JP5191375B2

JP5191375B2 - Method for producing vinyl sulfonic acid polymer

Info

Publication number: JP5191375B2
Application number: JP2008330165A
Authority: JP
Inventors: 裕秋風; 武彦宮井; 和彦一色
Original assignee: Asahi Kasei Finechem Co Ltd
Current assignee: Asahi Kasei Finechem Co Ltd
Priority date: 2008-02-27
Filing date: 2008-12-25
Publication date: 2013-05-08
Anticipated expiration: 2028-12-25
Also published as: JP2009227965A; JP5503723B2; JP2013079392A

Description

本発明は、ビニルスルホン酸単独重合体の製造方法、並びに当該方法によって得られるビニルスルホン酸単独重合体に主に関する。 The present invention mainly relates to a method for producing a vinyl sulfonic acid homopolymer and a vinyl sulfonic acid homopolymer obtained by the method.

近年、ビニルスルホン酸の重合体は、導電性材料などの材料やコーティング剤として、高い注目を集めるようになっている。 In recent years, polymers of vinyl sulfonic acid have attracted high attention as materials such as conductive materials and coating agents.

ビニルスルホン酸の重合方法としては、ラジカル開始剤による方法や光照射による方法が知られている。しかし、ラジカル開始剤による重合では、分子量の小さなポリマーしか得られていない（非特許文献１参照）。また、これまで紫外線やγ線による重合では長時間を要していた（特許文献１及び非特許文献２参照）。
米国特許第２３４８７０５号 J.Am.Chem.Soc.,76, 6399-6401, (1954) 工業化学雑誌、71巻、3号、pp.430-432（1968） As a polymerization method of vinyl sulfonic acid, a method using a radical initiator and a method using light irradiation are known. However, only a polymer having a small molecular weight is obtained by polymerization using a radical initiator (see Non-Patent Document 1). Moreover, until now, polymerization by ultraviolet rays or γ rays has required a long time (see Patent Document 1 and Non-Patent Document 2).
U.S. Pat. No. 2,348,705 J.Am.Chem.Soc., 76, 6399-6401, (1954) Occupational Chemical Journal, Vol. 71, No. 3, pp.430-432 (1968)

本発明は、短時間で高分子量のビニルスルホン酸単独重合体を製造する方法、及び当該方法によって得られるビニルスルホン酸単独重合体を提供することを主な目的とする。 The main object of the present invention is to provide a method for producing a high molecular weight vinylsulfonic acid homopolymer in a short time and a vinylsulfonic acid homopolymer obtained by the method.

本発明は、上記課題を解決することを主な目的として、鋭意検討を重ねた結果、特定のアミド化合物の存在下、ビニルスルホン酸に光を照射して重合を行うことにより、短時間で高分子量のビニルスルホン酸単独重合体が得られることを見出し、更に検討を行って、本願発明を完成するに至った。 As a result of intensive studies with the main purpose of solving the above-mentioned problems, the present invention achieves high performance in a short time by performing polymerization by irradiating vinylsulfonic acid with light in the presence of a specific amide compound. The present inventors have found that a vinylsulfonic acid homopolymer having a molecular weight can be obtained, and further studied, and have completed the present invention.

即ち、本発明は、以下の製造方法及び重合体に関する。 That is, the present invention relates to the following production method and polymer.

１．一般式 R-C(=O)-NR₁R₂
（Rは水素原子又は低級アルキル基を表す。R₁、R₂は、同一又は異なって、水素原子又は低級アルキル基を表す）
で表されるアミド化合物の存在下にビニルスルホン酸を光重合させるビニルスルホン酸単独重合体の製造方法であって、
前記アミド化合物の量が、ビニルスルホン酸１モルに対し０．４モル以上２．５モル以下
である方法。 1. General formula RC (= O) -NR ₁ R ₂
(R represents a hydrogen atom or a lower alkyl group. R ₁ and R ₂ are the same or different and represent a hydrogen atom or a lower alkyl group)
A method for producing a vinyl sulfonic acid homopolymer in which vinyl sulfonic acid is photopolymerized in the presence of an amide compound represented by
The method wherein the amount of the amide compound is 0.4 mol or more and 2.5 mol or less with respect to 1 mol of vinylsulfonic acid.

好ましくは、一般式 R-C(=O)-NR₁R₂
（Rは水素原子又は低級アルキル基を表す。R₁、R₂は、同一又は異なって、水素原子又は低級アルキル基を表す）
で表されるアミド化合物の存在下にビニルスルホン酸に紫外線を照射して重合させるビニルスルホン酸単独重合体の製造方法であって、
前記アミド化合物の量が、ビニルスルホン酸１モルに対し０．４モル以上２．５モル以下
である方法。 Preferably, the general formula RC (= O) -NR ₁ R ₂
(R represents a hydrogen atom or a lower alkyl group. R ₁ and R ₂ are the same or different and represent a hydrogen atom or a lower alkyl group)
A process for producing a vinyl sulfonic acid homopolymer in which vinyl sulfonic acid is polymerized by irradiating with ultraviolet light in the presence of an amide compound represented by
The method wherein the amount of the amide compound is 0.4 mol or more and 2.5 mol or less with respect to 1 mol of vinylsulfonic acid.

２．アミド化合物が、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルホルムアミド、ホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ，Ｎ−ジブチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、及び、Ｎ，Ｎ−ジエチルアセトアミドからなる群から選ばれる少なくとも１種である、項１に記載のビニルスルホン酸単独重合体の製造方法。 2. The amide compound is a group consisting of N, N-dimethylformamide, N-methylformamide, formamide, N, N-diethylformamide, N, N-dibutylformamide, N, N-dimethylacetamide, and N, N-diethylacetamide Item 2. The method for producing a vinyl sulfonic acid homopolymer according to Item 1, which is at least one selected from the group consisting of:

３．項１又は２に記載の方法によって得られるビニルスルホン酸単独重合体。 3. Item 3. A vinyl sulfonic acid homopolymer obtained by the method according to Item 1 or 2.

以下、本発明について、更に詳細に説明する。 Hereinafter, the present invention will be described in more detail.

製造方法
本発明におけるビニルスルホン酸重合体の製造方法は、特定のアミド化合物の存在下にビニルスルホン酸を光重合させることを特徴とする。 Production Method The production method of the vinyl sulfonic acid polymer in the present invention is characterized in that vinyl sulfonic acid is photopolymerized in the presence of a specific amide compound.

別言すると、本発明は、特定のアミド化合物の存在下、ビニルスルホン酸に光を照射して、ビニルスルホン酸を重合させることにより、ビニルスルホン酸重合体を製造する方法を提供する。 In other words, the present invention provides a method for producing a vinyl sulfonic acid polymer by polymerizing vinyl sulfonic acid by irradiating light to vinyl sulfonic acid in the presence of a specific amide compound.

特に、本発明は、分子量約２，０００以上、好ましくは約１０，０００以上、さらに好ましくは約２０，０００以上のビニルスルホン酸単独重合体の製造方法を提供する。 In particular, the present invention provides a method for producing a vinyl sulfonic acid homopolymer having a molecular weight of about 2,000 or more, preferably about 10,000 or more, more preferably about 20,000 or more.

（１）アミド化合物
本発明のアミド化合物は、下記一般式
R-C(=O)-NR₁R₂
（Rは水素原子又は低級アルキル基を表す。R₁、R₂は、同一又は異なって、水素原子又は低級アルキル基を表す）
で表される。 (1) Amide compound The amide compound of the present invention has the following general formula:
RC (= O) -NR ₁ R ₂
(R represents a hydrogen atom or a lower alkyl group. R ₁ and R ₂ are the same or different and represent a hydrogen atom or a lower alkyl group)
It is represented by

低級アルキル基としては、炭素数１〜１０程度のアルキル基、好ましくは炭素数１〜５程度のアルキル基を挙げることができる。アルキル基は、直鎖状であってもよく分岐状であってもよい。 Examples of the lower alkyl group include an alkyl group having about 1 to 10 carbon atoms, preferably an alkyl group having about 1 to 5 carbon atoms. The alkyl group may be linear or branched.

具体的に、Rとしては、水素、メチル基、エチル基が挙げられる。 Specifically, R includes hydrogen, a methyl group, and an ethyl group.

また、R₁、R₂としては、水素、メチル基、エチル基、ブチル基等が挙げられる。 Examples of R ₁ and R ₂ include hydrogen, a methyl group, an ethyl group, and a butyl group.

一般式（１）で表される化合物の具体例としては、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルホルムアミド、ホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ，Ｎ−ジ−ｎ−ブチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、及び、Ｎ，Ｎ−ジエチルアセトアミド等が挙げられる。 Specific examples of the compound represented by the general formula (1) include N, N-dimethylformamide, N-methylformamide, formamide, N, N-diethylformamide, N, N-di-n-butylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, etc. are mentioned.

アミド化合物は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
本発明においては、アミド化合物を特定量存在させることで、ビニルスルホン酸の光重合を促進させる。 An amide compound may be used individually by 1 type, and may be used in combination of 2 or more type.
In the present invention, the photopolymerization of vinyl sulfonic acid is promoted by the presence of a specific amount of the amide compound.

