JPH02153904A - Production of novel imidized acrylic resin - Google Patents
Production of novel imidized acrylic resinInfo
- Publication number
- JPH02153904A JPH02153904A JP18858089A JP18858089A JPH02153904A JP H02153904 A JPH02153904 A JP H02153904A JP 18858089 A JP18858089 A JP 18858089A JP 18858089 A JP18858089 A JP 18858089A JP H02153904 A JPH02153904 A JP H02153904A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- polymerization
- methyl methacrylate
- methanol
- acrylic resin
- 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
- 239000004925 Acrylic resin Substances 0.000 title claims description 22
- 229920000178 Acrylic resin Polymers 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 135
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 39
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 33
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical group O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 10
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 7
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 45
- 229940117913 acrylamide Drugs 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 16
- -1 Y is CONHR2 (R2 is H Chemical group 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 47
- 239000000243 solution Substances 0.000 description 21
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 13
- 125000003368 amide group Chemical group 0.000 description 13
- 238000000862 absorption spectrum Methods 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 8
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000005462 imide group Chemical group 0.000 description 3
- 150000003949 imides Chemical group 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- BDFAOUQQXJIZDG-UHFFFAOYSA-N 2-methylpropane-1-thiol Chemical compound CC(C)CS BDFAOUQQXJIZDG-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 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
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 description 1
- NAPDOWNULRULLI-UHFFFAOYSA-N 2-benzyl-1h-imidazole Chemical compound C=1C=CC=CC=1CC1=NC=CN1 NAPDOWNULRULLI-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
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 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 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- QZYRMODBFHTNHF-UHFFFAOYSA-N ditert-butyl benzene-1,2-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OOC(C)(C)C QZYRMODBFHTNHF-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 125000004492 methyl ester group Chemical group 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- CYTJMBLSQUBVMS-UHFFFAOYSA-N n-[[2-cyanopropan-2-yl(formyl)amino]hydrazinylidene]formamide Chemical compound N#CC(C)(C)N(C=O)NN=NC=O CYTJMBLSQUBVMS-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/48—Isomerisation; Cyclisation
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- 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〕
本発明は透明性および耐熱性の優れたイミド化アクリル
樹脂の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing an imidized acrylic resin having excellent transparency and heat resistance.
近年、弱電部品や工業部品特に車輌部品などの用途にお
いてアクリル樹脂の耐熱性向上に対する要求が強くなり
つつある。In recent years, there has been an increasing demand for improved heat resistance of acrylic resins in applications such as light electrical parts and industrial parts, especially vehicle parts.
メタクリル樹脂の耐熱性を向上させる従来の技術として
メタクリル系重合体をイミド化する方法が知られている
。例えば、日本特許第１．３６３４９７によれば実質的
に無水状態において押出機中でアクリル系重合体とアン
モニアまたは第一級アミンとを約２００℃〜４５０℃の
温度において反応させイミド単位を含むＤＭＦに可溶な
イミド化アクリル樹脂の製法が知られている。しかしな
がらこの方法は非常に特殊な構造の押出機を用いて、し
かも実質的に無水の条件を維持して製造する方法であり
、高価な装置経費と非常にわずられしい条件の維持が要
求されるばかりでなく、部分的にイミド化されたアクリ
ル樹脂を製造する場合、得られる生成物が組成的に不均
一になりやすいという問題がある。また実質的に無水の
条件維持に注意をはらっても、生成物中に酸および酸無
水物の副生が避けられず、そのために生成物の流動性が
低下し、また吸収率が増大するという問題がある。A method of imidizing a methacrylic polymer is known as a conventional technique for improving the heat resistance of methacrylic resin. For example, according to Japanese Patent No. 1.363497, an acrylic polymer and ammonia or a primary amine are reacted in an extruder in a substantially anhydrous state at a temperature of about 200°C to 450°C to form a DMF containing imide units. A method for producing imidized acrylic resin that is soluble in is known. However, this method uses an extruder with a very special structure and maintains substantially anhydrous conditions, requiring expensive equipment and maintenance of extremely difficult conditions. In addition, when producing a partially imidized acrylic resin, there is a problem that the resulting product tends to be compositionally non-uniform. Furthermore, even if care is taken to maintain substantially anhydrous conditions, acid and acid anhydride by-products are unavoidable in the product, which reduces the fluidity of the product and increases the absorption rate. There's a problem.
〔発明が解決しようとする課題〕
本発明の目的は、このような事情のもとで、反応試薬と
してアンモニアまたは第一級アミンを使用することな（
、−船釣な装置である種型反応器を用い、実質的に生成
ポリマー中に酸および酸無水物の副生がなく高品質の透
明なイミド化アクリル樹脂を工業的に有利に製造する方
法を提供することにある。[Problems to be Solved by the Invention] Under these circumstances, the purpose of the present invention is to solve the problem without using ammonia or primary amines as reaction reagents.
, - A method for industrially advantageous production of high-quality transparent imidized acrylic resin with virtually no acid or acid anhydride by-products in the resulting polymer using a type of reactor that can be used on a boat. Our goal is to provide the following.
上記目的は、本発明によりすなわち
一般式ＣＯ２・ＣＲ，（ｙ） （式中、Ｒ６は水素また
はメチル基を示し、ＹはＣ０ＮＩＩＲ２ただし、Ｒ２は
水素、アルキル基、アリール基、アラルキル基を示す。The above object is achieved by the present invention, namely by the general formula CO2.CR, (y) (wherein R6 represents hydrogen or a methyl group, and Y represents C0NIIR2, where R2 represents hydrogen, an alkyl group, an aryl group, or an aralkyl group.
）で表わされるアクリル系アミドとメタクリル酸メチル
とを、水を３０ｗｔ％以下含有するメタノール溶媒中で
ラジカル重合触媒の存在下に共重合するにあたり、アク
リル系アミドに対して０．５〜１０倍モルのメタクリル
酸メチルの一部を予めアクリル系アミドと共に該溶媒中
に加えて混合溶解し、その残りのメタクリル酸メチルを
供給しながら共重合した後、塩基性触媒の存在下でイミ
ド化反応を行い、共重合体中のアクリル系アミド単位を
グルタルイミド単位に実質的に完全に変換することによ
り達成される。) and methyl methacrylate in the presence of a radical polymerization catalyst in a methanol solvent containing 30 wt% or less of water, 0.5 to 10 times the mole of the acryl amide. A part of the methyl methacrylate is added in advance to the solvent together with the acrylic amide, mixed and dissolved, and the remaining methyl methacrylate is copolymerized while being supplied, followed by an imidization reaction in the presence of a basic catalyst. , is achieved by substantially completely converting the acrylamide units in the copolymer to glutarimide units.
また、上記目的は、前記方法においてアクリル系アミド
の重合率を少なくとも９０モル％以上になるように重合
反応を進めた後、イミド化反応を行うことにより達成さ
れる。Moreover, the above object is achieved by carrying out the imidization reaction after proceeding with the polymerization reaction so that the polymerization rate of the acrylamide becomes at least 90 mol % or more in the above method.
さらに、上記目的は、前記の方法等において、アクリル
系アミドの重合温度を８０〜１５０℃とすること、イミ
ド化反応を８０〜１５０℃で行うこと等により達成する
ことができる。Further, the above object can be achieved by, for example, setting the polymerization temperature of the acrylic amide at 80 to 150°C and carrying out the imidization reaction at 80 to 150°C in the above-mentioned method.
一般弐ｃｎｚ＝ｃＲ＋（Ｙ） （式中、Ｒ９は水素また
はメチル基を示し、ＹはＣ０Ｎ）ＩＲｚ ただし、Ｒ
２は水素、アルキル基、シクロアルキル基、アリール基
、アラルキル基を示す、）で表わされるアクリル系アミ
ドとメタクリル酸メチルはイミド形成性基となる原料単
量体であって同一ポリマー鎖の中にある３個炭素原子で
隔てられた２個の官能基Ｙまたは官能基Ｙとメタクリル
酸メチルに由来するエステル基の間で次の反応により６
員環イミド基が形成される。General2cnz=cR+(Y) (In the formula, R9 represents hydrogen or a methyl group, and Y is C0N)IRz However, R
2 represents hydrogen, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group) Acrylic amide and methyl methacrylate are raw material monomers that become imide-forming groups and are present in the same polymer chain. 6 by the following reaction between two functional groups Y separated by a certain 3 carbon atoms or between a functional group Y and an ester group derived from methyl methacrylate.
