JPH0254364B2 - - Google Patents
Info
- Publication number
- JPH0254364B2 JPH0254364B2 JP9507183A JP9507183A JPH0254364B2 JP H0254364 B2 JPH0254364 B2 JP H0254364B2 JP 9507183 A JP9507183 A JP 9507183A JP 9507183 A JP9507183 A JP 9507183A JP H0254364 B2 JPH0254364 B2 JP H0254364B2
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- maleic anhydride
- styrene
- polymerization
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 53
- 238000006116 polymerization reaction Methods 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 36
- 229920001577 copolymer Polymers 0.000 claims description 31
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 31
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000007870 radical polymerization initiator Substances 0.000 claims description 7
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 239000011347 resin Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 238000007872 degassing Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- GEJJECIDFXFUMI-UHFFFAOYSA-N dodecanethioic s-acid Chemical compound CCCCCCCCCCCC(S)=O GEJJECIDFXFUMI-UHFFFAOYSA-N 0.000 description 5
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000113 methacrylic resin Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- -1 K 11 /K 13 = 0.5 Chemical compound 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- OXOBLVKOVYDHQV-UHFFFAOYSA-N methyl 2-methylprop-2-enoate 3-(2-phenylethenyl)furan-2,5-dione Chemical compound COC(=O)C(C)=C.O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 OXOBLVKOVYDHQV-UHFFFAOYSA-N 0.000 description 3
- 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
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CUYHZUQBWIJJCT-UHFFFAOYSA-N 1-[(1-cyanocyclopentyl)diazenyl]cyclopentane-1-carbonitrile Chemical compound C1CCCC1(C#N)N=NC1(C#N)CCCC1 CUYHZUQBWIJJCT-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical class CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- JWKNCJFGBOQAQL-UHFFFAOYSA-N butyl dodecaneperoxoate Chemical group CCCCCCCCCCCC(=O)OOCCCC JWKNCJFGBOQAQL-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- NWADXBLMWHFGGU-UHFFFAOYSA-N dodecanoic anhydride Chemical compound CCCCCCCCCCCC(=O)OC(=O)CCCCCCCCCCC NWADXBLMWHFGGU-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical class CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 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
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- KOPQZJAYZFAPBC-UHFFFAOYSA-N propanoyl propaneperoxoate Chemical compound CCC(=O)OOC(=O)CC KOPQZJAYZFAPBC-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、メタクリル共重合体の製造方法に関
するものである。詳しく述べると、優れた耐熱
性、耐候性および透明性を有するメタクリル酸メ
チル―スチレン―無水マレイン酸共重合体の製造
方法に関するものである。
一般に、メタクリル酸メチルを主成分とするメ
タクリル樹脂は、その優れた耐候性および卓越し
た透明性により照明用カバー、自動車用部品、看
板、装飾品、雑貨等種々の分野で用いられている
が、耐熱性に関しては100℃程度が限界であり、
耐熱性を必要とする各分野からの要求には充分答
えられないのが現状である。例えば、自動車用部
品としてのテールランプの場合、従来のものに比
べてランプ自体の大型化あるいは照度増大からく
る発熱量の増加およびコスト低減に伴なう薄肉化
の両面から耐熱性の向上が要求され、また自動
車、二輪車(オートバイ)のメーターカバー、太
陽熱エネルギー利用の温水器カバー等直射日光下
での温度が非常に上昇する部品への用途の広がり
が期待されるので、水の沸点以上でも充分耐え得
るメタクリル樹脂の開発が期待されている。
従来、メタクリル樹脂の耐熱性向上を目的とし
て、メタクリル酸メチルとα―メチルスチレンを
共重合させる方法(米国特許第3135723号)、メタ
クリル酸メチル、α−メチルスチレンおよび無水
マレイン酸を共重合させる方法(特公昭45―
31953号、特公昭49―10156号)、メタクリル酸メ
チル、α―メチルスチレンおよびマレイミドを共
重合させる方法(特開昭48―95490号)等数多く
の方法が提案されている。
しかしながら、これらの方法はいずれも耐熱性
は向上するものの、重合速度が著しく遅かつた
り、重合率が上昇せずに高い重合収率が得られな
かつたり、また比較的短時間で効率よく重合体が
得られても、重合体の帯色が強く、透明性および
耐候性が低下するなど一長一短で、工業的生産が
極めて難かしく、実用化に至つていないのが現状
である。
このような問題点を解決するために、メタクリ
ル酸メチル36〜98.4重量%、無水マレイン酸1〜
40重量%およびスチレン0.6〜64重量%、かつ無
水マレイン酸に対するスチレンの割合が60重量%
以上からなる組成を有する単量体混合物を重合し
てなる共重合体であつて、残留単量体の合計が前
記共重合体に対して1.5重量%以下、メルトイン
デツクスが10g/10分以下であるメタクリル系樹
脂が提案されている(特開昭57―153008号)。し
かして、このようなメタクリル系樹脂は、前記範
囲内の各成分の混合物に、ラジカル重合開始剤を
配合したのち、該ラジカル重合開始剤の分解温度
付近の温度で反応を行なつて共重合体を得てい
る。しかしながら、このようなメタクル系樹脂
は、熱変形温度、ビツカース軟化点等の耐熱性が
不充分であり、帯色が強く、しかも全光線透過率
が低くかつヘイズが大きいという欠点があつた。
したがつて、本発明の目的は、新規なメタクリ
ル共重合体を提供することにある。本発明の他の
目的は、優れた耐熱性、耐候性および透明性を有
