JP2581541B2 - Polymerization method of vinyl acetate - Google Patents
Polymerization method of vinyl acetateInfo
- Publication number
- JP2581541B2 JP2581541B2 JP61124992A JP12499286A JP2581541B2 JP 2581541 B2 JP2581541 B2 JP 2581541B2 JP 61124992 A JP61124992 A JP 61124992A JP 12499286 A JP12499286 A JP 12499286A JP 2581541 B2 JP2581541 B2 JP 2581541B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl acetate
- polymerization
- polymerization method
- present
- proton
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000006116 polymerization reaction Methods 0.000 title claims description 21
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 11
- 239000000178 monomer Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical group NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- SYWIXHZXHQDFOO-UHFFFAOYSA-N methyl n-phenyliminocarbamate Chemical compound COC(=O)N=NC1=CC=CC=C1 SYWIXHZXHQDFOO-UHFFFAOYSA-N 0.000 description 9
- 239000007870 radical polymerization initiator Substances 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000007877 V-601 Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003495 polar organic solvent Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- -1 methanol and ethanol Chemical class 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical compound CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、アゾエステルをラジカル重合開始剤として
用いる酢酸ビニルの重合方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for polymerizing vinyl acetate using an azoester as a radical polymerization initiator.
従来、ラジカル重合開始剤として、アゾ化合物と有機
過酸化物がよく知られている。アゾ化合物は活性のわり
には比較的安定で、有機過酸化物にみられるような自己
誘導分解を起さず、正確に一次反応で分解するためコン
トロールが容易であるという特色を有していて、種々の
ビニル系モノマーのラジカル重合にひろく用いられてい
る。アゾニトリルはその代表的なものであるが、活性基
として−CN基を有しているので、毒性等の点で若干の問
題を有する。アゾエステルは、−CN基を持たず、種々の
溶媒に対する溶解性も優れているので、近時注目を集め
つつあり、その効果的な使用法についての関心が高まっ
ている。Conventionally, azo compounds and organic peroxides are well known as radical polymerization initiators. Azo compounds are relatively stable in terms of activity, do not undergo the self-induced decomposition seen in organic peroxides, and have the characteristic that they are easily decomposed by the primary reaction and are easy to control. Widely used for radical polymerization of various vinyl monomers. Azonitrile is a typical example, but has some problems in toxicity and the like since it has a -CN group as an active group. Azoesters do not have a —CN group and have excellent solubility in various solvents. Therefore, azoesters have recently been receiving attention, and interest in effective use thereof has been increasing.
本発明は、アゾエステルをラジカル重合開始剤として
用いた酢酸ビニルの効果的な重合方法を提供することを
目的とする。An object of the present invention is to provide an effective polymerization method for vinyl acetate using an azo ester as a radical polymerization initiator.
本発明は、一般式〔Ｉ〕 （但し、Ｒは炭素数１〜４の低級アルキル基を表わ
す。）で示されるアゾエステルを用い、プロトン供与性
極性有機溶媒中重合させることを特徴とする酢酸ビニル
を主たるモノマーとする重合方法（但し、酢酸ビニルと
開鎖状第３級Ｎ−ビニルアミド類を共重合させる場合を
除く。）である。The present invention relates to a compound of the general formula [I] (Where R represents a lower alkyl group having 1 to 4 carbon atoms), and polymerized in a proton-donating polar organic solvent using an azoester represented by the following formula (provided that vinyl acetate is the main monomer). , Except when vinyl acetate is copolymerized with an open-chain tertiary N-vinylamide).
一般に、ラジカル重合開始剤が重合を効果的に開始さ
せるためには、分解によって生成したラジカルが溶媒の
カゴから効果的に拡散し、拡散したラジカルがモノマー
に付加し、開始効率よく重合を開始させる必要がある。In general, in order for a radical polymerization initiator to effectively initiate polymerization, radicals generated by decomposition are effectively diffused from a cage of a solvent, and the diffused radicals are added to a monomer to initiate polymerization efficiently with initiation. There is a need.
本発明者らは、ラジカル重合開始剤としてのアゾエス
テルの効果的な使用法について鋭意研究の途上、上記一
般式〔Ｉ〕で示されるアゾエステルは、これをプロトン
供与性極性有機溶媒中で酢酸ビニルの重合に用いれば、
極めて高活性のラジカル重合開始剤として作用すること
を見出し、本発明を完成するに至った。The present inventors have made intensive studies on the effective use of azoesters as radical polymerization initiators, and found that the azoesters represented by the above general formula (I) can be converted to vinyl acetate in a proton-donating polar organic solvent in a polar organic solvent. If used for polymerization,
They have found that they act as radical polymerization initiators with extremely high activity, and have completed the present invention.
