JPH058724B2 - - Google Patents
Info
- Publication number
- JPH058724B2 JPH058724B2 JP27723484A JP27723484A JPH058724B2 JP H058724 B2 JPH058724 B2 JP H058724B2 JP 27723484 A JP27723484 A JP 27723484A JP 27723484 A JP27723484 A JP 27723484A JP H058724 B2 JPH058724 B2 JP H058724B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- maleic anhydride
- weight
- units
- methyl methacrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000006116 polymerization reaction Methods 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 43
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 38
- 239000000178 monomer Substances 0.000 claims description 25
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 24
- -1 aromatic vinyl compound Chemical group 0.000 claims description 19
- 239000002954 polymerization reaction product Substances 0.000 claims description 19
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 239000000113 methacrylic resin Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 17
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 12
- 239000011550 stock solution Substances 0.000 description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical group CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 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 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- DUZJXKYBSMFDIU-UHFFFAOYSA-N 4-tert-butyl-2-methylbenzenethiol Chemical compound CC1=CC(C(C)(C)C)=CC=C1S DUZJXKYBSMFDIU-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
- 238000004566 IR spectroscopy Methods 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- PQFQPCRRNRVBFK-UHFFFAOYSA-N N-[[formyl(propyl)amino]diazenyl]formamide Chemical compound C(CC)N(C=O)N=NNC=O PQFQPCRRNRVBFK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009826 distribution Methods 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
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- ZAKVZVDDGSFVRG-UHFFFAOYSA-N prop-1-en-2-ylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CC(=C)C1=CC=CC=C1 ZAKVZVDDGSFVRG-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Description
（産業上の利用分野）
本発明は、耐熱性メタクリル樹脂組成物の製造
方法に関し、より詳しくは透明で着色が少なく、
熱変形温度の高いメタクリル樹脂組成物の製造方
法に関する。
（従来技術）
一般に、メタクリル酸 チルを主成分とするメ
タクリル系樹脂は、光学的性質、耐候性等に極め
てすぐれ、かつ機械的性質、熱的性質ならびに成
形加工性などにおいてもバランスのとれた性能を
有しており、自動車部品、デイスプレー、照明部
品、看板、銘板、電気機器部品、光伝送機器部品
等の広い分野で使用されているが、耐熱性につい
ては必ずしも充分でなく、その用途展開が制約さ
れている分野もかなりあり、そのために耐熱性の
向上に対する要求が強く望まれている。
したがつて、メタクリル樹脂の耐熱性を向上さ
せる研究が広くおこなわれ、例えば特開昭56−
81322号公報記載のメチルメタクリレート、α−
メチルスチレン、スチレンおよび無水マレイン酸
を共重合させる方法は現実的に優れた方法であ
り、本発明者らは、すでにこれら樹脂について生
産性に優れた製造方法を提案した（特願昭59−
3317）。
しかし、現在市販されている無水マレイン酸に
は、熱着色を軽減し、熱安定性を向上させる目的
で安定剤を含有させており、そのためにメーカー
の違いや製造ロツトにより、得られる最終樹脂の
色調に差が認められ、原料調達や在庫管理上不便
であることがその後の検討で判明した。
また、無水マレイン酸使用重合反応物を、脱揮
工程で脱揮する際、残存する無水マレイン酸の量
が多いと装置が複雑化し、工業生産上デメリツト
となる。重合反応物中の残存無水マレイン酸の量
