JPH0597916A - Production of hydrogenated styrenic resin - Google Patents
Production of hydrogenated styrenic resinInfo
- Publication number
- JPH0597916A JPH0597916A JP25679191A JP25679191A JPH0597916A JP H0597916 A JPH0597916 A JP H0597916A JP 25679191 A JP25679191 A JP 25679191A JP 25679191 A JP25679191 A JP 25679191A JP H0597916 A JPH0597916 A JP H0597916A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- silica
- aromatic nucleus
- hydrogenated
- catalyst
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は芳香核水素化率が３０％
以上、１００％未満の高分子量水素化スチレン系樹脂の
製造方法に関するものであり、本発明に斯かる水素化ス
チレン系樹脂は光学及び光エレクトロニクス用材料とし
て好適である。FIELD OF THE INVENTION The present invention has an aromatic nucleus hydrogenation rate of 30%.
As described above, the present invention relates to a method for producing a high molecular weight hydrogenated styrene resin of less than 100%, and the hydrogenated styrene resin according to the present invention is suitable as a material for optical and optoelectronics.
【０００２】[0002]
【従来の技術】スチレン系樹脂を溶媒を用いて水素化触
媒の存在下核水素化することは既に知られている。水素
化触媒としてはロジウム、パラジウム、白金、ルテニウ
ム、レニウム等の金属もしくは金属化合物またはこれら
の金属もしくは金属化合物を活性炭、シリカ、アルミ
ナ、ケイソウ土等の担体に担持した触媒が知られている
（特開平１−１３２６０３号、特開平３−７６７０６
号、特開平３−８１３０１号等）。2. Description of the Related Art It is already known to subject a styrene resin to nuclear hydrogenation using a solvent in the presence of a hydrogenation catalyst. Known hydrogenation catalysts are metals or metal compounds such as rhodium, palladium, platinum, ruthenium, and rhenium, or catalysts in which these metals or metal compounds are supported on a carrier such as activated carbon, silica, alumina, or diatomaceous earth. Kaihei 1-132603, JP-A-3-76706
No. 3-81301).
【０００３】一方、水素化スチレン系樹脂を光学及び光
エレクトロニクス用材料として用いようとする場合、各
種他材料との接着性が必要とされる事が多いが、芳香核
水素化率を１００％とした水素化スチレン系樹脂は接着
性に乏しく、大きい接着性を必要とする用途に不適であ
る。この接着性改良の為には芳香族核水素化率を下げる
ことが有効であるが従来の水素化法では芳香核水素化率
を１００％未満の所定の値に止めた場合、得られた樹脂
が白濁化してしまい所望の低水素化率の高透明な樹脂が
得られないという現状であった。On the other hand, when the hydrogenated styrene resin is used as a material for optical and optoelectronics, it is often necessary to have adhesiveness with various other materials, but the aromatic nucleus hydrogenation rate is 100%. The hydrogenated styrenic resin has poor adhesiveness and is not suitable for applications that require high adhesiveness. In order to improve the adhesiveness, it is effective to reduce the aromatic nucleus hydrogenation rate, but when the aromatic nucleus hydrogenation rate is stopped at a predetermined value of less than 100% by the conventional hydrogenation method, the obtained resin is obtained. However, under the present circumstances, a highly transparent resin having a desired low hydrogenation rate cannot be obtained due to white turbidity.
【０００４】[0004]
【発明が解決しようとする課題】本発明者らは、接着
性、及び透明性に優れた水素化スチレン系樹脂の新規な
製造法を提案すべく鋭意検討の結果、特定のシリカ担体
に担持したパラジウム触媒を用いることにより所望の特
性を有する低水素化率水素化スチレン系樹脂が得られる
ことを見出し、本発明に至った。DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies to propose a novel method for producing a hydrogenated styrene resin having excellent adhesiveness and transparency, and as a result, carried it on a specific silica carrier. It was found that a low hydrogenation rate hydrogenated styrene resin having desired characteristics can be obtained by using a palladium catalyst, and the present invention has been completed.
