JPH02127407A - Heat-resistant thermoplastic resin - Google Patents
Heat-resistant thermoplastic resinInfo
- Publication number
- JPH02127407A JPH02127407A JP28035588A JP28035588A JPH02127407A JP H02127407 A JPH02127407 A JP H02127407A JP 28035588 A JP28035588 A JP 28035588A JP 28035588 A JP28035588 A JP 28035588A JP H02127407 A JPH02127407 A JP H02127407A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- resin
- polymerization
- heat
- formula
- 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
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 9
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 32
- 238000006116 polymerization reaction Methods 0.000 abstract description 13
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 abstract description 9
- 238000010557 suspension polymerization reaction Methods 0.000 abstract description 4
- 238000002845 discoloration Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 21
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 6
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 5
- -1 0-chlorostyrene Chemical compound 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- FPDBKGVONBYWIG-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione;styrene Chemical compound C=CC1=CC=CC=C1.O=C1C=CC(=O)N1C1CCCCC1 FPDBKGVONBYWIG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- VDNSZPNSUQRUMS-UHFFFAOYSA-N 1-cyclohexyl-4-ethenylbenzene Chemical compound C1=CC(C=C)=CC=C1C1CCCCC1 VDNSZPNSUQRUMS-UHFFFAOYSA-N 0.000 description 1
- HJKREWSZLFLSOQ-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butanoic acid Chemical compound CC(C)(C)OOC(CC)(OOC(C)(C)C)C(O)=O HJKREWSZLFLSOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- CIKJANOSDPPCAU-UHFFFAOYSA-N ditert-butyl cyclohexane-1,4-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1CCC(C(=O)OOC(C)(C)C)CC1 CIKJANOSDPPCAU-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical class CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 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
- 238000002834 transmittance Methods 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
Landscapes
- 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〕
本発明は耐熱性及び成形加工性が優れ、かつ透明性もす
ぐれた熱可塑性樹脂に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a thermoplastic resin that has excellent heat resistance and moldability as well as excellent transparency.
ポリスチレンをはじめとするビニル系重合体は、透明性
及び成形加工性が優れた樹脂であり、自動車部品、OA
部品、日用雑貨等、その用途は広い。Vinyl polymers such as polystyrene are resins with excellent transparency and moldability, and are used in automobile parts, OA
Its uses are wide, including parts and daily necessities.
しかるにその熱変形温度が低いため、ビニル系重合体は
用途に制限を受けている。However, the use of vinyl polymers is limited due to their low heat distortion temperatures.
したがって、ビニル系重合体の熱変形温度を向上させる
研究がなされている。例えば、メチルメタクリレートと
α−メチルスチレンを共重合させる方法(米国特許第3
.135.723号公報)、メチルメタクリレート、α
−メチルスチレン及び無水マレイン酸を共重合させる方
法(特公昭4531.953号公報)、メチルメタクリ
レート、α−メチルスチレン及びマレイミド(無置換)
を共重合させる方法等が報告されている。Therefore, research is being conducted to improve the heat distortion temperature of vinyl polymers. For example, a method of copolymerizing methyl methacrylate and α-methylstyrene (U.S. Patent No. 3
.. 135.723), methyl methacrylate, α
- Method of copolymerizing methylstyrene and maleic anhydride (Japanese Patent Publication No. 4531.953), methyl methacrylate, α-methylstyrene and maleimide (unsubstituted)
A method of copolymerizing these has been reported.
しかしながら、これらの方法では重合速度が著しく遅か
ったり、熱変形温度が不充分であったり、得られた樹脂
の着色が強く、透明性が損われたりしていて実用化には
到っていない。However, these methods have not been put to practical use because the polymerization rate is extremely slow, the heat distortion temperature is insufficient, and the resulting resin is strongly colored and loses transparency.
また、従来よりビニル系単量体とマレイミド系単量体と
からなる共重合体は、成形加工性及び耐熱性に優れるこ
とが知られている。しかしながらビニル系単量体とマレ
イミド系単量体混合物を通常のラジカル重合下で行った
場合には、交互共重合体が優先的に生成し、ついで残存
した単量体の単独重合体が生成し、ついには共重合組成
の不均質な不透明あるいは半透明な共重合体が得られる
。Furthermore, it has been known that copolymers made of vinyl monomers and maleimide monomers have excellent moldability and heat resistance. However, when a mixture of vinyl monomers and maleimide monomers is subjected to normal radical polymerization, alternating copolymers are preferentially formed, followed by homopolymers of the remaining monomers. Finally, an opaque or translucent copolymer with a heterogeneous copolymer composition is obtained.
しかもこの不均一な化学組成を有する共重合体は、耐熱
性に劣るという欠点がある。Moreover, this copolymer having a non-uniform chemical composition has the disadvantage of poor heat resistance.
本発明者らは、これらの問題点に鑑み、鋭意研究を行っ
た結果、特定の配合比を有する芳香族ビニル系単量体と
、アルキルマレイミド系単量体を共重合せしめることに
よって得られる共重合体が、耐熱性及び成形加工性に優
れるばかりか、驚くべきことに樹脂の透明性及び生産性
に優れ、かつ樹脂の帯色性が少ないという効果が得られ
ることを見出し、本発明に至った。In view of these problems, the present inventors conducted intensive research and found that a copolymer obtained by copolymerizing an aromatic vinyl monomer with a specific blending ratio and an alkylmaleimide monomer. It was discovered that the polymer not only has excellent heat resistance and molding processability, but also surprisingly produces resins with excellent transparency and productivity, and has low color discoloration, which led to the present invention. Ta.
すなわち本発明は、芳香族ビニル系単量体とアルキルマ
レイミド系単量体からなる共重合体であ65〜97:3
5〜3のモル比で、線状で不規則に配列した重量平均分
子量5万〜50万の耐熱性熱可塑性樹脂(ただし、上記
式中R,は水素原子、メチル基又はエチル基であり、R
2は芳香族炭化水素基であり、そしてR3は炭素数1〜
15のアルキル基又はシクロアルキル基である。)に関
する。That is, the present invention is a copolymer consisting of an aromatic vinyl monomer and an alkylmaleimide monomer with a ratio of 65 to 97:3.
A heat-resistant thermoplastic resin having a weight average molecular weight of 50,000 to 500,000 arranged irregularly in a linear manner at a molar ratio of 5 to 3 (wherein R in the above formula is a hydrogen atom, a methyl group or an ethyl group, R
2 is an aromatic hydrocarbon group, and R3 has 1 to 1 carbon atoms.
15 alkyl group or cycloalkyl group. ) regarding.
この共重合体は透明性がすぐれており、曇価が3%以下
である。This copolymer has excellent transparency and a haze value of 3% or less.
以下に本発明についてさらに詳細に説明する。The present invention will be explained in more detail below.
本発明の共重合体は、アルキルマレイミド系単量体単位
を3〜35モル%、好ましくは5〜25モル%を含有す
ることを必須とする。The copolymer of the present invention essentially contains 3 to 35 mol%, preferably 5 to 25 mol%, of alkylmaleimide monomer units.
本発明の樹脂である共重合体を構成する構造単R:I
アルキルマレイミド系単量体は、一般式%式%
(式中P、は、炭素数1〜15のアルキル基又はシクロ
アルキル基である。)
で示される。R1がアルキル基又はシクロアルキル基以
外のマレイミド系単量体、例えばN−フェニルマレイミ
ド等の芳香族マレイミド系単量体、O−クロロフェニル
マレイミド、O−ブロモフェニルマレイミド等のハロゲ
ン化アルキルマレイミド系単量体を用いた場合には、そ
れを用いた共重合体は着色が強く透明性が損われる。し
かし′、アルキルマレイミド系単量体を用いてもそれが
3モル%未満では、生成した共重合体樹脂の耐熱性の向
上が乏しく、35モル%を超えた場合には、樹脂の帯色
が激しくなるとともに、機械的強度が小さ(実用的でな
い。透明性及び耐熱性を備えた樹脂を目的とする本発明
ではN−シクロヘキシルマレイミドが好適である。The structural unit R:I alkylmaleimide monomer constituting the copolymer which is the resin of the present invention has the general formula % (in the formula, P is an alkyl group or a cycloalkyl group having 1 to 15 carbon atoms) ). A maleimide monomer in which R1 is an alkyl group or other than a cycloalkyl group, for example, an aromatic maleimide monomer such as N-phenylmaleimide, a halogenated alkylmaleimide monomer such as O-chlorophenylmaleimide, O-bromophenylmaleimide, etc. If a copolymer is used, the copolymer made using it will be strongly colored and its transparency will be impaired. However, even if an alkylmaleimide monomer is used, if it is less than 3 mol%, the heat resistance of the resulting copolymer resin will be poorly improved, and if it exceeds 35 mol%, the color of the resin will change. In the present invention, which aims to produce a resin with transparency and heat resistance, N-cyclohexylmaleimide is suitable.
は、一般弐 CH2=C(但し、式中R3は水素t
原子、メチル基又はエチル基であり、Rtは芳香族炭化
水素基である。)で示される。is represented by the general 2 CH2=C (wherein R3 is a hydrogen atom, a methyl group or an ethyl group, and Rt is an aromatic hydrocarbon group).
芳香族ビニル系単量体としては、例えば、スチレン、p
−メチルスチレン、α−メチルスチレン、0−クロロス
チレン、p−クロロスチレン、0−ブロモスチレン、p
−ブロモスチレン、p−シクロへキシルスチレン、p−
フェニルスチレンなどがあげられるがスチレン及びα−
メチルスチレンの一種以上が好適である。またα−メチ
ルスチレンは、耐熱性を向tさせる効果が大きいため、
αメチルスチレンを5〜25重量%含有させると樹脂の
耐熱性向上の発現は顕著となる。しかしαメチルスチレ
ンの含有率が25%を超えると重合速度が著しく遅くま
たα−メチルスチレンの残存モノマーが多くなったりし
て、耐熱性等の諸物性に悪影響を及ぼすため好ましくな
い。Examples of aromatic vinyl monomers include styrene, p
-Methylstyrene, α-methylstyrene, 0-chlorostyrene, p-chlorostyrene, 0-bromostyrene, p
-bromostyrene, p-cyclohexylstyrene, p-
Examples include phenylstyrene, but styrene and α-
One or more methylstyrenes are preferred. In addition, α-methylstyrene has a great effect on improving heat resistance, so
When α-methylstyrene is contained in an amount of 5 to 25% by weight, the heat resistance of the resin is significantly improved. However, if the content of α-methylstyrene exceeds 25%, the polymerization rate will be extremely slow and the residual monomer of α-methylstyrene will increase, which will have an adverse effect on various physical properties such as heat resistance, which is not preferable.
系単量体を共重合させることにより得られるが、その製
造法では、重合系へのアルキルマレイミド系単量体の連
続的あるいは断続的な供給を必須とする。この際の供給
速度は、Mayo−Lewisの共重合組成式において
、共重合体の微分組成比が一定になる様に供給すること
が好ましい。供給方法にはとくに制限はな(、アルキル
マレイミド系単量体を直接又はメチルエチルケトンなど
の溶媒やスチレン、αメチルスチレンなどの芳香族ビニ
ル系単量体で希釈して供給する方法が採用できる。It can be obtained by copolymerizing alkylmaleimide monomers, but the production method requires continuous or intermittent supply of the alkylmaleimide monomer to the polymerization system. At this time, it is preferable that the feed rate is such that the differential composition ratio of the copolymer becomes constant in the Mayo-Lewis copolymerization formula. There are no particular limitations on the supply method (the alkylmaleimide monomer can be supplied directly or after being diluted with a solvent such as methyl ethyl ketone or an aromatic vinyl monomer such as styrene or α-methylstyrene).
本発明の共重合体を製造するための重合は、塊状重合法
、懸濁重合法、乳化重合法及び溶液重合法など、−船釣
によく知られる重合法を任意に用いることができるが、
重合時の運転操作や重合物の回収が容易な懸濁重合法が
好適である。For the polymerization to produce the copolymer of the present invention, any polymerization method well known for boat fishing can be used, such as bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization.
Suspension polymerization is preferred because it facilitates operation during polymerization and recovery of polymerized products.
また懸濁重合反応は一般の重合条件、例えば10時間半
減期が30〜150℃であるラジカル重合開始剤を用い
て行われる。この種の開始剤としては、ベンゾイルパー
オキサイド、ラウロイルエート、t−ブチルパーオキシ
−2−エチルヘキサノエート、ジ−t−ブチルパーオキ
シへキサヒドロテレフタレート、t−ブチルパーオキシ
アセテート、エチル−33−ジー(t−ブチルパーオキ
シ)ブチレートなどの有機過酸化物や、アゾビスイソブ
チロニトリル、アゾビスシクロニl−IJル、アゾビス
シクロへキシルニトリルなどのアブ系化合物などのうち
1種以上を任意に用いてよい。Further, the suspension polymerization reaction is carried out under general polymerization conditions, for example, using a radical polymerization initiator having a 10-hour half-life of 30 to 150°C. Initiators of this type include benzoyl peroxide, lauroyl ate, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxy hexahydroterephthalate, t-butyl peroxy acetate, ethyl-33 - Optionally use one or more of organic peroxides such as di(t-butylperoxy)butyrate, and ab-based compounds such as azobisisobutyronitrile, azobiscyclonyl-IJ, azobiscyclohexylnitrile, etc. It's fine.
また共重合樹脂の成形加工性を良好に保つためそのため
必要ならばドデシルメルカプタン、オクチルメルカプタ
ンなどの連鎖移動剤を添加してもよい。Further, in order to maintain good moldability of the copolymer resin, a chain transfer agent such as dodecyl mercaptan or octyl mercaptan may be added if necessary.
懸濁安定剤としては、カルシウムハイドロアパタイトな
どのリン酸カルシウム塩、リン酸マグネシウム、シュウ
酸マグネシウム、硫酸マグネシウム等の無機分散剤や部
分ケン化ポリビニルアルコールなどの有機分散剤を用い
る。As the suspension stabilizer, an inorganic dispersant such as a calcium phosphate salt such as calcium hydroapatite, magnesium phosphate, magnesium oxalate, or magnesium sulfate, or an organic dispersant such as partially saponified polyvinyl alcohol is used.
本発明の耐熱性熱可塑性樹脂を製造するに際しての重合
温度は特に限定されないが60℃〜160℃の範囲であ
る。The polymerization temperature for producing the heat-resistant thermoplastic resin of the present invention is not particularly limited, but is in the range of 60°C to 160°C.
また本発明の熱可塑性樹脂を、ペレット化またはシート
化することにより、透明性、耐熱性、成形加工性にすぐ
れた成形材料が得られる。また本発明で得られる熱可塑
性樹脂をスチレン−ブタジェン共重合体、スチレン−ブ
タジェン−メチルメタクリレート共重合体(MBS樹脂
)、スチレンブタジェン−アクリロニトリル共重合体(
ABS樹脂)などに配合して、耐熱性を更に向上させる
ことも可能である。Furthermore, by forming the thermoplastic resin of the present invention into pellets or sheets, a molding material with excellent transparency, heat resistance, and moldability can be obtained. In addition, the thermoplastic resins obtained in the present invention are styrene-butadiene copolymer, styrene-butadiene-methyl methacrylate copolymer (MBS resin), styrene-butadiene-acrylonitrile copolymer (
It is also possible to further improve heat resistance by blending it with ABS resin.
また本発明の熱可塑性樹脂には、必要に応じてヒンダー
ドフェノール系、リン系、又はイオウ系の酸化防止剤、
ガラス繊維などの補強剤、紫外線吸収剤、難燃剤、顔料
を添加することもできる。In addition, the thermoplastic resin of the present invention may optionally contain a hindered phenol-based, phosphorus-based, or sulfur-based antioxidant,
Reinforcing agents such as glass fiber, ultraviolet absorbers, flame retardants, and pigments can also be added.
〔実施例〕
以下に実施例及び比較例をあげて本発明の効果をさらに
詳細に説明する。なお実施例及び比較例中の熱変形温度
は、ASTM D−648−56、曇価及び全光線透
過率はASTM D−1003、曲げ強度はASTM
D−790Methodに従った。[Example] The effects of the present invention will be explained in more detail with reference to Examples and Comparative Examples below. In addition, the heat distortion temperature in Examples and Comparative Examples is ASTM D-648-56, haze value and total light transmittance is ASTM D-1003, and bending strength is ASTM D-648-56.
D-790Method was followed.
なお重量平均分子量は、GPC法にてポリスチレン換算
の値で求めた。The weight average molecular weight was determined by GPC method in terms of polystyrene.
実施例1
スチレン3000 g、水6000g、t−ブチルパー
オキシベンゾエート6g1第3リン酸カルシウム42g
及び過硫酸カリウム0.24 gを窒素置換した15f
オートクレーブに仕込みはげしく攪拌した。Example 1 3000 g of styrene, 6000 g of water, 6 g of t-butyl peroxybenzoate, 42 g of tertiary calcium phosphate
and 15f in which 0.24 g of potassium persulfate was replaced with nitrogen.
The mixture was placed in an autoclave and stirred vigorously.
一方、別にN−シクロへキシルマレイミド20重量%の
スチレン溶液を調製して滴下ロートに仕込んだ。Separately, a styrene solution containing 20% by weight of N-cyclohexylmaleimide was prepared and charged into the dropping funnel.
次にオートクレーブ内温度を110℃に保ち、攪拌を行
いながら、プランジャーポンプを用いて滴下ロートから
、N−シクロへキシルマレイミド−スチレン溶液を50
0g/hrの速度で6時間滴下した。このときのモノマ
ー組成比はモル比でスチレン二N−シクロへキシルマレ
イミド−93,9=6.1である。さらに130℃に昇
温し、2時間保った後重合を終了した。脱水、乾燥後、
重合体の組成を元素分析及び”C−NMRにて確認を行
ったところモノマー組成比と等しかった。Next, while maintaining the temperature inside the autoclave at 110°C and stirring, 50% of the N-cyclohexylmaleimide-styrene solution was added from the dropping funnel using a plunger pump.
The mixture was added dropwise at a rate of 0 g/hr for 6 hours. The monomer composition ratio at this time was styrene diN-cyclohexylmaleimide-93,9=6.1 in molar ratio. The temperature was further raised to 130°C and maintained for 2 hours, after which the polymerization was completed. After dehydration and drying,
When the composition of the polymer was confirmed by elemental analysis and C-NMR, it was found to be equal to the monomer composition ratio.
得られた重合体を抽出機でペレット化した後、2オンス
の射出成形機で成形を行った。その性能を評価した。結
果を表1に示す。The resulting polymer was pelletized using an extractor and then molded using a 2-ounce injection molding machine. Its performance was evaluated. The results are shown in Table 1.
実施例2
スチレンを2500 g、α−メチルスチレンを500
gに変更した以外は、実施例1の方法に従った。このと
きのモノマー組成はモル比でスチレン:α−メチルスチ
レン二N−シクロへキシルマレイミド=86.1 :
7.776.1であり、重合体の組成は元素分析及び”
C−NMRにて確認を行ったところ、七ツマー組成比と
等しかった。物性を表1に示す。Example 2 2500 g of styrene, 500 g of α-methylstyrene
The method of Example 1 was followed except that g was changed. The monomer composition at this time is styrene: α-methylstyrene diN-cyclohexylmaleimide = 86.1 in molar ratio:
7.776.1, and the composition of the polymer was determined by elemental analysis and "
When confirmed by C-NMR, it was found to be equal to the seven-mer composition ratio. The physical properties are shown in Table 1.
実施例3
水6000 g、第3リン酸カルシウム42g、及び過
硫酸カリウム0.24 gを窒素置換した151オート
クレーブに仕込み撹拌した。Example 3 6000 g of water, 42 g of tertiary calcium phosphate, and 0.24 g of potassium persulfate were charged into a 151 autoclave purged with nitrogen and stirred.
一方別にN−シクロへキシルマレイミド1200 g、
スチレン4800g及びt−ブチルパーオキシベンゾニ
ーt−6gの混合溶液を調製して滴下ロートに仕込んだ
。On the other hand, 1200 g of N-cyclohexylmaleimide,
A mixed solution of 4,800 g of styrene and 6 g of t-butylperoxybenzony was prepared and charged into a dropping funnel.
次にオートクレーブ内の温度を110℃に保ち、攪拌を
行いながら、プランジャーポンプを用いて滴下ロートか
らN−シクロへキシルマレイミド−スチレン溶液を50
0g/hrの速度で12時間滴下した。このときのモノ
マー組成比はモル比で、スチレン:N−シクロへキシル
マレイミド=87.3:12.7である。さらに130
℃に昇温し、2時間保った後重合を終了した。脱水、乾
燥後、重合体の組成を元素分析及び”C−NMRにて確
認を行ったところ、モノマー組成比と等しかった。Next, while maintaining the temperature inside the autoclave at 110°C and stirring, 50% of the N-cyclohexylmaleimide-styrene solution was added from the dropping funnel using a plunger pump.
The mixture was added dropwise at a rate of 0 g/hr for 12 hours. The monomer composition ratio at this time is styrene:N-cyclohexylmaleimide=87.3:12.7 in terms of molar ratio. Another 130
The temperature was raised to .degree. C. and maintained for 2 hours, after which the polymerization was completed. After dehydration and drying, the composition of the polymer was confirmed by elemental analysis and C-NMR, and it was found to be equal to the monomer composition ratio.