アミド化合物の量は、ビニルスルホン酸１モルに対し、０．４〜２．５モル程度である。ビニルスルホン酸に対するアミド化合物の量が上記の範囲であると、重合率を高め、また高分子量の重合体を得ることが可能となる。 The amount of the amide compound is about 0.4 to 2.5 mol per 1 mol of vinyl sulfonic acid. When the amount of the amide compound relative to the vinyl sulfonic acid is within the above range, the polymerization rate can be increased and a high molecular weight polymer can be obtained.

通常、重合率を高くするためには、ビニルスルホン酸１モルに対するアミド化合物の割合が、０．５〜１．０モル程度であることが好ましい。 Usually, in order to increase the polymerization rate, the ratio of the amide compound to 1 mol of vinyl sulfonic acid is preferably about 0.5 to 1.0 mol.

また、高分子量のビニルスルホン酸重合体を得るためには、ビニルスルホン酸１モルに対するアミド化合物の割合が０．４〜１．０モル程度であることが好ましい。 In order to obtain a high molecular weight vinyl sulfonic acid polymer, the ratio of the amide compound to 1 mol of vinyl sulfonic acid is preferably about 0.4 to 1.0 mol.

照射光の波長は、本発明の効果を奏する範囲内で適宜設定することができ、特に限定されないが、通常１００〜８００ｎｍ程度、好ましくは、２００〜５００ｎｍ程度である。 The wavelength of the irradiation light can be appropriately set within the range where the effects of the present invention are exhibited, and is not particularly limited, but is usually about 100 to 800 nm, and preferably about 200 to 500 nm.

特に、紫外線（ＵＶ）を照射することが、重合速度が大きいなどの点で好ましい。 In particular, irradiation with ultraviolet rays (UV) is preferable from the viewpoint of a high polymerization rate.

重合時間、換言すると照射時間は、ビニルスルホン酸の量や目的等に応じて適宜設定し得るが、通常、１０分〜２４時間程度、特に２０分〜１２時間程度である。 The polymerization time, in other words, the irradiation time can be appropriately set according to the amount and purpose of the vinyl sulfonic acid, but is usually about 10 minutes to 24 hours, particularly about 20 minutes to 12 hours.

アミド化合物を存在させる方法は特に限定されない。例えば、アミド化合物を重合前にビニルスルホン酸に添加混合してもよく、ビニルスルホン酸を含む重合系に添加してもよい。例えば、本発明には、アミド化合物をビニルスルホン酸と混合する工程、得られた混合物に光を照射してビニルスルホン酸を重合する工程を有するビニルスルホン酸重合体の製法が含まれる。 The method for causing the amide compound to exist is not particularly limited. For example, an amide compound may be added and mixed with vinyl sulfonic acid before polymerization, or may be added to a polymerization system containing vinyl sulfonic acid. For example, the present invention includes a method for producing a vinyl sulfonic acid polymer comprising a step of mixing an amide compound with vinyl sulfonic acid, and a step of irradiating the resulting mixture with light to polymerize vinyl sulfonic acid.

重合の条件は、本発明の効果を奏する範囲内で適宜設定することができる。例えば、重合は適当な攪拌機を備えた装置を用いて、攪拌しながら、行うこともできる。また脱気を行って重合しても良く、或いは、酸素又は空気の存在下でも重合を行うことができる。 The conditions for the polymerization can be appropriately set within the range where the effects of the present invention are exhibited. For example, the polymerization can be carried out with stirring using an apparatus equipped with a suitable stirrer. The polymerization may be carried out by deaeration, or the polymerization can be carried out in the presence of oxygen or air.

また、重合温度も、本発明の効果を奏する範囲内で適宜設定することができるが、−３０〜１５０℃、好ましくは−２５〜８０℃程度である。 The polymerization temperature can also be set as appropriate within the range where the effects of the present invention are exhibited, but is about -30 to 150 ° C, preferably about -25 to 80 ° C.

重合温度が上記の範囲であると、重合率を高め、また高分子量の重合体を得ることが可能となる。 When the polymerization temperature is within the above range, the polymerization rate can be increased and a high molecular weight polymer can be obtained.

また、高分子量のビニルスルホン酸重合体を得るには重合温度を低めに設定することが好ましく、低分子量のビニルスルホン酸重合体を得るには重合温度を高めに設定することが好ましい。 In order to obtain a high molecular weight vinyl sulfonic acid polymer, the polymerization temperature is preferably set low, and in order to obtain a low molecular weight vinyl sulfonic acid polymer, the polymerization temperature is preferably set high.

前述のように、高分子量のビニルスルホン酸重合体を得るためには、ビニルスルホン酸１モルに対するアミド化合物の割合を比較的小さく設定することが好ましい。 As described above, in order to obtain a high molecular weight vinyl sulfonic acid polymer, it is preferable to set the ratio of the amide compound relative to 1 mol of vinyl sulfonic acid to be relatively small.

従って、重合温度を低めに設定し、更に、ビニルスルホン酸１モルに対するアミド化合物の割合を小さめに設定するという条件を組み合わせると、より高分子量のビニルスルホン酸重合体を得ることが可能となる。 Therefore, a higher molecular weight vinyl sulfonic acid polymer can be obtained by combining the conditions that the polymerization temperature is set lower and the ratio of the amide compound to 1 mol of vinyl sulfonic acid is set lower.

ビニルスルホン酸が重合して重合体となり、残存するビニルスルホン酸がほぼ消失することで、実質的に重合を完了させることができる。 Polymerization can be substantially completed by the vinyl sulfonic acid being polymerized to form a polymer and the remaining vinyl sulfonic acid almost disappearing.

得られた重合体は公知の方法で回収することができる。例えば、再沈殿等を用いて回収することができる。 The obtained polymer can be recovered by a known method. For example, it can be recovered using reprecipitation or the like.

また、得られた重合体は公知の方法に従って分離精製してもよい。 The obtained polymer may be separated and purified according to a known method.

２．ビニルスルホン酸単独重合体
本発明は、更に上記製造方法によって得られるビニルスルホン酸単独重合体を提供する。 2. Vinylsulfonic acid homopolymer The present invention further provides a vinylsulfonic acid homopolymer obtained by the above production method.

上記製造方法によって得られる重合体は、高分子量で、また着色が少なく、品質にも優れている。 The polymer obtained by the above production method has a high molecular weight, little coloration, and excellent quality.

特に、上記製造方法によれば、ゲルパーミエイションクロマトグラフィー（以下、ＧＰＣともいう）で測定した重量平均分子量が、約２，０００以上、特に約１０，０００以上、さらには約２０，０００以上の高分子量のビニルスルホン酸単独重合体が得られる。例えば、ＧＰＣで測定した重量平均分子量が約２，０００〜１００万程度、特に約１万〜１００万程度、さらには２万〜７０万程度のビニルスルホン酸単独重合体が得られる。 In particular, according to the above production method, the weight average molecular weight measured by gel permeation chromatography (hereinafter also referred to as GPC) is about 2,000 or more, particularly about 10,000 or more, further about 20,000 or more. The high molecular weight vinyl sulfonic acid homopolymer is obtained. For example, a vinylsulfonic acid homopolymer having a weight average molecular weight measured by GPC of about 2,000 to 1,000,000, particularly about 10,000 to 1,000,000, and further about 20,000 to 700,000 is obtained.

本発明のビニルスルホン酸単独重合体は、種々の用途に使用することができ、例えば、顔料分散剤、染料安定剤、増粘剤、粘着剤、化粧品用ポリマー、電池用バインダー、高分子電解質又は導電性ポリマー等として使用できる。 The vinyl sulfonic acid homopolymer of the present invention can be used in various applications, for example, pigment dispersants, dye stabilizers, thickeners, adhesives, cosmetic polymers, battery binders, polymer electrolytes or It can be used as a conductive polymer.

本発明によれば、ビニルスルホン酸の光重合を促進させることができ、高分子量のビニルスルホン酸重合体を短時間で製造することが可能となる。 According to the present invention, photopolymerization of vinyl sulfonic acid can be promoted, and a high molecular weight vinyl sulfonic acid polymer can be produced in a short time.

また、本発明の方法によれば、ラジカル重合を行う場合に必要となる脱気や酸素の除去は特に必要ない。これにより、ビニルスルホン酸重合体の生産性が格段に向上する。 Further, according to the method of the present invention, degassing and oxygen removal necessary for radical polymerization are not particularly necessary. Thereby, the productivity of the vinyl sulfonic acid polymer is significantly improved.

さらに、上記製造方法によって得られる本発明のビニルスルホン酸重合体は、着色が少なく、品質にも優れている。 Furthermore, the vinyl sulfonic acid polymer of the present invention obtained by the above production method is less colored and excellent in quality.

以下に実施例及び比較例を示し、本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

尚、特記しない限り、各例中の％はモル％を示す。また重合率は、単量体の重合体への転化率を示す。 Unless otherwise specified,% in each example represents mol%. Moreover, a polymerization rate shows the conversion rate of a monomer to a polymer.

また、ビニルスルホン酸を「ＶＳＡ」、Ｎ，Ｎ−ジメチルホルムアミドを「ＤＭＦ」として示す。 Vinylsulfonic acid is indicated as “VSA” and N, N-dimethylformamide is indicated as “DMF”.

また重合体の重量平均分子量は、下記Ａ又はＢの条件にて測定した。 Further, the weight average molecular weight of the polymer was measured under the following conditions A or B.

Ａ条件：アセトニトリル／５０ｍＭ塩化リチウム水溶液＝４／６を溶媒に、ポリエチレンオキシドを標準試料として、ゲルパーミエイションクロマトグラフィー（ＧＰＣ）で測定した。カラムは、Ｓｈｏｄｅｘ社製ＡｓａｈｉｐａｃｋＧＳ−２２０−ＨＱ、排除限界分子量（ＭＷ）約３０００を用いた。 A condition: Measured by gel permeation chromatography (GPC) using acetonitrile / 50 mM lithium chloride aqueous solution = 4/6 as a solvent and polyethylene oxide as a standard sample. As a column, Asahipack GS-220-HQ manufactured by Shodex and an exclusion limit molecular weight (MW) of about 3000 were used.

Ｂ条件：０．２Ｍ硝酸ナトリウム水溶液を溶媒に、ポリエチレンオキシドを標準試料として、ゲルパーミエイションクロマトグラフィー（ＧＰＣ）法で測定した。カラムは、東ソー株式会社製ＧＰＣカラムＴＳＫ−ＧＥＬのα−２５００とα−３０００とα−４０００の三本を連結して用いた。 B condition: Measured by gel permeation chromatography (GPC) method using 0.2M sodium nitrate aqueous solution as a solvent and polyethylene oxide as a standard sample. The column was used by connecting three α-2500, α-3000, and α-4000 of GPC column TSK-GEL manufactured by Tosoh Corporation.

実施例I−１
２０ｍｌのサンプル瓶内で、ＶＳＡ（旭化成ファインケム株式会社製）２ｇとＤＭＦ（片山化学社製試薬特級）１ｇを混合した後、ＵＶ照射機を用いて３６０ｎｍの紫外線を照射した。重合温度３５〜４５℃で１時間重合後、系内は透明樹脂状の固体となった。生成物をＧＰＣ（Ａ条件）で測定したところ、重合率は８５％であり、分子量２，０００以上の重合物の生成割合は８０％であった。他は分子量約４００の重合物であった。 Example I-1
In a 20 ml sample bottle, 2 g of VSA (manufactured by Asahi Kasei Finechem Co., Ltd.) and 1 g of DMF (special grade reagent manufactured by Katayama Chemical Co., Ltd.) were mixed, and then irradiated with ultraviolet rays of 360 nm using a UV irradiator. After polymerization at a polymerization temperature of 35 to 45 ° C. for 1 hour, the system became a transparent resinous solid. When the product was measured by GPC (A condition), the polymerization rate was 85%, and the production rate of the polymer having a molecular weight of 2,000 or more was 80%. The other was a polymer having a molecular weight of about 400.

実施例I−２
ＤＭＦの量を２ｇとする以外は、実施例I−１と同様に重合を行った。４時間後、系内は水飴状となった。生成物をＧＰＣ（Ａ条件）で測定したところ、重合率は３７％であり、分子量約２，０００以上の重合物の生成割合は２２％、他は分子量約４００の重合物であった。 Example I-2
Polymerization was carried out in the same manner as in Example I-1, except that the amount of DMF was 2 g. After 4 hours, the inside of the system became chickenpox. When the product was measured by GPC (A condition), the polymerization rate was 37%, the production ratio of the polymer having a molecular weight of about 2,000 or more was 22%, and the others were polymers having a molecular weight of about 400.

実施例I−３
ＶＳＡの量を１０ｇとし、ＤＭＦの量を２．７ｇとし、ＵＶに代えて自然光を照射する以外は、実施例I−１と同様に重合を行った。6時間後、系内は流動性が無い状態となった。生成物をＧＰＣ（Ａ条件）で測定したところ、重合率は５１％であり、分子量約２，０００以上の重合物の生成割合は５０％であった。 Example I-3
Polymerization was performed in the same manner as in Example I-1, except that the amount of VSA was 10 g, the amount of DMF was 2.7 g, and natural light was irradiated instead of UV. After 6 hours, the system became non-fluid. When the product was measured by GPC (A condition), the polymerization rate was 51%, and the production rate of the polymer having a molecular weight of about 2,000 or more was 50%.

実施例I−４
攪拌機を備えた３００ｍＬの四つ口フラスコで、１００ｇのＶＳＡを４０ｇのＤＭＦと混合し、攪拌しながら自然光を１２時間照射した。生成物をＧＰＣ（Ａ条件）で測定したところ、重合率は６１％であり、分子量約２，０００以上の重合物の生成割合は６０％であった。 Example I-4
In a 300 mL four-necked flask equipped with a stirrer, 100 g of VSA was mixed with 40 g of DMF and irradiated with natural light for 12 hours while stirring. When the product was measured by GPC (A condition), the polymerization rate was 61%, and the production rate of the polymer having a molecular weight of about 2,000 or more was 60%.

実施例I−５
ＶＳＡの量を２．３ｇとし、ＤＭＦの量を４．０ｇとする以外は、実施例I−１と同様の重合を行った。４時間後、系内はわずかに粘度が上昇した状態になった。 Example I-5
Polymerization was performed in the same manner as in Example I-1, except that the amount of VSA was 2.3 g and the amount of DMF was 4.0 g. After 4 hours, the viscosity of the system slightly increased.

生成物をＧＰＣ（Ａ条件）で測定したところ、重合率は３％であり、分子量約２，０００以上の重合物の生成割合は２％であった。 When the product was measured by GPC (A condition), the polymerization rate was 3%, and the production rate of the polymer having a molecular weight of about 2,000 or more was 2%.

比較例I−１
攪拌機を備えた３００ｍＬの四つ口フラスコで、３０ｇのＶＳＡを６０ｇのＤＭＦと混合し、ラジカル重合開始剤である０．０３ｇのアゾビスイソブチロニトリル（以下、「ＡＩＢＮ」ともいう）を添加して６０〜９０℃で、暗所で重合を行った。 Comparative Example I-1
In a 300 mL four-necked flask equipped with a stirrer, 30 g of VSA was mixed with 60 g of DMF, and 0.03 g of azobisisobutyronitrile (hereinafter also referred to as “AIBN”) as a radical polymerization initiator was added. The polymerization was carried out at 60 to 90 ° C. in the dark.

１０時間後ＧＰＣ（Ａ条件）で測定したところ、重合率は５０％であり、分子量約４００の重合物のみであった。重合物は褐色に着色した。 When measured by GPC (A condition) after 10 hours, the polymerization rate was 50%, and only a polymer having a molecular weight of about 400 was obtained. The polymer was colored brown.

比較例I−２
攪拌機を備えた３００ｍＬの四つ口フラスコで、３０ｇのＶＳＡを６０ｇの水と混合し、０．２ｇのＡＩＢＮを添加して６０〜９０℃で、暗所で重合を行った。１０時間後ＧＰＣ（Ａ条件）で測定したところ、重合率は５４％であり、分子量約２００の重合物のみであった。重合物は褐色に着色した。 Comparative Example I-2
In a 300 mL four-necked flask equipped with a stirrer, 30 g of VSA was mixed with 60 g of water, 0.2 g of AIBN was added, and polymerization was performed at 60 to 90 ° C. in the dark. When measured by GPC (A condition) after 10 hours, the polymerization rate was 54%, and only a polymer having a molecular weight of about 200 was obtained. The polymer was colored brown.

比較例I−３
２０ｍＬのサンプル瓶内で、１０ｇのＶＳＡを室温で自然光のもと重合を行った。6時間後ＧＰＣ（Ａ条件）で測定したところ、重合率は１％であり、分子量約４００の重合物のみであった。 Comparative Example I-3
In a 20 mL sample bottle, 10 g of VSA was polymerized at room temperature under natural light. When measured by GPC (A condition) after 6 hours, the polymerization rate was 1% and only a polymer having a molecular weight of about 400 was obtained.

比較例I−４
ＤＭＦを全く添加しない以外は、実施例I−１と同様に重合を行った。４時間後、ＧＰＣ（Ａ条件）で測定したところ全く重合は進行していなかった。 Comparative Example I-4
Polymerization was carried out in the same manner as in Example I-1 except that no DMF was added. After 4 hours, the polymerization did not proceed at all as measured by GPC (A condition).

比較例I−５
ＶＳＡの量を５ｇとし、ＤＭＦの量を０．５ｇとする以外は、実施例I−１と同様に重合を行った。２時間後、系内の粘度が僅かに上昇した状態となった。生成物をＧＰＣ（Ａ条件）で測定したところ、重合率は１％であり、分子量約４００の重合物のみであった。 Comparative Example I-5
Polymerization was carried out in the same manner as in Example I-1, except that the amount of VSA was 5 g and the amount of DMF was 0.5 g. After 2 hours, the viscosity in the system slightly increased. When the product was measured by GPC (A condition), the polymerization rate was 1% and only a polymer having a molecular weight of about 400 was obtained.