本発明の重合法に用いられる一般式〔Ｉ〕で示される
アゾエステルのＲとしては、例えばメチル、エチル、プ
ロピル、ブチル等炭素数１〜４の低級アルキル基が挙げ
られる。本発明の重合法に用いられるプロトン供与性極
性有機溶媒としては、例えば、メタノール、エタノール
等のアルコール類や、アセトニトリル等が挙げられる。Examples of R of the azoester represented by the general formula [I] used in the polymerization method of the present invention include lower alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl. Examples of the proton-donating polar organic solvent used in the polymerization method of the present invention include alcohols such as methanol and ethanol, and acetonitrile.
本発明に係る重合方法に於ては、ラジカル重合開始剤
として、例えば、2,2′−アゾビス（２−メチルプロピ
オン酸メチルエステル）や2,2′−アゾビス（２−メチ
ルプロピオン酸エチルエステル）等のアゾエステルを用
いることが必須であり、2,2′−アゾビス（２−メチル
プロピオニトリル）（AIBN）のようなアゾニトリルを用
いても、求めるような高活性触媒作用は得られない。ま
た、重合は、メタノール、エタノールなどのアルコール
類やアセトニトリル等、プロトン供与性有機溶媒中で行
うことが必須であり、他の溶媒を用いても、アゾエステ
ルは高活性には作用しない。In the polymerization method according to the present invention, as the radical polymerization initiator, for example, 2,2'-azobis (2-methylpropionic acid methyl ester) or 2,2'-azobis (2-methylpropionic acid ethyl ester) It is essential to use an azo ester such as azo ester, and even if an azonitrile such as 2,2'-azobis (2-methylpropionitrile) (AIBN) is used, the desired high activity catalytic action cannot be obtained. Further, it is essential that the polymerization is carried out in a proton-donating organic solvent such as alcohols such as methanol and ethanol, and acetonitrile. Even if other solvents are used, the azo ester does not act with high activity.
本発明の方法によれば、酢酸ビニルモノマーはこれを
単独で重合させた場合でも、また、これを主モノマーと
してこれと他のモノマー（但し、開鎖状第３級Ｎ−ビニ
ルアミド類を除く。）とを共重合させた場合でも、極め
て重合率良く効果的に重合させることができる。According to the method of the present invention, even when vinyl acetate monomer is polymerized alone, it is used as a main monomer and other monomers (excluding open-chain tertiary N-vinyl amides). Can be effectively polymerized at an extremely high polymerization rate.
本発明の重合方法はラジカル重合開始剤として一般式
〔Ｉ〕で示されるアゾエステルを用い、反応溶媒として
プロトン供与性極性溶媒を用いる以外は自体公知の溶液
重合等の重合方法に従うことで足りる。In the polymerization method of the present invention, it is sufficient to follow a polymerization method known per se, such as solution polymerization, except that an azoester represented by the general formula [I] is used as a radical polymerization initiator and a proton-donating polar solvent is used as a reaction solvent.
重合終了後は、常法に従い、生成ポリマーを分離し、
乾燥する。After completion of the polymerization, the produced polymer is separated according to a conventional method,
dry.
以下に実施例を示す。 Examples will be described below.
実施例1. 酢酸ビニル150mlをメタノール150mlに溶解し、N2気流
下加熱撹拌して50℃迄昇温させた。次いで同温度で2,
2′−アゾビス（２−メチルプロピオン酸メチルエステ
ル）（和光純薬工業株式会社製、商品名Ｖ−601）を酢
酸ビニルに対し0.5重量％添加し、重合を開始させた。
重合開始後、0.5時間後、１時間後、1.5時間後、２〜６
時間後に於ける重合率を測定したところ、次表に示され
る結果を得た。表には、比較のため、2,2′−アゾビス
（２−メチルプロピオニトリル）（AIBN）をＶ−601と
同量添加して得られた重合率が示されている。Example 1. Vinyl acetate (150 ml) was dissolved in methanol (150 ml), and the mixture was heated and stirred under a stream of N 2 to 50 ° C. Then at the same temperature,
0.5% by weight of 2'-azobis (2-methylpropionic acid methyl ester) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-601) was added to vinyl acetate to initiate polymerization.
0.5 hours, 1 hour, 1.5 hours, 2-6
When the polymerization rate after the time was measured, the results shown in the following table were obtained. In the table, for comparison, the conversion obtained by adding 2,2'-azobis (2-methylpropionitrile) (AIBN) in the same amount as V-601 is shown.
表１からも明らかなように、Ｖ−601はAIBNと比較し
て著しく高い重合活性を示す。 As is clear from Table 1, V-601 shows remarkably high polymerization activity as compared with AIBN.