を減少させる方法として、無水マレイン酸に対す
るスチレンおよび／またはα−メチルスチレンの
割合を増加させて無水マレイン酸の共重合性を増
し、重合反応物中の残存無水マレイン酸量を減少
させる方法も考えられるが、単に単量体の組成を
変更しても機械的強度が低下し、曇価が増大する
問題がある。
（発明が解決しようとする問題点）
本発明の目的は、上述したような従来技術の問
題を克服し、メタクリル樹脂本来の優れた光学的
性質、機械的性質および成形加工性などの特性を
低下させることなく、生産性に優れた耐熱性メタ
クリル樹脂組成物を製造する方法を提供すること
にある。
（問題点を解決するための手段）
本発明の耐熱性メタクリル樹脂組成物の製造方
法は、メチルメタクリレート単位40〜97重量％、
無水マレイン酸単位１〜20重量％および芳香族ビ
ニル化合物単位２〜40重量％からなるメタクリル
樹脂組成物を製造するにあたり、まずメチルメタ
クリレートおよび無水マレイン酸を必須成分とす
る単量体混合物を30〜70％の重合率まで重合さ
せ、次いでその重合反応物に芳香族ビニル化合物
の少なくとも１種を必須成分とする単量体を添加
して、重合率が添加前よりも10％以上高くなるよ
うに重合させた後、揮発性成分を除去することを
特徴とする。
本発明の製造方法の特徴は、従来、組成の異な
る共重合体を混合すると得られる樹脂は透明性を
損うが、共重合体中に占めるメチルメタクリレー
ト、芳香族ビニル化合物および無水マレイン酸の
各単位の割合を限定するように、重合反応物中に
特定量の単量体を添加し、その反応物中の単量体
の組成を特定の割合として反応させることによ
り、残存無水マレイン酸が大巾に低下した着色性
の少ない、透明性の良い機械的性質に優れた耐熱
性メタクリル樹脂組成物が得られることにある。
本発明の方法によつて得られるメタクリル樹脂
組成物中のメチルメタクリレート単位は、メタク
リル樹脂本来の光学的、耐候性あるいは機械的性
質を保持するために必要な成分であり、組成物中
40〜97重量％の単位を含有することが必要であ
り、40重量％未満では耐候性等の物性が損なわ
れ、97重量％をこえると耐熱性の向上が望めなく
なる。また無水マレイン酸単位は耐熱性向上のた
めの必須で、その割合は１〜20重量％であり、１
重量％未満では耐熱性の向上が不足し、20重量％
をこえると組成を得るには、反応液中に残存する
無水マレイン酸が多くなりやすい。
また芳香族ビニル単量体は、主として無水マレ
イン酸の共重合性を向上させるための成分であつ
て、２重量％未満では無水マレイン酸の共重合性
を高めることはできず、また40重量％を越える場
合には光学的性質や機械的性質低下の原因とな
る。
本発明の方法によつて得られる組成物を構成す
る芳香族ビニル化合物単位としては、スチレン、
α−メチルスチレン、クロルスチレン、ビニルト
ルエン等から選ばれたもので構成できる。
芳香族ビニル化合物単位がスチレンまたはビニ
ルトルエンで構成される場合の組成物中の組成割
合としては、メチルメタクリレート単位45〜97重
量％、スチレンまたはビニルトルエン単位２〜35
重量％および無水マレイン酸単位１〜20重量％の
範囲である。また芳香族ビニル単位がスチレンお
よびα−メチルスチレン単位で構成される場合の
組成物中の組成割合としては、メチルメタクリレ
ート単位40〜97重量％、スチレン単位１〜20重量
％、α−メチルスチレン単位１〜20重量％および
無水マレイン酸単位１〜20重量％の範囲である。
本発明に係る組成物の製造方法は、重合工程と
揮発分脱揮工程の２つに大別できる。
重合工程では、まずメチルメタクリレートおよ
び無水マレイン酸を必須成分とする単量体混合物
ならびにメルカプタンよりなる重合原料を重合反
応器に供給して30〜70％の重合率まで重合し、次
いでその重合反応物に芳香族ビニル化合物の少な
くとも１種を必須成分とする単量体を添加して重
合し、重合率を添加前よりも10％高める工程であ
る。揮発分脱揮工程は、重合工程で生成した単量
体を含む重合反応物から未反応単量体その他の揮
発物を分離除去して樹脂組成物を得る工程であ
る。重合工程においては、メルカプタンを含むメ
チルメタクリレートおよび無水マレイン酸を必須
成分とする単量体混合物を重合反応器に供給して
重合する。供給するメチルメタクリレートの無水
マレイン酸に対する割合は、重合条件によつて一
概に決められないが、重量比で1.5〜50の範囲、
より好ましくは２〜20の範囲である。
本発明においては、重合反応器に供給する単量
体混合物は、メチルメタクリレートと無水マレイ
ン酸を必須成分とするものであるが、本発明の目
的を阻害しない範囲であれば、芳香族ビニル化合
物を添加することもでき、その量は、単量体混合
物中２〜35重量％である。
本発明では、重合度を調節する目的でメルカプ
タンを用いることもできる。使用されるメルカプ
タンとしてはアルキル基または置換アルキル基を
有する第１級、第２級、第３級メルカプタン、例
えばｎ−ブチル、イソプロピル、ｎ−オクチル、
ｎ−ドデシル、sec−ブチル、sec−ドデシル、
tert−ブチルメチルカプタン；芳香族メルカプタ
ン、例えばフエニルメルカプタン、チオクレゾー
ル、４−tert−ブチル−ｏ−チオクレゾール；チ
オグリコール酸とそのアルキルエステル；β−メ
ルカプトプロピオン酸とそのアルキルエステル；
エチレンチオグリコール等の如き炭素数２〜18の
メルカプタンが挙げられる。これらは単独でまた
は２種以上を組み合わせて用いることができる。
これらのメルカプタンのうちtert−ブチル、ｎ−
ブチル、ｎ−オクチルおよびｎ−ドデシルメルカ
プタンが好ましい。
メルカプタンの使用量は０〜1.0モル％の範囲
である。1.0モル％を超えると重合度が低下し、
製品の機械的性質が低下する。
メチルメタクリレートと無水マレイン酸からな
る単量体混合物は30〜70％の重合率となるまで重
合させる。重合率が30％未満では、経済性の点で
好ましくなく、組成分布の広い共重合体が得られ
やすく、また70％を越えると重合反応物の粘度が
高くなり、撹拌、混合上問題が生じる。
次に、本発明の重合工程では、上記で得られた
重合率30〜70％の混合反応生成物に、芳香族ビニ
ル化合物の少なくとも１種を必須成分とする単量
体を添加して、全体の重合率が添加前の重合率よ
りも、10％以上となるように重合する。添加後の
重合率の上昇が10％未満では、重合反応物中の未
反応無水マレイン酸の割合を低下させることがで
きにくく、又、経済性の点でも不利である。添加
