JP2528876B2 - Method for producing heat-resistant methacrylic resin - Google Patents
Method for producing heat-resistant methacrylic resinInfo
- Publication number
- JP2528876B2 JP2528876B2 JP62107270A JP10727087A JP2528876B2 JP 2528876 B2 JP2528876 B2 JP 2528876B2 JP 62107270 A JP62107270 A JP 62107270A JP 10727087 A JP10727087 A JP 10727087A JP 2528876 B2 JP2528876 B2 JP 2528876B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- unit
- polymerization
- suspension
- sodium
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、メタクリル酸メチルおよびＮ−置換マレイ
ミドを主単量体とする共重合体よりなる透明性および耐
熱性にすぐれたメタクリル系樹脂の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Use) The present invention relates to a methacrylic resin having excellent transparency and heat resistance, which is composed of a copolymer containing methyl methacrylate and an N-substituted maleimide as a main monomer. Regarding manufacturing method.
（従来の技術） メタクリル酸メチルを主成分とするメタクリル樹脂は
優れた光学的性質、耐候性および機械的性質から自動車
部品、光学部品等に使用されている。一方、耐熱性の向
上に対する要望は多く、耐熱性の向上により更に幅広い
用途への展開が期待される。(Prior Art) Methacrylic resin containing methyl methacrylate as a main component is used for automobile parts, optical parts and the like because of its excellent optical properties, weather resistance and mechanical properties. On the other hand, there are many demands for improvement of heat resistance, and it is expected that the improvement of heat resistance will lead to further wide application.
メタクリル樹脂の耐熱性を向上させる方法については
数多くの提案がなされており、その中でもメタクリル酸
メチルとＮ−置換マレイミドを主単量体として共重合さ
せる方法が特公昭43−9753号に開示されている。A number of proposals have been made for improving the heat resistance of methacrylic resins, and among them, a method of copolymerizing methyl methacrylate and an N-substituted maleimide as a main monomer is disclosed in Japanese Examined Patent Publication No. 43-9753. There is.
上記提案はメタクリル系樹脂の耐熱性の改善において
効果的であり、製造方法としては基本的に制限はなく塊
状、溶液、乳化あるいは懸濁等いずれの重合法も可能と
されている反面、工業的生産の見地から確たる製造方法
の提案はなされておらず、製造方法によっては使用単量
体の残存から、本来得られるべき耐熱性が確保されない
等の問題もあり、この耐熱性メタクリル系樹脂の工業的
製造方法の確立が望まれている。The above proposal is effective in improving the heat resistance of the methacrylic resin, and there is basically no limitation as a manufacturing method, and it is possible to use any polymerization method such as bulk, solution, emulsion or suspension. There is no proposal of a reliable manufacturing method from the viewpoint of production, and depending on the manufacturing method, there is also a problem that the heat resistance that should be originally obtained cannot be ensured due to the remaining monomer used, and the industry of this heat-resistant methacrylic resin Establishment of a static manufacturing method is desired.
（発明が解決しようとする問題点） 本発明の目的は、光学的性質、機械的性質、耐候性お
よび耐熱性にすぐれたメタクリル系樹脂の生産性のよい
製造法を提供することである。(Problems to be Solved by the Invention) An object of the present invention is to provide a method for producing a methacrylic resin having excellent optical properties, mechanical properties, weather resistance and heat resistance with high productivity.
（問題点を解決するための手段） 本発明者らはメタクリル酸メチル、Ｎ−置換マレイミ
ドおよび芳香族ビニル化合物からなる共重合体の工業的
製造方法について鋭意検討した結果、特定の懸濁分散安
定剤を用いる懸濁重合方法により工業的製造が可能であ
り、かつ得られた共重合体も満足すべき耐熱性、透明性
を有することを見い出した。(Means for Solving Problems) As a result of diligent studies on the industrial production method of a copolymer comprising methyl methacrylate, an N-substituted maleimide and an aromatic vinyl compound, the present inventors have found that a specific suspension dispersion stability is obtained. It was found that industrial production is possible by the suspension polymerization method using an agent, and the obtained copolymer also has satisfactory heat resistance and transparency.
すなわち、本発明はメタクリル酸メチル単位90〜40重
量％、Ｎ−置換マレイミド単位５〜35重量％および芳香
族ビニル化合物単位５〜25重量％からなる共重合体を懸
濁重合で製造するに当り、一価の陽イオンを有する無機
塩（Ａ）および下記の懸濁分散剤（Ｂ）、あるいは
（Ａ），（Ｂ）および下記の懸濁分散剤（Ｃ）の存在下
に重合することを特徴とする耐熱性メタクリル系樹脂の
製造方法である。That is, in the present invention, a copolymer comprising 90 to 40% by weight of a methyl methacrylate unit, 5 to 35% by weight of an N-substituted maleimide unit and 5 to 25% by weight of an aromatic vinyl compound unit is prepared by suspension polymerization. Polymerization in the presence of an inorganic salt having a monovalent cation (A) and the following suspension dispersant (B), or (A), (B) and the following suspension dispersant (C). A method for producing a heat-resistant methacrylic resin characterized by the above.
ここで、懸濁分散剤（Ｂ）は で表わされる単量体単位95〜40重量％と、アクリル酸お
よび／またはメタクリル酸のリチウム、ナトリウム、カ
リウムおよびアンモニウム塩のうち少なくとも１種のア
クリル酸塩単位および／またはメタクリル酸塩単位０〜
60重量％と炭素数１〜８のアルキル基を有するアクリル
酸アルキルエステル単位および／またはメタクリル酸ア
ルキルエステル単位５〜50重量％からなる水溶性重合体
である。Here, the suspension dispersant (B) is 95 to 40% by weight of a monomer unit represented by and at least one acrylate unit and / or methacrylate unit of at least one lithium, sodium, potassium and ammonium salt of acrylic acid and / or methacrylic acid.
It is a water-soluble polymer comprising 60% by weight and 5 to 50% by weight of an acrylic acid alkyl ester unit and / or a methacrylic acid alkyl ester unit having an alkyl group having 1 to 8 carbon atoms.
懸濁分散剤（Ｃ）は、アクリル酸および／またはメタ
クリル酸のリチウム、ナトリウム、カリウムおよびアン
モニウム塩のうち少くとも１種のアクリル酸塩単位およ
び／またはメタクリル酸塩単位100〜50重量％と炭素数
１〜８のアルキル基を有するアクリル酸アルキルエステ
ル単位および／またはメタクリル酸アルキルエステル単
位０〜50重量％からなる水溶性重合体である。The suspension dispersant (C) is 100 to 50% by weight of at least one acrylate unit and / or methacrylate unit of lithium, sodium, potassium and ammonium salts of acrylic acid and / or methacrylic acid and carbon. It is a water-soluble polymer comprising 0 to 50% by weight of an acrylic acid alkyl ester unit and / or a methacrylic acid alkyl ester unit having an alkyl group of the number 1 to 8.
本発明の方法により得られる耐熱性メタクリル系樹脂
は、メタクリル酸メチル単位90〜40重量％、より好まし
くは80〜50重量％である。メタクリル酸メチル単位が40
重量％以下では機械的強度が著しく低下し実行的でな
い。The heat-resistant methacrylic resin obtained by the method of the present invention has a methyl methacrylate unit content of 90 to 40% by weight, more preferably 80 to 50% by weight. 40 units of methyl methacrylate
If it is less than 10% by weight, the mechanical strength is remarkably reduced and it is not practical.
本発明の方法で使用される共重合成分であるＮ−置換
マレイミド単位は耐熱性向上のための必須成分であり、
樹脂中の含有量は５〜35重量％、より好ましくは10〜30
重量％である。Ｎ−置換マレイミド単位から５重量％未
満では耐熱性が充分満足されず、また35重量％を超える
と機械的強度が低下し好ましくない。The N-substituted maleimide unit which is a copolymerization component used in the method of the present invention is an essential component for improving heat resistance,
The content in the resin is 5 to 35% by weight, more preferably 10 to 30
% By weight. If it is less than 5% by weight from the N-substituted maleimide unit, heat resistance is not sufficiently satisfied, and if it exceeds 35% by weight, mechanical strength is lowered, which is not preferable.
Ｎ−置換マレイミドとしてはＮ−フェニルマレイミ
ド、Ｎ−（２−クロロフェニル）マレイミド、Ｎ−（３
−クロロフェニル）マレイミド、Ｎ−（４−クロロフェ
ニル）マレイミド、Ｎ−（2,4,6−トリクロロフェニ
ル）マレイミド、Ｎ−（４−ブロモフェニル）マレイミ
ド、Ｎ−（2,4,6−トリブロモフェニル）マレイミド、
Ｎ−（２−メチルフェニル）マレイミド、Ｎ−（４−メ
チルフェニル）マレイミド、Ｎ−（2,6−ジメチルフェ
ニル）マレイミド、Ｎ−（２−ｔ−ブチルフェニル）マ
レイミド、Ｎ−シクロヘキシルマレイミド、Ｎ−メチル
マレイミド、Ｎ−エチルマレイミド、Ｎ−ｎ−ブチルマ
レイミド、Ｎ−tert−ブチルマレイミド、Ｎ−ラウリル
マレイミド等が挙げられる。As the N-substituted maleimide, N-phenylmaleimide, N- (2-chlorophenyl) maleimide, N- (3
-Chlorophenyl) maleimide, N- (4-chlorophenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-bromophenyl) maleimide, N- (2,4,6-tribromophenyl) ) Maleimide,
N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2-t-butylphenyl) maleimide, N-cyclohexylmaleimide, N -Methylmaleimide, N-ethylmaleimide, N-n-butylmaleimide, N-tert-butylmaleimide, N-laurylmaleimide and the like can be mentioned.
本発明の方法で使用される他の共重合成分である芳香
族ビニル化合物単位は、主としてＮ−置換マレイミドの
共重合性を高め耐熱性を向上させるための補助的な役割
を有し、樹脂中の含有量は５〜25重量％、より好ましく
は７〜20重量％である。芳香族ビニル化合物単位が５重
量％未満ではＮ−置換マレイミドが単量体として樹脂中
に残存して樹脂本来の耐熱性が得られにくく、また25重
量％を超えるとメタクリル系樹脂としての光学的性質が
低下し好ましくない。The aromatic vinyl compound unit, which is the other copolymerization component used in the method of the present invention, has an auxiliary role mainly for increasing the copolymerizability of N-substituted maleimide and improving the heat resistance. Is 5 to 25% by weight, more preferably 7 to 20% by weight. When the amount of the aromatic vinyl compound unit is less than 5% by weight, the N-substituted maleimide remains as a monomer in the resin and it is difficult to obtain the original heat resistance of the resin, and when it exceeds 25% by weight, the optical property as a methacrylic resin is high. It is not preferable because the properties are deteriorated.
かかる芳香族ビニル化合物としてはスチレン、ｐ−メ
チルスチレン、α−メチルスチレンおよびｐ−クロロス
チレン、ｐ−ブロモスチレン等のハロゲン化スチレンが
挙げられる。Examples of such aromatic vinyl compounds include halogenated styrenes such as styrene, p-methylstyrene, α-methylstyrene and p-chlorostyrene, p-bromostyrene.
本発明は上記共重合体を懸濁重合で製造するに当り、
一価の陽イオンを有する無機塩（Ａ）および懸濁分散剤
（Ｂ）と（Ｃ）の２成分または（Ｂ）を用いることによ
り初めて重合が可能であり、かつ得られた共重合体も満
足すべき耐熱性を有するものである。In the present invention, when the above copolymer is produced by suspension polymerization,
Polymerization is possible for the first time by using the inorganic salt (A) having a monovalent cation and the two components of the suspension dispersant (B) and (C) or (B), and the obtained copolymer is also available. It has satisfactory heat resistance.
本発明の方法で使用される一価の陽イオンを有する無
機塩（Ａ）、例えば塩酸、硫酸、硝酸、リン酸、炭酸、
ホウ酸、クエン酸、酢酸、乳酸および酒石酸等のナトリ
ウム、カリウム、アンモニウム塩が挙げられる。（Ａ）
の添加割合は水100重量部に対して0.01〜２重量部、よ
り好ましくは0.05〜１重量部である。0.01重量部以下で
は得られるビーズの形状粒径が不均一となったり、粒子
相互の合一をまねき好ましくない。また、２重量部を超
えると共重合体の光学的性質に好ましくない影響を与え
る。An inorganic salt (A) having a monovalent cation used in the method of the present invention, such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid,
Examples thereof include sodium, potassium and ammonium salts of boric acid, citric acid, acetic acid, lactic acid and tartaric acid. (A)
The addition ratio is 0.01 to 2 parts by weight, and more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of water. If the amount is less than 0.01 parts by weight, the shape and particle size of the obtained beads will be non-uniform, and the particles will not be united with each other, which is not preferable. If it exceeds 2 parts by weight, the optical properties of the copolymer are unfavorably affected.
懸濁分散剤（Ｂ）は で表わされる単量体単位95〜40重量％とアクリル酸およ
び／またはメタクリル酸のリチウム、ナトリウム、カリ
ウムおよびアンモニウム塩のうち少なくとも１種のアク
リル酸塩単位および／またはメタクリル酸塩単位０〜60
重量％と炭素数１〜８のアルキル基を有するアクリル酸
アルキルエステル単位および／またはメタクリル酸アル
キルエステル単位５〜50重量％からなる水溶性重合体で
ある。（Ｂ）の添加割合は、水100重量部に対して0.001
〜１重量部、より好ましくは0.005〜0.5重量部である。
0.001重量部以下ではビーズが不均一となったり、合一
をまねき好ましくない。また１重量部を超えてもビーズ
生成には影響はないが、重合系の泡立が生じやすくなっ
たり、共重合体に含まれてフィッシュアイの原因となり
やすく好ましくない。The suspension dispersant (B) is 95 to 40% by weight of a monomer unit and at least one acrylate unit and / or methacrylate unit of lithium, sodium, potassium and ammonium salts of acrylic acid and / or methacrylic acid 0 to 60
It is a water-soluble polymer comprising 5% to 50% by weight of an acrylic acid alkyl ester unit and / or a methacrylic acid alkyl ester unit having an alkyl group having 1 to 8 carbon atoms. The addition ratio of (B) is 0.001 with respect to 100 parts by weight of water.
To 1 part by weight, more preferably 0.005 to 0.5 part by weight.
If the amount is less than 0.001 part by weight, the beads will be non-uniform and coalescence will be unfavorable. Further, even if it exceeds 1 part by weight, there is no influence on the bead formation, but it is not preferable because foaming of the polymerization system is likely to occur or it is contained in the copolymer and causes fish eyes.
懸濁分散剤（Ｃ）は、アクリル酸および／またはメタ
クリル酸のリチウム、ナトリウム、カリウムおよびアン
モニウム塩のうち少くとも１種のアクリル酸塩単位およ
び／またはメタクリル酸塩単位100〜50重量％と炭素数
１〜８のアルキル基を有するアクリル酸アルキルエステ
ル単位および／またはメタクリル酸アルキルエステル単
位０〜50重量％からなることを特徴とする水溶性重合体
である。（Ｃ）の添加割合は、水100重量部に対して０
〜１重量部、より好ましくは0.003〜0.5重量部である。
（Ｃ）は併用しなくてもビーズ生成の安定性には問題を
生じないが、ビーズの均一化には併用する方が好まし
い。１重量部を超えてもビーズ生成には影響はないが、
重合系が泡立ちやすくなったり、共重合体に含まれてフ
ィッシュアイの原因となりやすく好ましくない。また
（Ａ）と（Ｂ）の２成分のみではビーズの生成は可能で
あるが、異形ビーズの混入、重合槽壁面や撹拌翼への付
着ポリマーの生成等重合安定性の面から好ましくない。The suspension dispersant (C) is 100 to 50% by weight of at least one acrylate unit and / or methacrylate unit of lithium, sodium, potassium and ammonium salts of acrylic acid and / or methacrylic acid and carbon. It is a water-soluble polymer characterized by comprising 0 to 50% by weight of an acrylic acid alkyl ester unit and / or a methacrylic acid alkyl ester unit having an alkyl group of the number 1 to 8. The addition ratio of (C) is 0 with respect to 100 parts by weight of water.
To 1 part by weight, more preferably 0.003 to 0.5 part by weight.
Even if (C) is not used in combination, there is no problem in the stability of bead formation, but it is preferable to use it together in order to make the beads uniform. Bead formation is not affected if the amount exceeds 1 part by weight,
The polymerization system is liable to foam, and it is included in the copolymer to cause fish eyes, which is not preferable. Further, although it is possible to form beads with only the two components (A) and (B), it is not preferable from the viewpoint of polymerization stability such as mixing of odd-shaped beads and formation of a polymer adhering to the wall of the polymerization tank or a stirring blade.
本発明の懸濁重合は公知の方法により撹拌下50〜150
℃の重合温度で所定時間重合を行なうことができる。ま
た懸濁重合を行なう際の単量体相と水相の重量比は単量
体相／水相＝1/10〜1/1であるが、生産性の面から1/3〜
1/1が好ましい。The suspension polymerization of the present invention is carried out by a known method under stirring at 50-150.
Polymerization can be carried out for a predetermined time at a polymerization temperature of ° C. In addition, the weight ratio of the monomer phase and the aqueous phase during the suspension polymerization is 1/10 to 1/1 of the monomer phase / aqueous phase, but from the aspect of productivity 1/3 to
1/1 is preferable.
本発明に用いることのできる重合開始剤としては単量
体に可溶なラジカル重合開始剤であれば特に限定はな
く、例えば2,2′−アゾビスイソブチロニトリル、2,2′
−アゾビス（2,4−ジメチルバレロニトリル），ジメチ
ル2,2′−アゾビスイソブチレート等のアゾ系開始剤、
ラウロイルパーオキサイド、ベンゾイルパーオキサイ
ド、ｔ−ブチルパーオキシイソブチレート、アセチルパ
ーオキサイド等の過酸化物が挙げられる。The polymerization initiator that can be used in the present invention is not particularly limited as long as it is a monomer-soluble radical polymerization initiator, for example, 2,2′-azobisisobutyronitrile, 2,2 ′.
-Azo initiators such as azobis (2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate,
Examples thereof include lauroyl peroxide, benzoyl peroxide, t-butylperoxyisobutyrate, and acetyl peroxide.
また本発明の樹脂は成形材料として用いることが主目
的であり、共重合体の重合度調節のため連鎖移動剤を用
いることが好ましく、かかる目的に使用される添加剤と
して、ｎ−ブチルメルカプタン、ｎ−オクチルメルカプ
タン、ｎ−ドデシルメルカプタン等のメルカプタン類、
チオグリコール酸およびチオグリコール酸エステル類が
挙げられる。Further, the resin of the present invention is mainly used as a molding material, and it is preferable to use a chain transfer agent for controlling the polymerization degree of the copolymer. As an additive used for such a purpose, n-butyl mercaptan, Mercaptans such as n-octyl mercaptan and n-dodecyl mercaptan,
Thioglycolic acid and thioglycolic acid esters are mentioned.
本発明の製造方法により得られた共重合体ビーズは公
知の方法によりベント付押出機などでペレット化し、射
出成形することができる。The copolymer beads obtained by the production method of the present invention can be pelletized by a known method such as a vented extruder and injection-molded.
また本発明の樹脂においては重合時あるいはペレット
化時に必要に応じて滑剤、染顔料、紫外線吸収剤、熱安
定剤等を使用してもよい。Further, in the resin of the present invention, a lubricant, a dye / pigment, an ultraviolet absorber, a heat stabilizer and the like may be used at the time of polymerization or pelletization, if necessary.
（実施例） 実施例中の単量体、無機塩（Ａ）および懸濁分散剤は
以下の略号を使用した。メタクリル酸メチル（MMA）、
Ｎ−フェニルマレイミド（P I）、Ｎ−（２−クロロフ
ェニル）マレイミド（CP I）、Ｎ−（２−メチルフェニ
ル）マレイミド（MP I）、Ｎ−シクロヘキシルマレイミ
ド（CH I）、Ｎ−（2,6−ジエチルフェニル）マレイミ
ド（EP I）、スチレン（ST）、α−メチルスチレン（MS
T）、燐酸二水素ナトリウム（Ａ−１）、燐酸水素
（二）ナトリウム（Ａ−２）、硫酸ナトリウム（Ａ−
３）、カルボキシメチルセルロース（CMC）。(Example) The following abbreviations were used for the monomer, inorganic salt (A) and suspension dispersant in the examples. Methyl methacrylate (MMA),
N-phenylmaleimide (PI), N- (2-chlorophenyl) maleimide (CP I), N- (2-methylphenyl) maleimide (MP I), N-cyclohexylmaleimide (CH I), N- (2,6 -Diethylphenyl) maleimide (EP I), styrene (ST), α-methylstyrene (MS
T), sodium dihydrogen phosphate (A-1), sodium hydrogen (di) phosphate (A-2), sodium sulfate (A-
3), carboxymethyl cellulose (CMC).
実施例中の熱変形温度はASTM D648に準じて測定した
値である。The heat distortion temperature in the examples is a value measured according to ASTM D648.
また実施例で使用した懸濁分散剤（Ｂ）および（Ｃ）
は下記により製造した。Also, the suspending and dispersing agents (B) and (C) used in the examples.
Was produced as follows.
（Ｂ）スチレンｐ−スルホン酸ナトリウム100g、メタク
リル酸ナトリウム20g、メタクリル酸メチル30g、イオン
交換水600gを２のセパラブルフラスコに仕込み、N2雰
囲気下、撹拌しながら60℃に昇温後、過硫酸アンモニウ
ム0.2gを添加して３時間保持し、ついで70℃で３時間保
持後冷却して370poise（25℃）の無色透明な溶液を得
た。(B) 100 g of styrene sodium p-sulfonate, 20 g of sodium methacrylate, 30 g of methyl methacrylate, and 600 g of ion-exchanged water were charged in a separable flask of 2 and heated to 60 ° C. under stirring in a N 2 atmosphere, and then overheated. Ammonium sulfate (0.2 g) was added and maintained for 3 hours, then maintained at 70 ° C for 3 hours and then cooled to obtain a colorless transparent solution of 370 poise (25 ° C).
（Ｃ−１）水酸化カリウム112g、イオン交換水300gを２
セパラブルフラスコに仕込み、N2雰囲気下、撹拌しな
がら50℃に昇温し、メタクリル酸メチル200gを添加す
る。ケン化発熱により内温が上昇し、70℃で1.5時間保
持後60℃まで降温し、過硫酸アンモニウム0.2gを添加し
て５時間後イオン交換水500gを加えて稀釈し、20poise
（25℃）の白濁した溶液を得た。(C-1) 112 g of potassium hydroxide and 300 g of ion-exchanged water
A separable flask is charged, the temperature is raised to 50 ° C. under stirring under N 2 atmosphere, and 200 g of methyl methacrylate is added. The internal temperature rises due to the heat generated by saponification, the temperature is maintained at 70 ° C for 1.5 hours, then the temperature is lowered to 60 ° C, 0.2g of ammonium persulfate is added, and after 5 hours, 500g of ion-exchanged water is added to dilute, and 20poise is added.
A white turbid solution (25 ° C) was obtained.
（Ｃ−２）イオン交換水580gを２セパラブルフラスコ
に仕込み、撹拌しながら80℃に昇温し、メタクリル酸単
位70重量％とメタクリル酸メチル単位30重量％からなる
微粉末ポリマー20gを添加して分散させ、ついでイオン
交換水20gに溶解した水酸化ナトリウム6.5gを添加す
る。２時間後冷却して2poise（25℃）の無色透明な溶液
を得た。(C-2) 580 g of ion-exchanged water was charged into a two-separable flask, heated to 80 ° C. with stirring, and 20 g of a fine powder polymer composed of 70% by weight of methacrylic acid unit and 30% by weight of methyl methacrylate unit was added. And dispersed, and then 6.5 g of sodium hydroxide dissolved in 20 g of ion-exchanged water is added. After cooling for 2 hours, a colorless transparent solution of 2 poise (25 ° C) was obtained.
実施例１ メタクリル酸メチル70重量部、Ｎ−（２−クロロフェ
ニル）マレイミド20重量部、スチレン10重量部、ラウロ
イルパーオキサイド0.3重量部およびｎ−オクチルメル
カプタン0.25重量部からなる単量体溶液20Kgと、イオン
交換水100重量部、リン酸二水素ナトリウム0.2重量部、
リン酸水素（二）ナトリウム0.2重量部、（Ｂ）0.2重量
部および（Ｃ−１）0.05重量部からなる水溶液50Kgを、
ジャケット付きの100耐圧重合槽に仕込み、N2雰囲気
下で撹拌し、ジャケットに温水を通して重合温度80℃で
重合を開始した。重合開始後２時間で重合槽を密閉し、
ジャケットにスチームを通して120℃に昇温し、さらに
２時間保持して重合を完結させた。Example 1 20 kg of a monomer solution consisting of 70 parts by weight of methyl methacrylate, 20 parts by weight of N- (2-chlorophenyl) maleimide, 10 parts by weight of styrene, 0.3 part by weight of lauroyl peroxide and 0.25 part by weight of n-octyl mercaptan. 100 parts by weight of deionized water, 0.2 parts by weight of sodium dihydrogen phosphate,
50 kg of an aqueous solution containing 0.2 part by weight of sodium (di) hydrogen phosphate, 0.2 part by weight of (B) and 0.05 part by weight of (C-1),
The mixture was charged into a 100-pressure polymerization tank with a jacket, stirred under a N 2 atmosphere, and warm water was passed through the jacket to initiate polymerization at a polymerization temperature of 80 ° C. 2 hours after the start of polymerization, the polymerization tank is closed,
Steam was passed through the jacket, the temperature was raised to 120 ° C., and the temperature was kept for 2 hours to complete the polymerization.
重合系は泡立ちもなく、非常に安定であり、平均粒径
0.26mmの均一なビーズが収率良く得られ、重合槽壁面あ
るいは撹拌翼への付着ポリマーは問題ない量であった。
ビーズを水洗、乾燥後60mmφのベント付押出機を用い25
0℃でペレット化し、ついで射出成形機を用い250℃で物
性試験片を成形し評価した結果、熱変形温度は118℃で
あり、成形品は透明でごくわずかに黄色味を有していた
他、フィッシュアイ、シルバーなどの外観上の欠点はな
かった。The polymerization system is very stable and has no average particle size.
Uniform beads of 0.26 mm were obtained in good yield, and the amount of polymer adhering to the wall of the polymerization tank or the stirring blade was not a problem.
After washing the beads with water and drying, use an extruder with a vent of 60 mmφ 25
As a result of pelletizing at 0 ° C, then molding a physical property test piece at 250 ° C using an injection molding machine and evaluating the result, the heat distortion temperature was 118 ° C, and the molded product was transparent and had a slight yellow tint. There were no visual defects such as, fisheye, and silver.
実施例２〜４、比較例１〜５ 第１表に実施例１に準じた製造方法により、単量体溶
液組成、水溶液組成を変化させて実施した結果を示す。Examples 2 to 4 and Comparative Examples 1 to 5 Table 1 shows the results obtained by changing the composition of the monomer solution and the composition of the aqueous solution by the manufacturing method according to Example 1.
実施例中の無機塩（Ａ）、懸濁分散剤（Ｂ）および
（Ｃ）の重量部は水100重量部に対する割合であり、単
量体相と水相の重量比は比較例も含めてすべて単量体相
／水相／＝1/2である。The weight parts of the inorganic salt (A), the suspension dispersant (B) and (C) in the examples are ratios with respect to 100 parts by weight of water, and the weight ratio of the monomer phase to the water phase is the same as that of the comparative example. All are monomer phase / water phase / = 1/2.
また得られたビーズからの評価は実施例１と同様の方
法により実施した。Further, evaluation from the obtained beads was carried out by the same method as in Example 1.
（発明の効果） 本発明の方法によれば、重合反応は極めて安定してお
り、粒子径の均一なビーズが得られ、重合槽壁面、撹拌
翼へのポリマーの付着は殆ど認められない。また得られ
た樹脂は優れた耐熱性、透明性および成形性を有してお
り、従来アクリル樹脂が用いられた分野に使用可能であ
る上に、特に高い耐熱性を要求される分野に使用するこ
とができるので、従来のメタクリル系樹脂では使用出来
なかった用途への幅広い展開が期待される。(Effect of the Invention) According to the method of the present invention, the polymerization reaction is extremely stable, beads having a uniform particle size are obtained, and the adhesion of the polymer to the wall surface of the polymerization tank and the stirring blade is hardly recognized. Further, the obtained resin has excellent heat resistance, transparency and moldability, and can be used in the fields where acrylic resins have been conventionally used, and also used in the fields where particularly high heat resistance is required. Therefore, it is expected that the methacrylic resin will be widely used in applications where conventional methacrylic resins could not be used.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭61−171708（ＪＰ，Ａ) 特開 昭58−15512（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-61-171708 (JP, A) JP-A-58-15512 (JP, A)
Claims (1)
−置換マレイミド単位５〜35重量％および芳香族ビニル
化合物単位５〜25重量％からなる共重合体を懸濁重合で
製造するに当り、一価の陽イオンを有する無機塩（Ａ）
および下記の懸濁分散剤（Ｂ）、あるいは（Ａ），
（Ｂ）および下記の懸濁分散剤（Ｃ）の存在下に重合す
ることを特徴とする耐熱性メタクリル系樹脂の製造方
法。 ここで、懸濁分散剤（Ｂ）は ただし、;SO3Mのフェニル基への置換位置がo,m,pのうち
いずれか一つであり、 ;RはＨまたはCH3であり、 ;MはLi,Na,KまたはNH4である で表される単量体単位95〜40重量％と、アクリル酸およ
び／またはメタクリル酸のリチウム、ナトリウム、カリ
ウムおよびアンモニウム塩のうち少なくとも１種のアク
リル酸塩の単位および／またはメタクリル酸塩単位０〜
60重量％と、炭素数１〜８のアルキル基を有するアクリ
ル酸アルキルエステル単位および／またはメタクリル酸
アルキルエステル単位５〜50重量％からなる水溶性重合
体であり、 懸濁分散剤（Ｃ）は、アクリル酸および／またはメタク
リル酸のリチウム、ナトリウム、カリウムおよびアンモ
ニウム塩のうち少なくとも１種のアクリル酸塩単位およ
び／またはメタクリル酸塩単位100〜50重量％と、炭素
数１〜８のアルキル基を有するアクリル酸アルキルエス
テル単位および／またはメタクリル酸アルキルエステル
単位０〜50重量％からなる水溶性重合体である。1. Methyl methacrylate unit 90 to 40% by weight, N
An inorganic salt (A) having a monovalent cation in the production of a copolymer comprising 5 to 35% by weight of a substituted maleimide unit and 5 to 25% by weight of an aromatic vinyl compound unit by suspension polymerization.
And the following suspension dispersant (B), or (A),
A method for producing a heat-resistant methacrylic resin, which comprises polymerizing in the presence of (B) and the following suspension dispersant (C). Here, the suspension dispersant (B) is However, the substitution position of SO 3 M to the phenyl group is any one of o, m and p,; R is H or CH 3 , and; M is Li, Na, K or NH 4 . 95 to 40% by weight of a monomer unit represented by the following formula, and at least one acrylate unit and / or methacrylate unit of lithium, sodium, potassium and ammonium salts of acrylic acid and / or methacrylic acid. 0 to
A water-soluble polymer comprising 60% by weight and 5 to 50% by weight of an alkyl acrylate unit and / or an alkyl methacrylate unit having an alkyl group having 1 to 8 carbon atoms. The suspension dispersant (C) is , 100 to 50% by weight of at least one acrylate unit and / or methacrylate unit of lithium, sodium, potassium and ammonium salts of acrylic acid and / or methacrylic acid, and an alkyl group having 1 to 8 carbon atoms. It is a water-soluble polymer comprising 0 to 50% by weight of an acrylic acid alkyl ester unit and / or a methacrylic acid alkyl ester unit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62107270A JP2528876B2 (en) | 1987-04-30 | 1987-04-30 | Method for producing heat-resistant methacrylic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62107270A JP2528876B2 (en) | 1987-04-30 | 1987-04-30 | Method for producing heat-resistant methacrylic resin |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6017033A Division JPH07145214A (en) | 1994-01-17 | 1994-01-17 | Production of heat-resistant methacrylic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63273616A JPS63273616A (en) | 1988-11-10 |
| JP2528876B2 true JP2528876B2 (en) | 1996-08-28 |
Family
ID=14454804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62107270A Expired - Fee Related JP2528876B2 (en) | 1987-04-30 | 1987-04-30 | Method for producing heat-resistant methacrylic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2528876B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS595201B2 (en) * | 1976-07-19 | 1984-02-03 | エヌオーケー株式会社 | Emulsion polymerization method using oligomers |
| JPS5815512A (en) * | 1981-07-22 | 1983-01-28 | Japan Exlan Co Ltd | Production of water-soluble polymer having good stability |
| JPS61171708A (en) * | 1984-12-14 | 1986-08-02 | Mitsubishi Rayon Co Ltd | Heat-resistant resin, its production and optical element thereof |
-
1987
- 1987-04-30 JP JP62107270A patent/JP2528876B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63273616A (en) | 1988-11-10 |
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