【０００５】[0005]
【課題を解決するための手段】本発明に係る水素化スチ
レン系樹脂の製造法は担体として粒径が１００μｍ未満
のシリカに担持したパラジウムを用いてスチレン系樹脂
を核水素化する事を特徴とする。本発明においてスチレ
ン系樹脂とは、スチレン単独重合体、又はスチレンを５
０重量％以上含み、スチレンと他の不飽和単量体１種以
上との共重合体をいう。かかる他の不飽和単量体として
は、ブロムスチレン、クロルスチレン、パラメチルスチ
レン、α−メチルスチレン等のスチレン類、アクリル酸
エステル、メタクリル酸エステル等のエステル類、ブタ
ジエン、イソプレン等のブタジエン類、アクリロニトリ
ル類等が例示される。スチレン類としてはα−メチルス
チレンが好ましい。共重合形式は特に限定されず、単純
なランダム共重合体、スチレン−ブタジエン−スチレン
重合体等のブロック共重合体、或いはグラフト共重合体
等が例示され、更にはスチレン単独重合体を含めたこれ
らのスチレン系樹脂のブレンド体であってもよい。The method for producing a hydrogenated styrene resin according to the present invention is characterized in that the styrene resin is nuclear hydrogenated by using palladium supported on silica having a particle size of less than 100 μm as a carrier. To do. In the present invention, the styrene-based resin means a styrene homopolymer or styrene.
A copolymer of styrene and at least one other unsaturated monomer is contained in an amount of 0% by weight or more. Examples of such other unsaturated monomers include styrenes such as bromstyrene, chlorostyrene, paramethylstyrene and α-methylstyrene, esters such as acrylic acid esters and methacrylic acid esters, butadienes such as butadiene and isoprene, Acrylonitriles and the like are exemplified. As the styrenes, α-methylstyrene is preferable. The copolymerization form is not particularly limited, and examples thereof include simple random copolymers, block copolymers such as styrene-butadiene-styrene polymers, and graft copolymers. Furthermore, styrene homopolymers are also included. It may be a blend of styrene resin.
【０００６】本発明においてこのような原料スチレン系
重合体の分子量は数平均分子量で３０，０００以上であ
ることが好ましい。スチレン系重合体の分子量が低過ぎ
ると水素化後得られる樹脂の耐熱性、靱性が低下する。
一方分子量の上限については特に制限はないが通常の場
合４０００００以下であることが望ましい。In the present invention, the molecular weight of such a raw material styrene polymer is preferably 30,000 or more in terms of number average molecular weight. If the molecular weight of the styrene-based polymer is too low, the heat resistance and toughness of the resin obtained after hydrogenation will decrease.
On the other hand, the upper limit of the molecular weight is not particularly limited, but in the usual case, it is preferably 400000 or less.
【０００７】本発明における反応溶媒としては水素化条
件で安定であり、かつ上記スチレン系樹脂を溶解するも
のであればよく、具体的には、シクロヘキサン、シクロ
オクタン、メチルシクロヘキサン、デカリン、テトラリ
ン等の炭化水素類、テトラヒドロフラン、ジオキサン、
エチレングリコール、ジメチルエーテル等のエーテル
類、酢酸メチル、酢酸ブチル等のエステル類が例示され
る。これらの溶媒を２種以上用いて混合溶媒として用い
てもよい。The reaction solvent in the present invention may be any solvent which is stable under hydrogenation conditions and dissolves the styrene resin, and specific examples thereof include cyclohexane, cyclooctane, methylcyclohexane, decalin and tetralin. Hydrocarbons, tetrahydrofuran, dioxane,
Examples thereof include ethers such as ethylene glycol and dimethyl ether, and esters such as methyl acetate and butyl acetate. You may use it as a mixed solvent using 2 or more types of these solvents.
【０００８】本発明で用いられる水素化触媒は、１００
μｍ未満の粒径を有しているシリカに担持した、パラジ
ウム触媒が用いられる。担体の粒径は小さすぎると水素
化反応後の重合体含有高粘性溶液からの触媒の分離が困
難になるので、好ましくは５μｍ以上である。また、シ
リカの粒径が１００μｍ以上であると水素化して得られ
た樹脂が白濁し、本願発明の高透明重合体が得られな
い。The hydrogenation catalyst used in the present invention is 100
A palladium catalyst supported on silica having a particle size of less than μm is used. If the particle size of the carrier is too small, it becomes difficult to separate the catalyst from the polymer-containing highly viscous solution after the hydrogenation reaction. Therefore, it is preferably 5 μm or more. Further, when the particle size of silica is 100 μm or more, the resin obtained by hydrogenation becomes cloudy and the highly transparent polymer of the present invention cannot be obtained.
【０００９】シリカの粒径は好ましくは７０μｍ未満で
ある。また、水素化活性の向上、及びより低水添率にお
いても透明な重合体を得るという観点から、シリカの比
表面積は１００ｍ2 ／ｇより大である事が好ましく、平
均細孔径は１００〜５００Åである事が好ましい。尚、
比表面積は、窒素吸着量を測定し、ＢＥＴ式を用いて算
出することとし、平均細孔径は水銀圧入法により測定す
るものとする。The particle size of silica is preferably less than 70 μm. Further, from the viewpoint of improving hydrogenation activity and obtaining a transparent polymer even at a lower hydrogenation rate, the specific surface area of silica is preferably larger than 100 m 2 / g, and the average pore diameter is 100 to 500 Å. Is preferred. still,
The specific surface area shall be calculated by measuring the nitrogen adsorption amount and using the BET formula, and the average pore diameter shall be measured by the mercury porosimetry method.
【００１０】本発明におけるシリカの粒径の定義は下記
の通りである。即ち、フルイにより所望の粒径のシリカ
を得るが、その際、用いたフルイのメッシュのサイズ
（μｍ）をもって粒径とする。例えば粒径が３７〜６３
μｍのシリカとは、目の粗さが６３μｍのフルイを通過
し、３７μｍのフルイ上に残ったシリカを言う。パラジ
ウム金属のシリカ担体への担持方法は、通常の担体担持
法を用いれば良い。例えばパラジウムの各種塩の水溶液
等を前記シリカ担体に含浸させた後還元すること等によ
ってシリカ担持触媒が得られる。The definition of the particle size of silica in the present invention is as follows. That is, silica having a desired particle size is obtained by sieving, and the size (μm) of the sieving mesh used is used as the particle size. For example, the particle size is 37-63
The silica having a size of μm means silica which has passed through a sieve having a mesh of 63 μm and remains on the sieve having a size of 37 μm. As a method for supporting the palladium metal on the silica carrier, an ordinary carrier supporting method may be used. For example, the silica-supported catalyst can be obtained by impregnating the silica carrier with an aqueous solution of various salts of palladium or the like and then reducing the same.
【００１１】シリカ担体へのパラジウム金属の担持量は
通常担体当り０．００１〜３０重量％であり好ましくは
０．０１〜１０重量％である。水素化反応は、粉末触媒
を用いてバッチ式オートクレーブ中で行ってもよく、ま
た、成形触媒を用いて連続固定床で行ってもよい。スチ
レン系樹脂を前記反応溶媒に５〜５０重量％の濃度で溶
解し、触媒を樹脂に対して１〜１００重量％添加する。
反応温度は５０〜３００℃であり、好ましくは、１００
〜２５０℃である。水素圧は大気圧〜３００kg／cm2 の
範囲であり、好ましくは５〜１５０kg／cm2 の範囲であ
る。バッチ式オートクレーブ中での反応は水素を蓄圧器
から２次圧調節器を用いオートクレーブに供給し、定圧
で反応を行うことにより、蓄圧器の圧力減少から水素化
率のコントロールが可能である。The amount of palladium metal supported on the silica carrier is usually 0.001 to 30% by weight, preferably 0.01 to 10% by weight, based on the carrier. The hydrogenation reaction may be carried out in a batch autoclave using a powder catalyst, or may be carried out in a continuous fixed bed using a shaped catalyst. The styrene resin is dissolved in the reaction solvent at a concentration of 5 to 50% by weight, and the catalyst is added to the resin in an amount of 1 to 100% by weight.
The reaction temperature is 50 to 300 ° C., preferably 100.
~ 250 ° C. Hydrogen pressure is in the range of atmospheric pressure ~300kg / cm 2, preferably in the range of 5~150kg / cm 2. For the reaction in the batch type autoclave, hydrogen is supplied from the pressure accumulator to the autoclave using the secondary pressure regulator, and the reaction is performed at a constant pressure, whereby the hydrogenation rate can be controlled from the pressure decrease in the pressure accumulator.
【００１２】水素化、反応終了後、担体担持触媒を濾過
法等により水素化スチレン樹脂含有溶液から分離し、し
かるのち、水素化スチレン樹脂を分離する。本発明にお
ける水素化ポリスチレンの芳香核水素化率は３０％以上
〜１００％未満であり、好ましくは、５０％以上〜１０
０％未満であり、特に６０％〜９０％の範囲でその効果
が顕著である。After the completion of hydrogenation and reaction, the carrier-supported catalyst is separated from the hydrogenated styrene resin-containing solution by a filtration method or the like, and then the hydrogenated styrene resin is separated. The aromatic nucleus hydrogenation rate of the hydrogenated polystyrene in the present invention is 30% or more and less than 100%, and preferably 50% or more and 10% or more.