する芳香族ビニル化合物の量は、特に限定されな
いが、重合反応物100重量部に対して、２〜100重
量部の範囲である。本発明の方法においては、芳
香族ビニル化合物を重合反応物に添加した時に、
重合反応物中の未反応単量体の組成割合が、メチ
ルメタクリレートを少なくとも50モル％含有し、
かつ無水マレイン酸のモル数をα、芳香族ビニル
のモル数をγとした時、γ／α＝1.2〜６となる
範囲にすることが、機械的性質、透明性および無
水マレイン酸の共重合性の観点よりよい結果を与
える。本発明においては、芳香族ビニル化合物と
して、前記したもののうち、スチレン、α−メチ
ルスチレン、ビニルトルエンから選ばれたものの
使用が特に好ましい、これらを使用する場合の、
無水マレイン酸に対する割合としては次式で示す
範囲がよい。
（β1＋1.5β2）＞1.8α
（1.5β1＋β2）＜6α
但し、α＝無水マレイン酸のモル数
β1＝スチレンまたはビニルトルエンのモル数
β2＝α−メチルスチレンのモル数
本発明の方法は、塊状重合または溶液重合法を
用いるのがよい。本発明の方法で溶液重合を採用
する際に使用される溶剤としては例えば、ベンゼ
ン、トルエン、キシレン、エチルベンゼン、アセ
トン、メチルエチルケトン、メチルイソブチルケ
トン、ジメチルホルムアミド、シクロヘキサノ
ン、テトラヒドロフラン等があげられる。これら
は１種または２種以上用いることができ、その使
用量は単量体全量に対して１〜50重量％の範囲で
ある。使用溶剤の量が50重量％をこえると工業的
生産性が低下する。
塊状重合および溶液重合における重合温度は、
芳香族ビニル化合物を重合反応物に添加する前は
50〜150℃、より好ましくは70〜140℃の範囲に保
つことが好ましい。50℃未満では多量の重合開始
剤を必要とし、150℃を越えると重合速度の管理
が複雑となり、また装置が複雑となる。一方芳香
族ビニル化合物添加後の重合温度は、重合反応物
中の残存無水マレイン酸が１重量％以上の場合に
は50〜150℃、１重量％未満の場合には50〜220℃
の範囲がよい。
本発明の方法は、単量体組成割合および重合条
件によつて重合開始剤を使用しなくても行いうる
が、ラジカル重合開始剤を用いて行うのが有利で
ある。使用されるラジカル重合開始剤としては、
例えばジ−tert−ブチルパーオキサイド、ジクミ
ルパーオキサイド、ジ−tert−ブチルパーフタレ
ート、ジ−tert−ブチル−パーベンゾエート、
tert−ブチルパーアセテート、２，５−ジメチル
−２，５−ジ（tert−ブチルパーオキシ）ヘキサ
ン、ジ−tert−アミルパーオキサイド、２，５−
ジメチル−２，５−ジ（tert−ブチルパーオキ
シ）ヘキサンおよびラウロイルパーオキサイド等
の有機過酸物；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−フエニルアゾ−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およびアゾビスイソブ
チロニトリル等のアゾ化合物があげられる。これ
らのラジカル重合開始剤は、１種または２種以上
組合せて使用できる。ラジカル重合開始剤の使用
量は、単量体全体に対して0.0001〜10重量％、好
ましくは0.005〜１重量％である。0.0001重量％
未満では重合速度が遅くて生産上不利であり、ま
た10重量％をこえると得られる樹脂の物性低下や
着色の原因となる。
本発明の方法において使用される重合装置とし
ては、特に限定されず、例えば槽型、塔型、管
型、ダクト型等の種々のものをあげることができ
るが、重合反応器内の重合反応性の均一性を保持
するという観点から充分な撹拌・混合を行うこと
のできる完全混合型反応槽、プラググロー型反応
器およびそれらの組合せたものから選ばれたもの
がよい。
これらの重合装置を用いる場合の重合は、回分
式または連続式のいずれも適用できる。
上述したような方法によつて製造された重合反
応物中には、未反応単量体および／または溶剤等
の揮発性成分を含有するので、引続き減圧下に加
熱して揮発物の大部分を分離除去するか、あるい
は溶解、再沈、乾燥の方法により所定量の残存単
量体含有量とする。揮発性物の除去に使用される
装置としては、例えば公知のベント押出機または
他のデボラタイザーがあげられる。揮発分離され
た樹脂組成物は、溶融状態でダイス等から押出さ
れて所望の形状に成形して使用される。
本発明の方法においては、品種および品質上の
要求から、必要に応じて他の少量のコモノマーの
併用、可塑剤、架橋剤、熱安定剤、着色剤、紫外
線吸収剤および離型剤等を添加することもでき
る。
（実施例）
以下、実施例により本発明をさらに詳しく説明
するが、実施例中の％は重量％を表わす。
なお、実施例中の樹脂組成物の物性評価は次の
方法を用いて行つた。
(1) 耐熱変形性
ASTM−Ｄ−1525によるビカート軟化温度
（VSP）（℃）を測定した。
(2) 全光線透過率
ASTM−Ｄ−1003
(3) 引張強度及び伸度
ASTM−Ｄ−638
(4) 組成分析
赤外分光光度、酸価滴定等より求めた。
(5) 射出成形板の色調および透明性
目視
(6) 固有粘度
25℃クロロホルム中で測定し求めた。
(7) メルトインデツクス
ASTM−Ｄ−1238
230℃、荷重3.8Kg
なお、実施例の表中で使用した記号は下記の化
合物を表わす。
MMA：メチルメタクリレート
α−MeSt：α−メチルスチレン
St：スチレン
MAH：無水マレイン酸
A1：ｎ−オクチルメルカプタン
A2：ｔ−ドデシルメルカプタン
B1：ラウロイルパーオキサイド
B2：１，１−ビス（ｔ−ブチルパーオキシ）−
３，３，５−トリメチルシクロヘキサン
B3：ジ−ｔ−ブチルパーオキサイド
C1：メチルエチルケトン
C2：エチルベンゼン
MA：メチルアクリレート
実施例１〜３、比較例１〜３
表１に示す組成の重合原液(1)を調整した。これ
を耐圧10Kgの撹拌機つき10の重合反応器に入
れ、実質的に酸素をのぞいた状況下で、表１に示
す温度と時間に保持して重合させ、次いで加圧ポ
ンプで表１に示す重合原液(2)を60℃に加温して追
加添加し、表１に示す条件でさらに重合させた。
重合終了10分前に140℃まで昇温した。引続き温
度180℃、真空圧10mmHgabs.に保持された揮発分
分離除去装置で処理し、重合物を得た。この重合
物を粉砕し、２つのベント孔を有する小型２軸押
出機に通して220〜245℃、ベント圧５mmHgabs.
