JPS63122713A - Production of heat-resistant halogenated vinylidene copolymer - Google Patents
Production of heat-resistant halogenated vinylidene copolymerInfo
- Publication number
- JPS63122713A JPS63122713A JP26933286A JP26933286A JPS63122713A JP S63122713 A JPS63122713 A JP S63122713A JP 26933286 A JP26933286 A JP 26933286A JP 26933286 A JP26933286 A JP 26933286A JP S63122713 A JPS63122713 A JP S63122713A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- parts
- copolymer
- formulas
- tables
- 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.)
- Granted
Links
- 229920001577 copolymer Polymers 0.000 title abstract description 46
- 238000004519 manufacturing process Methods 0.000 title description 5
- -1 vinylidene halide Chemical class 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 28
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 abstract description 21
- 230000009477 glass transition Effects 0.000 abstract description 20
- 238000006116 polymerization reaction Methods 0.000 abstract description 20
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 16
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 239000002685 polymerization catalyst Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- KPQOXMCRYWDRSB-UHFFFAOYSA-N 1-(2-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC=C1N1C(=O)C=CC1=O KPQOXMCRYWDRSB-UHFFFAOYSA-N 0.000 description 3
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000012748 slip agent Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- LJDGDRYFCIHDPX-UHFFFAOYSA-N 1-(2-methoxyphenyl)pyrrole-2,5-dione Chemical compound COC1=CC=CC=C1N1C(=O)C=CC1=O LJDGDRYFCIHDPX-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- CYAVCUNFWUJTHY-UHFFFAOYSA-N 1-ethyl-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(CC)C(=O)C=C1C1=CC=CC=C1 CYAVCUNFWUJTHY-UHFFFAOYSA-N 0.000 description 1
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical compound CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 description 1
- SXZSFWHOSHAKMN-UHFFFAOYSA-N 2,3,4,4',5-Pentachlorobiphenyl Chemical compound C1=CC(Cl)=CC=C1C1=CC(Cl)=C(Cl)C(Cl)=C1Cl SXZSFWHOSHAKMN-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 101100134925 Gallus gallus COR6 gene Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000002747 voluntary effect Effects 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)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、耐熱性、難燃性に優れ、ガスバリア性、耐薬
品性、熱可塑性を有する新規なハロゲン化ビニリデン系
共重合体の製造方法に関する。本発明の方法により製造
されるハロゲン化ビニリデン系共重合体は、そのまま又
は公知の可塑剤、熱安定剤、光安定剤、酸化防止剤、滑
り剤、着色剤等の添加剤を混合使用して熔融押出成形、
熔融圧縮成形、発泡剤含浸発泡成形、溶剤溶解塗布成膜
等公知の加工法により加工し、電線被覆材、繊維、フィ
ルム、シート、チューブ、カップ等の成形品、断熱材や
緩衝材等の発泡体等の加工品に利用することができる。[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a method for producing a novel vinylidene halide copolymer that has excellent heat resistance, flame retardancy, gas barrier properties, chemical resistance, and thermoplasticity. Regarding. The vinylidene halide copolymer produced by the method of the present invention may be used as it is or mixed with known additives such as plasticizers, heat stabilizers, light stabilizers, antioxidants, slip agents, and colorants. melt extrusion,
Processed using known processing methods such as melt-compression molding, foaming molding impregnated with a foaming agent, and solvent-dissolving coating film formation, to form molded products such as electric wire covering materials, fibers, films, sheets, tubes, and cups, as well as foaming materials such as insulation materials and cushioning materials. It can be used for processed products such as bodies.
ハロゲン化ビニリデン系共重合体は、優れた難燃性、ガ
スバリア性、耐薬品性等の特性を有しているため、電線
被覆材、繊維、食品包装フィルム、シート、チューブ、
カップ、発泡体等の加工品に近年益々その用途を広げて
いる。Vinylidene halide copolymers have excellent properties such as flame retardancy, gas barrier properties, and chemical resistance.
In recent years, its use has been expanding into processed products such as cups and foams.
ハロゲン化ビニリデン系共重合体、例えば塩化ビニリデ
ン系共重合体の難燃性、ガスバリア性、耐薬品性等の特
性は、共重合体中の塩化ビニリデンの二重結合が開いた
構造単位＋ＣＨ，−ＣＣＩ、＋の量が多ければ多い程優
れる傾向にあるので、従来、共重合体中の構造単位十Ｃ
Ｈ，−ＣＣ１，＋の含量が８５モル％を越える塩化ビニ
リデン系重合体が主として使用されている。しかし、構
造単位上０Ｈ，−ＣＣｌ□すが多ければ多い程共重合体
の結晶性が高くなり、又、脱塩酸し易くなる傾向にある
ので、熔融押出成形時の雑溶融性、熔融押出成膜時のフ
ィルム寸法制御の困難さ、熱分解、発泡剤含浸の困雑さ
、溶剤溶解塗布成膜時の溶剤への難溶性や塗液の短寿命
、加工品の変色等の欠点が生じる問題がある。The properties of vinylidene halide copolymers, such as vinylidene chloride copolymers, such as flame retardancy, gas barrier properties, and chemical resistance, are based on the structural units +CH, -, in which the double bond of vinylidene chloride in the copolymer is open. Since the larger the amount of CCI, +, the better it tends to be, conventionally, the structural unit 10C in copolymers
Vinylidene chloride polymers having a H, -CC1,+ content of more than 85 mol % are mainly used. However, the more 0H, -CCl□ in the structural unit, the higher the crystallinity of the copolymer and the easier it is to dehydrochloride. Difficulties in controlling film dimensions during coating, difficulty in thermal decomposition, difficulty in impregnating blowing agents, poor solubility in solvents during solvent-dissolved coating film formation, short lifespan of coating fluids, and discoloration of processed products. There is.
