JPH0621136B2 - Block copolymer - Google Patents
Block copolymerInfo
- Publication number
- JPH0621136B2 JPH0621136B2 JP8300584A JP8300584A JPH0621136B2 JP H0621136 B2 JPH0621136 B2 JP H0621136B2 JP 8300584 A JP8300584 A JP 8300584A JP 8300584 A JP8300584 A JP 8300584A JP H0621136 B2 JPH0621136 B2 JP H0621136B2
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- Japan
- Prior art keywords
- block copolymer
- weight
- polymerization
- added
- styrene
- Prior art date
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Description
【発明の詳細な説明】 本発明は新規な芳香族ビニル化合物−共役ジエンブロッ
ク共重合体に関し、粘着剤組成物などに有用な特定の構
造を有する芳香族ビニル系ブロックと共役ジエン系ブロ
ックとからなるブロック共重合体に関する。The present invention relates to a novel aromatic vinyl compound-conjugated diene block copolymer, which comprises an aromatic vinyl-based block and a conjugated diene-based block having a specific structure useful for an adhesive composition and the like. Block copolymers.
ビニル芳香族化合物と共役ジエンから成る直鎖状ブロッ
ク共重合体はアニオン重合の技術分野では公知のもので
あり、例えば特公昭４０−23798、特公昭46-32415に開
示されている。しかしこれらの方法で得られるブロック
共重合体は粘着剤として用いた場合、初期粘着力とはく
り強度とダイカット性のバランスの点で未だ十分満足出
来るもではない。A linear block copolymer composed of a vinyl aromatic compound and a conjugated diene is known in the technical field of anionic polymerization and is disclosed, for example, in Japanese Examined Patent Publication Nos. 40-23798 and 46-32415. However, when the block copolymer obtained by these methods is used as a pressure-sensitive adhesive, it is still not sufficiently satisfactory in terms of the balance between initial pressure-sensitive adhesive strength, peel strength and die-cutting property.
また特開昭51-146537にブロック共重合体粘着剤組成物
として開示されているB1−S1−B2−S2またはB1−S1−B2
−S2−B3（B1，B2，B3はブタジエン乃至イソプレンブロ
ック、S1，S2はスチレンブロック）はホットメルト型粘
着剤に応用した場合、低温タックとダンボール特性に劣
り、さらに保持力と接着力のバランスに欠ける欠点を有
している。Further, B 1 -S 1 -B 2 -S 2 or B 1 -S 1 -B 2 disclosed as a block copolymer pressure-sensitive adhesive composition in JP-A-51-146537.
-S 2 -B 3 case (B 1, B 2, B 3 butadiene or isoprene block, S 1, S 2 is a styrene block) is applied to the hot-melt adhesive, poor low-temperature tack and cardboard characteristics, further It has the drawback of lacking the balance between holding power and adhesive strength.
そこで本発明者らは粘着剤として用いた場合、低温タッ
クとダンボール特性に優れ、かつ保持力と接着力のバラ
ンスに優れたホットメルト型粘着組成物が得られるよう
なブロック共重合体を得るべく鋭意検討した結果、本発
明に到達した。Therefore, when the present inventors use it as a pressure-sensitive adhesive, it is desirable to obtain a block copolymer such that a hot-melt pressure-sensitive adhesive composition excellent in low-temperature tack and cardboard properties and excellent in balance between holding power and adhesive force can be obtained. As a result of intensive studies, the present invention has been reached.
すなわち本発明は一般式 （式中、B1，B2，B3は共役ジエン系ブロック、A1，A2は
芳香族ビニル系ブロックをあらわし、ｎ＝１〜５）で示
される構造を有し、芳香族ビニル化合物含量が５〜４５
重量％で、B2部分は共役ジエンと芳香族ビニル化合物と
の共重合体であって、芳香族ビニル化合物が漸増するテ
ーパーブロックを２〜１０個含有し、かつB2／(B1＋B2
＋B3)が重量比で０．４〜０．９８であるブロック共重
合体である。That is, the present invention has the general formula (Wherein B 1 , B 2 , and B 3 represent conjugated diene-based blocks, A 1 and A 2 represent aromatic vinyl-based blocks, and n = 1 to 5). Content is 5-45
In% by weight, the B 2 portion is a copolymer of a conjugated diene and an aromatic vinyl compound, contains 2 to 10 tapered blocks in which the aromatic vinyl compound gradually increases, and is B 2 / (B 1 + B 2
+ B 3 ) is a block copolymer having a weight ratio of 0.4 to 0.98.