の条件で脱揮押出しを行つて賦形した。このペレ
ツトを評価し、表２にその物性を示す。
なお、実施例４は、実施例１と同じ装置を用い
表２に示す重合原液(1)を表２の条件で重合し、次
いで重合原液(2)を添加して混合し、サンプリング
管を通じて両端にバルブがついた内径1.25cm×30
cmステンレス管に重合反応液をとり出し160℃で
４時間重合させた結果を示す。
(Industrial Application Field) The present invention relates to a method for producing a heat-resistant methacrylic resin composition, and more specifically, the present invention relates to a method for producing a heat-resistant methacrylic resin composition.
The present invention relates to a method for producing a methacrylic resin composition having a high heat distortion temperature. (Prior art) Generally, methacrylic resins containing methyl methacrylate as the main component have excellent optical properties, weather resistance, etc., and also have well-balanced performance in mechanical properties, thermal properties, and moldability. It is used in a wide range of fields such as automobile parts, display displays, lighting parts, signboards, nameplates, electrical equipment parts, and optical transmission equipment parts, but its heat resistance is not necessarily sufficient and its application development is limited. There are many fields in which heat resistance is restricted, and therefore there is a strong demand for improved heat resistance. Therefore, research to improve the heat resistance of methacrylic resin has been widely carried out;
Methyl methacrylate, α-, described in Publication No. 81322
The method of copolymerizing methylstyrene, styrene, and maleic anhydride is a practically excellent method, and the present inventors have already proposed a method for producing these resins with excellent productivity (Japanese Patent Application No.
3317). However, currently commercially available maleic anhydride contains stabilizers for the purpose of reducing thermal coloring and improving thermal stability, and for this reason, the final resin obtained varies depending on manufacturers and manufacturing lots. A subsequent study revealed that there was a difference in color tone, which was inconvenient in terms of raw material procurement and inventory management. Further, when a polymerization reaction product using maleic anhydride is devolatilized in the devolatilization step, if the amount of remaining maleic anhydride is large, the equipment becomes complicated, which is a disadvantage in industrial production. As a method for reducing the amount of residual maleic anhydride in the polymerization reaction product, the copolymerizability of maleic anhydride is increased by increasing the ratio of styrene and/or α-methylstyrene to maleic anhydride. Although a method of reducing the amount of residual maleic anhydride can be considered, simply changing the monomer composition has the problem of lowering mechanical strength and increasing haze value. (Problems to be Solved by the Invention) The purpose of the present invention is to overcome the problems of the prior art as described above, and to reduce the characteristics such as excellent optical properties, mechanical properties, and moldability inherent to methacrylic resin. It is an object of the present invention to provide a method for producing a heat-resistant methacrylic resin composition with excellent productivity without causing any problems. (Means for Solving the Problems) The method for producing a heat-resistant methacrylic resin composition of the present invention includes 40 to 97% by weight of methyl methacrylate units,
In producing a methacrylic resin composition comprising 1 to 20% by weight of maleic anhydride units and 2 to 40% by weight of aromatic vinyl compound units, first, a monomer mixture containing methyl methacrylate and maleic anhydride as essential components is mixed with 30 to 40% by weight of maleic anhydride units. Polymerize to a polymerization rate of 70%, then add a monomer containing at least one aromatic vinyl compound as an essential component to the polymerization reaction product so that the polymerization rate becomes 10% or more higher than before addition. It is characterized by removing volatile components after polymerization. A feature of the production method of the present invention is that conventionally, when copolymers with different compositions are mixed, the resulting resin loses transparency, but each of methyl methacrylate, aromatic vinyl compounds, and maleic anhydride, which occupy a copolymer, By adding a specific amount of monomer to the polymerization reaction product so as to limit the unit ratio, and reacting with the monomer composition in the reaction product at a specific ratio, residual maleic anhydride can be greatly reduced. The object of the present invention is to obtain a heat-resistant methacrylic resin composition with good transparency and excellent mechanical properties, with little coloration that deteriorates in width. The methyl methacrylate unit in the methacrylic resin composition obtained by the method of the present invention is a necessary component in order to maintain the optical, weather resistance, or mechanical properties inherent in the methacrylic resin, and is a necessary component in the composition.
It is necessary to contain 40 to 97% by weight of units; if it is less than 40% by weight, physical properties such as weather resistance will be impaired, and if it exceeds 97% by weight, no improvement in heat resistance can be expected. In addition, maleic anhydride units are essential for improving heat resistance, and the proportion thereof is 1 to 20% by weight.
If it is less than 20% by weight, the improvement in heat resistance will be insufficient.
