JP3264012B2 - Polymerization method of halogen-containing acrylic monomer - Google Patents
Polymerization method of halogen-containing acrylic monomerInfo
- Publication number
- JP3264012B2 JP3264012B2 JP01534893A JP1534893A JP3264012B2 JP 3264012 B2 JP3264012 B2 JP 3264012B2 JP 01534893 A JP01534893 A JP 01534893A JP 1534893 A JP1534893 A JP 1534893A JP 3264012 B2 JP3264012 B2 JP 3264012B2
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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
- 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
- C08F20/22—Esters containing halogen
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はハロゲンを含有するアク
リル系モノマーの新規な重合方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for polymerizing an acrylic monomer containing a halogen.
【０００２】[0002]
【従来の技術】ハロゲンを含有するアクリル系モノマー
はラジカル重合やイオン重合によって重合され、重合物
は透明な樹脂として光学材料や構造材料、塗料、接着剤
等広い分野において使用されている。しかしながら通常
の重合開始剤と連鎖移動剤を用いたラジカル重合では一
般に広い分子量分布を有するポリマーが得られる。その
場合分子量が高い部分が溶媒溶解性や溶融加工性を落と
したり、分子量の低い部分が力学特性を落とすなどの悪
影響を及ぼすことが予想される。また様々な分子量・分
子量分布を有するポリマーをブレンドによって作り出し
て様々な特徴を持たせたい場合にも分子量分布が広いこ
とで制約を受ける。イオン重合を行えば分子量を狭くす
ることも可能であるがモノマーの純度や水、酸素などの
不純物により大きく影響され、工業的な製造による大量
生産には適しない。2. Description of the Related Art Acrylic monomers containing halogen are polymerized by radical polymerization or ionic polymerization, and the polymer is used as a transparent resin in a wide range of fields such as optical materials, structural materials, paints and adhesives. However, radical polymerization using a usual polymerization initiator and a chain transfer agent generally yields a polymer having a wide molecular weight distribution. In this case, it is expected that a portion having a high molecular weight has an adverse effect such as a decrease in solvent solubility and melt processability, and a portion having a low molecular weight has a drop in mechanical properties. Also, when polymers having various molecular weights and molecular weight distributions are desired to be produced by blending to have various characteristics, there are restrictions due to the wide molecular weight distribution. If ionic polymerization is performed, the molecular weight can be reduced. However, the molecular weight is greatly affected by the purity of the monomer and impurities such as water and oxygen, and is not suitable for mass production by industrial production.
【０００３】[0003]
【発明が解決しようとする課題】本発明は簡便かつ分子
量分布の狭いハロゲン含有アクリル系ポリマーを合成す
ることができ、末端基を利用した応用も可能な、新規な
重合方法を提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a novel polymerization method capable of synthesizing a halogen-containing acrylic polymer having a simple and narrow molecular weight distribution and applicable to a terminal group. And
【０００４】[0004]
【課題を解決するための手段】上記課題を解決するため
本発明者は鋭意検討を加えた。その結果、一般式: ＣＨ２＝ＣＸＣＯＯＲ (式中、Ｘは水素原子、フッ素原子、塩素原子、メチル
基、またはトリフロロメチル基を表し、Ｒは１〜１６個
の炭素原子を有するアルキル基、フロロアルキル基、シ
ロキサン結合を含むアルキル基、ヒドロキシエチル基、
グリシジル基またはカリウム原子を表す。但し、Ｘがフ
ッ素原子または塩素原子以外の原子または基である場合
はＲはフロロアルキル基である) によって表されるハロゲン原子を含有するアクリル系モ
ノマーにＩ２，Ｂr２，Ｃl２，IＢrおよび／またはIＣl
を加えて光を照射することによって本発明の課題は解決
されることを見出して本発明を完成させた。すなわち本
発明は、一般式: ＣＨ２＝ＣＸＣＯＯＲ (式中、ＸおよびＲは前記と同意義。) によって表されるハロゲン原子を含有するアクリル系化
合物から選ばれた少なくとも一種のモノマーを、Ｉ２，
Ｂr２，Ｃl２，IＢrおよびIＣlよりなる群から選ばれた
少なくとも一種のハロゲン化合物の存在下、波長２００
〜７００nmの光を照射することを含んでなるハロゲン含
有アクリル系モノマーの重合方法を要旨とする。以下本
発明を詳細に説明する。Means for Solving the Problems In order to solve the above problems, the present inventors have made intensive studies. As a result, the general formula: CH 2 ＣCXCOOR (where X represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a trifluoromethyl group, and R is an alkyl group having 1 to 16 carbon atoms, A fluoroalkyl group, an alkyl group containing a siloxane bond, a hydroxyethyl group,
Represents a glycidyl group or a potassium atom. However, when X is an atom or a group other than a fluorine atom or a chlorine atom, R is a fluoroalkyl group.) I 2 , Br 2 , Cl 2 , IBr and / Or ICl
The present inventors have found that the object of the present invention can be solved by irradiating light with the addition of, and completed the present invention. That is, the present invention has the general formula: CH 2 = CXCOOR (. Wherein, X and R are the same as defined) of at least one monomer selected from acrylic compounds containing a halogen atom represented by, I 2 ,
In the presence of at least one halogen compound selected from the group consisting of Br 2 , Cl 2 , IBr and ICl, a wavelength of 200
The present invention provides a method for polymerizing a halogen-containing acrylic monomer, which comprises irradiating light of up to 700 nm. Hereinafter, the present invention will be described in detail.