するメタクリル酸メチル―スチレン―無水マレイ
ン酸共重合体の製造方法を提供することにある。
これらの諸目的は、メタクリル酸メチル35〜90
重量%、スチレン5〜35重量%および無水マレイ
ン酸5〜30重量%からなる仕込組成でかつスチレ
ンの無水マレイン酸に対する割合がモル比で0.5
〜2.0の範囲からなる単量体混合物を、1価また
は2価アルコールの存在下に、10時間半減期温度
が55℃以上のラジカル重合開始剤を用い、該10時
間半減期温度より5℃以上高い温度条件で重合
し、かつ該温度での発熱ピークが3時間以内であ
ることを特徴とするメタクリル共重合体の製造方
法により達成される。
すなわち、本発明者らは、従来技術の長所なら
びに短所について充分検討したのち、前記メタク
リル酸メチル―スチレン―無水マレイン酸系につ
いて鋭意検討した結果、特定の単量体組成、重合
開始剤および重合条件を組合わせることによつて
メタクリル樹脂本来の特徴を損なうことなく耐熱
性を付与できることを見出し、本発明に至つたも
のである。
本発明の背景を詳細に述べると、スチレンと無
水マレイン酸の共重合体が高い熱変形温度を有す
ることから、共重合性単量体としてスチレンと無
水マレイン酸を併用することにより耐熱性の向上
が期待される。しかしながら、スチレンと無水マ
レイン酸は、通常のラジカル重合条件下では、ス
チレンM1、無水マレイン酸をM2とすると、共重
合の単量体反性比はK11/K12=0.04、K22/K21
=0.05(70℃、Polymer Handbook、AWiley―
Interscience Pnblication)程度であり、広い範
囲の単量体仕込組成に対してモル比でほぼ1:1
の交互共重合体を生成しやすいのに対し、一般的
には無水マレイン酸が他の共重合性単量体と反応
し難い傾向にある。これは、他の共重合性単量体
としてメタクリル酸メチルを用いた場合も例外で
はない。すなわち、メタクリル酸メチルをM3と
すると、K22/K23=0.01、K33/K32=3.5(60℃、
Polymer Handbook)であるから、メタクリル
酸メチルと無水マレイン酸とは共重合し難く、メ
タクリル酸メチルの単独重合体が生成しやすいこ
とを意味している。
また、メタクリル酸メチルとスチレンの場合
は、K11/K13=0.5、K33/K31=0.5(60℃、
Polymer Handbook)程度であり、比較的ラン
ダムに共重合することからメタクリル酸メチル―
スチレン―無水マレイン酸単量体混合組成におい
ては、スチレン―無水マレイン酸共重合体、メタ
クリル酸メチル―スチレン―無水マレイン酸三元
共重合体、そして仕込単量体組成でスチレンが無
水マレイン酸よりある限度以上過多の場合は、メ
タクリル酸メチル―スチレン共重合体も共存し、
均一な三元共重合体組成ではなく、上記共重合体
のブレンド組成を取りやすい。このことは、上記
共重合体同士が完全相溶系でない限り、スチレン
―無水マレイン酸共重合体の屈折率がnD=1.564、
メタクリル酸メチル―スチレン―無水マレイン酸
三元共重合体の屈折率は組成により異なるが、メ
タクリル酸メチルの単独重合体がnD=1.491であ
ることから、1.491<nD≪1.564となり、屈折率の
違いからヘイズが高く、透明性が低下することを
意味するとともに、メタクリル酸メチル単位をほ
とんど含まない重合体が存在することから耐候性
の低下および帯色の原因となる。
以上のことから、スチレン―無水マレイン酸共
重合体の生成をいかに調節し、効率よく三元共重
合体を得るかを解決したのが本発明方法である。
まず、本発明方法においては、共重合に供され
る単量体混合物がメタクリル酸メチル35〜90重量
%、スチレン5〜35重量%および無水マレイン酸
5〜35重量%からなる仕込組成で、かつスチレン
の無水マレイン酸に対する割合がモル比で0.5〜
2.0の範囲のもので、しかも少量の1価または2
価のアルコールを含有してなるものである。無水
マレイン酸は周知のように、スチレンとの相互作
用により共重合体の耐熱性を向上させるが5重量
%未満では充分な耐熱温度が得られないため、5
重量%以上含有することが必要であり、また30重
量%を越えると共重合体の耐熱性は向上するが、
ヘイズおよび帯色が非常に強くなり、耐候性の低
下も著しく好ましない。スチレンも同様であり、
5重量%未満では耐熱性向上には寄与せず、また
35重量%を越えると無水マレイン酸量との相関も
あるが、ヘイズおよび帯色が非常に強くなる。ま
た、スチレンの無水マレイン酸に対するモル比が
0.5未満になると耐熱性が低下し、無水マレイン
酸を多く用いる意味がないばかりか重合速度が低
下し、ヘイズが高くなる傾向を有する。一方、該
モル比が2.0を越えると、耐熱性が低下するとと
もに帯色が強くなる。以上のことから、スチレン
の無水マレイン酸に対するモル比は0.5〜2.0であ
り、好ましくは1.0〜1.5である。
本発明方法において1価または2価アルコール
を使用する理由は、その機構は不明ではあるが、
該アルコールの添加により帯色性、特にb値を低
下させるためであり、また各成分の添加割合の範
囲が広くなるからである。アルコールの添加量は
メタクリル酸メチル、スチレンおよび無水マレイ
ン酸よりなる単量混合物100重量部当り0.01〜3.0
重量部、好ましくは0.1〜1.0重量部である。この
ようなアルコールとしては、メタノール、エタノ
ール、n―プロパノール、イソプロパノール、n
―ブタノール、イソブタノール、sec―ブタノー
ル、tert―ブタノール、ペンタノール類、ヘキサ
ノール類、n―オクタノール、2―エチルヘキサ
ノール等の脂肪族一価アルコール、エチレングリ
コール、プロピレングリコール、1,3―プロピ
レングリコール、1,2―ブタンジオール、1,
4―ブタンジオール、1,6―ヘキサンジオー
ル、ジエチレングリコール、トリエチレングリコ
ール、ジプロピレングリコール、トリプロピレン
グリコール等の脂肪族二価アルコール、シクロヘ
キサノール等の脂環族一価アルコール、水素化ビ
ス、フエノールA等の脂環族二価アルコール、ベ
ンジルアルコール等の芳香族一価アルコール等が
ある。
重合開始剤としは、公知の過酸化物系開始剤、
アゾ系開始剤等も使用可能であるが、重合開始剤
の10時間半減期温度が55℃以上であることが必要
であり、好ましくは60〜80℃であり、例えばラウ
イルパーオキイド、ベンゾイルパーオキサイド、
プロピオノイルパーオキサイド、ターシヤリブチ
ルパーオキラウレート、ジクミルパーオキサイ
ド、ジターシヤリブチルパーオキサイド、キユメ
ンハイドロパーオキサイド等の過酸化物系開始
剤、2,2′―アゾビスイソブチロニトリル、1,
1′―アゾビス―1―シクロペンタノニトリル、ジ
メチル―2,2′―アゾビスイソブチレート、1,
1′―アゾビスシクロヘキサンカルボニトリル、
4,4′―アゾビス―4―シアノバレイツクアシツ
ド、2,2′―アゾビス―2―ベンジルプロピオニ
トリル等のアゾ系開始剤等が例示される。すなわ
ち、10時間半減期温度が55℃未満の場合は、得ら
れた共重合体のヘイズが急激に増加するととも
に、重合率の高いものが得られず耐熱性が向上し
ない。また、10時間半減期温度が100℃を越える
と、得られる共重合体は良好であるが、重合条件
として加圧重合等特殊な装置を必要とするので、
100℃以上の重合開始剤を用いる場合は、55℃以
上100℃未満のものと併用するのが好ましい。
なお、ここでいうラジカル重合開始剤の10時間
半減期温度とは、一定温度においてベンゼン溶媒
中の重合開始剤量が10時間で2分の1になるその
温度をいう。
重合温度としては60〜150℃と、通常のメタク
リル酸メチルの温度条件と同じでよいが、用いる
重合開始剤中、最も低い10時半減期温度を有する
ものを基準として、その温度よりも5℃以上高い
温度、好ましくは5〜45℃以上高い温度、最も好
ましくは10〜25℃以上高い温度で重合する必要が
ある。この温度より低い場合には、ヘイズが増加
し、透明性が低下し、帯色性、特にb値が増大
し、しかも熱変形温度、ビツカート軟化点等の耐
熱性が低下するという欠点を生じる。
また、上記条件を満す場合にも、重合開始剤量
の種類、量、温度条件等の相関により発熱ピーク
が3時間を越えると、ヘイズおよび帯色が増加す
るとともに、耐熱性および透明性が低下し、また
工業的生産性の面から好ましくない。したがつて
前記発熱ピークは3時間以内であることが必要で
あり、好ましくは0.5〜2.5時間である。
本発明を具体的に実施する方法としては、無水
マレイン酸が水と容易に反応してマレイン酸に変
化し重合体中に入りにくくなるばかりか、仮りに
入つたとしても耐熱性向上に寄与しないことか
ら、水の存在しない系での重合方法が要求され
る。非水溶媒中での重合は可能であるが、多量の
有機溶媒を必要とし、溶媒の回収、重合体の後処
理等に莫大な経費を要するので、工業的見地から
好ましくなく、塊状重合法および連続塊状重合法
が最も良好である。
なお、上記条件を満足する範囲において、通常
用いられる連鎖移動剤としてのメルカプタン類、
滑剤、紫外線吸収剤、安定剤等の添加も可能であ
る。
本発明方法によるメタクリル共重合体は、型内
で単量体混合物から注型重合により直接成形品を
得ることもできるが、前記重合条件下で得られる
メタクリル共重合体をペレツト化するなどして成
形材料としたのち、射出成形、押出成形等の成形
方法により所定の成形品を得ることもできる。
つぎに、実施例を挙げて本発明方法をさらに詳
細に説明するが、耐熱性の尺度としての熱変形温
度はASTM D648(荷重:264p.s.i.)、ビツカート
軟化点はASTM D1502で、また、ヘイズは
ASTM D1003で測定した。また、ハンターの測
色々差計によつてL値、a値およびb値を測定
し、着色度の程度を判定した。
実施例 1〜10
メタクリル酸メチル690g、スチレン170g、無
水マレイン酸140g(スチレンの無水マレイン酸に
対するモル比=1.14、以下、「S/Mモル比」と
略す。)および第1表に示す添加量および種類の
アルコールに、10時間半減期温度62℃のラウロイ
ルパーオキサイド3.0gおよびラウロイルメカプタ
ン2.5gを添加して均一に混合した。加熱炉中の2
板の熱板の間に2枚の強化ガラス板をセツトして
その間隔を軟質ポリ塩化ビニルをガスケツトとし
て7mmに保持し、熱電対をセツトして上記混合物
を注入し、脱気後75℃で加熱重合した。重合開始
後1時20分で発熱ピークに達した。ついで、30分
後130℃で2時間後重合を行なつて厚さ6mmの樹
脂板を得た。得られたメタクリル共重合体の物性
は、第1表のとおりであつた。
比較例 1
実施例1の方法において、アルコールを全く使
用しなかつた以外は同様の方法を行なつたとこ
ろ、第1表の結果を得た。
比較例 2
実施例1の方法においてメタノールを4.0PHR
とした以外は同様の方法を行なつたところ、第1
表の結果を得た。
比較例 3
メタクリル酸メチル700g、スチレン200gおよ
び無水マレイン酸100g(S/Mモル比=1.88)に
ラウロイルパーオキサイド3gおよびn―オクチ
ルメルカプタン3gを添加して均一に混合したの
ち、実施例1と同様なガラス板の間に注入し、脱
気後62℃で加熱重合した。重合開始後3時間50分
で発熱ピークに達し、ついで30分後110℃で3時
間後重合を行なつて厚さ6mmの樹脂板を得た。得
られたメタクリル共重合体の物性は、第1表のと
おりであつた。
比較例 4
比較例3の方法においてエチレングリコールを
単量体混合物に対し4.0PHR添加した以外は同様
の方法を行なつたところ第1表の結果を得た。
比較例 5
メタクリル酸メチル600g、スチレン200gおよ
び無水マレイン酸100g(S/Mモル比=0.94)に、
n―ブタノールを単量体混合物に対し4.0PHR、
ラウロイルパーオキサイド2.0gおよびラウロイル
メルカプタン2.5gを添加して均一混合したのち、
実施例1と同様なガラス板の間に注入し、脱気後
75℃で加熱重合した。重合開始後1時間25分で発
熱ピークに達し、ついで30分後128℃で2時間後
重合を行なつて厚さ6mmの樹脂板を得た。得られ
たメタクリル共重合体の物性は第1表のとおりで
あつた。
The present invention relates to a method for producing a methacrylic copolymer. Specifically, the present invention relates to a method for producing a methyl methacrylate-styrene-maleic anhydride copolymer having excellent heat resistance, weather resistance, and transparency. Generally, methacrylic resin whose main component is methyl methacrylate is used in various fields such as lighting covers, automobile parts, signboards, decorations, and miscellaneous goods due to its excellent weather resistance and outstanding transparency. Regarding heat resistance, the limit is around 100℃,
At present, it is not possible to fully meet the demands of various fields that require heat resistance. For example, in the case of tail lamps as automobile parts, improvements in heat resistance are required from the standpoint of both an increase in heat generation due to larger lamps or increased illuminance compared to conventional ones, and thinner walls to reduce costs. In addition, it is expected to be used in parts whose temperature rises significantly under direct sunlight, such as meter covers for automobiles and two-wheeled vehicles (motorcycles), and covers for water heaters that use solar thermal energy. There are high expectations for the development of methacrylic resins. Conventionally, for the purpose of improving the heat resistance of methacrylic resin, there have been methods of copolymerizing methyl methacrylate and α-methylstyrene (US Patent No. 3135723), and methods of copolymerizing methyl methacrylate, α-methylstyrene, and maleic anhydride. (Tokuko Showa 45-
A number of methods have been proposed, including a method of copolymerizing methyl methacrylate, α-methylstyrene and maleimide (Japanese Patent Application Laid-open No. 48-95490). However, although all of these methods improve heat resistance, the polymerization rate is extremely slow, the polymerization rate does not increase and a high polymerization yield cannot be obtained, and the polymerization process cannot be performed efficiently in a relatively short period of time. Even if it is obtained, industrial production is extremely difficult due to its advantages and disadvantages, such as the strong discoloration of the polymer and decreased transparency and weather resistance, so that it has not yet been put to practical use. In order to solve these problems, 36-98.4% by weight of methyl methacrylate and 1-98.4% by weight of maleic anhydride were added.
40% by weight and styrene 0.6-64% by weight, and the ratio of styrene to maleic anhydride is 60% by weight
A copolymer obtained by polymerizing a monomer mixture having the above composition, in which the total residual monomers are 1.5% by weight or less based on the copolymer, and the melt index is 10 g/10 minutes or less. A methacrylic resin that is However, such methacrylic resins are produced by blending a radical polymerization initiator into a mixture of each component within the above range, and then reacting at a temperature near the decomposition temperature of the radical polymerization initiator to form a copolymer. I am getting . However, such metallized resins have the drawbacks of insufficient heat resistance such as heat distortion temperature and Vickers softening point, strong color banding, low total light transmittance, and large haze. Therefore, an object of the present invention is to provide a novel methacrylic copolymer. Another object of the present invention is to provide a method for producing a methyl methacrylate-styrene-maleic anhydride copolymer having excellent heat resistance, weather resistance, and transparency. For these purposes, methyl methacrylate 35-90
% by weight, a charging composition consisting of 5-35% by weight of styrene and 5-30% by weight of maleic anhydride, and the molar ratio of styrene to maleic anhydride is 0.5.
~2.0, in the presence of a monohydric or dihydric alcohol, using a radical polymerization initiator with a 10-hour half-life temperature of 55°C or higher, and at 5°C or higher than the 10-hour half-life temperature. This is achieved by a method for producing a methacrylic copolymer, which is polymerized under high temperature conditions and exhibits an exothermic peak at the temperature within 3 hours. That is, after thoroughly considering the advantages and disadvantages of the prior art, the present inventors conducted extensive studies on the methyl methacrylate-styrene-maleic anhydride system, and found that the specific monomer composition, polymerization initiator, and polymerization conditions were It was discovered that heat resistance can be imparted without impairing the inherent characteristics of methacrylic resin by combining the two, and the present invention was developed based on this discovery. To explain the background of the present invention in detail, since a copolymer of styrene and maleic anhydride has a high heat distortion temperature, heat resistance can be improved by using styrene and maleic anhydride together as copolymerizable monomers. There is expected. However, under normal radical polymerization conditions, styrene and maleic anhydride have a monomer reactivity ratio of K 11 /K 12 = 0.04, K 22 where styrene M 1 and maleic anhydride are M 2 . /K 21
= 0.05 (70℃, Polymer Handbook, AWiley)
Interscience Pnblication), and the molar ratio is approximately 1:1 for a wide range of monomer charge compositions.
Maleic anhydride generally tends to be difficult to react with other copolymerizable monomers. This is no exception even when methyl methacrylate is used as the other copolymerizable monomer. That is, if methyl methacrylate is M 3 , K 22 /K 23 = 0.01, K 33 /K 32 = 3.5 (60℃,
Polymer Handbook), this means that methyl methacrylate and maleic anhydride are difficult to copolymerize, and a homopolymer of methyl methacrylate is likely to be produced. In addition, in the case of methyl methacrylate and styrene, K 11 /K 13 = 0.5, K 33 /K 31 = 0.5 (60℃,
Polymer Handbook), and because it copolymerizes relatively randomly, methyl methacrylate-
In the styrene-maleic anhydride monomer mixture composition, styrene-maleic anhydride copolymer, methyl methacrylate-styrene-maleic anhydride terpolymer, and in the charging monomer composition, styrene is more than maleic anhydride. If the amount exceeds a certain limit, methyl methacrylate-styrene copolymer also coexists.
