JPS59221314A - Preparation of methacrylic copolymer - Google Patents
Preparation of methacrylic copolymerInfo
- Publication number
- JPS59221314A JPS59221314A JP58095070A JP9507083A JPS59221314A JP S59221314 A JPS59221314 A JP S59221314A JP 58095070 A JP58095070 A JP 58095070A JP 9507083 A JP9507083 A JP 9507083A JP S59221314 A JPS59221314 A JP S59221314A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- styrene
- maleic anhydride
- temperature
- 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.)
- Granted
Links
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
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。DETAILED DESCRIPTION OF THE INVENTION 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.
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、雑貨等積
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渇水
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。Generally, methacrylic resin, whose main component is methyl methacrylate, is used in a wide variety of fields such as lighting covers, automobile parts, signboards, decorations, and miscellaneous goods due to its excellent weather resistance and outstanding transparency. , 100 for heat resistance
Celsius is the limit, and currently 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 a wide range of applications, such as meter covers for automobiles and two-wheeled vehicles (motorcycles), water heater covers that use solar thermal energy, and other parts whose temperature rises significantly under direct sunlight. There are high expectations for the development of methacrylic resins.
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３，１３５，７２３号）、メタクリル酸
メチル、ａ−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４５−５１９５５号、特公昭４
９−１０，１５６号）、メタクリル酸メチル、α−メチ
ルスチレンおよびマレイ鷹ドを共重合させる方法（特開
昭４８−９５、４９０号）等数多くの方法が提案されて
いる。Conventionally, for the purpose of improving the heat resistance of methacrylic resin, a method of copolymerizing methyl methacrylate and α-methylstyrene (U.S. Pat. No. 3,135,723), a method of copolymerizing methyl methacrylate, α-methylstyrene, and maleic anhydride have been proposed. Copolymerization method (Special Publication No. 45-51955, Special Publication No. 4
A number of methods have been proposed, including a method of copolymerizing methyl methacrylate, α-methylstyrene, and Malayan acid (Japanese Unexamined Patent Publication No. 48-95, No. 490).
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ったり、重合率が上昇
せずに高い重合収率が得られなかったり、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
業的生産が極めて離かしく、実用化に至っていないのが
現状である０
このような問題を解決するために、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α６〜６４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って
、残留単量体の合計が前記共重合体に対して１５重量％
以下、メルトインデックスが１０ ｆ／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−ｊ
５４００８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って共重合体を得ている。しか
しながら、このようなメタクリル系樹脂は、熱変形温度
、ビッカース軟化点等の耐熱性が不充分であり、着色が
強く、しかも全光線透過率が低くかつヘイズが大きいと
いう欠点があった。However, although 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, or the polymer cannot be efficiently produced in a relatively short time. Even if it is obtained, it has advantages and disadvantages such as strong color banding of the polymer and decreased transparency and weather resistance, making it extremely difficult to produce it industrially, and it has not yet been put into practical use. 36-98.4% by weight of methyl methacrylate, 1-40% by weight of maleic anhydride.
A copolymer obtained by polymerizing a monomer mixture having a composition of 6 to 64% by weight of styrene α and 60% by weight or more of styrene to maleic anhydride, wherein the total residual monomer is 15% by weight based on copolymer
Below, methacrylic resins with a melt index of 10 f/10 minutes or less have been proposed (Japanese Patent Application Laid-open No. 57-J
No. 54008). Therefore, 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. It has gained. However, such methacrylic resins have drawbacks such as insufficient heat resistance such as heat distortion temperature and Vickers softening point, strong coloring, low total light transmittance, and large haze.
したがって、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。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.
これらの賭目的は、メタクリル酸メチル５０〜８６重量
％、スチレン７〜２５重量％および無水マレイン酸７〜
２５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α５〜２．０の範囲から
なる単量体混合物を、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。These targets include 50-86% by weight of methyl methacrylate, 7-25% by weight of styrene and 7-25% by weight of maleic anhydride.
A monomer mixture with a charging composition of 25% by weight and a molar ratio of styrene to maleic anhydride in the range of α5 to 2.0 was mixed with a radical polymerization initiator having a 10-hour half-life temperature of 55°C or higher. This is achieved by a method for producing a methacrylic copolymer, which is characterized in that it is polymerized at a temperature 5°C or more higher than the 10-hour half-life temperature, and that the exothermic peak at the temperature is within 3 hours.
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
わせることによって、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
至ったものである。That is, the present inventors, after fully considering the advantages and disadvantages of the prior art, developed the above-mentioned methyl methacrylate.
As a result of intensive studies on the styrene-maleic anhydride system, it was discovered that by combining a specific monomer composition, polymerization initiator, and polymerization conditions, heat resistance could be imparted without impairing the inherent characteristics of methacrylic resin. This is what led to this.
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、スチレンをＭ！、無水マレイン酸をＭ２とす
ると、共重合の単量体反応性比はＫｌｌ／に１２ ＝
０．０４ 、Ｋ！□／に２１ ＝ α ０５（７０℃
ｚ Ｐｏｌｙｍ＠ｒ Ｈａｎｄｂｏｏｋ 、
ＡＷｉｌｅｙ−Ｉｎｔｅｒｉｃｉ＊ｎａ＠Ｐｕｂｌ
ｉｃａｔｉｏｎ ）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、Ｋ鵞ｉ／に＊ｎ ＝α０１ 、Ｋｍｓ／Ｋｓａ
＝ ３．５（６０℃、Ｐｏｌｙｍ＠ｒ Ｈａｎｄｂｏ
ｏｋ）であるから、メタクリル酸メチルと無水マレイン
酸とは共重合し蝋く、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。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 convert styrene into M! , maleic anhydride is M2, the monomer reactivity ratio of copolymerization is Kll/12 =
0.04, K! □ / 21 = α 05 (70℃
z Polym@r Handbook,
AWiley-Interici*na@Publ
cation ), and it is easy to produce alternating copolymers with a molar ratio of approximately 1:1 for a wide range of monomer charging compositions, whereas maleic anhydride is generally It tends to be difficult to react with monomers. This is no exception even when methyl methacrylate is used as the other copolymerizable monomer. That is, if methyl methacrylate is M3, then Ks/N *n = α01, Kms/Ksa
= 3.5 (60℃, Polym@r Handbo
ok), which means that methyl methacrylate and maleic anhydride copolymerize to form a waxy homopolymer of methyl methacrylate.
