述べた３官能以上の架橋成分を用いてゲル
化した粒子状重合体を得る方法の他に、副反応を
利用してゲル化させる方法や焼結によりゲル化さ
せる方法などがある。例えば２官能同士のポリイ
ソシアネートと酸無水物基を有するポリカルボン
酸及び／又はポリカルボン酸の当量比を実質1.0
で反応させる際に120℃以上の高温で、反応を長
時間進めると副反応によりゲル化した粒子状重合
体が得られる。
連続相となる第一の非水有機液体と分散相とな
る反応剤（上記の（）、（）及び／又は
（）））との量比は第一の非水有機液体と反応剤
との総量に対して反応剤が10〜80重量％となる範
囲が好ましい。生産効率、コスト上の観点から40
重量％以上が特に好ましい。
第二の非水有機液体と反応剤との量比は第二の
非水有機液体と反応剤との総量に対して第二の非
水有機液体が0.5〜70重量％となる範囲が好まし
い。0.5重量％未満であると重合反応は高温での
み進行するため好ましくない副反応が起こり易く
なる。70重量％を越えると反応剤が第二の非水有
機液体に溶解した比重の大きい連続相が形成され
る結果、比重の小さい第一の非水有機液体と相分
離を起こし、分散相を形成しにくくなる。また、
分散相を形成しても重合反応中に凝集を起こし易
くなり、コスト的にも不利である。特に好ましく
は１〜30重量％の範囲が用いられる。
ポリイソシアネート、酸無水物基を有するポリ
カルボン酸及び／又はポリカルボン酸の反応温度
としては80〜250℃が好ましい。
重合反応は、実質上無水の状態で実施されるこ
とが好ましい。従つて、窒素ガスなどの不活性雰
囲気下で行なうのが望ましい。当然のことなが
ら、本発明の製造法によつて得られる粒子状重合
体はその反応剤、特にポリイソシアネートが水と
接触することによつて、すみやかに不活性な化合
物に変質するために、水を分散媒体として製造す
ることは不可能である。反応は、全ての原料を同
時に仕込んでもよいし、目的に応じて段階的に仕
込み、反応を進めてもよい。
反応剤の少なくとも一成分は第二の非水有機液
体に可溶性又は膨潤性であるか、反応温度で液体
であることが望ましい。好ましい具体例として
は、酸成分を除く全成分を混合した均一溶液又は
ポリイソシアネートと第二の非水有機液体との均
一溶液が第一の非水有機液体中に油滴状態で分散
した不均一溶液に、微粉末化した酸成分を添加し
て反応が進められる。この方法によれば、比較的
低い反応温度で重合反応を進めることができ、好
ましくない副反応を抑制することができる。
ポリイソシアネートを除く全成分を混合した均
一溶液又は酸成分と第二の非水有機液体との均一
溶液が第一の非水有機液体中に油滴状態で分散し
た不均一溶液にポリイソシアネートを添加して反
応を進めてもよい。もちろん最初から全成物を混
合して反応を進めることも可能である。重合反応
中における粒子状重合体の分散安定性を保持し、
小粒径化するために分散安定剤を段階的に仕込む
方法を用いてもよい。分散安定剤は溶液として用
いてもよい。
本発明により得られる粒子重合体は反応中又は
反応後に必要に応じてメタノール、ｎ−ブタノー
ル、ベンジルアルコール、ε−カプロラクタム、
メチルエチルケトンオキシム、アセトアルドキシ
ム、フエノール、クレゾールなどの活性水素を分
子内に１個有する適当なブロツク剤を添加反応さ
せて安定化させることができる。
反応におけるかくはん方法としては乳化器（ホ
モミキサー）による高速剪断を伴うかくはん方
法、プロペラ型かくはん器による粒子の機械的切
断、粉砕を伴わないかくはん方法などが用いられ
る。乳化器は重合体への反応剤の転解率が余り高
くない領域で使用することが好ましい。望ましい
かくはん方法としては、反応の初期に乳化器によ
つて粒子の小径化を行ない、その粒子の分散安定
性が良好なる重合率付近でプロペラ型かくはん器
に代えて、さらに反応を進める方法がある。この
方法によれば、比較的小粒径で粒度のそろつた粒
子状重合体を得ることができる。合成系によつて
は反応前に乳化器を使用して小粒子化することも
可能である。
本発明になる製造法によれば、粒子状重合体
は、第一の非水有機液体中に分散させて得られ、
分散相にはこの粒子状重合体の他に第二の非水有
機液体、分散安定剤、反応剤等が含まれるが、こ
れらは精製を行なうことによつて除去される。
本法において得られる粒子状重合体は、平均粒
度が0.05〜2000μｍ及びそれ以上の範囲にある非
塊状の粒子形態で得られる。好ましい平均粒度は
0.1〜500μｍ、最も好ましいものは0.5〜100μｍ
である。かかる粒子状重合体の回収方法は過又
はデカンテーシヨンし、次いで常圧又は減圧下で
乾燥することによつて分散体溶液から回収でき
る。
本発明によつて得られる粒子状重合体に必要に
応じて、エポキシ樹脂、アミノ樹脂、フエノール
ホルムアルデヒド樹脂、イソシアヌレート環含有
ポリイソシアネート及び酸成分としてテレフタル
酸及び／又はイソフタル酸を用いて得られる水酸
基を有するポリエステル樹脂のいずれか１又は２
以上を添加して、複合材料とすることができる。
エポキシ樹脂としてはエピコート828、1001、
1004、1007等のビスフエノール系エポキシ樹脂、
DEN431、438（以上、ダウ・ケミカル社製商品
名）等のエポキシ化ノボラツク樹脂、トリグリシ
ジルイソシアヌレートなどが好ましい。アミノ樹
脂としてはメラミンホルムアルデヒド樹脂及びこ
のアルコキシ変性樹脂、例えばブトキシベンゾグ
アナミンホルムアルデヒド樹脂、ヘキサメトキシ
メラミン樹脂などが好ましい。フエノールホルム
アルデヒド樹脂としては、フエノールホルムアル
デヒド樹脂、アルキルフエノールホルムアルデヒ
ド樹脂、これらの樹脂を主体としたメラミン変性
フエノールホルムアルデヒド樹脂、ベンゾグアナ
ミン変性フエノールホルムアルデヒド樹脂などが
好ましい。イソシアヌレート環含有ポリイソシア
ネートとしては芳香族ジイソシアネート、特にト
リレンジイソシアネートを第三級アミンの存在下
で反応させて得られた三量体又は三量体を含むイ
ソシアヌレート環含有ポリイソシアネート混合物
などが好ましい。酸成分としてテレフタル酸及
び／又はイソフタル酸を用いて得られる水酸基を
有するポリエステル樹脂としては、分岐成分とし
てトリス（２−ヒドロキシエチル）イソシアヌレ
ートを用いたポリエステル樹脂、ポリエステルイ
ミド樹脂、ポリエステルアミド樹脂などが好まし
い。このような粒子状重合体及びその複合材料は
良好な耐熱性、機械特性、電気特性を示し、耐熱
塗料、耐熱シート、耐熱接着剤、耐熱積層材料、
耐熱摺動材料、耐熱成形モールド品、ガラス繊
維、炭素繊維との耐熱複合材料などに有用であ
る。特に微粒子系では比較的安定な分散系が得ら
れるので分散体溶液のままで分散塗料として利用
することもできる。更に、ゲル化した粒子状重合
体は、耐熱揺変剤、耐熱充填剤、潤滑油の増稠
剤、無機元素の吸着剤、有機化合物の分離材料な
どに有用である。
本発明を実施例及び比較例を用いて説明する。
実施例 １
(1) 分散安定剤の合成
温度計、かきまぜ機、球管冷却器をつけた四
つ口フラスコに、ISOPAR−Ｈ（エツソスタン
ダード石油社製脂肪族炭化水素、商品名）152
ｇ、ラウリルメタクリレート87.5ｇ及びメタク
リル酸−２−ヒドロキシエチル20.5ｇを入れ、
145℃に昇温した。窒素ガスを通しながら、あ
らかじめ調製したラウリルメタクリレート87.0
ｇ、メタクリル酸−２−ヒドロキシエチル5.0
ｇ、過酸化ベンゾイルペースト（過酸化ベンゾ
イルの含分50重量％）9.6ｇの混合物をかくは
んしながら２時間かけて滴下した。引き続き同
温度で４時間反応させた。この分散安定剤溶液
は170℃で２時間乾燥した時の不揮発分が40重
量％であり、分散安定剤の数平均分子量（分子
量既知のポリスチレンを検量線とするゲルパー
ミエーシヨンクロマトグラフイ法によつて求め
た。以下同じ）は6400であつた。
(2) 粒子状重合体の合成
温度計、かきまぜ機、球管冷却器をつけた
500mlの四つ口フラスコに窒素ガスを通しなが
ら、４・4′−ジフエニルメタンジイソシアネー
ト75ｇ、(1)で得た分散安定剤溶液（不揮発分40
重量％）19ｇ、ISOPAR−Ｈ 150ｇ、Ｎ−メ
チルピロリドン33ｇを入れ、380r.p.mでかく
はんしながら90℃に昇温した。この状態でこれ
らの混合物は均一溶液となつた。あらかじめ、
微粉末化したトリメリツト酸無水物72ｇを添加
し、100℃で１時間、115℃で１時間、さらに
125℃に昇温して４時間反応を進めた。連続相
のISOPAR−Ｈ中に分散した褐色の粒子状重合
体を得たので、これを過によつて回収し、更
にメタノールで煮沸後別したものを減圧下、
60℃で５時間乾燥させた。この粒子状重合体の
赤外吸収スペクトルには、1780cm-1にイミド結
合、1650cm-1と1540cm-1にアミド結合の吸収が
認められた。このポリアミドイミド粒子状重合
体の主粒子径は約10〜80μｍであつた。
実施例 ２
分散安定剤溶液の使用量を24ｇとした以外は実
施例１、(2)と全く同様に粒子状重合体を合成し、
処理した。得られた粒子状重合体の赤外吸収スペ
クトルには1780cm-1にイミド結合、1650cm-1と
1540cm-1にアミド結合の吸収が認められた。この
ポリアミドイミド粒子状重合体の主粒子径は約10
〜50μｍであつた。
更に得られたポリアミドイミド粒子状重合体10
ｇ、ビスフエノール型エポキシ樹脂エピコート
828（シエル化学製、商品名）10ｇ及び硬化助剤
2PZ−CN（四国化成社製、商品名）0.1ｇを配合
し、常法に従い130℃３時間、160℃５時間、200
℃10時間加熱し、HDT試験片を作成した。HDT
は175℃と良好な耐熱性を示した。
実施例 ３
(1) 分散安定剤の合成
実施例１、(1)と同様の装置を用いて、フラス
コにISOPAR−H185.7ｇ、ラウリルメタクリレ
ート106.8ｇ、メタクリル酸−２−ヒドロキシ
エチル6.1ｇを入れ、100℃に昇温した。窒素ガ
スを通しながら、あらかじめ調製したラウリル
メタクリレート106.9ｇ、メタクリル酸−２−
ヒドロキシエチル24.5ｇ、過酸化ベンゾイルペ
ースト（過酸化ベンゾイルの含分50重量％）
2.4ｇの混合物をかくはんしながら２時間かけ
て滴下した。引き続き100℃で１時間保温後140
℃に昇温し、同温度で４時間反応させた。この
分散安定剤溶液は170℃で２時間乾燥した時の
不揮発分は55重量％であり、分散安定剤の数平
均分子量は66800であつた。
(2) 粒子状重合体の合成
分散安定剤溶液を(1)で得られたものとした以
外は実施例１、(2)と全く同様にして粒子状重合
体を合成し処理した。
得られた粒子状重合体の赤外吸収スペクトル
には1780cm-1にイミド結合、1650cm-1と1540cm
-1にアミド結合の吸収が認められた。このポリ
アミドイミド粒子状重合体の主粒子径は約20〜
40μｍであつた。
実施例 ４
(1) 分散安定剤の合成
実施例１、(1)と同様の装置を用いて、フラス
コにISOPAR−H92.9ｇ、ラウリルメタクリレ
ート106.8ｇ、メタクリル酸−２−ヒドロキシ
エチル6.1ｇを入れ、80℃に昇温した。窒素ガ
スを通しながら、あらかじめ調製したラウリル
メタクリレート106.9ｇ、メタクリル酸−２−
ヒドロキシエチル24.5ｇ、過酸化ベンゾイルペ
ースト（過酸化ベンゾイルの含分50重量％）
1.2ｇの混合物をかくはんしながら２時間かけ
て滴下した。引き続き80℃でISOPAR−H92.8
ｇを１時間かけて滴下し、更に80℃で１時間保
温後140℃に昇温し、同温度で４時間反応させ
た。この分散安定剤溶液は170℃で２時間乾燥
した時の不揮発分は47重量％であり、分散安定
剤の数平均分子量は290000であつた。
(2) 粒子状重合体の合成
分散安定剤溶液を(1)で得られたものとした以
外は実施例１、(2)と全く同様に粒子状重合体を
合成し、処理した。