Rather than a uniform terpolymer composition, it is easy to obtain a blend composition of the above copolymers. This means that unless the above copolymers are completely compatible with each other, the refractive index of the styrene-maleic anhydride copolymer is n D = 1.564,
The refractive index of the methyl methacrylate-styrene-maleic anhydride terpolymer differs depending on the composition, but since the homopolymer of methyl methacrylate has n D = 1.491, 1.491<n D ≪1.564, and the refractive index This difference means higher haze and lower transparency, and the presence of polymers that contain almost no methyl methacrylate units causes lower weather resistance and discoloration. Based on the above, the method of the present invention solves the problem of how to control the production of a styrene-maleic anhydride copolymer and efficiently obtain a terpolymer. First, in the method of the present invention, the monomer mixture to be subjected to copolymerization has a charging composition of 35 to 90% by weight of methyl methacrylate, 5 to 35% by weight of styrene, and 5 to 35% by weight of maleic anhydride, and The molar ratio of styrene to maleic anhydride is 0.5~
2.0 range, and a small amount of monovalent or divalent
It is made by containing alcohol of high valence. As is well known, maleic anhydride improves the heat resistance of copolymers through interaction with styrene, but if it is less than 5% by weight, sufficient heat resistance temperature cannot be obtained.
It is necessary to contain at least 30% by weight, and if it exceeds 30% by weight, the heat resistance of the copolymer will improve, but
Haze and discoloration become very strong, and weather resistance decreases significantly, which is undesirable. The same goes for styrene,
If it is less than 5% by weight, it will not contribute to improving heat resistance, and
If it exceeds 35% by weight, haze and color banding will become very strong, although there is a correlation with the amount of maleic anhydride. Also, the molar ratio of styrene to maleic anhydride is
When it is less than 0.5, heat resistance decreases and there is no point in using a large amount of maleic anhydride, and the polymerization rate tends to decrease and haze increases. On the other hand, if the molar ratio exceeds 2.0, the heat resistance will decrease and the color band will become stronger. From the above, the molar ratio of styrene to maleic anhydride is 0.5 to 2.0, preferably 1.0 to 1.5. The reason for using monohydric or dihydric alcohol in the method of the present invention is that although the mechanism is unknown,
This is because the addition of the alcohol lowers the coloring property, particularly the b value, and also because the range of addition ratios of each component becomes wider. The amount of alcohol added is 0.01 to 3.0 per 100 parts by weight of the monomer mixture consisting of methyl methacrylate, styrene, and maleic anhydride.
parts by weight, preferably 0.1 to 1.0 parts by weight. Such alcohols include methanol, ethanol, n-propanol, isopropanol, n-
-Aliphatic monohydric alcohols such as butanol, isobutanol, sec-butanol, tert-butanol, pentanols, hexanols, n-octanol, 2-ethylhexanol, ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,
Aliphatic dihydric alcohols such as 4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, alicyclic monohydric alcohols such as cyclohexanol, hydrogenated bis, phenol A and aromatic monohydric alcohols such as benzyl alcohol. As the polymerization initiator, known peroxide initiators,
Azo initiators can also be used, but it is necessary that the 10-hour half-life temperature of the polymerization initiator is 55°C or higher, preferably 60 to 80°C. For example, lauyl peroxide, benzoyl peroxide,
Peroxide initiators such as propionoyl peroxide, tertiary butyl peroxylaurate, dicumyl peroxide, ditertiary butyl peroxide, kyumene hydroperoxide, 2,2'-azobisisobutyro Nitrile, 1,
1'-azobis-1-cyclopentanonitrile, dimethyl-2,2'-azobisisobutyrate, 1,
1′-azobiscyclohexanecarbonitrile,
Examples include azo initiators such as 4,4'-azobis-4-cyanobarate acid and 2,2'-azobis-2-benzylpropionitrile. That is, when the 10-hour half-life temperature is less than 55° C., the haze of the obtained copolymer increases rapidly, and a product with a high polymerization rate cannot be obtained, resulting in no improvement in heat resistance. In addition, if the 10-hour half-life temperature exceeds 100°C, the resulting copolymer is good, but special equipment such as pressure polymerization is required for polymerization conditions.
When using a polymerization initiator with a temperature of 100°C or higher, it is preferable to use it in combination with a polymerization initiator with a temperature of 55°C or higher and lower than 100°C. The 10-hour half-life temperature of the radical polymerization initiator as used herein refers to the temperature at which the amount of the polymerization initiator in the benzene solvent is reduced to half in 10 hours at a constant temperature. The polymerization temperature may be 60 to 150°C, which is the same as the temperature conditions for normal methyl methacrylate, but the temperature should be 5°C higher than the one with the lowest 10:30 expiry temperature among the polymerization initiators used. It is necessary to carry out the polymerization at a temperature higher than 100°C, preferably at a temperature higher than 5°C to 45°C, most preferably at a temperature higher than 10°C to 25°C. If the temperature is lower than this, there will be disadvantages such as increased haze, decreased transparency, increased discoloration, especially b value, and decreased heat resistance such as heat distortion temperature and Bitchert softening point. In addition, even if the above conditions are met, if the exothermic peak exceeds 3 hours due to the correlation between the type and amount of polymerization initiator, temperature conditions, etc., haze and color band will increase, and heat resistance and transparency will decrease. This is also unfavorable from the viewpoint of industrial productivity. Therefore, the exothermic peak needs to occur within 3 hours, preferably 0.5 to 2.5 hours. As a concrete method of implementing the present invention, maleic anhydride easily reacts with water and changes to maleic acid, making it difficult to enter the polymer, and even if it does enter, it does not contribute to improving heat resistance. Therefore, a polymerization method in a water-free system is required. Polymerization in a non-aqueous solvent is possible, but it requires a large amount of organic solvent and requires enormous costs for recovering the solvent and post-processing the polymer, so it is not preferred from an industrial standpoint, and bulk polymerization and Continuous bulk polymerization is the best. In addition, within the range that satisfies the above conditions, mercaptans as commonly used chain transfer agents,
It is also possible to add lubricants, ultraviolet absorbers, stabilizers, etc. The methacrylic copolymer obtained by the method of the present invention can be directly molded by casting polymerization from a monomer mixture in a mold, but it is also possible to obtain a molded product directly by casting polymerization from a monomer mixture in a mold. After being made into a molding material, a predetermined molded product can be obtained by a molding method such as injection molding or extrusion molding. Next, the method of the present invention will be explained in more detail with reference to examples. The heat distortion temperature as a measure of heat resistance is ASTM D648 (load: 264 p.si), the Bitskart softening point is ASTM D1502, and the haze teeth
Measured using ASTM D1003. In addition, the L value, a value, and b value were measured using a Hunter colorimeter to determine the degree of coloration. Examples 1 to 10 690 g of methyl methacrylate, 170 g of styrene, 140 g of maleic anhydride (molar ratio of styrene to maleic anhydride = 1.14, hereinafter abbreviated as "S/M molar ratio") and the amounts added shown in Table 1 3.0 g of lauroyl peroxide with a 10-hour half-life temperature of 62°C and 2.5 g of lauroyl mecaptan were added to the alcohol of the same type and mixed uniformly. 2 in the heating furnace
Two tempered glass plates were set between the hot plates, the gap between them was maintained at 7 mm using a soft polyvinyl chloride gasket, a thermocouple was set, the above mixture was poured, and after degassing, the mixture was heated and polymerized at 75°C. did. An exothermic peak was reached at 1:20 after the start of polymerization. After 30 minutes, polymerization was carried out at 130° C. for 2 hours to obtain a resin plate with a thickness of 6 mm. The physical properties of the obtained methacrylic copolymer were as shown in Table 1. Comparative Example 1 The same method as in Example 1 was carried out except that no alcohol was used at all, and the results shown in Table 1 were obtained. Comparative Example 2 Using the method of Example 1, methanol was added at 4.0 PHR.
When I performed the same method except that
Obtained the results in the table. Comparative Example 3 After adding 3 g of lauroyl peroxide and 3 g of n-octyl mercaptan to 700 g of methyl methacrylate, 200 g of styrene, and 100 g of maleic anhydride (S/M molar ratio = 1.88) and mixing uniformly, the same procedure as in Example 1 was carried out. The mixture was poured between glass plates, and after degassing, polymerization was carried out by heating at 62°C. An exothermic peak was reached 3 hours and 50 minutes after the start of polymerization, and then, 30 minutes later, polymerization was carried out at 110° C. for 3 hours to obtain a resin plate with a thickness of 6 mm. The physical properties of the obtained methacrylic copolymer were as shown in Table 1. Comparative Example 4 The same method as in Comparative Example 3 was carried out except that 4.0 PHR of ethylene glycol was added to the monomer mixture, and the results shown in Table 1 were obtained. Comparative Example 5 To 600 g of methyl methacrylate, 200 g of styrene and 100 g of maleic anhydride (S/M molar ratio = 0.94),
4.0 PHR of n-butanol to the monomer mixture;
After adding 2.0 g of lauroyl peroxide and 2.5 g of lauroyl mercaptan and mixing uniformly,
Pour between the same glass plates as in Example 1, and after degassing
Polymerization was carried out by heating at 75°C. An exothermic peak was reached 1 hour and 25 minutes after the start of polymerization, and 30 minutes later, polymerization was carried out at 128° C. for 2 hours to obtain a resin plate with a thickness of 6 mm. The physical properties of the obtained methacrylic copolymer were as shown in Table 1.
【表】
実施例 11〜16
メタクリル酸メチル800g、スチレン100g、無
水マレイン酸100g(S/Mモル比=0.94)および
第2表に示す量および種類のアルコール類よりな
る混合物にラウロイルパーオキサイド2.5gおよび
ラウロイルメルカプタン12.5gを添加して均一に
混合したのち、実施例1と同様なガラス板の間に
注入し、脱気後加熱重合した。このときの加熱温
度および重合開始後の発熱ピークは、第2表に示
すとおりであつた。ついで30分後130℃で2時間
後重合を行なつて厚さ6mmの樹脂板を得た。得ら
れたメタクリル共重合体のb値は、第2表のとお
りであつた。
比較例 6
実施例14の方法において、アルコールを全く使
用しなかつた以外は同様の方法を行なつたとこ
ろ、第2表の結果を得た。[Table] Examples 11 to 16 2.5 g of lauroyl peroxide is added to a mixture consisting of 800 g of methyl methacrylate, 100 g of styrene, 100 g of maleic anhydride (S/M molar ratio = 0.94), and alcohols of the amounts and types shown in Table 2. After adding and uniformly mixing 12.5 g of lauroyl mercaptan, the mixture was poured between the same glass plates as in Example 1, degassed, and polymerized by heating. The heating temperature at this time and the exothermic peak after the start of polymerization were as shown in Table 2. After 30 minutes, polymerization was carried out at 130° C. for 2 hours to obtain a resin plate with a thickness of 6 mm. The b value of the obtained methacrylic copolymer was as shown in Table 2. Comparative Example 6 The same method as in Example 14 was carried out except that no alcohol was used at all, and the results shown in Table 2 were obtained.
【表】
リコー
ル
[Table] Ricoh
le
【表】
例6
実施例 17
メタクリル酸メチル750g、スチレン150gおよ
び無水マレイン酸100g(S/Mモル比=1.41)に、
メタノールを単量体混合物に対し0.3PHR、ラウ
ロイルパーオキサイド2.5gおよびラウロイルメル
カプタン2.5gを添加して均一混合したのち、実施
例1と同様なガラス板の間に注入し、脱気後80℃
で加熱重合した。重合開始後1時間50分で発熱ピ
ークに達し、ついで30分後130℃で1時間30分後
重合を行なつて厚さ6mmの樹脂板と得た。得られ
たメタクリル共重合体の物性は第3表のとおりで
あつた。ついで、この樹脂板を粉砕機で粗分砕、
ベント付き押出機でペレツト化し、このようにし
て得られたペレツトを射出成形して厚さ6.2mmの
樹脂板を得た。この樹脂板の物性は、第3表のと
おりであつた。
実施例 18
メタクリル酸メチル670g、スチレン180gおよ
び無水マレイン酸150g(S/Mモル比=1.13)に、
ベンジルアルコールを単量体混合物に対し、
0.2PHR、ラウロイルオキサイド2.5gおよびラウ
ロイルメルカプタン2.5gを添加して均一混合した
のち、実施例1と同様なガラス板の間に注入し、
脱気後80℃で加熱重合した。重合開始後1時間5
分で発熱ピークに達し、ついで30分後130℃で1
時間30分重合を行なつて厚さ6mmの樹脂板を得
た。得られたメタクリル共重合体の物性は、第3
表のとおりであつた。また、この樹脂板のペレツ
トを実施例17と同様にして射出成形したのちの厚
さ6.2mmの樹脂板の物性は、第3表のとおりであ
つた。
実施例 19
メタクリル酸メチル550g、スチレン240gおよ
び無水マレイン酸210g(S/Mモル比=1.08)に、
プロピレングリコールを単量体混合物に対し
0.5PHR、ラウロイルパーオキサイド2.5gおよび
ラウロイルメルカプタン2gを添加して均一混合
したのち、実施例1と同様なガラス板の間に注入
し、脱気後70℃で加熱重合した。重合開始後2時
間で発熱ピークに達し、ついで30分後125℃で2
時間後重合を行なつて厚さ6mmの樹脂板を得た。
得られたメタクリル共重合体の物性は、第3表の
とおりであつた。また、この樹脂板のペレツトを
実施例17と同様にして射出成形したのちの厚さ
6.2mmの樹脂板の物性は、第3表のとおりであつ
た。
比較例 7
実施例18の方法において、アルコールを全く使
用しなかつた以外は同様の方法を行なつたところ
第3表の結果を得た。[Table] Example 6
Example 17 To 750 g of methyl methacrylate, 150 g of styrene and 100 g of maleic anhydride (S/M molar ratio = 1.41),
After adding 0.3 PHR of methanol, 2.5 g of lauroyl peroxide, and 2.5 g of lauroyl mercaptan to the monomer mixture and mixing them uniformly, the mixture was poured between the same glass plates as in Example 1, and after degassing, the mixture was heated at 80°C.
Polymerization was carried out by heating. An exothermic peak was reached 1 hour and 50 minutes after the start of polymerization, and 30 minutes later, polymerization was carried out at 130°C for 1 hour and 30 minutes to obtain a resin plate with a thickness of 6 mm. The physical properties of the obtained methacrylic copolymer were as shown in Table 3. Next, this resin plate is coarsely crushed in a crusher,
The pellets were pelletized using a vented extruder, and the pellets thus obtained were injection molded to obtain a resin plate with a thickness of 6.2 mm. The physical properties of this resin plate were as shown in Table 3. Example 18 670 g of methyl methacrylate, 180 g of styrene and 150 g of maleic anhydride (S/M molar ratio = 1.13),
Benzyl alcohol to the monomer mixture,
After adding 0.2 PHR, 2.5 g of lauroyl oxide, and 2.5 g of lauroyl mercaptan and mixing them uniformly, the mixture was poured between the same glass plates as in Example 1.
After degassing, polymerization was carried out by heating at 80°C. 1 hour after the start of polymerization 5
The exothermic peak was reached in 1 minute, and then 1 at 130℃ after 30 minutes.
Polymerization was carried out for 30 minutes to obtain a resin plate with a thickness of 6 mm. The physical properties of the obtained methacrylic copolymer are as follows:
It was as shown in the table. Further, the physical properties of the resin plate having a thickness of 6.2 mm after injection molding the pellets of this resin plate in the same manner as in Example 17 were as shown in Table 3. Example 19 550 g of methyl methacrylate, 240 g of styrene and 210 g of maleic anhydride (S/M molar ratio = 1.08),
Propylene glycol to monomer mixture
After adding and uniformly mixing 0.5 PHR, 2.5 g of lauroyl peroxide, and 2 g of lauroyl mercaptan, the mixture was poured between the same glass plates as in Example 1, and after degassing, polymerization was carried out by heating at 70°C. An exothermic peak was reached 2 hours after the start of polymerization, and then 2 hours at 125℃ after 30 minutes.
After a period of time, polymerization was carried out to obtain a resin plate with a thickness of 6 mm.
The physical properties of the obtained methacrylic copolymer were as shown in Table 3. In addition, the thickness after injection molding of this resin plate pellet in the same manner as in Example 17 is
The physical properties of the 6.2 mm resin plate were as shown in Table 3. Comparative Example 7 The same method as in Example 18 was carried out except that no alcohol was used, and the results shown in Table 3 were obtained.
【表】
第1表から明らかなように、本発明方法におい
て、各単量体の仕込組成、ラジカル重合開始剤の
10時間半減期温度、該10時間半減期温度と重合温
度との温度差および発熱ピークまでの時間のいず
れか一つが前記範囲から外れても耐熱性、低帯色
性、透明性および低ヘイズ率の全てを満足するメ
タクリル共重合体は得られず、本発明方法によつ
て始めてこれらの要求を全て満足するメタクリル
共重合体が得られるのである。また、一価または
二価のアルコールを共存させて重合を行なうこと
により、帯色性、特にb値が著しく低いメタクリ
ル共重合体が得られるのである。[Table] As is clear from Table 1, in the method of the present invention, the charging composition of each monomer, the radical polymerization initiator
Even if any one of the 10-hour half-life temperature, the temperature difference between the 10-hour half-life temperature and the polymerization temperature, and the time to the exothermic peak is out of the above range, the heat resistance, low color discoloration, transparency, and low haze rate It is not possible to obtain a methacrylic copolymer that satisfies all of these requirements, and it is only through the method of the present invention that a methacrylic copolymer that satisfies all of these requirements can be obtained. Moreover, by carrying out polymerization in the coexistence of a monohydric or dihydric alcohol, a methacrylic copolymer with significantly low color chromatism, particularly a b value, can be obtained.