【０００５】本発明において使用できる含フッ素モノマ
ーを例示すれば以下のようなものがある。 (１) ＣＨ2＝ＣＦＣＯＯＣＨ2ＣＦ3(以下３ＦＦＡと略
す)、ＣＨ2＝ＣＦＣＯＯＣＨ2ＣＦ2ＣＦ2Ｈ(以下４ＦＦ
Ａと略す)、ＣＨ2＝ＣＦＣＯＯＣＨ2ＣＦ2ＣＦ3(以下５
ＦＦＡと略す)、ＣＨ2＝ＣＦＣＯＯＣＨ2(ＣＦ2)2ＣＦ3
(以下７ＦＦＡと略す)、ＣＨ2＝ＣＦＣＯＯＣＨ2(Ｃ
Ｆ2)3ＣＦ2Ｈ(以下８ＦＦＡと略す)、ＣＨ2＝ＣＦＣＯ
ＯＣＨ2(ＣＦ2)5ＣＦ2Ｈ(以下１２ＦＦＡと略す)、ＣＨ
2＝ＣＦＣＯＯＣＨ2(ＣＦ2)7ＣＦ2Ｈ(以下１６ＦＦＡと
略す)、ＣＨ2＝ＣＦＣＯＯＣＨ2ＣＨ2(ＣＦ2)7ＣＦ3(以
下１７ＦＦＡと略す)等のα−フロロアクリル酸(以下α
Ｆアクリル酸と略す)のフロロアルキルエステル並びに
これ等に対応するα−クロロアクリル酸(以下αＣlアク
リル酸と略す)のフロロアルキルエステル。The following are examples of fluorine-containing monomers that can be used in the present invention. (1) CH 2 = CFCOOCH 2 CF 3 (hereinafter abbreviated as 3FFA), CH 2 = CFCOOCH 2 CF 2 CF 2 H (hereinafter 4FFA)
A), CH 2 ＣＦCFCOOCH 2 CF 2 CF 3 (hereinafter 5)
FFA), CH 2 = CFCOOCH 2 (CF 2 ) 2 CF 3
(Hereinafter abbreviated as 7FFA), CH 2 = CFCOOCH 2 (C
F 2 ) 3 CF 2 H (hereinafter abbreviated as 8FFA), CH 2 = CFCO
OCH 2 (CF 2 ) 5 CF 2 H (hereinafter abbreviated as 12FFA), CH
Α-fluoroacrylic acid (hereinafter α) such as 2 ＣＦCFCOOCH 2 (CF 2 ) 7 CF 2 H (hereinafter abbreviated as 16FFA) and CH 2 ＣＦCFCOOCH 2 CH 2 (CF 2 ) 7 CF 3 (hereinafter abbreviated as 17FFA).
Fluoroalkyl esters of F-acrylic acid) and the corresponding fluoroalkyl esters of α-chloroacrylic acid (hereinafter abbreviated as αCl acrylic acid).