実施例2. Ｖ−601添加量（開始剤農度）を0.2〜0.7（wt％）と
し、実施例１と同様にして、酢酸ビニルを溶液重合さ
せ、各時間毎の重合率（％）を測定した。結果を第１図
に示す。但し、 は、Ｖ−601添加量0.2wt％、 は同0.25wt％、 は同0.3wt％、 は同0.5wt％、 は同0.7wt％の場合を夫々示し、 は、比較のため開始剤としてAIBNを0.5wt％用いた場合
の結果を示す。Example 2. V-601 was added in an amount of 0.2 to 0.7 (wt%), and vinyl acetate was solution-polymerized in the same manner as in Example 1 to obtain a polymerization rate (%) for each time. It was measured. The results are shown in FIG. However, Is V-601 addition amount 0.2wt%, Is 0.25wt% Is 0.3wt%, Is 0.5wt%, Indicates the case of 0.7wt% respectively, Shows the results when 0.5 wt% of AIBN was used as an initiator for comparison.
本発明は、アゾエステルを重合開始剤として用い、プ
ロトン供与性極性有機溶媒で酢酸ビニルモノマーをラジ
カル重合させる酢酸ビニルの重合方法を提供するもので
あり、他の重合開始剤を用いた場合、或は他の溶媒中で
重合させた場合と比べて、重合率が著しく高い点に甚だ
顕著な効果を奏するものである。The present invention provides a polymerization method of vinyl acetate in which a vinyl acetate monomer is radically polymerized with a proton-donating polar organic solvent using an azo ester as a polymerization initiator, and when another polymerization initiator is used, or Compared with the case where the polymerization is carried out in another solvent, a remarkable effect is exhibited in that the polymerization rate is extremely high.
第１図は、実施例２に於ける酢酸ビニルの溶液重合の結
果を表わし、横軸の各時間（hr.）毎に測定された重合
率（％）が縦軸に沿ってプロットされ、曲線で結ばれて
いる。但し、 はＶ−601添加量0.2wt％、 は同0.25wt％、 は同0.3wt％、 は同0.5wt％、 は同0.7wt％の場合を夫々示し、 は比較のため開始剤としてAIBNを0.5wt％用いた場合の
結果を示す。FIG. 1 shows the results of solution polymerization of vinyl acetate in Example 2, in which the polymerization rate (%) measured at each time (hr.) On the horizontal axis is plotted along the vertical axis, and the curve is plotted. Are tied together. However, Is V-601 added amount 0.2wt%, Is 0.25wt% Is 0.3wt%, Is 0.5wt%, Indicates the case of 0.7wt% respectively, Shows the results when 0.5 wt% of AIBN was used as an initiator for comparison.
フロントページの続き (72)発明者 藤江 啓利 川越市大字的場1633番地 和光純薬工業 株式会社東京研究所内 (56)参考文献 特公 昭40−23915（ＪＰ，Ｂ１)Continuation of front page (72) Inventor Hirotoshi Fujie 1633, Kawaji, Kawagoe-shi Wako Pure Chemical Industries, Ltd. Tokyo Research Laboratories (56) References Japanese Patent Publication No. 40-23915 (JP, B1)
Claims (1)
す。）で示されるアゾエステルを用い、プロトン供与性
極性溶媒中で重合させることを特徴とする酢酸ビニルを
主たるモノマーとする重合方法（但し、酢酸ビニルと開
鎖状第３級Ｎ−ビニルアミド類を共重合させる場合を除
く。）。1. A compound of the general formula [I] (Where R represents a lower alkyl group having 1 to 4 carbon atoms) and a polymerization method using vinyl acetate as a main monomer, characterized by polymerizing in a proton-donating polar solvent. , Vinyl acetate and open-chain tertiary N-vinylamides are excluded).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61124992A JP2581541B2 (en) | 1986-05-30 | 1986-05-30 | Polymerization method of vinyl acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61124992A JP2581541B2 (en) | 1986-05-30 | 1986-05-30 | Polymerization method of vinyl acetate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62283106A JPS62283106A (en) | 1987-12-09 |
| JP2581541B2 true JP2581541B2 (en) | 1997-02-12 |
Family
ID=14899224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61124992A Expired - Fee Related JP2581541B2 (en) | 1986-05-30 | 1986-05-30 | Polymerization method of vinyl acetate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2581541B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2813319A1 (en) * | 2000-08-29 | 2002-03-01 | Atofina | PROCESS FOR PRODUCING ACRYLONITRILE FIBERS |
-
1986
- 1986-05-30 JP JP61124992A patent/JP2581541B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62283106A (en) | 1987-12-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |