JP6091689B1 - Method for producing copolymer of vinyl acetate (VAc) and methyl methacrylate (MMA) - Google Patents
Method for producing copolymer of vinyl acetate (VAc) and methyl methacrylate (MMA) Download PDFInfo
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Abstract
【課題】VAc樹脂有機溶媒溶液とMMA樹脂有機溶媒とを混合することなくVAc樹脂へのMMA樹脂のグラフト重合法により、VA-MMA共重合体を作製する方法の提供。【解決手段】 VAc-MMAグラフト共重合体を作製するために有機溶媒トルエン中にて、先ず、VAcを一段重合する。次いで、MMAを二段重合することによりVAc-MMAグラフト共重合体を作製する。本重合体を作製するにあたり、重合用のラジカル発生開始剤としてBPO(ベンゾイルパ-オキサイド)の使用が必要不可欠な要件である。【選択図】なしThe present invention provides a method for producing a VA-MMA copolymer by graft polymerization of a MMA resin onto a VAc resin without mixing the VAc resin organic solvent solution and the MMA resin organic solvent. To produce a VAc-MMA graft copolymer, first, VAc is polymerized in one step in an organic solvent toluene. Next, a VAc-MMA graft copolymer is prepared by two-stage polymerization of MMA. In preparing this polymer, the use of BPO (benzoyl peroxide) as a radical generating initiator for polymerization is an indispensable requirement. [Selection figure] None
Description
本発明は、有機溶媒中におけるVAcとMMAとの共重合体の作製法に関するものである。 The present invention relates to a method for producing a copolymer of VAc and MMA in an organic solvent.
VAcとMMAとはモノマ-の反応性比 r1r2 が全く違うため通常の重合方法で共重合体を作るのは大変難しいと言われている。
事実、VAcとMMAとをモノマ-として用い、これを混ぜ合わせ、有機溶媒としてトルエンを、重合開始剤としてベンゾイルパ-オキサイド(BPO)を使って反応させ重合体を作製しようとしてもMMAのホモポリマ-ができるだけである。VAcは未反応であり、MMAとの共重合体は作らない。
これはBPOの熱分解により発生したフリ-ラジカルが、VAcモノマ-と反応するよりも先に、MMAポリマ−のほうへと連載移動する速度の方が早いためだと考えられている。
VAcポリマ-を塗料への応用として考えた場合、基材への接着性は優れている。しかし、耐候性は劣る。
MMAポリマ-は耐候性は優れているが、基材への接着力は劣る。
両者の特徴を生かすために、VAcとMMAの別々のホモポリマ-を作り、これらをブレンドして使う方法も講じられている。しかし、両者の相溶性が悪く脱混合を起こし充分な性能をもった塗膜を得ることができない。
基材への接着性のよいVAcと、優れた耐候性をもつMMAとの共重合体樹脂を作ることは、建築、塗料の産業分野において極めて有用である。
VAc and MMA are said to be very difficult to make a copolymer by a normal polymerization method because the monomer reactivity ratio r1r2 is completely different.
In fact, VAC and MMA are used as monomers, mixed together, and toluene is used as an organic solvent, and benzoyl peroxide (BPO) is used as a polymerization initiator to produce a polymer. As much as possible. VAc is unreacted and does not form a copolymer with MMA.
This is thought to be due to the fact that the free radicals generated by the thermal decomposition of BPO are serially moved toward the MMA polymer before reacting with the VAc monomer.
When the VAc polymer is considered as an application to paint, the adhesion to the substrate is excellent. However, the weather resistance is inferior.
MMA polymer has excellent weather resistance but poor adhesion to the substrate.
In order to take advantage of the features of both, separate homopolymers of VAc and MMA are made and blended to use them. However, the compatibility between the two is poor and it is impossible to obtain a coating film having sufficient performance due to demixing.
Making a copolymer resin of VAc having good adhesion to a substrate and MMA having excellent weather resistance is extremely useful in the fields of construction and paint industries.
VAcホモポリマ-としては、Tg(℃)が低くやわらかいため木工用、紙等の接着剤として広く使われていることは公知の事実である。
MMAホモポリマ-はTg(℃)が100℃と高く硬いため単独で使われることは少なく、一般にアクリルモノマ-との共重合体がTg(℃)を調整して用いられる
It is a known fact that VAc homopolymers are widely used as adhesives for woodwork, paper, etc. because of their low Tg (° C) and softness.
Since MMA homopolymer has a high Tg (° C) of 100 ° C and is hard, it is rarely used alone. Generally, a copolymer with an acrylic monomer is used by adjusting the Tg (° C).
特許 第5624201号 Patent No.5624201
本発明が解決しょうとする課題は、すでに述べてきたようなホモポリマ-同士をブレンドする方法とは異なる方法による。すなわち、従来の反応方法では出来得なかった重合方法でVAc-MMA共重合体を作製することにある The problem to be solved by the present invention is due to a method different from the method of blending homopolymers as already described. That is, a VAc-MMA copolymer is produced by a polymerization method that could not be achieved by a conventional reaction method.
本発明はVAc-MMA共重合体を得るために、開始剤としてBPOを用い有機溶媒中で先ずVAcを重合させる。ついで、VAcポリマ-が存在する有機溶媒溶液にMMAモノマ-を滴下し、開始剤としてBPOを用い重合を継続する。すなわち、先に重合したVAcの重合体にMMAモノマ-をグラフト重合することによりVAc-MMA共重合体を作製するものである。
本発明において、開始剤としてBPOを用いることは絶対必要条件である。開始剤としてはBPO以外種々の開始剤があるが、ラジカルの活性力が弱くVAc-MMAグラフト共重合体ができ難い。
In the present invention, in order to obtain a VAc-MMA copolymer, VAc is first polymerized in an organic solvent using BPO as an initiator. Next, MMA monomer is dropped into an organic solvent solution containing VAc polymer, and polymerization is continued using BPO as an initiator. That is, a VAc-MMA copolymer is produced by graft polymerization of a MMA monomer to a previously polymerized VAc polymer.
In the present invention, the use of BPO as an initiator is an absolute requirement. As the initiator, there are various initiators other than BPO, but the radical activity is weak and it is difficult to form a VAc-MMA graft copolymer.
本発明によって、VAc樹脂とMMA樹脂とをブレンドして使用することなく、接着性のよい、耐水、耐候性に優れた建築用・塗料用の塗膜を提供することができる。 According to the present invention, it is possible to provide a coating film for building and coating that has good adhesion, water resistance and weather resistance without using a blend of VAc resin and MMA resin.
本発明において、樹脂(ポリマ-)分を構成する成分の単量体(モノマ-)は、耐水性に劣るが、基材との密着性に優れているVAc(酢酸ビニ-ル)と、基材への密着性に劣るが、対候性に極めて優れているMMA(メチルメタクリレ−ト)である。
塗料を塗膜化した場合、塗膜が硬すぎるとクラックが発生し、柔らかいとブロッキングが発生することはよく知られている事実である。それ故に、適度な範囲のガラス転移点(℃)をもった硬度の塗膜に樹脂組成を調整する必要がある。
今回の樹脂組成の場合、VAc成分が20〜40%、MMA成分が80〜60%、更に言えばVAc30%、MMA70%が最も適当な範囲の樹脂組成であるといえる
In the present invention, the monomer (monomer) as a component constituting the resin (polymer) component is inferior in water resistance, but has excellent adhesion to the substrate, VAc (vinyl acetate), Although it is inferior in adhesion to the material, it is MMA (methyl methacrylate) which is extremely excellent in weather resistance.
It is a well-known fact that when a coating is formed into a coating, cracks occur when the coating is too hard, and blocking occurs when it is soft. Therefore, it is necessary to adjust the resin composition to a coating film having a hardness having a glass transition point (° C.) in an appropriate range.
In the case of the resin composition this time, the VAc component is 20 to 40%, the MMA component is 80 to 60%, more specifically, VAc 30% and MMA 70% are the most suitable resin compositions.
本発明は有機溶媒を用いた溶液重合法で作製することはすでに述べたとおりである。有機溶媒としては、トルエン、キシレン、などの芳香族炭化水素、酢酸エチル、酢酸ブチルなどのエステル類、メチルエチルケトン、メチルイソブチルケトンなどのケトン類が単独または2種以上併用される。
本発明に用いるラジカル重合用の開始剤はBPO(ベンゾイルパ-オキサイド)である。比較例として、他の有機過酸化物やアゾビスイソブチラ−トも用いたが、本発明の主旨には沿わない。BPOの使用量は、モノマ-(VAc+MMA)の総量に対し1〜3%使用するのが望ましい。
重合温度は選択する有機溶媒の沸点とBPOのラジカル発生温度を考慮すると70〜110℃が適当である。また、重合時間は重合開始時より4〜6時間で終了するのが実用的である。
As described above, the present invention is prepared by a solution polymerization method using an organic solvent. As the organic solvent, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, and ketones such as methyl ethyl ketone and methyl isobutyl ketone are used singly or in combination.
The initiator for radical polymerization used in the present invention is BPO (benzoyl peroxide). As comparative examples, other organic peroxides and azobisisobutyrate were also used, but they do not conform to the gist of the present invention. The amount of BPO used is preferably 1 to 3% based on the total amount of monomers (VAc + MMA).
The polymerization temperature is suitably from 70 to 110 ° C. in consideration of the boiling point of the organic solvent to be selected and the radical generation temperature of BPO. The polymerization time is practically 4 to 6 hours from the start of polymerization.
本発明品が、発明品か混合品であるかの違いは生成物溶液の希釈によって確認することができる。樹脂溶液は重合度の違いにより、同じ成分の樹脂であっても混合した際に分離することはよく知られている。ましてや、異種樹脂を混合した場合、容易に相分離や脱混合が生じる。本発明品がグラフと共重合体であることの確認は、この生成物を溶解することのできる有機溶媒にて数倍に希釈することにより見極めることが出来る。 The difference between the product of the present invention and the product of the invention can be confirmed by dilution of the product solution. It is well known that resin solutions are separated when mixed even if they are resins of the same component due to differences in the degree of polymerization. In addition, when different types of resins are mixed, phase separation and demixing easily occur. Confirmation that the product of the present invention is a graph and a copolymer can be determined by diluting the product several times with an organic solvent capable of dissolving the product.
以下、実施例により本発明の説明を行う。実施例中に(部)とあるのは重量部を意味する。また、VAcは酢酸ビニ-ル、MMAはメチルメタクリレ−トBPOはベンゾイルパ-オキサイドの略記である。有機溶媒はトルエンを用いた。
攪拌機、温度計、コンデンサ−、モノマ-用滴下ロート、重合開始剤用滴下ロ−トを備えた五つ口セパレート型フラスコにて、表1の内容物を定量し、重合を開始させグラフト共重合体を作製する。重合反応の基本操作は以下のとうりである。
実施例、配合例は表1のとうりである。先ず、VAcを所定量計り滴下ロ−トにいれる。トルエンを所定量フラスコに仕込んだ後、内温を65〜70℃まで昇温させる。この時点で滴下ロ−トに仕込んでおいたVAcと、トルエンに溶かしておいたBPOを同時に滴下し重合を開始する。重合開始から1時間30分で双方の滴下を終了する。そして、そのままの状態で30分間熟成させる。
この間に、MMAを滴下ロ−トに定量しておく。更に、BPOをトルエンに溶解しておく。VAc の熟成が終わった30分後から、上記双方を同時に滴下しはじめMMAの重合を開始する。反応熱により内温は上昇するが105〜110℃で温度コントロ−ルするのが望ましい。3時間で双方の滴下を終了する。その後、1時間熟成させた後冷却し取り出す。
Hereinafter, the present invention will be described with reference to examples. In the examples, (parts) means parts by weight. VAc is an abbreviation for vinyl acetate, MMA is an abbreviation for methyl methacrylate BPO, and benzoyl peroxide. Toluene was used as the organic solvent.
In a five-necked separate flask equipped with a stirrer, thermometer, condenser, dropping funnel for monomer, and dropping funnel for polymerization initiator, the contents in Table 1 were quantified to initiate polymerization and graft copolymerization. Create a coalescence. The basic operation of the polymerization reaction is as follows.
Examples and formulation examples are as shown in Table 1. First, a predetermined amount of VAc is measured and placed in a dropping funnel. After charging a predetermined amount of toluene into the flask, the internal temperature is raised to 65-70 ° C. At this time, VAc charged in the dropping funnel and BPO dissolved in toluene are dropped simultaneously to initiate polymerization. Both drippings are completed in 1 hour and 30 minutes from the start of polymerization. And let it mature for 30 minutes as it is.
During this time, MMA is quantified in a dropping funnel. Further, BPO is dissolved in toluene. Thirty minutes after the aging of VAc is completed, both of the above are started to drop simultaneously, and polymerization of MMA is started. Although the internal temperature rises due to the heat of reaction, it is desirable to control the temperature at 105 to 110 ° C. Complete both drops in 3 hours. Then, after aging for 1 hour, cool and take out.
評価方法は以下の方法による。結果は表1に記したとうりである。VAc/MMA比はTg(℃)から考えて、3/7が実用的な割合だとおもえる。開始財はBPO以外のものはグラフト共重合しないことがわかる。BPOの使用量は1〜3%対モノマ-が適当な範囲だとおもえる。
加熱残分:::試料約2gを精量し110〜115℃に設定した乾燥機で4時間乾燥後デシケ-タ-にて冷却後残分濃度を測定する。
相分離の確認:生成物100gを計量する。これに有機溶媒トルエンを400g加え希釈し十分攪拌する。24時間放置後相分離の有無を目視にて判定する。
The evaluation method is as follows. The results are as described in Table 1. Considering the Vac / MMA ratio from Tg (° C), 3/7 is a practical ratio. It can be seen that starting goods other than BPO do not graft copolymerize. I think that the amount of BPO used is in the proper range of 1 to 3% vs. monomer.
Residue on heating ::: About 2 g of sample was weighed and dried for 4 hours with a drier set at 110 to 115 ° C. After cooling with a desiccator, the residual concentration was measured.
Confirmation of phase separation: Weigh 100 g of product. 400 g of organic solvent toluene is added to this, diluted and stirred sufficiently. After standing for 24 hours, the presence or absence of phase separation is judged visually.
配合No 1,2,3,4,5 は開始剤としてベンゾイルパ−オキサイドを使用し、配合No 6は開始剤としてアゾビスイソブチロニトリルを使用し、配合No 7は開始剤としてクメンハイドロパ-オキサイドを使用し、配合No 8 は開始剤としてラウロイルパ-オキサイドを使用し、配合No 9 は開始剤としてジ・タ-シャルブチルパ-オキサイドを使用し、その他の成分は同じものを用いた。配合No 1.2,3 はVAc/MMA比のみを変えて、その他の成分は同量とした。配合No 2,4,5 はベンゾイルパ-オキサイド量のみを変え、その他の成分は同量とし反応性をみた。
以上
Benzoyl formulation No 1,2,3,4,5 as initiator - using oxide, compounded No 6 uses azobisisobutyronitrile as an initiator, blending No 7 is cumene hydroperoxide as initiator - Oxide was used , formulation No. 8 used lauroyl peroxide as an initiator, formulation No. 9 used di-tert-butyl peroxide as an initiator , and the other components were the same . Blending No 1.2,3 is changing only VAc / MMA ratio, the other components were the same amount. Formulations Nos. 2, 4, and 5 showed the reactivity with only the amount of benzoyl peroxide being changed and the other components being the same amount .
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JPS4826284A (en) * | 1971-08-10 | 1973-04-06 | ||
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JPS55147514A (en) * | 1979-04-27 | 1980-11-17 | Sumitomo Chem Co Ltd | Continuous preparation of rubber-modified methyl methacrylate syrup |
JPS59139503A (en) * | 1983-01-31 | 1984-08-10 | 大日本インキ化学工業株式会社 | Semiconductive resin composition |
JPH04296301A (en) * | 1991-03-25 | 1992-10-20 | Kuraray Co Ltd | Dispersion stabilizer for emulsion polymerization |
JPH06345933A (en) * | 1993-06-10 | 1994-12-20 | Kuraray Co Ltd | Methacrylic resin composition and its production |
CN103788281A (en) * | 2014-03-05 | 2014-05-14 | 山东世拓化学科技有限公司 | Core-shell structure processing agent for rigid polyvinyl chloride and synthetic method thereof |
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JPS4826284A (en) * | 1971-08-10 | 1973-04-06 | ||
JPS50138087A (en) * | 1974-04-23 | 1975-11-04 | ||
JPS55147514A (en) * | 1979-04-27 | 1980-11-17 | Sumitomo Chem Co Ltd | Continuous preparation of rubber-modified methyl methacrylate syrup |
JPS59139503A (en) * | 1983-01-31 | 1984-08-10 | 大日本インキ化学工業株式会社 | Semiconductive resin composition |
JPH04296301A (en) * | 1991-03-25 | 1992-10-20 | Kuraray Co Ltd | Dispersion stabilizer for emulsion polymerization |
JPH06345933A (en) * | 1993-06-10 | 1994-12-20 | Kuraray Co Ltd | Methacrylic resin composition and its production |
CN103788281A (en) * | 2014-03-05 | 2014-05-14 | 山东世拓化学科技有限公司 | Core-shell structure processing agent for rigid polyvinyl chloride and synthetic method thereof |
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