JPH021711A - Fluorine-containing copolymer and production thereof - Google Patents
Fluorine-containing copolymer and production thereofInfo
- Publication number
- JPH021711A JPH021711A JP1049558A JP4955889A JPH021711A JP H021711 A JPH021711 A JP H021711A JP 1049558 A JP1049558 A JP 1049558A JP 4955889 A JP4955889 A JP 4955889A JP H021711 A JPH021711 A JP H021711A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- fluorine
- weight
- containing copolymer
- copolymer
- 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
- 229920001577 copolymer Polymers 0.000 title claims abstract description 61
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 34
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000011737 fluorine Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- -1 fluoroalkyl methacrylate Chemical compound 0.000 claims abstract description 21
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 16
- 238000002834 transmittance Methods 0.000 claims description 13
- 239000013307 optical fiber Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 239000011162 core material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 3
- 239000013308 plastic optical fiber Substances 0.000 abstract description 2
- 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 8
- 229920000642 polymer Polymers 0.000 description 5
- 230000000007 visual effect Effects 0.000 description 5
- 238000012662 bulk polymerization Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- HGNRHPWYXDRKEA-UHFFFAOYSA-N [1,1,3,3,3-pentafluoro-2-(fluoromethyl)-2-methylpropyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(C)(CF)C(F)(F)F HGNRHPWYXDRKEA-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical class [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
Landscapes
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- 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、含フッ素共重合体、特にプラスチック系光学
繊維鞘材用に好適な含フッ素共重合体およびその製造方
法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a fluorine-containing copolymer, particularly a fluorine-containing copolymer suitable for a plastic optical fiber sheath material, and a method for producing the same.
従来、式：
〔式中、Ｘは水素原子、フッ素原子又は塩素原子、ｍは
１〜６、ｎは２〜１０の整数を示す。〕で表されるフル
オロアルキルメタクリレートからなる重合体又は共重合
体を光学繊維の鞘材にするのは公知である（特公昭４３
−８９７８号公報参照）。Conventionally, the formula: [wherein, ] It is known that a polymer or copolymer consisting of fluoroalkyl methacrylate represented by
(Refer to Publication No.-8978).
しかし、上記単量体とメチルメタクリレート （ＭＭＡ
）の共重合体を塊状重合すると著しく白濁する。これは
分子鎖の長いフルオロアルキルメタクリレートが重合の
後期で拡散障害を起こすためであると言われている。However, the above monomer and methyl methacrylate (MMA
) becomes significantly cloudy when bulk polymerized. This is said to be because fluoroalkyl methacrylate, which has a long molecular chain, causes diffusion hindrance in the late stage of polymerization.
光学繊維の鞘材用含フッ素重合体の重合は、懸濁重合の
場合の懸濁安定剤、乳化重合の場合の乳化剤などの混入
、■合体の′４＃製中のコンタミの混入を避けるため、
塊状重合で行うのが好ましい。Polymerization of fluorine-containing polymers for optical fiber sheath materials is carried out in order to avoid the contamination of suspension stabilizers in the case of suspension polymerization, emulsifiers in the case of emulsion polymerization, and contamination in the '4# product of coalescence. ,
It is preferable to carry out bulk polymerization.
このような方法で前記白濁を押さえるために、Ｈｚ
（１） ＣＩｈ＝ＣＣ００（ＣＨｚ）ｚ（ＣＦｚ）ｔ
ｃＰ＋３０〜６０重量％Ｈ３
（２） Ｃ１ｈ＝ＣＣＯＯＣ）ｌｚ（ＣＦｚ）、ｌＸ
２０〜５０重量％〔式中、χは水素原子又はフッ
素原子、ｎは１〜４の整数を示す。〕
（３） ＭＭＡ ２０〜５０重量％からなる
三元共重合体が提案されている（特開昭５１−６６７０
６号公報参照）。In order to suppress the cloudiness with such a method, Hz (1) CIh=CC00(CHz)z(CFz)t
cP+30-60% by weight H3 (2) C1h=CCOOC)lz(CFz),lX
20 to 50% by weight [In the formula, χ represents a hydrogen atom or a fluorine atom, and n represents an integer of 1 to 4. (3) A terpolymer consisting of 20 to 50% by weight of MMA has been proposed (Japanese Patent Laid-Open No. 51-6670).
(See Publication No. 6).
しかし、この方法は上記（１）〜（３）の組み合わせの
三元共重合体に限定され、しかも（３）のＭＭＡが２０
重看％以上で（２）の＄量体が２０重量％未満の場合は
白濁してしまうａまた、長鎖フルオロアルキルメタクリ
レートとＭＭＡの二元共重合体の場合や前記単量体と分
枝したフルオロアルキル基を持つメタクリレートとの三
元共重合体の場合には効果がなく、得られた共重合体は
白濁している。However, this method is limited to the terpolymer of the combination of (1) to (3) above, and moreover, the MMA of (3) is 20
If the amount of polymer (2) is less than 20% by weight, it will become cloudy.Also, in the case of a binary copolymer of long-chain fluoroalkyl methacrylate and MMA, or if the monomer and branched In the case of a terpolymer with a methacrylate having a fluoroalkyl group, there is no effect, and the resulting copolymer is cloudy.
本発明の目的は上記二元共重合体においても三元共重合
体においても透明性の良い含フッ素共重合体およびその
製造方法を提供することにある。An object of the present invention is to provide a fluorine-containing copolymer with good transparency, both in the binary copolymer and in the terpolymer, and a method for producing the same.
本発明の要旨は、メチルメタクリレートと少なくとも１
種の長鎖フルオロアルキルメタクリレートとの共重合体
であって、光透過率が９０％以上である含フッ素共重合
体に存する。The gist of the invention is that methyl methacrylate and at least one
The fluorine-containing copolymer is a copolymer with a long-chain fluoroalkyl methacrylate and has a light transmittance of 90% or more.
本発明において、好ましい含フッ素共重合体を具体的に
例示すると、
（ａ）式：
〔式中、ｎは６〜１０の整数を示す。〕で表されるフル
オロアルキルメタクリレート５０〜９５７ｍ枇％、
（ｂ）メチルメタクリレート５〜５０重量％及び（ｃ）
弐：
〔式中、Ｘ及びＸ”は互いに独立で水素原子、メチル基
又はエチル基、Ｙは水素原子又はフッ素原子、ｌは４〜
ｌＯの整数を示す。〕
及び／又は弐：
〔式中、ｎは６〜１０の整数を示す。〕で表されるフル
オロアルキルメタクリレート５０〜９５重量％及び
（ｂ）メチルメタクリレート５〜５０重量％との二元共
重合体、
（ａ）式：
で表されるフルオロアルキルメタクリレートＯ〜４０１
１λ景％との三元又は四元共重合体等であって、光透過
率が９０％以上である含フッ素共重合体を挙げることが
できる。In the present invention, specific examples of preferred fluorine-containing copolymers are as follows: Formula (a): [wherein, n represents an integer of 6 to 10]. ] fluoroalkyl methacrylate 50-957m%, (b) methyl methacrylate 5-50% by weight, and (c)
2: [In the formula, X and X'' are each independently a hydrogen atom, methyl group or ethyl group, Y is a hydrogen atom or a fluorine atom, and l is 4 to
Indicates an integer of lO. ] and/or 2: [In the formula, n represents an integer of 6 to 10. ] A binary copolymer of 50 to 95% by weight of fluoroalkyl methacrylate represented by (b) 5 to 50% by weight of methyl methacrylate, (a) fluoroalkyl methacrylate O to 401 represented by the formula:
Examples include fluorine-containing copolymers such as ternary or quaternary copolymers with a light transmittance of 90% or more.
上記の（ａ）のモノマーについては、特にｎが６〜８の
場合が好ましい。また、上記の（Ｃ）のモノマーについ
ては、（ｉ）Ｘ及びＸｏが水素原子であって、Ｙが水素
原子、ｍが４．６．８．１０の場合、（ｉｉ）Ｘ及びＸ
ｏがメチル基、Ｙが水素原子、ｍが４．６．８．１０の
場合が好ましい。Regarding the monomer (a) above, it is particularly preferable that n is 6 to 8. Regarding the monomer (C) above, (i) when X and Xo are hydrogen atoms, Y is a hydrogen atom, and m is 4.6.8.10, (ii) X and
It is preferable that o is a methyl group, Y is a hydrogen atom, and m is 4.6.8.10.
なお、本発明において光透過率とは、含フッ素共重合体
を１８０〜２５０℃の温度でプレス成形して厚み２１の
シートを作成し、このシートについて、ＵＶ可視スペク
トロメーターにて、波長４５０〜８００ｎｍの領域で測
定した値（入射光に対するｉ３過先の割合を％で表示、
Ｔ％という）をいう。In the present invention, light transmittance refers to a fluorine-containing copolymer press-molded at a temperature of 180 to 250°C to create a sheet with a thickness of 21°C, and this sheet is measured with a UV-visible spectrometer at a wavelength of 450 to 250°C. Value measured in the 800 nm region (displays the ratio of i3 past to the incident light in %,
(referred to as T%).
本発明の含フッ素共重合体の光透過率は９０％以上、こ
のましくは９５％以上である。The light transmittance of the fluorine-containing copolymer of the present invention is 90% or more, preferably 95% or more.
また、本発明の含フッ素共重合体のフロー値は１０〜４
００ｇ／１０分である。Further, the flow value of the fluorine-containing copolymer of the present invention is 10 to 4.
00g/10 minutes.
本発明の含フッ素共重合体は、メチルメタクリレートと
少なくとも１種の畏鎮フルオロアルキルメタクリレート
とを共重合するにあた引、共重合により生成する含フッ
素共重合体が溶解する溶媒をｒＪＬｆｔ体合計１．００
重量部に対して０．１〜２０重世部配合して共重合する
ことにより得られる。In copolymerizing methyl methacrylate and at least one kind of fluoroalkyl methacrylate, the fluorine-containing copolymer of the present invention is prepared by adding a total of rJLft of solvents in which the fluorine-containing copolymer produced by copolymerization is dissolved. 1.00
It is obtained by copolymerizing the mixture in an amount of 0.1 to 20 parts by weight.
本発明者らは、前記含フッ素共重合体が溶解する溶媒を
単量体合計１００重吋部に対して１〜２０重量部配合し
て共重合すると、前記溶媒が白濁防止剤として作用する
ことを見出し本発明を完成するに至ったものである。The present inventors discovered that when the fluorine-containing copolymer is dissolved in 1 to 20 parts by weight per 100 parts by weight of the total monomer and copolymerized, the solvent acts as an anti-whitening agent. This discovery led to the completion of the present invention.
なお、本発明において、長鎖フルオロアルキルメタクリ
レートとは、例えば弐：
ＣＩｌ□＝ ＣＣＯＯ（ＣＩｌ□）ｚｃ−ｈ□１〔式中
、ｎは６〜ｌＯの整数を示す。〕で表されるフルオロア
ルキルメタクリレートのようにフルオロアルキル基の炭
素数が６以上のものをいう。In the present invention, long-chain fluoroalkyl methacrylate means, for example, 2: CIl□=CCOO(CIl□)zc-h□1 [wherein n represents an integer of 6 to 1O]. ] refers to those in which the number of carbon atoms in the fluoroalkyl group is 6 or more, such as the fluoroalkyl methacrylate represented by the following.
本発明において使用できる溶媒としては、アセトン、メ
チルエチルケトン、メチルイソブチルケトン等のケトン
系、１５１１′酸エチル、酢酸ブチル等の酢酸エステル
系、メタキシレンへキサフルオライド、Ｌｌ、２− ト
リフルオロ−１，２，２−）リクロロエタン等のフッ素
系、１，１．１− ）リクロロエタン、１．２ジクロロ
エタン等の塩素系が挙げられ、これらの１種または２種
以上を混合して用いられる。好ましくは沸点が５０℃か
ら１５０℃のものであり、特に好ましくはメタキシレン
ヘキサフルオライドである。Examples of solvents that can be used in the present invention include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, acetate esters such as ethyl 1511' acid and butyl acetate, meta-xylene hexafluoride, Ll, 2-trifluoro-1, Examples include fluorine-based materials such as 2,2-)lichloroethane, chlorine-based materials such as 1,1.1-)lichloroethane, and 1.2-dichloroethane, and these may be used alone or in combination of two or more. Preferably, the boiling point is from 50°C to 150°C, and meta-xylene hexafluoride is particularly preferable.