本発明のブロック共重合体の特徴は芳香族ビニル化合物
の含量が５〜４５重量％、好ましくは１０〜４０重量％
でB2部分が特定範囲のテーパーブロック数を有し、かつ
B2部分がB2(B1＋B2＋B3)の重量比が特定範囲にあること
である。The block copolymer of the present invention is characterized in that the content of the aromatic vinyl compound is 5 to 45% by weight, preferably 10 to 40% by weight.
And the B 2 part has a certain number of tapered blocks, and
The B 2 part is that the weight ratio of B 2 (B 1 + B 2 + B 3 ) is within a specific range.
芳香族ビニル化合物の含量が５重量％未満では粘着剤と
して用いた場合、接着保持力が劣り、一方４５重量％を
超えると低温におけるタックとダンボール特性（ダンボ
ールとの接着保持力）が劣る。芳香族ビニル化合物の含
量はさらに好ましくは７〜３０重量％である。またｎは
１〜５であるが、好ましくは１〜３、更に好ましくは１
〜２、特に好ましくは１である。When the content of the aromatic vinyl compound is less than 5% by weight, the adhesive retention is poor when used as a pressure-sensitive adhesive, while when it exceeds 45% by weight, the tack and the cardboard property (adhesion retention with cardboard) at low temperature are inferior. The content of the aromatic vinyl compound is more preferably 7 to 30% by weight. N is 1 to 5, preferably 1 to 3, and more preferably 1
˜2, particularly preferably 1.
さらに本発明のブロック共重合体のB2部分が共役ジエン
と芳香族ビニル化合物との共重合体であって、芳香族ビ
ニル化合物が漸増するテーパーブロックを２〜１０個、
好ましくは２〜５個有していることが重要で、これによ
り本発明のブロック共重合体を粘着剤として用いた場
合、従来の共役ジエンと芳香族ビニル化合物のいかなる
ブロック共重合体に比べ顕著に優れた接着力を示す。Further, the B 2 portion of the block copolymer of the present invention is a copolymer of a conjugated diene and an aromatic vinyl compound, and 2 to 10 tapered blocks in which the aromatic vinyl compound gradually increases,
It is important to have 2 to 5 of them, and when the block copolymer of the present invention is used as a pressure-sensitive adhesive, it is more remarkable than any conventional block copolymer of conjugated diene and aromatic vinyl compound. Shows excellent adhesive strength.
またB2部分はB2／（B1＋B2＋B3）（重量比）として０．
４〜０．９８、好ましくは０．６〜０．９８であること
が必要で、粘着テープとした場合、上記特定範囲のテー
パーブロックと相俟って接着保持力、初期粘着性、粘着
力を優れたものにする。重量比がこの範囲を外れた場合
これらの特性は低下する。In addition, the B 2 portion is B 2 / (B 1 + B 2 + B 3 ) (weight ratio) of 0.
It is necessary to be 4 to 0.98, preferably 0.6 to 0.98. When used as an adhesive tape, the adhesive holding force, the initial adhesiveness, and the adhesive force are combined with the taper block in the above specific range. Make it excellent. When the weight ratio is out of this range, these properties are deteriorated.
本発明のブロック共重合体は次のような手順で製造され
る。The block copolymer of the present invention is produced by the following procedure.
炭化水素溶媒中にエーテルまたは第３級アミンを添加
し、有機リチウム化合物を開始剤として用い、 (1)まず共役ジエンを全モノマー使用量の１〜２８重量
％、好ましくは１〜１８重量％を重合し、重合反応が実
質的に終了した後、 (2)芳香族ビニル化合物を全モノマー使用量の２〜２２
重量％、好ましくは５〜１５重量％を重合し、重合反応
が実質的に終了した後、 (3)共役ジエン２２〜９３重量％、好ましくは38〜８８
重量％と芳香族ビニル化合物１〜１０重量％、好ましく
は１〜重量％の混合物を２回〜１０回に分けて重合し、
重合反応が実質的に終了すれば、 (4)芳香族ビニル化合物を全モノマー使用量の２〜２２
重量％、好ましくは５〜１５重量％を重合し、重合反応
が実質的に終了した後、更に必要に応じて(3)及び(4)の
モノマーをいくつかに分割して(3)、(4)を数回くり返し
た後、 (5)最後に共役ジエンを全モノマー使用量の１〜２８重
量％、好ましくは１〜１８重量％を重合反応(1)と同様
に重合し、完結させる。Ether or a tertiary amine is added to a hydrocarbon solvent and an organolithium compound is used as an initiator. (1) First, conjugated diene is added in an amount of 1 to 28% by weight, preferably 1 to 18% by weight based on the total amount of monomers used. After the polymerization is completed and the polymerization reaction is substantially completed, (2) the aromatic vinyl compound is used in an amount of 2 to 22 based on the total amount of the monomers used.