比較例I−６
ＤＭＦの量を４ｇとする以外は、実施例I−１と同様に重合を行った。４時間後、系内は透明樹脂状の固体となった。 Comparative Example I-6
Polymerization was conducted in the same manner as in Example I-1 except that the amount of DMF was changed to 4 g. After 4 hours, the system became a transparent resinous solid.

生成物をＧＰＣ（Ａ条件）で測定したところ、重合率は３４％であり、分子量約２，０００以上の重合物の生成割合は０％であった。 When the product was measured by GPC (A condition), the polymerization rate was 34%, and the production rate of the polymer having a molecular weight of about 2,000 or more was 0%.

比較例I−７
ＤＭＦの量を６ｇとする以外は、実施例I−１と同様に重合を行った。４時間後、系内は粘度がやや上昇した状態となった。 Comparative Example I-7
Polymerization was conducted in the same manner as in Example I-1, except that the amount of DMF was 6 g. After 4 hours, the viscosity in the system slightly increased.

生成物をＧＰＣ（Ａ条件）で測定したところ、重合率は２６％であり、分子量約２，０００以上の重合物は０％であった。 When the product was measured by GPC (A condition), the polymerization rate was 26%, and the polymer having a molecular weight of about 2,000 or more was 0%.

比較例I−８
ＶＳＡの量を５ｇとし、ＤＭＦの量を１ｇとする以外は、実施例I−１と同様に重合を行った。２時間後、系内は透明樹脂状の固体となった。生成物をＧＰＣ（Ａ条件）で測定したところ、重合率は２％であり、分子量約４００の重合物のみであった。 Comparative Example I-8
Polymerization was carried out in the same manner as in Example I-1, except that the amount of VSA was 5 g and the amount of DMF was 1 g. After 2 hours, the system became a transparent resinous solid. When the product was measured by GPC (A condition), the polymerization rate was 2% and only a polymer having a molecular weight of about 400 was obtained.

比較例I−９
重合管で、１０ｇのＶＳＡを１０ｇの水と混合し、０．２ｇのＡＩＢＮを添加して、十分に減圧脱気封管後、６０℃で、暗所で重合を行った。 Comparative Example I-9
In a polymerization tube, 10 g of VSA was mixed with 10 g of water, 0.2 g of AIBN was added, and after sufficiently degassing sealed tube, polymerization was performed at 60 ° C. in the dark.

３０時間後、生成物をＧＰＣ（Ａ条件）で測定したところ、重合率は９３％であり、分子量約２，０００以上の重合物の生成割合は３２％であった。 After 30 hours, the product was measured by GPC (A condition). As a result, the polymerization rate was 93%, and the production rate of the polymer having a molecular weight of about 2,000 or more was 32%.

比較例I−１０
重合管で、１０ｇのＶＳＡを１０ｇの水と混合し、０．２ｇの過硫酸アンモニウム（以下、「ＡＰＳ」ともいう）を添加して、十分に減圧脱気封管後、６０℃で、暗所で重合を行った。 Comparative Example I-10
In a polymerization tube, 10 g of VSA was mixed with 10 g of water, 0.2 g of ammonium persulfate (hereinafter also referred to as “APS”) was added, and after sufficiently degassing sealed tube at 60 ° C. in the dark The polymerization was carried out at

３０時間後、生成物をＧＰＣ（Ａ条件）で測定したところ、重合率は６７％であり、分子量約２，０００以上の重合物の生成割合は２７％であった。 After 30 hours, the product was measured by GPC (A condition). As a result, the polymerization rate was 67%, and the production rate of the polymer having a molecular weight of about 2,000 or more was 27%.

実施例I及び比較例Iのデータを表１にまとめて示す。なお、表１において、ＤＭＦ／ＶＳＡは、ビニルスルホン酸１モルに対するＮ，Ｎ−ジメチルホルムアミドのモル量を示す。また色調は生成物の色を目視で評価した結果を示す。 The data of Example I and Comparative Example I are summarized in Table 1. In Table 1, DMF / VSA represents the molar amount of N, N-dimethylformamide with respect to 1 mol of vinylsulfonic acid. Moreover, a color tone shows the result of having evaluated the color of the product visually.

上記結果から、Ｎ，Ｎ−ジメチルホルムアミドを特定量存在させることにより、短時間で分子量の大きいビニルスルホン酸重合体が得られることがわかった。更に脱気を行うことなく分子量の大きいビニルスルホン酸重合体を短時間で製造できることがわかった。 From the above results, it was found that a vinyl sulfonic acid polymer having a large molecular weight can be obtained in a short time when a specific amount of N, N-dimethylformamide is present. Furthermore, it has been found that a vinylsulfonic acid polymer having a large molecular weight can be produced in a short time without degassing.

また、ラジカル重合の場合は生成物が強く着色し、褐色となったが、Ｎ，Ｎ−ジメチルホルムアミドを存在させて光重合した場合、生成物の着色はほとんどみられなかった。 In the case of radical polymerization, the product was strongly colored and turned brown, but when photopolymerization was performed in the presence of N, N-dimethylformamide, the product was hardly colored.

実施例II−１
１０ｍｍ×１０ｍｍ×４３ｍｍの石英製セル内で、ＶＳＡ１ｇとＤＭＦ０．５ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。 Example II-1
In a 10 mm × 10 mm × 43 mm quartz cell, 1 g of VSA and 0.5 g of DMF were mixed, and then irradiated with UV rays of 250 to 370 nm using a UV irradiator (MAX302 manufactured by Asahi Spectra).

重合温度２５〜４０℃で２０分間重合後、系内は薄黄色透明樹脂状の固体となった。 After polymerization at a polymerization temperature of 25 to 40 ° C. for 20 minutes, the inside of the system became a light yellow transparent resinous solid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は７１％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約４４，０００であった。 When the product was measured by GPC (B condition), the polymerization rate was 71%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 44,000.

実施例II−２
ＤＭＦ０．５ｇをＮ−メチルホルムアミド０．５ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の樹脂状の固体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は８８％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約４１，０００であった。 Example II-2
Polymerization was carried out in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 0.5 g of N-methylformamide. After 20 minutes of UV irradiation, the inside of the system became a light yellow transparent resinous solid. When the product was measured by GPC (B condition), the polymerization rate was 88%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 41,000.

実施例II−３
ＤＭＦ０．５ｇをホルムアミド０．５ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の更に堅い樹脂状の固体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は６２％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約６２，０００であった。 Example II-3
Polymerization was carried out in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 0.5 g of formamide. After 20 minutes of UV irradiation, the inside of the system became a light yellow transparent, harder resinous solid. When the product was measured by GPC (Condition B), the polymerization rate was 62%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 62,000.

実施例II−４
ＤＭＦ０．５ｇをＮ，Ｎ−ジエチルホルムアミド０．５ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の粘調な液体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は２４％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約５９，０００であった。 Example II-4
Polymerization was carried out in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 0.5 g of N, N-diethylformamide. After 20 minutes of UV irradiation, the inside of the system became a pale yellow transparent viscous liquid. When the product was measured by GPC (B condition), the polymerization rate was 24%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 59,000.

実施例II−５
ＤＭＦ０．５ｇをＮ，Ｎ−ジ−ｎ−ブチルホルムアミド１．０ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の柔らかい樹脂状の固体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は４７％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約４２，０００であった。 Example II-5
Polymerization was carried out in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 1.0 g of N, N-di-n-butylformamide. After 20 minutes of UV irradiation, the inside of the system became a light yellow transparent soft resinous solid. When the product was measured by GPC (Condition B), the polymerization rate was 47%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 42,000.

実施例II−６
ＤＭＦ０．５ｇをＮ，Ｎ−ジメチルアセトアミド０．５ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の粘調な液体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３４％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約４７，０００であった。 Example II-6
Polymerization was carried out in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 0.5 g of N, N-dimethylacetamide. After 20 minutes of UV irradiation, the inside of the system became a pale yellow transparent viscous liquid. When the product was measured by GPC (Condition B), the polymerization rate was 34%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 47,000.

実施例II−７
ＤＭＦ０．５ｇをＮ，Ｎ−ジエチルアセトアミド０．５ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の柔らかい樹脂状の固体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は１４％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約５５，０００であった。 Example II-7
Polymerization was carried out in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 0.5 g of N, N-diethylacetamide. After 20 minutes of UV irradiation, the inside of the system became a light yellow transparent soft resinous solid. When the product was measured by GPC (Condition B), the polymerization rate was 14%. All the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 55,000.

比較例II−１
ＤＭＦ０．５ｇをＮ−メチルピロリドン０．５ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は変化せず更にＵＶ照射を２０分延長したが変化しなかった。反応物をＧＰＣ（Ｂ条件）で測定したところ、重合物は全く生成していなかった。 Comparative Example II-1
Polymerization was conducted in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 0.5 g of N-methylpyrrolidone. After 20 minutes of UV irradiation, the inside of the system did not change, and the UV irradiation was further extended for 20 minutes, but it did not change. When the reaction product was measured by GPC (B condition), no polymer was formed.

実施例II−８
ＤＭＦ０．５ｇをホルムアミド０．３ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の樹脂状の固体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は５９％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約８１，０００であった。 Example II-8
Polymerization was carried out in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 0.3 g of formamide. After 20 minutes of UV irradiation, the inside of the system became a light yellow transparent resinous solid. When the product was measured by GPC (B condition), the polymerization rate was 59%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 81,000.

実施例II−９
ＤＭＦ０．５ｇをホルムアミド１．０ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の一部樹脂状の固体を含んだ液体となった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３１％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約３７，０００であった。 Example II-9
Polymerization was carried out in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 1.0 g of formamide. After 20 minutes of UV irradiation, the inside of the system became a liquid containing a light yellow transparent partially resinous solid. When the product was measured by GPC (B condition), the polymerization rate was 31%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 37,000.

実施例II−１０
ＤＭＦ０．５ｇをＮ，Ｎ−ジエチルホルムアミド０．９４ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は一部液状の薄黄色透明の樹脂状の固体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３９％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約３４，０００であった。 Example II-10
Polymerization was carried out in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 0.94 g of N, N-diethylformamide. After 20 minutes of UV irradiation, the inside of the system became a liquid, light yellow, transparent resinous solid. When the product was measured by GPC (Condition B), the polymerization rate was 39%. All the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 34,000.

実施例II−１１
ＤＭＦ０．５ｇをＮ，Ｎ−ジエチルホルムアミド１．５ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の樹脂状の固体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は５１％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約２３，０００であった。 Example II-11
Polymerization was carried out in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 1.5 g of N, N-diethylformamide. After 20 minutes of UV irradiation, the inside of the system became a light yellow transparent resinous solid. When the product was measured by GPC (B condition), the polymerization rate was 51%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 23,000.

実施例II−１２
ＤＭＦ０．５ｇをＮ，Ｎ−ジ−ｎ−ブチルホルムアミド１．４６ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の一部樹脂状の固体を含む液体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３３％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約３０，０００であった。 Example II-12
Polymerization was carried out in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 1.46 g of N, N-di-n-butylformamide. After 20 minutes of UV irradiation, the inside of the system became a liquid containing a light yellow transparent partially resinous solid. When the product was measured by GPC (Condition B), the polymerization rate was 33%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 30,000.

実施例II−１３
ＤＭＦ０．５ｇをＮ，Ｎ−ジ−ｎ−ブチルホルムアミド２．０ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の一部樹脂状の固体を含む液体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は２７％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約２６，０００であった。 Example II-13
Polymerization was carried out in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 2.0 g of N, N-di-n-butylformamide. After 20 minutes of UV irradiation, the inside of the system became a liquid containing a light yellow transparent partially resinous solid. When the product was measured by GPC (B condition), the polymerization rate was 27%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 26,000.

実施例II−１４
ＤＭＦ０．５ｇをＮ，Ｎ−ジメチルアセトアミド０．８１ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の樹脂状の固体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は５０％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約２５，０００であった。 Example II-14
Polymerization was conducted in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 0.81 g of N, N-dimethylacetamide. After 20 minutes of UV irradiation, the inside of the system became a light yellow transparent resinous solid. When the product was measured by GPC (B condition), the polymerization rate was 50%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 25,000.

実施例II−１５
ＤＭＦ０．５ｇをＮ，Ｎ−ジメチルアセトアミド１．０ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の樹脂状の固体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３８％であり、得られた重合物は全て分子量１０，０００以上であって、その平均分子量は約１９，０００であった。 Example II-15
Polymerization was carried out in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 1.0 g of N, N-dimethylacetamide. After 20 minutes of UV irradiation, the inside of the system became a light yellow transparent resinous solid. When the product was measured by GPC (B condition), the polymerization rate was 38%, and all the obtained polymers had a molecular weight of 10,000 or more, and the average molecular weight was about 19,000.

実施例II−１６
ＤＭＦ０．５ｇをＮ，Ｎ−ジエチルアセトアミド１．０ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の液体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率１２％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約２６，０００であった。 Example II-16
Polymerization was carried out in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 1.0 g of N, N-diethylacetamide. After 20 minutes of UV irradiation, the inside of the system became a light yellow transparent liquid. When the product was measured by GPC (B condition), the polymerization rate was 12%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 26,000.

実施例II−１７
ＤＭＦ０．５ｇをＮ，Ｎ−ジエチルアセトアミド１．５ｇとする以外は、実施例II−１と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の液体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は１６％であり、得られた重合物は全て分子量１０，０００以上であって、その平均分子量は約２０，０００であった。 Example II-17
Polymerization was carried out in the same manner as in Example II-1, except that 0.5 g of DMF was changed to 1.5 g of N, N-diethylacetamide. After 20 minutes of UV irradiation, the inside of the system became a light yellow transparent liquid. When the product was measured by GPC (B condition), the polymerization rate was 16%. All the obtained polymers had a molecular weight of 10,000 or more, and the average molecular weight was about 20,000.

実施例II−１８
１０ｍｍ×１０ｍｍ×４３ｍｍの石英製セル内で、ＶＳＡ１ｇとＤＭＦ０．５ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度８０℃で２０分間重合後、系内は薄黄色透明の樹脂状の固体となった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は７３％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約２８，０００であった。 Example II-18
In a 10 mm × 10 mm × 43 mm quartz cell, 1 g of VSA and 0.5 g of DMF were mixed, and then irradiated with UV rays of 250 to 370 nm using a UV irradiator (MAX302 manufactured by Asahi Spectra). After polymerization for 20 minutes at a polymerization temperature of 80 ° C., the inside of the system became a light yellow transparent resinous solid. When the product was measured by GPC (B condition), the polymerization rate was 73%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 28,000.

実施例II−１９
重合温度を１０℃にする以外は、実施例II−１８と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の液体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は７３％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約６７，０００であった。 Example II-19
Polymerization was conducted in the same manner as in Example II-18 except that the polymerization temperature was 10 ° C. After 20 minutes of UV irradiation, the inside of the system became a light yellow transparent liquid. When the product was measured by GPC (B condition), the polymerization rate was 73%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 67,000.

実施例II−２０
重合温度を０℃にする以外は、実施例II−１８と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の液体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は４８％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約１１０，０００であった。 Example II-20
Polymerization was conducted in the same manner as in Example II-18 except that the polymerization temperature was 0 ° C. After 20 minutes of UV irradiation, the inside of the system became a light yellow transparent liquid. When the products were measured by GPC (Condition B), the polymerization rate was 48%. All the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 110,000.

実施例II−２１
重合温度を−１５℃にする以外は、実施例II−１８と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の液体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３１％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約１５５，０００であった。 Example II-21
Polymerization was conducted in the same manner as in Example II-18 except that the polymerization temperature was −15 ° C. After 20 minutes of UV irradiation, the inside of the system became a light yellow transparent liquid. When the product was measured by GPC (B condition), the polymerization rate was 31%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 155,000.

実施例II−２２
重合温度を−２０℃にする以外は、実施例II−１８と同様に重合を行った。ＵＶ照射２０分後、系内は薄黄色透明の液体になった。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３１％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約１８５，０００であった。 Example II-22
Polymerization was conducted in the same manner as in Example II-18 except that the polymerization temperature was −20 ° C. After 20 minutes of UV irradiation, the inside of the system became a light yellow transparent liquid. When the product was measured by GPC (B condition), the polymerization rate was 31%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 185,000.

実施例II−２３
１０ｍｍ×１０ｍｍ×４３ｍｍの石英製セル内で、ＶＳＡ１ｇとホルムアミド（東京化成工業社製）０．６４ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度−５℃近辺で２０分間重合後、系内は薄黄色の粘度の高い液体となった。 Example II-23
In a 10 mm x 10 mm x 43 mm quartz cell, VSA 1 g and formamide (Tokyo Chemical Industry Co., Ltd.) 0.64 g were mixed, and then irradiated with UV rays of 250 to 370 nm using a UV irradiator (Asahi Spectra MAX302). did. After polymerization for 20 minutes at a polymerization temperature of around -5 ° C, the system became a light yellow, highly viscous liquid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は２８％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約１３９，０００であった。 When the product was measured by GPC (Condition B), the polymerization rate was 28%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 139,000.

実施例II−２４
ホルムアミドの量を０．４１ｇにする以外は実施例II−２３と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３７％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約２１１，０００であった。 Example II-24
Polymerization was conducted in the same manner as in Example II-23 except that the amount of formamide was changed to 0.41 g. When the product was measured by GPC (Condition B), the polymerization rate was 37%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 211,000.

実施例II−２５
ホルムアミドの量を０．３１ｇにする以外は実施例II−２３と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３４％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約３８１，０００であった。 Example II-25
Polymerization was conducted in the same manner as in Example II-23 except that the amount of formamide was changed to 0.31 g. When the product was measured by GPC (Condition B), the polymerization rate was 34%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 381,000.

実施例II−２６
１０ｍｍ×１０ｍｍ×４３ｍｍの石英製セル内で、ＶＳＡ１ｇとホルムアミド(東京化成工業社製)０．６４ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度５℃近辺で２０分間重合後、系内は薄黄色の粘度の高い液体となった。 Example II-26
In a 10 mm × 10 mm × 43 mm quartz cell, 1 g of VSA and 0.64 g of formamide (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed, and then irradiated with UV rays of 250 to 370 nm using a UV irradiator (MAX302 manufactured by Asahi Spectra). did. After 20 minutes of polymerization at a polymerization temperature of around 5 ° C., the system became a light yellow, highly viscous liquid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は４６％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約１７１，０００であった。 When the product was measured by GPC (B condition), the polymerization rate was 46%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 171,000.

実施例II−２７
ホルムアミドの量を０．４１ｇにする以外は実施例II−２６と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は５６％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約２２７，０００であった。 Example II-27
Polymerization was carried out in the same manner as in Example II-26 except that the amount of formamide was changed to 0.41 g. When the product was measured by GPC (Condition B), the polymerization rate was 56%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 227,000.

実施例II−２８
ホルムアミドの量を０．３１ｇにする以外は実施例II−２６と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は７５％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約２８１，０００であった。 Example II-28
Polymerization was carried out in the same manner as in Example II-26 except that the amount of formamide was changed to 0.31 g. When the products were measured by GPC (Condition B), the polymerization rate was 75%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 281,000.

実施例II−２９
１０ｍｍ×１０ｍｍ×４３ｍｍの石英製セル内で、ＶＳＡ１ｇとホルムアミド(東京化成工業社製)０．６４ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度２３℃近辺で２０分間重合後、系内は薄黄色の粘度の高い液体となった。 Example II-29
In a 10 mm × 10 mm × 43 mm quartz cell, 1 g of VSA and 0.64 g of formamide (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed, and then irradiated with UV rays of 250 to 370 nm using a UV irradiator (MAX302 manufactured by Asahi Spectra). did. After polymerization for 20 minutes at a polymerization temperature of around 23 ° C., the system became a light yellow, highly viscous liquid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は７４％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約１０３，０００であった。 When the product was measured by GPC (B condition), the polymerization rate was 74%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 103,000.

実施例II−３０
ホルムアミドの量を０．４１ｇにする以外は実施例II−２９と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は７９％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約２２５，０００であった。 Example II-30
Polymerization was carried out in the same manner as in Example II-29 except that the amount of formamide was changed to 0.41 g. When the product was measured by GPC (B condition), the polymerization rate was 79%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 225,000.

実施例II−３１
ホルムアミドの量を０．３１ｇにする以外は実施例II−２９と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は７９％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約２０５，０００であった。 Example II-31
Polymerization was conducted in the same manner as in Example II-29 except that the amount of formamide was 0.31 g. When the product was measured by GPC (B condition), the polymerization rate was 79%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 205,000.

実施例II−３２
ホルムアミドの量を０．２６ｇにする以外は実施例II−２９と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は４３％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約４０８，０００であった。 Example II-32
Polymerization was carried out in the same manner as in Example II-29 except that the amount of formamide was changed to 0.26 g. When the products were measured by GPC (Condition B), the polymerization rate was 43%. All the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 408,000.

実施例II−３３
ホルムアミドの量を０．２０ｇにする以外は実施例II−２９と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は１２％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約５１３，０００であった。 Example II-33
Polymerization was carried out in the same manner as in Example II-29 except that the amount of formamide was changed to 0.20 g. When the product was measured by GPC (Condition B), the polymerization rate was 12%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 513,000.

実施例II−３４
１０ｍｍ×１０ｍｍ×４３ｍｍの石英製セル内で、ＶＳＡ１ｇとＮ，Ｎ−ジメチルアセトアミド(東京化成工業社製)１．２４ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度−２℃近辺で２０分間重合後、系内は薄黄色の液体となった。 Example II-34
In a 10 mm × 10 mm × 43 mm quartz cell, 1 g of VSA and 1.24 g of N, N-dimethylacetamide (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed, and then 250 to 250 using a UV irradiator (MAX302 manufactured by Asahi Spectra). Irradiated with ultraviolet rays of 370 nm. After polymerization for 20 minutes near the polymerization temperature of −2 ° C., the system became a pale yellow liquid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は１９％であり、得られた重合物は全て分子量１０，０００以上であって、その平均分子量は約１８，０００であった。 When the products were measured by GPC (Condition B), the polymerization rate was 19%. All the obtained polymers had a molecular weight of 10,000 or more, and the average molecular weight was about 18,000.

実施例II−３５
Ｎ，Ｎ−ジメチルアセトアミドの量を０．８０ｇにする以外は実施例II−３４と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は１０％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約４６，０００であった。 Example II-35
Polymerization was conducted in the same manner as in Example II-34 except that the amount of N, N-dimethylacetamide was changed to 0.80 g. When the product was measured by GPC (Condition B), the polymerization rate was 10%. All the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 46,000.

実施例II−３６
１０ｍｍ×１０ｍｍ×４３ｍｍの石英製セル内で、ＶＳＡ１ｇとＮ，Ｎ−ジメチルアセトアミド（東京化成工業社製）１．２４ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度６℃近辺で２０分間重合後、系内は薄黄色の液体となった。 Example II-36
In a 10 mm × 10 mm × 43 mm quartz cell, 1 g of VSA and 1.24 g of N, N-dimethylacetamide (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and then 250 to 250 using a UV irradiator (MAX 302 manufactured by Asahi Spectra). Irradiated with ultraviolet rays of 370 nm. After polymerization for 20 minutes near a polymerization temperature of 6 ° C., the system became a pale yellow liquid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は１８％であり、得られた重合物は全て分子量１０，０００以上であって、その平均分子量は約１８，０００であった。 When the product was measured by GPC (Condition B), the polymerization rate was 18%, all the obtained polymers had a molecular weight of 10,000 or more, and the average molecular weight was about 18,000.

実施例II−３７
Ｎ，Ｎ−ジメチルアセトアミドの量を０．８０ｇにする以外は実施例II−３６と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は４３％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約４８，０００であった。 Example II-37
Polymerization was conducted in the same manner as in Example II-36 except that the amount of N, N-dimethylacetamide was changed to 0.80 g. When the product was measured by GPC (B condition), the polymerization rate was 43%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 48,000.

実施例II−３８
Ｎ，Ｎ−ジメチルアセトアミドの量を０．６０ｇにする以外は実施例II−３６と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は６０％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約７２，０００であった。 Example II-38
Polymerization was conducted in the same manner as in Example II-36 except that the amount of N, N-dimethylacetamide was changed to 0.60 g. When the product was measured by GPC (B condition), the polymerization rate was 60%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 72,000.

実施例II−３９
１０ｍｍ×１０ｍｍ×４３ｍｍの石英製セル内で、ＶＳＡ１ｇとＮ，Ｎ−ジメチルアセトアミド（東京化成工業社製）１．２４ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度２０℃近辺で２０分間重合後、系内は薄黄色の液体となった。 Example II-39
In a 10 mm × 10 mm × 43 mm quartz cell, 1 g of VSA and 1.24 g of N, N-dimethylacetamide (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and then 250 to 250 using a UV irradiator (MAX 302 manufactured by Asahi Spectra). Irradiated with ultraviolet rays of 370 nm. After polymerization for 20 minutes near a polymerization temperature of 20 ° C., the inside of the system became a light yellow liquid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は１５％であり、得られた重合物は全て分子量１０，０００以上であって、その平均分子量は約１６，０００であった。 When the product was measured by GPC (B condition), the polymerization rate was 15%, and all the obtained polymers had a molecular weight of 10,000 or more, and the average molecular weight was about 16,000.

実施例II−４０
Ｎ，Ｎ−ジメチルアセトアミドの量を０．８０ｇにする以外は実施例II−３９と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３９％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約４２，０００であった。 Example II-40
Polymerization was conducted in the same manner as in Example II-39 except that the amount of N, N-dimethylacetamide was changed to 0.80 g. When the product was measured by GPC (B condition), the polymerization rate was 39%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 42,000.

実施例II−４１
Ｎ，Ｎ−ジメチルアセトアミドの量を０．６０ｇにする以外は実施例II−３９と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は４７％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約７７，０００であった。 Example II-41
Polymerization was conducted in the same manner as in Example II-39 except that the amount of N, N-dimethylacetamide was changed to 0.60 g. When the product was measured by GPC (B condition), the polymerization rate was 47%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 77,000.

実施例II−４２
１０ｍｍ×１０ｍｍ×４３ｍｍの石英製セル内で、ＶＳＡ１ｇとＮ，Ｎ−ジメチルアセトアミド（東京化成工業社製）１．２４ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度３４℃近辺で２０分間重合後、系内は薄黄色の液体となった。 Example II-42
In a 10 mm × 10 mm × 43 mm quartz cell, 1 g of VSA and 1.24 g of N, N-dimethylacetamide (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and then 250 to 250 using a UV irradiator (MAX 302 manufactured by Asahi Spectra). Irradiated with ultraviolet rays of 370 nm. After polymerization for 20 minutes near a polymerization temperature of 34 ° C., the inside of the system became a light yellow liquid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は２１％であり、得られた重合物は全て分子量１０，０００以上であって、その平均分子量は約１４，０００であった。 When the product was measured by GPC (Condition B), the polymerization rate was 21%, and all the obtained polymers had a molecular weight of 10,000 or more, and the average molecular weight was about 14,000.

実施例II−４３
Ｎ，Ｎ−ジメチルアセトアミドの量を０．８０ｇにする以外は実施例II−４２と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３８％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約３０，０００であった
実施例II−４４
Ｎ，Ｎ−ジメチルアセトアミドの量を０．６０ｇにする以外は実施例II−４２と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は５７％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約５９，０００であった。 Example II-43
Polymerization was conducted in the same manner as in Example II-42 except that the amount of N, N-dimethylacetamide was changed to 0.80 g. When the product was measured by GPC (B condition), the polymerization rate was 38%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 30,000.
Example II-44
Polymerization was conducted in the same manner as in Example II-42 except that the amount of N, N-dimethylacetamide was changed to 0.60 g. When the product was measured by GPC (B condition), the polymerization rate was 57%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 59,000.

実施例II−４５
１０ｍｍ×１０ｍｍ×４３ｍｍの石英製セル内で、ＶＳＡ１ｇとＮ，Ｎ−ジメチルアセトアミド（東京化成工業社製）１．２４ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度５４℃近辺で２０分間重合後、系内は薄黄色の液体となった。 Example II-45
In a 10 mm × 10 mm × 43 mm quartz cell, 1 g of VSA and 1.24 g of N, N-dimethylacetamide (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and then 250 to 250 using a UV irradiator (MAX 302 manufactured by Asahi Spectra). Irradiated with ultraviolet rays of 370 nm. After polymerization for 20 minutes near a polymerization temperature of 54 ° C., the inside of the system became a light yellow liquid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は２５％であり、得られた重合物は全て分子量１０，０００以上であって、その平均分子量は約１２，０００であった。 When the product was measured by GPC (B condition), the polymerization rate was 25%, and all the obtained polymers had a molecular weight of 10,000 or more, and the average molecular weight was about 12,000.

実施例II−４６
Ｎ，Ｎ−ジメチルアセトアミドの量を０．８０ｇにする以外は実施例II−４５と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３３％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約２３，０００であった。 Example II-46
Polymerization was conducted in the same manner as in Example II-45 except that the amount of N, N-dimethylacetamide was changed to 0.80 g. When the product was measured by GPC (Condition B), the polymerization rate was 33%. All the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 23,000.

実施例II−４７
Ｎ，Ｎ−ジメチルアセトアミドの量を０．６０ｇにする以外は実施例II−４５と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は５３％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約３６，０００であった。 Example II-47
Polymerization was conducted in the same manner as in Example II-45 except that the amount of N, N-dimethylacetamide was changed to 0.60 g. When the product was measured by GPC (Condition B), the polymerization rate was 53%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 36,000.

実施例II−４８
１０ｍｍ×１０ｍｍ×４３ｍｍの石英製セル内で、ＶＳＡ１ｇとＮ，Ｎ−ジメチルアセトアミド（東京化成工業社製）１．２４ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度６７℃近辺で２０分間重合後、系内は薄黄色の液体となった。 Example II-48
In a 10 mm × 10 mm × 43 mm quartz cell, 1 g of VSA and 1.24 g of N, N-dimethylacetamide (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and then 250 to 250 using a UV irradiator (MAX 302 manufactured by Asahi Spectra). Irradiated with ultraviolet rays of 370 nm. After polymerization for 20 minutes near a polymerization temperature of 67 ° C., the inside of the system became a light yellow liquid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は２５％であり、得られた重合物は全て分子量１０，０００以上であって、その平均分子量は約１１，０００であった。 When the product was measured by GPC (B condition), the polymerization rate was 25%, and all the obtained polymers had a molecular weight of 10,000 or more, and the average molecular weight was about 11,000.

実施例II−４９
Ｎ，Ｎ−ジメチルアセトアミドの量を０．８０ｇにする以外は実施例II−４８と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３０％であり、得られた重合物は全て分子量１０，０００以上であって、その平均分子量は約１９，０００であった。 Example II-49
Polymerization was conducted in the same manner as in Example II-48 except that the amount of N, N-dimethylacetamide was changed to 0.80 g. When the product was measured by GPC (B condition), the polymerization rate was 30%, and all the obtained polymers had a molecular weight of 10,000 or more, and the average molecular weight was about 19,000.

実施例II−５０
Ｎ，Ｎ−ジメチルアセトアミドの量を０．６０ｇにする以外は実施例II−４８と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は４４％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約３０，０００であった。 Example II-50
Polymerization was conducted in the same manner as in Example II-48 except that the amount of N, N-dimethylacetamide was changed to 0.60 g. When the product was measured by GPC (Condition B), the polymerization rate was 44%. All the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 30,000.

実施例II−５１
１０ｍｍ×１０ｍｍ×４３ｍｍの石英製セル内で、ＶＳＡ１ｇとＮ−メチルホルムアミド（東京化成工業社製）０．８４ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度９℃近辺で２０分間重合後、系内は薄黄色の粘度の高い液体となった。 Example II-51
In a 10 mm × 10 mm × 43 mm quartz cell, 1 g of VSA and 0.84 g of N-methylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and then 250-370 nm using a UV irradiator (MAX 302, manufactured by Asahi Spectra). Irradiated with ultraviolet rays. After polymerization for 20 minutes near a polymerization temperature of 9 ° C., the inside of the system became a light yellow viscous liquid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は２５％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約１０８，０００であった。 When the product was measured by GPC (B condition), the polymerization rate was 25%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 108,000.

実施例II−５２
Ｎ−メチルホルムアミドの量を０．５４ｇにする以外は実施例II−５１と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は２６％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約２０５，０００であった。 Example II-52
Polymerization was conducted in the same manner as in Example II-51 except that the amount of N-methylformamide was changed to 0.54 g. When the product was measured by GPC (Condition B), the polymerization rate was 26%. All the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 205,000.

実施例II−５３
Ｎ−メチルホルムアミドの量を０．４１ｇにする以外は実施例II−５１と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は２４％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約２７９，０００であった。 Example II-53
Polymerization was conducted in the same manner as in Example II-51 except that the amount of N-methylformamide was changed to 0.41 g. When the product was measured by GPC (B condition), the polymerization rate was 24%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 279,000.

実施例II−５４
１０ｍｍ×１０ｍｍ×４３ｍｍの石英製セル内で、ＶＳＡ１ｇとＮ−メチルホルムアミド（東京化成工業社製）０．８４ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度２０℃近辺で２０分間重合後、系内は薄黄色の粘度の高い液体となった。 Example II-54
In a 10 mm × 10 mm × 43 mm quartz cell, 1 g of VSA and 0.84 g of N-methylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and then 250-370 nm using a UV irradiator (MAX 302, manufactured by Asahi Spectra). Irradiated with ultraviolet rays. After polymerization for 20 minutes near a polymerization temperature of 20 ° C., the system became a light yellow, highly viscous liquid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３１％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約８４，０００であった。 When the product was measured by GPC (Condition B), the polymerization rate was 31%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 84,000.

実施例II−５５
Ｎ−メチルホルムアミドの量を０．５４ｇにする以外は実施例II−５４と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３２％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約１８５，０００であった。 Example II-55
Polymerization was conducted in the same manner as in Example II-54 except that the amount of N-methylformamide was changed to 0.54 g. When the product was measured by GPC (B condition), the polymerization rate was 32%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 185,000.

実施例II−５６
Ｎ−メチルホルムアミドの量を０．４１ｇにする以外は実施例II−５４と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は２７％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約２３６，０００であった。 Example II-56
Polymerization was conducted in the same manner as in Example II-54 except that the amount of N-methylformamide was changed to 0.41 g. When the product was measured by GPC (Condition B), the polymerization rate was 27%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 236,000.

実施例II−５７
１０ｍｍ×１０ｍｍ×４３ｍｍの石英製セル内で、ＶＳＡ１ｇとＮ−メチルホルムアミド（東京化成工業社製）０．８４ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度４５℃近辺で２０分間重合後、系内は薄黄色の粘度の高い液体となった。 Example II-57
In a 10 mm × 10 mm × 43 mm quartz cell, 1 g of VSA and 0.84 g of N-methylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and then 250-370 nm using a UV irradiator (MAX 302, manufactured by Asahi Spectra). Irradiated with ultraviolet rays. After 20 minutes of polymerization at a polymerization temperature of around 45 ° C., the system became a light yellow viscous liquid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３２％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約４８，０００であった。 When the products were measured by GPC (Condition B), the polymerization rate was 32%. All the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 48,000.

実施例II−５８
Ｎ−メチルホルムアミドの量を０．５４ｇにする以外は実施例II−５７と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は３３％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約９０，０００であった。 Example II-58
Polymerization was conducted in the same manner as in Example II-57 except that the amount of N-methylformamide was changed to 0.54 g. When the product was measured by GPC (B condition), the polymerization rate was 33%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 90,000.

実施例II−５９
Ｎ−メチルホルムアミドの量を０．４１ｇにする以外は実施例II−５７と同様に重合を行った。生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は４１％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約１１３，０００であった。 Example II-59
Polymerization was conducted in the same manner as in Example II-57 except that the amount of N-methylformamide was changed to 0.41 g. When the product was measured by GPC (B condition), the polymerization rate was 41%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 113,000.

実施例II−６０
φ３７ｍｍのテフロン（登録商標）製容器にＶＳＡ１２ｇとＤＭＦ６ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度１８℃近辺で１時間重合後、系内は薄黄色の固体となった。
生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は５９％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約６７，０００であった。
反応溶液に水３２ｇを加えて溶解した後，攪拌したテトラヒドロフラン（和光純薬工業社製）１９２ｍｌにゆっくり反応水溶液を滴下させた後，１０分かき混ぜた。静置後、上層部のテトラヒドロフランの層を除去した。残った重合物水溶液に水１６ｇを加えて溶解した後に、攪拌したテトラヒドロフラン１９２ｍｌにゆっくり滴下させた後，１０分かき混ぜた。静置後、上層部のテトラヒドロフランの層を除去し、残った重合物水溶液を真空下、６０℃で乾燥させ、フィルム状の重合物７．２ｇを得た。精製物をＧＰＣ（Ｂ条件）で測定したところ、重合物は平滑な１つのピークであり、その平均分子量は約８６，０００であった。残存ビニルスルホン酸は０．７％であった。 Example II-60
After mixing 12 g of VSA and 6 g of DMF in a Teflon (registered trademark) container having a diameter of 37 mm, UV rays of 250 to 370 nm were irradiated using a UV irradiator (MAX302 manufactured by Asahi Spectra). After polymerization for 1 hour at a polymerization temperature of around 18 ° C., the system became a pale yellow solid.
When the product was measured by GPC (Condition B), the polymerization rate was 59%, all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 67,000.
After adding 32 g of water to the reaction solution and dissolving, the reaction aqueous solution was slowly added dropwise to 192 ml of stirred tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), followed by stirring for 10 minutes. After standing, the upper layer of tetrahydrofuran was removed. The remaining aqueous polymer solution was dissolved by adding 16 g of water, and then slowly dropped into 192 ml of stirred tetrahydrofuran, followed by stirring for 10 minutes. After standing, the upper layer of tetrahydrofuran was removed, and the remaining aqueous polymer solution was dried at 60 ° C. under vacuum to obtain 7.2 g of a film-like polymer. When the purified product was measured by GPC (B condition), the polymer product was one smooth peak, and the average molecular weight was about 86,000. Residual vinyl sulfonic acid was 0.7%.

実施例II−６１
φ３７ｍｍのテフロン（登録商標）製容器にＶＳＡ１2ｇとＤＭＦ３．４ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度−１２〜２℃で１時間重合後、系内は薄黄色の固体となった。 Example II-61
VSA (12 g) and DMF (3.4 g) were mixed in a Teflon (registered trademark) container having a diameter of 37 mm, and then irradiated with UV rays of 250 to 370 nm using a UV irradiator (MAX302 manufactured by Asahi Spectra). After polymerization for 1 hour at a polymerization temperature of 12 to 2 ° C., the inside of the system became a light yellow solid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は４５％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約３５４，０００であった。 When the product was measured by GPC (B condition), the polymerization rate was 45%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 354,000.

実施例II−６２
φ３７ｍｍのテフロン（登録商標）製容器にＶＳＡ１２ｇとＤＭＦ３．４ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度−２６〜−１３℃で４時間重合後、系内は薄黄色の固体となった。 Example II-62
VSA 12 g and DMF 3.4 g were mixed in a Teflon (registered trademark) container having a diameter of 37 mm, and then irradiated with ultraviolet rays of 250 to 370 nm using a UV irradiator (MAX302 manufactured by Asahi Spectra). After polymerization for 4 hours at a polymerization temperature of −26 to −13 ° C., the inside of the system became a light yellow solid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は４６％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約５８２，０００であった。 When the product was measured by GPC (B condition), the polymerization rate was 46%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 582,000.

比較例II−２
φ３７ｍｍのテフロン（登録商標）製容器にＶＳＡ１２ｇとＤＭＦ２．８ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度−１２〜−９℃で１時間重合後、系内は薄黄色の液体であった。 Comparative Example II-2
After mixing 12 g of VSA and 2.8 g of DMF in a Teflon (registered trademark) container having a diameter of 37 mm, UV rays of 250 to 370 nm were irradiated using a UV irradiator (MAX302 manufactured by Asahi Spectra). After polymerization for 1 hour at a polymerization temperature of 12 to -9 ° C, the system was a pale yellow liquid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合物は全く生成していなかった。 When the product was measured by GPC (B condition), no polymer was formed.

実施例II−６３
φ３７ｍｍのテフロン（登録商標）製容器にＶＳＡ１２ｇとＤＭＦ２．１ｇ、ホルムアミド１．２８ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度−１３〜＋８℃で２時間重合後、系内は薄黄色の固体となった。 Example II-63
A Teflon (registered trademark) container having a diameter of 37 mm was mixed with 12 g of VSA, 2.1 g of DMF, and 1.28 g of formamide, and then irradiated with ultraviolet rays of 250 to 370 nm using a UV irradiator (MAX302 manufactured by Asahi Spectra). After polymerization at a polymerization temperature of 13 to + 8 ° C. for 2 hours, the system became a pale yellow solid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は６９％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約４７３，０００であった。 When the product was measured by GPC (Condition B), the polymerization rate was 69%, and all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 473,000.

実施例II−６４
φ３７ｍｍのテフロン（登録商標）製容器にＶＳＡ１２ｇとＤＭＦ１．９ｇ、ホルムアミド１．１５ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度−２８〜−４℃で約３．８時間重合後、系内は薄黄色の固体となった。 Example II-64
VSA 12 g, DMF 1.9 g, and formamide 1.15 g were mixed in a Teflon (registered trademark) container having a diameter of 37 mm, and then irradiated with ultraviolet rays of 250 to 370 nm using a UV irradiator (MAX302 manufactured by Asahi Spectra). After polymerization at a polymerization temperature of −28 to −4 ° C. for about 3.8 hours, the system became a pale yellow solid.

生成物をＧＰＣ（Ｂ条件）で測定したところ、重合率は４６％であり、得られた重合物は全て分子量２０，０００以上であって、その平均分子量は約６３０，０００であった。 When the product was measured by GPC (Condition B), the polymerization rate was 46%, all the obtained polymers had a molecular weight of 20,000 or more, and the average molecular weight was about 630,000.

比較例II−３
φ３７ｍｍのテフロン（登録商標）製容器にＶＳＡ４ｇとＤＭＦ０．８ｇを混合した後、ＵＶ照射器（アサヒスペクトラ社製ＭＡＸ３０２）を用いて２５０〜３７０ｎｍの紫外線を照射した。重合温度１２〜２１℃で１時間重合後、系内は薄黄色の液体であった。
生成物をＧＰＣ（Ｂ条件）で測定したところ、重合物は全く生成していなかった。 Comparative Example II-3
VSA 4 g and DMF 0.8 g were mixed in a Teflon (registered trademark) container having a diameter of 37 mm, and then irradiated with ultraviolet rays of 250 to 370 nm using a UV irradiator (Asahi Spectra MAX302). After polymerization for 1 hour at a polymerization temperature of 12 to 21 ° C., the system was a pale yellow liquid.
When the product was measured by GPC (B condition), no polymer was formed.

実施例II及び比較例IIのデータを表２、表３及び表４にまとめて示す。 The data of Example II and Comparative Example II are summarized in Table 2, Table 3, and Table 4.

上記結果から、ビニルスルホン酸の光重合において、アミド化合物を特定量存在させることにより、短時間で分子量の大きいビニルスルホン酸重合体が得られることがわかった。更に脱気を行うことなく分子量の大きいビニルスルホン酸重合体を短時間で製造できることがわかった。 From the above results, it was found that a vinyl sulfonic acid polymer having a large molecular weight can be obtained in a short time by the presence of a specific amount of an amide compound in the photopolymerization of vinyl sulfonic acid. Furthermore, it has been found that a vinylsulfonic acid polymer having a large molecular weight can be produced in a short time without degassing.

Claims

General formula
RC (= O) -NR ₁ R ₂
(R represents a hydrogen atom or a lower alkyl group. R ₁ and R ₂ are the same or different and represent a hydrogen atom or a lower alkyl group.)
A method for producing a vinyl sulfonic acid homopolymer in which vinyl sulfonic acid is photopolymerized in the presence of an amide compound represented by
The method wherein the amount of the amide compound is 0.4 mol or more and 2.5 mol or less with respect to 1 mol of vinylsulfonic acid.

The amide compound is a group consisting of N, N-dimethylformamide, N-methylformamide, formamide, N, N-diethylformamide, N, N-dibutylformamide, N, N-dimethylacetamide, and N, N-diethylacetamide The method for producing a vinylsulfonic acid homopolymer according to claim 1, wherein the vinylsulfonic acid homopolymer is at least one selected from the group consisting of: