JPH0912646A - Heat-resistant resin - Google Patents
Heat-resistant resinInfo
- Publication number
- JPH0912646A JPH0912646A JP18653995A JP18653995A JPH0912646A JP H0912646 A JPH0912646 A JP H0912646A JP 18653995 A JP18653995 A JP 18653995A JP 18653995 A JP18653995 A JP 18653995A JP H0912646 A JPH0912646 A JP H0912646A
- Authority
- JP
- Japan
- Prior art keywords
- butyrolactone
- heat
- methylene
- resistant resin
- acid
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐熱性に優れた濃縮
材、凝集剤、イオン交換樹脂、懸濁剤、結合剤、接着剤
等を得るのに用いられる耐熱性樹脂に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant resin used for obtaining a concentrate, an aggregating agent, an ion exchange resin, a suspending agent, a binder, an adhesive and the like having excellent heat resistance.
【０００２】[0002]
【従来の技術および発明が解決しようとする課題】ポリ
アクリル酸、ポリメタクリル酸は、荷電性のカルボン酸
基を有する構造的特徴から、濃縮材、凝集剤、イオン交
換樹脂、懸濁剤、結合剤、接着剤などの機能性ポリマー
を得るために用いられ、そしてそれらの機能性ポリマー
は、織物、化粧品、製紙、石油、塗料などの産業分野、
および農地ならびに水質の改質など幅広く用いられてい
る。また、アクリル酸、メタクリル酸のα位にフッ素原
子を導入させたポリフルオロアクリル酸、ポリフルオロ
メタクリル酸については、上記用途のほかにフッ素原子
の導入による撥水性、低屈折性の特徴をいかして防湿用
途、光ファイバー等の材料として用いられている。しか
し、上記の樹脂は、このような特性を持っている反面、
脆く、成形性が悪いという欠点を有するために、アクリ
ル酸エステル、メタクリル酸エステルなどと共重合し、
力学特性を向上させて用いられることが多い。しかしな
がら、アクリル酸エステル、メタクリ酸エステルを共重
合させるとガラス転移温度が低下し、耐熱性が要求され
る分野への展開が難しくなる。2. Description of the Related Art Polyacrylic acid and polymethacrylic acid are condensing agents, flocculants, ion exchange resins, suspending agents, binding agents, because of their structural characteristics having a charged carboxylic acid group. It is used to obtain functional polymers such as adhesives and adhesives, and those functional polymers are used in industrial fields such as textiles, cosmetics, papermaking, petroleum, and paints,
It is also widely used for agricultural land and water quality improvement. Further, regarding polyfluoroacrylic acid and polyfluoromethacrylic acid in which a fluorine atom is introduced at the α-position of acrylic acid and methacrylic acid, in addition to the above-mentioned applications, the characteristics of water repellency and low refractive index due to the introduction of a fluorine atom are utilized. It is used as a material for moisture-proof applications and optical fibers. However, while the above resins have such characteristics,
Since it is brittle and has the drawback of poor moldability, it is copolymerized with acrylic acid ester, methacrylic acid ester, etc.,
It is often used with improved mechanical properties. However, the copolymerization of acrylic acid ester and methacrylic acid ester lowers the glass transition temperature, making it difficult to develop into fields requiring heat resistance.
【０００３】そこで、このようなアクリル系樹脂の耐熱
性を改善する方法として、例えば特公昭４９−１０１５
６号公報、特公昭４３−９７５３号公報、特公平２−４
６６０５号公報等には、耐熱性の高いマレイン酸、α−
メチルスチレン、Ｎ−置換マレイミドなどの単量体を共
重合させる方法が提案されている。しかし、耐熱性の高
いマレイン酸、αメチルスチレン、Ｎ−置換マレイミド
等を共重合させる方法は、共重合化による機械的性質、
耐候性、光学的性質等を低下させる欠点がある。Therefore, as a method for improving the heat resistance of such an acrylic resin, for example, Japanese Patent Publication No. Sho 49-1015.
No. 6, Japanese Patent Publication No. 43-9753, Japanese Patent Publication No. 2-4
No. 6605 discloses maleic acid having high heat resistance, α-
A method of copolymerizing monomers such as methylstyrene and N-substituted maleimide has been proposed. However, the method of copolymerizing maleic acid, α-methylstyrene, N-substituted maleimide and the like, which have high heat resistance, is
There is a drawback that the weather resistance and optical properties are deteriorated.
【０００４】また、透明で高い耐熱性を有する重合体と
して、Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ 第１２巻 ５４
６頁（１９７９年）にα−メチレン−γ−ブチロラクト
ンの単独重合体が、そしてＰｏｌｙｍｅｒ 第２０巻
１２１５頁（１９７９年）にはα−メチレン−γ−ブチ
ロラクトンと、メタクリル酸メチル、スチレン等との共
重合体が開示されている。しかし、これらのα−メチレ
ン−γ−ブチロラクトンの単独重合体、または共重合体
は、荷電を有するカルボン酸基を有していないために、
濃縮材、凝集剤、イオン交換樹脂、懸濁剤、接着剤等に
使用しても十分な特性を発揮することができない。As a transparent polymer having high heat resistance, Macromolecules, Vol. 12, 54.
Homopolymer of α-methylene-γ-butyrolactone on page 6 (1979), and Polymer, Volume 20.
On page 1215 (1979), a copolymer of α-methylene-γ-butyrolactone and methyl methacrylate, styrene or the like is disclosed. However, since these α-methylene-γ-butyrolactone homopolymers or copolymers do not have a charged carboxylic acid group,
Even if it is used as a thickener, a flocculant, an ion exchange resin, a suspending agent, an adhesive, etc., sufficient properties cannot be exhibited.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上述した
如き状況に鑑み、優れた耐熱性を有し、濃縮材、凝集
剤、イオン交換樹脂、懸濁剤、接着剤等に使用できる樹
脂を得ることを目的として鋭意検討を進めた結果、α−
メチレン−γ−ブチロラクトンと特定のカルボン酸基含
有単量体とからなる共重合体が上記の目的を達成できる
ことを見い出し、本発明を完成した。In view of the above-mentioned situation, the present inventors have excellent heat resistance and can be used as a thickener, a flocculant, an ion exchange resin, a suspension, an adhesive and the like. As a result of intensive studies aimed at obtaining a resin, α-
The present invention has been completed by finding that a copolymer composed of methylene-γ-butyrolactone and a specific carboxylic acid group-containing monomer can achieve the above object.
【０００６】すなわち、本発明は、α−メチレン−γ−
ブチロラクトン（Ａ）と、アクリル酸、メタクリル酸、
α−フルオロアクリル酸およびα−トリフルオロメチル
アクリル酸からなる群より選ばれる少なくとも１種の単
量体（Ｂ）とを重合して得られる耐熱性樹脂にある。That is, the present invention relates to α-methylene-γ-
Butyrolactone (A), acrylic acid, methacrylic acid,
A heat-resistant resin obtained by polymerizing at least one monomer (B) selected from the group consisting of α-fluoroacrylic acid and α-trifluoromethylacrylic acid.
【０００７】本発明において用いられるα−メチレン−
γ−ブチロラクトン（Ａ）は、下記一般式（Ｉ）で示さ
れる構造を有するものである。Α-methylene-used in the present invention
The γ-butyrolactone (A) has a structure represented by the following general formula (I).
【０００８】[0008]
【化１】 Embedded image
【０００９】上記のα−メチレン−γ−ブチロラクトン
は、それ自体生理活性物質であることから、その合成法
はいくつか検討されており、例えば、Ａｎｇｅｗ．Ｃｈ
ｅｍ．Ｅｄ，Ｅｎｇｌ 第２４巻 ９４頁（１９８５
年）、有機合成化学協会誌第３９巻 ３５８頁（１９８
１年）等に記載されている。Since the above-mentioned α-methylene-γ-butyrolactone is a physiologically active substance in itself, several synthetic methods have been studied, for example, Angew. Ch
em. Ed, Engl, Vol. 24, p. 94 (1985)
, Pp. 358 (198)
1 year).
【００１０】また、本発明において、上記のα−メチレ
ン−γ−ブチロラクトン（Ａ）と共重合するのに用いら
れる単量体（Ｂ）は、アクリル酸、メタクリル酸、α−
フルオロアクリル酸およびα−トリフルオロメチルアク
リル酸からなる群より選ばれ少なくとも１種のカルボン
酸基含有単量体である。In the present invention, the monomer (B) used for copolymerization with the above-mentioned α-methylene-γ-butyrolactone (A) is acrylic acid, methacrylic acid, α-
It is at least one carboxylic acid group-containing monomer selected from the group consisting of fluoroacrylic acid and α-trifluoromethylacrylic acid.
【００１１】本発明におけるα−メチレン−γ−ブチロ
ラクトン（Ａ）と上記カルボン酸基含有単量体（Ｂ）の
使用割合は、使用用途により一概には決められないが、
荷電性と耐熱性の観点から、上記単量体（Ａ）と（Ｂ）
とからなる単量体混合物１００重量部中、α−メチレン
−γ−ブチロラクトン（Ａ）が３０〜７０重量部、カル
ボン酸基含有単量体（Ｂ）が７０〜３０重量部となる範
囲が好ましい。α−メチレン−γ−ブチロラクトン
（Ａ）の使用量が少なすぎると耐熱性が十分でなく、ま
た、多すぎると機械的性質が低下するようになる。The ratio of the α-methylene-γ-butyrolactone (A) to the carboxylic acid group-containing monomer (B) used in the present invention cannot be unconditionally determined depending on the intended use.
From the viewpoint of chargeability and heat resistance, the above monomers (A) and (B)
It is preferable that the α-methylene-γ-butyrolactone (A) is 30 to 70 parts by weight and the carboxylic acid group-containing monomer (B) is 70 to 30 parts by weight in 100 parts by weight of the monomer mixture consisting of . If the amount of α-methylene-γ-butyrolactone (A) used is too small, the heat resistance will be insufficient, and if it is too large, the mechanical properties will deteriorate.
【００１２】なお、本発明の耐熱性樹脂においては、さ
らに性能を向上させるために、必要に応じ、耐熱性、荷
電性を損なわない範囲において、例えば（メタ）アクリ
ルアマイド、ジメチルアミノエチル（メタ）アクリレー
ト、（メタ）アクリル酸エステル、スチレン、エチレン
グリコールジメタクリレート等の第三成分を共重合させ
てもよい。In order to further improve the performance of the heat-resistant resin of the present invention, (meth) acryl amide, dimethylaminoethyl (meth), etc. may be used, if necessary, within a range that does not impair heat resistance and chargeability. A third component such as acrylate, (meth) acrylic acid ester, styrene or ethylene glycol dimethacrylate may be copolymerized.
【００１３】本発明において用いられる重合方法として
は、特に限定されず、例えば塊状重合、溶液重合、懸濁
重合、乳化重合等を挙げることができる。The polymerization method used in the present invention is not particularly limited, and examples thereof include bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization.
【００１４】使用される重合開始剤は、重合時に副反応
や着色等の悪影響をおよぼさないものであれば、特に限
定されるものではなく、重合様式、重合温度、重合率、
重合時間に応じて任意に選択でき、１種でまたは２種以
上を併用して用いることができる。重合開始剤の例とし
ては、例えば２，２−アゾビスイソブチロニトリル、
２，２′−アゾビス−２，４−ジメチルバレロニトリル
等のアゾ系開始剤、ベンゾイルパーオキサイド、ジ−ｔ
−ブチルパーオキサイド、ジクルミルパーオキサイド、
ラウリルパーオキサイド等の有機過酸化物、ベンゾイン
メチルエーテル、ベンゾフェノン等の光開始剤、過硫酸
アンモニウム等の硫酸塩、亜硫酸ソーダ、レドックス系
開始剤などが挙げられる。The polymerization initiator used is not particularly limited as long as it does not adversely affect side reactions or coloring during the polymerization, and the polymerization mode, polymerization temperature, polymerization rate,
It can be arbitrarily selected depending on the polymerization time, and one kind can be used or two or more kinds can be used in combination. Examples of the polymerization initiator include, for example, 2,2-azobisisobutyronitrile,
Azo initiators such as 2,2′-azobis-2,4-dimethylvaleronitrile, benzoyl peroxide, di-t
-Butyl peroxide, dicrumyl peroxide,
Examples thereof include organic peroxides such as lauryl peroxide, photoinitiators such as benzoin methyl ether and benzophenone, sulfates such as ammonium persulfate, sodium sulfite, and redox initiators.
【００１５】また、重合において分子量を調節するため
に必要に応じて用いられる連鎖移動剤としては、重合時
に副反応や着色等の悪影響をおよぼさないものであれ
ば、特に限定されず、目的とする分子量に対して任意に
選択でき、１種でまたは２種以上を組み合わせて用いる
ことができる。連鎖移動剤の例としては、例えばｎ−ブ
チルメルカプタン、イソブチルメルカプタン、ｔ−ブチ
ルメルカプタン、オクチルメルカプタン等の第一級、第
二級、第三級メルカプタン、チオグリコール酸およびそ
のエステルなどが挙げられる。The chain transfer agent optionally used for controlling the molecular weight in the polymerization is not particularly limited as long as it does not adversely affect side reactions or coloring during the polymerization. The molecular weight can be arbitrarily selected, and one kind or a combination of two or more kinds can be used. Examples of the chain transfer agent include primary, secondary and tertiary mercaptans such as n-butyl mercaptan, isobutyl mercaptan, t-butyl mercaptan and octyl mercaptan, thioglycolic acid and its ester.
【００１６】重合温度は、使用する重合開始剤、および
重合形式により一概には決められないが、５０〜１５０
℃の範囲で行うことが好ましい。The polymerization temperature is not generally determined depending on the polymerization initiator used and the type of polymerization, but is 50 to 150.
It is preferable to carry out in the range of ° C.
【００１７】本発明の耐熱性樹脂は、上記の方法によっ
て製造されるが、品質上の要求から、必要に応じて可塑
剤、架橋剤、熱安定剤、着色剤、紫外線吸収剤、離型剤
等を添加することもできる。The heat-resistant resin of the present invention is produced by the above-mentioned method. However, in view of quality requirements, a plasticizer, a cross-linking agent, a heat stabilizer, a colorant, an ultraviolet absorber, a release agent may be added if necessary. Etc. can also be added.
【００１８】本発明の耐熱性樹脂の分子量は特に限定さ
れないが、高すぎる場合には成形加工性を低下させた
り、また、低すぎる場合には十分な機械的性質が得られ
なくなる等の欠点が生じるため、ＧＰＣのポリスチレン
換算により求めた分子量が重量平均分子量で１０，００
０〜１，０００，０００、好ましくは５０，０００〜２
００，０００の範囲のものが好適である。The molecular weight of the heat-resistant resin of the present invention is not particularly limited, but if it is too high, the moldability is lowered, and if it is too low, sufficient mechanical properties cannot be obtained. Therefore, the molecular weight determined by GPC polystyrene conversion is 10,000 as the weight average molecular weight.
0 to 1,000,000, preferably 50,000 to 2
Those in the range of 0,000 are suitable.
【００１９】[0019]
【実施例】以下、実施例により本発明をさらに詳しく説
明する。なお、実施例および比較例中のガラス転移温度
は、ＤＳＣ（示差走査熱量計法）により測定した。ま
た、例中の部は重量部を示す。The present invention will be described in more detail with reference to the following examples. The glass transition temperatures in the examples and comparative examples were measured by DSC (differential scanning calorimeter method). Parts in the examples indicate parts by weight.
【００２０】［実施例１］１０部のナトリウムエトキシ
ドを分散させた１００部の無水テトラヒドロフラン中
に、シュウ酸ジエチル２５部を加えた後、１５℃以下で
γ−ブチロラクトン１５部を滴下し、終夜放置した。こ
の反応液中にホルムアルデヒドを吹込み、溶媒を留去し
た後エーテル抽出を行った。このエーテル相を飽和炭酸
ナトリウム水溶液と混合し、１時間撹拌した。その後溶
媒を留去した後、残渣をビグリュウー管をつけて減圧蒸
留し、α−メチレン−γ−ブチロラクトンを得た（ＧＬ
Ｃ純度９９％以上）。Example 1 25 parts of diethyl oxalate was added to 100 parts of anhydrous tetrahydrofuran in which 10 parts of sodium ethoxide was dispersed, and then 15 parts of γ-butyrolactone was added dropwise at 15 ° C. or lower, and overnight. I left it. Formaldehyde was blown into the reaction solution, and the solvent was distilled off, followed by extraction with ether. This ether phase was mixed with saturated aqueous sodium carbonate solution and stirred for 1 hour. Then, the solvent was distilled off, and the residue was distilled under reduced pressure with a Vigreux tube attached to obtain α-methylene-γ-butyrolactone (GL
C purity 99% or more).
【００２１】次いで、このα−メチレン−γ−ブチロラ
クトン２０部を、メタクリル酸２０部、ラウリルパーオ
キサイド０．０４０部およびオクチルメルカプタン０．
０４８部と混合した。この混合液をガラスアンプルに入
れ真空下で封管して８０℃のオイルバス中で２４時間重
合反応を行った。重合後アンプルの内部物を５００部の
ジメチルホルムアミドに溶解し、メタノールに注いだ。
次いで、その沈澱した重合体を分離して取り出し、１０
０℃で４８時間真空乾燥してα−メチレン−γ−ブチロ
ラクトンとメタクリル酸とからなる共重合体を得た。得
られた共重合体のガラス転移温度は１６５℃であった。Then, 20 parts of this α-methylene-γ-butyrolactone was added to 20 parts of methacrylic acid, 0.040 part of lauryl peroxide and 0. 0% of octyl mercaptan.
Mixed with 048 parts. This mixed solution was placed in a glass ampoule, sealed under vacuum, and subjected to a polymerization reaction in an oil bath at 80 ° C. for 24 hours. After the polymerization, the inside of the ampoule was dissolved in 500 parts of dimethylformamide and poured into methanol.
The precipitated polymer is then separated and removed, 10
It was vacuum dried at 0 ° C. for 48 hours to obtain a copolymer composed of α-methylene-γ-butyrolactone and methacrylic acid. The glass transition temperature of the obtained copolymer was 165 ° C.
【００２２】［実施例２］実施例１において、メタクリ
ル酸をα−フルオロアクリル酸に代えて用いる以外は、
実施例１と同様にしてα−メチレン−γ−ブチロラクト
ンとα−フルオロアクリル酸とからなる共重合体を得
た。得られた共重合体のガラス転移温度は１７４℃であ
った。[Example 2] In Example 1, except that methacrylic acid was used in place of α-fluoroacrylic acid.
A copolymer of α-methylene-γ-butyrolactone and α-fluoroacrylic acid was obtained in the same manner as in Example 1. The glass transition temperature of the obtained copolymer was 174 ° C.
【００２３】［比較例１］実施例１において、メタクリ
ル酸をメタクリル酸メチルに代えて用いる以外は、実施
例１同様にしてα−メチレン−γ−ブチロラクトンとメ
タクリル酸メチルとからなる共重合体を得た。得られた
共重合体のガラス転移温度は１５３℃であった。Comparative Example 1 A copolymer of α-methylene-γ-butyrolactone and methyl methacrylate was prepared in the same manner as in Example 1 except that methacrylic acid was used instead of methyl methacrylate. Obtained. The glass transition temperature of the obtained copolymer was 153 ° C.
【００２４】[0024]
【発明の効果】本発明の耐熱性樹脂は、高い耐熱性を有
しており、さらにカルボン酸基を有しているため、耐熱
性の濃縮材、凝集剤、イオン交換樹脂、懸濁剤、結合
剤、接着剤などを得るための樹脂として極めて有用であ
る。EFFECTS OF THE INVENTION The heat-resistant resin of the present invention has high heat resistance and further has a carboxylic acid group. Therefore, the heat-resistant concentration material, coagulant, ion exchange resin, suspension agent, It is extremely useful as a resin for obtaining a binder, an adhesive and the like.
フロントページの続き (72)発明者 中村 一己 広島県大竹市御幸町20番１号 三菱レイヨ ン株式会社中央研究所内 (72)発明者 加茂 純 広島県大竹市御幸町20番１号 三菱レイヨ ン株式会社中央研究所内Front page continuation (72) Inventor Kazumi Nakamura 20-1 Miyuki-cho, Otake-shi, Hiroshima Mitsubishi Rayon Co., Ltd. Central Research Laboratory (72) Inventor Jun Kamo 20-1 Miyuki-cho, Otake-shi, Hiroshima Mitsubishi Rayon shares Company Central Research Institute
Claims (1)
（Ａ）と、アクリル酸、メタクリル酸、α−フルオロア
クリル酸およびα−トリフルオロメチルアクリル酸から
なる群より選ばれる少なくとも１種の単量体（Ｂ）とを
重合して得られる耐熱性樹脂。1. An α-methylene-γ-butyrolactone (A) and at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, α-fluoroacrylic acid and α-trifluoromethylacrylic acid ( A heat resistant resin obtained by polymerizing with B).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18653995A JP3580909B2 (en) | 1995-06-30 | 1995-06-30 | Heat resistant resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18653995A JP3580909B2 (en) | 1995-06-30 | 1995-06-30 | Heat resistant resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0912646A true JPH0912646A (en) | 1997-01-14 |
| JP3580909B2 JP3580909B2 (en) | 2004-10-27 |
Family
ID=16190276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18653995A Expired - Lifetime JP3580909B2 (en) | 1995-06-30 | 1995-06-30 | Heat resistant resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3580909B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002249522A (en) * | 2001-02-23 | 2002-09-06 | Nippon Mektron Ltd | Carboxy group-containing fluorocopolymer |
| WO2006025360A1 (en) * | 2004-08-30 | 2006-03-09 | Mitsubishi Rayon Co., Ltd. | Optical copolymer and molded product comprising the same |
| WO2006070824A1 (en) * | 2004-12-27 | 2006-07-06 | Mitsubishi Rayon Co., Ltd. | Polymer composition, plastic optical fiber, plastic optical fiber cable and method for producing plastic optical fiber |
| US8846817B2 (en) | 2010-11-11 | 2014-09-30 | Segetis, Inc. | Ionic polymers, method of manufacture, and uses thereof |
| US20140343222A1 (en) * | 2011-11-11 | 2014-11-20 | Segetis, Inc | Poly(lactone)s, method of manufacture, and uses thereof |
-
1995
- 1995-06-30 JP JP18653995A patent/JP3580909B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002249522A (en) * | 2001-02-23 | 2002-09-06 | Nippon Mektron Ltd | Carboxy group-containing fluorocopolymer |
| WO2006025360A1 (en) * | 2004-08-30 | 2006-03-09 | Mitsubishi Rayon Co., Ltd. | Optical copolymer and molded product comprising the same |
| WO2006070824A1 (en) * | 2004-12-27 | 2006-07-06 | Mitsubishi Rayon Co., Ltd. | Polymer composition, plastic optical fiber, plastic optical fiber cable and method for producing plastic optical fiber |
| KR100878084B1 (en) * | 2004-12-27 | 2009-01-13 | 미츠비시 레이온 가부시키가이샤 | Polymer composition, plastic optical fiber, plastic optical fiber cable and method for producing plastic optical fiber |
| US7512309B2 (en) | 2004-12-27 | 2009-03-31 | Mitsubishi Rayon Co, Ltd. | Polymer composition, plastic optical fiber, plastic optical fiber cable, and method for manufacturing plastic optical fiber |
| JP5340542B2 (en) * | 2004-12-27 | 2013-11-13 | 三菱レイヨン株式会社 | POLYMER MOLDED ARTICLE AND METHOD FOR PRODUCING THE SAME, PLASTIC OPTICAL FIBER, PLASTIC OPTICAL FIBER CABLE, AND METHOD FOR PRODUCING PLASTIC OPTICAL FIBER |
| US8846817B2 (en) | 2010-11-11 | 2014-09-30 | Segetis, Inc. | Ionic polymers, method of manufacture, and uses thereof |
| US20140343222A1 (en) * | 2011-11-11 | 2014-11-20 | Segetis, Inc | Poly(lactone)s, method of manufacture, and uses thereof |
| JP2014533322A (en) * | 2011-11-11 | 2014-12-11 | サジティス・インコーポレイテッド | Poly (lactones), production methods, and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3580909B2 (en) | 2004-10-27 |
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