JPH01266118A - Fluorinated acrylic copolymer - Google Patents
Fluorinated acrylic copolymerInfo
- Publication number
- JPH01266118A JPH01266118A JP9608688A JP9608688A JPH01266118A JP H01266118 A JPH01266118 A JP H01266118A JP 9608688 A JP9608688 A JP 9608688A JP 9608688 A JP9608688 A JP 9608688A JP H01266118 A JPH01266118 A JP H01266118A
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- acrylic copolymer
- fluorine
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006243 acrylic copolymer Polymers 0.000 title claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title 1
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 4
- 125000005353 silylalkyl group Chemical group 0.000 claims abstract description 4
- 230000009477 glass transition Effects 0.000 claims abstract description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract 2
- 125000003118 aryl group Chemical group 0.000 claims abstract 2
- 229910052801 chlorine Inorganic materials 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 3
- IRMZTQBFNCEPQF-UHFFFAOYSA-N 1-methyl-4-(1,2,2-trifluoroethenyl)benzene Chemical compound CC1=CC=C(C(F)=C(F)F)C=C1 IRMZTQBFNCEPQF-UHFFFAOYSA-N 0.000 abstract 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- -1 phenyl octyl Group Chemical group 0.000 description 3
- SUTQSIHGGHVXFK-UHFFFAOYSA-N 1,2,2-trifluoroethenylbenzene Chemical compound FC(F)=C(F)C1=CC=CC=C1 SUTQSIHGGHVXFK-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 240000006162 Chenopodium quinoa Species 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000013308 plastic optical fiber Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は耐熱性の含フッ素アクリル系共重合体に関する
。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a heat-resistant fluorine-containing acrylic copolymer.
（従来の技術）
含フッ素アクリル系重合体として例えば特開昭６１−１
１４２０８号にはａ、β、β−トリフルオロスチレンの
重合体がプラスチックオプティカルファイバーに用いら
れることが記載されているが、この重合体は可撓性に乏
しく、可撓性改良の為に共重合を行うと、得られる共重
合体のガラス転移温度（Ｔｇ）は下がり耐熱性が低下す
るという欠点がある。(Prior art) As a fluorine-containing acrylic polymer, for example, JP-A-61-1
No. 14208 describes that a, β, and β-trifluorostyrene polymers are used for plastic optical fibers, but this polymer has poor flexibility and needs to be copolymerized to improve flexibility. If this is carried out, the glass transition temperature (Tg) of the resulting copolymer is lowered, resulting in a decrease in heat resistance.
（発明が解決しようとする課題）
本発明の目的は可撓性及び耐熱性の優れた含フッ素アク
リル系共重合体を提供することにある。(Problems to be Solved by the Invention) An object of the present invention is to provide a fluorine-containing acrylic copolymer having excellent flexibility and heat resistance.
（課題を解決するための手段）
本発明は式
％式％（）
〔式中、Ｒ１は水素原子、フッ素原子、塩素原子又はメ
チル店、Ｒ２は水素原子、炭素数１〜５のアルキル基、
炭素数２〜１０のフルオロアルキル基、炭素数５〜１０
のシクロアルキル基、炭素数６〜１０の７リール基、炭
素数７〜１５の７ラルキル基、炭素数１〜６のヒドロキ
シアルキル基、アリル基、シリルアルキル基、置換シリ
ル（炭素数１〜５のアルキル基）を示す。〕で表わされ
るｖｔ構造単位ｂ）を有する含フッ素アクリル系共重合
体に係る。(Means for Solving the Problems) The present invention provides the following formula:
Fluoroalkyl group having 2 to 10 carbon atoms, 5 to 10 carbon atoms
Cycloalkyl group having 6 to 10 carbon atoms, 7ralkyl group having 7 to 15 carbon atoms, hydroxyalkyl group having 1 to 6 carbon atoms, allyl group, silylalkyl group, substituted silyl group (having 1 to 5 carbon atoms) alkyl group). The present invention relates to a fluorine-containing acrylic copolymer having the vt structural unit b) represented by the following.
本発明の含フッ素アクリル系共重合体は例えば光学繊維
の芯材或いはレンズ等の各種の光字材料などに使用でき
る。The fluorine-containing acrylic copolymer of the present invention can be used, for example, as a core material for optical fibers or various optical materials such as lenses.
本発明において構造単位（ａ）はａ、β、β−トリフル
オロー４−メチルスチレンより誘導されるもので、この
化合物は公知化合物で例えばＪ、Ｏｒ＋（。In the present invention, the structural unit (a) is derived from a,β,β-trifluoro-4-methylstyrene, and this compound is a known compound such as J, Or+(.
ＣＩｕｅ（２１４００（１９５６）に記載されている。CIue (21400 (1956)).
本発明の構造単位（ｂ）は式
ＣＨ２＝Ｃ（Ｒ１）ＣＯＯＲ２で表わされる化合物から
誘導され、Ｒ２としては水素原子；メチル、エチル、ペ
ンチル等の炭素数１〜５のアルキル基；ＣＨ２ＣＦ３．
ｃＨ２ＣＦ２ＣＦ、。The structural unit (b) of the present invention is derived from a compound represented by the formula CH2=C(R1)COOR2, where R2 is a hydrogen atom; an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, and pentyl; CH2CF3.
cH2CF2CF,.
ＣＩ（２ＣＦ２ＣＦ２Ｈ，ＣＨ２Ｃ，Ｆ、、 等の炭
素数２〜１０のフルオロアルキル基；シクロペンチル、
シクロヘキンル、ンクロオクチル等の炭素数５〜１０の
シクロアルキル基；フェニル、トリル、キシリル等の炭
素数６〜１０の７リール基；ベンノル、７エネチル、フ
ェニルオクチル等の炭素数７〜１５の７ラルキル基；ヒ
ドロキシエチル、ヒドロキシエチル等の炭素数１〜６の
ヒドロキシアルキル基；アリル基；シリルメチル、ンリ
ルブロピル等のシリルアルキル基；トリメチルシリル、
トリブチルシリル等の炭素１〜５のアルキル基の置換し
たシリル基を挙げることができる。CI (fluoroalkyl group having 2 to 10 carbon atoms such as 2CF2CF2H, CH2C, F, etc.; cyclopentyl,
Cycloalkyl groups having 5 to 10 carbon atoms such as cyclohexyl and cyclooctyl; 7-aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl, and xylyl; 7-ralkyl groups having 7 to 15 carbon atoms such as benol, 7enethyl, and phenyl octyl Group; Hydroxyalkyl group having 1 to 6 carbon atoms, such as hydroxyethyl and hydroxyethyl; Allyl group; Silylalkyl group, such as silylmethyl and nrylbropyl; Trimethylsilyl,
Examples include silyl groups substituted with C1-C5 alkyl groups such as tributylsilyl.
本発明のアクリル系共重合体において構造単位（、）と
構造単位（ｂ）の割合は広い範囲から選択できるが、好
ましくは曲者の５０〜９０モル％に対して後者の１０〜
５０モル％の範囲である。本発明のアクリル系共重合体
のＴｇは１２０〜２００℃の範囲が好ましく、屈折率η
、′。は１．４００〜１．５２５の範囲が好ましい。In the acrylic copolymer of the present invention, the ratio of the structural unit (,) and the structural unit (b) can be selected from a wide range, but preferably 50 to 90 mol% of the latter to 10 to 90 mol% of the latter.
It is in the range of 50 mol%. The Tg of the acrylic copolymer of the present invention is preferably in the range of 120 to 200°C, and the refractive index η
,′. is preferably in the range of 1.400 to 1.525.
本発明のアクリル系共重合体は通常公知の重合方法で得
ることができ、重合反応の方式や条件は、任意に選択で
き、例えばラジカル重合において塊状重合、溶液重合、
懸濁重合、乳化重合など各種の方式を採用することがで
きる。ラジカル重合の開始剤としては遊離ラノカルを生
じる化合物が使用される。好ましいラノカル開始剤とし
てノイソブロビルパーオキシノカーボネート、アンモニ
ワムパーサル７エートなどの過酸化物お上びアゾビスイ
ソブチロニトリルなどのアゾニトリル類などが挙げられ
る。ラノカル開始剤の使用量は単量体に対し１〜Ｉ Ｏ
Ｏ０１）ｌ）ｍ （重量）の範囲から選ばれる。The acrylic copolymer of the present invention can be obtained by a commonly known polymerization method, and the method and conditions of the polymerization reaction can be arbitrarily selected. For example, in radical polymerization, bulk polymerization, solution polymerization,
Various methods such as suspension polymerization and emulsion polymerization can be employed. As an initiator for radical polymerization, a compound that produces free Lanocal is used. Preferred lanocal initiators include peroxides such as neuisobrobyl peroxynocarbonate and ammonium persal 7ate, and azonitriles such as azobisisobutyronitrile. The amount of Lanocal initiator used is 1 to IO per monomer.
Selected from the range O01)l)m (weight).
しかし使用される開始剤の使用量の範囲は以上に限定さ
れるものではなく、目的の共重合体の重合度、反応時間
、重合温度などの因子に依って適宜選択される。重合温
度は開始剤の分解温度に応じて一８０゛Ｃ〜＋２５０°
Ｃである。一般に一４０°Ｃ〜＋１５０℃の範囲が好ま
しい。溶液重合で使用できる溶媒トシては、ベンゼン、
トルエン、キンレン等の芳香族炭化水素、クロロホルム
、塩化メチレン、塩化エチレンなどの低塩基性溶媒が使
用される。これは１種又は２種以上を部会して使用する
ことらできる。However, the range of the amount of the initiator to be used is not limited to the above, and is appropriately selected depending on factors such as the degree of polymerization of the desired copolymer, reaction time, and polymerization temperature. The polymerization temperature ranges from -80°C to +250°C depending on the decomposition temperature of the initiator.
It is C. Generally, a range of -40°C to +150°C is preferred. Solvents that can be used in solution polymerization include benzene,
Aromatic hydrocarbons such as toluene and quinoa, and low basic solvents such as chloroform, methylene chloride, and ethylene chloride are used. These can be used singly or in combination of two or more.
反応混合物から共重合体を回収する場合も通常の方法が
採用されてよく、例えば、ベンゼン、トルエン、塩化メ
チレン、塩化エチレン、クロロホルム中ｔ′重合した重
合生成物をノイソプロビルエーテル、ジメチルエーテル
、石油エーテル、＋１−ヘキサンの如く重合体が溶解し
ない貧溶剤に加えて重合体のみを沈殿させる。重合体の
精製には沈殿として得られた重合体をトルエン、７セト
ン、テトラヒドロ７ランなどの溶媒に溶解した後、上記
の貧溶媒に加えて重合体を再沈殿させることによって行
うのが好ましい。Conventional methods may be used to recover the copolymer from the reaction mixture. For example, a polymer product obtained by t' polymerization in benzene, toluene, methylene chloride, ethylene chloride, or chloroform may be recovered by t' polymerization in benzene, toluene, methylene chloride, ethylene chloride, or chloroform. In addition to a poor solvent such as ether or +1-hexane in which the polymer does not dissolve, only the polymer is precipitated. Purification of the polymer is preferably carried out by dissolving the polymer obtained as a precipitate in a solvent such as toluene, 7-cetone, or tetrahydro-7-ran, and then adding the solution to the above-mentioned poor solvent and reprecipitating the polymer.
本発明の共重合体において好ましい分子量は重量平均分
子量（簡Ｗ）で約１〜＋００万の範囲である。The preferred molecular weight of the copolymer of the present invention is in the range of about 1 to +0,000,000 in terms of weight average molecular weight (simple W).
（実 施 例） 以下に実施例及び比較例を挙げて説明する。(Example) Examples and comparative examples will be described below.
実施例１
ａＩβ、β−トリプルオロー４−メチルスチレン（以下
ＴＦＭＳと略す）１０部、メタクリル酸メチル（以下Ｍ
ＭＡと略す）１．５部、７ゾビスイソブチロニトリル０
．０６部の混合物を実質的に酸素の存在しない密閉系の
重合装置内において６０℃、２４時間のバルク重合を行
った。重合終了後は、重合溶液にア七トンを加え、均一
溶液にした後、メタノール中に注ぎ、得られた沈殿を回
収し、真空乾燥を行った。得られた重合体は、ＮＭＲに
よる組成分析の結果、ａ、β、β−トリフルオロー４−
メチルスチレンを６３モル％含有していた。又示差走査
熱量計（パーキンエルマ社製、ＤＳＣＩＩ型）に上りＴ
ｇを測定したところ１７９℃であった。又η、″は１．
５１４であった。η、′。の測定は７ツベ式屈折計を用
いて２０℃で行った。Example 1 aIβ, β-triple oro-4-methylstyrene (hereinafter abbreviated as TFMS) 10 parts, methyl methacrylate (hereinafter M
(abbreviated as MA) 1.5 parts, 7zobisisobutyronitrile 0
．． 06 parts of the mixture was subjected to bulk polymerization at 60° C. for 24 hours in a closed polymerization apparatus substantially free of oxygen. After the polymerization was completed, a7ton was added to the polymerization solution to make a homogeneous solution, which was then poured into methanol, and the resulting precipitate was collected and vacuum-dried. As a result of compositional analysis by NMR, the obtained polymer was found to have a, β, β-trifluoro-4-
It contained 63 mol% of methylstyrene. In addition, a differential scanning calorimeter (manufactured by Perkin Elma, Model DSCII) was used.
When g was measured, it was 179°C. Also, η,″ is 1.
It was 514. η,′. The measurement was carried out at 20°C using a 7-tube refractometer.
次に、この重合体粉末を金型に入れ、２３０℃の温度、
３０ｋｇ／ｃｍ”の圧力の条件で圧縮加熱成型を行った
。その結果、透明な板状成型物を得ることができた。Next, this polymer powder was put into a mold, and the temperature was 230°C.
Compression and heating molding was performed under a pressure of 30 kg/cm''. As a result, a transparent plate-shaped molded product could be obtained.
実施例２〜３
ＭＭＡを６部、及び２５部とした以外は、実施例１と同
様にして重合を行なった。得られた重合体の物性を第１
表に示す。Examples 2 to 3 Polymerization was carried out in the same manner as in Example 1, except that MMA was changed to 6 parts and 25 parts. The physical properties of the obtained polymer were
Shown in the table.
第 １ 表
次に、実施例１と同様の条件で圧縮加熱成型を行ったと
ころ、いずれも透明な板状成型物を得ることができた。Table 1 Next, compression and heating molding was performed under the same conditions as in Example 1, and transparent plate-shaped molded products could be obtained in all cases.
実施例４
ＴＦＭＳ（１０部）、２，２．２−Ｆ＋７ フルオロエ
チルメタクリレート１０部、７ゾビスイソブチロニトリ
ル０．０６部、ラウリルメルカプタン０．１部の混合物
を、実施例１と同様の条件で重合を行い、重合体を得た
。その結果、重合体はＴＦＭＳを４５モル％含み、’ｒ
ｇは１５８℃、几２０は１．４７８の特性を示した。Example 4 A mixture of TFMS (10 parts), 10 parts of 2,2.2-F+7 fluoroethyl methacrylate, 0.06 part of 7zobisisobutyronitrile, and 0.1 part of lauryl mercaptan was prepared in the same manner as in Example 1. Polymerization was carried out under the following conditions to obtain a polymer. As a result, the polymer contained 45 mol% TFMS and 'r
g was 158° C., and the temperature 20 was 1.478.
実施例１と同様の条件で圧縮加熱成型を試みたところ、
透明な板状成型物を得ることができた。When compression heating molding was attempted under the same conditions as in Example 1,
A transparent plate-shaped molded product could be obtained.
比較例１
α、β、β−トリフルオロスチレン］Ｏｌｉ、 ＭＭＡ
（６部）、アゾビスイソブチロニトリル０．０６部のｉ
見合物を実施例１と同様の条件で重合を行い重合体を得
た。その結果、重合体はα、β、β−トリフルオロスチ
レンを４４モル％含有し、Ｔｇは１２１℃、η、′。は
１．５２３であった。特にＴｇは実施例２と比較して３
０’Ｃも低下しており、耐熱性に乏しいことがわかる。Comparative Example 1 α, β, β-trifluorostyrene] Oli, MMA
(6 parts), i of azobisisobutyronitrile 0.06 parts
The mixture was polymerized under the same conditions as in Example 1 to obtain a polymer. As a result, the polymer contained 44 mol% of α,β,β-trifluorostyrene, and had a Tg of 121°C and η,′. was 1.523. In particular, Tg is 3 compared to Example 2.
0'C also decreased, indicating poor heat resistance.
（以 上） 出 願 人 ダイキン工業株式会社(that's all) Sender: Daikin Industries, Ltd.
Claims (4)
メチル基、Ｒ＾２は水素原子、炭素数１〜５のアルキル
基、炭素数２〜１０のフルオロアルキル基、炭素数５〜
１０のシクロアルキル基、炭素数６〜１０のアリール基
、炭素数７〜１５のアラルキル基、炭素数１〜６のヒド
ロキシアルキル基、アリル基、シリルアルキル基、置換
シリル（炭素数１〜５のアルキル基）を示す。〕で表わ
される構造単位（ｂ）を有する含フッ素アクリル系共重
合体。(1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (a) Structural unit represented by (a) and formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (b) [In the formula, R^1 is a hydrogen atom , a fluorine atom, a chlorine atom or a methyl group, R^2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a fluoroalkyl group having 2 to 10 carbon atoms, a fluoroalkyl group having 5 to 10 carbon atoms
10 cycloalkyl group, aryl group having 6 to 10 carbon atoms, aralkyl group having 7 to 15 carbon atoms, hydroxyalkyl group having 1 to 6 carbon atoms, allyl group, silylalkyl group, substituted silyl group (having 1 to 5 carbon atoms) alkyl group). ] A fluorine-containing acrylic copolymer having a structural unit (b) represented by:
ｂ）が１０〜５０モル％である請求項１記載の含フッ素
アクリル系共重合体。(2) Structural unit (a) is 50 to 90 mol%, structural unit (
The fluorine-containing acrylic copolymer according to claim 1, wherein b) is 10 to 50 mol%.
１又は２記載の含フッ素アクリル系共重合体。(3) The fluorine-containing acrylic copolymer according to claim 1 or 2, which has a glass transition temperature of 120 to 200°C.
である請求項１又は２記載の含フッ素アクリル系共重合
体。(4) Refractive index η_0^2^0 is 1.400 to 1.525
The fluorine-containing acrylic copolymer according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9608688A JPH01266118A (en) | 1988-04-19 | 1988-04-19 | Fluorinated acrylic copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9608688A JPH01266118A (en) | 1988-04-19 | 1988-04-19 | Fluorinated acrylic copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01266118A true JPH01266118A (en) | 1989-10-24 |
Family
ID=14155589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9608688A Pending JPH01266118A (en) | 1988-04-19 | 1988-04-19 | Fluorinated acrylic copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01266118A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005100421A1 (en) * | 2004-04-15 | 2005-10-27 | Daikin Industries, Ltd. | Fluorine-containing polymer and treating agent composition |
| US7250121B2 (en) | 2004-05-13 | 2007-07-31 | Nitto Denko Corporation | Non-linear optical device material composition |
| US7317058B2 (en) * | 2004-11-01 | 2008-01-08 | Nitto Denko Corporation | (Meth)acrylate polymer and non-linear optical device material composition |
-
1988
- 1988-04-19 JP JP9608688A patent/JPH01266118A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005100421A1 (en) * | 2004-04-15 | 2005-10-27 | Daikin Industries, Ltd. | Fluorine-containing polymer and treating agent composition |
| US7250121B2 (en) | 2004-05-13 | 2007-07-31 | Nitto Denko Corporation | Non-linear optical device material composition |
| US7317058B2 (en) * | 2004-11-01 | 2008-01-08 | Nitto Denko Corporation | (Meth)acrylate polymer and non-linear optical device material composition |
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