JP2003165813A - Methyl methacrylate-trifluoromethylacrylic acid copolymer and method for producing the same - Google Patents
Methyl methacrylate-trifluoromethylacrylic acid copolymer and method for producing the sameInfo
- Publication number
- JP2003165813A JP2003165813A JP2001295548A JP2001295548A JP2003165813A JP 2003165813 A JP2003165813 A JP 2003165813A JP 2001295548 A JP2001295548 A JP 2001295548A JP 2001295548 A JP2001295548 A JP 2001295548A JP 2003165813 A JP2003165813 A JP 2003165813A
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- JP
- Japan
- Prior art keywords
- methyl methacrylate
- acid copolymer
- acrylic acid
- producing
- reaction
- Prior art date
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、メチルメタクリレ
ートと、トリフルオロメチルアクリル酸をモノマーとす
る共重合体及びその製造方法に関する。TECHNICAL FIELD The present invention relates to a copolymer having methylmethacrylate and trifluoromethylacrylic acid as a monomer, and a method for producing the same.
【０００２】[0002]
【従来の技術】従来からポリメチルメタクリレート（以
下「ＰＭＭＡ」とする）は、その透明性や機械強度の点
で優れていることから種々の分野で広く使用されてき
た。かかるＰＭＭＡの諸性質を変えるべくメチルメタク
リレート（以下「ＭＭＡ」とする）と他の種々のメタク
リレート類似モノマーとの共重合体も数多く知られてい
る。2. Description of the Related Art Conventionally, polymethylmethacrylate (hereinafter referred to as "PMMA") has been widely used in various fields because of its excellent transparency and mechanical strength. Many copolymers of methyl methacrylate (hereinafter referred to as "MMA") and other various methacrylate-like monomers have been known to change various properties of PMMA.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、ＭＭＡとＴ
ＦＭＡとからなる新規共重合体及びその製造方法を提供
する。The present invention is based on MMA and T
Provided are a novel copolymer comprising FMA and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】このように従来公知のＰ
ＭＭＡの物性、特に機械的または光学的な物性を大きく
変え得る共重合体用モノマとして、フッ素で置換された
アクリル酸モノマが考えられる。しかしながらトリフル
オロメチルアクリル酸（以下「ＴＦＭＡ」とする）自体
は通常のラジカル反応では重合体は得られないことも知
られている。As described above, the conventionally known P
As a monomer for a copolymer that can greatly change the physical properties of MMA, particularly mechanical or optical properties, a fluorinated acrylic acid monomer is considered. However, it is also known that trifluoromethylacrylic acid (hereinafter referred to as “TFMA”) itself cannot be obtained as a polymer by an ordinary radical reaction.
【０００５】本発明者等はこのように興味ある物性を示
すであろう、ＭＭＡとＴＦＭＡとからなる共重合体を得
ることを目的として鋭意研究し、超臨界二酸化酸素中
で、α−メチルメタクリレートと、α−トリフルオロメ
チルアクリル酸とをラジカル重合させることにより、メ
チルメタクリレート−トリフルオロメチルアクリル酸共
重合体が得られることを見出し本発明を完成した。The present inventors diligently studied for the purpose of obtaining a copolymer consisting of MMA and TFMA, which would exhibit such interesting physical properties, and in α-methyl methacrylate in supercritical oxygen dioxide. The present invention has been completed by finding that a methyl methacrylate-trifluoromethyl acrylic acid copolymer can be obtained by radically polymerizing α-trifluoromethyl acrylic acid and α-trifluoromethyl acrylic acid.
【０００６】すなわち本発明は、新規なメチルメタクリ
レート−トリフルオロメチルアクリル酸共重合体に関す
る。また本発明は、超微粒子のメチルメタクリレート−
トリフルオロメチルアクリル酸共重合体に関する。That is, the present invention relates to a novel methyl methacrylate-trifluoromethyl acrylic acid copolymer. The present invention also provides ultrafine particles of methyl methacrylate-
It relates to a trifluoromethylacrylic acid copolymer.