また、メタクリル酸メチルとスチレンの場合は、Ｋｌｌ
／に１３ ＝ Ｏ１５、Ｋｓｓ／Ｋｓ１＝α５（６０℃
、Ｐｏｌｙ−ｍ＠ｒ 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ｎｐ、＝１．５
６４、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ｎＰ、＝１．４９１であるこ
とから、１．４９１ ＜ ｎ ｐ ＜＜ 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。In addition, in the case of methyl methacrylate and styrene, Kll
/ to 13 = O15, Kss/Ks1 = α5 (60℃
, Poly-m@r Handbook), and copolymerizes relatively randomly, so in the mixed composition of methyl methacrylate-styrene-maleic anhydride monomers, styrene-maleic anhydride copolymer, methyl methacrylate - Styrene-maleic anhydride terpolymer, and if styrene exceeds maleic anhydride by a certain limit in the monomer composition, methyl methacrylate-styrene copolymer also coexists, forming a uniform ternary copolymer. It is easy to use a blend composition of the above copolymers instead of a polymer composition. This means that unless the above copolymers are completely compatible with each other, the refractive index of the styrene-maleic anhydride copolymer is np, = 1.5.
64. The refractive index of the methyl methacrylate-styrene-maleic anhydride terpolymer varies depending on the composition, but since the homopolymer of methyl methacrylate has nP = 1.491, 1.491 < n p << 1.564, which means high haze and reduced transparency due to the difference in refractive index, and the presence of a polymer that contains almost no methyl methacrylate units may lead to reduced weather resistance and discoloration. Cause.
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。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.
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５０〜８６重量％、スチレ
ン７〜２５重量％および無水マレイン酸７〜２５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、７重量％
未満では充分な耐熱温度が得られないため、７重量％以
上含有することが必要であり、また２５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くない。First, in the method of the present invention, the monomer mixture subjected to copolymerization contains 50 to 86% by weight of methyl methacrylate, 7 to 25% by weight of styrene, and 7 to 25% by weight of maleic anhydride.
The molar ratio of styrene to maleic anhydride is in the range of 0.5 to 2.0. As is well known, maleic anhydride improves the heat resistance of copolymers through interaction with styrene, but at 7% by weight
If it is less than 25% by weight, sufficient heat resistance temperature cannot be obtained, so it is necessary to contain it in an amount of 7% by weight or more.If it exceeds 25% by weight, the heat resistance of the copolymer will improve, but haze and color banding will be very strong. Therefore, the weather resistance decreases significantly, which is also undesirable.
スチレンも同様であり、７重量−未満では耐熱性向上に
は寄与せず、また２５５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。The same applies to styrene; if it is less than 7% by weight, it will not contribute to improving heat resistance, and if it exceeds 255% by weight, haze and color banding will become very strong, although there is a correlation with the amount of maleic anhydride. Furthermore, when the molar ratio of styrene to maleic anhydride 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, when the molar ratio exceeds 2.0, heat resistance decreases and color banding becomes strong.
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。From the above, the molar ratio of styrene to maleic anhydride is 0.5 to 2.0, preferably 1.0 to 1.
It is 5.
重合開始剤としては、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６０〜１００’Ｃであり、例えばラウロイルパーオ
午サイド、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、ターシャリブチルパーオキシラウレー
ト、ジクミルパーオキサイド、ジターシャリブチルパー
オキサイド、午ユメンハイド四パーオキサイド等の過酸
化物系開始剤、２．２’−アゾビスイソブチ四ニトリル
、１１′−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、１１′−
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ッド、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５
５℃未満の場合は、得られた共重合体のへイスが急激に
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。As the polymerization initiator, known peroxide-based initiators, azo-based initiators, etc. can also be used, but it is necessary that the 10-hour half-life temperature of the polymerization initiator is 55°C or higher, and preferably 60 to 100'C, such as lauroyl peroxide, benzoyl peroxide, propionoyl peroxide, tertiary butyl peroxylaurate, dicumyl peroxide, ditertiary butyl peroxide, and tertiary butyl peroxide, etc. peroxide initiator, 2,2'-azobisisobutytetranitrile, 11'-azobis-1-cyclopentanonitrile, dimethyl-2,2'-azobisisobutyrate, 11'-
Examples include azo initiators such as azobiscyclohexanecarbonitrile, 4,4'-azobis-4-cyanobalate acid, and 2,2'-azobis-2-benzylpropionitrile. That is, the 10-hour half-life temperature is 5
If the temperature is less than 5°C, the heis of the obtained copolymer will increase rapidly, and a high polymerization rate will not be obtained, resulting in no improvement in heat resistance.
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。If the 10-hour half-life temperature exceeds 100°C, the obtained copolymer will be good, but special equipment such as pressure polymerization will be required as polymerization conditions, so a polymerization initiator with a temperature of 100°C or higher will be used. In this case, it is preferable to use it in combination with a temperature of 55°C or higher and lower than 100°C.
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。Note that 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 becomes one-half in 10 hours at a constant temperature.