In order to obtain a composition exceeding this amount, maleic anhydride tends to remain in the reaction solution in large amounts. Further, the aromatic vinyl monomer is a component mainly for improving the copolymerizability of maleic anhydride, and if it is less than 2% by weight, the copolymerizability of maleic anhydride cannot be improved, and if it is less than 2% by weight, the copolymerizability of maleic anhydride cannot be improved. If it exceeds this amount, it will cause deterioration of optical properties and mechanical properties. The aromatic vinyl compound units constituting the composition obtained by the method of the present invention include styrene,
It can be composed of one selected from α-methylstyrene, chlorostyrene, vinyltoluene, etc. When the aromatic vinyl compound unit is composed of styrene or vinyltoluene, the composition ratio in the composition is 45 to 97% by weight of methyl methacrylate units and 2 to 35% of styrene or vinyltoluene units.
% by weight and maleic anhydride units range from 1 to 20% by weight. In addition, when the aromatic vinyl unit is composed of styrene and α-methylstyrene units, the composition ratio in the composition is 40 to 97% by weight of methyl methacrylate units, 1 to 20% by weight of styrene units, and α-methylstyrene units. 1 to 20% by weight and 1 to 20% by weight of maleic anhydride units. The method for producing the composition according to the present invention can be roughly divided into two steps: a polymerization step and a volatile matter devolatilization step. In the polymerization process, a monomer mixture containing methyl methacrylate and maleic anhydride as essential components and a polymerization raw material consisting of a mercaptan are first fed into a polymerization reactor and polymerized to a polymerization rate of 30 to 70%, and then the polymerization reaction product is This is a step in which a monomer containing at least one aromatic vinyl compound as an essential component is added to polymerize the polymer, and the polymerization rate is increased by 10% compared to before the addition. The volatile matter devolatilization step is a step in which unreacted monomers and other volatiles are separated and removed from the polymerization reaction product containing monomers produced in the polymerization step to obtain a resin composition. In the polymerization step, a monomer mixture containing mercaptan-containing methyl methacrylate and maleic anhydride as essential components is supplied to a polymerization reactor and polymerized. The ratio of methyl methacrylate to maleic anhydride to be supplied cannot be determined unconditionally depending on the polymerization conditions, but it is in the range of 1.5 to 50 in terms of weight ratio,
More preferably, it is in the range of 2 to 20. In the present invention, the monomer mixture supplied to the polymerization reactor contains methyl methacrylate and maleic anhydride as essential components, but aromatic vinyl compounds may be added as long as they do not impede the purpose of the present invention. They can also be added in amounts of 2 to 35% by weight in the monomer mixture. In the present invention, mercaptan can also be used for the purpose of adjusting the degree of polymerization. The mercaptans used include primary, secondary and tertiary mercaptans having alkyl groups or substituted alkyl groups, such as n-butyl, isopropyl, n-octyl,
n-dodecyl, sec-butyl, sec-dodecyl,
tert-butyl methylcaptan; aromatic mercaptans such as phenylmercaptan, thiocresol, 4-tert-butyl-o-thiocresol; thioglycolic acid and its alkyl esters; β-mercaptopropionic acid and its alkyl esters;
Examples include mercaptans having 2 to 18 carbon atoms such as ethylene thioglycol. These can be used alone or in combination of two or more.
Among these mercaptans, tert-butyl, n-
Butyl, n-octyl and n-dodecyl mercaptan are preferred. The amount of mercaptan used ranges from 0 to 1.0 mol%. When it exceeds 1.0 mol%, the degree of polymerization decreases,
The mechanical properties of the product deteriorate. The monomer mixture consisting of methyl methacrylate and maleic anhydride is polymerized to a polymerization rate of 30 to 70%. If the polymerization rate is less than 30%, it is unfavorable from an economic point of view and a copolymer with a wide composition distribution is likely to be obtained, and if it exceeds 70%, the viscosity of the polymerization reaction product will increase, causing problems in stirring and mixing. . Next, in the polymerization process of the present invention, a monomer containing at least one aromatic vinyl compound as an essential component is added to the mixed reaction product obtained above with a polymerization rate of 30 to 70%, and the entire mixture is Polymerize so that the polymerization rate of is 10% or more than the polymerization rate before addition. If the increase in the polymerization rate after addition is less than 10%, it is difficult to reduce the proportion of unreacted maleic anhydride in the polymerization reaction product, and this is also disadvantageous from an economic point of view. The amount of the aromatic vinyl compound to be added is not particularly limited, but is in the range of 2 to 100 parts by weight based on 100 parts by weight of the polymerization reaction product. In the method of the present invention, when an aromatic vinyl compound is added to a polymerization reaction product,
The composition ratio of unreacted monomers in the polymerization reaction product contains at least 50 mol% of methyl methacrylate,
In addition, when the number of moles of maleic anhydride is α and the number of moles of aromatic vinyl is γ, it is important to keep γ/α = 1.2 to 6 in order to improve mechanical properties, transparency, and copolymerization of maleic anhydride. Gives better results from a sexual perspective. In the present invention, as the aromatic vinyl compound, it is particularly preferable to use a compound selected from styrene, α-methylstyrene, and vinyltoluene among those mentioned above.
The ratio to maleic anhydride is preferably in the range shown by the following formula. (β 1 +1.5β 2 )＞1.8α (1.5β 1 +β 2 )＜6α However, α = number of moles of maleic anhydride β 1 = number of moles of styrene or vinyltoluene β 2 = number of moles of α-methylstyrene The method of the present invention preferably uses bulk polymerization or solution polymerization. Examples of the solvent used when solution polymerization is employed in the method of the present invention include benzene, toluene, xylene, ethylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, cyclohexanone, and tetrahydrofuran. One or more of these can be used, and the amount used is in the range of 1 to 50% by weight based on the total amount of monomers. If the amount of solvent used exceeds 50% by weight, industrial productivity will decrease. The polymerization temperature in bulk polymerization and solution polymerization is
Before adding the aromatic vinyl compound to the polymerization reaction
It is preferable to maintain the temperature in the range of 50 to 150°C, more preferably 70 to 140°C. If it is less than 50°C, a large amount of polymerization initiator is required, and if it exceeds 150°C, it becomes complicated to control the polymerization rate and the equipment becomes complicated. On the other hand, the polymerization temperature after addition of the aromatic vinyl compound is 50 to 150°C if the residual maleic anhydride in the polymerization reaction product is 1% by weight or more, and 50 to 220°C if it is less than 1% by weight.