これらの欠点を改良するために可塑剤、熱安定剤、光安
定剤、酸化防止剤等の添加剤を混合使用することが提案
され、或いは実施されているが、必ずしも満足すべきも
のではない。In order to improve these drawbacks, it has been proposed or practiced to use a mixture of additives such as plasticizers, heat stabilizers, light stabilizers, and antioxidants, but this is not always satisfactory.
又、特開昭６０−４４５１０号公報には、共重合体が結
晶性であるが敢に主として起こる前記のような問題点を
解決するために非品性領域のハロゲン化ビニリデン共重
合体を提案している。そこには、塩化ビニリデン／メチ
ルアクリレートがモル比で４７１５３〜８１／１９の仕
込組成で重合して得られた共重合体が、可塑剤を添加す
ることなく溶融押出成膜できた例、塩化ビニリデン／メ
チルメタクリレートを７０／３０ （モル％）の仕込組
成で重合して得られた共重合体から押出発泡体を得た例
等が挙げられているが、何れもガラス転移点が低く、フ
ィルムは高い温度での腰が弱く、発泡体は耐熱変形性に
乏しいものである。Furthermore, Japanese Patent Application Laid-open No. 60-44510 proposes a vinylidene halide copolymer with low quality in order to solve the above-mentioned problems that mainly occur even though the copolymer is crystalline. are doing. There is an example in which a copolymer obtained by polymerizing vinylidene chloride/methyl acrylate at a molar ratio of 47153 to 81/19 could be formed into a film by melt extrusion without adding a plasticizer. Examples have been given in which extruded foams were obtained from copolymers obtained by polymerizing /methyl methacrylate with a charging composition of 70/30 (mol%), but all of them had low glass transition points and the films were The foam is weak at high temperatures and has poor heat deformation resistance.
本発明の目的は、耐熱性、難燃性に優れ、ガスバリア性
、耐薬品性等のハロゲン化ビニリデン系共重合体の特性
を有し、かつ、結晶性ハロゲン化ビニリデン系共重合体
の持つ前記欠点が改良され、しかも８５℃以上のガラス
転移点を有する新規なハロゲン化ビニリデン系共重合体
の製造方法を提供することである。The object of the present invention is to have the properties of a vinylidene halide copolymer such as excellent heat resistance and flame retardancy, gas barrier properties, and chemical resistance, and the above properties of a crystalline vinylidene halide copolymer. The object of the present invention is to provide a method for producing a novel vinylidene halide copolymer which has improved drawbacks and has a glass transition point of 85° C. or higher.
即ち、本発明は、ハロゲン化ビニリデンを３０〜６５モ
ル％、下記の一般式（１）で表されるＮ−置換マレイミ
ドのＬ種以上を１〜１０モル％、下記の一般式（ＩＩ）
で表される共重合性不飽和単量体の１種以上を２５〜７
０モル％（但し、上記３成分の合計を１００モル％とす
る）、及び下記の一般式（Ｉ［［）で表される二重結合
を１分子中に２個有する化合物の１種以上のＯ〜０．１
モル％を、ラジカル重合開始剤を用いて重合することを
特徴とするガラス転移点が８５℃以上の新規なハロゲン
化ビニリデン系共重合体の製造方法。That is, the present invention comprises 30 to 65 mol% of vinylidene halide, 1 to 10 mol% of L or more N-substituted maleimide represented by the following general formula (1), and the following general formula (II).
One or more copolymerizable unsaturated monomers represented by 25 to 7
0 mol% (however, the total of the above three components is 100 mol%), and one or more compounds having two double bonds in one molecule represented by the following general formula (I[[) O~0.1
1. A method for producing a novel vinylidene halide copolymer having a glass transition point of 85° C. or higher, which comprises polymerizing mol % of the copolymer using a radical polymerization initiator.
記 ＯＣＨ，、−Ｈを表す。）。Record Represents OCH,, -H. ).
ＨユＣ＝ ＣＲ４Ｒ５（ＩＩ ）
〔ξは、−Ｈｌ−ＣＨ，を表し、Ｒ５はハロゲン基、−
ＣＯＲ６を表す（但し、Ｒ６は炭素数１〜４のアルル
キル基又は２−エチルヒドロキシル基を表す、）〕（Ｒ
，は−Ｈ１又は−ＣＲ３を表し、Ｒ８は〜３の整数を表
す。） 、−０−ＣえＨ２Ｎ０−（ｋは３〜６の整数を
表す。）、フェニレン基を表す。〕に関するものである
。HyuC=CR4R5(II) [ξ represents -Hl-CH, R5 is a halogen group, -
COR6 (wherein R6 represents an alkyl group having 1 to 4 carbon atoms or a 2-ethylhydroxyl group)] (R
, represents -H1 or -CR3, and R8 represents an integer of ~3. ), -0-CeH2N0- (k represents an integer of 3 to 6), represents a phenylene group. ].
