JP2001151817A - Method of manufacturing for acrylic syrup - Google Patents
Method of manufacturing for acrylic syrupInfo
- Publication number
- JP2001151817A JP2001151817A JP33969999A JP33969999A JP2001151817A JP 2001151817 A JP2001151817 A JP 2001151817A JP 33969999 A JP33969999 A JP 33969999A JP 33969999 A JP33969999 A JP 33969999A JP 2001151817 A JP2001151817 A JP 2001151817A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- monomer
- reaction
- syrup
- polymerization initiator
- 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
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
- C08F20/00—Homopolymers and 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
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はメタクリル酸メチル
を主成分とする単量体の重合方法に関する。TECHNICAL FIELD The present invention relates to a method for polymerizing a monomer containing methyl methacrylate as a main component.
【０００２】[0002]
【従来の技術】アクリルシラップはメタクリル樹脂注型
板、光伝送繊維や光導波路などの光学材料、アクリル人
造大理石、人工印材、床材、接着剤、粘着剤、文化財・
剥製等修復材料または医用材料などの中間原料として従
来より用いられている。2. Description of the Related Art Acrylic syrup is a methacrylic resin casting plate, an optical material such as an optical transmission fiber or an optical waveguide, an acrylic artificial marble, an artificial stamping material, a flooring material, an adhesive, an adhesive, and a cultural property.
It has been conventionally used as an intermediate material such as a stuffing restoration material or a medical material.
【０００３】このうちメタクリル酸メチルを主成分とす
るシラップの製造方法は特公昭３６−３３９２号公報、
特公平１−１１６５２号公報、特開昭４９−１０４９３
７号公報、特開平３−１１１４０８号公報、特開平９−
６７４９５号公報、および特開平９−１９４６７３号公
報等、多数出願されている。[0003] Among them, a method for producing a syrup containing methyl methacrylate as a main component is disclosed in JP-B-36-3392.
JP-B-1-11652, JP-A-49-10493
7, JP-A-3-111408, JP-A-9-
A number of applications have been filed, such as 67495, and JP-A-9-19467.
【０００４】アクリルシラップの製造方法は２つに大別
される。１つは特開昭４９−１０４９３７号公報、特開
平９−１９４６７３号公報等に開示されている、別途調
製した重合体を単量体に溶解する方法である。本発明と
は基本的に異なる製造方法であり、しかも一旦重合体を
取り出した後再度単量体に溶解するため、エネルギー的
にも経済的にも不利である。もう１つは特公昭３６−３
３９２号公報や特公平１−１１６５２号公報等で開示さ
れている、単量体を部分的に塊状重合させる方法であり
部分重合法とも呼ばれる。部分重合法は更に回分法と連
続法とに分けられる。The method for producing acrylic syrup is roughly classified into two. One is a method of dissolving a separately prepared polymer in a monomer, which is disclosed in JP-A-49-104937 and JP-A-9-19467. This is a production method basically different from that of the present invention, and is disadvantageous in terms of energy and economy since a polymer is once taken out and then dissolved in a monomer again. The other is Japanese Patent Publication No. 36-3
No. 392, Japanese Patent Publication No. 1-11652, etc., this is a method of partially bulk polymerizing a monomer and is also called a partial polymerization method. The partial polymerization method is further divided into a batch method and a continuous method.
【０００５】部分重合法のうち第一の回分法による製造
方法として、例えば特公昭３６−３３９２号公報には、
メタクリル酸メチルを主成分とする単量体および連鎖移
動剤からなる原料を８０℃に昇温し、少量のアゾビスイ
ソブチロニトリルまたは過酸化ベンゾイルを重合開始剤
として加え、同時に１００℃に昇温し還流下で２７〜５
０分重合し、所定の粘度になった時点で重合禁止剤とし
てハイドロキノンを含有する冷たいメタクリル酸メチル
を加えて急冷することによりアクリルシラップを製造す
る方法が開示されている。しかしながら、この方法では
重合開始剤が完全に分解しない状態で重合を停止するた
め、得られたシラップ中に重合開始剤が残存しており、
たとえ重合禁止剤を加えても貯蔵安定性の劣ったものと
なる。例えば重合開始剤に用いる過酸化ベンゾイルの１
００℃での半減期は約２２分であるから、所定の粘度に
達した時点では加えた量に対して４２〜２０％の重合開
始剤が製品中に残存している。また反応に必要な量の重
合開始剤を一度に添加するために反応の制御が困難であ
り、一旦重合開始剤を加えた後に昇温を行い還流下で反
応させるが、昇温速度や還流量などについての詳細な記
述はなく、僅かな温度の変化の影響により製品の重合
率、粘度が大きく変化するから安定した製造は行えな
い。特公平１−１１６５２号公報では、ＳＭＣまたはＢ
ＭＣの中間原料としてシラップを製造するに際し、撹拌
機、温度計、窒素ガス導入管を備えた反応容器にメタク
リル酸メチル８９重量％、メタクリル酸５重量％、トリ
メチロールプロパントリメタクリレート６重量％からな
る単量体１００部に対しｎ−ドデシルメルカプタン０．
４部、２，２’−アゾビスイソブチロニトリル０．０５
部を含む原料を仕込み、８０℃、窒素雰囲気下で重合を
行い、反応液が所定の粘度に達した時点で重合禁止剤と
してハイドロキノンおよびｐ−メトキシフェノールを加
え速やかに室温まで冷却し重合を禁止する方法により、
カルボン酸を含むアクリルシラップを製造する方法が開
示されている。しかしながらこの方法においては、所定
の粘度に達した時点で重合禁止剤を加えて強制的に重合
を停止しており、得られたシラップ中には重合開始剤が
残存しているので、たとえ重合禁止剤を加えても貯蔵安
定性の劣ったものとなる。また反応に必要な量の重合開
始剤を一度に添加するために反応の制御が困難である。
僅かな温度の変化の影響により製品の重合率、粘度が大
きく変化するため安定した製造は行えない。また特開平
９−６７４９５号公報ではＳＭＣまたはＢＭＣの中間原
料としてシラップを製造するに際し、メタクリル酸メチ
ル１９０部、メタクリル酸１０部からなる単量体を窒素
雰囲気下８０℃に昇温し、重合開始剤として２，２’−
アゾビスイソブチロニトリル０．０５部と連鎖移動剤と
してｎ−ドデシルメルカプタン０．８部を加え重合を行
い、反応液が所定の粘度に達した時点でメタクリル酸メ
チル５０部を加え急冷する方法により、シラップ中の重
合体にカルボン酸を含むアクリルシラップを製造する方
法が開示されている。しかしながらこの方法において
は、所定の粘度に達した時点で単量体を加え急冷するこ
とで強制的に重合を停止しており、得られたシラップ中
には重合開始剤が残存しているので、貯蔵安定性の劣っ
たものとなる。また反応に必要な量の重合開始剤を一度
に添加するために反応の制御が困難である。僅かな温度
の変化の影響により製品の重合率、粘度が大きく変化す
るため安定した製造は行えない。As a production method by the first batch method among the partial polymerization methods, for example, Japanese Patent Publication No. 36-3392 discloses
The raw material comprising a monomer having methyl methacrylate as a main component and a chain transfer agent is heated to 80 ° C, a small amount of azobisisobutyronitrile or benzoyl peroxide is added as a polymerization initiator, and the temperature is raised to 100 ° C at the same time. 27 to 5 under reflux
There is disclosed a method for producing an acrylic syrup by adding a hydroquinone-containing cold methyl methacrylate as a polymerization inhibitor and quenching when a predetermined viscosity is reached after polymerization for 0 minutes. However, in this method, since the polymerization is stopped in a state where the polymerization initiator is not completely decomposed, the polymerization initiator remains in the obtained syrup,
Even if a polymerization inhibitor is added, storage stability will be poor. For example, 1 of benzoyl peroxide used as a polymerization initiator
Since the half-life at 00 ° C. is about 22 minutes, when the viscosity reaches a predetermined value, 42 to 20% of the polymerization initiator based on the added amount remains in the product. In addition, it is difficult to control the reaction because the amount of polymerization initiator required for the reaction is added all at once, and the temperature is raised once the polymerization initiator is added and the reaction is carried out under reflux. There is no detailed description of such factors, and a stable production cannot be performed because the polymerization rate and viscosity of the product greatly change due to a slight change in temperature. In Japanese Patent Publication No. 1-11652, SMC or B
In producing a syrup as an intermediate material for MC, a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube is composed of 89% by weight of methyl methacrylate, 5% by weight of methacrylic acid, and 6% by weight of trimethylolpropane trimethacrylate. N-Dodecyl mercaptan 0.1 part per 100 parts of monomer.
4 parts, 2,2'-azobisisobutyronitrile 0.05
Parts, and polymerization is performed at 80 ° C. under a nitrogen atmosphere. When the reaction solution reaches a predetermined viscosity, hydroquinone and p-methoxyphenol are added as polymerization inhibitors, and the mixture is immediately cooled to room temperature to inhibit polymerization. Depending on how you
A method for producing an acrylic syrup containing a carboxylic acid is disclosed. However, in this method, when a predetermined viscosity is reached, polymerization is forcibly stopped by adding a polymerization inhibitor, and the polymerization initiator remains in the obtained syrup. Even if an agent is added, storage stability will be poor. In addition, it is difficult to control the reaction because the amount of the polymerization initiator required for the reaction is added all at once.
Stable production cannot be performed because the degree of polymerization and viscosity of the product greatly change under the influence of a slight change in temperature. In JP-A-9-67495, when producing syrup as an intermediate material for SMC or BMC, a monomer composed of 190 parts of methyl methacrylate and 10 parts of methacrylic acid is heated to 80 ° C. in a nitrogen atmosphere to initiate polymerization. 2,2'-
A method in which 0.05 part of azobisisobutyronitrile and 0.8 part of n-dodecylmercaptan as a chain transfer agent are added to carry out polymerization, and when the reaction solution reaches a predetermined viscosity, 50 parts of methyl methacrylate is added and quenched. Discloses a method for producing an acrylic syrup containing a carboxylic acid in the polymer in the syrup. However, in this method, when a predetermined viscosity is reached, the polymerization is forcibly stopped by adding the monomer and quenching, and the polymerization initiator remains in the obtained syrup. Inferior storage stability. In addition, it is difficult to control the reaction because the amount of the polymerization initiator required for the reaction is added all at once. Stable production cannot be performed because the degree of polymerization and viscosity of the product greatly change under the influence of a slight change in temperature.
【０００６】従来行われてきた回分法では反応に必要な
量の重合開始剤を一度に添加するために反応の制御が困
難であり、僅かな温度変化の影響により製品の重合率、
粘度が大きく変化するため、安定した品質の製品は得ら
れがたい。また重合開始剤が残存しないようにするため
反応温度での半減期が短い重合開始剤を用いると、一度
に多量の重合開始剤が分解し、重合反応が急速に進行す
るため重合反応を制御することができない。このため回
分法で使用可能な重合開始剤は重合温度での半減期が長
いものに限定されるので、得られたシラップ中に重合開
始剤が残存しており、たとえ重合禁止剤を加えても貯蔵
安定性の劣ったものとなる。[0006] In the conventional batch method, the amount of polymerization initiator required for the reaction is added all at once, which makes it difficult to control the reaction.
Since the viscosity changes greatly, it is difficult to obtain a product of stable quality. In addition, when a polymerization initiator having a short half-life at the reaction temperature is used to prevent the polymerization initiator from remaining, a large amount of the polymerization initiator is decomposed at once, and the polymerization reaction proceeds rapidly, so that the polymerization reaction is controlled. Can not do. For this reason, the polymerization initiator that can be used in the batch method is limited to those having a long half-life at the polymerization temperature, so the polymerization initiator remains in the obtained syrup, even if the polymerization inhibitor is added. Inferior storage stability.
【０００７】部分重合法のうち第二に連続法による製造
方法として、例えば特開平３−１１１４０８号公報には
原料中の溶存酸素を１ｐｐｍ未満とし、反応液の沸騰を
抑え、１３０〜１６０℃において重合率が４５〜７０％
となるように重合させる方法が開示されている。この完
全混合槽による連続法においても、原料中の溶存酸素を
除去する必要があり、重合反応は窒素雰囲気下で行われ
るので多量の窒素を必要とする。また上記の完全混合槽
による連続法では連続キャスト板向けなど大量少品種生
産には適しているとしても、種々の用途に適した製品を
作るための少量多品種の生産には不向きである。Among the partial polymerization methods, as a second continuous production method, for example, Japanese Unexamined Patent Publication (Kokai) No. 3-111408 discloses a method in which the dissolved oxygen in the raw material is reduced to less than 1 ppm, the boiling of the reaction solution is suppressed, Polymerization rate is 45-70%
There is disclosed a method of polymerizing so that Also in the continuous method using the complete mixing tank, it is necessary to remove dissolved oxygen in the raw materials, and a large amount of nitrogen is required because the polymerization reaction is performed in a nitrogen atmosphere. Although the above-described continuous method using a complete mixing tank is suitable for mass production of small variety such as for continuous cast plate, it is not suitable for production of small quantity and large variety for producing products suitable for various uses.
【０００８】このように、メタクリル酸メチルを主成分
とする単量体の重合を行う場合、窒素等の不活性ガスを
単量体中に導入することにより単量体中の溶存酸素を除
去することが広く行われている。酸素は重合反応におい
て重合禁止剤あるいは重合開始剤として働くことが知ら
れている。例えばＪ．Ｃ．Ｂｅｖｉｎｇｔｏｎ（Ｊ．
Ｃ．Ｂｅｖｉｎｇｔｏｎ、大津 隆行ほか訳、東京化学
同人、「ラジカル重合」、１９６６年、ｐ．１８２〜１
８３）によれば、ポリマーラジカルが酸素に対して高い
反応性を有し、付加反応によりパーオキシラジカルを生
成すること、およびこのパーオキシラジカルと単量体の
反応速度が非常に小さいので、通常の場合酸素は重合を
抑制することが記されている。また松本ら（高分子化
学、２６、１９６９、ｐ．１８０〜１８６）によれば、
精製した単量体と酸素とが反応してパーオキサイドが生
成し、このうち特にヒドロキシパーオキサイドは通常の
重合開始剤のようにラジカルを発生し重合開始反応を起
こすこと、多量の酸素が存在すると単量体との共重合体
を生成するため、通常の単量体だけの重合を抑制するこ
とが記されている。このように単量体中に酸素が溶存し
ていると、酸素が単量体と反応してパーオキサイドや共
重合体を生成し、温度や酸素濃度等の条件により、重合
を抑制したり、あるいは逆に重合を開始したりするので
重合反応が不安定となる。メタクリル酸メチルを主成分
とする単量体の重合を工業的にかつ安定的に実施するに
は、重合に及ぼす影響が実質的になくなる程度まで溶存
酸素を除去することが必要である。As described above, when polymerizing a monomer containing methyl methacrylate as a main component, dissolved oxygen in the monomer is removed by introducing an inert gas such as nitrogen into the monomer. That is widely done. It is known that oxygen acts as a polymerization inhibitor or a polymerization initiator in a polymerization reaction. For example, C. Bevington (J.
C. Bevington, translated by Takatsu Otsu et al., Tokyo Kagaku Doujin, "Radical Polymerization", 1966, p. 182-1
According to 83), since the polymer radical has high reactivity to oxygen and generates a peroxy radical by an addition reaction, and the reaction rate between the peroxy radical and the monomer is very small, In this case, it is described that oxygen suppresses polymerization. According to Matsumoto et al. (Polymer Chemistry, 26, 1969, pp. 180-186),
The purified monomer and oxygen react with each other to form peroxides, of which hydroxyperoxide, in particular, generates radicals and initiates a polymerization initiation reaction like a normal polymerization initiator. It is described that polymerization of ordinary monomers alone is suppressed in order to form a copolymer with monomers. When oxygen is dissolved in the monomer as described above, the oxygen reacts with the monomer to generate a peroxide or a copolymer, and the polymerization is suppressed by conditions such as temperature and oxygen concentration, Or, conversely, polymerization is started, so that the polymerization reaction becomes unstable. In order to industrially and stably carry out polymerization of a monomer containing methyl methacrylate as a main component, it is necessary to remove dissolved oxygen to such an extent that the effect on polymerization is substantially eliminated.
【０００９】同様に、半回分法においても重合に及ぼす
影響が実質的になくなる程度まで溶存酸素を除去するた
めには多量の不活性ガスを用いる必要があり、製造コス
ト上昇の一因となる。重合の阻害要因を除去し、しかも
製造コストを削減できる方法が待ち望まれている。Similarly, even in the semi-batch process, a large amount of inert gas must be used to remove dissolved oxygen to such an extent that the effect on polymerization is substantially eliminated, which causes an increase in production cost. There is a long-awaited need for a method capable of eliminating the factors inhibiting polymerization and reducing the production cost.
【００１０】[0010]
【発明が解決しようとする課題】本発明の目的は、従来
法の上記のような問題点を解決し、種々の用途に適しか
つ安定した品質のアクリルシラップを効率的にかつ容易
に製造する方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the conventional method and to efficiently and easily produce an acrylic syrup having a stable quality suitable for various uses. Is to provide.
【００１１】[0011]
【課題を解決するための手段】本発明者らは鋭意研究し
た結果、特定の製造方法によって、種々の用途に適しか
つ安定した品質のアクリルシラップを、効率的にかつ容
易に製造し得ることを見いだし、本発明を完成した。Means for Solving the Problems As a result of intensive studies, the present inventors have found that an acrylic syrup suitable for various uses and having stable quality can be efficiently and easily produced by a specific production method. We have found and completed the present invention.
【００１２】すなわち本発明は、メタクリル酸メチルを
主成分とする単量体、重合開始剤および連鎖移動剤を含
む混合物からアクリルシラップを製造するに際し、
（１）原料の全量に対し２０〜７０重量％の単量体を用
い、単量体に対し２００〜１０００ｖｏｌ％の不活性ガ
スを単量体に接触させて溶存酸素を置換した後に昇温
し、（２）系内組成物の沸点に達し還流を開始した時点
で連鎖移動剤を添加し、（３）次いで反応温度を系内組
成物の沸点とし、かつ還流を維持しながら、原料の全量
に対し８０〜３０重量％の単量体を不活性ガスを単量体
に接触させずに、０．１〜１０時間の範囲から選ばれた
時間かけて連続的にまたは分割して添加し、（４）単量
体の添加と同時に、反応温度での半減期が１０〜３００
秒の重合開始剤を連続的にまたは分割して加え反応を行
う、ＧＰＣで測定したシラップ中重合体の重量平均分子
量が２万〜５０万であり、２５℃における粘度が１．０
×１０2 〜５．０×１０5 ｍＰａ・ｓであるアクリルシ
ラップの製造方法に関するものである。That is, the present invention relates to the production of an acrylic syrup from a mixture containing a monomer containing methyl methacrylate as a main component, a polymerization initiator and a chain transfer agent.
(1) A monomer is used in an amount of 20 to 70% by weight based on the total amount of the raw material, and an inert gas of 200 to 1000 vol% with respect to the monomer is brought into contact with the monomer to displace dissolved oxygen, and then the temperature is raised. (2) a chain transfer agent is added when the boiling point of the in-system composition is reached and reflux is started; (3) Then, the reaction temperature is adjusted to the boiling point of the in-system composition, and the total amount of the raw materials is maintained while maintaining the reflux. 80 to 30% by weight of the monomer is added continuously or in portions over a time selected from the range of 0.1 to 10 hours without bringing the inert gas into contact with the monomer, (4) Simultaneously with the addition of the monomer, the half-life at the reaction temperature is 10 to 300.
The polymerization initiator in the syrup has a weight average molecular weight of 20,000 to 500,000 as measured by GPC, and a viscosity at 25 ° C of 1.0.
The present invention relates to a method for producing an acrylic syrup having a density of × 10 2 to 5.0 × 10 5 mPa · s.
【００１３】[0013]
【発明の実施の形態】以下、本発明のアクリルシラップ
の製造方法について具体的に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for producing an acrylic syrup of the present invention will be specifically described.
【００１４】本発明では単量体成分としてメタクリル酸
メチルを主成分とし、メタクリル酸メチルと共重合可能
な他の単量体成分を５０％未満の範囲で任意に加えて用
いることができる。この単量体成分はメタクリル酸メチ
ルと共重合可能な単量体であれば特に限定されず、アク
リル酸、メタクリル酸、マレイン酸および／またはフマ
ル酸などの不飽和カルボン酸、メタクリル酸メチルを除
く不飽和カルボン酸エステル、不飽和ニトリル、不飽和
カルボン酸アミド、不飽和カルボン酸のイミド及び／ま
たは酸無水物、スチレンなどの芳香族ビニル、酢酸ビニ
ルなどのカルボン酸ビニルなど、エチレン性二重結合を
有する化合物が挙げられる。In the present invention, methyl methacrylate is used as a main component as a monomer component, and other monomer components copolymerizable with methyl methacrylate can be optionally added in an amount of less than 50%. This monomer component is not particularly limited as long as it is a monomer copolymerizable with methyl methacrylate, and excludes unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and / or fumaric acid, and methyl methacrylate. Ethylenic double bonds such as unsaturated carboxylic acid esters, unsaturated nitriles, unsaturated carboxylic acid amides, imides and / or acid anhydrides of unsaturated carboxylic acids, aromatic vinyls such as styrene, vinyl carboxylates such as vinyl acetate, etc. A compound having the following formula:
【００１５】本発明においては、初期に仕込む原料の
み、単量体に対し２００〜１０００ｖｏｌ％の不活性ガ
スを単量体に接触させて溶存酸素を置換すればよく、系
内組成物の沸点で、かつ還流を維持しながら反応を行う
ことにより、添加原料中に不活性ガスを接触させなくて
も、酸素が実質的に系内から除去された状態で重合を行
うことができる。不活性ガスの量が単量体に対し２００
ｖｏｌ％未満では溶存酸素を十分低減することができな
い。１０００ｖｏｌ％を超える量を用いることも可能で
あるがいたずらに不活性ガスの消費量を増加させるだけ
で経済的でない。また不活性ガスを単量体に接触させる
手段には、バブリング、アトマイジングあるいはモーシ
ョンレスミキサーによる気液接触および気液の分離な
ど、公知の手段を用いることができる。In the present invention, only the raw materials to be initially charged may be brought into contact with the monomer by an inert gas of 200 to 1000 vol% with respect to the monomer to replace dissolved oxygen. By carrying out the reaction while maintaining the reflux, the polymerization can be carried out in a state in which oxygen is substantially removed from the system without bringing the added raw material into contact with an inert gas. The amount of inert gas is 200
If it is less than vol%, the dissolved oxygen cannot be reduced sufficiently. Although it is possible to use an amount exceeding 1000 vol%, it is not economical only to increase the consumption of the inert gas unnecessarily. As a means for bringing the inert gas into contact with the monomer, known means such as bubbling, atomizing, gas-liquid contact with a motionless mixer, and gas-liquid separation can be used.
【００１６】本発明においては、反応槽中の反応液１０
０重量部に対し、１分あたりの還流量を０．０１重量部
〜１０．０重量部であるように還流状態を維持すること
により系内の酸素を系外に除去する。１分あたりの還流
量が０．０１重量部未満では原料の添加により系内にも
たらされる酸素の系外への除去が不完全であり、設定通
りの重合率を得ることができない。逆に１分あたりの還
流量が１０．０重量部を超えるのは急激な重合反応が起
こっている場合かまたは過剰な熱量がジャケットから与
えられている場合であり、前者では重合反応の制御が不
可能であり、後者ではエネルギー効率が悪く、いずれも
好ましくない。In the present invention, the reaction solution 10
Oxygen in the system is removed from the system by maintaining the reflux state so that the amount of reflux per minute is 0.01 to 10.0 parts by weight per 0 parts by weight. If the reflux rate per minute is less than 0.01 parts by weight, the removal of oxygen brought into the system by the addition of the raw materials to the outside of the system is incomplete, and the set polymerization rate cannot be obtained. Conversely, the amount of reflux per minute exceeds 10.0 parts by weight when a rapid polymerization reaction is occurring or when an excessive amount of heat is supplied from the jacket. In the former case, the polymerization reaction is controlled. It is impossible, and the latter has poor energy efficiency, and neither is preferable.
【００１７】本発明においては、反応温度での半減期が
１０〜３００秒になるような重合開始剤を用い、単量体
及び重合開始剤の添加終了後０〜５時間還流状態を維持
することにより、重合開始剤を完全に分解させ、得られ
るシラップの貯蔵安定性を向上させることができる。In the present invention, a polymerization initiator having a half-life at the reaction temperature of 10 to 300 seconds is used, and the reflux state is maintained for 0 to 5 hours after the addition of the monomer and the polymerization initiator is completed. Thereby, the polymerization initiator can be completely decomposed, and the storage stability of the obtained syrup can be improved.
【００１８】重合開始剤の半減期は例えば日本油脂
（株）「有機過酸化物」資料第１３版、アトケム吉富
（株）技術資料および和光純薬工業（株）「Ａｚｏ Ｐ
ｏｌｙｍｅｒｉｚａｔｉｏｎ Ｉｎｉｔｉａｔｏｒｓ」
等に記載の諸定数等により容易に求めることができ、例
えば２，２’−アゾビス（２，４−ジメチルバレロニト
リル）、２，２’−アゾビス（２，４ジメチル−４−メ
トキシバレロニトリル）、１，１’−アゾビスシクロヘ
キサンカルボニトリル、ラウロイルパーオキサイド、ｔ
−ブチルパーオキシピバレート、ｔ−ブチルパーオキシ
−２−エチルヘキサノエート、ｔ−アミルパーオキシ−
２−エチルヘキサノエート、ジイソプロピルパーオキシ
ジカーボネートおよび／またはビス( ４−ｔ−ブチルシ
クロヘキシル)パーオキシジカーボネートなどが用いら
れる。The half-life of the polymerization initiator can be determined by, for example, the 13th edition of “Nippon Yushi Co., Ltd.“ Organic Peroxide ”, Atochem Yoshitomi Co., Ltd. and Wako Pure Chemical Industries, Ltd.“ Azo P ”.
oligomerization Initiators "
And the like, for example, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4dimethyl-4-methoxyvaleronitrile) , 1,1'-azobiscyclohexanecarbonitrile, lauroyl peroxide, t
-Butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-amylperoxy-
For example, 2-ethylhexanoate, diisopropyl peroxydicarbonate and / or bis (4-t-butylcyclohexyl) peroxydicarbonate are used.
【００１９】用いられる重合開始剤は、単独であるいは
２種以上組み合わせて用いることができ、重合反応槽で
所望の重合率を得るために必要な量が添加される。また
重合開始剤を単独で添加する方法、単量体原料と混合し
て添加する方法のいずれも用いることができる。本発明
によるアクリルシラップの粘度は重合率、重合体の分子
量および重合体中のメタクリル酸メチルと共重合可能な
不飽和単量体単位の分率により影響を受けるが、必要な
粘度範囲を満足するためには、原料全体に対する重合開
始剤の使用量として５．０×１０-5〜２．０ｗｔ％が好
ましく、５．０×１０-4〜１．０ｗｔ％がさらに好まし
い。The polymerization initiators to be used can be used alone or in combination of two or more kinds, and an amount necessary for obtaining a desired polymerization rate in a polymerization reaction tank is added. Either a method of adding the polymerization initiator alone or a method of adding the polymerization initiator by mixing with the monomer raw material can be used. The viscosity of the acrylic syrup according to the present invention is affected by the polymerization rate, the molecular weight of the polymer and the fraction of unsaturated monomer units copolymerizable with methyl methacrylate in the polymer, but satisfies the required viscosity range. For this purpose, the amount of the polymerization initiator to be used is preferably 5.0 × 10 −5 to 2.0 wt%, and more preferably 5.0 × 10 −4 to 1.0 wt%.
【００２０】連鎖移動剤としては重合反応を阻害せず所
望の分子量の製品が得られるものであれば何でもよい。
通常はメルカプタン類が用いられる。連鎖移動剤として
メルカプタン類を用いた場合には、僅かづつ重合が進行
することが知られている。最初に仕込む原料中にメルカ
プタン類が含まれた状態で昇温すると、昇温パターンの
変動により添加開始前のポリマー濃度が変動し、製品の
重合率が変動するため安定した製造が行えない。従っ
て、昇温が完了して単量体および／または重合開始剤の
供給を開始する直前に連鎖移動剤の全量を添加すること
が好ましい。Any chain transfer agent can be used as long as it can obtain a product having a desired molecular weight without inhibiting the polymerization reaction.
Usually, mercaptans are used. It is known that when mercaptans are used as a chain transfer agent, polymerization proceeds little by little. If the temperature is increased in a state where mercaptans are contained in the raw materials to be initially charged, the concentration of the polymer before the start of the addition varies due to the variation in the heating pattern, and the polymerization rate of the product varies, so that stable production cannot be performed. Therefore, it is preferable to add the entire amount of the chain transfer agent just before the temperature increase is completed and immediately before the supply of the monomer and / or the polymerization initiator is started.
【００２１】本発明において原料は大きく分けて、初め
から仕込まれる原料、すなわち初期仕込分および重合開
始剤とともに後で添加される残りの原料、すなわち添加
分に分けられる。この初期仕込分と添加分の重量比は通
常２０：８０〜７０：３０の範囲である。反応装置にも
よるが、初期仕込分が２０ｗｔ％未満では攪拌翼の大部
分が液面より上にあるため攪拌効率が悪く、好ましくな
い。In the present invention, the raw materials are roughly divided into raw materials charged from the beginning, that is, the initial raw materials and the remaining raw materials added later together with the polymerization initiator, that is, the added materials. The weight ratio of the initial charge and the additive is usually in the range of 20:80 to 70:30. Although it depends on the reactor, if the initial charge is less than 20 wt%, the stirring efficiency is poor because most of the stirring blades are above the liquid level, which is not preferable.
【００２２】添加原料の供給速度は添加中を通じ一定と
なるように制御される。また添加時間は０．１〜１０時
間であり、好ましくは０．５〜８時間である。添加時間
が０．１時間未満では発熱量が多く、しかも反応槽内液
量の増加速度が大きいため大容量の熱交換器、大流量の
定量ポンプなどを必要とし好ましくない。また１０時間
を超えると仕込から製品取出までの工程時間が長くなり
生産性の点から好ましくない。The supply rate of the additive material is controlled so as to be constant throughout the addition. The addition time is 0.1 to 10 hours, preferably 0.5 to 8 hours. If the addition time is less than 0.1 hour, a large amount of heat is generated, and the rate of increase in the amount of liquid in the reaction tank is large. On the other hand, if the time exceeds 10 hours, the process time from preparation to product removal becomes longer, which is not preferable in terms of productivity.
【００２３】単量体および／または重合開始剤の添加終
了後、０．０１〜５時間、好ましくは０．０１〜１時間
さらに加熱を継続する。この反応時間は重合開始剤が９
９％以上分解する時間とするのが望ましい。重合開始剤
が残存していると冷却時の影響により最終製品の重合率
および粘度が変動しメタクリル酸メチルシラップを安定
に製造することが困難となるばかりでなく、得られたメ
タクリル酸メチルシラップの貯蔵安定性が低下し好まし
くない。５時間を超えて加熱を継続することも可能であ
るが、仕込から製品取出までの工程時間が長くなり生産
性の点から好ましくない。最終的な重合率は設定分子量
およびメタクリル酸メチルと共重合可能な単量体の濃度
にもよるが、１５〜５０重量％である。After the addition of the monomer and / or the polymerization initiator is completed, the heating is further continued for 0.01 to 5 hours, preferably 0.01 to 1 hour. The reaction time was 9 hours for the polymerization initiator.
It is desirable to set the time to decompose by 9% or more. If the polymerization initiator remains, the polymerization rate and viscosity of the final product fluctuate due to the effect of cooling, and it becomes difficult not only to stably produce methyl methacrylate syrup, but also to obtain the obtained methyl methacrylate syrup. Storage stability is undesirably reduced. Although it is possible to continue heating for more than 5 hours, the process time from preparation to product removal becomes longer, which is not preferable from the viewpoint of productivity. The final polymerization rate is 15 to 50% by weight, depending on the set molecular weight and the concentration of the monomer copolymerizable with methyl methacrylate.
【００２４】本発明においては一定時間加熱を継続した
後重合禁止剤を加えてから冷却し、製品を取り出すこと
が好ましい。冷却する前に重合禁止剤を加えることによ
り、冷却操作中にメルカプタン類による重合が進行する
ことを抑制し、さらに安全に安定した条件でアクリルシ
ラップを製造することができる。また冷却する前に重合
禁止剤を加えることにより連鎖移動剤にメルカプタン類
を用いる場合であってもアクリルシラップの貯蔵安定性
は良好となり、アクリルシラップ中に残存するメルカプ
タン類の不活性化処理を行う必要はない。In the present invention, it is preferable that after heating is continued for a certain period of time, a polymerization inhibitor is added, followed by cooling, and the product is taken out. By adding the polymerization inhibitor before cooling, the progress of polymerization by the mercaptans during the cooling operation can be suppressed, and the acrylic syrup can be produced safely and under stable conditions. In addition, even when mercaptans are used as a chain transfer agent by adding a polymerization inhibitor before cooling, the storage stability of the acrylic syrup becomes good, and a deactivation treatment of the mercaptans remaining in the acrylic syrup is performed. No need.
【００２５】得られたシラップの着色をさけるため、重
合禁止剤としてはヒンダードフェノール系重合禁止剤を
用いることが好ましい。ヒンダードフェノール系重合禁
止剤としては、例えば２，６−ジ−ｔ−ブチル−４−メ
チルフェノール（ＢＨＴ）、６−ｔ−ブチル−２，４−
ジメチルフェノール、４，４’−チオビス−（６−ｔ−
ブチル−３−メチルフェノール）および／または２，
２’−メチレンビス−（４−メチル−６−ｔ−ブチルフ
ェノール）等が挙げられる。これらのヒンダードフェノ
ール系重合禁止剤は単独で、あるいは２種以上組み合わ
せて用いることができる。また上記ヒンダードフェノー
ル系重合禁止剤の存在下、例えばリン系重合禁止剤のよ
うな、ヒンダードフェノール系重合禁止剤と併用するこ
とでさらに着色を抑制することが公知である重合禁止剤
を併用することも可能である。In order to prevent coloring of the obtained syrup, it is preferable to use a hindered phenol-based polymerization inhibitor as the polymerization inhibitor. Examples of the hindered phenol polymerization inhibitor include 2,6-di-t-butyl-4-methylphenol (BHT) and 6-t-butyl-2,4-
Dimethylphenol, 4,4'-thiobis- (6-t-
Butyl-3-methylphenol) and / or 2,
2'-methylenebis- (4-methyl-6-t-butylphenol) and the like. These hindered phenol-based polymerization inhibitors can be used alone or in combination of two or more. In addition, in the presence of the hindered phenol-based polymerization inhibitor, for example, a polymerization inhibitor, such as a phosphorus-based polymerization inhibitor, is used in combination with a hindered phenol-based polymerization inhibitor, which is known to further suppress coloration. It is also possible.
【００２６】さらに、冷却時においては酸素を含むガス
を導入することが望ましい。酸素を含むガスとしては空
気または空気と窒素の混合ガス等が挙げられる。ヒンダ
ードフェノール系化合物存在下でシラップ中に酸素を十
分溶存させることにより、アクリルシラップの貯蔵安定
性が良好となる。Further, at the time of cooling, it is desirable to introduce a gas containing oxygen. Examples of the gas containing oxygen include air or a mixed gas of air and nitrogen. By sufficiently dissolving oxygen in the syrup in the presence of the hindered phenol compound, the storage stability of the acrylic syrup is improved.
【００２７】以上のようにして得られたアクリルシラッ
プはＧＰＣ（ゲルパーミエーションクロマトグラフィ
ー）で測定したシラップ中重合体の重量平均分子量が３
万〜３０万であり、２５℃における粘度が１．０×１０
2 〜５．０×１０5 ｍＰａ・ｓ、好ましくは１．０×１
０2 〜１．０×１０5 ｍＰａ・ｓであることを特徴とす
るものとなる。The acrylic syrup obtained as described above has a polymer in the syrup having a weight average molecular weight of 3 as measured by GPC (gel permeation chromatography).
And the viscosity at 25 ° C. is 1.0 × 10
2 to 5.0 × 10 5 mPa · s, preferably 1.0 × 1
0 2 to 1.0 × 10 5 mPa · s.
【００２８】得られたアクリルシラップは注型板、光伝
送繊維や光導波路などの光学材料、アクリル人造大理
石、人工印材、床材、接着剤、粘着剤、文化財・剥製等
修復材料または医用材料などの中間原料として用いるこ
とができる。必要に応じ充填材、繊維補強材、低収縮
剤、滑剤、可塑剤、増粘剤、有機溶剤等の希釈剤、架橋
剤、レベリング剤、脱泡剤、沈降防止剤、離型剤、酸化
防止剤、重合禁止剤、ＵＶ吸収剤、顔料および／または
染料等の公知の添加剤と本発明のアクリルシラップを混
合し用いることもできる。The obtained acrylic syrup is a casting plate, an optical material such as an optical transmission fiber or an optical waveguide, an acrylic artificial marble, an artificial stamping material, a floor material, an adhesive, an adhesive, a cultural property, a stuffing and the like, or a medical material. It can be used as an intermediate material. Fillers, fiber reinforcements, low-shrinkage agents, lubricants, plasticizers, thickeners, diluents such as organic solvents, crosslinking agents, leveling agents, defoamers, anti-settling agents, release agents, anti-oxidants as required A known additive such as an agent, a polymerization inhibitor, a UV absorber, a pigment and / or a dye may be mixed with the acrylic syrup of the present invention.
【００２９】[0029]
【実施例】本発明をさらに具体的に例示するが、これら
に限定されるものではない。重合率は重量法により、試
料を大量の冷ヘキサン中に投入し生じた沈澱物を精製・
減圧乾燥し求めた。シラップ中重合体の分子量は東ソー
（株）製８０１０型ゲルパーミエーションクロマトグラ
フィーにより測定した。粘度はＢ型粘度計を用い２５℃
で測定した。 実施例１ 撹拌機、冷却管、定量ポンプを備えた３Ｌセパラブルフ
ラスコにメタクリル酸メチル９１１ｇ、メタクリル酸２
８ｇを仕込み、１００ｍｌ／分の流量で３０分間（単量
体に対し３００ｖｏｌ％）窒素バブリングを行った後、
窒素雰囲気下で昇温した。１００℃に達し還流が始まっ
た時点で１−ドデカンチオール１１ｇを加え、還流量を
２０ｇ／分に維持しながらメタクリル酸メチル９４０ｇ
および２，２’−アゾビス（２，４−ジメチルバレロニ
トリル）０．１４ｇ（１００℃における半減期＝９６
秒）からなる溶液を３時間かけて定量ポンプを用いて添
加した。添加終了後０．３時間加熱を継続し、２，６−
ジ−ｔ−ブチル−４−メチルフェノール２．９８ｇを加
えた後、冷却管を通して空気が入り得る状態で室温まで
攪拌しながら冷却した。得られたシラップの重合率は３
５．１％、酸価は７．４ｍｇＫＯＨ／ｇ、２５℃におけ
る粘度は２１００ｍＰａ・ｓであった。またＧＰＣによ
り測定したシラップ中重合体の重量平均分子量は５．１
万であった。同じ実験を３回繰り返したところ、重合率
は３５．１±０．２％、酸価はいずれも７．４ｍｇＫＯ
Ｈ／ｇ、２５℃における粘度は２１００±１００ｍＰａ
・ｓ、ＧＰＣにより測定したシラップ中重合体の重量平
均分子量はいずれも５．１万であった。The present invention will now be described in more detail with reference to Examples, but it should not be construed that the invention is limited thereto. The polymerization rate can be determined by the gravimetric method by pouring the sample into a large amount of cold hexane and purifying the resulting precipitate.
It was dried under reduced pressure. The molecular weight of the polymer in the syrup was measured by 8010 type gel permeation chromatography manufactured by Tosoh Corporation. The viscosity was measured at 25 ° C using a B-type viscometer.
Was measured. Example 1 911 g of methyl methacrylate and methacrylic acid 2 were placed in a 3 L separable flask equipped with a stirrer, a condenser, and a metering pump.
After charging 8 g and performing nitrogen bubbling at a flow rate of 100 ml / min for 30 minutes (300 vol% based on the monomer),
The temperature was raised under a nitrogen atmosphere. When the temperature reached 100 ° C. and the reflux started, 11 g of 1-dodecanethiol was added, and 940 g of methyl methacrylate was added while maintaining the reflux rate at 20 g / min.
And 0.14 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (half-life at 100 ° C. = 96
Sec) was added over 3 hours using a metering pump. After the addition, heating was continued for 0.3 hour,
After adding 2.98 g of di-t-butyl-4-methylphenol, the mixture was cooled to room temperature with stirring so that air could enter through a cooling tube. The polymerization rate of the obtained syrup is 3
5.1%, the acid value was 7.4 mg KOH / g, and the viscosity at 25 ° C. was 2,100 mPa · s. The weight average molecular weight of the polymer in the syrup measured by GPC was 5.1.
It was 10,000. When the same experiment was repeated three times, the polymerization rate was 35.1 ± 0.2%, and the acid value was 7.4 mg KO in each case.
H / g, viscosity at 25 ° C. is 2100 ± 100 mPa
The weight average molecular weight of the polymer in the syrup measured by s and GPC was 51,000.
【００３０】比較例１ 還流を行わなかった以外は実施例１と同様に反応を行っ
た。得られたシラップの重合率は３１．１％、酸価は
７．４ｍｇＫＯＨ／ｇ、２５℃における粘度は６１０ｍ
Ｐａ・ｓであった。またＧＰＣにより測定したシラップ
中重合体の重量平均分子量は５．０万であった。同じ実
験を３回繰り返したところ、重合率は３１．３±０．８
％、酸価はいずれも７．４ｍｇＫＯＨ／ｇ、２５℃にお
ける粘度は６５０±１８０ｍＰａ・ｓ、ＧＰＣにより測
定したシラップ中重合体の重量平均分子量は５．０〜
５．１万であり、再現性あるデータは得られなかった。Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that reflux was not performed. The resulting syrup had a polymerization rate of 31.1%, an acid value of 7.4 mg KOH / g and a viscosity at 25 ° C. of 610 m.
Pa · s. The weight average molecular weight of the polymer in the syrup measured by GPC was 500000. When the same experiment was repeated three times, the conversion was 31.3 ± 0.8.
%, The acid value was 7.4 mg KOH / g, the viscosity at 25 ° C. was 650 ± 180 mPa · s, and the weight average molecular weight of the polymer in the syrup measured by GPC was 5.0 to 5.0.
51,000, and no reproducible data was obtained.
【００３１】参考例１ 還流を行わず、昇温前に、原料に対し３倍量の窒素バブ
リングを行いかつ窒素雰囲気下で反応を行った以外は実
施例１と同様に反応を行った。得られたシラップの重合
率は３５．１％、酸価は７．４ｍｇＫＯＨ／ｇ、２５℃
における粘度は２１００ｍＰａ・ｓであった。またＧＰ
Ｃにより測定したシラップ中重合体の重量平均分子量は
５．１万であった。同じ実験を３回繰り返したところ、
重合率は３５．１±０．２％、酸価はいずれも７．４ｍ
ｇＫＯＨ／ｇ、２５℃における粘度は２１００±１００
ｍＰａ・ｓ、ＧＰＣにより測定したシラップ中重合体の
重量平均分子量はいずれも５．１万であり、実施例１と
同じ性状のシラップが得られた。Reference Example 1 A reaction was carried out in the same manner as in Example 1 except that the material was subjected to nitrogen bubbling in a three-fold amount and reacted under a nitrogen atmosphere before the temperature was raised without reflux. The polymerization rate of the obtained syrup was 35.1%, the acid value was 7.4 mgKOH / g, and the temperature was 25 ° C.
Was 2100 mPa · s. Also GP
The weight average molecular weight of the polymer in the syrup measured by C was 51,000. After repeating the same experiment three times,
The polymerization rate was 35.1 ± 0.2%, and the acid value was 7.4 m in each case.
gKOH / g, viscosity at 25 ° C. is 2100 ± 100
The weight average molecular weight of the polymer in the syrup measured by mPa · s and GPC was 51,000, and syrup having the same properties as in Example 1 was obtained.
【００３２】実施例２〜３ 表１に示した反応条件で実施例１と同様に反応を行い、
表１に示す性状を有する無色透明なアクリルシラップを
得た。同じ実験を３回繰り返したところ、重合率、粘度
およびシラップ重合体中の重量平均分子量ともに再現性
あるデータを有するシラップが得られた。Examples 2-3 The reaction was carried out in the same manner as in Example 1 under the reaction conditions shown in Table 1,
A colorless and transparent acrylic syrup having the properties shown in Table 1 was obtained. When the same experiment was repeated three times, a syrup having reproducible data in polymerization rate, viscosity and weight average molecular weight in the syrup polymer was obtained.
【００３３】比較例２〜３ 表１に示した反応条件で比較例１と同様に反応を行い、
表１に示す性状を有する無色透明なアクリルシラップを
得た。同じ実験を３回繰り返したところ、シラップ重合
体中の重量平均分子量は同じ値を示したが、重合率は平
均値の５％、２５℃における粘度は平均値の３割程度変
動し、再現性あるデータは得られなかった。Comparative Examples 2-3 Reaction was carried out in the same manner as in Comparative Example 1 under the reaction conditions shown in Table 1,
A colorless and transparent acrylic syrup having the properties shown in Table 1 was obtained. When the same experiment was repeated three times, the weight average molecular weight in the syrup polymer showed the same value, but the polymerization rate fluctuated about 5% of the average value, and the viscosity at 25 ° C. fluctuated about 30% of the average value. No data was available.
【００３４】参考例２〜３ 表１に示した条件で参考例１と同様に反応を行い、表１
に示す性状を有する無色透明なアクリルシラップを得
た。同じ実験を３回繰り返したところ、重合率、粘度お
よびシラップ重合体中の重量平均分子量ともに再現性あ
るデータを有するシラップが得られた。Reference Examples 2 to 3 The reaction was carried out in the same manner as in Reference Example 1 under the conditions shown in Table 1, and
A colorless and transparent acrylic syrup having the properties shown in Table 1 was obtained. When the same experiment was repeated three times, a syrup having reproducible data in polymerization rate, viscosity and weight average molecular weight in the syrup polymer was obtained.
【００３５】[0035]
【発明の効果】本発明により所望の特性を有するアクリ
ルシラップを安定に製造することができ、工業的意義は
大きい。According to the present invention, an acrylic syrup having desired characteristics can be stably produced, and has great industrial significance.
【００３６】[0036]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 黒川 正弘 神奈川県平塚市東八幡５丁目６番２号 三 菱瓦斯化学株式会社平塚研究所内 Ｆターム(参考） 4J011 AB07 AC05 BA07 BB06 BB17 FA05 FB09 FB15 FB19 4J100 AB02Q AG04Q AJ02Q AJ09Q AK31Q AL01Q AL03P AM01Q AM14Q AM41Q CA01 CA04 DA01 DA09 FA03 FA04 FA18 FA43 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masahiro Kurokawa 5-6-1 Higashi-Hachiman, Hiratsuka-shi, Kanagawa F-term in Hiratsuka Research Laboratory, Mitsubishi Ritsumeikan Chemical Co., Ltd. 4J011 AB07 AC05 BA07 BB06 BB17 FA05 FB09 FB15 FB19 4J100 AB02Q AG04Q AJ02Q AJ09Q AK31Q AL01Q AL03P AM01Q AM14Q AM41Q CA01 CA04 DA01 DA09 FA03 FA04 FA18 FA43
Claims (1)
体、重合開始剤および連鎖移動剤を含む混合物からアク
リルシラップを製造するに際し、（１）原料の全量に対
し２０〜７０重量％の単量体を用い、単量体に対し２０
０〜１０００ｖｏｌ％の不活性ガスを単量体に接触させ
て溶存酸素を置換した後に昇温し、（２）系内組成物の
沸点に達し還流を開始した時点で連鎖移動剤を添加し、
（３）次いで反応温度を系内組成物の沸点とし、かつ還
流を維持しながら、原料の全量に対し８０〜３０重量％
の単量体を０．１〜１０時間の範囲から選ばれた時間か
けて連続的にまたは分割して添加し、（４）単量体の添
加と同時に、反応温度での半減期が１０〜３００秒の重
合開始剤を連続的にまたは分割して加え反応を行うこと
を特徴とする、ＧＰＣで測定したシラップ中重合体の重
量平均分子量が２万〜５０万であり、２５℃における粘
度が１．０×１０2 〜５．０×１０5 ｍＰａ・ｓである
アクリルシラップの製造方法。In producing an acrylic syrup from a mixture containing a monomer containing methyl methacrylate as a main component, a polymerization initiator and a chain transfer agent, (1) 20-70% by weight of a total amount of the raw material; Monomer and 20
After dissolving dissolved oxygen by bringing 0 to 1000 vol% of inert gas into contact with the monomer, the temperature is raised, and (2) a chain transfer agent is added when the boiling point of the in-system composition is reached and reflux is started;
(3) Then, while maintaining the reaction temperature at the boiling point of the in-system composition and maintaining reflux, 80 to 30% by weight based on the total amount of the raw materials.
Is added continuously or in portions over a time selected from the range of 0.1 to 10 hours, and (4) the half-life at the reaction temperature is 10 to 10 at the same time as the addition of the monomer. The polymerization initiator of 300 seconds is continuously or dividedly added to carry out the reaction, the weight average molecular weight of the polymer in the syrup measured by GPC is 20,000 to 500,000, and the viscosity at 25 ° C. A method for producing an acrylic syrup having a density of 1.0 × 10 2 to 5.0 × 10 5 mPa · s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33969999A JP4296364B2 (en) | 1999-11-30 | 1999-11-30 | Acrylic syrup manufacturing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33969999A JP4296364B2 (en) | 1999-11-30 | 1999-11-30 | Acrylic syrup manufacturing method |
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|---|---|
| JP2001151817A true JP2001151817A (en) | 2001-06-05 |
| JP4296364B2 JP4296364B2 (en) | 2009-07-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33969999A Expired - Fee Related JP4296364B2 (en) | 1999-11-30 | 1999-11-30 | Acrylic syrup manufacturing method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001151801A (en) * | 1999-11-30 | 2001-06-05 | Mitsubishi Gas Chem Co Inc | Method for producing acrylic syrup |
| JP2003221403A (en) * | 2002-01-29 | 2003-08-05 | Daicel Chem Ind Ltd | Method for manufacturing polymer for photoresist |
| WO2022230916A1 (en) * | 2021-04-28 | 2022-11-03 | 三菱ケミカル株式会社 | Methyl-methacrylate-containing composition and method for producing methyl methacrylate polymer |
-
1999
- 1999-11-30 JP JP33969999A patent/JP4296364B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001151801A (en) * | 1999-11-30 | 2001-06-05 | Mitsubishi Gas Chem Co Inc | Method for producing acrylic syrup |
| JP4553078B2 (en) * | 1999-11-30 | 2010-09-29 | 三菱瓦斯化学株式会社 | Acrylic syrup manufacturing method |
| JP2003221403A (en) * | 2002-01-29 | 2003-08-05 | Daicel Chem Ind Ltd | Method for manufacturing polymer for photoresist |
| WO2022230916A1 (en) * | 2021-04-28 | 2022-11-03 | 三菱ケミカル株式会社 | Methyl-methacrylate-containing composition and method for producing methyl methacrylate polymer |
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| Publication number | Publication date |
|---|---|
| JP4296364B2 (en) | 2009-07-15 |
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