It is less than 0%, and the effect is particularly remarkable in the range of 60% to 90%.
【００１３】[0013]
【実施例】以下本発明を実施例により更に詳細に説明す
るが本発明はその要旨を越えない限りこれら等の実施例
に限定されるものではない。なお、実施例中の核水素化
率の算定は、紫外線吸収スペクトル分析により行い、生
成物の透明性は、得られた水素化スチレン系樹脂を加熱
成形し、厚さ１mmの板を作製し、７８０nmの可視光の透
過率を測定した。EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples unless it exceeds the gist. The calculation of the nuclear hydrogenation rate in the examples was carried out by ultraviolet absorption spectrum analysis, and the transparency of the product was determined by heat-molding the obtained hydrogenated styrene resin to prepare a plate with a thickness of 1 mm. The transmittance of visible light at 780 nm was measured.
【００１４】実施例１ 担体として比表面積１９０ｍ2 ／ｇ、細孔容積１．４０
ml／ｇ、平均細孔径２９５Å、粒度１０５〜２１０μｍ
のシリカ（洞海化学社製Ｄ−１５０−３００Ａ）をメノ
ウ乳鉢で粉砕し、ふるいで分級し、３７〜６３μｍのシ
リカを得た。このものをＰｄＣｌ2 の水溶液に含浸した
後、窒素雰囲気下で１５０℃で２時間焼成後、水素雰囲
気下で３００℃で２時間還元して５％Pd／ＳｉＯ2 を得
た。Example 1 A carrier having a specific surface area of 190 m 2 / g and a pore volume of 1.40
ml / g, average pore size 295Å, particle size 105-210 μm
Silica (D-150-300A manufactured by Dokai Kagaku Co., Ltd.) was crushed in an agate mortar and classified by a sieve to obtain silica of 37 to 63 μm. After impregnating this with an aqueous solution of PdCl 2 , it was baked in a nitrogen atmosphere at 150 ° C. for 2 hours and then reduced in a hydrogen atmosphere at 300 ° C. for 2 hours to obtain 5% Pd / SiO 2 .
【００１５】数平均分子量７．６万のスチレン樹脂（三
菱化成ポリテック（株）製：商品名ＹＧ−６６）１３５
ｇをテトラヒドロフラン３３８ｇに溶解し、上記の方法
で調製した触媒９．０ｇと共に１リットル誘導攪拌オー
トクレーブに仕込み、攪拌速度１０００ｒｐｍ、水素圧
力１００kg／cm2 −Ｇ、温度１７０℃にて定圧反応を
４．３時間行った。反応後水素化ポリスチレン含有反応
液をテトラヒドロフラン１リットルで希釈し濾過により
触媒を除去した。多量のメタノール中に反応液を注ぎ水
素化ポリスチレンを回収した。このものの水素化率は６
９．５％であり加熱成形品の光線透過率は９１％であっ
た。Styrene resin having a number average molecular weight of 76,000 (trade name: YG-66, manufactured by Mitsubishi Kasei Polytech Co., Ltd.) 135
g of tetrahydrofuran was dissolved in 338 g of tetrahydrofuran, and charged into a 1-liter induction stirring autoclave together with 9.0 g of the catalyst prepared by the above method, and a constant pressure reaction was performed at a stirring speed of 1000 rpm, a hydrogen pressure of 100 kg / cm 2 -G and a temperature of 170 ° C. I went for 3 hours. After the reaction, the reaction solution containing hydrogenated polystyrene was diluted with 1 liter of tetrahydrofuran and the catalyst was removed by filtration. The reaction solution was poured into a large amount of methanol to collect hydrogenated polystyrene. The hydrogenation rate of this product is 6
It was 9.5%, and the light transmittance of the heat-molded product was 91%.
【００１６】実施例２ 数平均分子量６．７万のスチレン樹脂（三菱化成ポリテ
ック（株）、商品名ＨＨ−１０２）３０ｇをテトラヒド
ロフラン７５ｇに溶解し、実施例１で使用した触媒２ｇ
と共に２００ml誘導攪拌オートクレーブに仕込み、攪拌
速度１０００ｒｐｍ、水素圧力１００kg／cm2 −Ｇ、温
度１７０℃にて定圧反応を４．７時間行った。反応後水
素化ポリスチレン含有反応液をテトラヒドロフラン２０
０mlで希釈し、濾過により触媒を除去した。多量のメタ
ノール中に反応液を注ぎ水素化ポリスチレンを回収し
た。このものの水素化率は７０．０％であり加熱成形品
の光線透過率は９１．５％であった。Example 2 30 g of a styrene resin having a number average molecular weight of 677,000 (trade name: HH-102, manufactured by Mitsubishi Kasei Polytech Co., Ltd.) was dissolved in 75 g of tetrahydrofuran, and 2 g of the catalyst used in Example 1 was dissolved.
A 200 ml induction stirring autoclave was charged together with this, and a constant pressure reaction was carried out for 4.7 hours at a stirring speed of 1000 rpm, a hydrogen pressure of 100 kg / cm 2 -G and a temperature of 170 ° C. After the reaction, the reaction liquid containing hydrogenated polystyrene was added to tetrahydrofuran 20
Dilute with 0 ml and remove the catalyst by filtration. The reaction solution was poured into a large amount of methanol to collect hydrogenated polystyrene. The hydrogenation ratio of this product was 70.0%, and the light transmittance of the heat-formed product was 91.5%.
【００１７】比較例１ 比表面積１９０ｍ2 ／ｇ、細孔容積１．４０ml／ｇ、平
均細孔径２９５Å、粒度１０５〜２１０μｍのシリカ
（洞海化学社製Ｄ−１５０−３００Ａ）を粉砕すること
なくそのまま用い、実施例１と同様の方法で触媒を調整
した。Comparative Example 1 Silica having a specific surface area of 190 m 2 / g, a pore volume of 1.40 ml / g, an average pore diameter of 295Å and a particle size of 105 to 210 μm (D-150-300A manufactured by Dokai Kagaku Co.) was not crushed. Used as it was, a catalyst was prepared in the same manner as in Example 1.
【００１８】数平均分子量７．６万のスチレン樹脂（三
菱化成ポリテック（株）製、ＹＧ−６６）３０ｇをテト
ラヒドロフラン７５ｇに溶解し、上記触媒２．０ｇと共
に２００ml誘導攪拌オートクレーブに仕込み、攪拌速度
１０００ｒｐｍ、水素圧力１００kg／cm2 −Ｇ、温度１
７０℃にて、定圧反応を３．７時間行った。反応後、実
施例２と同様の後処理を行い、水素化ポリスチレンを回
収した。このものの水素化率は６９．５％であり、光線
透過率は０．２１％であった。30 g of a styrene resin having a number average molecular weight of 76,000 (YG-66, manufactured by Mitsubishi Kasei Polytech Co., Ltd.) was dissolved in 75 g of tetrahydrofuran, charged with a 200 ml induction stirring autoclave together with 2.0 g of the above catalyst, and the stirring speed was 1000 rpm. , Hydrogen pressure 100kg / cm 2 -G, temperature 1
The constant pressure reaction was carried out at 70 ° C. for 3.7 hours. After the reaction, the same post-treatment as in Example 2 was performed to recover hydrogenated polystyrene. The hydrogenation rate of this product was 69.5%, and the light transmittance was 0.21%.
【００１９】比較例２ 比較例１の触媒を用いた以外は実施例２と同様の条件で
反応を６．９時間行った。得られた水素化ポリスチレン
の水素化率は７３．９％であり光線透過率は０．２３％
であった。Comparative Example 2 The reaction was carried out for 6.9 hours under the same conditions as in Example 2 except that the catalyst of Comparative Example 1 was used. The hydrogenated polystyrene obtained had a hydrogenation rate of 73.9% and a light transmittance of 0.23%.
Met.
【００２０】実施例３ 担体として比表面積２１７ｍ2 ／ｇ、細孔容積１．６０
ml／ｇ、平均細孔径２９５Å、粒径２０〜５０μｍの球
状シリカ（洞海化学社製Ｄ−４０−３００Ａ）に実施例
−１と同様の方法でパラジウムを担持した。この触媒を
用いる以外は実施例−１と同様にして水素化率６８．３
％の水素化ポリスチレンを得た。このものの、光線透過
率は９０．８％であった。Example 3 A carrier having a specific surface area of 217 m 2 / g and a pore volume of 1.60
Palladium was loaded on spherical silica (D-40-300A manufactured by Dokai Kagaku Co., Ltd.) having a volume of ml / g, an average pore size of 295Å and a particle size of 20 to 50 μm in the same manner as in Example-1. The hydrogenation rate was 68.3 in the same manner as in Example 1 except that this catalyst was used.
% Hydrogenated polystyrene was obtained. However, the light transmittance was 90.8%.
【００２１】[0021]
【発明の効果】本発明にかかわる特定のシリカに担持し
たパラジウム触媒を用いると、低水素化率で透明な水素
化ポリスチレン系樹脂を製造することができる。EFFECT OF THE INVENTION By using the palladium catalyst supported on the specific silica according to the present invention, a transparent hydrogenated polystyrene resin having a low hydrogenation rate can be produced.
Claims (1)
担持させたパラジウム触媒を用い溶媒存在下部分的に水
素化し、芳香核水素化率３０％以上、１００％未満の水
素化スチレン系樹脂を製造する方法において担体として
粒径が１００μｍ未満のシリカを用いる事を特徴とする
水素化スチレン系樹脂の製造方法。1. A hydrogenated styrene resin having an aromatic nucleus hydrogenation rate of 30% or more and less than 100% by partially hydrogenating in the presence of a solvent using a palladium catalyst in which an aromatic nucleus of a styrene resin is supported on a silica carrier. A method for producing a hydrogenated styrenic resin, characterized in that silica having a particle size of less than 100 μm is used as a carrier in the method for producing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03256791A JP3094555B2 (en) | 1991-10-03 | 1991-10-03 | Method for producing hydrogenated styrene resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03256791A JP3094555B2 (en) | 1991-10-03 | 1991-10-03 | Method for producing hydrogenated styrene resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0597916A true JPH0597916A (en) | 1993-04-20 |
| JP3094555B2 JP3094555B2 (en) | 2000-10-03 |
Family
ID=17297495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03256791A Expired - Fee Related JP3094555B2 (en) | 1991-10-03 | 1991-10-03 | Method for producing hydrogenated styrene resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3094555B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003212923A (en) * | 2002-01-29 | 2003-07-30 | Nippon Zeon Co Ltd | Alicyclic-structure-containing polymer hydrogenate and method for producing the same |
| EP1702934A1 (en) * | 2005-03-14 | 2006-09-20 | Mitsubishi Gas Chemical Company, Inc. | Method of producing hydrogenated polymers |
| JP2006291184A (en) * | 2005-03-14 | 2006-10-26 | Mitsubishi Gas Chem Co Inc | Manufacturing method of hydrogenated polymer |
| JP2011057981A (en) * | 2009-08-28 | 2011-03-24 | Tsrc Corp | Method for selectively hydrogenating block copolymer and composition thereby |
| TWI396701B (en) * | 2006-02-27 | 2013-05-21 | Mitsubishi Gas Chemical Co | Manufacturing method of hydrogenated polymer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8575277B2 (en) | 2007-08-06 | 2013-11-05 | Mitsubishi Gas Chemical Company, Inc. | Process for production of nucleus-hydrogenated aromatic vinyl/(meth)acrylate copolymers |
-
1991
- 1991-10-03 JP JP03256791A patent/JP3094555B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003212923A (en) * | 2002-01-29 | 2003-07-30 | Nippon Zeon Co Ltd | Alicyclic-structure-containing polymer hydrogenate and method for producing the same |
| EP1702934A1 (en) * | 2005-03-14 | 2006-09-20 | Mitsubishi Gas Chemical Company, Inc. | Method of producing hydrogenated polymers |
| JP2006291184A (en) * | 2005-03-14 | 2006-10-26 | Mitsubishi Gas Chem Co Inc | Manufacturing method of hydrogenated polymer |
| TWI396701B (en) * | 2006-02-27 | 2013-05-21 | Mitsubishi Gas Chemical Co | Manufacturing method of hydrogenated polymer |
| JP2011057981A (en) * | 2009-08-28 | 2011-03-24 | Tsrc Corp | Method for selectively hydrogenating block copolymer and composition thereby |
| JP2015071773A (en) * | 2009-08-28 | 2015-04-16 | ティーエスアールシー コーポレイション | Method for selectively hydrogenating block copolymer and composition thereof |
| US9051396B2 (en) | 2009-08-28 | 2015-06-09 | Tsrc Corporation | Partially hydrogenated polymer and method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3094555B2 (en) | 2000-10-03 |
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