Claims (1)
5〜35重量%および無水マレイン酸5〜30重量%
からなる仕込組成でかつスチレンの無水マレイン
酸に対する割合がモル比で0.5〜2.0の範囲からな
る単量体混合物を、1価または2価アルコールの
存在下に、10時間半減期温度が55℃以上のラジカ
ル重合開始剤を用い、該10時間半減期温度より5
℃以上高い温度条件で重合し、かつ該温度での発
熱ピークが3時間以内であることを特徴とするメ
タクリル共重合体の製造方法。 2 10時間半減期温度より5〜45℃高い温度条件
である特許請求の範囲第1項に記載のメタクリル
共重合体の製造方法。 3 アルコールの存在量が単量体混合物100重量
部当り0.01〜3.0重量部である特許請求の範囲第
1項または第2項に記載の方法。 4 10時間半減期における発熱ピークが0.5〜2.5
時間である特許請求の範囲第1項ないし第3項の
いずれか一つに記載のメタクリル共重合体の製造
方法。 5 ラジカル重合開始剤の10時間半減期温度が60
〜80℃である特許請求の範囲第1項ないし第4項
のいずれか一つに記載のメタクリル共重合体の製
造方法。[Claims] 1. 35-90% by weight of methyl methacrylate, 5-35% by weight of styrene, and 5-30% by weight of maleic anhydride.
A monomer mixture with a charging composition of styrene and maleic anhydride in a molar ratio of 0.5 to 2.0 is heated in the presence of a monohydric or dihydric alcohol to a temperature with a half-life temperature of 55°C or higher for 10 hours. Using a radical polymerization initiator of
A method for producing a methacrylic copolymer, characterized in that the polymerization is carried out at a temperature higher than 0.degree. C., and the exothermic peak at the temperature is within 3 hours. 2. The method for producing a methacrylic copolymer according to claim 1, wherein the temperature is 5 to 45°C higher than the 10-hour half-life temperature. 3. The method according to claim 1 or 2, wherein the amount of alcohol present is 0.01 to 3.0 parts by weight per 100 parts by weight of the monomer mixture. 4 Exothermic peak at half-life of 10 hours is 0.5 to 2.5
3. The method for producing a methacrylic copolymer according to any one of claims 1 to 3, wherein the time is 100%. 5 The 10-hour half-life temperature of the radical polymerization initiator is 60
The method for producing a methacrylic copolymer according to any one of claims 1 to 4, wherein the temperature is 80°C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9507183A JPS59221315A (en) | 1983-05-31 | 1983-05-31 | Preparation of methacrylic copolymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9507183A JPS59221315A (en) | 1983-05-31 | 1983-05-31 | Preparation of methacrylic copolymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59221315A JPS59221315A (en) | 1984-12-12 |
JPH0254364B2 true JPH0254364B2 (en) | 1990-11-21 |
Family
ID=14127753
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9507183A Granted JPS59221315A (en) | 1983-05-31 | 1983-05-31 | Preparation of methacrylic copolymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59221315A (en) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4866136A (en) * | 1987-08-12 | 1989-09-12 | Pennwalt Corporation | Process for producing polymer bound hindered amine light stabilizers |
US4868246A (en) * | 1987-08-12 | 1989-09-19 | Pennwalt Corporation | Polymer bound UV stabilizers |
US5096977A (en) * | 1987-08-12 | 1992-03-17 | Atochem North America, Inc. | Process for preparing polymer bound UV stabilizers |
US4981914A (en) * | 1987-08-12 | 1991-01-01 | Atochem North America, Inc. | Polymer bound UV stabilizers |
US4857596A (en) * | 1987-08-12 | 1989-08-15 | Pennwalt Corporation | Polymer bound antioxidant stabilizers |
US5206378A (en) * | 1987-08-12 | 1993-04-27 | Elf Atochem North America, Inc. | Hydrazido functionalized 2-(2-hydroxyphenyl)-2h-benzotriazoles |
US5096974A (en) * | 1987-08-12 | 1992-03-17 | Atochem North America, Inc. | Process for preparing multipurpose polymer bound stabilizers and polymer bound stabilizer produced thereby |
US4857595A (en) * | 1987-08-12 | 1989-08-15 | Pennwalt Corporation | Polymer bound hindered amine light stabilizers |
US4863999A (en) * | 1987-08-12 | 1989-09-05 | Pennwalt Corporation | Multipurpose polymer bound stabilizers |
US4975489A (en) * | 1987-08-12 | 1990-12-04 | Atochem North America, Inc. | Process for preparing polymer bound hindered amine light stabilizers |
US4981917A (en) * | 1987-08-12 | 1991-01-01 | Atochem North America, Inc. | Process for preparing polymer bound antioxidant stabilizers |
US4981915A (en) * | 1987-08-12 | 1991-01-01 | Atochem North America, Inc. | Multipurpose polymer bound stabilizers |
US4956416A (en) * | 1988-08-18 | 1990-09-11 | Atochem North America, Inc. | Amino or hydrazino peroxides, derivatives and their uses |
US5272219A (en) * | 1988-08-18 | 1993-12-21 | Elf Atochem North America, Inc. | Process for preparing amino or hydrazino peroxides, derivatives and their uses |
US5037894A (en) * | 1988-11-07 | 1991-08-06 | Atochem North America, Inc. | Polymer bound flame retardants |
US5220015A (en) * | 1988-11-07 | 1993-06-15 | Elf Atochem North America, Inc. | Flame retardants compounds |
US5140070A (en) * | 1988-11-07 | 1992-08-18 | Elf Atochem North America, Inc | Compositions comprising polymer bond flame retardants |
JP2001270905A (en) | 2000-01-21 | 2001-10-02 | Mitsubishi Rayon Co Ltd | Heat-resistant methacrylic copolymer, manufacturing method therefor and optical element therefrom |
KR102354641B1 (en) * | 2014-08-11 | 2022-01-24 | 덴카 주식회사 | Copolymer suitable for improving heat resistance of methacrylic resin |
-
1983
- 1983-05-31 JP JP9507183A patent/JPS59221315A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS59221315A (en) | 1984-12-12 |
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