得られた粒子状重合体の赤外吸収スペクトル
には1780cm-1にイミド結合、1650cm-1と1540cm
-1にアミド結合の吸収が認められた。このポリ
アミドイミド粒子状重合体の主粒子径は約２〜
20μｍであつた。
実施例 ５
(1) 分散安定剤の合成
実施例１、(1)と同様の装置を用いて、フラス
コにISOPAR−H152ｇを入れ、120℃に昇温し
た。窒素ガスを通しながら、あらかじめ調製し
たラウリルメタクリレート183ｇ、メタクリル
酸−２−ヒドロキシエチル18.7ｇ、過酸化ベン
ゾイルペースト（過酸化ベンゾイルの含分50重
量％）10ｇの混合物をかくはんしながら２時間
かけて滴下した。引き続き140℃に昇温し、同
温度で４時間反応させた。この分散安定剤溶液
は170℃で２時間乾燥した時の不揮発分は41重
量％であり、分散安定剤の数平均分子量は
10000であつた。
(2) 粒子状重合体の合成
分散安定剤溶液を本実施例(1)で得られたもの
を100ｇ、ISOPAR−Ｈを100ｇ用いた以外は実
施例１、(2)と全く同様に粒子状重合体を合成
し、処理した。
得られた粒子状重合体の赤外吸収スペクトル
には1780cm-1にイミド結合、1650cm-1と1540cm
-1にアミド結合の吸収が認められた。このポリ
アミドイミド粒子状重合体の主粒子径は約30〜
40μｍであつた。
実施例 ６
分散安定剤溶液の使用量を9.0ｇとした以外は
実施例５、(2)と全く同様に粒子状重合体を合成
し、処理した。
得られた粒子状重合体の赤外吸収スペクトルに
は、1780cm-1にイミド結合、1650cm-1と1540cm-1
にアミド結合の吸収が認められた。このポリアミ
ドイミド粒子状重合体の主粒子径は数50〜500μ
ｍであつた。
実施例 ７
(1) 分散安定剤の合成
実施例１、(1)と同様の装置を用いて、フラス
コにISOPAR−H152ｇ、ラウリルメタクリレ
ート74.5ｇ、メタクリル酸−２−ヒドロキシエ
チル10.2ｇを入れ、120℃に昇温した。窒素ガ
スを通しながら、あらかじめ調製したラウリル
メタクリレート74.5ｇ、メタクリル酸−２−ヒ
ドロキシエチル40.8ｇ、過酸化ベンゾイルペー
スト（過酸化ベンゾイルの含分50重量％）２ｇ
の混合物をかくはんしながら２時間かけて滴下
した。引き続き120℃でISOPAR−H100ｇを１
時間かけて滴下し、140℃に昇温し、同温度で
４時間反応させた。この分散安定剤溶液は白濁
しており、170℃で２時間乾燥した時の不揮発
分は51重量％であり、分散安定剤の数平均分子
量は44500であつた。
(2) 粒子状重合体の合成
分散安定剤溶液を(1)で得られたものとした以
外は、実施例１、(2)と全く同様に粒子状重合体
を合成し、処理した。
得られた粒子状重合体の赤外吸収スペクトル
には1780cm-1にイミド結合、1650cm-1と1540cm
-1にアミド結合の吸収が認められた。このポリ
アミドイミド粒子状重合体の主粒子径は約10〜
30μｍであつた。
実施例 ８
実施例１、(2)と同じ装置を用いて、窒素ガスを
通しながら、４・4′−ジフエニルメタンジイソシ
アネート75ｇ、実施例３、(1)で得た分散安定剤溶
液（不揮発分55重量％）19ｇ、ISOPAR−H150
ｇ、Ｎ−メチルピロリドン33ｇを入れ、かくはん
しながら90℃に昇温した。あらかじめ微粉末化し
たピロメリツト酸無水物64.7ｇを添加し、100℃
に１時間、120℃で１時間、140℃で１時間、さら
に180℃に昇温して反応を進め、重合体の酸価が
60〔KOHmg／ｇ〕となつたところを終点とし
た。ISOPAR−Ｈ中に分散した褐色の粒子状重合
体を得たので、これを過によつて回収し、更に
メタノールで煮沸後別したものを減圧下、60℃
で５時間乾燥させた。この粒子状重合体の赤外吸
収スペクトルには1780cm-1にイミド結合の吸収を
認められ、1650cm-1、1540cm-1にアミド結合の吸
収は認められなかつた。このポリイミド粒子状重
合体の主粒子は約10〜80μｍであつた。
実施例 ９
実施例１、(2)と同じ装置を用いて、窒素ガスを
通しながら、４・4′−ジフエニルメタンジイソシ
アネート75ｇ、実施例３、(1)で得た分散安定剤溶
液（不揮発分55重量％）25ｇ、ISOPAR−H150
ｇ、Ｎ−メチルピロリドン33ｇを入れ、かくはん
しながら90℃に昇温した。あらかじめ微粉末化し
たイソフタル酸49.3ｇを添加し、100℃で１時
間、115℃で１時間、さらに130℃に昇温して反応
を進め、重合体の酸価が70〔KOHmg／ｇ〕とな
つたところを終点とした。連続相のISOPAR−Ｈ
中に分散した白色の粒子状重合体を得たので、こ
れを過によつて回収し、ｎ−ヘキサンで洗浄し
たのち、減圧下、60℃で５時間乾燥させた。この
粒子状重合体の赤外吸収スペクトルには、1780cm
-1のイミド結合の吸収は認められず、1650cm-1と
1540cm-1にアミド結合の吸収のみが認められた。
このポリアミド粒子状重合体の主粒子径は約20〜
80μｍであつた。
実施例 10
(1) 分散安定剤の合成
実施例１、(1)と同様の装置を用いて、フラス
コにISOPAR−H100ｇ、ステアリルメタクリ
レート142.2ｇ、メタクリル酸−２−ヒドロキ
シエチル12.2ｇを入れ、100℃に昇温した。窒
素ガスを通しながら、あらかじめ調製した
ISOPAR−H85.7ｇ、ステアリルメタクリレー
ト142.2ｇ、メタクリル酸−２−ヒドロキシエ
チル49.0ｇ、過酸化ベンゾイルペースト（過酸
化ベンゾイルの含分50重量％）4.8ｇの混合物
をかくはんしながら２時間かけて滴下した。引
き続き100℃で１時間保温した後140℃に昇温
し、同温度で４時間反応させた。この分散安定
剤溶液は170℃で２時間乾燥した時の不揮発分
は51重量％であり、分散安定剤の数平均分子量
は65000であつた。
(2) 粒子状重合体の合成
分散安定剤溶液を(1)で得られたものとした以
外は実施例１、(2)と全く同様に粒子状重合体を
合成し、処理した。
得られた粒子状重合体の赤外吸収スペクトル
には1780cm-1にイミド結合、1650cm-1と1540cm
-1にアミド結合の吸収が認められた。このポリ
アミドイミド粒子状重合体の主粒子径は約10〜
30μｍであつた。
実施例 11
４・4′−ジフエニルメタンジイソシアネート
257.1ｇ、トリメリツト酸無水物246.9ｇ、Ｎ−
メチルピロリドン113.1ｇ、ISOPAR−H514.3ｇ
および実施例３、(1)で得た分散安定剤溶液68.6ｇ
を混合してホモミキサーを使用して高速かくはん
下に100℃１時間反応を進めた。その後実施例
１、(1)と同様の装置に移し、115℃１時間、さら
に125℃に昇温して４時懐反応を進め、反応終了
後メタノール処理し乾燥した。得られた粒子状重
合体の赤外吸収スペクトルには1780cm-1にイミド
結合、1650cm-1と1540cm-1にアミド結合の吸収が
認められた。このポリアミドイミド粒子状重合体
の主粒子径は約0.5〜２μｍであつた。
実施例 12
(1) トリレンジイソシアネート３量体の合成温度
計、かきまぜ機、球管冷却器をつけた四つ口フ
ラスコにトリレンジイソシアネート1000ｇ、ア
ニス酸0.52ｇ、ジメチルアミノエタノール
0.300ｇを入れ、窒素を通しながら80℃に昇温
した。同温度でイソシアネート基の含有量（初
期濃度：48重量％）が32重量％になるまで反応
させた。このものの赤外吸収スペクトルには
1710cm-1と1410cm-1にイソシアヌレート環の吸
収が認められ、2260cm-1にはイソシアネート基
の吸収が認められた。
(2) ゲル化した粒子状重合体の合成
温度計、かきまぜ機、球管冷却器をつけた四
つ口フラスコに窒素ガスを通しながら、４・
4′−ジフエニルメタンジイソシアネート48.4
ｇ、(2)で得たトリレンジイソシアネート３量体
48.4ｇ、実施例７、(1)で得た分散安定剤溶液
（不揮発分51重量％）19.0ｇ、ISOPAR−H150
ｇ、Ｎ−メチルピロリドン33ｇ、トリメリツト
酸無水物37.2ｇを添加し、110℃で１時間、120
℃で１時間、130℃で１時間、140℃で１時間、
150℃で１時間、160℃で２時間反応させた。
ISOPAR−Ｈ中に分散した茶色の粒子状重合体
の一部をヒペツトで取り出して、Ｎ−メチルピ
ロリドン中に加えたところ粒子状重合体は、Ｎ
−メチルピロリドンに溶解せず、Ｎ−メチルピ
ロリドンは着色しなかつた。ついでこれを過
によつて回収し、ｎ−ヘキサンさらにアセトン
で洗浄したのち減圧下、60℃で５時間乾燥させ
た。この粒子状重合体の赤外吸収スペクトルに
は、1780cm-1にイミド結合、1650cm-1と1540cm
-1にアミド結合の吸収が認められた。この粒子
状重合体を走査電子顕微鏡で観察すると形状は
球形であり、主粒子径は約10〜30μｍであつ
た。
比較例 １
(1) 分散安定剤の合成
実施例１、(1)と同様の装置を用いて、フラス
コにISOPAR−H152ｇを入れ、160℃に昇温し
た。窒素ガスを通しながら、あらかじめ調製し
たラウリルメタクリレート183.3ｇ、メタクリ
ル酸−２−ヒドロキシエチル30.6ｇ、過酸化ベ
ンゾイルペースト（過酸化ベンゾイルの含分50
重量％）11.7ｇの混合物をかくはんしながら２
時間かけて滴下した。引き続き同温度で４時間
反応させた。この分散安定剤溶液は170℃で２
時間乾燥した時の不揮発分は25重量％であり、
分散安定剤の数平均分子量は2800であつた。
(2) 粒子状重合体の合成
分散安定剤溶液を(1)で得られたものを64ｇ用
いた以外は実施例１、(2)と全く同様に粒子状重
合体を合成した。125℃に昇温したところ15分
後に凝集した。
比較例 ２
(1) 分散安定剤の合成
実施例１、(1)と同様の装置を用いて、フラス
コにISOPAR−H152ｇを入れ、80℃に昇温し
た。窒素ガスを通しながら、あらかじめ調製し
たラウリルメタクリレート183.0ｇ、メタクリ
ル酸−２−ヒドロキシエチル12.0ｇ、過酸化ベ
ンゾイルペースト（過酸化ベンゾイルの含分50
重量％）1.0ｇの混合物をかくはんしながら２
時間かけて滴下した。更にISOPAR−H100ｇ
を１時間かけて滴下し、引き続き80℃に１時間
保温した後、140℃に昇温し、同温度で４時間
反応させた。この分散安定剤溶液は170℃で２
時間乾燥した時の不揮発分は50重量％であり、
分散安定剤の数平均分子量は230000であつた。
(2) 粒子状重合体の合成
分散安定剤溶液を(1)で得られたものを38ｇ用
いた以外は実施例１、(2)と全く同様に合成を行
なつたが115℃に昇温後30分で凝集した。
比較例 ３
(1) 分散安定剤の合成
実施例１、(1)と同様の装置を用いて、フラス
コにISOPAR−H74.3ｇをラウリルメタクリレ
ート97.8ｇを入れ、80℃に昇温した。窒素ガス
を通しながら、あらかじめ調製したラウリルメ
タクリレート97.8ｇ、過酸化ベンゾイルペース
ト（過酸化ベンゾイルの含分50重量％）1.0ｇ
の混合物をかくはんしながら２時間かけて滴下
した。更にISOPAR−H74.3ｇを１時間かけて
滴下し、引き続き80℃１時間保温した後、100
℃で１時間、140℃で５時間反応させた。この
分散安定剤溶液は170℃で２時間乾燥した時の
不揮発分は53％であり、分散安定剤の数平均分
子量は134000であつた。
(2) 粒子状重合体の合成
分散安定剤溶液を(1)で得られたものを30ｇ用
いた以外は実施例１、(2)と全く同様に合成を行
なつたがトリメリツト酸無水物を添加し、100
℃で30分反応させたところ凝集した。
比較例 ４
分散安定剤溶液を実施例５、(1)で得られたもの
を1.0ｇ用いた以外は実施例１、(1)と全く同様に
合成を行なつたが、トリメリツト酸無水物を添加
し、115℃に昇温後30分で凝集した。
比較例 ５
(1) 分散安定剤の合成
実施例１、(1)と同様の装置を用いて、フラス
コにISOPAR−H152ｇを入れ、120℃に昇温し
た。窒素ガスを通しながら、あらかじめ調製し
たラウリルメタクリレート183ｇ、メタクリル
酸−２−ヒドロキシエチル16.1ｇ、過酸化ベン
ゾイルペースト（過酸化ベンゾイルの含分50重
量％）10ｇの混合物をかくはんしながら２時間
かけて滴下した。引き続き140℃に昇温し、同
温度で４時間反応させた。この分散安定剤溶液
は170℃で２時間焼付けした時の不揮発分は40
重量％であり、分散安定剤の数平均分子量は
9000であつた。
(2) 粒子状重合体の合成
分散安定剤溶液を(1)で得られたものを25ｇ用
いた以外は実施例１、(2)と全く同様に粒子状重
合体を合成し、処理した。得られた粒子状重合
体の赤外吸収スペクトルには1780cm-1にイミド
結合、1650cm-1と1540cm-1にアミド結合の吸収
が認められた。このポリアミドイミド粒子状重
合体の主粒子径は約60〜1000μｍであつた。
同一条件で再度粒子状重合体の製造を試みたと
ころ125℃に昇温後15分で凝集した。
更に同一条件で合計10回粒子状重合体の製造を
試み、最終的に４回粒子状重合体が得られ、６回
凝集した。
以上のようにして得られた実施例１〜11と比較
例１〜５のうち、分散安定剤と粒子状重合体の合
成について表１にまとめた。
The present invention relates to a method for producing particulate polymers, and more specifically, mainly to sheets, molded products, adhesives,
This article relates to a method for producing particulate polymers with excellent heat resistance that can be applied to paints, composite materials, etc. A polyisocyanate and a polycarboxylic acid having an acid anhydride group are reacted in a solution state in an expensive solvent such as N-methylpyrrolidone, dimethylformamide, or dimethylacetamide to produce a polymer solution having an imide group, such as polyamideimide. solution,
It is known to obtain polyimide solutions and the like.
However, in order to obtain a solid polymer from such a polymer solution, it is necessary to remove or recover the solvent by an extremely uneconomical process, which poses a major cost problem in industrial scale production. One promising method for obtaining solid polymers is a bulk polymerization method that does not require a solvent. however,
Polymers having imide groups generally have a rigid and highly polar molecular structure and are characterized by a high glass transition temperature. Therefore, when applying the bulk polymerization method, it is generally necessary to proceed with the reaction under harsh conditions of high temperature and high pressure, making it difficult to control the reaction and suppress side reactions, and it is still difficult to put into practical use. There are no successful examples. Furthermore, among polyamide resins, aromatic polyamides are known to have very good heat resistance, but generally the reactivity between aromatic dicarboxylic acids and aromatic diamines is not sufficient. In order to obtain high molecular weight polymers such as 6,6-nylon and 6-nylon, a polymerization reaction of aromatic dicarboxylic acid dichloride, which is more reactive than free carboxylic acid, and aromatic diamine is used. However, in the reaction of aromatic diamine and aromatic dicarboxylic acid dichloride, hydrochloric acid is produced as a by-product, and side reactions such as formation of undesirable amine hydrochloride occur, so it is necessary to remove the hydrochloric acid, which requires industrial-scale production. That leaves a problem. As a result of repeated studies on an inexpensive method for producing a particulate polymer with excellent heat resistance, the present inventors have completed a method for producing a particulate polymer dispersed in a non-aqueous organic liquid. . The present invention provides a first non-aqueous organic liquid that is insoluble in the particulate polymer to be produced, a dispersion stabilizer that is soluble in the first non-aqueous organic liquid, and a dispersion stabilizer that is soluble or insoluble in the particulate polymer to be produced. In the presence of a second non-aqueous organic liquid that is swellable and essentially immiscible with the first non-aqueous organic liquid, a polyisocyanate () and a polycarboxylic acid () having acid anhydride groups and / or a method for producing a particulate polymer dispersed in a first non-aqueous organic liquid by reacting with a polycarboxylic acid (), wherein the dispersion stabilizer is a particulate polymer having 6 or more carbon atoms. The molar ratio of ethylenically unsaturated monomer (A) having a side chain consisting of a hydrocarbon group and ethylenically unsaturated monomer (B) having a hydroxyl group
A hydroxyl group-containing vinyl polymer having a number average molecular weight of 6000 or more obtained by reacting (A)/(B) in a ratio of 1/1 to 5/1 is mixed with a second non-aqueous organic liquid, a polyisocyanate, an acid anhydride, etc. The present invention relates to a method for producing a particulate polymer, characterized in that it is used in an amount of 0.5% by weight or more based on the polycarboxylic acid and/or polycarboxylic acid having a chemical group. According to the production method of the present invention, the particulate polymer is obtained as a dispersion of relatively small particles in the first non-aqueous organic liquid, and therefore can be easily recovered from the dispersion by a filtration operation. Furthermore, particularly in the production method of the present invention, an inexpensive general-purpose solvent that is insoluble in the particulate polymer produced as the first non-aqueous organic liquid can be used. Unlike solution polymerization methods, which limit high solid fractionation due to the insolubility of polymers in solvents, the present invention allows polymerization of 50% by weight in non-aqueous organic liquids.
It is possible to obtain a high solid content. In addition, the conversion rate of monomers into particulate polymers in the present invention can be sufficiently increased in the reaction temperature range of solution polymerization, and the reaction can be completed under relatively mild conditions, resulting in purity due to side reactions etc. does not cause a decrease in The first non-aqueous organic liquid in the present invention includes:
insoluble in the particulate polymer produced;
A nonaqueous organic liquid is used that has inert properties that do not inhibit the polymerization reaction. For example, n-hexane, octane, dodecane, liquid paraffin, ISOPAR-E, ISOPAR-H,
Aliphatic or alicyclic hydrocarbons such as ISOPAR-K (trade name manufactured by Etsuo Standard Oil Co., Ltd.; a petroleum-based saturated aliphatic or alicyclic hydrocarbon with a boiling point range of about 40 to 300°C) are used. It will be done. Considering the reaction temperature, those having a boiling point of 80°C or higher are preferred. These can be used alone or in combination of two or more. In the present invention, the second non-aqueous organic liquid that is essentially immiscible with the first non-aqueous organic liquid is a non-aqueous organic liquid that has inert properties that do not inhibit the polymerization reaction, and is a non-aqueous organic liquid that does not inhibit the polymerization reaction. It is soluble or swellable in at least one of (), () and/or ()), and contacts the reaction between end groups in the polymerization reaction process, thereby achieving high molecular weight of the resulting polymer. A substance that acts as a solvent is used. Here, "essentially immiscible" with the first non-aqueous organic liquid means that it is completely insoluble in the first non-aqueous organic liquid, and is not completely insoluble in the first non-aqueous organic liquid, but is immiscible at a certain mixing ratio. This is meant to include non-aqueous organic liquids that are immiscible to the extent that the liquids phase separate. The second non-aqueous organic liquid is preferably a polar liquid that has a greater affinity for the resulting polymer or reactant contained in the dispersed phase than the first non-aqueous organic liquid. Such a second non-aqueous organic liquid includes, for example, N-methylpyrrolidone,
N-vinylpyrrolidone, dimethylformamide, dimethylacetamide, γ-butyrolactone, phenol, cresol, etc. are used.
These may be used alone or in combination of two or more. Preferably, a combination of an aliphatic or alicyclic hydrocarbon and N-methylpyrrolidone is used as the first non-aqueous organic liquid. Examples of the ethylenically unsaturated monomer having a side chain consisting of a hydrocarbon group having 6 or more carbon atoms used in the production of the dispersion stabilizer in the present invention include 1-octene, 1- or 2-nonene, 1- or 2-decene, 1- or 2-dodecene, 1- or 2-hexadecene, 1- or 2-heptadecene, 2-methyl-1-nonene, 2-methyl-1-decene, 2-methyl-1-dodecene, 2 -Aliphatic linear unsaturated hydrocarbons containing vinyl, propenyl or isopropenyl groups such as methyl-1-hexadecene and 2-methyl-1-heptadecene, acrylic acid or methacrylic acid and carbon such as 2-ethylhexyl alcohol and hexyl alcohol Esters with aliphatic alcohols having six or more carbon atoms or alicyclic alcohols having six or more carbon atoms such as cyclohexanol, norbonanol, and adamantanol are used. The ethylenically unsaturated monomer having a hydroxyl group used in the present invention includes allyl alcohol, 3-buten-1-ol, 4- or 3-penten-1-ol, 5- or 4-hexene-1-ol,
ol, 6- or 5-hepten-1-ol, 7
- or 6-octen-1-ol, 8- or 7-
nonen-1-ol, 2-methylallyl alcohol, 3-methyl-3-buten-1-ol, 4-
Methyl-4-penten-1-ol, 5-methyl-5-hexen-1-ol, 6-methyl-6-
Hepten-1-ol, 7-methyl-7-octen-1-ol, 8-methyl-8-nonene-1-
Aliphatic unsaturated alcohols such as acrylic acid or methacrylic acid and ethylene glycol, 1.
Monoesters with 2- or 1,3-propanediol, 1,3- or 1,4-butanediol, etc. are used. These ethylenically unsaturated monomers having side chains consisting of hydrocarbon groups having 6 or more carbon atoms and ethylenically unsaturated monomers having hydroxyl groups are random copolymers, block copolymers, or graft copolymers. It functions as a dispersion stabilizer. The copolymer is preferably a random copolymer of lauryl methacrylate, stearyl methacrylate, lauryl acrylate, or stearyl acrylate and acrylic acid or 2-hydroxyethyl methacrylate. There are no particular restrictions on the polymerization method for obtaining the dispersion stabilizer.
An ordinary method of polymerizing ethylenic monomers using a radical initiator as a reaction initiator can be used. That is, the side chain portion of the dispersion stabilizer consisting of a hydrocarbon group having 6 or more carbon atoms is a portion that is soluble in the first non-aqueous organic liquid, and the dispersion stabilizer is a portion that is soluble in the first non-aqueous organic liquid. Retain your sexuality. Furthermore, this portion forms a repellent layer covering the surface of the dispersed particles to prevent fusion of the dispersed particles. Also, the hydroxyl group is a moiety that is essentially insoluble in the first non-aqueous organic liquid, but rather is soluble in the second non-aqueous organic liquid. Furthermore, the polyisocyanate constituting the particulate polymer and the hydroxyl group chemically bond to each other, thereby fixing the dispersant to the surface of the dispersed particles, thereby forming a stable repellent layer on each dispersed particle. Therefore, the balance between the above two different functions determines the effectiveness of the dispersion stabilizer. The molar ratio (A)/(B) of the ethylenically unsaturated monomer (A) having a side chain consisting of a hydrocarbon group having 6 or more carbon atoms and the ethylenically unsaturated monomer (B) having a hydroxyl group is If it exceeds 5/1, the solubility in the first non-aqueous organic liquid will be greater than the affinity for the dispersed particles, and the effect of the dispersion stabilizer will not be fully exhibited. If it is less than 1/1, the solubility in the first non-aqueous organic liquid will be so low that it will not be effective as a dispersion stabilizer. On the other hand, the number average molecular weight of the copolymer must be 6000 or more in order to form a repellent layer covering the surface of the dispersed particles and prevent the fusion of the dispersed particles, that is, to exert its effect as a dispersion stabilizer. . If the number average molecular weight is less than 6,000, the formation of a repellent layer is insufficient and the proportion of fusion of dispersed particles increases, making it easy for the dispersed particles to aggregate and making it difficult to synthesize a stable particulate polymer. There are no particular restrictions on the use of a copolymer with a large number average molecular weight obtained by a conventional polymerization method as a dispersion stabilizer. Furthermore, when a particulate polymer is synthesized under certain conditions, there is a relationship between the particle size obtained and the number average molecular weight of the copolymer. For example, when a copolymer with a number average molecular weight of 6000 was used as a dispersion stabilizer, the main particle diameter was 50 to 500μ, but the number average molecular weight
In the copolymer of No. 60,000, the main particle size was 20 to 40 μm, and in the case of a number average molecular weight of 300,000, the main particle size was 5 to 20 μm. This is an industrially effective technology that allows particle size adjustment of particulate polymers obtained simply by using copolymers with different number average molecular weights as dispersion stabilizers without using special manufacturing equipment. It shows. However, if the number average molecular weight is made larger than 300,000, the viscosity will naturally increase and it will become difficult to handle.For the purpose of obtaining even finer particles, it is better to use an emulsifier (homo mixer) than to use a dispersant with a large number average molecular weight.
It would be advantageous to improve the synthesis equipment, such as by using From the above, as a dispersion stabilizer, the copolymer must have a number average molecular weight of 6000 or more.
A range of 6,000 to 300,000 is preferred. The number average molecular weight is determined by gel permeation chromatography using polystyrene of known molecular weight as a calibration curve. The number average molecular weight of the dispersion stabilizer is controlled by the reaction temperature and catalyst amount during its production. The amount of the dispersion stabilizer used is 0.5% by weight or more based on the weight of the dispersed particles (second non-aqueous organic liquid, polyisocyanate, polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group). The amount of the dispersion stabilizer to be used is preferably in the range of 2 to 20% by weight in consideration of heat resistance and economic efficiency. The dispersion stabilizer is usually produced in the form of a solution and used in the form of a solution, and the amount used is calculated, for example, by the weight of nonvolatile matter in the solution after drying at 170° C. for 2 hours. Examples of the polyisocyanates used in the present invention include aromatic polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, naphthalene-1,5-diisocyanate, and 4,4'-diphenylmethane diisocyanate. Aliphatic diisocyanates such as diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutene 1.
3-diisocyanate, cyclohexane 1,3-
and cycloaliphatic diisocyanates such as 1,4-diisocyanate and isophorone diisocyanate,
Triphenylmethane-4,4',4''-triisocyanate, polyphenylmethyl polyisocyanate, polyisocyanates such as phosgenated condensates of aniline and formaldehyde, and trimerization reactions of these polyisocyanates. The isocyanurate ring-containing polyisocyanate thus obtained is used. Considering heat resistance, cost, etc., tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and 4,4'-diphenyl ether are preferably used. Aromatic polyisocyanates such as diisocyanate, triphenylmethane-4,4',4''-triisocyanate, and polyisocyanates having isocyanurate rings obtained by trimerization reaction of aromatic diisocyanates among these can be used. preferable.
A suitable method for producing isocyanurate ring-containing polyisocyanates is disclosed in Japanese Patent Publication No. 34209/1983. Isocyanurate ring-containing polyisocyanates are used as branching components, and the isocyanurate ring core provides excellent heat resistance. Difunctional polyisocyanates are used in the synthesis of particulate polymers that are substantially linear and thermoplastic. Furthermore, trifunctional or higher functional polyisocyanates are used to synthesize branched thermosetting particulate polymers. These polyisocyanates may be used alone or in combination of two or more depending on the purpose. Polyisocyanate is used in combination with methanol, n-butanol, benzyl alcohol, ε-
caprolactam, methyl ethyl ketone oxime,
It may be partially or completely stabilized with a suitable blocking agent having one active hydrogen in the molecule, such as phenol or cresol. As a polycarboxylic acid having an acid anhydride group,
For example, trimellitic anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, 3,4,
Tricarboxylic acid anhydrides such as 4'-benzophenone tricarboxylic acid-3, 4'-anhydride, 1, 2, 3, 4
-butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, ethylenetetracarboxylic acid, bicyclo-[2.2.2]-oct-(7)-ene-2:
3,5: Aliphatic and alicyclic tetrabasic acids such as 6-tetracarboxylic acid, pyromellitic acid, 3,3',
4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether,
2,3,6,7-naphthalenetetracarboxylic acid,
1, 2, 5, 6-naphthalenetetracarboxylic acid,
Ethylene glycol bistrimelitate, 2.
2'-bis(3,4-biscarboxyphenyl)propane, 2,2',3,3'- or 3,3',4,4'-
Biphenyltetracarboxylic acid, perylene-3.
4,9,10-tetracarboxylic acid, bis3,4-dicarboxyphenyl sulfone, 2,2-bis[4
-(3,4-dicarboxyphenoxy)phenyl]propane, 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane, 4
-(2,3-dicarboxyphenoxy)-4'-
Aromatic tetrabasic acids such as (3,4-dicarboxyphenoxy)-diphenyl-2,2-propane, heterocyclic acids such as thiophene-2,3,4,5-tetracarboxylic acid, pyrazinetetracarboxylic acid, etc. Examples include tetrabasic acid dianhydrides or monoanhydrides such as tetrabasic acids. A polyamide-imide is obtained from a polycarboxylic acid containing an acid anhydride group having a free carboxyl group, such as tricarboxylic anhydride, and a polyisocyanate. Further, a polyimide can be obtained from a polycarboxylic acid having only an acid anhydride group, such as tetracarboxylic dianhydride, and a polyisocyanate. Generally speaking, considering heat resistance, cost, etc., trimellitic anhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride or pyromellitic dianhydride is preferred. Examples of polycarboxylic acids include terephthalic acid,
Isophthalic acid, 2,6-, 2,5- or 3,6-
Dicarboxytoluene, 2,6-dicarboxynaphthalene, 3,3'- or 4,4'-dicarboxybiphenyl, bis(3- or 4-carboxyphenyl) ether, bis(3- or 4-carboxyphenyl) enyl)ketone, bis(3- or 4-carboxyphenyl)sulfone, bis(3- or 4-carboxyphenyl)methane, bis(3- or 4-carboxyphenyl)dimethylmethane, trimellitic acid, trimesic acid, Pyromellitic acid, Tris (2
-carboxyethyl) isocyanate, tricarballylic acid, nitrilotriacetic acid, nitrilotripropionic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, and the like. In consideration of heat resistance, isophthalic acid or terephthalic acid, trimesic acid, tris(2-carboxyethyl)isocyanurate or nitrilotriacetic acid are preferred. The amount of polyisocyanate and polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group to be used is based on the total isocyanate group of the polyisocyanate.
Or the equivalent ratio of all carboxyl groups of polycarboxylic acid (total carboxyl groups/total isocyanate groups) is 0.5
It is preferably within the range of ~2.0. here,
One equivalent of acid anhydride group is treated as one equivalent of carboxyl group. When a particulate polymer having a sufficiently high molecular weight and high heat resistance and flexibility is required, the equivalent ratio of carboxyl groups to isocyanate groups is preferably from 0.85 to 1.15, more preferably substantially Adjusted to be equivalent. According to the present invention, gelled particulate polymers can also be obtained. In order to obtain a gelled particulate polymer, the reaction may be allowed to proceed until gelation is achieved using a resin composition containing a trifunctional or higher functional crosslinking component sufficient for gelation. Among the above-mentioned polyisocyanates, compounds that can be used as trifunctional or higher-functional crosslinking components include compounds obtained by trimerizing diisocyanates, such as tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, and naphthalene diisocyanate. Aromatic diisocyanate trimers such as 1,5-diisocyanate and 4,4'-diphenylmethane diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate Trimers of aliphatic diisocyanates such as cyclobutene 1,3-diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate, isophorone diisocyanate, triisocyanate compounds such as triphenyl Methane-4,4',4''-triisocyanate, polyphenylmethyl polyisocyanate, for example, a product obtained by reacting a condensate of aniline and formaldehyde with phosgene, etc. are used.Polyisocyanates that can be used as crosslinking components are , can be used as all or a part of the polyisocyanate component.Among the polycarboxylic acids and/or polycarboxylic acids having an acid anhydride group, those that can serve as trifunctional or higher functional crosslinking components include trimellitic acid,
Trimesic acid, pyromellitic acid, tris(2-carboxyethyl)isocyanurate, tricarbalyllic acid, nitrilotriacetic acid, nitrilotripropionic acid, etc. are used. In the present invention, either or both of the polycarboxylic acid and the polycarboxylic acid having an acid anhydride group to be reacted with the polyisocyanate are used. These polycarboxylic acids that can serve as crosslinking components can be used for all or part of the polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group. In addition to the method of obtaining a gelled particulate polymer using a trifunctional or higher functional crosslinking component as described above, there are a method of gelling using a side reaction and a method of gelling by sintering. For example, the equivalent ratio of bifunctional polyisocyanate and polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group is substantially 1.0.
If the reaction is allowed to proceed for a long time at a high temperature of 120°C or higher, a gelled particulate polymer will be obtained due to side reactions. The quantitative ratio of the first non-aqueous organic liquid to be the continuous phase and the reactant to be the dispersed phase ((), () and/or ()) above) is determined by the ratio of the first non-aqueous organic liquid to the reactant. It is preferable that the amount of the reactant is 10 to 80% by weight based on the total amount. 40 from a production efficiency and cost perspective
Particularly preferred is % by weight or more. The amount ratio of the second non-aqueous organic liquid and the reactant is preferably within a range of 0.5 to 70% by weight of the second non-aqueous organic liquid based on the total amount of the second non-aqueous organic liquid and the reactant. If it is less than 0.5% by weight, the polymerization reaction will proceed only at high temperatures, making undesirable side reactions more likely to occur. If it exceeds 70% by weight, a continuous phase with a high specific gravity is formed in which the reactant is dissolved in the second non-aqueous organic liquid, resulting in phase separation from the first non-aqueous organic liquid with a low specific gravity, forming a dispersed phase. It becomes difficult to do. Also,
Even if a dispersed phase is formed, aggregation tends to occur during the polymerization reaction, which is disadvantageous in terms of cost. Particularly preferably, a range of 1 to 30% by weight is used. The reaction temperature of polyisocyanate, polycarboxylic acid having an acid anhydride group and/or polycarboxylic acid is preferably 80 to 250°C. Preferably, the polymerization reaction is carried out in substantially anhydrous conditions. Therefore, it is desirable to carry out the process under an inert atmosphere such as nitrogen gas. Naturally, when the particulate polymer obtained by the production method of the present invention comes into contact with water, its reactant, particularly polyisocyanate, quickly transforms into an inert compound. is not possible to produce as a dispersion medium. The reaction may be carried out by charging all the raw materials at the same time, or by charging them in stages depending on the purpose. Preferably, at least one component of the reactant is soluble or swellable in the second non-aqueous organic liquid, or is liquid at the reaction temperature. Preferred specific examples include a homogeneous solution in which all components except the acid component are mixed, or a heterogeneous solution in which a homogeneous solution of polyisocyanate and a second non-aqueous organic liquid is dispersed in the form of oil droplets in the first non-aqueous organic liquid. The reaction proceeds by adding a finely powdered acid component to the solution. According to this method, the polymerization reaction can proceed at a relatively low reaction temperature, and undesirable side reactions can be suppressed. Polyisocyanate is added to a homogeneous solution in which all components except the polyisocyanate are mixed, or to a heterogeneous solution in which a homogeneous solution of an acid component and a second non-aqueous organic liquid is dispersed in the form of oil droplets in the first non-aqueous organic liquid. The reaction may proceed as follows. Of course, it is also possible to proceed with the reaction by mixing all the components from the beginning. Maintains dispersion stability of particulate polymer during polymerization reaction,
In order to reduce the particle size, a method of adding a dispersion stabilizer in stages may be used. The dispersion stabilizer may be used as a solution. The particle polymer obtained by the present invention may contain methanol, n-butanol, benzyl alcohol, ε-caprolactam, etc. as necessary during or after the reaction.
Stabilization can be achieved by adding a suitable blocking agent having one active hydrogen in the molecule, such as methyl ethyl ketone oxime, acetaldoxime, phenol, or cresol. Stirring methods used in the reaction include stirring methods involving high-speed shearing using an emulsifier (homomixer), mechanical cutting of particles using a propeller-type stirrer, and stirring methods that do not involve pulverization. The emulsifier is preferably used in an area where the conversion rate of the reactant into the polymer is not very high. A desirable stirring method is to use an emulsifier to reduce the particle diameter at the beginning of the reaction, and then use a propeller-type stirrer to further advance the reaction at around the polymerization rate at which the dispersion stability of the particles is good. . According to this method, a particulate polymer having a relatively small particle size and uniform particle size can be obtained. Depending on the synthesis system, it is also possible to use an emulsifier to form small particles before the reaction. According to the production method of the present invention, the particulate polymer is obtained by dispersing it in a first non-aqueous organic liquid,
In addition to this particulate polymer, the dispersed phase contains a second non-aqueous organic liquid, a dispersion stabilizer, a reactant, etc., which are removed by purification. The particulate polymer obtained in this method is obtained in the form of non-agglomerated particles with an average particle size ranging from 0.05 to 2000 μm and above. The preferred average particle size is
0.1-500μm, most preferably 0.5-100μm
It is. The particulate polymer can be recovered from the dispersion solution by filtration or decantation and then drying under normal pressure or reduced pressure. A hydroxyl group obtained by adding an epoxy resin, an amino resin, a phenol formaldehyde resin, an isocyanurate ring-containing polyisocyanate, and terephthalic acid and/or isophthalic acid as an acid component to the particulate polymer obtained by the present invention, if necessary. Any 1 or 2 of polyester resins having
By adding the above, a composite material can be obtained.
Epoxy resins include Epicote 828, 1001,
Bisphenol epoxy resins such as 1004 and 1007,
Preferred are epoxidized novolak resins such as DEN431 and 438 (trade names manufactured by Dow Chemical Company), triglycidyl isocyanurate, and the like. As the amino resin, melamine formaldehyde resin and its alkoxy-modified resin, such as butoxybenzoguanamine formaldehyde resin, hexamethoxymelamine resin, etc. are preferred. Preferred examples of the phenol formaldehyde resin include phenol formaldehyde resins, alkyl phenol formaldehyde resins, melamine-modified phenol formaldehyde resins based on these resins, and benzoguanamine-modified phenol formaldehyde resins. The isocyanurate ring-containing polyisocyanate is preferably a trimer obtained by reacting an aromatic diisocyanate, especially tolylene diisocyanate in the presence of a tertiary amine, or a mixture of isocyanurate ring-containing polyisocyanates containing a trimer. . Examples of polyester resins having hydroxyl groups obtained using terephthalic acid and/or isophthalic acid as an acid component include polyester resins using tris(2-hydroxyethyl) isocyanurate as a branching component, polyesterimide resins, polyesteramide resins, etc. preferable. Such particulate polymers and their composite materials exhibit good heat resistance, mechanical properties, and electrical properties, and can be used as heat-resistant paints, heat-resistant sheets, heat-resistant adhesives, heat-resistant laminated materials,
It is useful for heat-resistant sliding materials, heat-resistant molded products, and heat-resistant composite materials with glass fiber and carbon fiber. In particular, since a relatively stable dispersion system can be obtained in the case of a fine particle system, the dispersion solution can also be used as a dispersion paint. Further, the gelled particulate polymer is useful as a heat-resistant thixotropic agent, a heat-resistant filler, a lubricating oil thickener, an adsorbent for inorganic elements, a separation material for organic compounds, and the like. The present invention will be explained using Examples and Comparative Examples. Example 1 (1) Synthesis of dispersion stabilizer ISOPAR-H (aliphatic hydrocarbon manufactured by Etsuo Standard Oil Co., Ltd., trade name) 152 was added to a four-necked flask equipped with a thermometer, stirrer, and bulb condenser.
g, 87.5 g of lauryl methacrylate and 20.5 g of 2-hydroxyethyl methacrylate,
The temperature was raised to 145°C. Pre-prepared lauryl methacrylate 87.0 while passing nitrogen gas
g, 2-hydroxyethyl methacrylate 5.0
A mixture of 9.6 g of benzoyl peroxide paste (benzoyl peroxide content: 50% by weight) was added dropwise over 2 hours with stirring. Subsequently, the reaction was continued at the same temperature for 4 hours. This dispersion stabilizer solution has a non-volatile content of 40% by weight when dried at 170°C for 2 hours. (hereinafter the same) was 6400. (2) Synthesis of particulate polymer Equipped with thermometer, stirrer, and bulb/tube cooler
While passing nitrogen gas into a 500 ml four-necked flask, add 75 g of 4,4'-diphenylmethane diisocyanate to the dispersion stabilizer solution obtained in (1) (non-volatile content: 40
% by weight), 150 g of ISOPAR-H, and 33 g of N-methylpyrrolidone were added, and the temperature was raised to 90° C. while stirring at 380 rpm. In this state, these mixtures became a homogeneous solution. in advance,
Add 72 g of finely powdered trimellitic anhydride and heat at 100°C for 1 hour, then at 115°C for 1 hour, and then heat at 115°C for 1 hour.
The temperature was raised to 125°C and the reaction proceeded for 4 hours. A brown particulate polymer dispersed in the continuous phase ISOPAR-H was obtained, which was recovered by filtration, boiled with methanol, separated, and separated under reduced pressure.
It was dried at 60°C for 5 hours. In the infrared absorption spectrum of this particulate polymer, imide bond absorption was observed at 1780 cm -1 and amide bond absorption was observed at 1650 cm -1 and 1540 cm -1 . The main particle diameter of this polyamide-imide particulate polymer was about 10 to 80 μm. Example 2 A particulate polymer was synthesized in exactly the same manner as in Example 1 (2) except that the amount of dispersion stabilizer solution used was 24 g,
Processed. The infrared absorption spectrum of the obtained particulate polymer shows an imide bond at 1780 cm -1 and an imide bond at 1650 cm -1 .
Absorption of amide bond was observed at 1540 cm -1 . The main particle diameter of this polyamide-imide particulate polymer is approximately 10
It was ~50 μm. Further obtained polyamideimide particulate polymer 10
g. Bisphenol type epoxy resin Epicoat
828 (manufactured by Ciel Chemical, trade name) 10g and curing aid
Blend 0.1 g of 2PZ-CN (manufactured by Shikoku Kasei Co., Ltd., trade name) and heat at 130°C for 3 hours and at 160°C for 5 hours according to the usual method.
It was heated at ℃ for 10 hours to prepare an HDT test piece. HDT
showed good heat resistance at 175℃. Example 3 (1) Synthesis of dispersion stabilizer Using the same equipment as in Example 1 (1), 185.7 g of ISOPAR-H, 106.8 g of lauryl methacrylate, and 6.1 g of 2-hydroxyethyl methacrylate were placed in a flask. , the temperature was raised to 100℃. While passing nitrogen gas, 106.9 g of lauryl methacrylate prepared in advance, methacrylic acid-2-
24.5g hydroxyethyl, benzoyl peroxide paste (benzoyl peroxide content 50% by weight)
2.4 g of the mixture was added dropwise over 2 hours with stirring. Continue to heat at 100℃ for 1 hour and then heat to 140℃.
The temperature was raised to .degree. C., and the reaction was continued at the same temperature for 4 hours. When this dispersion stabilizer solution was dried at 170°C for 2 hours, the nonvolatile content was 55% by weight, and the number average molecular weight of the dispersion stabilizer was 66,800. (2) Synthesis of particulate polymer A particulate polymer was synthesized and treated in exactly the same manner as in Examples 1 and (2) except that the dispersion stabilizer solution obtained in (1) was used. The infrared absorption spectrum of the obtained particulate polymer shows an imide bond at 1780 cm -1 and 1650 cm -1 and 1540 cm
Absorption of amide bond was observed in -1 . The main particle diameter of this polyamide-imide particulate polymer is approximately 20~
It was 40μm. Example 4 (1) Synthesis of dispersion stabilizer Using the same equipment as in Example 1 (1), 92.9 g of ISOPAR-H, 106.8 g of lauryl methacrylate, and 6.1 g of 2-hydroxyethyl methacrylate were placed in a flask. , the temperature was raised to 80℃. While passing nitrogen gas, 106.9 g of lauryl methacrylate prepared in advance, methacrylic acid-2-
24.5g hydroxyethyl, benzoyl peroxide paste (benzoyl peroxide content 50% by weight)
1.2 g of the mixture was added dropwise over 2 hours with stirring. Continue to ISOPAR-H92.8 at 80℃
g was added dropwise over 1 hour, and after keeping the temperature at 80°C for 1 hour, the temperature was raised to 140°C and reacted at the same temperature for 4 hours. When this dispersion stabilizer solution was dried at 170°C for 2 hours, the nonvolatile content was 47% by weight, and the number average molecular weight of the dispersion stabilizer was 290,000. (2) Synthesis of Particulate Polymer A particulate polymer was synthesized and treated in exactly the same manner as in Examples 1 and (2), except that the dispersion stabilizer solution obtained in (1) was used. The infrared absorption spectrum of the obtained particulate polymer shows an imide bond at 1780 cm -1 and 1650 cm -1 and 1540 cm
Absorption of amide bond was observed in -1 . The main particle diameter of this polyamide-imide particulate polymer is about 2 to
It was 20μm. Example 5 (1) Synthesis of dispersion stabilizer Using the same apparatus as in Example 1 (1), 152 g of ISOPAR-H was placed in a flask and the temperature was raised to 120°C. While passing nitrogen gas, a mixture of 183 g of lauryl methacrylate, 18.7 g of 2-hydroxyethyl methacrylate, and 10 g of benzoyl peroxide paste (benzoyl peroxide content: 50% by weight) prepared in advance was added dropwise over 2 hours while stirring. did. Subsequently, the temperature was raised to 140°C, and the reaction was continued at the same temperature for 4 hours. When this dispersion stabilizer solution was dried at 170℃ for 2 hours, the nonvolatile content was 41% by weight, and the number average molecular weight of the dispersion stabilizer was
It was 10,000. (2) Synthesis of particulate polymer A particulate polymer was prepared in the same manner as in Examples 1 and (2) except that 100 g of the dispersion stabilizer solution obtained in Example (1) and 100 g of ISOPAR-H were used. Polymers were synthesized and processed. The infrared absorption spectrum of the obtained particulate polymer shows an imide bond at 1780 cm -1 and 1650 cm -1 and 1540 cm
Absorption of amide bond was observed in -1 . The main particle diameter of this polyamide-imide particulate polymer is approximately 30~
It was 40μm. Example 6 A particulate polymer was synthesized and treated in exactly the same manner as in Example 5 (2) except that the amount of dispersion stabilizer solution used was 9.0 g. The infrared absorption spectrum of the obtained particulate polymer shows an imide bond at 1780 cm -1 and an imide bond at 1650 cm -1 and 1540 cm -1
Absorption of amide bonds was observed. The main particle diameter of this polyamide-imide particulate polymer is several 50 to 500 μm.
It was m. Example 7 (1) Synthesis of dispersion stabilizer Using the same equipment as in Example 1 (1), put 152 g of ISOPAR-H, 74.5 g of lauryl methacrylate, and 10.2 g of 2-hydroxyethyl methacrylate into a flask, and add 120 g of 2-hydroxyethyl methacrylate. The temperature was raised to ℃. While passing nitrogen gas, add 74.5 g of lauryl methacrylate prepared in advance, 40.8 g of 2-hydroxyethyl methacrylate, and 2 g of benzoyl peroxide paste (benzoyl peroxide content: 50% by weight).
The mixture was added dropwise over 2 hours while stirring. Continue to add 100g of ISOPAR-H at 120℃.
The mixture was added dropwise over time, heated to 140°C, and reacted at the same temperature for 4 hours. This dispersion stabilizer solution was cloudy, and when dried at 170°C for 2 hours, the nonvolatile content was 51% by weight, and the number average molecular weight of the dispersion stabilizer was 44,500. (2) Synthesis of particulate polymer A particulate polymer was synthesized and treated in exactly the same manner as in Examples 1 and (2), except that the dispersion stabilizer solution obtained in (1) was used. The infrared absorption spectrum of the obtained particulate polymer shows an imide bond at 1780 cm -1 and 1650 cm -1 and 1540 cm
Absorption of amide bond was observed in -1 . The main particle diameter of this polyamide-imide particulate polymer is about 10~
It was 30 μm. Example 8 Using the same equipment as in Example 1 (2), 75 g of 4,4'-diphenylmethane diisocyanate and the dispersion stabilizer solution (non-volatile 55% by weight) 19g, ISOPAR-H150
33 g of N-methylpyrrolidone were added thereto, and the temperature was raised to 90° C. while stirring. Add 64.7 g of pyromellitic anhydride that has been finely powdered in advance, and heat at 100°C.
1 hour at 120°C, 1 hour at 140°C, and then raised to 180°C to proceed with the reaction, until the acid value of the polymer increased.
The end point was 60 [KOHmg/g]. A brown particulate polymer dispersed in ISOPAR-H was obtained, which was recovered by filtration, further boiled with methanol, separated, and heated at 60°C under reduced pressure.
It was dried for 5 hours. In the infrared absorption spectrum of this particulate polymer, imide bond absorption was observed at 1780 cm -1 and no amide bond absorption was observed at 1650 cm -1 and 1540 cm -1 . The main particles of this polyimide particulate polymer were about 10 to 80 μm. Example 9 Using the same equipment as in Example 1 (2), 75 g of 4,4'-diphenylmethane diisocyanate and the dispersion stabilizer solution (non-volatile 55% by weight) 25g, ISOPAR-H150
g and 33 g of N-methylpyrrolidone were added thereto, and the temperature was raised to 90°C while stirring. 49.3 g of isophthalic acid, which had been pulverized in advance, was added, and the reaction was carried out at 100°C for 1 hour, at 115°C for 1 hour, and further heated to 130°C, until the acid value of the polymer was 70 [KOHmg/g]. The end point was the point where I got tired. Continuous phase ISOPAR-H
A white particulate polymer dispersed therein was obtained, which was recovered by filtration, washed with n-hexane, and then dried at 60° C. for 5 hours under reduced pressure. The infrared absorption spectrum of this particulate polymer includes 1780cm
-1 imide bond absorption was not observed, and 1650 cm -1
Only absorption of amide bond was observed at 1540 cm -1 .
The main particle diameter of this polyamide particulate polymer is about 20~
It was 80μm. Example 10 (1) Synthesis of dispersion stabilizer Using the same equipment as in Example 1 (1), put 100 g of ISOPAR-H, 142.2 g of stearyl methacrylate, and 12.2 g of 2-hydroxyethyl methacrylate into a flask, and add 100 g of 2-hydroxyethyl methacrylate. The temperature was raised to ℃. Prepared in advance by passing nitrogen gas
A mixture of 85.7 g of ISOPAR-H, 142.2 g of stearyl methacrylate, 49.0 g of 2-hydroxyethyl methacrylate, and 4.8 g of benzoyl peroxide paste (benzoyl peroxide content: 50% by weight) was added dropwise over 2 hours while stirring. . Subsequently, the mixture was kept at 100°C for 1 hour, then raised to 140°C, and reacted at the same temperature for 4 hours. When this dispersion stabilizer solution was dried at 170° C. for 2 hours, the nonvolatile content was 51% by weight, and the number average molecular weight of the dispersion stabilizer was 65,000. (2) Synthesis of Particulate Polymer A particulate polymer was synthesized and treated in exactly the same manner as in Examples 1 and (2), except that the dispersion stabilizer solution obtained in (1) was used. The infrared absorption spectrum of the obtained particulate polymer shows an imide bond at 1780 cm -1 and 1650 cm -1 and 1540 cm
Absorption of amide bond was observed in -1 . The main particle diameter of this polyamide-imide particulate polymer is approximately 10~
It was 30 μm. Example 11 4,4'-diphenylmethane diisocyanate 257.1g, trimellitic anhydride 246.9g, N-
Methylpyrrolidone 113.1g, ISOPAR-H514.3g
and Example 3, 68.6 g of the dispersion stabilizer solution obtained in (1)
The mixture was mixed and the reaction proceeded at 100°C for 1 hour with high speed stirring using a homomixer. Thereafter, the mixture was transferred to the same apparatus as in Example 1 (1), and the reaction was carried out at 115° C. for 1 hour, then further heated to 125° C. for 4 hours, and after the reaction was completed, it was treated with methanol and dried. In the infrared absorption spectrum of the obtained particulate polymer, imide bond absorption was observed at 1780 cm -1 and amide bond absorption was observed at 1650 cm -1 and 1540 cm -1 . The main particle diameter of this polyamide-imide particulate polymer was about 0.5 to 2 μm. Example 12 (1) Synthesis of tolylene diisocyanate trimer In a four-necked flask equipped with a thermometer, stirrer, and bulb condenser, add 1000 g of tolylene diisocyanate, 0.52 g of anisic acid, and dimethylaminoethanol.
0.300g was added, and the temperature was raised to 80°C while passing nitrogen. The reaction was carried out at the same temperature until the content of isocyanate groups (initial concentration: 48% by weight) reached 32% by weight. The infrared absorption spectrum of this substance is
Absorption of isocyanurate rings was observed at 1710 cm -1 and 1410 cm -1 , and absorption of isocyanate groups was observed at 2260 cm -1 . (2) Synthesis of gelled particulate polymer While passing nitrogen gas through a four-necked flask equipped with a thermometer, stirrer, and bulb condenser,
4'-Diphenylmethane diisocyanate 48.4
g, tolylene diisocyanate trimer obtained in (2)
48.4g, Example 7, dispersion stabilizer solution obtained in (1) (non-volatile content 51% by weight) 19.0g, ISOPAR-H150
g, 33 g of N-methylpyrrolidone, and 37.2 g of trimellitic anhydride were added, and the mixture was heated at 110°C for 1 hour at 120°C.
℃ for 1 hour, 130℃ for 1 hour, 140℃ for 1 hour,
The reaction was carried out at 150°C for 1 hour and at 160°C for 2 hours.
When a part of the brown particulate polymer dispersed in ISOPAR-H was taken out with a hippet and added to N-methylpyrrolidone, the particulate polymer was
- Not dissolved in methylpyrrolidone, and N-methylpyrrolidone did not color. This was then collected by filtration, washed with n-hexane and then with acetone, and then dried at 60° C. for 5 hours under reduced pressure. The infrared absorption spectrum of this particulate polymer includes an imide bond at 1780 cm -1 and an imide bond at 1650 cm -1 and 1540 cm
Absorption of amide bond was observed in -1 . When this particulate polymer was observed with a scanning electron microscope, it was found to be spherical in shape, and the main particle diameter was about 10 to 30 μm. Comparative Example 1 (1) Synthesis of dispersion stabilizer Using the same apparatus as in Example 1 (1), 152 g of ISOPAR-H was placed in a flask and the temperature was raised to 160°C. While passing nitrogen gas, add 183.3 g of lauryl methacrylate prepared in advance, 30.6 g of 2-hydroxyethyl methacrylate, and benzoyl peroxide paste (benzoyl peroxide content: 50
% by weight) while stirring 11.7 g of the mixture.
It dripped over time. Subsequently, the reaction was continued at the same temperature for 4 hours. This dispersion stabilizer solution was
The non-volatile content when dried for hours is 25% by weight,
The number average molecular weight of the dispersion stabilizer was 2,800. (2) Synthesis of particulate polymer A particulate polymer was synthesized in exactly the same manner as in Examples 1 and (2), except that 64 g of the dispersion stabilizer solution obtained in (1) was used. When the temperature was raised to 125°C, aggregation occurred after 15 minutes. Comparative Example 2 (1) Synthesis of dispersion stabilizer Using the same apparatus as in Example 1 (1), 152 g of ISOPAR-H was placed in a flask and the temperature was raised to 80°C. While passing nitrogen gas, add 183.0 g of lauryl methacrylate prepared in advance, 12.0 g of 2-hydroxyethyl methacrylate, and benzoyl peroxide paste (benzoyl peroxide content: 50 g).
% by weight) while stirring 1.0 g of the mixture.
It dripped over time. Furthermore, ISOPAR-H100g
was added dropwise over 1 hour, and then kept at 80°C for 1 hour, then raised to 140°C, and reacted at the same temperature for 4 hours. This dispersion stabilizer solution was
The non-volatile content when dried for hours is 50% by weight,
The number average molecular weight of the dispersion stabilizer was 230,000. (2) Synthesis of particulate polymer Synthesis was carried out in the same manner as in Examples 1 and (2) except that 38 g of the dispersion stabilizer solution obtained in (1) was used, but the temperature was raised to 115°C. It aggregated after 30 minutes. Comparative Example 3 (1) Synthesis of dispersion stabilizer Using the same apparatus as in Example 1 (1), 74.3 g of ISOPAR-H and 97.8 g of lauryl methacrylate were placed in a flask, and the temperature was raised to 80°C. While passing nitrogen gas, add 97.8 g of lauryl methacrylate prepared in advance and 1.0 g of benzoyl peroxide paste (benzoyl peroxide content 50% by weight).
The mixture was added dropwise over 2 hours while stirring. Furthermore, 74.3 g of ISOPAR-H was added dropwise over 1 hour, and after keeping at 80℃ for 1 hour,
The reaction was carried out at 140°C for 1 hour and 5 hours at 140°C. When this dispersion stabilizer solution was dried at 170°C for 2 hours, the nonvolatile content was 53%, and the number average molecular weight of the dispersion stabilizer was 134,000. (2) Synthesis of particulate polymer Synthesis was carried out in exactly the same manner as in Example 1 and (2) except that 30 g of the dispersion stabilizer solution obtained in (1) was used, but trimellitic anhydride was not used. Add 100
When reacted at ℃ for 30 minutes, aggregation occurred. Comparative Example 4 Synthesis was carried out in exactly the same manner as in Example 1 (1) except that 1.0 g of the dispersion stabilizer solution obtained in Example 5 (1) was used, but trimellitic anhydride was not used. The mixture was added and coagulated 30 minutes after the temperature was raised to 115°C. Comparative Example 5 (1) Synthesis of dispersion stabilizer Using the same apparatus as in Example 1 (1), 152 g of ISOPAR-H was placed in a flask and the temperature was raised to 120°C. While passing nitrogen gas, a mixture of 183 g of lauryl methacrylate, 16.1 g of 2-hydroxyethyl methacrylate, and 10 g of benzoyl peroxide paste (benzoyl peroxide content: 50% by weight) prepared in advance was added dropwise over 2 hours while stirring. did. Subsequently, the temperature was raised to 140°C, and the reaction was continued at the same temperature for 4 hours. This dispersion stabilizer solution has a non-volatile content of 40 when baked at 170℃ for 2 hours.
% by weight, and the number average molecular weight of the dispersion stabilizer is
It was 9000. (2) Synthesis of particulate polymer A particulate polymer was synthesized and treated in exactly the same manner as in Examples 1 and (2), except that 25 g of the dispersion stabilizer solution obtained in (1) was used. In the infrared absorption spectrum of the obtained particulate polymer, imide bond absorption was observed at 1780 cm -1 and amide bond absorption was observed at 1650 cm -1 and 1540 cm -1 . The main particle diameter of this polyamide-imide particulate polymer was about 60 to 1000 μm. When we tried to produce a particulate polymer again under the same conditions, it agglomerated 15 minutes after raising the temperature to 125°C. Furthermore, production of particulate polymer was attempted a total of 10 times under the same conditions, and finally particulate polymer was obtained 4 times and agglomerated 6 times. Among Examples 1 to 11 and Comparative Examples 1 to 5 obtained as described above, the synthesis of the dispersion stabilizer and particulate polymer is summarized in Table 1.
【表】
表１から明らかなように、本発明によれば耐熱
性のすぐれた粒子状重合体を安定に製造できるこ
とが示される。[Table] As is clear from Table 1, it is shown that according to the present invention, particulate polymers with excellent heat resistance can be stably produced.
Claims (1)
第一の非水有機液体、第一の非水有機液体に可溶
な分散安定剤及び生成する粒子状重合体に対して
可溶性又は膨潤性であり、第一の非水有機液体と
は本質上非混和性である第二の非水有機液体の存
在下で、ポリイソシアネート（）と酸無水物基
を有するポリカルボン酸（）及び／又はポリカ
ルボン酸（）とを反応させて、第一の非水有機
液体中に分散された粒子状重合体とする粒子状重
合体の製造法において、該分散安定剤として炭素
数６以上の炭化水素基からなる側鎖を有するエチ
レン性不飽和単量体(A)とヒドロキシル基を有する
エチレン性不飽和単量体(B)をモル比で(A)／(B)を
１／１から５／１の範囲として反応させて得られ
る数平均分子量6000以上のヒドロキシル基含有ビ
ニル重合体を、第２の非水有機液体、ポリイソシ
アネート、酸無水物基を有するポリカルボン酸及
び／又はポリカルボン酸に対して0.5重量％以上
用いることを特徴とする粒子状重合体の製造法。 ２ ヒドロキシル基含有ビニル重合体がラウリル
メタクリレート、ステアリルメタクリレート、ラ
ウリルアクリレート又はステアリルアクリレート
とアクリル酸又はメタクリル酸−２−ヒドロキシ
エチルとのランダム共重合体である特許請求の範
囲第１項記載の粒子状重合体の製造法。 ３ 第一の非水有機液体が脂肪族又は脂環族炭化
水素であり、第二の非水有機液体がＮ−メチルピ
ロリドンである特許請求の範囲第１項又は第２項
記載の粒子状重合体の製造法。 ４ ポリイソシアネート（）が４・4′−ジフエ
ニルメタンジイソシアネート、４・4′−ジフエニ
ルエーテルジイソシアネート、トリレンジイソシ
アネート、トリフエニルメタン−４・4′・4″−ト
リイソシアネート又はイソシアヌレート環を有す
るポリイソシアネートである特許請求の範囲第１
項、第２項又は第３項記載の粒子状重合体の製造
法。 ５ 酸無水物基を有するポリカルボン酸（）が
トリメリツト酸無水物、ピロメリツト酸二無水
物、３・3′・４・4′−ベンゾフエノンテトラカル
ボン酸二無水物又は２・２−ビス〔４−（３・４
−ジカルボキシフエノキシ）フエニル〕プロパン
二無水物である特許請求の範囲第１項、第２項、
第３項又は第４項記載の粒子状重合体の製造法。 ６ ポリカルボン酸（）がイソフタル酸、テレ
フタル酸、トリメシン酸、トリス（２−カルボキ
シエチル）イソシアヌレート又はニトリロ三酢酸
である特許請求の範囲第１項、第２項、第３項、
第４項又は第５項記載の粒子状重合体の製造法。[Claims] 1. A first non-aqueous organic liquid that is insoluble in the particulate polymer to be produced, a dispersion stabilizer that is soluble in the first non-aqueous organic liquid, and a particulate polymer to be produced. A polyisocyanate () and a polycarboxylic acid having acid anhydride groups in the presence of a second non-aqueous organic liquid that is soluble or swellable with the first non-aqueous organic liquid and essentially immiscible with the first non-aqueous organic liquid. () and/or polycarboxylic acid () to form a particulate polymer dispersed in a first non-aqueous organic liquid, the dispersion stabilizer has a carbon number of An ethylenically unsaturated monomer (A) having a side chain consisting of 6 or more hydrocarbon groups and an ethylenically unsaturated monomer (B) having a hydroxyl group in a molar ratio of (A)/(B) to 1 A hydroxyl group-containing vinyl polymer having a number average molecular weight of 6,000 or more, which is obtained by reacting the hydroxyl group-containing vinyl polymer in the range of /1 to 5/1, is mixed with a second nonaqueous organic liquid, a polyisocyanate, a polycarboxylic acid having an acid anhydride group, and a polycarboxylic acid having an acid anhydride group. Or a method for producing a particulate polymer, characterized in that it is used in an amount of 0.5% by weight or more based on polycarboxylic acid. 2. The particulate polymer according to claim 1, wherein the hydroxyl group-containing vinyl polymer is a random copolymer of lauryl methacrylate, stearyl methacrylate, lauryl acrylate, or stearyl acrylate and acrylic acid or 2-hydroxyethyl methacrylate. Coalesce manufacturing method. 3. The particulate polymer according to claim 1 or 2, wherein the first non-aqueous organic liquid is an aliphatic or alicyclic hydrocarbon, and the second non-aqueous organic liquid is N-methylpyrrolidone. Coalesce manufacturing method. 4 Polyisocyanate () has 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, tolylene diisocyanate, triphenylmethane-4,4',4''-triisocyanate or isocyanurate ring Claim 1 which is polyisocyanate
A method for producing a particulate polymer according to item 1, 2 or 3. 5 Polycarboxylic acid () having an acid anhydride group is trimellitic anhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, or 2,2-bis[ 4-(3・4
-dicarboxyphenoxy)phenyl]propane dianhydride, claims 1 and 2;
A method for producing a particulate polymer according to item 3 or 4. 6. Claims 1, 2 and 3, wherein the polycarboxylic acid () is isophthalic acid, terephthalic acid, trimesic acid, tris(2-carboxyethyl)isocyanurate or nitrilotriacetic acid,
A method for producing a particulate polymer according to item 4 or 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58145214A JPS6036523A (en) | 1983-08-09 | 1983-08-09 | Manufacture of granular polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58145214A JPS6036523A (en) | 1983-08-09 | 1983-08-09 | Manufacture of granular polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6036523A JPS6036523A (en) | 1985-02-25 |
| JPS6244764B2 true JPS6244764B2 (en) | 1987-09-22 |
Family
ID=15380006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58145214A Granted JPS6036523A (en) | 1983-08-09 | 1983-08-09 | Manufacture of granular polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6036523A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01245013A (en) * | 1988-03-28 | 1989-09-29 | Nippon Polyurethan Kogyo Kk | Dispersant composition for nonaqueous dispersion polymerization and polyurethane composition using said composition |
| JP2594117B2 (en) * | 1988-06-27 | 1997-03-26 | 日本ポリウレタン工業 株式会社 | Method for producing polyurethane polymer gel |
| JP6930110B2 (en) * | 2017-01-16 | 2021-09-01 | 荒川化学工業株式会社 | Thermosetting release coating agent, release film and its manufacturing method |
-
1983
- 1983-08-09 JP JP58145214A patent/JPS6036523A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6036523A (en) | 1985-02-25 |
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