本発明におけるモル％は、ハロゲン化ビニリデン、前記
一般式（Ｉ）で表されるＮ−置換マレイミド及び前記一
般式（ＩＦ）で表される共重合性不飽和単量体の合計量
を１００モル％とする値である。In the present invention, mol% refers to the total amount of vinylidene halide, the N-substituted maleimide represented by the general formula (I), and the copolymerizable unsaturated monomer represented by the general formula (IF) to 100 mol. The value is expressed as %.
本発明で使用するハロゲン化ビニリデンは、フッ化ビニ
リデン、塩化ビニリデン、臭化ビニリデンである。中で
も、塩化ビニリデンが工業的に入手し易く、沸点が常温
付近（３２℃）で取扱が容易な点から特に好ましい。そ
の使用量は３０〜６５モル％である。３０モル％未満で
は得られる共重合体の難燃性、ガスバリア性、耐薬品性
が低下し好ましくない、６５モル％を越えると共重合体
に結晶性が発現し、又脱ハロゲン酸し易くなるとともに
一般的にガラス転移点が低下し好ましくない。The vinylidene halides used in the present invention are vinylidene fluoride, vinylidene chloride, and vinylidene bromide. Among these, vinylidene chloride is particularly preferred because it is industrially easily available, has a boiling point around room temperature (32° C.), and is easy to handle. The amount used is 30 to 65 mol%. If it is less than 30 mol%, the resulting copolymer will have poor flame retardancy, gas barrier properties, and chemical resistance, which is undesirable. If it exceeds 65 mol%, the copolymer will develop crystallinity and will be susceptible to dehalogenation. This generally lowers the glass transition point, which is undesirable.
本発明で使用する一般式（Ｉ）で表されるＮ−置換マレ
イミドとしては、Ｎ−メチルマレイミド、Ｎ−エチルマ
レイミド、Ｎ−プロピルマレイミド、Ｎ−ブチルマレイ
ミド、Ｎ−シクロへキシルマレイミド、Ｎ−フェニルマ
レイミド、Ｎ−２−メチルフェニルマレイミド、Ｎ−２
−エチルフェニルマレイミド、Ｎ−２−クロロフェニル
マレイミド、Ｎ−２−メトキシフェニルマレイミド、Ｎ
−２，６−シメチルフエニルマレイミド等であり、これ
らの１種以上を使用することができる。中でもＮ−フェ
ニルマレイミド、Ｎ−２−クロロフェニルマレイミド、
Ｎ−２−メチルフェニルマレイミドが工業的に入手し易
く好ましい。Ｎ−フェニルマレイミドが特に好ましい。Examples of the N-substituted maleimide represented by the general formula (I) used in the present invention include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N- Phenylmaleimide, N-2-methylphenylmaleimide, N-2
-Ethylphenylmaleimide, N-2-chlorophenylmaleimide, N-2-methoxyphenylmaleimide, N
-2,6-dimethylphenylmaleimide, etc., and one or more of these can be used. Among them, N-phenylmaleimide, N-2-chlorophenylmaleimide,
N-2-methylphenylmaleimide is preferred because it is industrially easily available. N-phenylmaleimide is particularly preferred.
Ｎ−置換マレイミドの使用量は、１〜１０モル％である
。１モル％未満では得られる共重合体のガラス転移点が
低下し好ましくない。１０モル％を越えたランダム共重
合体を得ることは困難であり、又仮に得られたとしても
高価であり経済的でない。The amount of N-substituted maleimide used is 1 to 10 mol%. If it is less than 1 mol %, the glass transition point of the resulting copolymer will be lowered, which is not preferable. It is difficult to obtain a random copolymer exceeding 10 mol %, and even if it were obtained, it would be expensive and uneconomical.
本発明で使用する一般式（ＩＩ）で表される共重合性不
飽和単量体としては、塩化ビニル、アクリロニトリル、
メタクリレートリ、スチレン、α−メチルスチレン、酢
酸ビニル、アクリル酸、メタクリル酸、メチルアクリレ
ート、エチルアクリレート、ブチルアクリレート、メチ
ルメタクリレート、エチルメタクリレート、２−エチル
へキシルアクリレート、２−エチルへキシルメタクリレ
ート、ヒドロキシエチルアクリレート、グリシジルメタ
クリレート等であり、これらの１種以上を使用すること
ができる。中でもアクリロニトリル、スチレン、メチル
メタクリレートが共重合体のガラス転移点を上げ易く好
ましい。又、アクリロニトリルは難燃性付与の点からも
好ましいが、アクリロニトリルとスチレンを混合して使
用すると共重合体の熱可塑性、高温での伸度も太き（な
り、更に好ましい。The copolymerizable unsaturated monomer represented by the general formula (II) used in the present invention includes vinyl chloride, acrylonitrile,
Methacrylate, styrene, α-methylstyrene, vinyl acetate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl Acrylate, glycidyl methacrylate, etc., and one or more of these can be used. Among them, acrylonitrile, styrene, and methyl methacrylate are preferred because they can easily raise the glass transition point of the copolymer. Further, acrylonitrile is preferable from the viewpoint of imparting flame retardancy, but when acrylonitrile and styrene are used in combination, the thermoplasticity of the copolymer and the elongation at high temperatures are increased (this is more preferable).
その使用量は２５〜７０モル％であり、２５モル％未満
では得られる共重合体のガラス転移点が低下し好ましく
ない。７０モル％を越えると共重合体の難燃性、ガスバ
リア性、耐薬品性が低下し好ましくない。The amount used is 25 to 70 mol%, and if it is less than 25 mol%, the glass transition point of the resulting copolymer will be lowered, which is not preferable. If it exceeds 70 mol%, the flame retardance, gas barrier properties, and chemical resistance of the copolymer will deteriorate, which is not preferable.
本発明で使用する一般式（Ｉｆｆ）で表される二重結合
を１分子中に２個有する化合物としては、ジビニルベン
ゼン、１，３−ブチレングリコールジメタクリレート、
１．６−ヘキサンジオールジアクリレート、ネオペンチ
ルグリコールジメタクリレート、エチレングリコールジ
メタクリレート、その他エチレングリコール系ジメタク
リレート、プロピレングリコール系ジメタクリレート、
１，６−ヘキサンジオールジアクリレート、ネオペンチ
ルグリコールジアクリレート、エチレングリコール系ジ
アクリレート、プロピレングリコール系ジアクリレート
が挙げられ、これらの１種以上を使用することができる
。Compounds having two double bonds in one molecule represented by the general formula (Iff) used in the present invention include divinylbenzene, 1,3-butylene glycol dimethacrylate,
1.6-hexanediol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, other ethylene glycol dimethacrylate, propylene glycol dimethacrylate,
Examples include 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, and propylene glycol diacrylate, and one or more of these can be used.
一般式（ＩＩＩ）で表される二重結合を１分子中に２個
有する化合物を使用することにより、共重合体中にテト
ラヒドロフランに不溶なハロゲン化ビニリデン系共重合
体（以後単に不溶分と云う）を導入することができる。By using a compound having two double bonds in one molecule represented by general formula (III), a vinylidene halide copolymer that is insoluble in tetrahydrofuran (hereinafter simply referred to as insoluble content) is added to the copolymer. ) can be introduced.
不溶分は各単量体がラジカル重合理論により律せられる
ランダムな順序に結合し、二重結合を１分子中に２個有
する化合物で三次元架橋された構造を有し、分子量分布
を持ったハロゲン化ビニリデン系架橋共重合体と考えら
れる。不溶分は得られる共重合体の高温での引張強度の
向上に寄与するが、伸度の低下を招く。The insoluble portion has a three-dimensional cross-linked structure with a compound in which each monomer is bonded in a random order determined by radical polymerization theory and has two double bonds in one molecule, and has a molecular weight distribution. It is thought to be a halogenated vinylidene-based crosslinked copolymer. Although the insoluble content contributes to improving the tensile strength of the obtained copolymer at high temperatures, it causes a decrease in elongation.
テトラヒドロフランに可溶な共重合体（以後単に可溶分
と云う）は、各単量体がラジカル重合理論により律せら
れるランダムな順序に結合し、主として二次元の鎖状構
造を有し、分子量分布を持ったハロゲン化ビニリデン系
鎖状共重合体と考えられる。可溶分は得られる共重合体
の流動性の向上に寄与する。共重合体中の可溶分と不溶
分の好ましい含有量は、目的とする用途により選択され
るべきものである。例えば、本発明の共重合体を“フィ
ルムに加工する場合には、溶融押出成膜時の均一な流動
性が重要なので、不溶分を含まないか又は不溶分含有量
の少ない共重合体が好ましい。A copolymer soluble in tetrahydrofuran (hereinafter simply referred to as the soluble component) has monomers bonded in a random order determined by radical polymerization theory, has a mainly two-dimensional chain structure, and has a molecular weight of It is thought to be a vinylidene halide chain copolymer with a distribution. The soluble content contributes to improving the fluidity of the resulting copolymer. The preferred content of soluble and insoluble components in the copolymer should be selected depending on the intended use. For example, when processing the copolymer of the present invention into a film, uniform fluidity during melt extrusion film formation is important, so a copolymer that does not contain insoluble matter or has a low insoluble matter content is preferable. .
又、本発明の共重合体が発泡剤を含浸した後発泡され発
泡体に加工される場合には、発泡過程で独立気泡を維持
させるために高温でのセル膜の強度を高く保持する必要
があるので、不溶分含有量の比較的多い共重合体が好ま
しい。しかし、不溶分含有量が多すぎると発泡しに（く
なり不適当となる。Furthermore, when the copolymer of the present invention is impregnated with a blowing agent and then foamed and processed into a foam, it is necessary to maintain high strength of the cell membrane at high temperatures in order to maintain closed cells during the foaming process. Therefore, copolymers with relatively high insoluble content are preferred. However, if the insoluble content is too large, foaming may occur, which is inappropriate.
一般式（ＩＩＩ）の化合物の使用量は、０〜０．１モル
％である。The amount of the compound of general formula (III) used is 0 to 0.1 mol%.
本発明における重合プロセスには、懸濁重合、乳化重合
、溶液重合、塊状重合等の諸方法を採用することができ
る。重合開始剤としてはラジカル重合開始剤を使用する
ことができる。重合温度、重合時間は、使用するラジカ
ル重合開始剤及び重合熱除去、収率等を勘案して適宜選
択することができる０Ｍ合反応は液状で行われる。反応
液から共重合体を分離、取得する方法としては、公知の
凝集、蒸発、濾過、乾燥等の方法を採用することができ
る。共重合体組成物に必要に応じて、公知の方法により
可塑剤、熱安定剤、光安定剤、酸化防止剤、滑り剤、着
色剤等の添加剤を添加混合することもできる。Various methods such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization can be employed for the polymerization process in the present invention. A radical polymerization initiator can be used as the polymerization initiator. The polymerization temperature and time can be appropriately selected in consideration of the radical polymerization initiator used, polymerization heat removal, yield, etc. The 0M polymerization reaction is carried out in a liquid state. As a method for separating and obtaining the copolymer from the reaction solution, known methods such as coagulation, evaporation, filtration, and drying can be employed. If necessary, additives such as plasticizers, heat stabilizers, light stabilizers, antioxidants, slip agents, and colorants may be added to the copolymer composition by known methods.
懸濁重合、乳化重合の場合、一般式（１）で表されるＮ
−置換マレイミド（例えばＮ−フェニルマレイミド）は
ハロゲン化ビニリデン（例えば塩化ビニリデン）への溶
解度が小さいので、予め一般式（Ｉｌｌ）で表される共
重合性不飽和単量体（例えばアクリロニトリル、スチレ
ン、メチルメタクリレート）に熔解した後使用する注意
が必要である。In the case of suspension polymerization and emulsion polymerization, N represented by general formula (1)
-Substituted maleimides (e.g. N-phenylmaleimide) have low solubility in vinylidene halides (e.g. vinylidene chloride). Care must be taken to use it after dissolving it in methyl methacrylate).
次に本発明のハロゲン化ビニリデン系共重合体の製造法
について実施例を挙げて更に詳しく説明するが、本発明
の範囲はその内容のみに限定されない、実施例における
部は重量部である。Next, the method for producing a halogenated vinylidene copolymer of the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the contents thereof. Parts in the Examples are parts by weight.
実施例１
反応容器に純水１５０部、懸濁剤としてヒドロキシプロ
ピルメチルセルロース０，２部を仕込み、ラジカル重合
開始剤としてラウリルパーオキサイドを０．６部添加し
溶解液とする。予め塩化ビニリデンに熔解し難いＮ−フ
ェニルマレイミド５部（２，４モル％）を、アクリロニ
トリル３０ｆｌＥ （４５，１モル％）、スチレン１５
部（１１，４モル％）に溶解し、これを塩化ビニリデン
５０部（４１，１モル％）と混合して均一溶液とし、こ
の均一混合液を、前記熔解液と均一に混合する。Example 1 A reaction vessel was charged with 150 parts of pure water and 0.2 parts of hydroxypropyl methyl cellulose as a suspending agent, and 0.6 parts of lauryl peroxide was added as a radical polymerization initiator to prepare a solution. In advance, 5 parts (2.4 mol%) of N-phenylmaleimide, which is difficult to dissolve in vinylidene chloride, were mixed with 30 flE (45.1 mol%) of acrylonitrile and 15 parts of styrene.
This is mixed with 50 parts of vinylidene chloride (41.1 mol%) to form a homogeneous solution, and this homogeneous mixture is uniformly mixed with the melt.
得られた均一混合液を窒素置換後、攪拌を開始し、６０
℃で２４時間反応させる。重合終了後、生成ポリマーを
濾過分離し、乾燥させる。残存単量体が０．２％以下に
なるように処理した。重合率は９８％であった。得られ
た共重合体はテトラヒドロフラン（Ｔ）ＩＰ ’）に完
全に溶解した。重量平均分子量は、ゲルパーミェーショ
ンクロマトグラフィー分析法により、２９９，０００で
あった。ガラス転移点はＡＳＴＭ Ｄ−３４１８−７５
に準じて示差熱量針法により測定して９６℃であった。After purging the resulting homogeneous mixture with nitrogen, stirring was started and the mixture was heated to 60
React for 24 hours at °C. After the polymerization is completed, the resulting polymer is separated by filtration and dried. The treatment was carried out so that the residual monomer content was 0.2% or less. The polymerization rate was 98%. The obtained copolymer was completely dissolved in tetrahydrofuran (T)IP'). The weight average molecular weight was determined to be 299,000 by gel permeation chromatography analysis. Glass transition point is ASTM D-3418-75
The temperature was determined to be 96°C by the differential calorimetry needle method according to the above.
限界酸素指数はＪＩＳ Ｋ−７２０１により測定し３２
％を得た。The limiting oxygen index is measured according to JIS K-7201 and is 32
I got %.
実施例２
塩化ビニ９フフ５０部（４１，１モル％）、Ｎ−フェニ
ルマレイミド５部（２，４モル％）、アクリロニトリル
３０部（４５，１モル％）、スチレン１５部（１１，４
モル％）、ジビニルベンゼン０．０２部（０，０１３モ
ル％）を実施例１と同様に反応、処理した。Example 2 50 parts of vinyl chloride 9 fufu (41.1 mol%), 5 parts of N-phenylmaleimide (2.4 mol%), 30 parts of acrylonitrile (45.1 mol%), 15 parts of styrene (11.4 mol%)
mol %) and 0.02 part (0,013 mol %) of divinylbenzene were reacted and treated in the same manner as in Example 1.
テトラヒドロフラン不溶分は、得られた共重合体１〜２
ｇをテトラヒドロフラン１００ｍ１に４０℃で１時間攪
拌下に浸漬させた後、不溶な部分と熔解した部分に濾別
し、テトラヒドロフランを除去して得られた不溶の部分
の共重合体である。不溶分含有量は３４重量％であった
。The tetrahydrofuran-insoluble portion is the obtained copolymer 1 to 2.
This is a copolymer of the insoluble portion obtained by immersing g in 100 ml of tetrahydrofuran at 40° C. for 1 hour with stirring, filtering the mixture into an insoluble portion and a dissolved portion, and removing the tetrahydrofuran. The insoluble content was 34% by weight.
重合率は９８％、ガラス転移点は９６℃であった。The polymerization rate was 98% and the glass transition point was 96°C.
結果を第１表に示す。The results are shown in Table 1.
実施例３
塩化ビニリデン５０部（４１，１モル％）、Ｎ−フェニ
ルマレイミド５部（２，４モル％）、アクリロニトリル
３０部（４５，１モル％）、スチレン１５部（１１，４
モル％）、ジビニルベンゼン０．０４部（０，０２５モ
ル％）を実施例１と同様に反応、処理した。Example 3 50 parts of vinylidene chloride (41.1 mol%), 5 parts of N-phenylmaleimide (2.4 mol%), 30 parts of acrylonitrile (45.1 mol%), 15 parts of styrene (11.4 mol%)
%) and 0.04 part (0,025 mol%) of divinylbenzene were reacted and treated in the same manner as in Example 1.
重合率は９８％、ＴＩＰ不溶分は５９％、ガラス転移点
は９６℃であった。The polymerization rate was 98%, the TIP insoluble content was 59%, and the glass transition point was 96°C.
結果を第１表に示す。The results are shown in Table 1.
実施例４
塩化ビニリデン５０部（５２，９モル％）、メチルメタ
クリレート４０！ （４１，１モル％）、Ｎ−フェニル
マレイミド１０部（６，０モル％）をを実施例１と同様
に反応、処理した。Example 4 50 parts of vinylidene chloride (52.9 mol%), 40 parts of methyl methacrylate! (41.1 mol%) and 10 parts (6.0 mol%) of N-phenylmaleimide were reacted and treated in the same manner as in Example 1.
重合率は９６％、ガラス転移点は８５℃であった。The polymerization rate was 96% and the glass transition point was 85°C.
結果を第２表に示す。The results are shown in Table 2.
実施例５
塩化ビニリデン５０部（４１，１モル％） 、Ｎ−２−
メチルフェニルマレイミド５部（２，２モル％）、アク
リロニトリル３０部（４５，２モル％）、スチレン１５
部（１１，５モル％）を実施例１と同様に反応、処理し
た。Example 5 50 parts of vinylidene chloride (41.1 mol%), N-2-
Methylphenylmaleimide 5 parts (2.2 mol%), acrylonitrile 30 parts (45.2 mol%), styrene 15
(11.5 mol %) was reacted and treated in the same manner as in Example 1.
重合率は９８％、ガラス転移点は９８℃であった。The polymerization rate was 98% and the glass transition point was 98°C.
結果を第２表に示す。The results are shown in Table 2.
実施例６
塩化ビニリデン４０部ｔ３０．８モル％）、Ｎ−フェニ
ルマレイミド６部（２，６モル％）、アクリロニトリル
４０部（５６，５モル％）、スチレン１４部（１０，１
モル％）を実施例１と同様に反応、処理した。Example 6 40 parts of vinylidene chloride (30.8 mol%), 6 parts of N-phenylmaleimide (2.6 mol%), 40 parts of acrylonitrile (56.5 mol%), 14 parts of styrene (10.1 mol%)
% by mole) was reacted and treated in the same manner as in Example 1.
重合率は９８％、ガラス転移点は１０７℃であった。The polymerization rate was 98% and the glass transition point was 107°C.
結果を第２表に示す。The results are shown in Table 2.
実施例７
塩化ビニリデン５５部（５９，４モル％）、Ｎ−フェニ
ルマレイミド１５部（９，１モル％）、メチルメタクリ
レート３０部（３１，５モル％）を実施例１と同様に反
応、処理した。Example 7 55 parts (59.4 mol%) of vinylidene chloride, 15 parts (9.1 mol%) of N-phenylmaleimide, and 30 parts (31.5 mol%) of methyl methacrylate were reacted and treated in the same manner as in Example 1. did.
重合率は９６％、ガラス転移点は８５℃であった。The polymerization rate was 96% and the glass transition point was 85°C.
結果を第２表に示す。The results are shown in Table 2.
実施例８
反応容器にｎ−ヘキサン３００部を仕込む、そこへＲ量
体として塩化ビニリデン５０部（４１，１モル％）、Ｎ
−フェニルマレイミド５部（２，４モル％）、アクリロ
ニトリル３０部（４５，１モル％）、スチレン１５部（
１１，４モル％）及び重合開始剤としてジイソプロピル
パーオキシジカーボネート０．２部を添加する。Example 8 300 parts of n-hexane was charged into a reaction vessel, and 50 parts of vinylidene chloride (41.1 mol%) and N
- 5 parts of phenylmaleimide (2.4 mol%), 30 parts of acrylonitrile (45.1 mol%), 15 parts of styrene (
11.4 mol%) and 0.2 part of diisopropyl peroxydicarbonate as a polymerization initiator.
Ｍ素置換後、攪拌させながら、４０℃で４８時間反応さ
せる。重合終了後、析出している生成ポリマーを濾過に
より分離し、残存しているｎ−ヘキサンを除去する。After replacing the M element, the mixture is reacted at 40° C. for 48 hours with stirring. After the polymerization is completed, the precipitated polymer is separated by filtration, and the remaining n-hexane is removed.
重合率は９７％、ガラス転移点は９６℃であった。The polymerization rate was 97% and the glass transition point was 96°C.
結果を第２表に示す。The results are shown in Table 2.
実施例９
塩化ビニリデン５０部（４１，２モル％） 、Ｎ−２−
クロロフェニルマレイミド５部（２，０モル％）、アク
リロニトリル３０部（４５，３モル％）、スチレン１５
部（１１，５モル％）を実施例１と同様に反応、処理し
た。Example 9 50 parts of vinylidene chloride (41.2 mol%), N-2-
Chlorophenylmaleimide 5 parts (2.0 mol%), acrylonitrile 30 parts (45.3 mol%), styrene 15
(11.5 mol %) was reacted and treated in the same manner as in Example 1.
重合率は９７％、ガラス転移点は１０１℃であった。The polymerization rate was 97% and the glass transition point was 101°C.
結果を第２表に示す。The results are shown in Table 2.
実施例１０
塩化ビニ９フフ５０部（４１，１モル％）、Ｎ−シクロ
ヘキシルマレイミド５部（２，２モル％）、アクリロニ
トリル３０部（４５，２モル％）、スチレン１５部（１
１，５モル％）を実施例１と同様に反応、処理した。Example 10 Vinyl chloride 9 fufu 50 parts (41.1 mol%), N-cyclohexylmaleimide 5 parts (2.2 mol%), acrylonitrile 30 parts (45.2 mol%), styrene 15 parts (1 mol%)
1.5 mol %) was reacted and treated in the same manner as in Example 1.
重合率は９７％、ガラス転移点は９４℃であった。The polymerization rate was 97% and the glass transition point was 94°C.
結果を第２表に示す。The results are shown in Table 2.
実施例１１
塩化ビニリデン５０部（４０，５モル％）、Ｎ−メチル
マレイミド５部（３，６モル％）、アクリロニトリル３
０部（４４，６モル％）、スチレン１５部（１１，３モ
ル％）を実施例１と同様に反応、処理した。Example 11 50 parts of vinylidene chloride (40.5 mol%), 5 parts of N-methylmaleimide (3.6 mol%), 3 parts of acrylonitrile
0 parts (44.6 mol%) and 15 parts (11.3 mol%) of styrene were reacted and treated in the same manner as in Example 1.
重合率は９７％、ガラス転移点は９８℃であった。The polymerization rate was 97% and the glass transition point was 98°C.
結果を第２表に示す。The results are shown in Table 2.
比較例１
塩化ビニリデン５０部（４０，４モル％）、アクリロニ
トリル３０部（４４，５モル％）、スチレン２０部（１
５，１モル％）を実施例１と同様に反応、処理した。Comparative Example 1 50 parts of vinylidene chloride (40.4 mol%), 30 parts of acrylonitrile (44.5 mol%), 20 parts of styrene (1
5.1 mol%) was reacted and treated in the same manner as in Example 1.
結果を第１表に示す。The results are shown in Table 1.
比較例２
塩化ビニリデン５０部（５０，７モル％）、メチルメタ
クリレート５０部（４９，３モル％）を実施例１と同様
に反応、処理した。Comparative Example 2 50 parts (50.7 mol%) of vinylidene chloride and 50 parts (49.3 mol%) of methyl methacrylate were reacted and treated in the same manner as in Example 1.
結果を第２表に示す。The results are shown in Table 2.
比較例３
塩化ビニリデン５０部（３５，３モル％）、アクリロニ
トリル５０部（６４，７モル％）を実施例１と同様に反
応、処理した。Comparative Example 3 50 parts (35.3 mol%) of vinylidene chloride and 50 parts (64.7 mol%) of acrylonitrile were reacted and treated in the same manner as in Example 1.
結果を第２表に示す。The results are shown in Table 2.
比較例４
塩化ビニリデン５０部（５５，３モル％）、Ｎ−フェニ
ルマレイミド２０部（１２，５モル％）、メチルメタク
リレート３０部（３２，２モル％）を実施例１と同様に
反応、処理した。Comparative Example 4 50 parts (55.3 mol%) of vinylidene chloride, 20 parts (12.5 mol%) of N-phenylmaleimide, and 30 parts (32.2 mol%) of methyl methacrylate were reacted and treated in the same manner as in Example 1. did.
重合率は８７％であった。得られた共重合体には未反応
のＮ−フェニルマレイミドが存在していた。The polymerization rate was 87%. Unreacted N-phenylmaleimide was present in the obtained copolymer.
結果を第１表に示す。The results are shown in Table 1.
（以下余白） 第１表 第２表 手続補正書（自発） 昭和６１年１２月１６日(Margin below) Table 1 Table 2 Procedural amendment (voluntary) December 16, 1986
Claims (1)
の一般式（ I ）で表されるＮ−置換マレイミドの１種
以上を１〜１０モル％、下記の一般式（II）で表される
共重合性不飽和単量体の１種以上を２５〜７０モル％（
但し、上記３成分の合計を１００モル％とする）、及び
下記の一般式（III）で表される二重結合を１分子中に
２個有する化合物の１種以上の０〜０．１モル％を、ラ
ジカル重合開始剤を用いて重合することを特徴とするガ
ラス転移点が８５℃以上の新規なハロゲン化ビニリデン
系共重合体の製造方法。 記 ▲数式、化学式、表等があります▼（ I ） 〔Ｒ＿１は炭素数１〜４のアルキル基、シクロヘキシル
基、フェニル基又は▲数式、化学式、表等があります▼
で表される基である（但し、Ｒ＿２、Ｒ＿３は−ＣＨ＿
３、−Ｃ＿２Ｈ＿５、−Ｂｒ、−ＯＣＨ＿３、−Ｈを表
す。）。 Ｈ＿２Ｃ＝ＣＲ＿４Ｒ＿５（II） 〔Ｒ＿４は、−Ｈ、−ＣＨ＿３を表し、Ｒ＿５はハロゲ
ン基、−ＣＮ、▲数式、化学式、表等があります▼、▲
数式、化学式、表等があります▼、−ＣＯＯＨ又は▲数
式、化学式、表等があります▼を表す（但し、Ｒ＿６は
炭素数１〜４のアルルキル基又は２−エチルヒドロキシ
ル基を表す。）〕 ▲数式、化学式、表等があります▼（III） 〔Ｒ＿７は−Ｈ、又は−ＣＨ＿３を表し、Ｒ＿８は▲数
式、化学式、表等があります▼（ｍは１〜２５、ｎは２
〜３の整数を表す。）、−Ｏ−Ｃ＿ｋＨ＿２＿ｋＯ−（
ｋは３〜６の整数を表す。）、フェニレン基を表す。〕(1) 30 to 65 mol% of vinylidene halide, 1 to 10 mol% of one or more N-substituted maleimides represented by the following general formula (I), and 1 to 10 mol% of one or more N-substituted maleimides represented by the following general formula (II). 25 to 70 mol% of one or more copolymerizable unsaturated monomers (
However, the total of the above three components is 100 mol%), and 0 to 0.1 mol of one or more compounds having two double bonds in one molecule represented by the following general formula (III). % using a radical polymerization initiator. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [R_1 is an alkyl group with 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼
(However, R_2 and R_3 are -CH_
3, -C_2H_5, -Br, -OCH_3, -H. ). H_2C=CR_4R_5 (II) [R_4 represents -H, -CH_3, R_5 is a halogen group, -CN, ▲There are numerical formulas, chemical formulas, tables, etc.▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, -COOH or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R_6 represents an aralkyl group or a 2-ethylhydroxyl group having 1 to 4 carbon atoms.)] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) [R_7 represents -H or -CH_3, R_8 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (m is 1 to 25, n is 2
Represents an integer from ~3. ), -O-C_kH_2_kO-(
k represents an integer from 3 to 6. ), represents a phenylene group. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26933286A JPS63122713A (en) | 1986-11-12 | 1986-11-12 | Production of heat-resistant halogenated vinylidene copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26933286A JPS63122713A (en) | 1986-11-12 | 1986-11-12 | Production of heat-resistant halogenated vinylidene copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63122713A true JPS63122713A (en) | 1988-05-26 |
| JPH0357129B2 JPH0357129B2 (en) | 1991-08-30 |
Family
ID=17470887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26933286A Granted JPS63122713A (en) | 1986-11-12 | 1986-11-12 | Production of heat-resistant halogenated vinylidene copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63122713A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100479686B1 (en) * | 2002-02-25 | 2005-03-30 | 한국과학기술연구원 | A thermally stable polymer containing n-hydroxyphenylmaleimide, and an anti-reflective coating compositon for photolithography comprising the same |
-
1986
- 1986-11-12 JP JP26933286A patent/JPS63122713A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100479686B1 (en) * | 2002-02-25 | 2005-03-30 | 한국과학기술연구원 | A thermally stable polymer containing n-hydroxyphenylmaleimide, and an anti-reflective coating compositon for photolithography comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0357129B2 (en) | 1991-08-30 |
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