A membered ring imide group is formed.
Ｒｚ Ｒｚ
ここでＲ，、Ｒ，は上記のとおりであるが、Ｒ２は特に
水素、メチル、エチル、シクロヘキシル基である場合が
好適であり、さらに好適なのは水素の場合である。また
使用するメタクリル酸メチルノ０．１ 倍モル以下の量
でアクリル酸エステル類および芳香族ビニル化合物を併
用してもよい。０，１倍モル以上の量でアクリル酸エス
テル類および芳香族ビニル化合物を併用すると、アミド
基の残存や生成ポリマーの熱変形温度の低下をもたらす
ので好ましくない。Rz Rz Here, R,, R, are as described above, but R2 is preferably hydrogen, methyl, ethyl, or cyclohexyl group, and more preferably hydrogen. Further, acrylic esters and aromatic vinyl compounds may be used in combination in an amount of 0.1 times the mole or less of methyl methacrylate to be used. If acrylic esters and aromatic vinyl compounds are used together in an amount of 0.1 times the mole or more, it is not preferable because amide groups remain or the heat distortion temperature of the resulting polymer decreases.
本発明において、最も特徴とするところは、重合反応お
よびイミド化反応の溶媒として微量乃至少量の水を含有
してもよいメタノールを使用することであるが、それは
以下に述べるようにきわめて重要な意義を有している。The most distinctive feature of the present invention is the use of methanol, which may contain a trace to a small amount of water, as a solvent for the polymerization reaction and imidization reaction, which has extremely important significance as described below. have.
第一に、後で詳しく説明するイミド化反応の有効な触媒
である塩基性触媒に対して十分な溶解力を有すること。First, it must have sufficient dissolving power for basic catalysts that are effective catalysts for imidization reactions, which will be explained in detail later.
第二に、水分の混入があってもメタノールの存在で酸あ
るいは酸無水物の副生を完全に防止できること。Second, even if water is mixed in, the presence of methanol can completely prevent acid or acid anhydride by-products.
第三に、他のアルコール類を用いた場合、メタクリル酸
メチルのエステル基が溶媒のアルコールとエステル交換
反応を起し生成ポリマーの熱変形温度を低下させたりす
るし、また多価アルコールやそのエステル化物を用いた
場合には、架橋構造が生成し流動性を失うことがあるが
、メタノールの場合はメチルエステル基を維持できるこ
と。Third, when other alcohols are used, the ester group of methyl methacrylate causes a transesterification reaction with the alcohol in the solvent, lowering the heat distortion temperature of the resulting polymer. If methanol is used, a crosslinked structure may be formed and fluidity may be lost, but methanol can maintain the methyl ester group.
第四に、特に好ましいアクリル系アミドであるメタクリ
ルアミドまたはアクリルアミドを使用する場合、これら
はメタクリル酸メチルに溶解せず、溶媒を使用しなけれ
ば均一な組成の共重合体は生成しないが、水を３０％以
下含有するメタノールは両者を溶解して均一溶液にする
ことができる。Fourth, when using methacrylamide or acrylamide, which is a particularly preferred acrylic amide, these do not dissolve in methyl methacrylate and do not produce copolymers of uniform composition without the use of a solvent, but they do not dissolve in water. Methanol containing 30% or less can dissolve both to form a homogeneous solution.
またメタクリルアミドおよびアクリルアミドは純粋な状
態では結晶質固体であり重合防止剤が有効に作用できず
保存中に一部がポリマー化しやすい。In addition, methacrylamide and acrylamide are crystalline solids in their pure state, so polymerization inhibitors cannot effectively act on them, and a portion of them tends to polymerize during storage.
このホモポリマーは少量でも目的物質であるイミド化ア
クリル樹脂の透明性を著しく損うものである。メタクリ
ルアミドやアクリルアミドをメタノール溶液状で保存す
ることは重合防止剤の有効な作用をもたらし保存中の重
合を完全に防止できる。Even in small amounts, this homopolymer significantly impairs the transparency of the imidized acrylic resin, which is the target substance. Storing methacrylamide or acrylamide in the form of a methanol solution brings about the effective action of a polymerization inhibitor and can completely prevent polymerization during storage.
第五に、通常メタノールまたは含水メタノールはポリメ
タクリル酸メチルを溶解しないと考えられているが、意
外にもアクリル系アミドに対して０．５〜１０倍モルの
範囲のメタクリル酸メチルを使用して本発明の方法に従
って得られたイミド化する前の共重合体はオートクレー
ブ中で加圧下にて８０℃以上、好ましくは１００℃以上
に加熱された状態では工業的に実施するに必要な十分に
高濃度において、メタノールまたは水を３０−ｔ％まで
含有する含水メタノールにほぼ均一に溶解した状態にな
ることが判明した。生成共重合体が均一に溶解している
ことは透明なイミド化アクリル樹脂を得るためのきわめ
て重要な事項である。含水量が３０−ｔ％を超えると、
該共重合体は、工業的に実施するに必要な十分に高濃度
において、均一に溶解せず、透明なイミド樹脂が得られ
ない。Fifth, it is usually thought that methanol or aqueous methanol does not dissolve polymethyl methacrylate, but surprisingly, methyl methacrylate in a molar range of 0.5 to 10 times the amount of acrylamide was used. When the copolymer obtained according to the method of the present invention before imidization is heated in an autoclave under pressure to 80°C or higher, preferably 100°C or higher, the temperature is sufficiently high for industrial implementation. It has been found that the concentration is almost uniformly dissolved in methanol or water-containing methanol containing up to 30-t% water. It is extremely important that the resulting copolymer is uniformly dissolved in order to obtain a transparent imidized acrylic resin. When the water content exceeds 30-t%,
The copolymer does not dissolve uniformly at a sufficiently high concentration required for industrial implementation, and a transparent imide resin cannot be obtained.
第六に、イミド化反応が完結したポリマーは一般に常温
付近ではメタノールまたは含水メタノールに不溶であり
、反応液を常温付近まで冷却することでポリマーは反応
液から固体状で析出し、濾過等による分離、さらにメタ
ノールによる洗滌を行うことで塩基性触媒が有効に除去
され、目的物を容易に回収することができる。Sixth, the polymer that has undergone the imidization reaction is generally insoluble in methanol or water-containing methanol at around room temperature, and when the reaction solution is cooled to around room temperature, the polymer precipitates from the reaction solution in solid form and can be separated by filtration etc. By further washing with methanol, the basic catalyst can be effectively removed and the target product can be easily recovered.
以上述べた第一〜第六の理由により、本発明者らが溶媒
として水を３０−ｔ％以下含有したメタノールが使用で
きることを見い出したことは本発明においてきわめて重
要な意義を有している。For the first to sixth reasons mentioned above, the fact that the present inventors discovered that methanol containing 30-t% or less of water can be used as a solvent has extremely important significance in the present invention.
使用するメタノールは無水メタノールでも、また微量（
５ｗｔ％以下）あるいは少量（５〜３０ｗｔ％）の水分
を混入したものでもよ（、それにより有害な酸および酸
無水物の副生をもたらす恐れはない。重合反応およびイ
ミド化反応において使用する溶媒の量は使用する全単量
体の重量の０．１〜１０倍量、好ましくは０．５〜２倍
量である。The methanol used can be anhydrous methanol or a trace amount (
5wt% or less) or mixed with a small amount (5 to 30wt%) of water (there is no risk of producing harmful acids and acid anhydrides as by-products.Solvents used in polymerization reactions and imidization reactions) The amount is 0.1 to 10 times, preferably 0.5 to 2 times the weight of all monomers used.