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時間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
〜４０℃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、ピッカート軟化点
等の耐熱性が低下するという欠点を生じる。The polymerization temperature may be 60 to 150°C, which is the same as the temperature conditions for normal methyl methacrylate, but the polymerization temperature should be 5°C higher than the one with the lowest 10-hour half-life temperature among the polymerization initiators used. or higher temperature, preferably 5
It is necessary to polymerize at a temperature of -40°C or more, most preferably 10-25°C or more. If the temperature is lower than this, there will be disadvantages such as increased haze, decreased transparency, increased coloration, especially b value, and decreased heat resistance such as heat distortion temperature and Pickert softening point.
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。したがって、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α５〜２．５時間であ
る。In addition, even if the above conditions are met, the type of polymerization initiator amount,
If the exothermic peak exceeds 3 hours due to the correlation between amount, temperature conditions, etc., haze and discoloration will increase, heat resistance and transparency will decrease, and this is not preferred from the viewpoint of industrial productivity. Therefore, the exothermic peak needs to occur within 3 hours, preferably α5 to 2.5 hours.
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が、仮りに入ったとしても耐熱性
向上に寄与しないことがら、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。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, but 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.
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。In addition, within the range that satisfies the above conditions, it is also possible to add commonly used mercaptans as chain transfer agents, lubricants, ultraviolet absorbers, stabilizers, and the like.
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
ペレッ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。The methacrylic copolymer obtained by the method of the present invention can be directly formed into a molded product by cast 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 article can be obtained by a molding method such as injection molding or extrusion molding.
？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
Ｄ６４Ｂ （荷重： ２６４ ｐ、ｓ、ｉ、）、ピッカ
ート軟化点はＡＳＴＭ Ｄ１５２５で、またヘイズはＡ
ＳＴＭ Ｄ１００５で測定した。また、ハンターの測
色々差計によってＬ値、ａ値およびｂ値を測定し、着色
度の程度を判定した。? Next, the method of the present invention will be explained in more detail with reference to examples.
D64B (load: 264 p, s, i,), Pickert softening point is ASTM D1525, and haze is A
Measured with STM D1005. In addition, the L value, a value, and b value were measured using a Hunter colorimeter to determine the degree of coloration.
実施例１
メタクリル酸メチル６７ Ｏｆ、スチレン１８０ｔおよ
び無水マレイン酸１５ｏｙ（スチレンの無水マレイン酸
に対するモル比＝１．７３、以下「８７Ｍモル比」と略
す。）に、１０時間半減期温度６２℃のラウロイルパー
オキサイド２．５ｆおよびラウロイルメルカプタン２．
５ｆ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板の強化ガラス板をセットしてその間隔を軟質
ポリ塩化ビニルをガスケットとして７闘に保持し、熱電
対をセットして上記混合物を注入し、脱気後８０℃で加
熱重合した。重合開始後：井欄ら５分で発熱ピークに達
した。ついで、５０分後１３０℃で１時間３０分後重合
して厚さ６酪の樹脂板を得た。Example 1 67 Of methyl methacrylate, 180 t of styrene, and 15 oy of maleic anhydride (molar ratio of styrene to maleic anhydride = 1.73, hereinafter abbreviated as "87 M molar ratio") were added with a half-life temperature of 62° C. for 10 hours. Lauroyl peroxide 2.5f and lauroyl mercaptan 2.
5f was added and mixed uniformly. Two tempered glass plates are set between two hot plates in a heating furnace, the gap between them is maintained at 7 mm using soft polyvinyl chloride as a gasket, a thermocouple is set, the above mixture is injected, and the mixture is degassed. Thereafter, heating polymerization was carried out at 80°C. After initiation of polymerization: An exothermic peak was reached in 5 minutes. Then, after 50 minutes, polymerization was carried out at 130° C. for 1 hour and 30 minutes to obtain a resin plate with a thickness of 6 mm.
得られたメタクリル共重合体の物性は、第１表のとおり
であった。The physical properties of the obtained methacrylic copolymer were as shown in Table 1.
実施例２
メタクリル酸メチル７２０？、スチレン１５０２および
無水マレイン酸１ｓｏｒ（Ｓ／ａモル比＝１．０９）に
ラウロイルパーオキサイド２．５７およびラウロイルメ
ルカプタン２．５２を添加して均一に混合したのち、実
施例１と同様の方法で重合を行なって厚さ６闘の樹脂板
を得た。このときの発熱ピークは重合開始後１時間２０
分であった。Example 2 Methyl methacrylate 720? , 2.57 lauroyl peroxide and 2.52 lauroyl mercaptan were added to styrene 1502 and maleic anhydride 1 sor (S/a molar ratio = 1.09) and mixed uniformly, followed by the same method as in Example 1. Polymerization was carried out to obtain a resin plate with a thickness of 6mm. The exothermic peak at this time was 1 hour after the start of polymerization.
It was a minute.
得られたメタクリル共重合体の物性は、第１表のとおり
であった。The physical properties of the obtained methacrylic copolymer were as shown in Table 1.
実施例３
メタクリル酸メチル７５０ ｆ、スチレン１５０ｆおよ
び無水マレイン酸１ｏｏｒ（ｓ／Ｍモル比＝１．４１）
にラウロイルパーオキサイド２．５ｖおよびラウロイル
メルカプタン２．５ｆを添加して均一に混合したのち、
実施例１と同様の方法で重合を行なって厚さ６朋の樹脂
板を得た。このときの発熱ピークは重合開始後１時間４
５分であった。Example 3 Methyl methacrylate 750 f, styrene 150 f and maleic anhydride 1 oor (s/M molar ratio = 1.41)
After adding 2.5v of lauroyl peroxide and 2.5f of lauroyl mercaptan to and mixing uniformly,
Polymerization was carried out in the same manner as in Example 1 to obtain a resin plate with a thickness of 6 mm. The exothermic peak at this time was 1 hour after the start of polymerization.
It was 5 minutes.
得られたメタクリル共重合体の物性は、第１表のとおり
であった。The physical properties of the obtained methacrylic copolymer were as shown in Table 1.