得られた重合体を抽出機でペレット化した後、2オンス
の射出成形機で成形を行った。その性能を評価した結果
を表1に示す。The resulting polymer was pelletized using an extractor and then molded using a 2-ounce injection molding machine. Table 1 shows the results of evaluating the performance.
比較例I
N−シクロへキシルマレイミドをN−フェニルマレイミ
ド、第3リン酸カルシウムを部分ケン化ポリビニルアル
コール8gに変更した以外は、実施例1の方法に従った
。このときのモノマー組成比はモル比でスチレン二N−
フェニルマレイミド=93.8:6.2である。性能を
評価した結果を表1に示す。この表より黄みが濃く、透
明材料として実用的でないことがわかる。Comparative Example I The method of Example 1 was followed except that N-cyclohexylmaleimide was changed to N-phenylmaleimide and tertiary calcium phosphate was changed to 8 g of partially saponified polyvinyl alcohol. The monomer composition ratio at this time is styrene diN-
Phenylmaleimide=93.8:6.2. Table 1 shows the results of performance evaluation. From this table, it can be seen that the yellow color is deep and it is not practical as a transparent material.
比較例2
N−フェニルマレイミドをN−0−クロロフェニルマレ
イミドに変更した以外は比較例1の方法に従った。この
ときのモノマー組成比は、モル比でスチレン:N−0−
クロロフェニルマレイミド=94.8:5.2である。Comparative Example 2 The method of Comparative Example 1 was followed except that N-phenylmaleimide was changed to N-0-chlorophenylmaleimide. The monomer composition ratio at this time is styrene:N-0-
Chlorophenylmaleimide = 94.8:5.2.
性能を評価した結果を表1に示す。この表より黄みが濃
<、透明材料として実用的でないことがわかる。Table 1 shows the results of performance evaluation. From this table, it can be seen that if the yellowness is too deep, it is not practical as a transparent material.
比較例3
N−シクロへキシルマレイミド1000g、スチレン5
000g、水6000g、t−ブチルパーオキシベンゾ
エート6g、第3リン酸カルシウム42g及び過硫酸カ
リウム0.24 gを窒素置換した151オートクレー
ブに仕込みはげしく攪拌した。このときのモノマー組成
比はモル比で、スチレン二N−シクロへキシルマレイミ
ド−93,9:6.1である。Comparative example 3 N-cyclohexylmaleimide 1000g, styrene 5
000 g, water 6000 g, t-butyl peroxybenzoate 6 g, tertiary calcium phosphate 42 g and potassium persulfate 0.24 g were charged into a 151 autoclave purged with nitrogen and stirred vigorously. The monomer composition ratio at this time was styrene diN-cyclohexylmaleimide-93.9:6.1 in terms of molar ratio.
オートクレーブ内温度を110℃に6時間保った後、1
30℃に昇温し、2時間保った後重合を終了した。脱水
、乾燥後成形を行い、その物性値を表1に示す。After keeping the temperature inside the autoclave at 110℃ for 6 hours,
The temperature was raised to 30°C and maintained for 2 hours, after which the polymerization was completed. After dehydration and drying, molding was performed, and the physical properties are shown in Table 1.
比較例4
N−シクロへキシルマレイミド8重量%のスチレン溶液
を滴下ロートに仕込んだ以外は、実施例1に従った。こ
のときのモノマー組成比はモル比で、スチレン二N−シ
クロへキシルマレイミド−97,6:2.4である。物
性値を表1に示す。表より充分な耐熱性が得られないこ
とがわかる。Comparative Example 4 Example 1 was followed except that a styrene solution containing 8% by weight of N-cyclohexylmaleimide was charged into the dropping funnel. The monomer composition ratio at this time was styrene diN-cyclohexylmaleimide-97.6:2.4 in terms of molar ratio. The physical property values are shown in Table 1. It can be seen from the table that sufficient heat resistance cannot be obtained.
比較例5
N−シクロへキシルマレイミド20重量%のスラリーを
滴下ロートに仕込んだ以外は実施例1に従った。このと
きのモノマー組成比はモル比でスチレン二N−シクロへ
キシルマレイミド= 63.3:36.1である。物性
値を表1に示す。表より強度に劣ることがわかる。Comparative Example 5 Example 1 was followed except that a slurry containing 20% by weight of N-cyclohexylmaleimide was charged into the dropping funnel. The monomer composition ratio at this time was styrene diN-cyclohexylmaleimide = 63.3:36.1 in molar ratio. The physical property values are shown in Table 1. It can be seen from the table that the strength is inferior.
上記のとおり、本発明の共重合体樹脂は耐熱度が
形性、透明性及び成形加工性勾すぐれている。そしてこ
の樹脂は電子レンジ用耐熱PSP、耐熱OPS及び自動
車用途など耐熱変形性が必要な用途への展開が見込まれ
、有用なものである。As mentioned above, the copolymer resin of the present invention has excellent heat resistance, shapeability, transparency, and moldability. This resin is expected to be useful in applications that require heat deformation resistance, such as heat-resistant PSP for microwave ovens, heat-resistant OPS, and automobile applications.
Claims (1)
体からなる共重合体であって、式 ▲数式、化学式、表等があります▼で示される構造単位
と 式▲数式、化学式、表等があります▼で示される構造単
位が65 〜97:35〜3のモル比で、線状で不規則に配列した
重量平均分子量5万〜50万の耐熱性熱可塑性樹脂。 (ただし、上記式中R_1は水素原子、メチル基又はエ
チル基であり、R_2は芳香族炭化水素基であり、そし
てR_3は炭素数1〜15のアルキル基又はシクロアル
キル基である。) 2、曇価が3%以下である特許請求の範囲第1項記載の
耐熱性熱可塑性樹脂。[Scope of Claims] 1. A copolymer consisting of an aromatic vinyl monomer and an alkylmaleimide monomer, which comprises a structural unit represented by the formula ▲, which includes mathematical formulas, chemical formulas, tables, etc.▼, and the formula ▲ A heat-resistant thermoplastic resin with a weight average molecular weight of 50,000 to 500,000, in which the structural units shown by ▼ are linearly and irregularly arranged in a molar ratio of 65 to 97:35 to 3. (However, in the above formula, R_1 is a hydrogen atom, a methyl group, or an ethyl group, R_2 is an aromatic hydrocarbon group, and R_3 is an alkyl group or cycloalkyl group having 1 to 15 carbon atoms.) 2. The heat-resistant thermoplastic resin according to claim 1, which has a haze value of 3% or less.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63280355A JP2840645B2 (en) | 1988-11-08 | 1988-11-08 | Heat resistant thermoplastic resin and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63280355A JP2840645B2 (en) | 1988-11-08 | 1988-11-08 | Heat resistant thermoplastic resin and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02127407A true JPH02127407A (en) | 1990-05-16 |
JP2840645B2 JP2840645B2 (en) | 1998-12-24 |
Family
ID=17623851
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP63280355A Expired - Fee Related JP2840645B2 (en) | 1988-11-08 | 1988-11-08 | Heat resistant thermoplastic resin and method for producing the same |
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Country | Link |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58162616A (en) * | 1982-03-24 | 1983-09-27 | Toray Ind Inc | Production of maleimide copolymer |
JPS6176512A (en) * | 1984-09-21 | 1986-04-19 | Toa Nenryo Kogyo Kk | Methylstyrene copolymer |
JPS61157550A (en) * | 1984-12-24 | 1986-07-17 | アトランテイツク・リツチフイ−ルド・カンパニ− | Moldable composition, production of molded article and random copolymer |
JPS61278509A (en) * | 1985-06-05 | 1986-12-09 | Toray Ind Inc | Optical disc base |
-
1988
- 1988-11-08 JP JP63280355A patent/JP2840645B2/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58162616A (en) * | 1982-03-24 | 1983-09-27 | Toray Ind Inc | Production of maleimide copolymer |
JPS6176512A (en) * | 1984-09-21 | 1986-04-19 | Toa Nenryo Kogyo Kk | Methylstyrene copolymer |
JPS61157550A (en) * | 1984-12-24 | 1986-07-17 | アトランテイツク・リツチフイ−ルド・カンパニ− | Moldable composition, production of molded article and random copolymer |
JPS61278509A (en) * | 1985-06-05 | 1986-12-09 | Toray Ind Inc | Optical disc base |
Also Published As
Publication number | Publication date |
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JP2840645B2 (en) | 1998-12-24 |
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