%, Preferably 5 to 15% by weight, and after the polymerization reaction is substantially completed, (3) conjugated diene 22 to 93% by weight, preferably 38 to 88
A mixture of 1% by weight of the aromatic vinyl compound and 1% by weight of the aromatic vinyl compound, preferably 1% by weight, is polymerized in 2 to 10 times,
If the polymerization reaction is substantially completed, (4) the aromatic vinyl compound is added in an amount of 2 to 22 of the total amount of the monomers used.
% By weight, preferably 5 to 15% by weight, is polymerized, and after the polymerization reaction is substantially completed, the monomers of (3) and (4) are further divided into some (3), ( After repeating 4) several times, (5) finally, conjugated diene is polymerized in the same manner as in the polymerization reaction (1) in an amount of 1 to 28% by weight, preferably 1 to 18% by weight based on the total amount of the monomer used.
これによって芳香族ビニル化合物５〜４５重量％、B2部
分の芳香族ビニル化合物のテーパーブロックが２〜１０
個でB2／（B1＋B2＋B3）が０．４〜０．９８のブロック
共重合体が得られる。As a result, the aromatic vinyl compound is 5 to 45% by weight, and the taper block of the aromatic vinyl compound in the B 2 portion is 2 to 10%.
Block copolymer of B 2 / (B 1 + B 2 + B 3) is 0.4 to 0.98 is obtained in pieces.
上記の共役ジエンと芳香族ビニル化合物の混合物を２回
〜１０回に分けて重合する工程において各回の単量体使
用量は同程度の方が好ましく、また各回においてほぼ１
００％の重合を行なうことが望ましい。また２〜１０回
に分けてモノマーを添加する方法としてモノマー混合物
を添加する方法、または共役ジエンと芳香族ビニル化合
物を同時に添加する方法等が用いられる。In the step of polymerizing the above-mentioned mixture of the conjugated diene and the aromatic vinyl compound in 2 to 10 times, it is preferable that the amount of the monomer used in each time is approximately the same, and in each step, the amount is almost 1
It is desirable to carry out a polymerization of 00%. As a method of adding the monomer in 2 to 10 times, a method of adding a monomer mixture, a method of simultaneously adding a conjugated diene and an aromatic vinyl compound, or the like is used.
本発明に使用する芳香族ビニル化合物としては、スチレ
ン、α−メチルスチレン、ｐ−メチルスチレン、ｍ−メ
チルスチレン、ｏ−メチルスチレン、ｐ−tert−ブチル
スチレン、ジメチルスチレン、ビニルナフタレン等が使
用出来る。このうちスチレンが好ましい。また共役ジエ
ンとしては、ブタジエン、イソプレン、ピペリレンなど
が使用出来る。このうちイソプレン、ブタジエンが好ま
しいものとして挙げられる。As the aromatic vinyl compound used in the present invention, styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-tert-butylstyrene, dimethylstyrene, vinylnaphthalene and the like can be used. . Of these, styrene is preferred. As the conjugated diene, butadiene, isoprene, piperylene, etc. can be used. Of these, isoprene and butadiene are preferable.
本発明のブロック共重合体の重量平均分子量は好ましく
は10,000〜500,000、更に好ましくは30,000〜300,000で
ある。このうちＡ部分の重量平均分子量は3,000〜50,00
0、Ｂ部分の重量平均分子量は44,000〜200,000が好まし
い。The weight average molecular weight of the block copolymer of the present invention is preferably 10,000 to 500,000, more preferably 30,000 to 300,000. The weight average molecular weight of A part is 3,000-50,00
The weight average molecular weights of 0 and B are preferably 44,000 to 200,000.
本発明のブロック共重合体は等温重合法でも、断熱重合
法でも得られる。また好ましい重合温度範囲は３０〜１
２０℃である。The block copolymer of the present invention can be obtained by either an isothermal polymerization method or an adiabatic polymerization method. The preferred polymerization temperature range is 30 to 1
It is 20 ° C.
本発明のブロック共重合体の製造に用いられる炭化水素
溶媒として、例えばシクロペンタン、シクロヘキサン、
ベンゼン、エチルベンゼン、キシレン及びこれらとペン
タン、ヘキサン、ヘプタン、ブタンなどの混合物が用い
られる。As the hydrocarbon solvent used in the production of the block copolymer of the present invention, for example, cyclopentane, cyclohexane,
Benzene, ethylbenzene, xylene and mixtures thereof with pentane, hexane, heptane, butane and the like are used.
有機リチウム化合物としては例えばｎ−ブチルリチウ
ム、sec−ブチルリチウム、tert−ブチルリチウム、ｎ
−ヘキシルリチウム、iso−ヘキシルリチウム、フェニ
ルリチウム、ナフチルリチウム等があり、モノマー１０
０重量部当り、０．０４〜１．０重量部で用いられる。Examples of the organic lithium compound include n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n
-Hexyl lithium, iso-hexyl lithium, phenyl lithium, naphthyl lithium, etc.
It is used in an amount of 0.04 to 1.0 part by weight per 0 part by weight.
エーテルまたは第３級アミンとしては例えばテトラハイ
ドロフラン、ジエチルエーテル、アニソール、ジメトキ
シベンゼン、エチレングリコールジメチルエーテル、ト
リエルアミン、Ｎ−ジメチルアニリン、ピリジンなどの
エーテル化合物、及び第３級アミン化合物が用いられ
る。使用量はモノマー１００重量部あたり0.005〜５重
量が好ましく、さらに好ましくは0.005〜２重量部であ
る。As the ether or tertiary amine, for example, an ether compound such as tetrahydrofuran, diethyl ether, anisole, dimethoxybenzene, ethylene glycol dimethyl ether, trielamine, N-dimethylaniline, pyridine and the like, and a tertiary amine compound are used. The amount used is preferably 0.005 to 5 parts by weight, more preferably 0.005 to 2 parts by weight, per 100 parts by weight of the monomer.
また本発明のブロック共重合体は、重合体中にビニル芳
香族化合物がモノマー単位で１個および２〜４個連らな
ったビニル芳香族化合物の合計量が全ビニル芳香族化合
物含量の５〜３０重量％が好ましく、更に好ましくは１
５〜３０重量％である。この範囲であると粘着剤として
用いた場合はくり強度および初期粘着強度とダイカット
性が優れたものが得られる。In the block copolymer of the present invention, the total amount of the vinyl aromatic compound in which 1 and 2 to 4 vinyl aromatic compounds are connected in the polymer as monomer units is 5 to 5% of the total vinyl aromatic compound content. 30% by weight is preferable, and 1 is more preferable.
It is 5 to 30% by weight. Within this range, when used as a pressure-sensitive adhesive, a product having excellent peeling strength, initial adhesive strength and die-cutting property can be obtained.
上記スチレン連鎖の量は農工大田中教授等によって開発
された方法（高分子学会予稿集、第２９巻７号2055頁）
に準拠した方法で求めることができる。The amount of the styrene chain was determined by the method developed by Professor Tanaka of Agricultural Science and Technology (Proceedings of the Polymer Society of Japan, Vol. 29, No. 7, page 2055).
Can be obtained by a method according to.
全スチレン含量は赤外法により求めた。The total styrene content was determined by the infrared method.
本発明のブロック共重合体は主に熱溶融型粘着剤に用い
られる。The block copolymer of the present invention is mainly used for hot-melt pressure-sensitive adhesives.
そのほか本発明のブロック共重合体の用途は広範囲な領
域にわたるが、その例を示すならば履物、容器などの射
出成形品、玩具、家庭用品などのフロー成形品、パッキ
ング、シート、プレートなどの圧搾成型品等に好適に使
用することができる。更に本発明のブロック共重合体は
ＳＢＲやＮＢＲなどの他のゴム、ポリスチレンなどのプ
ラスチック等に混合しその物性を改変されるものに用い
られる。例えばゴム用途としてはクレープ調スポンジ、
プラスチック用途として汎用ポリスチレンの耐衝撃性等
の向上剤として利用される。更に本発明のブロック共重
合体はアスファルトに混合してアスファルトの耐寒性を
改良するために利用される。In addition, the use of the block copolymer of the present invention covers a wide range of areas, and if examples thereof are shown, injection molded products such as footwear and containers, flow molded products such as toys and household products, compression products such as packing, sheets and plates. It can be suitably used for molded products and the like. Furthermore, the block copolymer of the present invention can be used in a material whose physical properties are modified by mixing it with other rubber such as SBR or NBR, or plastic such as polystyrene. For example, for rubber use, crepe-like sponge,
Used as a plasticizer for improving impact resistance of general-purpose polystyrene. Further, the block copolymer of the present invention can be used in admixture with asphalt to improve the cold resistance of the asphalt.
以下に本発明の実施例をあげて詳細に説明するが、本発
明の主旨を越えない限り、本発明が限定されるものでは
ない。Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited as long as the gist of the present invention is not exceeded.
実施例 〔Ｉ−Ｓ−(I/S)3−Ｓ−Ｉ線状ブロックコポリマーの
製造法〕 洗浄、乾燥した撹拌機、ジャケット付きのオートクレー
ブに窒素雰囲気下でシクロヘキサン／ｎ−ペンタン＝9/
1混合液1600gr、テトラヒドロフラン0.12grを仕込んだ
後、内温を60℃にした。次にｎ−ブチルリチウム0.5gr
を含むヘキサン溶液を添加後、イソプレン14grを添加し
２０分間重合した。イソプレンの重合転化率は１００％
であった。次いでスチレン２８grを添加し２０分間重合
した。スチレンの重合転化率は１００％であった。次い
でイソプレン104grとスチレン1.2grの混合物を添加し、
２０分間重合した。更にこの操作を２回繰返した。次い
で、スチレン28grを添加し２０分間重合した。このスチ
レンの重合転化率は１００％であった。最後にイソプレ
ン14grを添加し、２０分間重合した。イソプレンの重合
転化率は１００％であった。なお、重合中は温度が６０
〜７０℃になる様に調節した。重合終了跡、重合体溶液
に2,6−ジ−tert−ブチル−ｐ−クレゾールを添加した
後、シクロヘキサン／ｎ−ペンタンを加熱除去してブロ
ック共重合体を得た。Example [Method for producing I-S- (I / S) 3- S-I linear block copolymer] Cyclohexane / n-pentane = 9 / in a nitrogen atmosphere in a washed, dried stirrer and jacketed autoclave
After charging 1600 gr of 1 mixed solution and 0.12 gr of tetrahydrofuran, the internal temperature was set to 60 ° C. Then n-butyllithium 0.5gr
Was added to the hexane solution, 14 g of isoprene was added, and the mixture was polymerized for 20 minutes. Polymerization conversion of isoprene is 100%
Met. Then, 28 gr of styrene was added and polymerized for 20 minutes. The polymerization conversion rate of styrene was 100%. Then add a mixture of isoprene 104 gr and styrene 1.2 gr,
Polymerized for 20 minutes. Further, this operation was repeated twice. Then, 28 gr of styrene was added and polymerized for 20 minutes. The polymerization conversion rate of this styrene was 100%. Finally, 14 gr of isoprene was added and polymerization was carried out for 20 minutes. The polymerization conversion rate of isoprene was 100%. The temperature is 60 during the polymerization.
The temperature was adjusted to ~ 70 ° C. After the completion of the polymerization, 2,6-di-tert-butyl-p-cresol was added to the polymer solution, and then cyclohexane / n-pentane was removed by heating to obtain a block copolymer.
〔Ｉ−Ｓ−(I/S)3−Ｓ−Ｉ線状ブロックコポリマーの
製造法〕 前述と同じオートクレーブにシクロヘサン／ｎ−ペンタ
ン＝9/1混合液1600gr、テトラヒドロフラン0.12grを仕
込んだ後、内温を60℃にした。次にｎ−ブチルリチウム
0.5grを含むヘキサン溶液を添加後、イソプレン40grを
添加し２０分間重合した。イソプレンの重合転化率は１
００％であった。その後スチレン２８grを添加し２０分
間重合した。スチレンの重合転化率は１００％であっ
た。次いでイソプレン86.5grとスチレン1.2grの混合物
を添加し、２０分間重合した。更にこの操作を２回繰返
した。次いでスチレン28grを添加し２０分間重合した。
このスチレンの重合転化率は１００％であった。最後に
イソプレン40grを添加し、１５分間重合した。イソプレ
ンの重合転化率は１００％であった。なお、重合中は温
度が６０〜７０℃になる様に調節した。重合終了後、重
合体溶液に2,6−ジ−tert−ブチル−ｐ−クレゾールを
添加した後、シクロヘキサン／ｎ−ペンタンを加熱除去
してブロック共重合体を得た。[Method for Producing I-S- (I / S) 3- S-I Linear Block Copolymer] Into the same autoclave as described above, 1600 gr of cyclohesane / n-pentane = 9/1 mixture and 0.12 gr of tetrahydrofuran were charged. The temperature was 60 ° C. Then n-butyl lithium
After adding a hexane solution containing 0.5 gr, 40 gr of isoprene was added and polymerization was carried out for 20 minutes. Polymerization conversion of isoprene is 1
It was 00%. After that, 28 gr of styrene was added and polymerized for 20 minutes. The polymerization conversion rate of styrene was 100%. Then, a mixture of 86.5 gr of isoprene and 1.2 gr of styrene was added and polymerization was carried out for 20 minutes. Further, this operation was repeated twice. Then, 28 gr of styrene was added and polymerized for 20 minutes.
The polymerization conversion rate of this styrene was 100%. Finally, 40 gr of isoprene was added and polymerization was carried out for 15 minutes. The polymerization conversion rate of isoprene was 100%. During the polymerization, the temperature was adjusted to 60 to 70 ° C. After completion of the polymerization, 2,6-di-tert-butyl-p-cresol was added to the polymer solution, and then cyclohexane / n-pentane was removed by heating to obtain a block copolymer.
〔Ｉ−Ｓ−(I/S)3−Ｓ−Ｉ線状ブロックコポリマーの
製造法〕 前述と同じオートクレーブにシクロヘキサン／ｎ−ペン
タン＝9/1混合液1600gr、テトラヒドロフラン0.12grを
仕込んだ後、内温を60℃にした。次にｎ−ブチルリチウ
ム0.5grを含むヘキサン溶液を添加後、イソプレン120gr
を添加し３０分間重合した。イソプレンの重合転化率は
１００％であった。その後スチレン28grを添加し２０分
間重合した。スチレンの重合転化率は１００％であっ
た。次いでイソプレン33grとスチレン1.2grの混合物を
添加し２０分間重合した。更にこの操作を２回繰返し
た。次いでスチレン28grを添加し２０分間重合した。こ
のスチレンの重合転化率は１００％であった。最後にイ
ソプレン120grを添加し３０分間重合した。スチレンと
イソプレンの重合転化率は１００％であった。なお、重
合中は温度が６０〜７０℃になる様に調節した。重合終
了後、重合体溶液に2,6−ジ−tert−ブチル−ｐ−クレ
ゾールを添加した後、シクロヘキサン／ｎ−ペンタンを
加熱除去してブロック共重合体を得た。[Method for producing I-S- (I / S) 3- S-I linear block copolymer] The same autoclave as described above was charged with 1600 gr of cyclohexane / n-pentane = 9/1 mixed solution and 0.12 gr of tetrahydrofuran, and then The temperature was 60 ° C. Next, after adding a hexane solution containing 0.5gr of n-butyllithium, 120gr of isoprene
Was added and polymerized for 30 minutes. The polymerization conversion rate of isoprene was 100%. Thereafter, 28 gr of styrene was added and polymerization was carried out for 20 minutes. The polymerization conversion rate of styrene was 100%. Then, a mixture of 33 gr of isoprene and 1.2 gr of styrene was added and polymerized for 20 minutes. Further, this operation was repeated twice. Then, 28 gr of styrene was added and polymerized for 20 minutes. The polymerization conversion rate of this styrene was 100%. Finally, 120 gr of isoprene was added and polymerized for 30 minutes. The polymerization conversion rate of styrene and isoprene was 100%. During the polymerization, the temperature was adjusted to 60 to 70 ° C. After completion of the polymerization, 2,6-di-tert-butyl-p-cresol was added to the polymer solution, and then cyclohexane / n-pentane was removed by heating to obtain a block copolymer.
〔Ｉ−Ｓ−(I/S)13−Ｓ−Ｉ 線状ブロックコポリマー
の製造法〕 前述と同じオートクレーブにシクロヘキサン／ｎ−ペン
タン＝9/1混合液1600gr、テトラヒドロフラン0.12grを
仕込んだ後内温を６０℃にした。次にｎ−ブチルリチウ
ム0.5grを含むヘキサン溶液を添加後、イソプレン14gr
を添加し２０分間重合した。イソプレンの重合転化率は
１００％であった。その後スチレン２８grを添加し２０
分間重合した。スチレンの重合転化率は１００％であっ
た。次いでイソプレン24grとスチレン0.28grの混合物を
添加し、２０分間重合した。更にこの操作を１２回繰返
した。次いでスチレン28grを添加し２０分間重合した。
スチレンの重合転化率は１００％であった。最後にイソ
プレン14grを添加し１０分間重合した。イソプレンの重
合転化率は１００％であった。なお、重合中は温度が６
０〜７０℃になる様に調節した。重合終了後重合体溶液
に2,6−ジ−tert−ｐ−クレゾールを添加した後、シク
ロヘキサン／ｎ−ペンタンを加熱除去してブロック共重
合体を得た。[Method for producing I-S- (I / S) 13 -S-I linear block copolymer] Cyclohexane / n-pentane = 9/1 mixed solution 1600 gr and tetrahydrofuran 0.12 gr were charged in the same autoclave as described above, and then the internal temperature was increased. To 60 ° C. Next, after adding a hexane solution containing 0.5gr of n-butyllithium, 14gr of isoprene
Was added and polymerized for 20 minutes. The polymerization conversion rate of isoprene was 100%. Then add styrene 28gr and add 20
Polymerized for minutes. The polymerization conversion rate of styrene was 100%. Then, a mixture of 24 gr of isoprene and 0.28 gr of styrene was added, and the mixture was polymerized for 20 minutes. Further, this operation was repeated 12 times. Then, 28 gr of styrene was added and polymerized for 20 minutes.
The polymerization conversion rate of styrene was 100%. Finally, 14 gr of isoprene was added and polymerized for 10 minutes. The polymerization conversion rate of isoprene was 100%. The temperature is 6 during the polymerization.
The temperature was adjusted to 0 to 70 ° C. After completion of the polymerization, 2,6-di-tert-p-cresol was added to the polymer solution, and then cyclohexane / n-pentane was removed by heating to obtain a block copolymer.
法〕[Method for producing I-S-I-S-I linear block copolymer]
前述と同じオートクレーブにシクロヘキサン／ｎ−ペン
タン＝9/1混合液1600grを仕込んだ後内温を６０℃にし
た。次にｎ−ブチルリチウム05grを含むヘキサン溶液を
添加後、イソプレン14grを添加し２０分間重合した。イ
ソプレンの重合転化率は１００％であった。その後スチ
レン30grを添加し２０分間重合した。スイレンの重合転
化率は１００％であった。次いでイソプレン312grを添
加し３０分間重合した。イソプレンの重合転化率１００
％であった。更にスチレン30grを添加し２０分間重合し
た。スチレンの重合転化率は１００％であった。最後に
イソプレン14grを添加し２０分間重合した。イソプレン
の重合転化率は１００％であった。なお重合中は温度が
６０〜７０℃になる様に調節した。重合終了後、重合体
溶液に2,6−ジ−tert−ブチル−ｐ−クレゾールを添加
した後、シクロヘキサン／ｎ−ペンタンを加熱除去して
ブロック共重合体を得た。The same autoclave as described above was charged with 1600 gr of a cyclohexane / n-pentane = 9/1 mixed solution, and then the internal temperature was adjusted to 60 ° C. Next, after adding a hexane solution containing 05 gr of n-butyllithium, 14 gr of isoprene was added and polymerized for 20 minutes. The polymerization conversion rate of isoprene was 100%. After that, 30 gr of styrene was added and polymerized for 20 minutes. The polymerization conversion rate of water lily was 100%. Next, 312 gr of isoprene was added and polymerization was carried out for 30 minutes. Polymerization conversion of isoprene 100
%Met. Further, 30 gr of styrene was added and polymerized for 20 minutes. The polymerization conversion rate of styrene was 100%. Finally, 14 gr of isoprene was added and polymerized for 20 minutes. The polymerization conversion rate of isoprene was 100%. During the polymerization, the temperature was adjusted to 60 to 70 ° C. After completion of the polymerization, 2,6-di-tert-butyl-p-cresol was added to the polymer solution, and then cyclohexane / n-pentane was removed by heating to obtain a block copolymer.
〔Ｓ−(I/S)3−Ｓ線状ブロックコポリマーの製造法〕 前述と同じオートクレーブにシクロヘキサン／ｎ−ペン
タン＝9/1混合液1600gr、テトラヒドロフラン0.12grを
仕込んだ後内温を６０℃にした。次にｎ−ブチルリチウ
ム0.5grを含むヘキサン溶液を添加後スチレン28grを添
加し２０分間重合した。スチレンの重合転化率は１００
％であった。次いでイソプレン113grとスチレン1.2grの
混合液を添加し３０分間重合した。更にこの操作を２回
繰返した。最後にスチレン28grを添加し２０分間重合し
た。スチレンの重合転化率は１００％であった。なお、
重合中は温度が６０〜７０℃になる様に調節した。重合
終了後、重合体溶液に2,6−ジ−tert−ブチル−ｐ−ク
レゾールを添加した後、シクロヘキサン／ｎ−ペンタン
を加熱除去してブロック共重合体を得た。[Method for producing S- (I / S) 3 -S linear block copolymer] Cyclohexane / n-pentane = 9/1 mixed solution 1600gr and tetrahydrofuran 0.12gr were charged in the same autoclave as described above, and then the internal temperature was brought to 60 ° C. did. Next, a hexane solution containing 0.5 gr of n-butyllithium was added, and then 28 gr of styrene was added and polymerization was carried out for 20 minutes. The polymerization conversion rate of styrene is 100.
%Met. Then, a mixed solution of 113 gr of isoprene and 1.2 gr of styrene was added and polymerized for 30 minutes. Further, this operation was repeated twice. Finally, 28 gr of styrene was added and polymerized for 20 minutes. The polymerization conversion rate of styrene was 100%. In addition,
During the polymerization, the temperature was adjusted to 60 to 70 ° C. After completion of the polymerization, 2,6-di-tert-butyl-p-cresol was added to the polymer solution, and then cyclohexane / n-pentane was removed by heating to obtain a block copolymer.
図は実施例１に用いた本発明の重合体のスチレン連鎖を
示すゲルパーミエーションクロマトグラフィーである。The figure is a gel permeation chromatography showing the styrene chain of the polymer of the present invention used in Example 1.
Claims (2)
Ａ１，Ａ２は芳香族ビニル系ブロック、ｎ＝１〜５をあ
らわす） で示される構造を有し、芳香族ビニル化合物含量が５〜
４５重量％で、Ｂ２部分は共役ジエンと芳香族ビニル化
合物との共重合体であって芳香族ビニル化合物が漸増す
るテーパーブロックを２〜１０個含有し、かつＢ２／
（Ｂ１＋Ｂ２＋Ｂ３）が重量比で０．４〜０．９８であ
り、重量平均分子量が10,000〜500,000であり、かつＡ
部分の重量平均分子量が 3,000〜50,000及びＢ部分の重
量平均分子量が44,000〜200,000 であるブロック共重合
体。1. A general formula (Wherein B 1 , B 2 and B 3 are conjugated diene-based blocks,
A 1 and A 2 have a structure represented by an aromatic vinyl block, where n = 1 to 5), and the aromatic vinyl compound content is 5 to 5.
45% by weight, the B 2 portion is a copolymer of a conjugated diene and an aromatic vinyl compound and contains 2 to 10 tapered blocks in which the aromatic vinyl compound gradually increases, and B 2 /
(B 1 + B 2 + B 3 ) is 0.4 to 0.98 in weight ratio, the weight average molecular weight is 10,000 to 500,000, and A
A block copolymer in which the weight average molecular weight of the portion is 3,000 to 50,000 and the weight average molecular weight of the B portion is 44,000 to 200,000.
特許請求の範囲第１項に記載のブロック共重合体。2. The block copolymer according to claim 1, which has a weight average molecular weight of 30,000 to 300,000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8300584A JPH0621136B2 (en) | 1984-04-26 | 1984-04-26 | Block copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8300584A JPH0621136B2 (en) | 1984-04-26 | 1984-04-26 | Block copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60228520A JPS60228520A (en) | 1985-11-13 |
| JPH0621136B2 true JPH0621136B2 (en) | 1994-03-23 |
Family
ID=13790140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8300584A Expired - Lifetime JPH0621136B2 (en) | 1984-04-26 | 1984-04-26 | Block copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0621136B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1222429B (en) * | 1987-07-31 | 1990-09-05 | Enichem Elastromeri S P A | BLOCK COPOLYMER PROCEDURE FOR ITS PREPARATION |
| US5589542A (en) * | 1993-11-03 | 1996-12-31 | Shell Oil Company | Multiblock hydrogenated polymers for adhesives |
| KR100458169B1 (en) * | 2002-07-26 | 2004-11-20 | 금호석유화학 주식회사 | Unbalanced multi-block SBS and method for the preparation thereof |
| CN101628959A (en) * | 2008-07-15 | 2010-01-20 | 中国石油化工集团公司 | Foamed styrene monomer-diolefin copolymer, and preparation method and application thereof |
-
1984
- 1984-04-26 JP JP8300584A patent/JPH0621136B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60228520A (en) | 1985-11-13 |
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