JPH0257805B2 - - Google Patents
Info
- Publication number
- JPH0257805B2 JPH0257805B2 JP61068517A JP6851786A JPH0257805B2 JP H0257805 B2 JPH0257805 B2 JP H0257805B2 JP 61068517 A JP61068517 A JP 61068517A JP 6851786 A JP6851786 A JP 6851786A JP H0257805 B2 JPH0257805 B2 JP H0257805B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- polymer
- block copolymer
- modified
- 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.)
- Expired - Lifetime
Links
- 229920001400 block copolymer Polymers 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- -1 vinyl aromatic hydrocarbon Chemical class 0.000 claims description 9
- 238000006011 modification reaction Methods 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 229920005992 thermoplastic resin Polymers 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000004925 denaturation Methods 0.000 description 2
- 230000036425 denaturation Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
〔産業上の利用分野〕
本発明は、ビニル芳香族化合物と共役ジエンか
らなるブロツク共重合体又は該ブロツク共重合体
と熱可塑性樹脂との混合物を不飽和カルボン酸及
びその誘導体から選ばれた少なくとも１種の変性
剤で変換する重合体の変性方法に関する。
〔従来の技術〕
従来より、樹脂あるいはゴムを官能性に富む不
飽和カルボン酸化合物等、例えばマレイン酸化合
物で変性し、接着性、グリーン強度などを改善す
る試みが数多くなされている。例えば特開昭50−
56427号にはラジカル開始剤あるいは加熱によつ
てラジカルを発生させ、ゴム展開油の共存下にブ
タジエンとスチレンからなるブロツク共重合体を
マレイン化する方法が示唆されている。又、特開
昭55−13720号、特開昭55−25315号にはブタジエ
ンとスチレンからなるブロツク共重合体をラジカ
ル重合触媒の存在下、有機溶媒中にてマレイン化
する方法が開示されている。更に、特開昭52−
123443号にはラジカル開始剤の存在下、スクリユ
ー型押出機内においてポリエチレンと共にブタジ
エンとスチレンからなるブロツク共重合体をマレ
イン化する方法も示唆されている。
〔発明が解決しようとする問題点〕
しかしながら、これら何れの方法もラジカル発
生下でマレイン化するため、得られる変性ブロツ
ク共重合体のゲル化が避け難い。そして変性ブロ
ツク共重合体は、熱可塑性ゴムとしての性質、例
えば溶融流動特性や外観特性を著しく低下させる
結果となる。
この様な状況下において、本発明者は上記問題
を解決すべく鋭意研究を重ねた結果、スクリユー
押出機を用い、ラジカル開始剤の不存在下特定の
反応条件下で変性反応を行なうと溶融特性に優
れ、トルエン不溶分の少ない変性重合体が得られ
ることを見い出し、既に特開昭55−38803号及び
特開昭55−60511号に開示した。しかしながら、
これらに開示された方法で得られた変性ブロツク
共重合体は色調が必ずしも良好でなくその改良が
必要であつた。
〔問題点を解決するための手段及び作用〕
かかる現状において、本発明者は色調、溶融特
性に優れ、ゲル状物質の混在が少ない変性重合体
を得る方法について検討し、特定のフエノール系
化合物を特定量使用することにより、今までの酸
化防止剤類からはとうてい予測できない効果が発
揮されることを見い出し、本発明に至つた。
即ち、本発明は、少なくとも１個のビニル芳香
族炭化水素を主とする重合体セグメントと少なく
とも１個の共役ジエンを主とする重合体セグメン
トを有し、ビニル芳香族炭化水素含有量が５〜60
重量％であるブロツク共重合体又は該ブロツク共
重合体と熱可塑性樹脂若しくはゴム状重合体との
混合重量比99／１〜３／97の混合物100重量部当
り、不飽和カルボン酸及びその誘導体から選ばれ
た少なくとも１種の変性剤0.1〜100重量部を180
〜320℃の温度で反応させるに際し、前記ブロツ
ク共重合体又は前記混合物100重量部当り0.05〜
２重量部の一般式〔〕、〔〕、〔〕及び〔〕で
示さ
れるフエノール系化合物から選ばれた少なくとも
１種、0.05〜２重量部のリン系安定剤の存在下で
変性反応を行なうことを特徴とする重合体の変性
方法を提供する。
（上記各式において、R1は炭素数１〜４のアル
キル基を、R2は炭素数２〜20のアルキル基を示
す。）
（上式においてR3は
[Industrial Application Field] The present invention provides a block copolymer comprising a vinyl aromatic compound and a conjugated diene, or a mixture of the block copolymer and a thermoplastic resin, with at least one selected from unsaturated carboxylic acids and derivatives thereof. This invention relates to a method for modifying a polymer using one type of modifier. [Prior Art] Many attempts have been made to improve adhesiveness, green strength, etc. by modifying resins or rubbers with highly functional unsaturated carboxylic acid compounds, such as maleic acid compounds. For example, Japanese Patent Application Publication No. 1973-
No. 56427 suggests a method of maleating a block copolymer of butadiene and styrene in the coexistence of a rubber developing oil by generating radicals using a radical initiator or heating. Furthermore, JP-A-55-13720 and JP-A-55-25315 disclose a method of maleating a block copolymer of butadiene and styrene in an organic solvent in the presence of a radical polymerization catalyst. . Furthermore, JP-A-52-
No. 123443 also suggests a method of maleating a block copolymer consisting of butadiene and styrene together with polyethylene in a screw type extruder in the presence of a radical initiator. [Problems to be Solved by the Invention] However, in both of these methods, maleation occurs under the generation of radicals, so gelation of the resulting modified block copolymer is unavoidable. The modified block copolymer results in a significant deterioration in properties as a thermoplastic rubber, such as melt flow characteristics and appearance characteristics. Under these circumstances, the inventor of the present invention has conducted extensive research to solve the above problems, and has found that when a modification reaction is carried out under specific reaction conditions in the absence of a radical initiator using a screw extruder, the melting properties It has been discovered that a modified polymer with excellent properties and a small amount of toluene insoluble matter can be obtained, and this has already been disclosed in JP-A-55-38803 and JP-A-55-60511. however,
The modified block copolymers obtained by the methods disclosed in these publications did not necessarily have good color tone and needed to be improved. [Means and effects for solving the problems] Under the current circumstances, the present inventors have investigated a method for obtaining a modified polymer that has excellent color tone and melting properties and contains less gel-like substances, and has developed a method for obtaining a modified polymer with a specific phenolic compound. It has been discovered that when used in a specific amount, effects that cannot be predicted from conventional antioxidants can be exhibited, leading to the present invention. That is, the present invention has at least one polymer segment mainly composed of vinyl aromatic hydrocarbon and at least one polymer segment mainly composed of conjugated diene, and the vinyl aromatic hydrocarbon content is 5 to 5. 60
From unsaturated carboxylic acids and derivatives thereof, per 100 parts by weight of a block copolymer or a mixture of the block copolymer and a thermoplastic resin or rubbery polymer at a mixed weight ratio of 99/1 to 3/97. 0.1 to 100 parts by weight of at least one selected modifier
0.05 to 100 parts by weight of the block copolymer or mixture when reacting at a temperature of ~320°C
Conducting the modification reaction in the presence of 2 parts by weight of at least one phenol compound represented by the general formulas [], [], [] and [] and 0.05 to 2 parts by weight of a phosphorus stabilizer. A method for modifying a polymer is provided. (In each of the above formulas, R 1 represents an alkyl group having 1 to 4 carbon atoms, and R 2 represents an alkyl group having 2 to 20 carbon atoms.) (In the above formula, R 3 is
本発明は、不飽和カルボン酸或いはその誘導体
で変性された重合体を安定的に得る工業的製造方
法を提供するのみならず、色調、溶融粘度特性に
優れ、ゲル状物質の混在が少ない変性重合体が得
られる。本発明により得られる変性重合体は、不
飽和カルボン酸或いはその誘導体で変性されてい
ることを生かして、各種熱可塑性樹脂・熱硬化性
樹脂の改質材、履物の素材、粘着剤・接着剤の素
材、アスフアルトの改質材、電線ケーブルの素
材、加硫ゴムの改質材等に利用できる。
〔実施例〕
本発明を更に詳細に説明するために以下に実施
例を示すが、これらの実施例は本発明によつて得
られる優れた効果を示すためのものであつて、本
発明の範囲を限定するものではない。尚、本発明
の実施例で使用するブロツク共重合体は、次のよ
うにして製造した。
〔ブロツク共重合体(A)〕
窒素ガス雰囲気下において、１，３−ブタジエ
ン15重量部とスチレン20重量部を含むｎ−ヘキサ
ン溶液にｎ−ブチルリチウムを添加し、70℃で２
時間重合した後、更に１，３−ブタジエン45重量
部とスチレン20重量部を含むｎ−ヘキサン溶液を
加えて70℃で２時間重合した。得られた重合体は
スチレン含有量40重量％、MI(G)10ｇ／10minの
Ｂ−Ａ−Ｂ−Ａ構造のブロツク共重合体であつ
た。
〔ブロツク共重合体(B)〕
窒素ガス雰囲気下において、スチレン30重量部
を含むシクロヘキサン溶液にｎ−ブチルリチウム
を添加し、70℃で１時間重合した後、１，３−ブ
タジエン70重量部を含むシクロヘキサン溶液を加
えて70℃で２時間重合した。その後テトラクロル
シランを、使用したｎ−ブチルリチウムの1/4モ
ル添加してスチレン含有量30重量％、MI(G)20
ｇ／10minの（Ａ−Ｂ）−4Si構造のブロツク共重
合体を得た。
実施例１〜９及び比較例１〜４
ブロツク共重合体(A)100重量部と無水マレイン
酸２重量部及び第１表に示された安定剤類を配合
した後、30mmφ押出機に供給し240℃でマレイン
化反応を行なつた。押出機内の平均滞留時間は約
90秒であつた。未反応の無水マレイン酸は押出機
の先端に近い部分に付設されたベント部より減圧
により除去し、変性重合体中の残存無水マレイン
酸量は0.2重量％以下になる様にした。
得られた変性ブロツク共重合体に付加している
無水マレイン酸の量はいずれも0.4〜0.6重量％で
あつた。又得られた変性ブロツク共重合体の溶融
粘度保持率、トルエン不溶分及び色調を第１表に
示した。本発明で規定するフエノール系化合物の
存在下で変性反応を行なつた変性ブロツク共重合