【０００７】さらには、本発明は、超臨界二酸化酸素中
で、少なくとも７ＭＰａ以上の圧力下でα−メチルメタ
クリレートと、α−トリフルオロメチルアクリル酸とを
ラジカル重合させて、超微粒子メチルメタクリレート−
トリフルオロメチルアクリル酸共重合体を製造する方法
に関する。Further, according to the present invention, α-methyl methacrylate and α-trifluoromethyl acrylic acid are radically polymerized in supercritical oxygen dioxide under a pressure of at least 7 MPa to obtain ultrafine particle methyl methacrylate-
The present invention relates to a method for producing a trifluoromethylacrylic acid copolymer.
【０００８】なお、本発明にかかるメチルメタクリレー
ト−トリフルオロメチルアクリル酸共重合体には、種々
の立体規則性を有するそれぞれの重合体を含むものであ
る。具体的には、シンジオタクチックから、ランダム、
さらにはアイソタクチックの立体規則性に富んだ重合体
である。The methylmethacrylate-trifluoromethylacrylic acid copolymer according to the present invention includes each polymer having various stereoregularity. Specifically, from syndiotactic, random,
Furthermore, it is a polymer rich in isotactic stereoregularity.
【０００９】さらには、本発明にかかるメチルメタクリ
レート−トリフルオロメチルアクリル酸共重合体には、
約１４０〜１５６℃にそのＴｇを有することを特徴とす
る重合体を含むものである。Further, the methyl methacrylate-trifluoromethyl acrylic acid copolymer according to the present invention comprises
It includes a polymer characterized by having its Tg at about 140-156 ° C.
【００１０】[0010]
【発明の実施の形態】以下、本発明を実施の形態に即し
て詳細に説明する。メチルメタクリレート−トリフルオロメチルアクリル酸
共重合体
本発明にかかるメチルメタクリレート−トリフルオロメ
チルアクリル酸共重合体はメチルメタクリレートと、ト
リフルオロメチルアクリル酸とをモノマとする新規な重
合体である。また、本発明にかかるメチルメタクリレー
ト−トリフルオロメチルアクリル酸共重合体の分子量
（Ｍｎ）、および分子量分布（Ｍｗ／Ｍｎ）は、以下で
説明する重合条件により１０００〜３０００００、およ
び１.４〜２.６の範囲である。また、本発明にかかるメ
チルメタクリレート−トリフルオロメチルアクリル酸共
重合体のＴＦＭＡモノマの存在比も重合条件で制御する
ことができ、約３０モル％まで可能である。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to embodiments. Methyl methacrylate-trifluoromethyl acrylic acid
Copolymer The methylmethacrylate-trifluoromethylacrylic acid copolymer according to the present invention is a novel polymer having methylmethacrylate and trifluoromethylacrylic acid as monomers. The molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the methylmethacrylate-trifluoromethylacrylic acid copolymer according to the present invention are 1000 to 300,000 and 1.4 to 2 depending on the polymerization conditions described below. It is in the range of 0.6. Further, the abundance ratio of the TFMA monomer in the methyl methacrylate-trifluoromethyl acrylic acid copolymer according to the present invention can be controlled by the polymerization conditions and can be up to about 30 mol%.
【００１１】さらに、本発明にかかるメチルメタクリレ
ート−トリフルオロメチルアクリル酸共重合体の立体規
則性については共重合体のＴＦＭＡモノマの存在比によ
って、シンジオタクチックリッチな立体規則性を示す重
合体から、ランダムな立体規則性を示す重合体、さらに
はアイソタクチックリッチな立体規則性に富んだ重合体
にする制御が可能である。かかるミクロな立体規則性
は、従来のＮＭＲ（1Ｈ、13Ｃ）により容易に決定され
る。具体的にはＰＭＭＡの1Ｈ−ＮＭＲでα−メチルの
シグナル相対強度比（mm、mr、rr）と、13Ｃ−ＮＭＲの
カルボニル基（エステルとカルボン酸の）のシグナルの
相対強度から求めることができる。Further, regarding the stereoregularity of the methylmethacrylate-trifluoromethylacrylic acid copolymer according to the present invention, depending on the abundance ratio of the TFMA monomer in the copolymer, the stereoregularity of the polymer showing syndiotactic rich stereoregularity It is possible to control the polymer to exhibit random stereoregularity, and further to be a polymer rich in isotactic rich stereoregularity. Such microscopic stereoregularity is easily determined by conventional NMR ( 1 H, 13 C). Specifically, it should be determined from the relative intensity ratio of α-methyl signals (mm, mr, rr) in 1 H-NMR of PMMA and the relative intensity of signals of carbonyl group (ester and carboxylic acid) in 13 C-NMR. You can
【００１２】また、メチルメタクリレート−トリフルオ
ロメチルアクリル酸共重合体はそのＴｇを有しＰＭＭＡ
が約１２９℃であるのに対し、約１０度以上高くなる傾
向のあり、ＴＦＭモノマの含有量が多くなるとより高く
なる。The methylmethacrylate-trifluoromethylacrylic acid copolymer also has its Tg and PMMA.
Is about 129 ° C., while it tends to be about 10 ° C. or higher, and becomes higher as the content of TFM monomer increases.
【００１３】メチルメタクリレート−トリフルオロメチ
ルアクリル酸共重合体の形状
また、本発明のメチルメタクリレート−トリフルオロメ
チルアクリル酸共重合体は以下説明するように種々の重
合条件に依存して、生成物として不定形形状から、非常
に細かい粒子からなる微粒子形状を示す。かかる微粒子
形状の重合体はは、図１に示すように球状を呈しかつそ
の直径はナノオーダーである。 Methyl methacrylate-trifluoromethy
Further , the methyl methacrylate-trifluoromethyl acrylic acid copolymer of the present invention has a very fine particle shape due to an amorphous shape as a product depending on various polymerization conditions as described below. 2 shows the shape of fine particles. Such a fine particle-shaped polymer has a spherical shape as shown in FIG. 1 and its diameter is on the order of nanometers.
【００１４】メチルメタクリレート−トリフルオロメチ
ルアクリル酸共重合体の製造方法
本発明にかかる新規なメチルメタクリレート−トリフル
オロメチルアクリル酸共重合体は、超臨界二酸化炭素を
溶媒とし２つのモノマを共存させ、通常のラジカル重合
開始剤を用いて重合反応をさせて得られる。さらに、反
応に使用するモノマも存在比を０〜１００まで任意に変
えることができるが、ＭＭＡが１００％の場合、通常の
反応で得られるＰＭＭＡと実質的に同じ重合体（シンジ
オタクチックリッチ）が得られる。一方。ＴＦＭＡが１
００％の場合には重合反応は進行しない。 Methyl methacrylate-trifluoromethy
Method for producing luacrylic acid copolymer The novel methylmethacrylate-trifluoromethylacrylic acid copolymer according to the present invention comprises two monomers coexisting with supercritical carbon dioxide as a solvent and using a usual radical polymerization initiator. It is obtained by a polymerization reaction. Further, the abundance ratio of the monomer used in the reaction can be arbitrarily changed from 0 to 100, but when MMA is 100%, the polymer is substantially the same as PMMA obtained in a normal reaction (syndiotactic rich). Is obtained. on the other hand. TFMA is 1
When it is 00%, the polymerization reaction does not proceed.
【００１５】使用可能なラジカル開始剤は特に制限され
ないが、反応開始温度が４０〜８０℃程度が好ましいこ
とから、例えばＡＩＢＮの使用が可能である。重合反応
温度も特に限定されないが、４０〜８０℃が好ましく、
特に６０℃付近が好ましい。反応はその圧力により大き
く影響を受ける。超臨界二酸化炭素であれば、少なくと
も７ＭＰａ、より好ましくは９ＭＰａ以上である。特
に、微粒子状の重合体を得るにはより高い圧力（９ＭＰ
ａ以上、好ましくは１２ＭＰａ）であるほうが好まし
い。The usable radical initiator is not particularly limited, but since the reaction initiation temperature is preferably about 40 to 80 ° C., it is possible to use AIBN, for example. The polymerization reaction temperature is not particularly limited, but is preferably 40 to 80 ° C,
Particularly, about 60 ° C. is preferable. The reaction is greatly affected by the pressure. In the case of supercritical carbon dioxide, it is at least 7 MPa, more preferably 9 MPa or more. In particular, a higher pressure (9MP
It is preferably a or more, preferably 12 MPa).
【００１６】反応装置には特に制限はないが、上の反応
条件が設定できるものであればよい。通常はハステロイ
製の円筒筒状の反応容器であり、カートリッジ型の温度
調節装置、また攪拌装置がついてるものが好ましい。反
応装置の容量の特に制限はない。The reaction apparatus is not particularly limited as long as the above reaction conditions can be set. Usually, a cylindrical cylindrical reaction vessel made of Hastelloy, with a cartridge type temperature control device and a stirring device being preferred. There is no particular limitation on the capacity of the reactor.
【００１７】反応時間は適当なモニタ手段により反応を
モニタすることで最適化できる。具体的には２４〜７２
時間程度である。反応はラジカル重合開始剤が分解する
温度付近で行う。例えばＡＩＢＮでは約６０℃である。
一定時間経過のち、温度を下げ、反応を停止させる。
後、二酸化炭素を除き生成物を得る。有機溶媒等で洗浄
して最終重合体を得る。収率は５０〜９５％程度であ
る。The reaction time can be optimized by monitoring the reaction with suitable monitoring means. Specifically, 24-72
It's about time. The reaction is carried out near the temperature at which the radical polymerization initiator decomposes. For example, AIBN has a temperature of about 60 ° C.
After a certain period of time, the temperature is lowered to stop the reaction.
After that, carbon dioxide is removed to obtain the product. The final polymer is obtained by washing with an organic solvent or the like. The yield is about 50 to 95%.
【００１８】[0018]
【実施例】以下、本発明を実施例によりさらに詳細に説
明するが、本発明はこれらの実施例に何ら限定されるも
のではない。なお、実施例で物理的性質の測定には以下
の装置及び条件を用いた。1
Ｈ−ＮＭＲ：日本電子(株)製、ＡＬ４００ＭＨｚ−Ｎ
ＭＲスペクトロメータ（共鳴周波数、３９９.６５ＭＨ
ｚ）。重合体は重ＴＨＦ中、測定温度は室温で測定。13
Ｃ−ＮＭＲ：日本電子(株)製、ＥＣＰ５００ＭＨｚ−
ＮＭＲスペクトロメータ（共鳴周波数、５００.１６Ｍ
Ｈｚ）。重合体は重ＴＨＦ中、測定温度は室温で測定。
Ｔｇ：セイコー電子工業(株)製のＴＧ／ＤＴＧ６２００
熱量分析計。窒素気流中(１００ml／min)で、昇温速度
１０℃／minで測定。
ＧＰＣ：東ソー製ＨＬＣ−８２２０ＧＰＣ／ＨＴ高温ゲ
ル浸透クロマトグラフ。試料濃度０.１w／v％、溶媒Ｔ
ＨＦ、測定温度４０℃、流量１０００μl／minで測定。
屈折率：(株)ＡＴＡＧＯ製精密アッベ屈折計３Ｔ。室温
で測定。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The following apparatus and conditions were used for measuring the physical properties in the examples. 1 H-NMR: manufactured by JEOL Ltd., AL400MHz-N
MR spectrometer (resonance frequency, 399.65MH
z). The polymer is measured in deuterated THF and the measurement temperature is room temperature. 13 C-NMR: manufactured by JEOL Ltd., ECP 500 MHz-
NMR spectrometer (resonance frequency, 500.16M
Hz). The polymer is measured in deuterated THF and the measurement temperature is room temperature. Tg: TG / DTG6200 manufactured by Seiko Instruments Inc.
Calorimeter. Measured in a nitrogen stream (100 ml / min) at a heating rate of 10 ° C / min. GPC: Tosoh HLC-8220 GPC / HT high temperature gel permeation chromatograph. Sample concentration 0.1w / v%, solvent T
Measured at HF, measurement temperature 40 ° C, flow rate 1000 μl / min. Refractive index: Precision Abbe refractometer 3T manufactured by ATAGO Co., Ltd. Measured at room temperature.
【００１９】（実験）攪拌装置とカートリッジ型加熱装
置を備えた、直径４cm、９６mlの容量のハステロイ製円
筒筒状の反応容器（最高使用温度４００℃、最高使用圧
力４０ＭＰａ）を反応温度である６０℃に加熱してか
ら、メチルメタクリレート（４.００５ｇ、関東化学
(株)社製一級試薬）を蒸留して重合禁止剤を取り除いた
ものと、２−(トリフルオロメチル)アクリル酸（１.４
０１ｇ、エフテック(株)社製）、アゾビスイソブチロニ
トリル（ＡＩＢＮ）（０.０８２ｇ、和光純薬工業(株)
社製）を予熱器で６０℃まで加熱した二酸化酸素（昭和
炭酸(株)製純度９９.９９％）と共に種々の圧力（７、
９ＭＰa）まで封入し、約２４時間攪拌しつつ反応を行
った後、温度を下げて反応を停止させた。また、仕込み
ＴＦＭＡ組成比が６０％を超える場合は反応セルに直
接、試料を導入して二酸化炭素で置換を行なう。(Experiment) A Hastelloy cylindrical cylindrical reaction vessel (maximum operating temperature 400 ° C., maximum operating pressure 40 MPa) having a diameter of 4 cm and a volume of 96 ml equipped with a stirrer and a cartridge type heating device was used as a reaction temperature. After heating to ℃, methylmethacrylate (4.005g, Kanto Chemical
(First-class reagent manufactured by Co., Ltd.) by distillation to remove the polymerization inhibitor, and 2- (trifluoromethyl) acrylic acid (1.4
01 g, manufactured by F-Tech Co., Ltd.), Azobisisobutyronitrile (AIBN) (0.082 g, Wako Pure Chemical Industries, Ltd.)
Various pressures (7, made by Showa Carbonate Co., Ltd.) with oxygen dioxide heated to 60 ° C by a preheater (7,
It was sealed up to 9 MPa) and the reaction was carried out while stirring for about 24 hours, and then the temperature was lowered to stop the reaction. When the composition ratio of the charged TFMA exceeds 60%, the sample is directly introduced into the reaction cell and replaced with carbon dioxide.
【００２０】二酸化炭素をＴＨＦ中でバブリングさせな
がら除き、生成したポリマを得た。必要な場合はＴＨＦ
で溶解し、ヘキサンで再沈殿させたのち分別回収し、真
空加温して乾燥した。Carbon dioxide was removed by bubbling in THF to obtain a polymer produced. THF if needed
Was dissolved in hexane, reprecipitated with hexane, collected by fractionation, heated under vacuum and dried.
【００２１】表１に、種々の条件で行った重合反応の結
果をまとめた。Table 1 summarizes the results of the polymerization reactions carried out under various conditions.
【表１】 [Table 1]
【００２２】[0022]
【発明の効果】本発明により、α−メチルメタクリレー
トと、α−トリフルオロメチルアクリル酸とを超臨界二
酸化炭素中でラジカル重合させることによりメチルメタ
クリレート−トリフルオロメチルアクリル酸共重合体を
得る。According to the present invention, a methyl methacrylate-trifluoromethyl acrylic acid copolymer is obtained by radical polymerization of α-methyl methacrylate and α-trifluoromethyl acrylic acid in supercritical carbon dioxide.
【図１】微粒子状のメチルメタクリレート−トリフルオ
ロメチルアクリル酸共重合体を示す電子顕微鏡写真であ
る。FIG. 1 is an electron micrograph showing a fine particle-shaped methyl methacrylate-trifluoromethyl acrylic acid copolymer.
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【手続補正書】[Procedure amendment]
【提出日】平成１３年１０月１０日（２００１．１０．
１０）[Submission date] October 10, 2001 (2001.10.
10)
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】特許請求の範囲[Name of item to be amended] Claims
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【特許請求の範囲】[Claims]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００５[Name of item to be corrected] 0005
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００５】本発明者等はこのように興味ある物性を示
すであろう、ＭＭＡとＴＦＭＡとからなる共重合体を得
ることを目的として鋭意研究し、超臨界二酸化炭素中
で、α−メチルメタクリレートと、α−トリフルオロメ
チルアクリル酸とをラジカル重合させることにより、メ
チルメタクリレート−トリフルオロメチルアクリル酸共
重合体が得られることを見出し本発明を完成した。The present inventors diligently studied for the purpose of obtaining a copolymer consisting of MMA and TFMA, which would exhibit such interesting physical properties, and in supercritical carbon dioxide, α-methylmethacrylate. The present invention has been completed by finding that a methyl methacrylate-trifluoromethyl acrylic acid copolymer can be obtained by radically polymerizing α-trifluoromethyl acrylic acid and α-trifluoromethyl acrylic acid.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００７[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００７】さらには、本発明は、超臨界二酸化炭素中
で、少なくとも７ＭＰａ以上の圧力下でα−メチルメタ
クリレートと、α−トリフルオロメチルアクリル酸とを
ラジカル重合させて、超微粒子メチルメタクリレート−
トリフルオロメチルアクリル酸共重合体を製造する方法
に関する。Further, according to the present invention, α-methyl methacrylate and α-trifluoromethylacrylic acid are radically polymerized in supercritical carbon dioxide under a pressure of at least 7 MPa to obtain ultrafine particle methyl methacrylate-
The present invention relates to a method for producing a trifluoromethylacrylic acid copolymer.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１９[Correction target item name] 0019
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１９】（実験）攪拌装置とカートリッジ型加熱装
置を備えた、直径４cm、９６mlの容量のハステロイ製円
筒筒状の反応容器（最高使用温度４００℃、最高使用圧
力４０ＭＰａ）を反応温度である６０℃に加熱してか
ら、メチルメタクリレート（４.００５ｇ、関東化学
(株)社製一級試薬）を蒸留して重合禁止剤を取り除いた
ものと、２−(トリフルオロメチル)アクリル酸（１.４
０１ｇ、エフテック(株)社製）、アゾビスイソブチロニ
トリル（ＡＩＢＮ）（０.０８２ｇ、和光純薬工業(株)
社製）を予熱器で６０℃まで加熱した二酸化炭素（昭和
炭酸(株)製純度９９.９９％）と共に種々の圧力（７、
９ＭＰa）まで封入し、約２４時間攪拌しつつ反応を行
った後、温度を下げて反応を停止させた。また、仕込み
ＴＦＭＡ組成比が６０％を超える場合は反応セルに直
接、試料を導入して二酸化炭素で置換を行なう。(Experiment) A Hastelloy cylindrical cylindrical reaction vessel (maximum operating temperature 400 ° C., maximum operating pressure 40 MPa) having a diameter of 4 cm and a volume of 96 ml equipped with a stirrer and a cartridge type heating device was used as a reaction temperature. After heating to ℃, methylmethacrylate (4.005g, Kanto Chemical
(First-class reagent manufactured by Co., Ltd.) by distillation to remove the polymerization inhibitor, and 2- (trifluoromethyl) acrylic acid (1.4
01 g, manufactured by F-Tech Co., Ltd.), Azobisisobutyronitrile (AIBN) (0.082 g, Wako Pure Chemical Industries, Ltd.)
Carbon dioxide (made by Showa Carbonate Co., Ltd., purity 99.99%) heated to 60 ° C. with a preheater at various pressures (7,
It was sealed up to 9 MPa) and the reaction was carried out while stirring for about 24 hours, and then the temperature was lowered to stop the reaction. When the composition ratio of the charged TFMA exceeds 60%, the sample is directly introduced into the reaction cell and replaced with carbon dioxide.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 越智 健二 東京都千代田区神田駿河台１−８−14 日 本大学理工学部内 (72)発明者 矢野 彰一郎 東京都千代田区神田駿河台１−８−14 日 本大学理工学部内 (72)発明者 戸田 篤志 埼玉県所沢市若狭２−2605−27 (72)発明者 粉川 喜靖 千葉県市川市新浜１−15−14 サマセット ハイツ202 (72)発明者 常世田 和彦 山口県新南陽市古市２丁目７番地20号 Ｆターム(参考） 4J011 AA05 AA07 AA08 AB04 HA01 HB04 HB22 4J100 AJ03Q AL03P BB18Q CA04 CA11 CA12 DA01 DA04 DA25 EA05 FA03 FA19 FA29 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Kenji Ochi 1-8-14 days Kanda Surugadai, Chiyoda-ku, Tokyo Faculty of Science and Engineering of this university (72) Inventor Shoichiro Yano 1-8-14 days Kanda Surugadai, Chiyoda-ku, Tokyo Faculty of Science and Engineering of this university (72) Inventor Atsushi Toda 2-2605-27 Wakasa, Tokorozawa City, Saitama Prefecture (72) Inventor Kiyasu Kokawa 1-15-14 Niihama, Ichikawa, Chiba Somerset Heights 202 (72) Inventor Kazuhiko Tsuneda 2-7-20 Furuichi, Shinnanyo, Yamaguchi Prefecture F-term (reference) 4J011 AA05 AA07 AA08 AB04 HA01 HB04 HB22 4J100 AJ03Q AL03P BB18Q CA04 CA11 CA12 DA01 DA04 DA25 EA05 FA03 FA19 FA29
Claims (3)
フルオロメチルアクリル酸とからなる共重合体。1. A copolymer composed of α-methyl methacrylate and α-trifluoromethyl acrylic acid.
クリレートと、α−トリフルオロメチルアクリル酸とを
ラジカル重合させて、メチルメタクリレート−トリフル
オロメチルアクリル酸共重合体を製造する方法。2. A method for producing a methyl methacrylate-trifluoromethyl acrylic acid copolymer by radically polymerizing α-methyl methacrylate and α-trifluoromethyl acrylic acid in supercritical oxygen dioxide.
Ｐａ以上の圧力下でα−メチルメタクリレートと、α−
トリフルオロメチルアクリル酸とをラジカル重合させ
て、超微粒子メチルメタクリレート−トリフルオロメチ
ルアクリル酸共重合体を製造する方法。3. At least 7M in supercritical oxygen dioxide.
Under pressure of Pa or higher, with α-methyl methacrylate, α-
A method for producing an ultrafine particle methyl methacrylate-trifluoromethyl acrylic acid copolymer by radical polymerization with trifluoromethyl acrylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001295548A JP2003165813A (en) | 2001-09-20 | 2001-09-27 | Methyl methacrylate-trifluoromethylacrylic acid copolymer and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001286335 | 2001-09-20 | ||
| JP2001-286335 | 2001-09-20 | ||
| JP2001295548A JP2003165813A (en) | 2001-09-20 | 2001-09-27 | Methyl methacrylate-trifluoromethylacrylic acid copolymer and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003165813A true JP2003165813A (en) | 2003-06-10 |
Family
ID=26622565
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004020476A1 (en) * | 2002-08-28 | 2004-03-11 | Daikin Industries, Ltd. | Process for production of fluoropolymer |
| JP2012017438A (en) * | 2010-07-09 | 2012-01-26 | Noda Screen:Kk | Fluorine-based copolymer, method for producing the same and coating agent |
-
2001
- 2001-09-27 JP JP2001295548A patent/JP2003165813A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004020476A1 (en) * | 2002-08-28 | 2004-03-11 | Daikin Industries, Ltd. | Process for production of fluoropolymer |
| JP2012017438A (en) * | 2010-07-09 | 2012-01-26 | Noda Screen:Kk | Fluorine-based copolymer, method for producing the same and coating agent |
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