【０００６】(２) ＣＨ2＝ＣＦＣＯＯＣＨ3、ＣＨ2＝
ＣＦＣＯＯＣ2Ｈ5、ＣＨ2＝ＣＦＣＯＯＣＨ(ＣＨ3)2、
ＣＨ2＝ＣＦＣＯＯＣ(ＣＨ3)3、ＣＨ2＝ＣＦＣＯＯＣＨ
2ＣＨ(ＣＨ3)2、ＣＨ2＝ＣＦＣＯＯＣＨ2ＣＨ2ＣＨ3、
ＣＨ2＝ＣＦＣＯＯ(ＣＨ2)3ＣＨ3、(2) CH 2 ＣＦCFCOOCH 3 , CH 2 ＝
CFCOOC 2 H 5 , CH 2 ＣＦCFCOOOCH (CH 3 ) 2 ,
CH 2 ＣＦCFCOOC (CH 3 ) 3 , CH 2 ＣＦCFCOOOCH
2 CH (CH 3 ) 2 , CH 2 ＣＦCFCOOCH 2 CH 2 CH 3 ,
CH 2 ＣＦCFCOO (CH 2 ) 3 CH 3 ,
【化１】 等のαＦアクリル酸のアルキルエステル、シロキサン結
合を含むアルキルエステルおよび塩、並びにこれ等に対
応するαＣlアクリル酸のアルキルエステル、シクロヘ
キサン結合を含むアルキルエステルおよび塩。Embedded image Alkyl esters of αF acrylic acid, alkyl esters and salts containing siloxane bonds, and the corresponding alkyl esters of αCl acrylic acid and alkyl esters and salts containing cyclohexane bonds.
【０００７】(３) ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ3、Ｃ
Ｈ2＝ＣＨＣＯＯＣＨ2ＣＦ2ＣＦ2Ｈ、ＣＨ2＝ＣＨＣＯ
ＯＣＨ2ＣＦ2ＣＦ3、ＣＨ2＝ＣＨＣＯＯＣＨ2(ＣＦ2)2
ＣＦ3、ＣＨ2＝ＣＨＣＯＯＣＨ2(ＣＦ2)3ＣＦ2Ｈ、ＣＨ
2＝ＣＨＣＯＯＣＨ2(ＣＦ2)5ＣＦ2Ｈ、ＣＨ2＝ＣＨＣＯ
ＯＣＨ2(ＣＦ2)7ＣＦ2Ｈ、ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ
2(ＣＦ2)7ＣＦ3、ＣＨ2＝ＣＨＣＯＯＣＨ(ＣＦ3)2等の
アクリル酸のフロロアルキルエステル、並びにこれ等に
対応するメタアクリル酸およびα−トリフロロメチルア
クリル酸のフロロアルキルエステル。以上の如きモノマ
ーを単独で重合する場合はもとより、二以上のモノマー
を共重合する場合にも本発明の効果を得ることができ
る。特にαＦアクリルモノマーを多く存在させた系は、
Ｏ2などの不純物の影響をうけにくく、反応速度も大き
く、分子量分布も狭くなりやすい。(3) CH 2 ＣＨCHCOOCH 2 CF 3 , C
H 2 ＣＨCHCOOCH 2 CF 2 CF 2 H, CH 2 ＣＨCHCO
OCH 2 CF 2 CF 3 , CH 2 ＣＨCHCOOCH 2 (CF 2 ) 2
CF 3 , CH 2 ＣＨCHCOOCH 2 (CF 2 ) 3 CF 2 H, CH
2 ＣＨCHCOOCH 2 (CF 2 ) 5 CF 2 H, CH 2 ＣＨCHCO
OCH 2 (CF 2 ) 7 CF 2 H, CH 2 ＣＨCHCOOCH 2 CH
2 (CF 2) 7 CF 3 , CH 2 = CHCOOCH (CF 3) fluoroalkyl esters of acrylic acid 2 like, and meta fluoroalkyl esters of acrylic acid and α- trifluoromethyl acrylate corresponding thereto or the like. The effects of the present invention can be obtained not only when the above monomers are polymerized alone but also when two or more monomers are copolymerized. In particular, a system in which a large amount of αF acrylic monomer is present,
It is hardly affected by impurities such as O 2 , the reaction rate is large, and the molecular weight distribution is likely to be narrow.
【０００８】本発明においてはＩ2，Ｂr2，Ｃl2，IＢr
およびIＣlからなる群より選ばれた少なくとも一種のハ
ロゲン化合物を、特に限定されないが、好ましくはモノ
マーに対して５００〜１００,０００ppm加える。５００
ppm以下では本発明の効果すなわち分子量分布の狭いポ
リマーを得ることができないし、１００,０００ppm以上
とすると未反応ハロゲンが多量に残留するうえ、逆に反
応速度が非常におそくなり、未反応モノマーも多くなる
ので好ましくない。In the present invention, I 2 , Br 2 , Cl 2 , IBr
And at least one halogen compound selected from the group consisting of ICl and, although not particularly limited, preferably 500 to 100,000 ppm based on the monomer. 500
Below ppm, the effect of the present invention, i.e., a polymer having a narrow molecular weight distribution cannot be obtained. It is not preferable because it increases.
【０００９】照射する光の波長は２００〜７００nm、好
ましくは２８０〜４００nmである。特に３００nm付近の
波長は有効である。光の強度は限定的ではなく僅かな光
でも重合は進行する。従って光の波長や強度は、重合速
度の調節や副反応の抑制の観点から決定すべきである。
またハロゲン化ヨウ素の大部分は、可視・紫外領域に大
きな吸収をもつことと重合禁止剤としてはたらくことか
ら、反応は二段階の過程を経ることが多い。一段階目は
着色が減少する過程、二段階目はポリマー鎖の生長反応
である。これらの二段階の反応は同時に進行する場合も
ある。The wavelength of the irradiated light is 200 to 700 nm, preferably 280 to 400 nm. Particularly, a wavelength around 300 nm is effective. The intensity of light is not limited, and polymerization proceeds even with a small amount of light. Therefore, the wavelength and intensity of light should be determined from the viewpoint of controlling the polymerization rate and suppressing side reactions.
In addition, most of the iodine halide has a large absorption in the visible / ultraviolet region and acts as a polymerization inhibitor, so that the reaction often goes through a two-step process. The first stage is the process of decreasing coloration, and the second stage is the growth reaction of the polymer chains. These two-step reactions may proceed simultaneously.
【００１０】本発明においては一般式(Ｉ)で表されるモ
ノマーにＩ2，Ｂr2，Ｃl2，IＢrおよび／またはIＣlを
加えた重合系で行うが、モノマーを溶媒で適度に希釈し
て行うこともできる。溶媒としてはアセトン、ベンゼ
ン、ＴＨＦ m−ＸＨＦ(６−フッ化メタキシレン)等の
モノマーを溶解し得る一般的な溶剤が使用可能である。
好ましくは生成するポリマーをも溶解する溶媒を用い
る。モノマーが長鎖フロロアルキル基のエステルの場合
にはフッ素系溶剤、例えばヘキサフロロメタキシレン、
ヘキサフロロイソプロパノールなどを用いることが好ま
しい。またフッ素含量が小さいモノマーの場合には含フ
ッ素溶媒を用いると反応が加速される場合がある。これ
は光の吸収スペクトルが溶媒効果によって変化し光の吸
収効率が上がるためと考えられる。従って、近紫外部に
大きな吸収をもつ溶媒の使用は好ましくない。重合によ
って得られるポリマーの分子量分布を狭くするには溶剤
の使用量は、モノマーと溶媒の合計重量を基準にして５
０重量％まで、好ましくは２０重量％までとする。以上
のような塊状重合や溶液重合の外に、水や有機溶媒中で
の懸濁重合、さらには乳化重合も可能である。In the present invention, the polymerization is carried out in a polymerization system in which I 2 , Br 2 , Cl 2 , IBr and / or ICl are added to the monomer represented by the general formula (I). You can do it too. As the solvent, a general solvent that can dissolve a monomer such as acetone, benzene, THF m-XHF (6-meta-xylene fluoride) can be used.
Preferably, a solvent that also dissolves the produced polymer is used. When the monomer is an ester of a long-chain fluoroalkyl group, a fluorinated solvent such as hexafluoromethaxylene,
It is preferable to use hexafluoroisopropanol or the like. In the case of a monomer having a low fluorine content, the use of a fluorinated solvent may accelerate the reaction. This is presumably because the light absorption spectrum changes due to the solvent effect and the light absorption efficiency increases. Therefore, it is not preferable to use a solvent having a large absorption in the near ultraviolet region. In order to narrow the molecular weight distribution of the polymer obtained by polymerization, the amount of the solvent used is 5 based on the total weight of the monomer and the solvent.
Up to 0% by weight, preferably up to 20% by weight. In addition to the bulk polymerization and solution polymerization as described above, suspension polymerization in water or an organic solvent, and furthermore, emulsion polymerization are also possible.
【００１１】αＦアクリル酸エステルのモノマーが主成
分となる系の例では、重合系またはその雰囲気中に存在
するＯ2を不活性ガスで置換することは必ずしも必要で
はなく、Ｏ2の存在により反応が促進されることもあ
る。[0011] In the example of a system monomer αF acrylate ester as the main component, it is not necessarily required to replace the polymerization system or the O 2 present in the atmosphere with an inert gas, reaction by the presence of O 2 May be promoted.
【００１２】重合温度は限定的ではないが室温以下で重
合を行うのが好ましい。重合時間はモノマーの種類、使
用する溶剤量、収率、照射する光の波長、強度等によっ
て任意であるが通常１〜３０時間程度である。The polymerization temperature is not limited, but it is preferable to carry out the polymerization at room temperature or lower. The polymerization time is optional depending on the type of the monomer, the amount of the solvent used, the yield, the wavelength of the irradiated light, the intensity, etc., but is usually about 1 to 30 hours.
【００１３】本発明の重合はＩ2，Ｂr2，Ｃl2，IＢrお
よび／またはIＣlの存在下に行うので、得られるポリマ
ーはその末端にＣ−Ｉ結合、Ｃ−Ｂr結合またはＩ−Ｃl
結合を有し、従って反応性を有すると考えられる。例え
ば得られたポリマーに他のモノマーを加えて重合させブ
ロックポリマーにすることも可能であるし、また末端の
Ｉ、ＢrもしくはＣlを他の反応性置換基に変性させマク
ロモノマーを得ることも可能である。さらに末端のＩ、
ＢrもしくはＣlを安定な基で置換し、通常の開始剤残基
を末端に持つポリマーに比較して熱安定性を高めること
もできる。これらの点も、本発明の他の重合方法に優る
点である。Since the polymerization of the present invention is carried out in the presence of I 2 , Br 2 , Cl 2 , IBr and / or ICl, the resulting polymer has a C—I, C—Br or I—Cl bond at its terminal.
It is considered to have a bond and thus to be reactive. For example, it is possible to add another monomer to the obtained polymer and polymerize it to form a block polymer, or it is also possible to obtain a macromonomer by modifying the terminal I, Br or Cl to another reactive substituent. It is. Further terminal I,
Br or Cl can be substituted with a stable group to increase the thermal stability as compared to a polymer having a normal initiator residue at the end. These points are also superior to the other polymerization methods of the present invention.
【００１４】[0014]
【実施例】以下に本発明を実施例によって具体的に説明
する。本発明がこれ等実施例によって限定されるもので
ないことは勿論である。The present invention will be specifically described below with reference to examples. Of course, the present invention is not limited by these examples.
【００１５】実施例１ ３ＦＦＡ(ＣＨ2＝ＣＦＣＯＯＣＨ2ＣＦ3) １０gと、Ｉ2
の１重量％アセトン溶液１.５gとを混合し、不活性ガス
による置換を行うことなく空気とともにガラス容器に密
閉し、室温で高圧水銀ランプ(ウシオ電機製 ＵＳＨ−２
５０Ｄ)の光を室温で６時間照射した。Ｉ2による着色は
消え、無色透明の固体となった。そのポリマーをアセト
ンに溶かし、メタノール中に投入して再沈殿によって精
製した。以上のようにして得たポリマーの、ポリスチレ
ン換算の重量平均分子量および重量平均分子量／数平均
分子量をＧＰＣ(溶媒：ＴＨＦ，カラム：(ＧＭＨＸＬ)
×２，Ｇ２００Ｈ×Ｌ，東ソー製，温度：４０℃，検出
器：島津ＲＩＤ−６Ａ)の方法により測定した。結果を
表１に示す。Example 1 10 g of 3FFA (CH 2 = CFCOOCH 2 CF 3 ) and I 2
And 1.5 g of a 1% by weight acetone solution, and sealed in a glass container with air without replacement with an inert gas, and a high-pressure mercury lamp (USH-2 manufactured by Ushio Inc.) at room temperature.
50D) was irradiated for 6 hours at room temperature. The coloring by I 2 disappeared, and a colorless and transparent solid was obtained. The polymer was dissolved in acetone, poured into methanol, and purified by reprecipitation. The weight average molecular weight in terms of polystyrene and the weight average molecular weight / number average molecular weight of the polymer obtained as described above were measured by GPC (solvent: THF, column: (GMHXL)).
× 2, G200H × L, manufactured by Tosoh Corporation, temperature: 40 ° C., detector: Shimadzu RID-6A). Table 1 shows the results.
【００１６】実施例２ ５ＦＦＡ(ＣＨ2＝ＣＦＣＯＯＣＨ2ＣＦ2ＣＦ3) １０g
と、Ｉ2の１重量％アセトン溶液１.５gとを混合し空気
とともにガラス容器に密閉し、高圧水銀ランプの光を室
温で６時間照射した。以下実施例１におけるのと同様に
してポリマーを得て、ポリスチレン換算の重量平均分子
量および重量平均分子量／数平均分子量を求めた。結果
を表１に示す。Example 2 10 g of 5FFA (CH 2 = CFCOOCH 2 CF 2 CF 3 )
And 1.5 g of a 1% by weight acetone solution of I 2 were mixed, sealed in a glass container with air, and irradiated with light from a high-pressure mercury lamp at room temperature for 6 hours. Thereafter, a polymer was obtained in the same manner as in Example 1, and the weight average molecular weight in terms of polystyrene and the weight average molecular weight / number average molecular weight were determined. Table 1 shows the results.
【００１７】実施例３ ３ＦＦＡ １０gと、Ｉ2の１重量％アセトン溶液０.７５
gとを混合し空気とともにガラス容器に密閉し、高圧水
銀ランプの光を室温で６時間照射した。以下実施例１に
おけるのと同様にしてポリマーを得て、ポリスチレン換
算の重量平均分子量および重量平均分子量／数平均分子
量を求めた。結果を表１に示す。Example 3 10 g of 3FFA and 0.75 of a 1% by weight solution of I 2 in acetone
g, mixed with air and sealed in a glass container, and irradiated with light from a high-pressure mercury lamp at room temperature for 6 hours. Thereafter, a polymer was obtained in the same manner as in Example 1, and the weight average molecular weight in terms of polystyrene and the weight average molecular weight / number average molecular weight were determined. Table 1 shows the results.
【００１８】実施例４ ３ＦＦＡ ５gと、IＢr １５mgとを混合し、空気ととも
にガラス容器に密閉し、高圧水銀ランプの光を室温で３
時間照射した。以下実施例１におけるのと同様にしてポ
リマーを得て、ポリスチレン換算の重量平均分子量およ
び重量平均分子量／数平均分子量を求めた。結果を表１
に示す。Example 4 5 g of 3FFA and 15 mg of IBr were mixed, sealed in a glass container with air, and the light of a high-pressure mercury lamp was irradiated at room temperature for 3 hours.
Irradiated for hours. Thereafter, a polymer was obtained in the same manner as in Example 1, and the weight average molecular weight in terms of polystyrene and the weight average molecular weight / number average molecular weight were determined. Table 1 shows the results
Shown in
【００１９】実施例５ ３ＦＦＡ １０gと、IＣl ２５mgとを混合し、空気とと
もにガラス容器に密閉し、高圧水銀ランプの光を４時間
照射した。以下実施例１におけるのと同様にしてポリマ
ーを得て、ポリスチレン換算の重量平均分子量および重
量平均分子量／数平均分子量を求めた。結果を表１に示
す。Example 5 10 g of 3FFA and 25 mg of ICl were mixed, sealed in a glass container with air, and irradiated with light from a high-pressure mercury lamp for 4 hours. Thereafter, a polymer was obtained in the same manner as in Example 1, and the weight average molecular weight in terms of polystyrene and the weight average molecular weight / number average molecular weight were determined. Table 1 shows the results.
【００２０】実施例６ １７ＦＭＡ(ＣＨ2＝Ｃ(ＣＨ3)ＣＯＯ(ＣＨ2)2(ＣＦ2)8
Ｆ) ３gと、Ｉ2の１重量％アセトン溶液０.１gとを混合
し、室温で水銀ランプの光を照射したところ１０時間で
固化した。一方Ｉ2溶液を加えない１７ＦＭＡに同じ光
源の光を照射した場合１６時間経過しても固化せず液状
のままであった。すなわちＩ2の添加により、光による
重合が加速された。Example 6 17FMA (CH 2 ＣC (CH 3 ) COO (CH 2 ) 2 (CF 2 ) 8
F) 3 g and 0.1 g of a 1% by weight acetone solution of I 2 were mixed, and the mixture was irradiated with light from a mercury lamp at room temperature and solidified in 10 hours. On the other hand, when 17FMA to which the I 2 solution was not added was irradiated with light from the same light source, it did not solidify even after 16 hours had elapsed and remained liquid. That is, the addition of I 2 accelerated the polymerization by light.
【００２１】実施例７ この実施例では本発明の方法によって得られたポリマー
の反応性を利用したブロック共重合体の製造例を示す。
１７ＦＦＡ(ＣＨ2＝ＣＦＣＯＯＣＨ2ＣＨ2(ＣＦ2)7ＣＦ
3) ０.５gと、Ｉ2の１重量％ＴＨＦ溶液０.５gを混合
し、容器に密閉した後、高圧水銀ランプの光を２０時間
照射すると固化した。再沈殿によって精製したポリマー
(以下ポリマー６Ａと呼ぶ)０.２gに１０gのm−ＸＨＦを
加えて溶解し、更に３ＦＦＡ １.０gを加えた後、高圧
水銀ランプの光を９時間照射し、真空乾燥でモノマーを
除去して精製した(以下ポリマー６Ｂと呼ぶ)。ポリマー
６Ａ(１７ＦＦＡの単独重合体)はアセトンに不溶であっ
たが、ポリマー６Ｂはアセトンに溶解し、青みがかった
均一な溶液となった。ポリマー６Ｂは、１７ＦＦＡと３
ＦＦＡとのブロック共重合体と考えられる。Example 7 This example shows a production example of a block copolymer utilizing the reactivity of a polymer obtained by the method of the present invention.
17FFA (CH 2 = CFCOOCH 2 CH 2 (CF 2 ) 7 CF
3 ) 0.5 g and 0.5 g of a 1% by weight solution of I 2 in THF were mixed, sealed in a vessel, and solidified by irradiation with a high pressure mercury lamp for 20 hours. Polymer purified by reprecipitation
10 g of m-XHF was added to and dissolved in 0.2 g of polymer (hereinafter referred to as polymer 6A), and further 1.0 g of 3FFA was added. Then, light from a high-pressure mercury lamp was applied for 9 hours, and monomers were removed by vacuum drying. And purified (hereinafter referred to as polymer 6B). The polymer 6A (a homopolymer of 17FFA) was insoluble in acetone, but the polymer 6B was dissolved in acetone, resulting in a bluish uniform solution. Polymer 6B has 17FFA and 3
It is considered a block copolymer with FFA.
【００２２】比較例１ ３ＦＭＡ(ＣＨ2＝Ｃ(ＣＨ3)ＣＯＯＣＨ2ＣＦ3) １００
g、アゾビスイソブチロニトリル０.０２５g、およびラ
ウリルメルカプタン０.０５gを混合した。その混合物を
窒素ガスで置換した後、７０℃で１００時間重合させ
た。得られたポリマーのポリスチレン換算重量平均分子
量、重量平均分子量／数平均分子量を実施例１の方法で
求めた。結果を表１に示す。Comparative Example 1 3FMA (CH 2 ＣC (CH 3 ) COOCH 2 CF 3 ) 100
g, azobisisobutyronitrile 0.025 g and lauryl mercaptan 0.05 g were mixed. After the mixture was replaced with nitrogen gas, polymerization was carried out at 70 ° C. for 100 hours. The weight average molecular weight in terms of polystyrene and the weight average molecular weight / number average molecular weight of the obtained polymer were determined by the method of Example 1. Table 1 shows the results.
【００２３】比較例２ ３ＦＦＡ １００g、アゾビスイソブチロニトリル０.０
１５g、およびメルカプト酢酸イソオクチル２.０gを混
合した。反応混合物を窒素で置換し、５０℃で２４時間
加熱した。重合終了後１５０℃で真空乾燥してモノマー
を除去し、ポリマーを得た。実施例１の方法でポリスチ
レン換算重量平均分子量、重量平均分子量／数平均分子
量を求めた。結果を表１に示す。Comparative Example 2 100 g of 3FFA, azobisisobutyronitrile 0.0
15 g and 2.0 g of isooctyl mercaptoacetate were mixed. The reaction mixture was purged with nitrogen and heated at 50 ° C. for 24 hours. After the polymerization was completed, the monomer was removed by vacuum drying at 150 ° C. to obtain a polymer. The weight average molecular weight in terms of polystyrene and the weight average molecular weight / number average molecular weight were determined by the method of Example 1. Table 1 shows the results.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【発明の効果】以上説明してきたように、本発明の方法
によれば従来のラジカル重合の場合に比べより狭い分子
量分布をもつポリマーを得ることができる。またイオン
重合の場合にくらべ不純物の影響を受けにくい、操作が
簡便である等の利点を有する。さらに本発明の方法によ
って得たポリマーは末端に反応性のＩ、ＢrまたはＣlを
有することもできるのでブロックポリマーやマクロモノ
マーの合成に用いることができる。As described above, according to the method of the present invention, a polymer having a narrower molecular weight distribution can be obtained as compared with the conventional radical polymerization. Further, it has advantages such as being less susceptible to impurities and easier to operate than ionic polymerization. Further, the polymer obtained by the method of the present invention can have reactive I, Br or Cl at the terminal, and can be used for synthesis of a block polymer or a macromonomer.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｆ 30/08 Ｃ０８Ｆ 30/08 (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 20/04 - 20/06 C08F 20/22 - 20/28 C08F 30/08 C08F 2/44 C08F 2/48 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 identification code FI C08F 30/08 C08F 30/08 (58) Field surveyed (Int.Cl. 7 , DB name) C08F 20/04-20/06 C08F 20/22-20/28 C08F 30/08 C08F 2/44 C08F 2/48
Claims (2)
基、またはトリフロロメチル基を表し、Ｒは１〜１６個
の炭素原子を有するアルキル基、フロロアルキル基、シ
ロキサン結合を含むアルキル基、ヒドロキシエチル基、
グリシジル基またはカリウム原子を表す。但し、Ｘがフ
ッ素原子または塩素原子以外の原子または基である場合
はＲはフロロアルキル基である) によって示されるハロゲン原子を含有するアクリル系化
合物から選ばれた少なくとも一種のモノマーに、Ｉ２，
Ｂr２，Ｃl２，IＢrおよびIＣlよりなる群から選ばれた
少なくとも一種のハロゲン化合物の存在下、波長２００
〜７００nmの光を照射することを含んでなるハロゲン含
有アクリル系モノマーの重合方法。1. General formula: CH 2 ＣCXCOOR (I) wherein X represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a trifluoromethyl group, and R represents 1 to 16 carbon atoms Having an alkyl group, a fluoroalkyl group, an alkyl group containing a siloxane bond, a hydroxyethyl group,
Represents a glycidyl group or a potassium atom. However, when X is an atom or a group other than a fluorine atom or a chlorine atom, R is a fluoroalkyl group.) At least one monomer selected from acrylic compounds containing a halogen atom represented by I 2 ,
In the presence of at least one halogen compound selected from the group consisting of Br 2 , Cl 2 , IBr and ICl, a wavelength of 200
A method for polymerizing a halogen-containing acrylic monomer, comprising irradiating light having a wavelength of about 700 nm.
ある請求項１に記載の重合方法。2. The polymerization method according to claim 1, wherein in the general formula (I), X is a fluorine atom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01534893A JP3264012B2 (en) | 1993-02-02 | 1993-02-02 | Polymerization method of halogen-containing acrylic monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01534893A JP3264012B2 (en) | 1993-02-02 | 1993-02-02 | Polymerization method of halogen-containing acrylic monomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06228231A JPH06228231A (en) | 1994-08-16 |
| JP3264012B2 true JP3264012B2 (en) | 2002-03-11 |
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ID=11886298
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