溶媒が０９１重量部より少ないと得られだ共重合体が白
濁し、２０重量部をこえると溶液重合の様になり分子量
が大幅に低下するうえ、重合速度が遅くなる。また、溶
媒が２０重量部をこえると溶媒より該共重合体をとり出
すために再沈澱が必要となったり、溶媒の除去する量が
多くなり、コスト高になる上、製造上面倒である。本発
明において、好ましい溶媒の配合量は、１−１５重量部
である。If the amount of solvent is less than 0.91 parts by weight, the resulting copolymer becomes cloudy, and if it exceeds 20 parts by weight, solution polymerization occurs, resulting in a significant decrease in molecular weight and a slow polymerization rate. Furthermore, if the amount of the solvent exceeds 20 parts by weight, reprecipitation is required to extract the copolymer from the solvent, and the amount of solvent to be removed increases, resulting in high costs and troublesome production. In the present invention, the preferred amount of solvent is 1-15 parts by weight.
開始剤は通常のラジカル共重合開始剤例えばアゾビスイ
ソブチロニトリル、ヘンシイルバーオキサイド等が使用
される。As the initiator, common radical copolymerization initiators such as azobisisobutyronitrile and hensyl peroxide are used.
重合法は連続塊状重合、回分式塊状重合、注型重合等通
常の塊状重合と同じ方法ができる１重合塩度は室温〜１
００℃で５０〜８０℃が好ましい。Polymerization methods include continuous bulk polymerization, batch bulk polymerization, cast polymerization, etc. The same methods as normal bulk polymerization can be used. 1 Polymerization Salinity is from room temperature to 1.
At 00°C, 50 to 80°C is preferred.
また、ドデシルメルカプタン等重合度調整剤を使用する
こともできる。Further, a degree of polymerization regulator such as dodecyl mercaptan can also be used.
重合後はただちに減圧度１１００ｆｆＩｎＨ以下で１５
０〜２００℃に加熱して、溶剤（白濁防止剤）および残
モノマーを留去する。Immediately after polymerization, the degree of vacuum is 1100ffInH or less.
It is heated to 0 to 200°C to distill off the solvent (anti-clouding agent) and residual monomers.
このようにして得られた共重合体は透明性が高（、光学
繊維の鞘材とした場合、透光性能が優れている。また、
該共重合体を鞘材とし、通常の芯材とを組み合わせてな
る光学繊維は導光損失が極めて少ないという特色を示す
。通常の芯材としては、Ｐ Ｍ Ｍ Ａ 、ボリスチ、
レン、ポリカーボネート、ポリエステル等を例示するこ
とができる。The copolymer thus obtained has high transparency (and has excellent light transmission performance when used as a sheath material for optical fibers.
Optical fibers made by using the copolymer as a sheath material in combination with a normal core material are characterized by extremely low light guide loss. Usual core materials include PMMA, Boristi,
Examples include polycarbonate, polycarbonate, and polyester.
以下、実施例で説明する。なお、実施例中のフロー値と
は高化式フローテスター（島津製作所製）により、２３
０℃で共重合体を５分保持した後の流失速度である（荷
重７ｋｇ／ｃｊａ、ノズル２１■φＸ８１■Ｉり。Examples will be described below. In addition, the flow value in the examples is 23
This is the flow-off rate after holding the copolymer at 0°C for 5 minutes (load 7 kg/cja, nozzle 21 x 81 x I).
実施例１
減圧蒸留によって精製した
Ｈ３
ＣＨｚ＝ＣＣＯＯＣＨｔＣＨｚ（ＣＦり、Ｃｈ （
以下、１７部ＭＡと称する）７５部、メチルメタクリレ
ート２５部、ｎ−ラウリルメルカプタン０．０４部、ア
ゾビスイソブチロニトリル０．０２５部、及びメタキシ
レンへキサフルオライド１１部を酸素不在下で調合し、
次いで７０℃に維持された反応槽において１８時間共重
合を行った。得られた共重合体を減圧下１７０℃で１０
時間乾燥を行い、９８ｇの共重合体を得た（収率９８％
）。Example 1 H3 purified by vacuum distillation CHz=CCOOCHtCHz (CF, Ch (
75 parts of methyl methacrylate (hereinafter referred to as 17 parts MA), 25 parts of methyl methacrylate, 0.04 parts of n-lauryl mercaptan, 0.025 parts of azobisisobutyronitrile, and 11 parts of meta-xylene hexafluoride in the absence of oxygen. mix,
Copolymerization was then carried out for 18 hours in a reaction tank maintained at 70°C. The obtained copolymer was heated at 170°C under reduced pressure for 10
After drying for several hours, 98 g of copolymer was obtained (yield: 98%).
).
得られた共重合体のフロー値は１００ｇ／１０分（２３
０℃、７ｋｇ／ｃＡ荷重）であった。この共重合体を２
３０℃でプレスして、厚み２１１のシートを作った。The flow value of the obtained copolymer was 100 g/10 min (23
0°C, 7 kg/cA load). This copolymer is 2
A sheet with a thickness of 211 mm was made by pressing at 30°C.
目視で観察したところ無色透明であり、光透過率は９５
％であった。When visually observed, it was colorless and transparent, and the light transmittance was 95.
%Met.
実施例２
減圧蒸留によって精製した１７部ＭＡ６０部、メチルメ
タクリレート２０部、ヘキサフルオロネオペンチルメタ
クリレート２０部、ｎ−ラウリルメルカプタン０．０３
部、アゾビスイソブチロニトリル０．０２５部、及びメ
タキシレンへキサフルオライド１１部を酸素不在下で調
合し、実施例１と同様の操作で共重合を行い、９８ｇの
共重合体を得た（収率９８％）。得られた共重合体のフ
ロー値は９０ｇ／１０分（２３０℃、７ｋｇ／ｃｎ！荷
重）、であった、この共重合体を２３０℃でプレスして
、厚み２龍のシートを作った。目視で観察したところ無
色透明であり、光透過率は９５％であった。Example 2 17 parts purified by vacuum distillation 60 parts of MA, 20 parts of methyl methacrylate, 20 parts of hexafluoroneopentyl methacrylate, 0.03 parts of n-lauryl mercaptan
1 part, 0.025 parts of azobisisobutyronitrile, and 11 parts of meta-xylene hexafluoride were prepared in the absence of oxygen, and copolymerization was carried out in the same manner as in Example 1 to obtain 98 g of copolymer. (yield 98%). The flow value of the obtained copolymer was 90 g/10 min (230° C., 7 kg/cn! load). This copolymer was pressed at 230° C. to make a sheet with a thickness of 2. Visual observation revealed that it was colorless and transparent, and the light transmittance was 95%.
実施例３
減圧蒸留によって精製した１７部ＭＡ７５部、メチル−
メタクリレート２０部、
ｎ−ラウリルメルカプタン０．０２５部、アゾビスイソ
ブチロニトリル０．０２５部及びメタキシレンへキサフ
ルオライド１１部を酸素不在下で調合し、次いで実施例
１と同様の操作で重合を行い９８ｇの共重合体を得た（
収率９８％）、得られた共重合体のフロー値は１０５ｇ
／１０分（２３０℃、７ｋｇ／ｃｄ荷重）であった。こ
の共重合体を２３０℃でプレスして、厚み２ｍｍのシー
トを作った。目視で観察したところ無色透明であり、光
透過率は９５％であった。Example 3 17 parts MA purified by vacuum distillation 75 parts methyl
20 parts of methacrylate, 0.025 parts of n-lauryl mercaptan, 0.025 parts of azobisisobutyronitrile and 11 parts of metaxylene hexafluoride were prepared in the absence of oxygen, and then polymerized in the same manner as in Example 1. to obtain 98 g of copolymer (
Yield: 98%), flow value of the obtained copolymer: 105g
/10 minutes (230°C, 7kg/cd load). This copolymer was pressed at 230°C to produce a sheet with a thickness of 2 mm. Visual observation revealed that it was colorless and transparent, and the light transmittance was 95%.
実施例４
しｉ３
の代わりにＣ）ＩＺ＝Ｃ（ＣＨ，）ＣＯＯＣＨ！（ＣＦ
、）６１１ １５部を用いる以外は、実施例３と同様に
操作して９７ｇの共重合体を得たく収率９７％）。得ら
れた共重合体のフロー値は１０３ ｇ ／ １０分（２
３０℃、りｋｇ ／ ｃＩＩｔ荷重）であった、この共
重合体を２３０℃でプレスして、厚み２龍のシートを作
った。目視で観察したところ無色透明であり、光透過率
は９５％であった。Example 4 C) IZ=C(CH,)COOCH! instead of i3 (CF
, ) 611 (yield 97%) was carried out in the same manner as in Example 3 to obtain 97 g of a copolymer (yield 97%). The flow value of the obtained copolymer was 103 g/10 min (2
This copolymer was pressed at 230°C to form a sheet with a thickness of 2.0°C. Visual observation revealed that it was colorless and transparent, and the light transmittance was 95%.
比較例１
メタキシレンヘキサフルオライドを使用しない以外は、
実施例１と同様の操作で重合した共重合体を２３０℃で
プレスして、厚み２１■のシートを作った。目視で観察
したところ白濁しており、光透過率は８５％であった。Comparative Example 1 Except for not using meta-xylene hexafluoride,
The copolymer polymerized in the same manner as in Example 1 was pressed at 230°C to produce a sheet with a thickness of 21 cm. Visual observation revealed that it was cloudy and the light transmittance was 85%.
比較例２
メタキシレンヘキサフルオライドを使用しない以外は、
実施例２と同様の操作で重合した共重合体を２３０℃で
プレスして、厚み２ ａｍのシートを作った。目視で観
察したところ白濁しており、光透過率は８５％であった
。Comparative Example 2 Except for not using meta-xylene hexafluoride,
The copolymer polymerized in the same manner as in Example 2 was pressed at 230°C to produce a sheet with a thickness of 2 am. Visual observation revealed that it was cloudy and the light transmittance was 85%.
用途例
ＰＭＭＡ （三菱レイヨン社製アクリベット）を２５０
℃に加熱したベットつき押し出し機に供給し、２３５℃
に維持された二重押し出しノズルの中心より直径１ｍ−
のストランド状の該重合体を芯成分として吐出しながら
、実施例１の共重合体（屈折率１゜３９８）を鞘成分と
してＣ６融被覆した。芯−鞘重合体の配合比は９０対１
０とした。ついで強靭性を付与するため１．７倍に延伸
して直径約０ 、７１＊の光学繊維を得た。この光学繊
維の導光損失をＬＥＤ光源を用いて測定したところ６５
０ｒ＋ｍの波長において１８０ｄＢ／Ｋｍであった。Application example PMMA (Mitsubishi Rayon Acrybet) 250
Feed into an extruder with a bed heated to 235°C.
1m in diameter from the center of the double extrusion nozzle maintained at
The copolymer of Example 1 (refractive index: 1°398) was used as a sheath component and C6 fusion coated while discharging the strand-shaped polymer as a core component. Core-sheath polymer blending ratio is 90:1
It was set to 0. Then, in order to impart toughness, the fiber was stretched 1.7 times to obtain an optical fiber with a diameter of approximately 0.71*. When the light guide loss of this optical fiber was measured using an LED light source, it was 65.
It was 180 dB/Km at the wavelength of 0r+m.
比較用途例
鞘成分を比較例１で得た共重合体を用いる以外は、用途
例と同様にして、光学株維を得た。この光学繊維の導光
損失をＬＥＤ光源を用いて７！ｌｌ＋定したところ６５
０ｎｍの波長において１ｏ００ｄＢ／Ｋｍであった。Comparative Application Example Optical fibers were obtained in the same manner as in the Application Example except that the copolymer obtained in Comparative Example 1 was used as the sheath component. Using an LED light source, the light guide loss of this optical fiber can be reduced to 7! ll + determined 65
It was 1000 dB/Km at a wavelength of 0 nm.
本発明によれば、光学繊維鞘材に使用するのに好適な透
明性の良い含フッ素共重合体が得られる。According to the present invention, a fluorine-containing copolymer with good transparency suitable for use in optical fiber sheath materials can be obtained.
以上that's all
Claims (1)
オロアルキルメタクリレートとの共重合体であって、光
透過率が９０％以上である含フッ素共重合体。 ２、（ａ）式： ▲数式、化学式、表等があります▼ 〔式中、ｎは６〜１０の整数を示す。〕 で表されるフルオロアルキルメタクリレート５０〜９５
重量％及び （ｂ）メチルメタクリレート５〜５０重量％の共重合体
であって、光透過率が９０％以上である含フッ素共重合
体。 ３、（ａ）式： ▲数式、化学式、表等があります▼ 〔式中、ｎは６〜１０の整数を示す。〕 で表されるフルオロアルキルメタクリレート５０〜９５
重量％、 （ｂ）メチルメタクリレート５〜５０重量％及び （ｃ）式： ▲数式、化学式、表等があります▼ 〔式中、Ｘ及びＸ’は互いに独立で水素原子、メチル基
又はエチル基、Ｙは水素原子又はフッ素原子、ｍは４〜
１０の整数を示す。〕及び／又は式： ▲数式、化学式、表等があります▼ で表されるフルオロアルキルメタクリレート０〜４０重
量％の共重合体であって、光透過率が９０％以上である
含フッ素共重合体。 ４、請求項１ないし３記載の含フッ素共重合体からなる
光学繊維鞘材。 ５、請求項４の鞘材と通常の芯材とを組み合わせてなる
光学繊維。 ６、メチルメタクリレートと少なくとも１種の長鎖フル
オロアルキルメタクリレートとを共重合するにあたり、
共重合により生成する含フッ素共重合体が溶解する溶媒
を単量体合計１００重量部に対して０．１〜２０重量部
配合して共重合することを特徴とする含フッ素共重合体
の製造方法。 ７、含フッ素共重合体が、 （ａ）式： ▲数式、化学式、表等があります▼ 〔式中、ｎは６〜１０の整数を示す。〕 で表されるフルオロアルキルメタクリレート５０〜９５
重量％及び （ｂ）メチルメタクリレート５〜５０重量％の共重合体
である請求項５記載の含フッ素共重合体の製造方法。 ８、含フッ素共重合体が、 （ａ）式： ▲数式、化学式、表等があります▼ 〔式中、ｎは６〜１０の整数を示す。〕 で表されるフルオロアルキルメタクリレート５０〜９５
重量％、 （ｂ）メチルメタクリレート５〜５０重量％及び （ｃ）式： ▲数式、化学式、表等があります▼ 〔式中、Ｘ及びＸ’は互いに独立で水素原子、メチル基
又はエチル基、Ｙは水素原子又はフッ素原子、ｍは４〜
１０の整数を示す。〕及び／又は式： ▲数式、化学式、表等があります▼ で表されるフルオロアルキルメタクリレート０〜４０重
量％の共重合体である請求項５記載の含フッ素共重合体
の製造方法。 ９、含フッ素共重合体が溶解する溶媒がメタキシレンヘ
キサフルオライドである請求項５ないし７記載の含フッ
素共重合体の製造方法。[Scope of Claims] 1. A fluorine-containing copolymer having a light transmittance of 90% or more, which is a copolymer of methyl methacrylate and at least one long-chain fluoroalkyl methacrylate. 2. Formula (a): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, n represents an integer from 6 to 10. ] Fluoroalkyl methacrylate 50-95 represented by
% by weight and (b) 5 to 50% by weight of methyl methacrylate, a fluorine-containing copolymer having a light transmittance of 90% or more. 3. Formula (a): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, n represents an integer from 6 to 10. ] Fluoroalkyl methacrylate 50-95 represented by
Weight%, (b) Methyl methacrylate 5-50% by weight and (c) Formula: ▲ Numerical formulas, chemical formulas, tables, etc. Y is a hydrogen atom or a fluorine atom, m is 4-
Indicates an integer of 10. ] and/or formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A fluorine-containing copolymer containing 0 to 40% by weight of fluoroalkyl methacrylate and having a light transmittance of 90% or more . 4. An optical fiber sheath material comprising the fluorine-containing copolymer according to claims 1 to 3. 5. An optical fiber formed by combining the sheath material of claim 4 and a normal core material. 6. In copolymerizing methyl methacrylate and at least one long-chain fluoroalkyl methacrylate,
Production of a fluorine-containing copolymer, which comprises copolymerizing by blending 0.1 to 20 parts by weight of a solvent in which the fluorine-containing copolymer produced by copolymerization is dissolved, based on 100 parts by weight of the total monomers. Method. 7. The fluorine-containing copolymer has the formula (a): ▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, n represents an integer from 6 to 10. ] Fluoroalkyl methacrylate 50-95 represented by
The method for producing a fluorine-containing copolymer according to claim 5, which is a copolymer containing 5 to 50% by weight of (b) methyl methacrylate. 8. The fluorine-containing copolymer has the formula (a): ▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, n represents an integer from 6 to 10. ] Fluoroalkyl methacrylate 50-95 represented by
Weight%, (b) Methyl methacrylate 5-50% by weight and (c) Formula: ▲ Numerical formulas, chemical formulas, tables, etc. Y is a hydrogen atom or a fluorine atom, m is 4-
Indicates an integer of 10. ] and/or formula: ▲ Numerical formula, chemical formula, table, etc. ▼ The method for producing a fluorine-containing copolymer according to claim 5, which is a copolymer containing 0 to 40% by weight of fluoroalkyl methacrylate. 9. The method for producing a fluorine-containing copolymer according to claims 5 to 7, wherein the solvent in which the fluorine-containing copolymer is dissolved is metaxylene hexafluoride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1049558A JPH021711A (en) | 1988-03-01 | 1989-02-28 | Fluorine-containing copolymer and production thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4845988 | 1988-03-01 | ||
| JP63-48459 | 1988-03-01 | ||
| JP1049558A JPH021711A (en) | 1988-03-01 | 1989-02-28 | Fluorine-containing copolymer and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH021711A true JPH021711A (en) | 1990-01-08 |
Family
ID=26388732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1049558A Pending JPH021711A (en) | 1988-03-01 | 1989-02-28 | Fluorine-containing copolymer and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH021711A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04298514A (en) * | 1991-01-31 | 1992-10-22 | Dainippon Ink & Chem Inc | Curable composition and optical fiber coated therewith |
-
1989
- 1989-02-28 JP JP1049558A patent/JPH021711A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04298514A (en) * | 1991-01-31 | 1992-10-22 | Dainippon Ink & Chem Inc | Curable composition and optical fiber coated therewith |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3575946A (en) | Method of preparing soluble polymers of ethylene glycol | |
| KR910008999B1 (en) | Monomeric composition | |
| US5149753A (en) | Fluorine-containing copolymer and process for preparing the same | |
| JP4091689B2 (en) | Method for producing methyl methacrylate polymer and method for producing plastic optical fiber | |
| JPH021711A (en) | Fluorine-containing copolymer and production thereof | |
| JPS6166706A (en) | Polymer for sheath material of optical fiber | |
| JPS61114208A (en) | Plastic optical fiber | |
| JPH02103210A (en) | Substituted (2-haloalkoxy-1,1,2- trifluoroethoxy)styrene polymer, and its preparation and use | |
| JPH0249009A (en) | Monomer composition | |
| JP3102185B2 (en) | Manufacturing method of optical fiber clad material | |
| US4048260A (en) | Thermoplastic compositions with improved processing properties | |
| JP2009227787A (en) | Method for producing methyl methacrylate-based copolymer, and method for producing plastic optical fiber | |
| JPH0385502A (en) | Optical fiber clad material | |
| JPS61151212A (en) | Methacrylate copolymer and its production | |
| JPS60199007A (en) | Optical material | |
| JPH0574049B2 (en) | ||
| JP3102181B2 (en) | Manufacturing method of optical fiber clad material | |
| JPS6272706A (en) | Vinyl acetate copolymer | |
| JP2507385B2 (en) | Plastic optical fiber with excellent heat resistance | |
| JPH0255301A (en) | Organic glass | |
| JPH02265907A (en) | High-refractive index optical resin | |
| JPH11147916A (en) | Production of polyvinyl alcohol of high syndiotacticity | |
| JP3527928B2 (en) | Organic glass for optical materials | |
| JPS60149005A (en) | Plastic optical fiber | |
| JPS6173101A (en) | Plastic lens high in refractive index |