本発明において使用するラジカル重合触媒としては、例
えばジーｔｅｒ ｔブチルパーオキサイド、ジクミルパ
ーオキサイド、メチルエチルケトンパーオキサイド、ジ
ーｔｅｒｔブチルパーフタレート、ｔｅｒ ｔブチルパ
ーベンゾエート、ｔｅｒｔブチルパーアセテート等の有
機過酸化物、アゾビスイソブタノールジアセテート、１
．１アゾビスシクロヘキサンカルボニトリル、２−フェ
ニルアゾ−２，４−ジメチル−４−メトキシバレロニト
リル、２−シアノ−２プロピルアゾホルムアミド等のア
ゾ化合物が挙げられる。これらのラジカル重合触媒は単
独でまたは２種類以上混合して使用することができる。Examples of the radical polymerization catalyst used in the present invention include organic peroxides such as di-tert-butyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, di-tert-butyl perphthalate, tert-butyl perbenzoate, and tert-butyl peracetate. , azobisisobutanol diacetate, 1
．． Examples include azo compounds such as 1-azobiscyclohexanecarbonitrile, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, and 2-cyano-2propylazoformamide. These radical polymerization catalysts can be used alone or in combination of two or more.
重合度調節剤を使用して所望の重合度に調節することが
できるが、それにはメルカプタン類が使用できる。例え
ば、ｎブチルメルカプタン、イソブチルメルカプタン、
ｎオクチルメルカプタン、ｎ−ドデシルメルカプタン、
５ｅｃ−ブチルメルカプタン、５ｅｃ−ドデシルメルカ
プタン、ｔ−ブチルメルカプタン、フェニルメルカプタ
ン、チオクレゾール、チオグリコール酸とそのエステル
等が挙げられる。The degree of polymerization can be adjusted to a desired degree using a polymerization degree regulator, and mercaptans can be used for this purpose. For example, n-butyl mercaptan, isobutyl mercaptan,
n-octyl mercaptan, n-dodecyl mercaptan,
Examples include 5ec-butylmercaptan, 5ec-dodecylmercaptan, t-butylmercaptan, phenylmercaptan, thiocresol, thioglycolic acid and its esters.
ラジカル重合触媒および重合度調節剤の使用量は、それ
らの種類、重合温度、重合時間、所望する重合度等に応
じて適宜決定される。The amounts of the radical polymerization catalyst and polymerization degree regulator to be used are appropriately determined depending on their types, polymerization temperature, polymerization time, desired degree of polymerization, and the like.
本発明における重合工程は半回分法が採用される。アク
リル系アミドとメタクリル酸メチルの反応性は一般に異
っており、−括して両方の単量体全量を槽壁反応器に仕
込んで重合する回分式重合法では重合反応の進行ととも
に、共重合比の異なるポリマーが生成し、イミド化反応
を経て得られるイミド化アクリル樹脂の透明性が著しく
劣ったものになり、不透明な白濁したポリマーになるこ
ともある。この問題を避けて常に一定の共重合比の共重
合体を得るのに、原理的には流通式の完全混合槽型反応
器を使用すれば可能ではあるが、未反応のアクリル系ア
ミドの残存がイミド化反応工程で著しい着色をもたらす
ために、その重合率を少なくとも９０モル％以上まで高
める必要があり、流通式では反応時間が極端に長くなり
経済的でない。A semi-batch method is adopted for the polymerization step in the present invention. The reactivity of acrylic amide and methyl methacrylate is generally different, and in the batch polymerization method in which the entire amount of both monomers is charged into a tank wall reactor and polymerized, copolymerization occurs as the polymerization reaction progresses. Polymers with different ratios are produced, and the imidized acrylic resin obtained through the imidization reaction has significantly poor transparency, and may become an opaque, cloudy polymer. In principle, it is possible to avoid this problem and always obtain a copolymer with a constant copolymerization ratio by using a flow-type complete mixing tank reactor, but unreacted acrylamide remains. Because it causes significant coloring in the imidization reaction step, it is necessary to increase the polymerization rate to at least 90 mol% or more, and a flow type method is uneconomical because the reaction time is extremely long.
半回分法による重合法の採用により透明性に優れるイミ
ド化アクリル樹脂が得られることが本発明者の検討によ
り確認された。本発明の重合工程をさらに詳しく説明す
る。The inventor's studies have confirmed that an imidized acrylic resin with excellent transparency can be obtained by employing a semi-batch polymerization method. The polymerization process of the present invention will be explained in more detail.
例えば、オートクレーブにメタノール、水、アクリル系
アミド＊ｉ体、ラジカル重合触媒および重合度調節剤そ
してメタクリル酸メチルの一部を仕込み均一に溶解する
。ここで系内に窒素ガスを導入して酸素を除去すること
が望ましい。ここで仕込むメタクリル酸メチルとアクリ
ル系アミドのモル比は、所望の共重合体組成比、両車量
体の間のその重合温度での混合溶媒中で実測された共重
合反応性比ｒＩ、ｒｚ （１，２はそれぞれメタクリ
ル酸メチル、アクリル系アミドを指す。）に従い、計算
により決定する。オートクレーブは８０〜１５０℃、好
ましくは１００〜１２０℃の範囲まで昇温しで重合を開
始する。それとともに定量ポンプを使用して残りのメタ
クリル酸メチルを連続的に圧入する。その注入する速度
の設定が透明性の優れるイミド化アクリル樹脂を得るた
めに重要である。その原理は重合反応の進行過程におい
て、常に重合系でのアクリル系アミドとメタクリル酸メ
チルの両車量体の組成比が最初に仕込んだ両車量体の組
成比になるように消費速度の大きいメタクリル酸メチル
を追加しながら重合することである。For example, methanol, water, acrylic amide *i-form, a radical polymerization catalyst, a degree of polymerization regulator, and a portion of methyl methacrylate are charged into an autoclave and uniformly dissolved. Here, it is desirable to introduce nitrogen gas into the system to remove oxygen. The molar ratio of methyl methacrylate and acrylamide charged here is based on the desired copolymer composition ratio, the copolymerization reactivity ratio rI, rz actually measured in the mixed solvent between the two polymers at the polymerization temperature. (1 and 2 refer to methyl methacrylate and acrylamide, respectively), and are determined by calculation. The temperature of the autoclave is raised to 80 to 150°C, preferably 100 to 120°C to initiate polymerization. At the same time, the remaining methyl methacrylate is continuously pumped in using a metering pump. Setting the injection speed is important in order to obtain an imidized acrylic resin with excellent transparency. The principle is that during the progress of the polymerization reaction, the consumption rate is high so that the composition ratio of both acrylamide and methyl methacrylate polymers in the polymerization system is always the same as the composition ratio of both polymers initially charged. The method is to polymerize while adding methyl methacrylate.
上述の両車量体の組成比は目的物質であるイミド化アク
リル樹脂のグルタルイミド含有量に応じて決定されるも
のである。また採用した重合系における両車量体の消費
速度は予め同一反応条件で回分操作での重合反応にて、
例えば反応液中の両車量体の残存量をガスクロ分析法で
測定することにより求めることができる。The composition ratio of the above-mentioned two weight bodies is determined depending on the glutarimide content of the imidized acrylic resin which is the target substance. In addition, the consumption rate of both polymers in the adopted polymerization system was determined by the polymerization reaction in batch operation under the same reaction conditions.
For example, it can be determined by measuring the residual amount of both mercury molecules in the reaction solution by gas chromatography.
上述の原理に従えば、重合進行中に供給するメタクリル
酸メチルの供給速度は重合時間とともに連続的に変化す
る曲線となるが、実際には、この曲線に近似できる段階
的な供給速度の調節でも十分に目的が達成され、透明な
イミド化アクリル樹脂を得ることができる。According to the above principle, the supply rate of methyl methacrylate supplied during polymerization will be a curve that changes continuously with the polymerization time, but in reality, the supply rate can be adjusted in stages that can approximate this curve. The purpose is fully achieved and a transparent imidized acrylic resin can be obtained.
以上述べた半回分法による重合法を採用して、アクリル
系アミドに対して０．５〜１０倍モルの範囲のメタクリ
ル酸メチルの一部を予めアクリル系アミドと混合し、残
りを連続的に供給しなから共重合反応を行う。０．５倍
モル以下のメタクリル酸メチルを使用した場合は後で詳
しく述べるイミド化反応が円滑に進行せず、好ましくな
いアミド基の残存が起りやすく、また１０倍モル以上の
メタクリル酸メチルを使用するとポリメタクリル酸メチ
ルと比較して、はとんど耐熱性の向上が得られない。Adopting the semi-batch polymerization method described above, a part of methyl methacrylate in the range of 0.5 to 10 times the mole of acrylamide is mixed with the acrylamide in advance, and the rest is continuously mixed. The copolymerization reaction is carried out before the supply. If less than 0.5 times the mole of methyl methacrylate is used, the imidization reaction described in detail later will not proceed smoothly and undesirable amide groups will likely remain, and if more than 10 times the mole of methyl methacrylate is used. As a result, compared to polymethyl methacrylate, the heat resistance is hardly improved.
重合反応においては特にアクリル系アミドの重合率が少
なくとも９０モル％以上になるまで進めることが望まし
い。アクリル系アミド単量体の残存が、１０モル％以上
であると次のイミド化工程において反応液が黄色に強く
着色し、得られるイミド化アクリル樹脂Ｃども着色をも
たらすので好ましくない。In the polymerization reaction, it is particularly desirable to proceed until the polymerization rate of the acrylamide reaches at least 90 mol%. If the acrylic amide monomer remains in an amount of 10 mol % or more, the reaction solution will be strongly colored yellow in the next imidization step, and the resulting imidized acrylic resin C will be colored, which is not preferable.
重合反応が終了すると、引き続きイミド化反応に進むが
、その反応は重合反応槽において、好ましくは別の種型
反応器に反応液を移送して行う。When the polymerization reaction is completed, the imidization reaction continues, and this reaction is carried out in the polymerization reaction tank, preferably by transferring the reaction solution to another seed reactor.
本発明においては前述の２通りのイミド化反応を促進す
るために塩基性触媒を使用する。塩基性触媒としては無
機塩基化合物および有機塩基化合物が挙げられる。無機
塩基化合物としては、水酸化カリウム、水酸化ナトリウ
ム、水酸化リチウム等のアルカリ金属水酸化物、有機塩
基化合物としては２−フェニルメチルイミダゾール、グ
アニジン、１．８−ジアザビシクロ−（５，４，０）ウ
ンデセン−７などのイミン類、ナトリウムメトキシド、
カリウムメトキシド、ナトリウムエトキシド、カリウム
エトキシド等のアルカリ重合アルコキシドが挙げられ、
なかでもナトリウムメトキシドが特に好ましい。その添
加方法はメタノール溶液にして反応器に圧入する方法が
好適である。In the present invention, a basic catalyst is used to promote the above-mentioned two types of imidization reactions. Basic catalysts include inorganic base compounds and organic base compounds. Examples of inorganic base compounds include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and lithium hydroxide; examples of organic base compounds include 2-phenylmethylimidazole, guanidine, and 1,8-diazabicyclo-(5,4,0 ) imines such as undecene-7, sodium methoxide,
Examples include alkali polymerized alkoxides such as potassium methoxide, sodium ethoxide, and potassium ethoxide.
Among them, sodium methoxide is particularly preferred. A suitable method for adding it is to make a methanol solution and pressurize it into the reactor.
塩基性触媒の添加量は重合に供した全単量体重量の０．
００１〜１重量％の範囲の量であり、好ましくは０．０
１〜０．５重量％である。塩基性触媒の添加量が０．０
０１重量％以下の場合、次に述べる好適なイミド化反応
温度において反応が円滑に進行しない。また１重量％以
上では触媒の回収されたポリマーへの混入量が増加して
ポリマー品質を劣化させるので好ましくない。The amount of the basic catalyst added is 0.0% of the total monomer weight subjected to polymerization.
0.001 to 1% by weight, preferably 0.0
It is 1 to 0.5% by weight. The amount of basic catalyst added is 0.0
If the amount is less than 0.01% by weight, the reaction will not proceed smoothly at the suitable imidization reaction temperature described below. Moreover, if it is more than 1% by weight, the amount of the catalyst mixed into the recovered polymer increases and the quality of the polymer deteriorates, which is not preferable.
イミド化反応は、塩基性触媒の存在下で８０〜１５０℃
の温度範囲、好ましくは１００〜１２０℃の温度範囲で
行う。８０℃以下の温度では反応が円滑に進行しないし
、また１ ５０ ”ｃ以上の温度でイミド化反応を行う
と著しくポリマーが着色するので好ましくない。反応時
間は反応温度、塩基性触媒の種類と量、アクリル系アミ
ドの種類と共重合比等により変化するが、共重合体中の
アクリル系アミドに由来するアミド基をグルタルイミド
基単位に実質的に完全に変換するまで、さらに具体的に
は、例えば９５％以上変換するまで反応を進めるに十分
な時間である。反応が不完全でアミド基が残存すると目
的物であるイミド化アクリル樹脂の熱安定性、色相を損
い、またその吸水率が増加し耐候性も悪化するので好ま
しくない。イミド化反応の反応率は、例えば生成ポリマ
ーの＋Ｈ−ＮＭＲスペクトルを測定することで求めるこ
とができる。アクリル系アミドとしてメタクリルアミド
を用いた場合、ｄ−ＤＭＳＯ中で６．６ ｐｐｍ付近に
残存アミドの吸収が現われ、その積分強度より残存アミ
ド基を定量し反応率を求めることができる。The imidization reaction is carried out at 80-150°C in the presence of a basic catalyst.
The temperature range is preferably 100 to 120°C. The reaction does not proceed smoothly at temperatures below 80°C, and imidization at temperatures above 150°C causes significant coloring of the polymer, which is undesirable.The reaction time depends on the reaction temperature and the type of basic catalyst. The amount varies depending on the type of acrylamide, copolymerization ratio, etc., but more specifically, until the amide groups derived from the acrylamide in the copolymer are substantially completely converted into glutarimide group units For example, this is sufficient time to allow the reaction to proceed until 95% or more conversion is achieved.If the reaction is incomplete and amide groups remain, the thermal stability and hue of the imidized acrylic resin, which is the target product, will be impaired, and its water absorption rate will be reduced. This is undesirable because it increases the d Absorption of the remaining amide appears at around 6.6 ppm in -DMSO, and the reaction rate can be determined by quantifying the remaining amide group from the integrated intensity.
イミド化反応が完結したポリマーは反応液を常温付近ま
で冷却することで固化析出するので、母液より分離し、
さらに多量のメタノールで洗滌し乾燥することで回収で
きる。また、使用した塩基性触媒の量が極く少量である
場合は反応液をそのまま脱気機能を有する押出機に導き
、未反応単量体、溶媒等を除去することにより、ベレッ
ト状にて回収することができる。The polymer that has completed the imidization reaction solidifies and precipitates by cooling the reaction solution to around room temperature, so it is separated from the mother liquor,
It can be recovered by washing with a large amount of methanol and drying. In addition, if the amount of basic catalyst used is extremely small, the reaction solution can be directly fed into an extruder with a degassing function to remove unreacted monomers, solvent, etc., and then recovered in pellet form. can do.
このようにして得られたイミド化アクリル樹脂はそのま
までも、射出成形や押出成形に提供することができるが
、必要に応じ、さらに亜りん酸エステル等の熱安定剤や
ベンゾトリアゾール系、ヒンダードアミン系などの光安
定剤を添加してもよく、さらに滑剤として流動パラフィ
ン、ｃｌｌ−０２□の高級脂肪酸、０４〜Ｃ２ｔの高級
脂肪酸の金属塩、エチレンビス脂肪酸アミド、ステアリ
ルアルコールなどの高級脂肪族アルコール、アジピン酸
やセバシン酸のジプチルまたはジオクチルエステル、高
級脂肪酸のモノ、ジ、トリグリセリドなどを添加しても
よい。The imidized acrylic resin thus obtained can be used as is for injection molding or extrusion molding, but if necessary, heat stabilizers such as phosphite, benzotriazole type, hindered amine type etc. A light stabilizer may be added, and as a lubricant, liquid paraffin, higher fatty acids of CLL-02□, metal salts of higher fatty acids of 04 to C2t, ethylene bis fatty acid amide, higher aliphatic alcohols such as stearyl alcohol, adipine Acid, diptyl or dioctyl ester of sebacic acid, mono-, di- and triglycerides of higher fatty acids, etc. may be added.
以下、実施例により本発明を具体的に説明するが、重合
体の物性測定は次の方法によった。The present invention will be specifically explained below with reference to Examples, and the physical properties of the polymer were measured by the following method.
＋１１ 重合体の還元粘度はオストワルド粘度計によ
り重合体濃度０．５ ｇ ／ ｄ １のジメチルホルム
アミド溶液の流動時間（ｔｓ）とジメチルホルムアミド
の流動時間（ｔｏ）とを温度２５±０．１℃で測定し、
ｔ Ｓ ／ ｔ ｏ値から重合体の相対粘度ηｒａｔを
求め、次式より算出した値である。+11 The reduced viscosity of the polymer is calculated using an Ostwald viscometer by calculating the flow time (ts) of a dimethylformamide solution with a polymer concentration of 0.5 g/d1 and the flow time (to) of dimethylformamide at a temperature of 25 ± 0.1 °C. measure,
The relative viscosity ηrat of the polymer is determined from the t S / t o value, and is a value calculated from the following formula.
還元粘度−（η、□−１）１０．５
ｆ２１ 成形品ノ全光線透過率（％）はＡＳＴＭ Ｄ
−１００３法によって測定した。Reduced viscosity - (η, □-1) 10.5 f21 The total light transmittance (%) of the molded product is ASTM D
Measured by the -1003 method.
（３）熱変形温度はＡＳＴ？ｌ Ｄ−６４８に基いゼ測
定した。(3) Is the heat distortion temperature AST? Measurements were made based on lD-648.
（４）グルタルイミド組成（ｍｏｌｅ％）は２００ＭＨ
２核磁気共鳴スペクトルを用いグルタルイミドに特有な
吸収３．５７ｐｐｍの積分強度をもとに算出した。(4) Glutarimide composition (mole%) is 200MH
It was calculated based on the integrated intensity of absorption 3.57 ppm, which is unique to glutarimide, using a binary magnetic resonance spectrum.
（５）熱分解開始温度は熱重量測定装置（ＴＧＡ）を使
用して求めた。試料型Ｎ５ｍｇでＮ！ガス雰囲気中昇温
速度１り℃／分で昇温し重量減少が始まる温度を熱分解
開始温度とした。(5) The thermal decomposition initiation temperature was determined using a thermogravimetric analyzer (TGA). N with sample type N5mg! The temperature was raised at a temperature increase rate of 1 °C/min in a gas atmosphere, and the temperature at which weight loss began was defined as the thermal decomposition start temperature.
実施例１
撹拌装置、温度計および定量ポンプを装備した２１オー
トクレーブを用い、メタクリル酸メチル２８２ ｇ、メ
タクリルアミド１５２ｇ、メタノール５６５ｇ、ジ−ｔ
−ブチルパーオキサイド４．３ｇおよびｎ−オクチルメ
ルカプタン０．７ｇを加え、撹拌下に１２０℃へ昇温し
共重合を開始した。重合の進行とともに定量ポンプを用
いてメタクリル酸メチル４００ｇを３．０ｍｊ！／分の
速度で３０分間、２．５ｍ１１分の速度で４０分間、２
．Ｏｔｍｌ１分の速度で５０分間、１．５ｍ７！／分の
速度で６０分間、最後に０．５ｒｒｌβ／分の速度で４
０分間と変化させながら連続的に供給して共重合を６時
間行った。Example 1 Using a 21 autoclave equipped with a stirrer, a thermometer, and a metering pump, 282 g of methyl methacrylate, 152 g of methacrylamide, 565 g of methanol, and di-t
4.3 g of -butyl peroxide and 0.7 g of n-octyl mercaptan were added, and the temperature was raised to 120° C. while stirring to start copolymerization. As the polymerization progresses, use a metering pump to add 400 g of methyl methacrylate to 3.0 mj! /min for 30 minutes, 2.5m for 40 minutes at a speed of 11 minutes, 2
．． Otml 1 minute speed for 50 minutes, 1.5m7! /min for 60 minutes, and finally 4 at a rate of 0.5rrlβ/min.
Copolymerization was carried out for 6 hours by continuously supplying the water while changing the time from 0 minutes to 0 minutes.
引き続き同一装置、同一温度でナトリウムメトキシド１
．１ｇ含むメタノール溶液５０ｍ１を定量ポンプを用い
て供給し撹拌下で１．５時間反応を行った。反応終了後
、系内の温度が４５℃となった時に沈澱したポリマーを
取り出し、メタノールで洗滌後１３０℃で１昼夜減圧乾
燥を行い重合体を得た。Continuing to add sodium methoxide 1 in the same equipment and at the same temperature.
．． 50 ml of a methanol solution containing 1 g was supplied using a metering pump, and the reaction was carried out for 1.5 hours with stirring. After the reaction was completed, the precipitated polymer was taken out when the temperature in the system reached 45°C, washed with methanol, and dried under reduced pressure at 130°C for one day and night to obtain a polymer.
この反応生成物の赤外吸収スペクトル、’Ｈ−ＮＭＲを
測定したところ、赤外吸収スペクトルではグルタルイミ
ドのイミド基にもとづ＜ 、３２５０ｃａ＋−３１００
ｃｍ−’、 １６９０ｃｍ−’に見られ、さらに’ＩＩ
−ＮＭＲではグルタルイミドプロトンのスペクトルが１
０ｐｐｍに、グルタルイミドのメチルプロトンが１．２
５ ｐｐｍに見られ、グルタルイミド含有共重合体であ
ることが確認された。また反応しなかったアミド基の吸
収は６．６ ｐｐｍに現われるはずであるが、検出され
なかった。When the infrared absorption spectrum, 'H-NMR, of this reaction product was measured, it was found that the infrared absorption spectrum was
cm-', 1690 cm-', and 'II
-In NMR, the spectrum of glutarimide proton is 1
At 0 ppm, 1.2 methyl protons of glutarimide
5 ppm, confirming that it was a glutarimide-containing copolymer. Further, absorption of unreacted amide groups should have appeared at 6.6 ppm, but was not detected.
得られた重合体の物性を第１表に示す。Table 1 shows the physical properties of the obtained polymer.
実施例２
実施例１と同じ装置を用い、メタクリル酸メチル２５７
ｇ、メタクリルアミド２５７ｇ、水２０ｇを含有したメ
タノール７９０ ｇ、ジ−ｔ−ブチルパーオキサイド
６．５ｇおよびオクチルメルカプタン１．３ｇを加え、
撹拌下に１２０℃へ昇温し共重合を開始した。重合の進
行とともに定量ポンプを用いてメタクリル酸メチル２２
４ｇを１．５ｍ１１分の速度で６０分間、１．０ｍｌ／
分の速度で６０分間、最後に０．５ｎ＋１！／分の速度
で１８０分間と変化させながら連続的に供給して共重合
を７時間行った。Example 2 Using the same equipment as in Example 1, methyl methacrylate 257
g, 257 g of methacrylamide, 790 g of methanol containing 20 g of water, di-t-butyl peroxide.
Add 6.5 g and 1.3 g of octyl mercaptan,
While stirring, the temperature was raised to 120°C to start copolymerization. As the polymerization progresses, methyl methacrylate 22 is added using a metering pump.
4g for 60 minutes at a speed of 1.5ml/11 minutes, 1.0ml/
60 minutes at a speed of 0.5n+1 at the end! The copolymerization was carried out for 7 hours by continuously feeding the solution at a rate of 180 minutes.
引き続き同一装置、同一温度でナトリウムメトキシドを
１．１ ｇ含むメタノール溶液５０ｍｊ！を定量ポンプ
を用いて供給し、撹拌下１．５時間反応を行った０反応
終了後、系内の温度が４５℃となった時に沈澱したポリ
マーを取り出し、メタノールで洗滌後、１４０℃で一昼
夜減圧乾燥を行い、重合体を得た。Subsequently, 50 mj of methanol solution containing 1.1 g of sodium methoxide was prepared using the same equipment and the same temperature! was fed using a metering pump, and the reaction was carried out for 1.5 hours with stirring. After the reaction, the precipitated polymer was taken out when the temperature in the system reached 45°C, washed with methanol, and then kept at 140°C overnight. Drying under reduced pressure was performed to obtain a polymer.
この反応生成物の赤外吸収スペクトル、’１１−ＮＭＲ
を測定したところ、赤外吸収スペクトルではグルタルイ
ミドのイミド基にもとづく吸収が、３２５０ｃｓ−’、
３１００ｃｍ−’、 １６９０ｃｍ−’に見られ、さ
らに１１１−ＮＭＲではグルタルイミドプロトンのスペ
クトルが１０ｐｐｍに、グルタルイミドのメチルプロト
ンが１、２５ ｐｐｍに見られ、グルタルイミド含有共
重合体であることが確認された。また、６．６ ｐｐｍ
に未反応アミド基の吸収が痕跡として認められ、その積
分強度から求めたアミド基の反応率は９．９％であった
・
得られた重合体の物性値を第１表に示す。熱変形温度は
１６７℃と高く、全光ｖＡｉ３過率は９０％と透明性に
優れたものであった。Infrared absorption spectrum of this reaction product, '11-NMR
When measured, the infrared absorption spectrum showed that the absorption based on the imide group of glutarimide was 3250 cs-',
3100 cm-' and 1690 cm-', and in 111-NMR, the spectrum of glutarimide protons was found at 10 ppm, and the methyl proton of glutarimide was seen at 1.25 ppm, confirming that it was a glutarimide-containing copolymer. It was done. Also, 6.6 ppm
Traces of absorption of unreacted amide groups were observed in the polymer, and the reaction rate of the amide groups determined from the integrated intensity was 9.9%. The physical properties of the obtained polymer are shown in Table 1. The heat distortion temperature was as high as 167°C, and the total optical vAi3 pass rate was 90%, indicating excellent transparency.
実施例３
実施例１と同じ装置を用い、メタクリル酸メチル１５８
ｇ、メタクリルアミド２６７ｇ、メタノール７８９ｇ、
ジ−ｔ−ブチルパーオキサイド６．１ｇおよびｎ−オク
チルメルカプタン１．２ｇを加え、撹拌下に１２０℃へ
昇温し共重合を開始した。重合の進行とともに定量ポン
プを用いてメタクリル酸メチル１５４ｇを１．０ｍｆｆ
１／分の速度で１００分、０．５ｒａｌ１７分の速度で
５０分間と変えながら連続的に供給して共重合を７時間
行った。Example 3 Using the same equipment as in Example 1, methyl methacrylate 158
g, methacrylamide 267g, methanol 789g,
6.1 g of di-t-butyl peroxide and 1.2 g of n-octyl mercaptan were added, and the temperature was raised to 120°C with stirring to start copolymerization. As the polymerization progresses, 154 g of methyl methacrylate is added at 1.0 mff using a metering pump.
Copolymerization was carried out for 7 hours by continuously feeding at a rate of 1/min for 100 minutes and at a rate of 0.5 ral/17 minutes for 50 minutes.
引き続き、同一装置、同一温度でナトリウムメトキシド
１．１ｇを含むメタノール溶液５０ｍｊｉを定量ポンプ
を用いて供給し撹拌下で１．５時間反応を行った。反応
終了後、系内の温度が４５℃となったとき、沈澱したポ
リマーを取り出し、メタノールで洗滌後、１４０℃で一
昼夜減圧乾燥を行い重合体を得た。Subsequently, in the same apparatus and at the same temperature, 50 mji of a methanol solution containing 1.1 g of sodium methoxide was supplied using a metering pump, and the reaction was carried out for 1.5 hours with stirring. After completion of the reaction, when the temperature in the system reached 45°C, the precipitated polymer was taken out, washed with methanol, and dried under reduced pressure at 140°C all day and night to obtain a polymer.
この反応生成物の赤外吸収スペクトル、’Ｈ−Ｎ？ｆＲ
を測定したところ、グルタルイミド含有共重合体である
ことが確認された。’Ｈ−ＮＭＲの６．６ ｐｐｍに未
反応アミド基の吸収が痕跡として認められ、その積分強
度から求めたアミド基の反応率は９６％であった。得ら
れた重合体の物性値を第１表に示す。Infrared absorption spectrum of this reaction product, 'H-N? fR
When measured, it was confirmed that it was a glutarimide-containing copolymer. Trace absorption of unreacted amide groups was observed at 6.6 ppm in 'H-NMR, and the reaction rate of the amide groups determined from the integrated intensity was 96%. Table 1 shows the physical properties of the obtained polymer.
熱変形温度は１９３℃と極めて高く、全光線透過率も８
７％と透明性に優れるものであった。The heat distortion temperature is extremely high at 193℃, and the total light transmittance is 8.
The transparency was excellent at 7%.
実施例４
実施例１と同じ装置を用い、メタクリル酸メチル２４５
ｇ、アクリルアミド１１０ｇ、メタノール９１６ｇ、
ジ−ｔ−ブチルパーオキサイド５．０ｇおよびｎ−オク
チルメルカプタン０．８ｇを加え撹拌下に１２０℃へ昇
温しで共重合を開始した。Example 4 Using the same equipment as in Example 1, methyl methacrylate 245
g, acrylamide 110g, methanol 916g,
5.0 g of di-t-butyl peroxide and 0.8 g of n-octyl mercaptan were added, and the temperature was raised to 120°C with stirring to initiate copolymerization.
重合の進行とともに定量ポンプを用いてメタクリル酸メ
チル３７３ｇを２．Ｏａ＋ｊ！／分の速度で６０分間、
１．５ｍｊ！／分の速度で６０分間、１，０ｍ１７分の
速度で１２０分間、０．５ｍｌ／分の速度で８０分間と
変化させながら連続的に供給して共重合を７時間行った
。As the polymerization progresses, 373 g of methyl methacrylate is added using a metering pump. Oa+j! /minute for 60 minutes,
1.5mj! Copolymerization was carried out for 7 hours by continuously supplying at a rate of 1.0 ml/min for 60 minutes, a rate of 1.0 ml/min for 120 minutes, and a rate of 0.5 ml/min for 80 minutes.
引き続き、同一装置、同一温度でナトリウムメトキシド
１．１ｇを含むメタノール溶液５０ｍ１を定量ポンプを
用いて供給し、撹拌下で１．５時間反応を行った。反応
終了後、系内の温度が４５℃となった時、沈澱したポリ
マーを取り出し、メタノールで洗滌後、１２０℃で一昼
夜減圧乾燥を行い重合体を得た。Subsequently, in the same apparatus and at the same temperature, 50 ml of a methanol solution containing 1.1 g of sodium methoxide was supplied using a metering pump, and the reaction was carried out for 1.5 hours with stirring. After the reaction was completed, when the temperature in the system reached 45°C, the precipitated polymer was taken out, washed with methanol, and dried under reduced pressure at 120°C all day and night to obtain a polymer.
この反応生成物の赤外吸収スペクトル、’Ｈ−ＮＭＲを
測定したところ、赤外吸収スペクトルではグルタルイミ
ドのイミドに基づく吸収が、３２５０ａａ−’３１００
ｃｍ−’、 １７００ｃａ−’に見られ、さらに’Ｈ−
ＮＭＲではグルタルイミドプロトンのスペクトルが１０
ｐｐｍ。When the infrared absorption spectrum, 'H-NMR, of this reaction product was measured, the infrared absorption spectrum showed that the absorption based on the imide of glutarimide was 3250aa-'3100aa.
cm-', 1700 ca-', and 'H-
In NMR, the spectrum of glutarimide proton is 10
ppm.
グルタルイミドのメチルプロトンが１．２５ｐｐｎ＋に
見られグルタルイミド含有重合体であることが確認され
た。また、未反応アミド基の吸収が６．６ ｐｐｍ付近
に痕跡として認められ、その積分強度より求めたアミド
基の反応率は９６％であった。The methyl proton of glutarimide was found at 1.25 ppn+, confirming that it was a glutarimide-containing polymer. Further, absorption of unreacted amide groups was observed as a trace around 6.6 ppm, and the reaction rate of the amide groups determined from the integrated intensity was 96%.
得られた重合体は熱変形温度１２９℃、全光線透過率８
５％であり、耐熱性、透明性に優れたものであった。The obtained polymer had a heat distortion temperature of 129°C and a total light transmittance of 8.
5%, and was excellent in heat resistance and transparency.
実施例５
実施例１と同じ装置を用い、メタクリル酸メチル１５８
ｇ、Ｎ−メチルメタクリルアミド３０７ｇ、メタノール
７８９ ｇ、ジ−ｔ−ブチルパーオキサイド６．１ｇお
よびｎ−オクチルメルカプタン１．２ｇを加え、撹拌下
に１２０℃へ昇温し共重合を開始した。重合の進行とと
もに定量ポンプを用いてメタクリル酸メチル１６０ｇを
１．０ｍｆ／分の速度で１００分間、０．５ｍｊ！／分
の速度で５０分間と変化させながら連続的に供給して共
重合を７時間行った。Example 5 Using the same equipment as in Example 1, methyl methacrylate 158
g, 307 g of N-methyl methacrylamide, 789 g of methanol, 6.1 g of di-t-butyl peroxide and 1.2 g of n-octyl mercaptan were added, and the temperature was raised to 120° C. with stirring to start copolymerization. As the polymerization progresses, 160 g of methyl methacrylate is added at a rate of 1.0 mf/min for 100 minutes using a metering pump, 0.5 mj! The copolymerization was carried out for 7 hours by continuously feeding the solution at a rate of 1/min for 50 minutes.
引き続き、同一装置、同一温度でナトリウムメトキシド
１．１ｇを含むメタノール溶液５０ｍ１を定量ポンプを
用いて供給し撹拌下１．５時間反応を行った。反応終了
後、系内の温度が４５℃となった時、沈澱したポリマー
を取り出しメタノールで洗滌して１３０℃で一昼夜減圧
乾燥を行い重合体を得た。Subsequently, in the same apparatus and at the same temperature, 50 ml of a methanol solution containing 1.1 g of sodium methoxide was supplied using a metering pump, and the reaction was carried out for 1.5 hours with stirring. After the reaction, when the temperature in the system reached 45°C, the precipitated polymer was taken out, washed with methanol, and dried under reduced pressure at 130°C all day and night to obtain a polymer.
この反応生成物の赤外吸収スペクトルではグルタルイミ
ドの特有な吸収が１６６０ ｃｍ−’、 ７４２ ａｍ
−’に見られ、また’Ｈ−ＮＭＲではグルタルイミドの
メチルプロトンが１．２５ ｐｐｍに見られグルタルイ
ミド含有重合体であることが確認された。重合体の物性
を第１表に示す。The infrared absorption spectrum of this reaction product shows the characteristic absorption of glutarimide at 1660 cm-' and 742 am.
-', and 'H-NMR showed 1.25 ppm of methyl protons of glutarimide, confirming that it was a glutarimide-containing polymer. The physical properties of the polymer are shown in Table 1.
実施例６
実施例１と同じ装置を用い、メタクリル酸メチル２８２
ｇ、メタクリルアミド１５２ｇ、メタノール５９０
ｇ、水５６ｇ、ジ−ｔ−ブチルパーオキサイド４．３ｇ
およびｎ−オクチルメルカプタン０．７ｇを加え、撹拌
下に１２０℃へ昇温し共重合を開始した。重合の進行と
ともに定量ポンプを用いてメタクリル酸メチル４００ｇ
を３．０ｍｌ！／分の速度で３０分間、２．５ｍｊｉ！
／分の速度で４０分間、２．０ｍ６／分の速度で５０分
間、１．５ｍ７！／分の速度で６０分間、最後に０．５
ｍ！！／分の速度で４０分間と変化させながら連続的に
供給して共重合を６時間行った。Example 6 Using the same equipment as in Example 1, methyl methacrylate 282
g, methacrylamide 152g, methanol 590g
g, water 56g, di-t-butyl peroxide 4.3g
and 0.7 g of n-octyl mercaptan were added, and the temperature was raised to 120° C. while stirring to start copolymerization. As the polymerization progresses, add 400 g of methyl methacrylate using a metering pump.
3.0ml! 2.5 mji for 30 minutes at a speed of / min!
/min speed for 40 minutes, 2.0m6/min speed for 50 minutes, 1.5m7! /min for 60 minutes, and finally 0.5
m! ! The copolymerization was carried out for 6 hours by continuously feeding the solution at a rate of 1/min for 40 minutes.
引き続き同一装置、同一温度でナトリウムメトキシド１
．１ｇを含むメタノール溶液５０ｍＡを定量ポンプを用
いて供給し撹拌下で１，５時間反応を行った。Continuing to add sodium methoxide 1 in the same equipment and at the same temperature.
．． A methanol solution containing 1 g at 50 mA was supplied using a metering pump, and the reaction was carried out with stirring for 1.5 hours.
反応終了後、オートクレーブのサンプリング用ノズルを
用いて別の２１オートクレーブと配管で連結し、サンプ
リング用ノズルと配管部分をリボンヒーターで１２０℃
に加熱するとともに新たに連続したオートクレーブをＮ
２ガスで５ ｋｇ ／ ｃｍ ２に加圧した。ポリマー
溶液が入っているオートクレーブをＮ２ガスで７ｋｇ／
ｃ＋ｎ”まで昇圧し、サンプリング用ノズルのバルブを
開いてポリマー溶液を新たに連結したオートクレーブに
移送した。系内の温度が４５℃となった時に沈澱したポ
リマーを取り出し、メタノールで洗滌後１３０℃で一昼
夜減圧乾燥を行い重合体を得た。After the reaction is complete, the autoclave's sampling nozzle is connected to another 21 autoclave via piping, and the sampling nozzle and piping are heated to 120°C using a ribbon heater.
Heat the autoclave to N
It was pressurized to 5 kg/cm2 with 2 gases. The autoclave containing the polymer solution was heated with N2 gas to
The pressure was increased to c + n'', the valve of the sampling nozzle was opened, and the polymer solution was transferred to a newly connected autoclave. When the temperature in the system reached 45°C, the precipitated polymer was taken out, washed with methanol, and then heated to 130°C. Drying under reduced pressure was carried out all day and night to obtain a polymer.
この反応生成物の赤外吸収スペクトル、’Ｈ−ＮＭＲを
測定したところ、赤外吸収スペクトルではグルタルイミ
ドのイミド基にもとづ＜ 、３２５０ｃｍ−’３１００
ｃｍ−’ 、 １６９０ ａｍ−’に見られ、さらに’
Ｈ−ＮＭＲではグルタルイミドプロトンのスペクトルが
１０ｐｐｍに、グルタルイミドのメチルプロトンが１．
２５ｐｐｍに見られ、グルタルイミド含有共重合体であ
ることが確認された。また反応しなかったアミド基の吸
収は６．６ ｐｐｍに現われるはずであるが、検出され
なかった。When the infrared absorption spectrum, 'H-NMR, of this reaction product was measured, it was found that the infrared absorption spectrum was based on the imide group of glutarimide.
cm-', 1690 am-', and further '
In H-NMR, the spectrum of glutarimide proton is 10 ppm, and the methyl proton of glutarimide is 1.5 ppm.
It was found at 25 ppm and was confirmed to be a glutarimide-containing copolymer. Further, absorption of unreacted amide groups should have appeared at 6.6 ppm, but was not detected.
また、”Ｃ−ＮＭＲではカルボン酸のカルボニル炭素の
吸収は１８０ｐｐｍ付近に現われるはずであるが、検出
されなかった。Furthermore, in C-NMR, absorption of the carbonyl carbon of carboxylic acid should appear around 180 ppm, but it was not detected.
比較例１
実施例１と同じ装置を用い、メタクリル酸メチル２４４
ｇ、メタクリルアミド１３１ ｇ、メタノール７５１
ｇ、ジ−ｔ−ブチルパーオキサイド５．０ｇおよびオク
チルメルカプタン０．８ｇを加え撹拌下に１２０℃八ｙ
温へ共重合を開始し、そのまま、メタクリル酸メチルを
供給することなく重合を３時間行った。Comparative Example 1 Using the same equipment as Example 1, methyl methacrylate 244
g, methacrylamide 131 g, methanol 751 g
g, 5.0 g of di-t-butyl peroxide and 0.8 g of octyl mercaptan, and heated to 120°C with stirring.
Copolymerization was started at a temperature of 100 mL, and the polymerization was continued for 3 hours without supplying methyl methacrylate.
引き続き、同一装置、同一温度でナトリウムメトキシド
を１．０ｇ含むメタノール）容ｌ夜５０ｎ＋ｊ！を定量
ポンプを用いて供給し撹拌下１．５時間反応を行った。Subsequently, methanol containing 1.0 g of sodium methoxide in the same apparatus and at the same temperature) volume 1 night 50n+j! was supplied using a metering pump, and the reaction was carried out for 1.5 hours with stirring.
反応終了後、系内の温度が４５℃となった時、沈澱した
ポリマーを取り出しメタノールで洗滌後１２０℃−昼夜
減圧乾燥を行い重合体を得た。After the reaction was completed, when the temperature in the system reached 45°C, the precipitated polymer was taken out, washed with methanol, and dried under reduced pressure at 120°C day and night to obtain a polymer.
この反応生成物は赤外吸収スペクトル、’）Ｉ−ＮＭＲ
よりグルタルイミド含有重合体であることが確認され、
熱変形温度も１５９°Ｃと耐熱性に優れたものであった
が、全光線透過率が５８％と透明性に劣るものであった
。This reaction product has an infrared absorption spectrum,')I-NMR
It was confirmed that the polymer was a glutarimide-containing polymer.
Although the heat deformation temperature was 159°C, which was excellent in heat resistance, the total light transmittance was 58%, which was poor in transparency.
本発明によれば、アクリル系アミドとメタクリル酸メチ
ルとから工業的有利に耐熱性に優れた透明なイミド化ア
クリル樹脂が得られる。この熱可望性重合体は例えば弱
電部品や工業部品特に車輌部品などの各種用途に好適に
用いられる。According to the present invention, an industrially advantageous transparent imidized acrylic resin having excellent heat resistance can be obtained from an acrylic amide and methyl methacrylate. This thermoplastic polymer is suitably used for various purposes such as light electrical parts, industrial parts, especially vehicle parts.
Claims (5)
は水素またはメチル基を示し、ＹはＣＯＮＨＲ＿２ただ
し、Ｒ＿２は水素、アルキル基、アリール基、アラルキ
ル基を示す。）で表わされるアクリル系アミドとメタク
リル酸メチルとをメタノール溶媒中でラジカル重合触媒
の存在下に共重合するにあたり、アクリル系アミドに対
して０．５〜１０倍モルのメタクリル酸メチルの一部を
予めアクリル系アミドと混合し、その残りを供給しなが
ら共重合した後、塩基性触媒の存在下でイミド化反応を
行い、共重合体中のアクリル系アミド単位をグルタルイ
ミド単位に実質的に完全に変換することを特徴とする新
規なイミド化アクリル樹脂の製造法。(1) General formula CH_2=CR_1(Y) (where R_1
represents hydrogen or a methyl group, and Y is CONHR_2. However, R_2 represents hydrogen, an alkyl group, an aryl group, or an aralkyl group. ) and methyl methacrylate in a methanol solvent in the presence of a radical polymerization catalyst, a portion of methyl methacrylate in an amount of 0.5 to 10 times the mole of the acryl amide is added. After mixing with acrylamide in advance and copolymerizing while supplying the remainder, an imidization reaction is performed in the presence of a basic catalyst to substantially completely convert the acrylamide units in the copolymer into glutarimide units. A novel method for producing imidized acrylic resin characterized by converting it into .
ールを用いる、請求項１における新規なイミド化アクリ
ル樹脂の製造法。(2) The novel method for producing an imidized acrylic resin according to claim 1, wherein methanol containing 30 wt% or less of water is used as a solvent.
％以上になるように重合反応を進めた後、イミド化反応
を行う、請求項１または２における新規なイミド化アク
リル樹脂の製造法。(3) The novel method for producing an imidized acrylic resin according to claim 1 or 2, wherein the imidization reaction is carried out after the polymerization reaction is carried out so that the polymerization rate of the acrylic amide is at least 90 mol % or more.
する、請求項１〜３における新規なイミド化アクリル樹
脂の製造法。(4) The novel method for producing an imidized acrylic resin according to claims 1 to 3, wherein the polymerization temperature of the acrylic amide is 80 to 150°C.
〜３における新規なイミド化アクリル樹脂の製造法。(5) Claim 1, wherein the imidization reaction is carried out at 80 to 150°C.
3. A method for producing a novel imidized acrylic resin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-182961 | 1988-07-22 | ||
| JP18296188 | 1988-07-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02153904A true JPH02153904A (en) | 1990-06-13 |
| JP2744291B2 JP2744291B2 (en) | 1998-04-28 |
Family
ID=16127361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1188580A Expired - Fee Related JP2744291B2 (en) | 1988-07-22 | 1989-07-20 | Manufacturing method of imidized acrylic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2744291B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5324793A (en) * | 1991-09-14 | 1994-06-28 | Rohm Gmbh | Method for making polymethacrylimide polymers |
| WO2001037007A1 (en) * | 1999-11-12 | 2001-05-25 | Kaneka Corporation | Transparent film |
| JPWO2005054311A1 (en) * | 2003-12-02 | 2007-12-06 | 株式会社カネカ | Imide resin, and production method and use thereof |
| JP2013167761A (en) * | 2012-02-15 | 2013-08-29 | Konica Minolta Inc | Polarizing plate and display device using the same |
| WO2016152646A1 (en) * | 2015-03-23 | 2016-09-29 | 株式会社日本触媒 | Glutarimide resin and method for producing glutarimide resin |
-
1989
- 1989-07-20 JP JP1188580A patent/JP2744291B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5324793A (en) * | 1991-09-14 | 1994-06-28 | Rohm Gmbh | Method for making polymethacrylimide polymers |
| WO2001037007A1 (en) * | 1999-11-12 | 2001-05-25 | Kaneka Corporation | Transparent film |
| US6964814B2 (en) | 1999-11-12 | 2005-11-15 | Kaneka Corporation | Transparent film |
| JPWO2005054311A1 (en) * | 2003-12-02 | 2007-12-06 | 株式会社カネカ | Imide resin, and production method and use thereof |
| JP4796846B2 (en) * | 2003-12-02 | 2011-10-19 | 株式会社カネカ | Polarizer protective film, and production method and use thereof |
| JP2013167761A (en) * | 2012-02-15 | 2013-08-29 | Konica Minolta Inc | Polarizing plate and display device using the same |
| WO2016152646A1 (en) * | 2015-03-23 | 2016-09-29 | 株式会社日本触媒 | Glutarimide resin and method for producing glutarimide resin |
| JPWO2016152646A1 (en) * | 2015-03-23 | 2017-10-12 | 株式会社日本触媒 | Glutarimide resin and method for producing glutarimide resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2744291B2 (en) | 1998-04-28 |
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