実施例４
メタクリル酸メチル６５Ｏｆ、スチレン２００Ｖおよび
無水マレイン酸１５０ｆ（Ｓ／Ｍモル比＝１２６）にラ
ウロイルパーオキサイド２ ｔ Ｎ １０時間半減期温
度１２４℃のジターシャリブチルパーオキサイド１ｆお
よびラウロイルメルカプタン２．５ｆ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８７℃で加熱重合した。重合開始後１時間で発
熱ピークに達し、ついで３０分後１３０℃で２時間後重
合を行なって厚さ６酩の樹脂板を得た。得られたメタク
リル共重合体の物性は、第１表のとおりであった。Example 4 Methyl methacrylate 65Of, styrene 200V and maleic anhydride 150f (S/M molar ratio = 126) with lauroyl peroxide 2tN 10 hours ditert-butyl peroxide 1f and lauroyl mercaptan with half-life temperature 124°C 2. After adding 5f and mixing uniformly, the mixture was poured between glass plates similar to those in Example 1, and after degassing, polymerization was carried out by heating at 87°C. An exothermic peak was reached 1 hour after the start of polymerization, and then 30 minutes later, 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.
実施例５
メタクリル酸メチル７７０ ｔ、スチレン１１０２およ
び無水マレイン酸１２０９（Ｓ／Ｍモル比＝Ｏ，ＳＳ）
に、１０時間半減期温度７４℃のベンゾイルパーオキサ
イド１ｆ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８５℃で加熱重合し
た。重合開始後１時間４０分で発熱ピークに達し、つい
で３０分後１２０℃で２時間後重合を行なって厚さ６鱈
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表のとおりであった。Example 5 Methyl methacrylate 770 t, styrene 1102 and maleic anhydride 1209 (S/M molar ratio = O, SS)
After adding benzoyl peroxide 1f having a half-life temperature of 74° C. for 10 hours and mixing uniformly, the mixture was poured between the same glass plates as in Example 1, and after degassing was heated and polymerized at 85° C. An exothermic peak was reached 1 hour and 40 minutes after the start of polymerization, and then, 30 minutes later, polymerization was carried out at 120° 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.
実施例６
メタクリル酸メチル７００ ｆ、スチレン２００２およ
び無水マレイン酸１００Ｆ（８／Ｍモル比＝ １．８８
）にラウロイルパーオキサイド２．Ｏｆおよびラウロ
イルメルカプタン２．５２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７
５℃で加熱重合した。重合開始後２時間４６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
行なって厚さ６ ｍｍ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表のとおりであった。Example 6 Methyl methacrylate 700f, styrene 2002 and maleic anhydride 100F (8/M molar ratio = 1.88
) with lauroyl peroxide 2. After adding 2.52 kg of Of and lauroyl mercaptan and mixing uniformly, the mixture was poured between the same glass plates as in Example 1, and after degassing,
Polymerization was carried out by heating at 5°C. An exothermic peak was reached 2 hours and 46 minutes after the start of polymerization, and then 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.
実施例７
メタクリル酸メチル６００ ｆ、スチレン２００２およ
び無水マレイン酸２００Ｆ（８／Ｍモル比＝α９４）に
、ラウロイルパーオキサイド２．Ｏｆおよびラウロイル
メルカプタン２．５ｆを添加して均一に混合したのち、
実施例６と同様の方法で重合を行なって厚さ６鴎の樹脂
板を得た。このときの発熱ピークは重合開始後１時間１
３分であった。Example 7 Methyl methacrylate 600F, styrene 2002 and maleic anhydride 200F (8/M molar ratio = α94) were mixed with lauroyl peroxide 2. After adding Of and 2.5 f of lauroyl mercaptan and mixing uniformly,
Polymerization was carried out in the same manner as in Example 6 to obtain a resin plate with a thickness of 6 mm. The exothermic peak at this time was 1 hour after the start of polymerization.
It was 3 minutes.
得られたメタクリル共重合体の物性は、第１表のとおり
であった。The physical properties of the obtained methacrylic copolymer were as shown in Table 1.
実施例８
メタクリル酸メチル７００ ｆ、スチレン２００？およ
び無水マレイン酸１１００１（８７モル比＝１ａａ）に
、１０時間半減期温度６６℃の２，２′−アゾビスイソ
ブチロニトリルα２ｆおよびラウロイルメルカプタン２
．５ｆを添加して均一に混合したのち、実施例６と同様
の方法で重合を行なって厚さ６ａｓの樹脂板を得た。こ
のときの発熱ピークは重合開始後１時間２４分であった
。得られたメタクリル共重合体の物性は、第１表のとお
りであった。Example 8 Methyl methacrylate 700f, styrene 200? and maleic anhydride 11001 (87 molar ratio = 1aa), 2,2'-azobisisobutyronitrile α2f and lauroyl mercaptan 2 with a 10-hour half-life temperature of 66°C.
．． After adding 5f and mixing uniformly, polymerization was carried out in the same manner as in Example 6 to obtain a resin plate with a thickness of 6as. The exothermic peak at this time was 1 hour and 24 minutes after the start of polymerization. The physical properties of the obtained methacrylic copolymer were as shown in Table 1.
実施例９
メタクリル酸メチル６７０９．スチレン１７０Ｖおよび
無水マレイン酸１６ｏｔ（ｓ／Ｍモル比＝ｔｏｏ）に、
２．２′−アゾビスイソブチロニトリＩＬ１０．５ Ｆ
およびラウロイルメルカプタン２ｆ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８０℃で加熱重合した。重合開始後１時間４０分
で発熱ピークに達し、ついで３０分後１２５℃で２時間
後重合を行なって厚さ６ｆｌ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表のとおりであった
。Example 9 Methyl methacrylate 6709. Styrene 170V and maleic anhydride 16ot (s/M molar ratio = too),
2.2'-azobisisobutyronitri IL10.5 F
and lauroyl mercaptan 2f were added and mixed uniformly, and then poured between the same glass plates as in Example 1,
After degassing, polymerization was carried out by heating at 80°C. An exothermic peak was reached 1 hour and 40 minutes after the start of polymerization, and 30 minutes later, polymerization was carried out at 125° C. for 2 hours to obtain a resin plate with a thickness of 6 fl. The physical properties of the obtained methacrylic copolymer were as shown in Table 1.
実施例１０
メタクリル酸メチル５５０ ｆｚスチレン２４０Ｖおよ
び無水マレイン酸２１０ｆ（Ｓ／Ｍモル比＝ １．０８
）に、ラウロイルパーオキサイド２．５ｖおよびラウ
ロイルメルカプタン２ｆ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７０
℃で加熱重合した。重合開始後２時間２０分で発熱ピー
クに達し、ついで３０分後１２５℃で２時間後重合を行
なって厚さ６關の樹脂板を得た。得られたメタクリル共
重合体の物性は、第１表のとおりであった。Example 10 Methyl methacrylate 550fz styrene 240V and maleic anhydride 210f (S/M molar ratio = 1.08
), 2.5v of lauroyl peroxide and 2f of lauroyl mercaptan were added and mixed uniformly, and then poured between the same glass plates as in Example 1, and after degassing,
Polymerization was carried out by heating at ℃. An exothermic peak was reached 2 hours and 20 minutes after the start of polymerization, and then, 30 minutes later, polymerization was carried out at 125° 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.
比較例１
メタクリル酸メチル７００ ｆ、スチレン２００ｔおよ
び無水マレイン酸１００ｆに、ラウロイルパーオキサイ
ド３２およびｎ−オクチルメルカプタン３ｔ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時間後重合を行なって厚さ６闘の樹脂板を得た。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
あった。Comparative Example 1 To 700 f of methyl methacrylate, 200 tons of styrene, and 100 f of maleic anhydride, 32 tons of lauroyl peroxide and 3 tons of n-octyl mercaptan were added and mixed uniformly, and then poured between the same glass plates as in Example 1. 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 110°C after 30 minutes.
After 3 hours, polymerization was carried out to obtain a resin plate with a thickness of 6 cm. The physical properties of the obtained methacrylic copolymer were as shown in Table 1.
比較例２
メタクリル酸メチル６００ ｆ、スチレン２０Ｏｆおよ
び無水マレイン酸２００ｆに、ラウロイルパーオキサイ
ド３ｆおよびｎ−オクチルメルカプタン３ｆを添加して
均一に混合したのち、比較例１と同様な方法で重合を行
なって厚さ６ｕの樹脂板を得た。このときの発熱ピーク
は重合開始後２時間３０分であった。得られたメタクリ
ル共重合体の物性は、第１表のとおりであった。Comparative Example 2 To 600 f of methyl methacrylate, 20 Of styrene, and 200 F of maleic anhydride, 3 F of lauroyl peroxide and 3 F of n-octyl mercaptan were added and mixed uniformly, and then polymerization was carried out in the same manner as in Comparative Example 1. A resin plate with a thickness of 6u was obtained. The exothermic peak at this time was 2 hours and 30 minutes after the start of polymerization. The physical properties of the obtained methacrylic copolymer were as shown in Table 1.
比較例３
メタクリル酸メチル４５０ ｆ、スチレン３００Ｖおよ
び無水マレイン酸２５ｏ ｙ （ｓ ／Ｍモル比＝１．
１３）に、ラウロイルパーオキサイド２２およびラウロ
イルメルカプタン２ｆ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８０℃
に加熱重合した。重合開始後１時間３０分で発熱ピーク
に達し、ついで５０分後１３０℃で２時間後重合を行な
って厚さく５１に＋１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表のとおりであった。Comparative Example 3 Methyl methacrylate 450 f, styrene 300 V and maleic anhydride 25 o y (s/M molar ratio=1.
After adding lauroyl peroxide 22 and lauroyl mercaptan 2f to 13) and mixing uniformly,
Injected between glass plates similar to Example 1, and heated to 80°C after degassing.
Polymerization was carried out by heating. An exothermic peak was reached 1 hour and 30 minutes after the start of polymerization, and then, 50 minutes later, polymerization was carried out at 130° C. for 2 hours to obtain a resin plate with a thickness of 51 and +1. The physical properties of the obtained methacrylic copolymer were as shown in Table 1.
比較例４
メタクリル酸メチル８４０ ｆ、スチレン１００２およ
び無水マレイン酸６０ｆに（Ｓ／Ｍモル比＝ １．５７
）に、ラウロイルパーオキサイド５ｖ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８５℃に加熱重合した。重合開始後１時間１
５分で発熱ピークに達し、ついで１２０℃で２時間後重
合を行なって厚さ６間の樹脂板を得た。得られたメタク
リル共重合体の物性は、第１表のとおりであった。Comparative Example 4 Methyl methacrylate 840 f, styrene 1002 and maleic anhydride 60 f (S/M molar ratio = 1.57
) was added with 5v of lauroyl peroxide and mixed uniformly, and then poured between the same glass plates as in Example 1, and after degassing, polymerization was carried out by heating at 85°C. 1 hour after the start of polymerization 1
The exothermic peak was reached in 5 minutes, and then polymerization was carried out at 120° 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.
比較例５
メタクリル酸メチル７００ ｔ、スチレン１００ｔおよ
び無水マレイン酸２００ｆ（Ｓ／Ｍモル比＝０．４７）
にラウロイルパーオキサイド３ｆおよびラウロイルメル
カプタン１ｔ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８０℃で加熱重
合した。重合開始後１時間１０分で発熱ピークに達し、
ついで３０分後１２．５℃で２時間後重合を行なって厚
さ６闘の樹脂板を得た。得られたメタクリル共重合体の
物性は、第１表のとおりであった。Comparative Example 5 Methyl methacrylate 700t, styrene 100t and maleic anhydride 200f (S/M molar ratio = 0.47)
After adding 3f of lauroyl peroxide and 1 t of lauroyl mercaptan to and mixing uniformly,
The mixture was poured between glass plates similar to the above, and after degassing, polymerization was carried out by heating at 80°C. An exothermic peak was reached 1 hour and 10 minutes after the start of polymerization.
After 30 minutes, polymerization was carried out at 12.5° 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.
比較例６
メタクリル酸メチル６８０ ｆ、スチレン１７０Ｖおよ
び無水マレイン酸１５０ｆ（８／Ｍモル比＝１０７）に
、１０時間半減期温度５３℃の２．４−ジクロｐベンゾ
イルパーオキサイド２ｖおよびラウロイルメルカプタン
１，５ｆ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６５℃で加熱重合し
た。重合開始後２時間１０分で発熱ピークに達し、つい
で３０分後１２５℃で２時間後重合を行なって厚さ６隨
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表のとおりであった。Comparative Example 6 Methyl methacrylate 680 f, styrene 170 V and maleic anhydride 150 f (8/M molar ratio = 107) were mixed with 2,4-dichloro p-benzoyl peroxide 2 v and lauroyl mercaptan 1, with a 10 hour half-life temperature of 53°C. After adding 5f and mixing uniformly, the mixture was poured between glass plates similar to those in Example 1, and after degassing, polymerization was carried out by heating at 65°C. An exothermic peak was reached 2 hours and 10 minutes after the start of polymerization, and then 30 minutes later, polymerization was carried out at 125° 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.
比較例７
メタクリル共重合体７ Ｂ Ｏｆ、スチレン１２０２お
よび無水マレイン酸１００ｆ（８／Ｍモル比＝１１３）
に、ラウロイルパーオキサイドａ０５Ｖ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７０℃で加熱重合した。重合開始後３時間２
０分で発熱ピークに達し、ついで５０分後１２０℃で２
時間後重合を行なって厚さ６闘の樹脂板を得た。得られ
たメタクリル共重合体の物性は、第１表のとおりであっ
た。Comparative Example 7 Methacrylic copolymer 7 B Of, styrene 1202 and maleic anhydride 100f (8/M molar ratio = 113)
After adding lauroyl peroxide a05V and mixing uniformly, the mixture was poured between glass plates similar to those in Example 1, and after degassing, polymerization was carried out by heating at 70°C. 3 hours after the start of polymerization2
The exothermic peak was reached in 0 minutes, and then 50 minutes later at 120℃
After a period of time, polymerization was carried out to obtain a resin plate with a thickness of 6 cm. The physical properties of the obtained methacrylic copolymer were as shown in Table 1.
実施例１１
メタクリル酸メチル６９０ ｆ、スチレン１７０ｔおよ
び無水マレイン酸１４０ｆ（Ｓ／Ｍモル比＝１１４）に
、ラウロイルパーオキサイド３ｆおよびラウロイルメル
カプタン３ｆを添加して均一に混合したのぢ、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時間で発熱ピークに達し、ついで
３０分後１３０℃で２時間後重合を行なって厚さ６１１
１１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２表のとおりであった。Example 11 3 f lauroyl peroxide and 3 f lauroyl mercaptan were added to 690 f methyl methacrylate, 170 t styrene, and 140 f maleic anhydride (S/M molar ratio = 114) and mixed uniformly. Example 1
The mixture was poured between glass plates similar to the above, and after degassing, polymerization was carried out by heating at 80°C. An exothermic peak was reached 1 hour after the start of polymerization, and then 30 minutes later, polymerization was carried out at 130°C for 2 hours, resulting in a thickness of 611 mm.
11 resin plates were obtained. The physical properties of the obtained methacrylic copolymer were as shown in Table 2.
ついで、この樹脂板を粉砕機で粗粉砕、ベント付き押出
機でペレット化し、このようにして得られたペレットを
射出成形して厚さくＳ、 ２ ＠ＩＩの樹脂板を得た。Next, this resin plate was coarsely pulverized using a pulverizer, pelletized using a vented extruder, and the pellets thus obtained were injection molded to obtain a resin plate having a thickness of S, 2 @II.
この樹脂板の物性は、第２表のとおりであった。The physical properties of this resin plate were as shown in Table 2.
実施例１２
実施例１１の方法において、重合温度を７０℃にした以
外は同様の方法を行なったところ、発熱ピークは重合開
始後１時間５７分であった。得られたメタクリル共重合
体の物性は、第２表のとおりであった。また、この樹脂
板のペレットを実施例１１と同様にして射出成形したの
ちの厚さ６．２簡の樹脂板の物性は、第２表のとおりで
あった。Example 12 The same method as in Example 11 was carried out except that the polymerization temperature was changed to 70° C., and the exothermic peak occurred 1 hour and 57 minutes after the start of polymerization. The physical properties of the obtained methacrylic copolymer were as shown in Table 2. Further, the physical properties of the resin plate having a thickness of 6.2 sheets after injection molding the pellets of this resin plate in the same manner as in Example 11 were as shown in Table 2.
比較例８
実施例１１の方法において、重合温度を６０℃にした以
外は同様の方法を行なったところ、発熱ピークは重合開
始後４時間であった。得られたメタクリル共重合体の物
性は、第２表のとおりであった。また、この樹脂板のペ
レットを実施例１１と同様にして射出成形したのちの厚
さ６２關の樹脂板の物性は、第２表のとおりであった。Comparative Example 8 When the same method as in Example 11 was carried out except that the polymerization temperature was changed to 60° C., the exothermic peak occurred 4 hours after the start of polymerization. The physical properties of the obtained methacrylic copolymer were as shown in Table 2. Furthermore, after injection molding the resin plate pellets in the same manner as in Example 11, the physical properties of a 62 mm thick resin plate were as shown in Table 2.
第１〜２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湿度との温度差
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
発明方法によっ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。As is clear from Tables 1 and 2, in the method of the present invention,
Heat resistant even if any one of the charging composition of each monomer, the 10-hour half-life temperature of the radical polymerization initiator, the temperature difference between the 10-hour half-life temperature and the polymerization humidity, and the time to the exothermic peak deviate from the above ranges. It has not been possible to obtain a methacrylic copolymer that satisfies all of the properties of color, low coloration, transparency, and low haze, and it is only through the method of the present invention that a methacrylic copolymer that satisfies all of these requirements can be obtained.
特 許 出願人 協和ガス化学工業株式会社手続補正
書
昭和５８年１０月５日
特許庁長官 若 杉 和 夫 殿
１、事件の表示
昭和５８年 特許願 第９５．０７０号２、発明の名称
メタクリル共重合体の製造方法
３、補正をする者
事件との関係 特許出願人
住 所 東京都中央区日本橋３丁目８番２号名 称
協和ガス化学工業株式会社
４、代理人
住 所 東京都千代田区二番町１１番地９ダイアパレ
ス二番町５、補正命令の日イ」
自発補正
６、補正の対象
明細内の「特許請求の範囲」おＪ：び「発明の詳細な説
明」の欄７、補正の内容
明細１１を以下の通り補正する。Patent Applicant Kyowa Gas Chemical Industry Co., Ltd. Procedural Amendment October 5, 1980 Commissioner of the Patent Office Kazuo Wakasugi 1, Indication of the Case 1988 Patent Application No. 95.070 2, Name of Invention Methacryl Co., Ltd. Polymer manufacturing method 3, relationship with the amended person case Patent applicant address 3-8-2 Nihonbashi, Chuo-ku, Tokyo Name
Kyowa Gas Chemical Industry Co., Ltd. 4, Agent Address: Dia Palace Nibancho 5, 11-9 Nibancho, Chiyoda-ku, Tokyo, Japan, Date of Amendment Order (I) Voluntary Amendment 6, "Scope of Claims" in the Specifications Subject to Amendment J: Column 7 of "Detailed Description of the Invention" and Specification of Amendment 11 are amended as follows.
（１）第１頁第４行〜第２頁第４行に記載の特許請求の
範囲を別紙の通り訂正する。(1) The scope of claims described in page 1, line 4 to page 2, line 4 are corrected as shown in the attached sheet.
（２）第９頁第１８行に記載の「６０〜１００」乞、「
６０〜８０」と訂正する。(2) "60-100" listed on page 9, line 18, "
60-80,” he corrected.
（３）第１１頁第７行に記載の「５〜４０Ｊを、「５へ
・４５」と訂正する。(3) "5-40J" written on page 11, line 7 is corrected to "5 to 45."
（４）第２６頁第２表中に記載の「実施例８」を、「比
較例８」と訂正する。(4) "Example 8" in Table 2 on page 26 is corrected to "Comparative Example 8."
特許請求の範囲
（１）メタクリル酸メヂル５０〜８６重量％、スチレン
７〜２５重量％および無水マレイン酸７〜２５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、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。Claims (1) A charging composition consisting of 50 to 86% by weight of methyl methacrylate, 7 to 25% by weight of styrene, and 7 to 25% by weight of maleic anhydride, and the molar ratio of styrene to maleic anhydride is 0. Polymerize a monomer mixture in the range of 5 to 2°C using a radical polymerization initiator with a 10-hour half-life temperature of 55°C or higher at a temperature that is 5°C or higher than the 10-hour half-life temperature, and The exothermic peak at this temperature is 3
A method for producing a methacrylic copolymer, characterized in that the production time is within hours.
（２）１０時間半減期温度より５〜上１℃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。(2) The method for producing a methacrylic copolymer according to claim 1, wherein the temperature is 5 to 1°C higher than the 10-hour half-life temperature.
（３）１０時間半減明渇麿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項または第２項
に記載のメタクリル共重合体の製造方法。(3) The exothermic peak at Akimaro decreased by half in 10 hours by 0.5
The method for producing a methacrylic copolymer according to claim 1 or 2, wherein the heating time is 2.5 hours.
（４）ラジカル重合開始剤の１０時間半減期温度が６０
−８０’Ｃ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。(4) The 10-hour half-life temperature of the radical polymerization initiator is 60
-80'C, the method for producing a methacrylic copolymer according to any one of claims 1 to 3.
Claims (4)
レン７〜２５重量％および無水マレイン酸７〜２５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０５〜２．０の範囲からなる単量
体混合物を、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。(1) A charging composition consisting of 50 to 86% by weight of methyl methacrylate, 7 to 25% by weight of styrene, and 7 to 25% by weight of maleic anhydride, and the molar ratio of styrene to maleic anhydride is 05 to 2.0. Using a radical polymerization initiator with a 10-hour half-life temperature of 55°C or higher, a monomer mixture consisting of A method for producing a methacrylic copolymer, characterized in that the time is within 3 hours.
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。(2) The method for producing a methacrylic copolymer according to claim 1, wherein the temperature is 5 to 40°C higher than the 10-hour half-life temperature.
〜２．５時間である特許請求の範囲第１項または第２項
に記載のメタクリル共重合体の製造方法。(3) The exothermic peak at the 10-hour half-life temperature is 0.5
The method for producing a methacrylic copolymer according to claim 1 or 2, wherein the heating time is 2.5 hours.
６０〜１００℃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。(4) Claims 1 to 3, wherein the radical polymerization initiator has a 10-hour half-life temperature of 60 to 100°C.
A method for producing a methacrylic copolymer according to any one of Items.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58095070A JPS59221314A (en) | 1983-05-31 | 1983-05-31 | Preparation of methacrylic copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58095070A JPS59221314A (en) | 1983-05-31 | 1983-05-31 | Preparation of methacrylic copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59221314A true JPS59221314A (en) | 1984-12-12 |
| JPH0251445B2 JPH0251445B2 (en) | 1990-11-07 |
Family
ID=14127727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58095070A Granted JPS59221314A (en) | 1983-05-31 | 1983-05-31 | Preparation of methacrylic copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59221314A (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4857596A (en) * | 1987-08-12 | 1989-08-15 | Pennwalt Corporation | Polymer bound antioxidant stabilizers |
| 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 |
| 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 |
| US4956416A (en) * | 1988-08-18 | 1990-09-11 | Atochem North America, Inc. | Amino or hydrazino peroxides, derivatives and their uses |
| US4975489A (en) * | 1987-08-12 | 1990-12-04 | Atochem North America, Inc. | Process for preparing polymer bound hindered amine light stabilizers |
| US4981914A (en) * | 1987-08-12 | 1991-01-01 | Atochem North America, Inc. | Polymer bound UV 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 |
| US5037894A (en) * | 1988-11-07 | 1991-08-06 | Atochem North America, Inc. | Polymer bound flame retardants |
| 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 |
| US5096977A (en) * | 1987-08-12 | 1992-03-17 | Atochem North America, Inc. | Process for preparing polymer bound UV stabilizers |
| US5140070A (en) * | 1988-11-07 | 1992-08-18 | Elf Atochem North America, Inc | Compositions comprising polymer bond flame retardants |
| US5206378A (en) * | 1987-08-12 | 1993-04-27 | Elf Atochem North America, Inc. | Hydrazido functionalized 2-(2-hydroxyphenyl)-2h-benzotriazoles |
| US5220015A (en) * | 1988-11-07 | 1993-06-15 | Elf Atochem North America, Inc. | Flame retardants compounds |
| US5272219A (en) * | 1988-08-18 | 1993-12-21 | Elf Atochem North America, Inc. | Process for preparing amino or hydrazino peroxides, derivatives and their uses |
| WO2010013557A1 (en) * | 2008-07-31 | 2010-02-04 | 旭化成ケミカルズ株式会社 | Thermoplastic acrylic resin, and molded product thereof |
| US8779076B2 (en) | 2007-12-27 | 2014-07-15 | Asahi Kasei Chemicals Corporation | Thermoplastic acrylic resin and molded body for optical member |
| JP2015067735A (en) * | 2013-09-30 | 2015-04-13 | 積水化成品工業株式会社 | Method for producing acrylic polymerization molded body, and method for producing acrylic foam molded body |
| JP2019073582A (en) * | 2017-10-12 | 2019-05-16 | 株式会社日本触媒 | Organic fine particle and method for producing the same |
-
1983
- 1983-05-31 JP JP58095070A patent/JPS59221314A/en active Granted
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5096977A (en) * | 1987-08-12 | 1992-03-17 | Atochem North America, Inc. | Process for preparing polymer bound UV stabilizers |
| USRE34791E (en) * | 1987-08-12 | 1994-11-15 | Atochem North America, Inc. | Polymer bound hindered amine light stabilizers |
| US4857596A (en) * | 1987-08-12 | 1989-08-15 | Pennwalt Corporation | Polymer bound antioxidant stabilizers |
| 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 |
| US5206378A (en) * | 1987-08-12 | 1993-04-27 | Elf Atochem North America, Inc. | Hydrazido functionalized 2-(2-hydroxyphenyl)-2h-benzotriazoles |
| US4975489A (en) * | 1987-08-12 | 1990-12-04 | Atochem North America, Inc. | Process for preparing polymer bound hindered amine light stabilizers |
| US4981914A (en) * | 1987-08-12 | 1991-01-01 | Atochem North America, Inc. | Polymer bound UV 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 |
| US4857595A (en) * | 1987-08-12 | 1989-08-15 | Pennwalt Corporation | Polymer bound hindered amine light stabilizers |
| 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 |
| US4863999A (en) * | 1987-08-12 | 1989-09-05 | Pennwalt Corporation | Multipurpose polymer bound stabilizers |
| US5399630A (en) * | 1988-08-18 | 1995-03-21 | Elf Atochem North America, Inc. | Process for curing polymers using amino or hydrazino peroxides |
| US5457162A (en) * | 1988-08-18 | 1995-10-10 | Elf Atochem North America, Inc. | Use of amino or hydrazino peroxides in preparing and curing polymers |
| 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 |
| US5360867A (en) * | 1988-08-18 | 1994-11-01 | Elf Atochem North America, Inc. | Process for preparing block or graft copolymers using amino or hydrazino peroxides |
| 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 |
| US8779076B2 (en) | 2007-12-27 | 2014-07-15 | Asahi Kasei Chemicals Corporation | Thermoplastic acrylic resin and molded body for optical member |
| WO2010013557A1 (en) * | 2008-07-31 | 2010-02-04 | 旭化成ケミカルズ株式会社 | Thermoplastic acrylic resin, and molded product thereof |
| JP5283701B2 (en) * | 2008-07-31 | 2013-09-04 | 旭化成ケミカルズ株式会社 | Acrylic thermoplastic resin and molded article thereof |
| US8895682B2 (en) | 2008-07-31 | 2014-11-25 | Asahi Kasei Chemicals Corporation | Thermoplastic acrylic resin, and molded product thereof |
| JP2015067735A (en) * | 2013-09-30 | 2015-04-13 | 積水化成品工業株式会社 | Method for producing acrylic polymerization molded body, and method for producing acrylic foam molded body |
| JP2019073582A (en) * | 2017-10-12 | 2019-05-16 | 株式会社日本触媒 | Organic fine particle and method for producing the same |
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|---|---|
| JPH0251445B2 (en) | 1990-11-07 |
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