体は色調及び溶融粘度特性に優れ、トルエン不溶
のゲル状物質の混在が少ないことが分かる。
尚、実施例１において、未反応の無水マレイン
酸をベント部より除去する操作を行なわなかつた
場合、得られた変性重合体ペレツトのｂ値は37で
色調はやや劣つていた。
The present invention not only provides an industrial production method for stably obtaining a polymer modified with an unsaturated carboxylic acid or its derivative, but also provides a modified polymer with excellent color tone and melt viscosity characteristics and with less inclusion of gel-like substances. A union is obtained. The modified polymer obtained by the present invention is modified with an unsaturated carboxylic acid or its derivative, and can be used as a modification material for various thermoplastic resins and thermosetting resins, as a material for footwear, and as a pressure-sensitive adhesive. It can be used as a material for asphalt, as a modifying material for electric wires and cables, as a modifying material for vulcanized rubber, etc. [Examples] Examples are shown below to explain the present invention in more detail, but these examples are intended to demonstrate the excellent effects obtained by the present invention, and do not exceed the scope of the present invention. It is not limited to. The block copolymers used in the examples of the present invention were produced as follows. [Block copolymer (A)] In a nitrogen gas atmosphere, n-butyllithium was added to an n-hexane solution containing 15 parts by weight of 1,3-butadiene and 20 parts by weight of styrene, and the mixture was heated at 70°C for 2 hours.
After polymerization for an hour, an n-hexane solution containing 45 parts by weight of 1,3-butadiene and 20 parts by weight of styrene was further added, and the mixture was polymerized at 70 DEG C. for 2 hours. The obtained polymer was a block copolymer having a B-A-B-A structure with a styrene content of 40% by weight and an MI(G) of 10 g/10 min. [Block copolymer (B)] In a nitrogen gas atmosphere, n-butyllithium was added to a cyclohexane solution containing 30 parts by weight of styrene, and after polymerization at 70°C for 1 hour, 70 parts by weight of 1,3-butadiene was added. A cyclohexane solution containing the mixture was added and polymerization was carried out at 70°C for 2 hours. After that, tetrachlorosilane was added to 1/4 mole of the n-butyllithium used to make the styrene content 30% by weight and MI(G)20.
A block copolymer having an (A-B) -4Si structure was obtained at a rate of g/10 min. Examples 1 to 9 and Comparative Examples 1 to 4 After blending 100 parts by weight of block copolymer (A), 2 parts by weight of maleic anhydride, and the stabilizers shown in Table 1, the mixture was fed to a 30 mmφ extruder. The maleation reaction was carried out at 240°C. The average residence time in the extruder is approximately
It was hot in 90 seconds. Unreacted maleic anhydride was removed under reduced pressure from a vent installed near the tip of the extruder, so that the amount of residual maleic anhydride in the modified polymer was 0.2% by weight or less. The amount of maleic anhydride added to the obtained modified block copolymers was 0.4 to 0.6% by weight in each case. Table 1 also shows the melt viscosity retention, toluene insoluble content, and color tone of the modified block copolymer obtained. It can be seen that the modified block copolymer subjected to the modification reaction in the presence of the phenolic compound specified in the present invention has excellent color tone and melt viscosity characteristics, and contains less toluene-insoluble gel-like substances. In Example 1, when the operation of removing unreacted maleic anhydride from the vent part was not performed, the b value of the modified polymer pellets obtained was 37 and the color tone was slightly inferior.
【表】【table】
【表】【table】
【表】
比較例 ６
実施例１においてフエノール系化合物の代わり
にフエノチアジン0.5重量部を用いて実施例１と
同様の方法により変性反応を行なつた。得られた
変性ブロツク共重合体の溶融粘度保持率、トルエ
ン不溶分はいずれも良好（ランク◎）で、色調は
ランク△のレベルであつた。上記変性ブロツク共
重合体を１週間日光にさらしたところ赤褐色に変
性し、色調に劣るものであつた（ランク×）。尚、
実施例１〜９の変性ブロツク共重合体は同様の日
光暴露条件下でほとんど変色は認められなかつ
た。
比較例 ７
実施例１の変性反応を330℃で行なつたところ、
変性反応時ゲル化が起こり、スムーズな変性反応
が実施できなかつた。
実施例 10〜22
第２表に示した配合処理法に従い、ブロツク共
重合体と熱可塑性樹脂或いはゴム状重合体との混
合物100重量部に無水マレイン酸５重量部及び安
定剤類を配合した後、シリンダー温度が第２表に
示された温度に設定されている30mmφ押出機に供
給し、マレイン化反応を行なつた。押出機内の平
均滞留時間は60〜120秒の範囲に調整した。又未
反応の無水マレイン酸は押出機の先端に近い部分
に付設されたベント部より減圧により除去し、変
性重合体中の残存無水マレイン酸量が0.3重量％
以下になる様にした。
得られた変性ブロツク共重合体に付加している
無水マレイン酸の量は0.2〜1.5重量％であつた。
又、得られた変性ブロツク共重合体の溶融粘度は
本発明の範囲外の安定剤類を用いて得た変性ブロ
ツク共重合体より格段に優れた溶融粘度を示し、
また色調も良好でゲル状の不溶物の混在も少なか
つた。
尚、実施例10及び15において安定剤類Ｃの変わ
りに安定剤類Ａを用いた場合には変性重合体のメ
ルトフローと比較重合体のメルトフローとの差が
２ｇ／10min以上で、良り優れた溶融粘度特性を
示した。[Table] Comparative Example 6 A modification reaction was carried out in the same manner as in Example 1 except that 0.5 parts by weight of phenothiazine was used in place of the phenol compound. The melt viscosity retention and toluene insoluble content of the obtained modified block copolymer were both good (rank ◎), and the color tone was at the rank △ level. When the above-mentioned modified block copolymer was exposed to sunlight for one week, it changed to a reddish-brown color and had an inferior color tone (rank x). still,
The modified block copolymers of Examples 1 to 9 showed almost no discoloration under similar sunlight exposure conditions. Comparative Example 7 When the modification reaction of Example 1 was carried out at 330°C,
Gelation occurred during the denaturation reaction, making it impossible to carry out the denaturation reaction smoothly. Examples 10 to 22 After blending 5 parts by weight of maleic anhydride and stabilizers with 100 parts by weight of a mixture of block copolymer and thermoplastic resin or rubbery polymer according to the compounding method shown in Table 2. The mixture was fed to a 30 mmφ extruder whose cylinder temperature was set to the temperature shown in Table 2, and a maleation reaction was carried out. The average residence time in the extruder was adjusted to a range of 60 to 120 seconds. In addition, unreacted maleic anhydride was removed under reduced pressure from a vent installed near the tip of the extruder, and the amount of residual maleic anhydride in the modified polymer was reduced to 0.3% by weight.
I made it look like the following. The amount of maleic anhydride added to the obtained modified block copolymer was 0.2 to 1.5% by weight.
Furthermore, the melt viscosity of the obtained modified block copolymer was significantly superior to that of modified block copolymers obtained using stabilizers outside the range of the present invention,
In addition, the color tone was good and there was little inclusion of gel-like insoluble matter. In addition, in Examples 10 and 15, when stabilizer A was used instead of stabilizer C, the difference between the melt flow of the modified polymer and the melt flow of the comparative polymer was 2 g/10 min or more, which was good. It showed excellent melt viscosity properties.
【表】【table】
Claims (1)
とする重合体セグメントと少なくとも１個の共役
ジエンを主とする重合体セグメントを有し、ビニ
ル芳香族炭化水素含有量が５〜60重量％であるブ
ロツク共重合体又は該ブロツク共重合体と熱可塑
性樹脂若しくはゴム状重合体との混合重量比99／
１〜３／97の混合物100重量部当り、不飽和カル
ボン酸及びその誘導体から選ばれた少なくとも１
種の変性剤0.1〜100重量部を180〜320℃の温度で
反応させるに際し、前記ブロツク共重合体又は前
記混合物100重量部当り0.05〜２重量部の一般式
〔〕、〔〕、〔〕及び〔〕で示されるフエノー
ル系
化合物から選ばれた少なくとも１種、0.05〜２重
量部のリン系安定剤の存在下で変性反応を行なう
ことを特徴とする重合体の変性方法。 （上記各式において、R1は炭素数１〜４のアル
キル基を、R2は炭素数２〜20のアルキル基を示
す。） （上式においてR3は【式】を示 す。）[Scope of Claims] 1. A polymer having at least one polymer segment mainly composed of a vinyl aromatic hydrocarbon and at least one polymer segment mainly composed of a conjugated diene, and having a vinyl aromatic hydrocarbon content of 5 ~60% by weight of a block copolymer or a mixed weight ratio of the block copolymer and a thermoplastic resin or rubbery polymer of 99/
At least 1 selected from unsaturated carboxylic acids and derivatives thereof per 100 parts by weight of the 1-3/97 mixture
When reacting 0.1 to 100 parts by weight of a seed modifier at a temperature of 180 to 320°C, 0.05 to 2 parts by weight of the general formula [], [], [] and A method for modifying a polymer, characterized in that the modification reaction is carried out in the presence of 0.05 to 2 parts by weight of at least one phosphorus stabilizer selected from the phenolic compounds represented by []. (In each of the above formulas, R 1 represents an alkyl group having 1 to 4 carbon atoms, and R 2 represents an alkyl group having 2 to 20 carbon atoms.) (In the above formula, R 3 represents [formula].)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6851786A JPS62225511A (en) | 1986-03-28 | 1986-03-28 | Modification of polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6851786A JPS62225511A (en) | 1986-03-28 | 1986-03-28 | Modification of polymer |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8818690A Division JPH03115301A (en) | 1990-04-04 | 1990-04-04 | Modification of polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62225511A JPS62225511A (en) | 1987-10-03 |
| JPH0257805B2 true JPH0257805B2 (en) | 1990-12-06 |
Family
ID=13375989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6851786A Granted JPS62225511A (en) | 1986-03-28 | 1986-03-28 | Modification of polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62225511A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0655772B2 (en) * | 1988-01-12 | 1994-07-27 | 旭化成工業株式会社 | How to get a polymer |
| JPH0699503B2 (en) * | 1988-05-16 | 1994-12-07 | 旭化成工業株式会社 | Polymer modification method |
| JP2952387B2 (en) * | 1989-08-31 | 1999-09-27 | 住友化学工業株式会社 | Gamma-ray discoloration-resistant styrene-butadiene block copolymer composition |
| US5246987A (en) * | 1992-05-14 | 1993-09-21 | Shell Oil Company | Bitumen and halogenated vinyl aromatic-conjugated diolefin block copolymer compositions |
| JPH06256740A (en) * | 1993-03-05 | 1994-09-13 | Nippon Synthetic Chem Ind Co Ltd:The | Water-soluble hot-melt adhesive |
| JP4962705B2 (en) * | 2006-09-25 | 2012-06-27 | ジェイエスアール クレイトン エラストマー株式会社 | Thermoplastic elastomer composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50122547A (en) * | 1974-03-13 | 1975-09-26 | ||
| JPS5560511A (en) * | 1978-10-31 | 1980-05-07 | Asahi Chem Ind Co Ltd | Modified block copolymer resin composition and its preparation |
| JPS5971341A (en) * | 1982-10-16 | 1984-04-23 | Sumitomo Chem Co Ltd | Stabilizer for synthetic resin |
-
1986
- 1986-03-28 JP JP6851786A patent/JPS62225511A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50122547A (en) * | 1974-03-13 | 1975-09-26 | ||
| JPS5560511A (en) * | 1978-10-31 | 1980-05-07 | Asahi Chem Ind Co Ltd | Modified block copolymer resin composition and its preparation |
| JPS5971341A (en) * | 1982-10-16 | 1984-04-23 | Sumitomo Chem Co Ltd | Stabilizer for synthetic resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62225511A (en) | 1987-10-03 |
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