A range of is good. Although the method of the present invention can be carried out without using a polymerization initiator depending on the monomer composition ratio and polymerization conditions, it is advantageous to carry out the method using a radical polymerization initiator. The radical polymerization initiator used is
For example, di-tert-butyl peroxide, dicumyl peroxide, di-tert-butyl perphthalate, di-tert-butyl perbenzoate,
tert-butyl peracetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di-tert-amyl peroxide, 2,5-
Organic peroxides such as dimethyl-2,5-di(tert-butylperoxy)hexane and lauroyl peroxide; azobisisobutanol diacetate, 1,1-azobiscyclohexanecarbonitrile, 2-phenylazo-2,4 -dimethyl-
4-methoxyvaleronitrile, 2-cyano-2-
Examples include azo compounds such as propylazoformamide and azobisisobutyronitrile. These radical polymerization initiators can be used alone or in combination of two or more. The amount of the radical polymerization initiator used is 0.0001 to 10% by weight, preferably 0.005 to 1% by weight, based on the total monomer. 0.0001% by weight
If it is less than 10% by weight, the polymerization rate will be slow, which is disadvantageous in terms of production, and if it exceeds 10% by weight, it will cause a decrease in the physical properties of the resulting resin and cause discoloration. The polymerization apparatus used in the method of the present invention is not particularly limited, and various types such as a tank type, tower type, pipe type, and duct type can be mentioned, but the polymerization reactivity inside the polymerization reactor is From the viewpoint of maintaining the uniformity of the reaction mixture, it is preferable to use a complete mixing type reactor, a plug glow type reactor, or a combination thereof, which can perform sufficient stirring and mixing. When using these polymerization apparatuses, either a batch method or a continuous method can be applied to the polymerization. Since the polymerization reaction product produced by the method described above contains volatile components such as unreacted monomers and/or solvents, most of the volatiles are removed by subsequent heating under reduced pressure. The residual monomer content is adjusted to a predetermined amount by separating and removing, or by dissolving, reprecipitating, or drying. Equipment used to remove volatiles includes, for example, conventional vent extruders or other devolatizers. The resin composition that has been volatilized and separated is extruded in a molten state through a die or the like, and is used after being molded into a desired shape. In the method of the present invention, depending on the product variety and quality requirements, small amounts of other comonomers may be used in combination, plasticizers, crosslinking agents, heat stabilizers, colorants, ultraviolet absorbers, mold release agents, etc. may be added as necessary. You can also. (Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, in which % represents weight %. The physical properties of the resin compositions in Examples were evaluated using the following method. (1) Heat deformation resistance Vicatt softening temperature (VSP) (°C) was measured according to ASTM-D-1525. (2) Total light transmittance ASTM-D-1003 (3) Tensile strength and elongation ASTM-D-638 (4) Composition analysis Determined by infrared spectrophotometry, acid value titration, etc. (5) Color tone and transparency of injection molded plate Visual observation (6) Intrinsic viscosity Measured in chloroform at 25°C. (7) Melt index ASTM-D-1238 230°C, load 3.8Kg The symbols used in the tables of Examples represent the following compounds. MMA: Methyl methacrylate α-MeSt: α-methylstyrene St: Styrene MAH: Maleic anhydride A1: n-octyl mercaptan A2: t-dodecyl mercaptan B1: lauroyl peroxide B2: 1,1-bis(t-butylperoxy) )−
3,3,5-Trimethylcyclohexane B3: Di-t-butyl peroxide C1: Methyl ethyl ketone C2: Ethylbenzene MA: Methyl acrylate Examples 1 to 3, Comparative Examples 1 to 3 Polymerization stock solution (1) with the composition shown in Table 1 It was adjusted. This was placed in a 10 polymerization reactor equipped with a stirrer with a pressure resistance of 10 kg, and was polymerized by maintaining it at the temperature and time shown in Table 1 under conditions substantially excluding oxygen, and then using a pressure pump as shown in Table 1. The polymerization stock solution (2) was heated to 60°C, additionally added, and further polymerized under the conditions shown in Table 1.
The temperature was raised to 140°C 10 minutes before the end of polymerization. Subsequently, the mixture was treated with a volatile matter separation and removal device maintained at a temperature of 180° C. and a vacuum pressure of 10 mmHgabs, to obtain a polymer. This polymer was pulverized and passed through a small twin-screw extruder with two vent holes at a temperature of 220 to 245°C and a vent pressure of 5 mmHgabs.
It was shaped by devolatilizing extrusion under the following conditions. This pellet was evaluated and its physical properties are shown in Table 2. In Example 4, the polymerization stock solution (1) shown in Table 2 was polymerized under the conditions shown in Table 2 using the same equipment as in Example 1, and then the polymerization stock solution (2) was added and mixed, and the polymerization stock solution (2) was added and mixed, and the mixture was passed through a sampling tube at both ends. Inner diameter 1.25cm x 30 with valve attached
The polymerization reaction solution was taken out into a cm stainless steel tube and polymerized at 160°C for 4 hours.
【表】【table】
【表】【table】
【表】【table】
【表】
実施例 ５
反応容積40の均一撹拌槽からなる第一反応
器、引き続きスタテイツクミキサーとこれに接続
されたＬ／Ｄ＝20、内容積20のプラグフロー型
第２反応器と、脱揮装置として３段ペント付押出
機からなる装置を用いた。追加の重合原液(2)は、
スタテツクミキサーの直前で小型ポンプで連続的
に計量しながら加圧注入する方式をとつた。
重合原液(1)組成はメチルメタクリレート66部、
スチレン10部、α−メチルスチレン２部、無水マ
レイン酸12部、ラウロイルパーオキサイド0.4部、
ｎ−オクチルメルカプタン0.11部およびエチルベ
ンゼン35部とし、混合槽で窒素をバブリングさせ
ながら混合し実質的に酸素をのぞき、窒素シール
されたホールドタンクに移液し、ここから連続的
に上記の第１反応器に供給した。第１反応器を温
度80℃、平均滞留時間４時間で運転した。第１反
応器より取り出される重合反応物の重合率は51％
で、下記組成を有していた。
重合体組成：
メチルメタクリレート単位 67.4％
スチレン単位 14.4％
α−メチルスチレン単位 3.1％
無水マレイン酸単位 15.1％
次に、第１反応器より取り出される上記の重合
反応物に、メチルメタクリレート６部、スチレン
２部、α−メチルスチレン２部、ラウロイルパー
オキサイド0.01部、ｔ−ブチルパーオキシベンゾ
エート0.02部およびエチルベンゼン８部からなる
重合原液(2)を1.8／時間割合で添加して混合し、
この混合物を第２反応器に供給し、入口温度が80
℃、出口温度が140℃となるように徐々に昇温さ
せて重合した。定常状態（16時間後）における重
合反応物の重合率は90％であつた。
なお、第２反応器に供給した重合反応物中の未
反応単量体の組成は下記のものであつた。
メチルメタクリレート 70.4％
スチレン 11.4％
α−メチルスチレン 6.5％
無水マレイン酸 11.7％
第２反応器より取り出された重合反応物を、第
１ベント160℃、500Torr.；第２ベント210℃、
10Torr.；第３ベント230℃、5Torr.に保持した
脱揮押出機に通して揮発物を除去して、樹脂組成
物のペレツトを製造した。下記に得られた樹脂組
成物の物性を示す。
樹脂組成物の組成：
メチルメタクリレート単位 66.9％
スチレン単位 14.0％
α−メチルスチレン単位 4.7％
無水マレイン酸単位 14.4％
残存モノマー：
メチルメタクリレート 0.3％
スチレン
α−メチルスチレン
無水マレイン酸痕跡程度
固有粘度（dl／ｇ）：0.55
メルトインデツクス：2.1ｇ／10分
耐熱変形性（VSP）：136℃
一方、この重合条件において、重合原液(2)を添
加しないでくり返したところ、得られた樹脂組成
物の成形品に白い曇りが発生した。
（発明の効果）
以上において詳述したとおり、本発明の耐熱性
メタクリル樹脂組成物は、透明性、耐熱変形性、
帯色性、機械的性質等にすぐれるため、デイスプ
レー、照明部品、自動車部品、電機部品、光学デ
イスク、レンズ等の成形品、光学繊維、看板等の
シート材料などの用途に有用である。[Table] Example 5 A first reactor consisting of a uniformly stirred tank with a reaction volume of 40, followed by a static mixer and a plug flow type second reactor with L/D = 20 and an internal volume of 20 connected to this, and a desorption reactor. A device consisting of a three-stage pent extruder was used as a vaporization device. The additional polymerization stock solution (2) is
We adopted a method of pressurized injection while continuously metering with a small pump just before the static mixer. Polymerization stock solution (1) composition: 66 parts of methyl methacrylate;
10 parts of styrene, 2 parts of α-methylstyrene, 12 parts of maleic anhydride, 0.4 parts of lauroyl peroxide,
0.11 parts of n-octyl mercaptan and 35 parts of ethylbenzene were mixed in a mixing tank while bubbling nitrogen to substantially remove oxygen, and the liquid was transferred to a nitrogen-sealed hold tank, from which the above first reaction was continued. supplied to the vessel. The first reactor was operated at a temperature of 80° C. and an average residence time of 4 hours. The polymerization rate of the polymerization reaction product taken out from the first reactor is 51%.
It had the following composition. Polymer composition: Methyl methacrylate units 67.4% Styrene units 14.4% α-methylstyrene units 3.1% Maleic anhydride units 15.1% Next, 6 parts of methyl methacrylate and 2 parts of styrene were added to the above polymerization reaction product taken out from the first reactor. 1 part, α-methylstyrene 2 parts, lauroyl peroxide 0.01 part, t-butyl peroxybenzoate 0.02 part and ethylbenzene 8 parts polymerization stock solution (2) was added and mixed at a rate of 1.8/hour;
This mixture is fed to the second reactor and the inlet temperature is 80°C.
℃, and polymerization was carried out by gradually increasing the temperature so that the outlet temperature was 140℃. The polymerization rate of the polymerization reaction product in steady state (after 16 hours) was 90%. The composition of unreacted monomers in the polymerization reaction product supplied to the second reactor was as follows. Methyl methacrylate 70.4% Styrene 11.4% α-methylstyrene 6.5% Maleic anhydride 11.7% The polymerization reaction product taken out from the second reactor was heated to the first vent at 160°C, 500 Torr; the second vent at 210°C,
Volatile matter was removed by passing through a devolatilizing extruder maintained at 230° C. and 5 Torr. in the third vent to produce pellets of the resin composition. The physical properties of the resin composition obtained are shown below. Composition of the resin composition: Methyl methacrylate units 66.9% Styrene units 14.0% α-methylstyrene units 4.7% Maleic anhydride units 14.4% Residual monomers: Methyl methacrylate 0.3% Styrene α-methylstyrene Maleic anhydride traces Intrinsic viscosity (dl/ g): 0.55 Melt index: 2.1 g/10 min Heat deformation resistance (VSP): 136°C On the other hand, when this polymerization condition was repeated without adding the polymerization stock solution (2), the resulting resin composition was molded. A white cloudy appearance appeared on the product. (Effects of the Invention) As detailed above, the heat-resistant methacrylic resin composition of the present invention has transparency, heat deformation resistance,
Because of its excellent colorability and mechanical properties, it is useful for applications such as display displays, lighting parts, automobile parts, electrical parts, optical disks, molded products such as lenses, optical fibers, and sheet materials such as signboards.
Claims (1)
水マレイン酸単位１〜20重量％および芳香族ビニ
ル化合物単位２〜40重量％からなるメタクリル樹
脂組成物を製造するにあたり、まずメチルメタク
リレートおよび無水マレイン酸を必須成分とする
単量体混合物を30〜70％の重合率まで重合させ、
次いでその重合反応物に芳香族ビニル化合物の少
なくとも１種を必須成分とする単量体を添加して
重合率が添加前よりも10％以上高くなるように重
合させた後、揮発性成分を除去することを特徴と
する耐熱性メタクリル樹脂組成物の製造方法。1. In producing a methacrylic resin composition consisting of 40 to 97% by weight of methyl methacrylate units, 1 to 20% by weight of maleic anhydride units, and 2 to 40% by weight of aromatic vinyl compound units, first methyl methacrylate and maleic anhydride are essential. Polymerize the monomer mixture as a component to a polymerization rate of 30 to 70%,
Next, a monomer containing at least one type of aromatic vinyl compound as an essential component is added to the polymerization reaction product, and after polymerization is performed such that the polymerization rate is 10% or more higher than before addition, volatile components are removed. A method for producing a heat-resistant methacrylic resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27723484A JPS61151216A (en) | 1984-12-25 | 1984-12-25 | Production of heat-resistant methacrylate resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27723484A JPS61151216A (en) | 1984-12-25 | 1984-12-25 | Production of heat-resistant methacrylate resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61151216A JPS61151216A (en) | 1986-07-09 |
| JPH058724B2 true JPH058724B2 (en) | 1993-02-03 |
Family
ID=17580686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27723484A Granted JPS61151216A (en) | 1984-12-25 | 1984-12-25 | Production of heat-resistant methacrylate resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61151216A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2007008855A (en) * | 2003-10-18 | 2008-03-13 | Roehm Gmbh | Core and shell particle for modifying impact resistance of a mouldable poly(meth)acrylate material. |
| JPWO2005070978A1 (en) * | 2004-01-26 | 2007-12-27 | 新日鐵化学株式会社 | Optical resin material and optical prism or lens obtained therefrom |
-
1984
- 1984-12-25 JP JP27723484A patent/JPS61151216A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61151216A (en) | 1986-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1306828C (en) | Transparent heat-resistant styrene-base copolymer | |
| JPS60147417A (en) | Production of heat-resistant methacrylic resin | |
| KR20190013569A (en) | Copolymer and method for preparing the same | |
| JP4416190B2 (en) | Rubber-modified copolymer resin composition and process for producing the same | |
| KR101432597B1 (en) | Method for producing a thermoplastic having highly heat resistance and scratch resistance | |
| US5146535A (en) | Light-transmitting fiber | |
| CN114891147B (en) | Methyl methacrylate copolymer and preparation method and application thereof | |
| JPH0251514A (en) | Preparation of maleimide copolymer | |
| JPH058724B2 (en) | ||
| JP2592332B2 (en) | Maleimide copolymer and method for producing the same | |
| CN112126001B (en) | Methyl methacrylate polymer and preparation method thereof | |
| JP3858948B2 (en) | Method for producing styrene-methyl methacrylate polymer | |
| JPS5998156A (en) | Acrylic resin composition having excellent heat resistance and impact resistance | |
| JP2594289B2 (en) | Production method of transparent heat-resistant resin | |
| JP3472308B2 (en) | Impact resistant methacrylic resin | |
| JPH0616744A (en) | Rubber-modified copolymer resin composition and production thereof | |
| KR100409074B1 (en) | Method for preparing rubber-modified styrene transparent resin having superior fluidity | |
| KR20050015877A (en) | Continuous Process for Preparing High Impact Polystyrene Resin | |
| KR100415151B1 (en) | Transparent high impact polystyrenic resins composition with good mold release and their prodution method | |
| JP3297180B2 (en) | Maleimide copolymer | |
| KR20100045858A (en) | Method for producing a thermoplastic having highly heat resistance and scratch resistance and its components | |
| CN115160479B (en) | Methyl methacrylate polymer with chemical resistance and preparation method and application thereof | |
| CN101367902B (en) | High heat-resistant crushing-resistant copolymerization composition and continuous preparation method | |
| JPS60141708A (en) | Heat-resistant methacrylic resin and manufacture thereof | |
| JPH1087739A (en) | Methacrylic resin excellent in heat stability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |