JPH0461007B2 - - Google Patents
Info
- Publication number
- JPH0461007B2 JPH0461007B2 JP12819583A JP12819583A JPH0461007B2 JP H0461007 B2 JPH0461007 B2 JP H0461007B2 JP 12819583 A JP12819583 A JP 12819583A JP 12819583 A JP12819583 A JP 12819583A JP H0461007 B2 JPH0461007 B2 JP H0461007B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- meth
- weight
- reaction
- acrylamide
- 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 92
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 23
- 229920001169 thermoplastic Polymers 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 15
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical group O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 238000005979 thermal decomposition reaction Methods 0.000 description 13
- 238000000862 absorption spectrum Methods 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000003708 ampul Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 8
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 7
- 238000006482 condensation reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- -1 acrylic ester Chemical class 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 208000012839 conversion disease Diseases 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229920006037 cross link polymer Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 150000003949 imides Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229920006027 ternary co-polymer Polymers 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- YQIGLEFUZMIVHU-UHFFFAOYSA-N 2-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C(C)=C YQIGLEFUZMIVHU-UHFFFAOYSA-N 0.000 description 1
- CCIDRBFZPRURMU-UHFFFAOYSA-N 2-methyl-n-propylprop-2-enamide Chemical compound CCCNC(=O)C(C)=C CCIDRBFZPRURMU-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- VXVUDUCBEZFQGY-UHFFFAOYSA-N 4,4-dimethylpentanenitrile Chemical compound CC(C)(C)CCC#N VXVUDUCBEZFQGY-UHFFFAOYSA-N 0.000 description 1
- OPPHXULEHGYZRW-UHFFFAOYSA-N 4-methoxy-2,4-dimethyl-2-phenyldiazenylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC1=CC=CC=C1 OPPHXULEHGYZRW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- FYLJKQFMQFOLSZ-UHFFFAOYSA-N cyclohexylperoxycyclohexane Chemical compound C1CCCCC1OOC1CCCCC1 FYLJKQFMQFOLSZ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 125000004492 methyl ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MGJXBDMLVWIYOQ-UHFFFAOYSA-N methylazanide Chemical compound [NH-]C MGJXBDMLVWIYOQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JBLADNFGVOKFSU-UHFFFAOYSA-N n-cyclohexyl-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1CCCCC1 JBLADNFGVOKFSU-UHFFFAOYSA-N 0.000 description 1
- PMJFVKWBSWWAKT-UHFFFAOYSA-N n-cyclohexylprop-2-enamide Chemical compound C=CC(=O)NC1CCCCC1 PMJFVKWBSWWAKT-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本考案は、ポリマ−主鎖中にグルタルイミド基
の構造単位を含む熱可塑性重合体の製造法に関す
る。
ポリメチルメタクリレート、ポリスチレンなど
の透明性を有する樹脂は、溶融賦形材料として家
庭電器製品、車輌用光学部品、計器板、採光用窓
材、さらに近年に至つては光学繊維用素材として
用いられるようになつてきている。
これらの用途開発の高度化に伴つて、これら用
途に供されるプラスチツクスに求められる性能の
高度化も要求されており、近年においては特に耐
熱性の向上が強く求められて来ている。
これらビニル重合型熱可塑性重合体の耐熱性を
向上せしめる方法として、特開昭55−102614号お
よび特開昭57−153008号の各公報において記載さ
れる如く、無水マレイン酸構造を導入する方法が
提案されている。無水マレイン酸は共重合特性の
他のビニルモノマーとは可成り異つており、その
共重合性を向上するにはスチレンを共重合モノマ
ーとして併用する方法がよい方法であることが知
られているが、そのポリマーは、例えばメチルメ
タクリレート／無水マレイン酸／スチレン三元コ
ポリマーやさらにこれら三元系コポリマーに他の
ビニルモノマーを共重合せしめた四元コポリマー
の如く、多成分共重合ポリマーとなり、その製造
が難しくなるばかりでなく、得られたポリマーの
透明性が必ずしも良好なものではない。
このようにポリマー主鎖中に環構造を形成させ
て、その剛直性を付与させることにより耐熱性を
増大させる提案がなされている。すなわち、無水
マレイン酸−スチレン系共重合体は、ポリマー主
鎖中にマレイン酸無水物により五員環構造を形成
されることにより、その耐熱性は向上する。一
方、メタクリルアミド重合体を熱分解することに
より得られるグルタルイミド環構造をポリマー主
鎖中に形成させる方法がある。
ここでいうグルタルイミド環どは、重合体中の
メタクリルアミドまたはアクリルアミドユニツト
のアミド間で縮合し、脱アンモニア反応の結果生
じたイミド環を意味するものである。従来、この
ような重合体側鎖反応に関してK.Crauwels，G.
Smets，Bull，Soc，Chim，Belgique 59 182
（1950）に記載の如くポリメタクリルアミドポリ
マーの熱分解縮合反応によりグルタルイミド環を
主鎖中に含み重合体を得ているが、この縮合反応
は分子内反応としてばかりでなく、ポリマー間で
も縮合反応が起り、架橋した重合体しか得られて
いない。実際に上記文献記載の方法を追試するこ
とにより得られたポリマーは、黒かつ色に着色し
た不溶解性の架橋重合体であつた。また、特公昭
44−8743号公報には、メタクリル酸とメタクリロ
ニトリルの混合物またはメタクリル酸とメタクリ
ルニトリルおよびメタクリルアミド混合物を尿素
またはＮ−N′−ジメチル尿素存在下で重合した
のち、熱分解することによりグルタルイミド環を
主鎖中に有するポリマーを得ているが、このポリ
マーのイミド基生成反応が分子間においても起つ
ている架橋構造の耐熱性発砲材料が得られると報
告されている。
上述のように、従来検討されてきたポリマー側
鎖アミド基の縮合反応を利用した重合体の改質に
おいては分子内セグメント間の反応だけではな
く、分子間でも反応が起り、架橋した重合体しか
得られていない現状にある。
そこで本発明者らは、高分子主鎖中にイミド環
構造を有するとともに実質的に熱可塑性を示す重
合体で良好な耐熱性と賦形加工性を得るべく鋭意
検討した結果、本発明に到達した。
すなわち、本発明の要旨とするところは、炭素
数１〜６のアルキル基、シクロアルキル基から選
ばれた基で置換されたＮ−モノ−置換（メタ）ア
クリルアミド単位５〜100重量％と（メタ）アク
リル酸エステル単位95〜０重量％からなる重合体
または（メタ）アクリルアミド単位５〜30重量％
と（メタ）アクリル酸エステル単位95〜70重量％
からなる共重合体より選ばれる重合体を200℃以
上の温度で加熱処理して、
次の一般式
（式中、R1、R2は同一または異種の水素原子
または炭素数１〜４のアルキル基から選ばれた基
であり、R3は水素原子または炭素数１〜６のア
ルキル基、シクロアルキル基またはフエニル基か
ら選ばれた基を表す）で示される構造単位を重合
体中に５重量％以上を含み、固有粘度が0.01〜２
dl／ｇである重合体を得ることを特徴とする熱可
塑性重合体の製造法にある。
本発明の上記一般式〔〕で示される構造単位
を５重量％以上する熱可塑性重合体は、
(1) Ｎ−モノ−置換（メタ）アクリルアミド単位
５〜100重量％と（メタ）アクリル酸エステル
単位95〜０重量％からなる重合体、又は
(2) （メタ）アクリルアミド単位５〜30重量％と
（メタ）アクリル酸エステル単位95〜70重量％
とからなる重合体
を加熱分解し、分子内セグメント間縮合環化反応
を行なわしめることにより製造される。
上記(1)の方法により本発明の熱可塑性重合体を
製造する場合、原料とするＮ−モノ−置換（メ
タ）アクリルアミドから得られる重合体またはＮ
−モノ−置換−（メタ）アクリルアミドと（メタ）
アクリル酸エステル単量体との共重合体を熱分解
すると重合体中のＮ−（メチル）アミドセグメン
トは分子内に隣接するＮ−モノ−置換（メタ）ア
クリルアミドまたは隣接する（メタ）アクリル酸
エステルセグメントと脱アンモニアまたは脱アル
キルアミン反応を経てグルタルイミド環化反応を
主に行い、実質的に熱可塑性重合体が得られるも
のと考えられる。
それ故に、この方法によると本発明の熱可塑性
重合体を極めて効率よく製造できる。この方法の
出発原料である重合体中のＮ−モノ−置換（メ
タ）アクリルアミド単位と（メタ）アクリル酸エ
ステル単位との含有量は、Ｎ−モノ−置換（メ
タ）アクリルアミド単位５〜100重量％、（メタ）
アクリル酸エステル単位95〜０重量％の範囲であ
り、Ｎ−モノ−置換（メタ）アクリルアミド単位
の含有量が５重量％未満では、耐熱性のすぐれた
重合体を得ることはできない。
Ｎ−モノ−置換（メタ）アクリルアミドの例と
しては、１〜６の炭素原子を有するアルキル基、
例えばＮ−メチルメタクリルアミド、Ｎ−メチル
アクリルアミド、Ｎ−エチルメタクリルアミド、
Ｎ−エチルアクリルアミド、Ｎ−プロピルメタク
リルアミド、Ｎ−プロピルアクリルアミド、Ｎ−
イソプロピルメタクリルアミド、Ｎ−イソプロピ
ルアクリルアミド、Ｎ−tert.−ブチルメタクリル
アミド、Ｎ−tert.−ブチルアクリルアミド、Ｎ−
sec.−ブチルメタクリルアミド、Ｎ−sec.−ブチ
ルメタクリルアミド、Ｎ−シクロヘキシルメタク
リルアミド、Ｎ−シクロヘキシルアクリルアミド
などがあげられる。
また、Ｎ−モノ−置換（メタ）アクリルアミド
と共重合させて使用される（メタ）アクリル酸エ
ステルの例としては、メチルメタクリレート、メ
チルアクリレート、エチルメタクリレート、エチ
ルアクリレート、プロピルメタクリレート、プロ
ピルアクリレート、ｎ−プチルメタクリレート、
ｎ−ブチルアクリレート、２−エチルヘキシルメ
タクリレート、２−エチルヘキシルアクリレー
ト、ラウリルメタクリレート、ラウリルアクリレ
ート、シクロヘキシルメタクリレート、シクロヘ
キシルアクリレート、ベンジルメタクリレート、
ベンジルアクリレートなどの炭素数１〜18を有す
る脂肪族または芳香族官能基を含むアルキルメタ
クリレートまたはアクリレート等をあげることが
できる。しかしながら、できるだけ得られる重合
体は加熱により着色し難いもの、並びに分子間架
橋構造を形成しないものであることが望ましく、
この観点よりメチルメタクリレート、メチルアク
リレート、エチルメタクリレート、エチルアクリ
レート、ｎ−ブチルメタクリレート、ｎ−ブチル
アクリレート、iso−ブチルメタクリレート、iso
−ブチルアクリレート、２−エチルヘキシルメタ
クリレート、２−エチルヘキシルアクリレート、
ラウリルメタクリレート、ラウリルアクリレート
などの使用が好ましい。
上記のうち、Ｎ−モノ−置換（メタ）アクリル
アミドとしてＮ−メチルメタクリルアミド、（メ
タ）アクリル酸エステルとしてメチルメタクリレ
ートの使用がさらに好ましい。
この理由は余り明確でないが、Ｎ−メチルメタ
クリルアミド構造単位を含む重合体を加熱処理し
てゆくと、重合体側鎖間で連続して分子内の隣接
セグメントである同様のＮ−メチルアミド構造単
位間同士またはＮ−メチルアミド基とメチルエス
テル基間での脱アンモニア反応ないし脱メチルア
ミン反応が優先的に起る結果、一般式〔〕で示
した構造単位の生成反応を主とする本発明の熱可
塑性重合体が得られると考えられる。これはＮ−
メチルアミド基中の窒素原子に結合した水素原子
が隣接セグメントの側鎖カルボニル基との間で水
素結合の如き相互作用により固定され、その結果
分子内セグメント間縮合反応が効率よく優先的に
進行するためと考えられる。
この方法によるとＮ−モノ−置換（メタ）アク
リルアミドの共重合量の制限を受けないという特
徴がある。
上記(2)の方法により本発明の熱可塑性重合体の
製造方法は、遊離状態で重合体側鎖として存在す
るアミド基間またはエステル基間での縮合環化反
応である。この縮合反応は分子内セグメント間の
反応ばかりでなく、分子間でも容易に起るために
本発明の熱可塑性重合体をつくる際に用いられる
原料である（メタ）アクリルアミドと（メタ）ア
クリル酸エステルの共重合体中の（メタ）アクリ
ルアミド単位の含有量は30重量％以下であること
が必要である。（メタ）アクリルアミド共重合量
が30重量％を越えた場合の共重合体を縮合反応せ
しめると実質的に溶媒可溶、かつ実質的に溶融可
能な本発明の目的とする重合体は得ることが出来
ない。
本発明の製造方法において出発原料として使用
されるＮ−モノ−置換（メタ）アクリルアミド含
有重合体または（メタ）アクリルアミド含有共重
合体を得るために使用される重合開始剤として
は、通常のラジカル重合開始剤を使用することが
出来る。具体例としては、たとえばジ−tert.−ブ
チルペルオキシド、ジクミルペルオキシド、メチ
ルエチルケトンペルオキシド、tert−ブチルペル
フタレート、tert.−ブチルペルベンゾエート、メ
チルイソブチルケトンペルオキシド、ラウロイル
ペルオキシド、シクロヘキシルペルオキシド、
２，５ジメチル２，５ジ−tert.−ブチルペルオキ
シヘキサン、tert.−ブチルペルオクタノエート、
tert.−ブチルペルイソブチレート、tert.−ブチル
ペルオキシイソプロピルカーボネート等の有機過
酸化物やメチル２−2′−アゾビスイソブチレー
ト、１，1′−アゾビスシクロヘキサンカルボニト
リル、２−フエニルアゾ−２，４−ジメチル−４
−メトキシバレロニトリル、２−カルバモイル−
アゾビスイソブチロニトリル、２−2′−アゾビス
（2.4ジメチルバレロニトリル）、２，2′−アゾビ
スイソブチロニトリル等のアゾ化合物が挙げられ
る。また過硫酸アンモニウム、過硫酸カリウム等
が使用出来る。また過硫酸アンモニウム、過硫酸
カリウム等が使用出来る。連鎖移動剤としては、
特に限定されず、通常の重合度調整剤が使用され
る。たとえば、アルキルメルカプタン、四塩化炭
素、四臭化炭素、ジメチルアセトアミド、ジメチ
ルホルムアミド、トリエチルアミンなどが挙げら
れるが、その中でアルキルメルカプタンが最も好
ましい。
重合方法としてはフリーラジカル開始の場合、
乳化重合、懸濁重合、塊状重合および溶液重合が
挙げられるが、目的に応じて他の製造方法を採用
することが出来る。またグリニヤール試薬、重合
開始触媒、アルキルリチウム系イオン重合触媒な
どを使用して得ることが出来る。
Ｎ−モノ−置換（メタ）アクリルアミド含有重
合体または（メタ）アクリルアミド含有共重合体
を熱分解し、本発明の熱可塑性重合体を得る際の
重合体または共重合体の熱処理温度は200℃以上、
好ましくは200℃〜450℃、さらに好ましくは200
℃〜300℃の温度であり、処理時間は0.5時間以上
である。
本発明の方法によつて得られる熱可塑性重合体
は、一般式〔〕で示されるグルタルイミド環構
造を少なくとも５重量％含むとともに、実質的に
溶剤に溶解可能であり、また実質的に加熱溶融可
能であることに大きな特徴を有する。本発明の重
合体は一般式〔〕で示すグルタルイミド環の構
造単位をポリマー主鎖中に５重量％以上、好まし
くは10重量％以上含まれているため、その耐熱性
は従来開発されてきた比較されうる同系統のビニ
ル重合体に比べて５〜10℃以上改良されたにもか
かわらず、その透明性、成形加工性は良好であ
る。
本発明の熱可塑性重合体は、その固有粘度が
0.01〜２dl／ｇであることが必要である。固有粘
度が0.01dl／ｇ未満重合体からは機械的強度に優
れた成形体を作ることができない。また固有粘度
２dl／ｇを超える重合体は、粘度が大となり溶融
成形などの賦形性に問題が生じ、また溶液にする
場合の溶解性が低下するなどの問題が生じる。
本発明の熱可塑性重合体は、比較されうる同系
統のビニル重合体に比べ耐熱温度が５〜10℃以上
と改良されているにもかかわらず、その透明性、
加熱溶融流動性、各種溶剤、例えばジメチルホル
ムアミドやクロロホルムなどに対する溶解性は良
好である。それ故、本発明の重合体は多種の成形
材料や被覆材、レジスト材、光学材料、耐熱フイ
ルムまたは繊維などとして、またこの重合体は低
分子量ポリアミン、尿素、アンモニア、ジアルキ
ル尿素等架橋剤を併用すると架橋硬化性を示す樹
脂組成物とすることが出来る。
以下実施例により本発明をさらに詳しく説明す
るが、重合体の特性の測定法としては次のものを
用いた。
赤外吸収スペクトルは、赤外線分光光度計（日
立製作所(株)製、285型）を用いKBrデイスク法に
て測定した。
数平均分子量（Mn）、重量平均分子量（Mw）
およびＺ平均分子量（Mz）は東洋曹達(株)製、ゲ
ルパーミエーシヨンクロマトグラフイーHLC−
802URを用い、試料濃度は0.1（重量／体積）％、
エリユーシヨンは溶媒としてジメチルホルムアミ
ドを用い、流速1.2ml／分、単分散ポリスチレン
検量線を用いた。
耐熱性試験はASTM−Ｄ−1525に準じ、ビガ
ー軟化点測定機（東洋精器製作所製）を用い、昇
温速度50±５℃／Hrとし、試料片は５×10×10
mmのものを用いた。
貯蔵弾性率（E′）と損失弾性率（E″）は動的
粘弾性装置（東洋ボルドウイン(株)製）を用い、
110Hz、昇温速度２℃／分で測定した。
熱可塑性重合体の固有粘度は次の如くして測定
した。ポリマー濃度0.5重量％のジメチルホルム
アミド溶液を試料とし、デロービシヨツプ
（Deereax−Bischoff）粘度計にて、測定温度25
±0.1℃でジメチルホルムアミドの流動時間：to
と前記ポリマー溶液の流動時間：tsとを測定し、
ts／to値からポリマーの相対粘度ηreを求め、
次式により算出した。
ηinh＝（nηre）／Ｃ 〔〕
（式中、Ｃは溶媒100mlあたりのポリマーのグラ
ム数を示す）
なお、実施例中の部は重量部を表わす。
実施例 １
メチルメタクリレート50部、Ｎ−メチルメタク
リルアミド50部、2.2′−アゾビスイソブチロニト
リル0.01部およびtert.−ドデシルメルカプタン0.1
部を溶解してガラス製アンプル内に入れ、液体窒
素温度下で冷却した後、脱気をくり返して窒素雰
囲気で封管した。
次いでこの封管アンプルを加熱浴中に入れ、70
℃で15時間加熱した後、さらに120℃で３時間加
熱して重合を完結させた。この重合における単量
体の反応転化率は95％であつた。
次にこの生成重合体をテトラヒドロフランに溶
解した後、ｎ−ヘキサン中へ投入して沈殿させる
操作を数回くり返して重合体の精製した。この精
製重合体は次のような物性を有していた；
数平均分子量（Mn）；8.5×104
重量平均分子量（Mw）；21.2×104
Ｚ平均分子量（Mz）；33.5×104
Mw／Mn＝2.49，Mz／Mn＝3.94
固有粘度；0.45dl／ｇ
またこの重合体の赤外吸収スペクトルを測定し
た結果を第１図に示す。波数1720cm-1にエステル
カルボニルの伸縮振動に基づく吸収がまた波数、
1620〜1640cm-1、1540cm-1に酸アミドに基づく吸
収が測定された。
次にこの重合体を50mlの試験官に30ｇ入れ、
230℃のオイル浴中で５時間加熱分解反応させた。
この反応において揮発性有機ガス分としてメチル
アミンが生成し、その他メタノールの生成も確認
された。反応終了後、１時間1.0mmHgの減圧下で
揮発成分を除去して発泡した白色の樹脂体を得
た。この樹脂体を粉砕した。この粉砕した重合体
は次のような物性を有していた；
数平均分子量（Mn）；7.95×104
重量平均分子量（Mw）；18.5×104
Ｚ平均分子量（Mz）；28.5×104
Mw／Mn＝2.32、Mz／Mn＝3.58
固有粘度；0.40dl／ｇ
この重合体試料を250℃、150Kg／cm2で加熱・加
圧成形して厚さ150μのフイルムを作製し、動的
粘弾性を測定した。損失弾性率（E″）の分散ピ
ークは140℃であつた。
同様にして10mm×10mm×５mm（厚さ）の平板を
作成してビガー軟化点を測定したところ、147℃
の値を示した。
また差動走査熱量計を使用してガラス転移温度
を測定したところ140〜161℃の間であつた。
さらに上記成形フイルムの赤外吸収スペクトル
の測定を行なつた。その結果を第２図に示す。第
２図から判るように波数1720cm-1にエステルカル
ボニルの伸縮振動の吸収の他、波数1756cm-1、
1802cm-1、742cm-1にグルタルイミド基の生成に
よる吸収が確認された。グルタルイミドに基づく
吸収とエステルカルボニルに基づく吸収比からグ
ルタルイミド生成量は63重量％であつた。
また加熱分解重合体をメルトインデクサー（東
洋精機製作所製）にかけて230℃、10Kg荷重下で
押出したところ、良好なストランド状樹脂体が得
られ、5.5ｇ／10分のMI値を示した。この重合体
を25φベント式押出機（第一実業(株)製、フルフラ
イトスクリユーＬ／Ｄ＝24）に通して、バレル温
度200℃、およびダイ温度230℃で押出成形してペ
レツト化した。ペレツト化した重合体を１オンス
立型スクリユー式射出成形機（山城精機製作所製
SAV−30A）にかけて60mm×80mm×２mmの成形
板を作製した。この成形板は耐熱性に優れてい
た。
以上の結果での、Ｎ−メチルメタクリルアミド
とメチルメタクリレート共重合体を出発原料とし
た重合体のゲルパーミエシヨンクロマトグラフイ
ー（GPC）測定による分子量および分子量分布
と、この原料重合体を加熱処理することにより得
た本発明の熱可塑性重合体のGPC法による分子
量および分子量分布の測定から、加熱分解によ
り、脱メチルアミン化、脱メタノール化が行なわ
れ、さらにその熱分解初期にわずかなポリマー鎖
の分解が生じ、見掛上分子量の低下はみられる
が、分子間架橋反応に基づく分子量の増大化なら
びに分子量分布の拡大および主鎖切断に基づく分
子量の大幅な変化は認められなかつた。
実施例 ２〜７
表１に示すような単量体組成物を用いて実施例
１と同様な操作をくり返して重合体を作製し、加
熱処理させて重合体の物性を測定した。その結果
を表１に示す。
実施例 ８〜11
メチルメタクリレート50部、Ｎ−メチルメタク
リルアミド50部、２，2′−アゾビスイソブチロニ
トリル0.01部およびtert.−ドデシルメルカプタン
0.1部を溶解してガラス製アンプル内に入れ、実
施例１と同じようにして重合体を作り、そして精
製重合体を得た。この重合体30ｇを実施例１と同
様に、230℃のオイル浴で30分間加熱分解反応さ
せた。この加熱反応分解物は、赤外吸収スペクト
ルのエステルカルボニルの吸収量から反応転化率
が30％と確認された。
さらにこの加熱分解反応を230℃のオイル浴中
で表１に示した時間続けて得られた重合体の樹脂
特性を測定した。結果を表１に示す。
実施例 12
Ｎ−メチルメタクリルアミド100部、２，2′−
アゾビスイソブチロニトリル0.01部およびtert.−
ドデシルメルカプタン0.1部を溶解してガラス製
アンプル内に入れ、液体窒素温度下で冷却した
後、脱気をくり返して窒素雰囲気で封管した。
次いでこの封管アンプルを加熱浴中に入れ、70
℃で15時間加熱した後、さらに120℃で３時間加
熱して重合を完結させた。この重合における単量
体の反応転化率は96％であつた。
この重合体の赤外吸収スペクトルを測定した結
果を第３図に示す。波数1620〜1640cm-1に酸アミ
ドに基づくカルボニルの吸収が測定された。
次にこの重合体を50mlの試験管に30ｇ入れ、
230℃のオイル浴中で５時間加熱分解反応させた。
この反応において揮発性有機ガス分としてメチル
アミンが生成した。反応終了後、１時間、1.0mm
Hgの減圧下で揮発成分を除去して発泡した白色
の樹脂体を得た。この樹脂体を粉砕した。
この重合体試料を250℃、150Kg／cm2で加熱・加
圧成形して厚さ150μのフイルムを作製し、動的
粘弾性を測定した。損失弾性率（E″）の分散ピ
ークは165℃であつた。
同様にして10mm×10mm×５mm（厚さ）の平板を
作成してビガー軟化点を測定したところ、167℃
の値を示した。
また差動走査熱量計を使用してガラス転移温度
を測定したところ162〜188℃の間であつた。
さらに上記成形フイルムの赤外吸収スペクトル
の測定を行なつた。その結果を第４図に示す。第
４図から判るように波数1720cm-1、1660cm-1およ
び742cm-1にグルタルイミド基の生成による吸収
が確認された。グルタルイミドに基づく吸収とエ
ステルカルボニルに基づく吸収比からグルタルイ
ミド生成の量は95重量％であつた。
また加熱分解重合体をメルトインデクサー（東
洋精機製作所製）にかけて230℃、10Kg荷重下で
押出したところ、良好なストランド状樹脂体が得
られ、2.9ｇ／10分のMI値を示した。
実施例 13〜16
Ｎ−メチルメタクリルアミド100部、２，2′−
アゾビスイソブチロニトリル0.01部およびtert.−
ドデシルメルカプタン0.1部を溶解してガラス製
アンプル内に入れ、実施例12と同じようにして重
合体を作り、そして精製重合体を得た。この重合
体30ｇを実施例１と同様に230℃のオイル浴で30
分間加熱分解反応させた。この加熱反応分解物
は、赤外吸収スペクトルのカルボニルとイミドカ
ルボニルの吸収量から反応転化率が40％と確認さ
れ、さらにこの加熱分解反応を230℃のオイル浴
中で表１に示した時間続けて得られた重合体の樹
脂特性を測定した。結果を表１に示す。
比較例 １
メチルメタクリレート100部、２，2′−アゾビ
スイソブチロニトリル0.01部およびtert.−ドデシ
ルメルカプタン0.1部を溶解してガラス製アンプ
ル内に入れ、液体窒素温度下で冷却した後、脱気
をくり返して窒素雰囲気で封管した。
次いでこの封管アンプルを加熱浴中に入れ、70
℃で15時間加熱した後、さらに120℃で３時間加
熱して重合を完結させた。この重合における単量
体の反応転化率は97％であつた。
次にこの生成重合体をテトラヒドロフランに溶
解した後、ｎ−ヘキサン中へ投入して沈殿させる
操作を数回くり返して重合体を精製した。この精
製重合体は次のような物性を有していた；
数平均分子量（Mn）；5.71×104
重量平均分子量（Mw）；14.3×104
Ｚ平均分子量（Mz）；20.0×104
Mw／Mn＝2.68、Mz／Mn＝3.50
固有粘度；0.30dl／ｇ
またこの重合体の赤外吸収スペクトルを測定し
たところ、波数1720cm-1にエステルカルボニルの
伸縮振動に基づく吸収が測定された。
次にこの重合体を50mlの試験管に30ｇ入れ、
230℃のオイル浴中で５時間加熱分解反応させた。
この反応において揮発性有機ガスが生成したが、
揮発成分はメチルメタクリレート単量体であり、
これは重合体主鎖の解重合にもとづくものであ
る。反応終了後、１時間1.0mmHgの減圧下で揮発
成分を除去して発泡した白色の樹脂体を得た。こ
の樹脂体を粉砕した。この粉砕した重合体は次の
ような物性を有していた；
数平均分子量（Mn）；5.20×104
重量平均分子量（Mw）；13.5×104
Ｚ平均分子量（Mz）；17.8×104
Mw／Mn＝2.60、Mz／Mn＝3.42
固有粘度；0.27dl／ｇ
この重合体試料を250℃、150Kg／cm2で加熱・加
圧成形して厚さ150μのフイルムを作製し、動的
粘弾性を測定した。損失弾性率（E″）の分散ピ
ークは107℃であつた。
同様にして10mm×10mm×５mm（厚さ）の平板を
作成してビガー軟化点を測定したところ、98℃の
値を示した。
また差動走査熱量計を使用してガラス転移温度
を測定したところ78〜109℃の間であつた。
さらに上記成形フイルムの赤外吸収スペクトル
の測定を行なつたところ、波数1720cm-1にエステ
ルカルボニルの伸縮振動の吸収を示したが、加熱
分解反応前の重合体と同様、グルタルイミドに基
づく吸収は認められなかつた。
また加熱分解重合体をメルトインデクサー（東
洋精機製作所製）にかけて230℃、10Kg荷重下で
押出したところ、良好なストランド状樹脂体が得
られ、10.5ｇ／10分のMI値を示した。
比較例 ２
メタクリルアミド100部、水500部、過硫酸カリ
ウム0.05部およびtert.−ドデシルメルカプタン0.1
部を混合溶解させガラス製アンプル内に仕込み、
実施例12と同様にして熱処理した。得られた重合
体は、黄褐色で溶媒に溶解せず、また溶融もしな
い架橋ポリマーが生成した。
以上の実施例および比較例においては得られた
熱分解反応後の重合体の主な物性を表１に示す。
The present invention relates to a method for producing thermoplastic polymers containing structural units of glutarimide groups in the polymer backbone. Transparent resins such as polymethyl methacrylate and polystyrene are used as melt-forming materials for home appliances, vehicle optical parts, instrument panels, lighting window materials, and, in recent years, as materials for optical fibers. I'm getting used to it. As the development of these uses becomes more sophisticated, there is also a demand for more sophisticated performance in the plastics used for these uses, and in recent years there has been a strong demand for improved heat resistance in particular. As a method for improving the heat resistance of these vinyl polymerizable thermoplastic polymers, there is a method of introducing a maleic anhydride structure, as described in JP-A-55-102614 and JP-A-57-153008. Proposed. Maleic anhydride has copolymerizability properties that are quite different from other vinyl monomers, and it is known that a good way to improve its copolymerizability is to use styrene as a copolymerizable monomer. The polymer is a multicomponent copolymer, such as a methyl methacrylate/maleic anhydride/styrene ternary copolymer or a quaternary copolymer obtained by copolymerizing these ternary copolymers with other vinyl monomers, and its production is difficult. Not only is this difficult, but the transparency of the obtained polymer is not necessarily good. As described above, proposals have been made to increase heat resistance by forming a ring structure in the polymer main chain and imparting rigidity to the ring structure. That is, the heat resistance of the maleic anhydride-styrene copolymer is improved by forming a five-membered ring structure with maleic anhydride in the polymer main chain. On the other hand, there is a method in which a glutarimide ring structure obtained by thermally decomposing a methacrylamide polymer is formed in the polymer main chain. The term glutarimide ring as used herein refers to an imide ring produced as a result of a deammoniation reaction by condensation between amides of methacrylamide or acrylamide units in a polymer. Conventionally, regarding such polymer side chain reactions, K.Crauwels, G.
Smets, Bull, Soc, Chim, Belgium 59 182
(1950), a polymer containing a glutarimide ring in the main chain is obtained by thermal decomposition condensation reaction of polymethacrylamide polymer, but this condensation reaction is not only an intramolecular reaction, but also a condensation reaction between polymers. A reaction occurs and only a crosslinked polymer is obtained. The polymer actually obtained by repeating the method described in the above-mentioned literature was an insoluble crosslinked black colored polymer. Also, Tokko Akira
44-8743 discloses that glutarimide is produced by polymerizing a mixture of methacrylic acid and methacrylonitrile or a mixture of methacrylic acid, methacrylonitrile, and methacrylamide in the presence of urea or N-N'-dimethylurea, and then thermally decomposing it. A polymer having a ring in the main chain has been obtained, and it has been reported that a heat-resistant foam material with a crosslinked structure in which the imide group-forming reaction of this polymer also occurs intermolecularly is obtained. As mentioned above, in the modification of polymers that utilizes the condensation reaction of amide groups in polymer side chains, which has been studied in the past, reactions occur not only between intramolecular segments but also between molecules, resulting in only crosslinked polymers. The current situation is that we are not getting it. Therefore, the present inventors conducted intensive studies to obtain good heat resistance and shaping processability with a polymer that has an imide ring structure in the polymer main chain and is substantially thermoplastic, and as a result, they arrived at the present invention. did. That is, the gist of the present invention is that 5 to 100% by weight of N-mono-substituted (meth)acrylamide units substituted with a group selected from an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group; ) Polymer consisting of 95 to 0% by weight of acrylic ester units or 5 to 30% by weight of (meth)acrylamide units
and (meth)acrylic acid ester units 95-70% by weight
A polymer selected from copolymers consisting of (In the formula, R 1 and R 2 are groups selected from the same or different hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and R 3 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group. The polymer contains 5% by weight or more of a structural unit represented by (representing a group selected from group or phenyl group) and has an intrinsic viscosity of 0.01 to 2.
dl/g. The thermoplastic polymer of the present invention containing 5% by weight or more of the structural unit represented by the above general formula [] includes: (1) 5 to 100% by weight of N-mono-substituted (meth)acrylamide units and (meth)acrylic acid ester A polymer consisting of 95 to 0% by weight of units, or (2) 5 to 30% by weight of (meth)acrylamide units and 95 to 70% by weight of (meth)acrylic acid ester units.
It is produced by thermally decomposing a polymer consisting of and performing an intramolecular intersegment condensation cyclization reaction. When producing the thermoplastic polymer of the present invention by the method (1) above, the polymer obtained from N-mono-substituted (meth)acrylamide as a raw material or N
-Mono-substituted-(meth)acrylamide and (meth)
When a copolymer with an acrylic ester monomer is thermally decomposed, the N-(methyl)amide segment in the polymer is converted into an adjacent N-mono-substituted (meth)acrylamide or an adjacent (meth)acrylic ester in the molecule. It is thought that a glutarimide cyclization reaction is mainly performed through a deammonia or dealkylamine reaction with the segment, and a substantially thermoplastic polymer is obtained. Therefore, according to this method, the thermoplastic polymer of the present invention can be produced extremely efficiently. The content of N-mono-substituted (meth)acrylamide units and (meth)acrylic acid ester units in the polymer that is the starting material for this method is 5 to 100% by weight of N-mono-substituted (meth)acrylamide units. , (meta)
The content of acrylic acid ester units is in the range of 95 to 0% by weight, and if the content of N-mono-substituted (meth)acrylamide units is less than 5% by weight, a polymer with excellent heat resistance cannot be obtained. Examples of N-mono-substituted (meth)acrylamides include alkyl groups having 1 to 6 carbon atoms,
For example, N-methylmethacrylamide, N-methylacrylamide, N-ethylmethacrylamide,
N-ethylacrylamide, N-propylmethacrylamide, N-propylacrylamide, N-
Isopropyl methacrylamide, N-isopropylacrylamide, N-tert.-butyl methacrylamide, N-tert.-butyl acrylamide, N-
Examples include sec.-butyl methacrylamide, N-sec.-butyl methacrylamide, N-cyclohexyl methacrylamide, and N-cyclohexyl acrylamide. Furthermore, examples of (meth)acrylic acid esters used by copolymerizing with N-mono-substituted (meth)acrylamide include methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, n- butyl methacrylate,
n-butyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, lauryl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, benzyl methacrylate,
Examples include alkyl methacrylates or acrylates containing an aliphatic or aromatic functional group having 1 to 18 carbon atoms, such as benzyl acrylate. However, it is desirable that the obtained polymer be one that is difficult to be colored by heating and one that does not form an intermolecular crosslinked structure.
From this point of view, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-butyl methacrylate, n-butyl acrylate, iso-butyl methacrylate,
-butyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate,
The use of lauryl methacrylate, lauryl acrylate, etc. is preferred. Among the above, it is more preferable to use N-methylmethacrylamide as the N-mono-substituted (meth)acrylamide and methyl methacrylate as the (meth)acrylic acid ester. The reason for this is not very clear, but when a polymer containing N-methylmethacrylamide structural units is heat-treated, similar N-methylamide structural units that are adjacent segments within the molecule are As a result of preferential deammonification or demethylamine reaction between N-methylamide groups and methyl ester groups, the thermoplasticity of the present invention is mainly characterized by the formation reaction of the structural unit represented by the general formula []. It is believed that a polymer is obtained. This is N-
The hydrogen atom bonded to the nitrogen atom in the methylamide group is fixed by interaction such as hydrogen bonding with the side chain carbonyl group of the adjacent segment, and as a result, the intramolecular intersegment condensation reaction proceeds efficiently and preferentially. it is conceivable that. This method is characterized in that it is not subject to any restrictions on the amount of N-mono-substituted (meth)acrylamide copolymerized. The method for producing the thermoplastic polymer of the present invention by the method (2) above is a condensation cyclization reaction between amide groups or ester groups that are present as polymer side chains in a free state. This condensation reaction easily occurs not only between intramolecular segments but also between molecules, so (meth)acrylamide and (meth)acrylic acid ester, which are the raw materials used to produce the thermoplastic polymer of the present invention, The content of (meth)acrylamide units in the copolymer must be 30% by weight or less. When a copolymer with a (meth)acrylamide copolymerization amount exceeding 30% by weight is subjected to a condensation reaction, it is possible to obtain a substantially solvent-soluble and substantially meltable polymer, which is the object of the present invention. Can not. As the polymerization initiator used to obtain the N-mono-substituted (meth)acrylamide-containing polymer or (meth)acrylamide-containing copolymer used as a starting material in the production method of the present invention, ordinary radical polymerization Initiators can be used. Specific examples include di-tert.-butyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, tert-butyl perphthalate, tert.-butyl perbenzoate, methyl isobutyl ketone peroxide, lauroyl peroxide, cyclohexyl peroxide,
2,5 dimethyl 2,5 di-tert.-butyl peroxyhexane, tert.-butyl peroctanoate,
Organic peroxides such as tert.-butylperisobutyrate, tert.-butylperoxyisopropyl carbonate, methyl 2-2'-azobisisobutyrate, 1,1'-azobiscyclohexanecarbonitrile, 2-phenylazo- 2,4-dimethyl-4
-Methoxyvaleronitrile, 2-carbamoyl-
Examples include azo compounds such as azobisisobutyronitrile, 2-2'-azobis(2.4 dimethylvaleronitrile), and 2,2'-azobisisobutyronitrile. Also, ammonium persulfate, potassium persulfate, etc. can be used. Also, ammonium persulfate, potassium persulfate, etc. can be used. As a chain transfer agent,
There are no particular limitations, and ordinary polymerization degree regulators can be used. Examples include alkylmercaptan, carbon tetrachloride, carbon tetrabromide, dimethylacetamide, dimethylformamide, triethylamine, and the like, among which alkylmercaptan is most preferred. In the case of free radical initiation as a polymerization method,
Examples include emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization, but other production methods can be employed depending on the purpose. It can also be obtained using a Grignard reagent, a polymerization initiation catalyst, an alkyllithium-based ionic polymerization catalyst, etc. When thermally decomposing the N-mono-substituted (meth)acrylamide-containing polymer or (meth)acrylamide-containing copolymer to obtain the thermoplastic polymer of the present invention, the heat treatment temperature of the polymer or copolymer is 200°C or higher. ,
Preferably 200℃~450℃, more preferably 200℃
The temperature is from ℃ to 300℃, and the processing time is more than 0.5 hours. The thermoplastic polymer obtained by the method of the present invention contains at least 5% by weight of a glutarimide ring structure represented by the general formula [], is substantially soluble in a solvent, and is substantially meltable by heating. The major feature is that it is possible. Since the polymer of the present invention contains the glutarimide ring structural unit represented by the general formula [] in the polymer main chain in an amount of 5% by weight or more, preferably 10% by weight or more, its heat resistance is higher than that of conventionally developed polymers. Despite being improved by 5 to 10°C compared to comparable vinyl polymers of the same type, its transparency and moldability are good. The thermoplastic polymer of the present invention has an intrinsic viscosity of
It is necessary that it is 0.01 to 2 dl/g. A molded article with excellent mechanical strength cannot be made from a polymer having an intrinsic viscosity of less than 0.01 dl/g. Further, a polymer having an intrinsic viscosity exceeding 2 dl/g has a high viscosity, which causes problems in shaping properties such as melt molding, and also causes problems such as a decrease in solubility when made into a solution. Although the thermoplastic polymer of the present invention has an improved heat resistance temperature of 5 to 10°C or more compared to comparable vinyl polymers of the same type, its transparency
It has good heat melt fluidity and solubility in various solvents such as dimethylformamide and chloroform. Therefore, the polymer of the present invention can be used in various molding materials, coating materials, resist materials, optical materials, heat-resistant films, fibers, etc., and this polymer can be used in combination with crosslinking agents such as low molecular weight polyamines, urea, ammonia, dialkyl urea, etc. Then, a resin composition exhibiting crosslinking and curable properties can be obtained. The present invention will be explained in more detail with reference to Examples below, and the following methods were used to measure the properties of the polymer. The infrared absorption spectrum was measured by the KBr disk method using an infrared spectrophotometer (manufactured by Hitachi, Ltd., model 285). Number average molecular weight (Mn), weight average molecular weight (Mw)
and Z average molecular weight (Mz) are Gel Permeation Chromatography HLC-manufactured by Toyo Soda Co., Ltd.
Using 802UR, the sample concentration was 0.1 (weight/volume)%,
Elution used dimethylformamide as a solvent, a flow rate of 1.2 ml/min, and a monodisperse polystyrene calibration curve. The heat resistance test was conducted in accordance with ASTM-D-1525, using a Vigar softening point measuring device (manufactured by Toyo Seiki Seisakusho), with a heating rate of 50 ± 5°C/Hr, and a sample size of 5 × 10 × 10
mm was used. Storage modulus (E′) and loss modulus (E″) were measured using a dynamic viscoelasticity device (manufactured by Toyo Baldwin Co., Ltd.).
Measurement was performed at 110 Hz and a heating rate of 2° C./min. The intrinsic viscosity of the thermoplastic polymer was measured as follows. A dimethylformamide solution with a polymer concentration of 0.5% by weight was used as a sample, and measured at a temperature of 25% using a Deereax-Bischoff viscometer.
Flow time of dimethylformamide at ±0.1℃: to
and the flow time of the polymer solution: ts is measured,
Determine the relative viscosity ηre of the polymer from the ts/to value,
Calculated using the following formula. ηinh=(nηre)/C [] (In the formula, C represents the number of grams of polymer per 100 ml of solvent.) In the examples, parts represent parts by weight. Example 1 50 parts of methyl methacrylate, 50 parts of N-methyl methacrylamide, 0.01 part of 2,2'-azobisisobutyronitrile and 0.1 part of tert.-dodecyl mercaptan.
The sample was melted and placed in a glass ampoule, cooled under liquid nitrogen temperature, degassed repeatedly, and sealed in a nitrogen atmosphere. Next, place this sealed ampoule in a heating bath and heat it for 70 minutes.
After heating at 120°C for 15 hours, the mixture was further heated at 120°C for 3 hours to complete polymerization. The reaction conversion rate of monomers in this polymerization was 95%. Next, the resulting polymer was dissolved in tetrahydrofuran and then poured into n-hexane for precipitation, which was repeated several times to purify the polymer. This purified polymer had the following physical properties; Number average molecular weight (Mn); 8.5×10 4 Weight average molecular weight (Mw); 21.2×10 4 Z average molecular weight (Mz); 33.5×10 4 Mw /Mn=2.49, Mz/Mn=3.94 Intrinsic viscosity: 0.45 dl/g Further, the results of measuring the infrared absorption spectrum of this polymer are shown in FIG. At wave number 1720 cm -1, absorption based on stretching vibration of ester carbonyl also occurs at wave number,
Absorption based on acid amide was measured at 1620 to 1640 cm -1 and 1540 cm -1 . Next, put 30g of this polymer into a 50ml tester,
Thermal decomposition reaction was carried out in an oil bath at 230°C for 5 hours.
In this reaction, methylamine was produced as a volatile organic gas, and methanol was also produced. After the reaction was completed, volatile components were removed under reduced pressure of 1.0 mmHg for 1 hour to obtain a foamed white resin body. This resin body was crushed. This pulverized polymer had the following physical properties; Number average molecular weight (Mn): 7.95×10 4 Weight average molecular weight (Mw): 18.5×10 4 Z average molecular weight (Mz): 28.5×10 4 Mw/Mn=2.32, Mz/Mn=3.58 Intrinsic viscosity: 0.40dl/g This polymer sample was heated and pressure molded at 250℃ and 150Kg/ cm2 to produce a film with a thickness of 150μ. Elasticity was measured. The dispersion peak of the loss modulus (E″) was at 140°C. When a flat plate of 10 mm x 10 mm x 5 mm (thickness) was similarly prepared and the Vigor softening point was measured, it was found to be 147°C.
The value of Further, the glass transition temperature was measured using a differential scanning calorimeter and was found to be between 140 and 161°C. Furthermore, the infrared absorption spectrum of the above molded film was measured. The results are shown in FIG. As can be seen from Figure 2, in addition to the absorption of the stretching vibration of ester carbonyl at a wave number of 1720 cm -1 , the wave number of 1756 cm -1 ,
Absorption due to the formation of glutarimide groups was confirmed at 1802 cm -1 and 742 cm -1 . The amount of glutarimide produced was 63% by weight from the ratio of absorption based on glutarimide and absorption based on ester carbonyl. Further, when the thermally decomposed polymer was extruded using a melt indexer (manufactured by Toyo Seiki Seisakusho) at 230°C under a load of 10 kg, a good strand-shaped resin body was obtained, showing an MI value of 5.5 g/10 min. This polymer was passed through a 25φ vented extruder (manufactured by Daiichi Jitsugyo Co., Ltd., full flight screw L/D = 24) and extruded into pellets at a barrel temperature of 200°C and a die temperature of 230°C. . A 1 ounce vertical screw type injection molding machine (manufactured by Yamashiro Seiki Seisakusho)
SAV-30A) to produce a molded plate of 60 mm x 80 mm x 2 mm. This molded plate had excellent heat resistance. The above results show the molecular weight and molecular weight distribution measured by gel permeation chromatography (GPC) of a polymer using N-methyl methacrylamide and methyl methacrylate copolymer as starting materials, and heat treatment of this raw material polymer. From the measurement of the molecular weight and molecular weight distribution of the thermoplastic polymer of the present invention obtained by the GPC method, it was found that demethylamination and demethanolization were performed by thermal decomposition, and that a small number of polymer chains were formed during the initial stage of thermal decomposition. decomposition occurred, and an apparent decrease in molecular weight was observed, but no increase in molecular weight due to intermolecular cross-linking reaction, widening of molecular weight distribution, or significant change in molecular weight due to main chain scission was observed. Examples 2 to 7 Polymers were prepared by repeating the same operations as in Example 1 using the monomer compositions shown in Table 1, and the polymers were heat-treated and their physical properties were measured. The results are shown in Table 1. Examples 8-11 50 parts of methyl methacrylate, 50 parts of N-methylmethacrylamide, 0.01 part of 2,2'-azobisisobutyronitrile and tert.-dodecylmercaptan
0.1 part was dissolved and put into a glass ampoule, and a polymer was prepared in the same manner as in Example 1, and a purified polymer was obtained. As in Example 1, 30 g of this polymer was subjected to a thermal decomposition reaction in an oil bath at 230° C. for 30 minutes. The reaction conversion rate of this thermal reaction decomposition product was confirmed to be 30% based on the absorption amount of ester carbonyl in the infrared absorption spectrum. Further, this thermal decomposition reaction was continued in an oil bath at 230° C. for the time shown in Table 1, and the resin properties of the resulting polymer were measured. The results are shown in Table 1. Example 12 100 parts of N-methylmethacrylamide, 2,2'-
0.01 part of azobisisobutyronitrile and tert.−
0.1 part of dodecyl mercaptan was dissolved and placed in a glass ampoule, and after cooling at liquid nitrogen temperature, deaeration was repeated and the tube was sealed in a nitrogen atmosphere. Next, place this sealed ampoule in a heating bath and heat it for 70 minutes.
After heating at 120°C for 15 hours, the mixture was further heated at 120°C for 3 hours to complete polymerization. The reaction conversion rate of monomers in this polymerization was 96%. The results of measuring the infrared absorption spectrum of this polymer are shown in FIG. Carbonyl absorption based on acid amide was measured at wavenumbers of 1620 to 1640 cm -1 . Next, put 30g of this polymer into a 50ml test tube,
Thermal decomposition reaction was carried out in an oil bath at 230°C for 5 hours.
In this reaction, methylamine was produced as a volatile organic gas. 1 hour after reaction, 1.0mm
Volatile components were removed under reduced pressure of Hg to obtain a foamed white resin body. This resin body was crushed. This polymer sample was heated and pressure-molded at 250° C. and 150 kg/cm 2 to prepare a film with a thickness of 150 μm, and its dynamic viscoelasticity was measured. The dispersion peak of the loss modulus (E'') was at 165°C. When a flat plate of 10 mm x 10 mm x 5 mm (thickness) was similarly prepared and the Vigor softening point was measured, it was found to be 167°C.
The value of Further, the glass transition temperature was measured using a differential scanning calorimeter and was found to be between 162 and 188°C. Furthermore, the infrared absorption spectrum of the above molded film was measured. The results are shown in FIG. As can be seen from FIG. 4, absorption due to the formation of glutarimide groups was confirmed at wave numbers of 1720 cm -1 , 1660 cm -1 and 742 cm -1 . From the ratio of absorption based on glutarimide to absorption based on ester carbonyl, the amount of glutarimide produced was 95% by weight. Further, when the thermally decomposed polymer was extruded using a melt indexer (manufactured by Toyo Seiki Seisakusho) at 230°C under a load of 10 kg, a good strand-shaped resin body was obtained, showing an MI value of 2.9 g/10 min. Examples 13-16 100 parts of N-methyl methacrylamide, 2,2'-
0.01 part of azobisisobutyronitrile and tert.−
0.1 part of dodecyl mercaptan was dissolved and placed in a glass ampoule to prepare a polymer in the same manner as in Example 12, and a purified polymer was obtained. 30 g of this polymer was heated in an oil bath at 230°C for 30 g as in Example 1.
A thermal decomposition reaction was carried out for a minute. The reaction conversion rate of this thermally decomposed product was confirmed to be 40% based on the absorption amount of carbonyl and imidocarbonyl in the infrared absorption spectrum, and the thermally decomposed reaction was continued for the time shown in Table 1 in an oil bath at 230°C. The resin properties of the obtained polymer were measured. The results are shown in Table 1. Comparative Example 1 100 parts of methyl methacrylate, 0.01 part of 2,2'-azobisisobutyronitrile and 0.1 part of tert.-dodecylmercaptan were dissolved and placed in a glass ampoule, cooled at liquid nitrogen temperature, and then desorbed. The tube was sealed in a nitrogen atmosphere after repeated stirring. Next, place this sealed ampoule in a heating bath and heat it for 70 minutes.
After heating at 120°C for 15 hours, the mixture was further heated at 120°C for 3 hours to complete polymerization. The reaction conversion rate of monomers in this polymerization was 97%. Next, the resulting polymer was dissolved in tetrahydrofuran and then poured into n-hexane for precipitation, which was repeated several times to purify the polymer. This purified polymer had the following physical properties; Number average molecular weight (Mn); 5.71×10 4 Weight average molecular weight (Mw); 14.3×10 4 Z average molecular weight (Mz); 20.0×10 4 Mw /Mn=2.68, Mz/Mn=3.50 Intrinsic viscosity: 0.30 dl/g When the infrared absorption spectrum of this polymer was measured, absorption based on stretching vibration of ester carbonyl was measured at a wave number of 1720 cm -1 . Next, put 30g of this polymer into a 50ml test tube,
Thermal decomposition reaction was carried out in an oil bath at 230°C for 5 hours.
Volatile organic gas was produced in this reaction, but
The volatile component is methyl methacrylate monomer,
This is based on the depolymerization of the polymer main chain. After the reaction was completed, volatile components were removed under reduced pressure of 1.0 mmHg for 1 hour to obtain a foamed white resin body. This resin body was crushed. This pulverized polymer had the following physical properties; Number average molecular weight (Mn); 5.20×10 4 Weight average molecular weight (Mw); 13.5×10 4 Z average molecular weight (Mz); 17.8×10 4 Mw/Mn=2.60, Mz/Mn=3.42 Intrinsic viscosity: 0.27 dl/g This polymer sample was heated and pressure molded at 250°C and 150 kg/ cm2 to produce a film with a thickness of 150 μ. Elasticity was measured. The dispersion peak of the loss modulus (E″) was 107°C. When a flat plate of 10 mm x 10 mm x 5 mm (thickness) was similarly prepared and the Vigor softening point was measured, it showed a value of 98°C. Furthermore, when the glass transition temperature was measured using a differential scanning calorimeter, it was found to be between 78 and 109°C.Furthermore, when the infrared absorption spectrum of the above molded film was measured, it was found that the wave number was 1720 cm -1 . It showed absorption of the stretching vibration of the ester carbonyl, but like the polymer before the thermal decomposition reaction, no absorption due to glutarimide was observed.The thermally decomposed polymer was also subjected to a melt indexer (manufactured by Toyo Seiki Seisakusho) at 230°C. When extruded at ℃ under a load of 10 kg, a good strand-shaped resin body was obtained, showing an MI value of 10.5 g/10 min. Comparative Example 2 100 parts of methacrylamide, 500 parts of water, 0.05 parts of potassium persulfate and tert.-dodecyl mercaptan 0.1
Mix and melt the parts and place in a glass ampoule.
Heat treatment was performed in the same manner as in Example 12. The resulting polymer was a crosslinked polymer that was yellowish brown in color and did not dissolve or melt in the solvent. Table 1 shows the main physical properties of the polymers obtained after the thermal decomposition reaction in the above Examples and Comparative Examples.
【表】【table】
第１図および第２図は実施例１における共重合
体の熱分解反応前および反応後の赤外吸収スペク
トルを、第３図および第４図は実施例12における
重合体の熱分解反応前および反応後の赤外吸収ス
ペクトルをそれぞれ示す。
Figures 1 and 2 show infrared absorption spectra of the copolymer in Example 1 before and after the thermal decomposition reaction, and Figures 3 and 4 show the infrared absorption spectra of the polymer in Example 12 before and after the thermal decomposition reaction. The infrared absorption spectra after the reaction are shown.
Claims (1)
基から選ばれた基で置換されたＮ−モノ−置換
（メタ）アクリルアミド単位５〜100重量％と（メ
タ）アクリル酸エステル単位95〜０重量％からな
る重合体または（メタ）アクリルアミド単位５〜
30重量％と（メタ）アクリル酸エステル単位95〜
70重量％からなる共重合体より選ばれる重合体を
200℃以上の温度で加熱処理して、 次の一般式 （式中、R1、R2は同一または異種の水素原子
または炭素数１〜４のアルキル基から選ばれた基
であり、R3は水素原子または炭素数１〜６のア
ルキル基、シクロアルキル基またはフエニル基か
ら選ばれた基を表す）で示される構造単位を重合
体中に５重量％以上を含み、固有粘土が0.01〜２
dl／ｇである重合体を得ることを特徴とする熱可
塑性重合体の製造法。[Scope of Claims] 1 5 to 100% by weight of N-mono-substituted (meth)acrylamide units substituted with a group selected from an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group and a (meth)acrylic acid ester Polymer consisting of 95 to 0% by weight of units or 5 to (meth)acrylamide units
30% by weight and (meth)acrylic acid ester units 95~
A polymer selected from copolymers consisting of 70% by weight.
After heat treatment at a temperature of 200℃ or higher, the following general formula (In the formula, R 1 and R 2 are groups selected from the same or different hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and R 3 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group. The polymer contains 5% by weight or more of a structural unit represented by (representing a group selected from groups or phenyl groups), and has an inherent clay of 0.01 to 2.
1. A method for producing a thermoplastic polymer, characterized in that a polymer having a dl/g is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12819583A JPS6020904A (en) | 1983-07-14 | 1983-07-14 | Novel thermoplastic polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12819583A JPS6020904A (en) | 1983-07-14 | 1983-07-14 | Novel thermoplastic polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6020904A JPS6020904A (en) | 1985-02-02 |
| JPH0461007B2 true JPH0461007B2 (en) | 1992-09-29 |
Family
ID=14978802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12819583A Granted JPS6020904A (en) | 1983-07-14 | 1983-07-14 | Novel thermoplastic polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6020904A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4727117A (en) * | 1985-08-27 | 1988-02-23 | Rohm And Haas Company | Imide polymers |
| JPH0613569B2 (en) * | 1987-02-05 | 1994-02-23 | 旭化成工業株式会社 | Heat resistant methacrylic resin |
| US5123994A (en) * | 1989-05-30 | 1992-06-23 | Motorola, Inc. | Ramped oxide formation method |
| EP1136506A1 (en) * | 2000-03-23 | 2001-09-26 | Dsm N.V. | Compound comprising a supramolecular complex, method of preparation and use thereof, and process for preparing a glutar imide containing polymer |
| JP2006328329A (en) * | 2005-05-30 | 2006-12-07 | Kaneka Corp | Base material for surface-protective film and surface-protective film |
| WO2016152646A1 (en) * | 2015-03-23 | 2016-09-29 | 株式会社日本触媒 | Glutarimide resin and method for producing glutarimide resin |
| JP2017039850A (en) * | 2015-08-20 | 2017-02-23 | 三菱レイヨン株式会社 | Copolymer, method for producing copolymer, resin composition, molded article, and vehicle |
-
1983
- 1983-07-14 JP JP12819583A patent/JPS6020904A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6020904A (en) | 1985-02-02 |
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