CN1643067A - 来自受控分布嵌段共聚物的凝胶 - Google Patents

来自受控分布嵌段共聚物的凝胶 Download PDF

Info

Publication number
CN1643067A
CN1643067A CNA03807477XA CN03807477A CN1643067A CN 1643067 A CN1643067 A CN 1643067A CN A03807477X A CNA03807477X A CN A03807477XA CN 03807477 A CN03807477 A CN 03807477A CN 1643067 A CN1643067 A CN 1643067A
Authority
CN
China
Prior art keywords
block
alkenyl arene
mono alkenyl
copolymer
conjugated diene
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
Application number
CNA03807477XA
Other languages
English (en)
Other versions
CN1288209C (zh
Inventor
D·L·小汉德林
C·L·威利斯
D·J·圣克莱尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CLATON POLYMERS RESEARCH BV
Original Assignee
CLATON POLYMERS RESEARCH BV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by CLATON POLYMERS RESEARCH BV filed Critical CLATON POLYMERS RESEARCH BV
Publication of CN1643067A publication Critical patent/CN1643067A/zh
Application granted granted Critical
Publication of CN1288209C publication Critical patent/CN1288209C/zh
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • 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
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D153/02—Vinyl aromatic monomers and conjugated dienes
    • C09D153/025—Vinyl aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof

Abstract

本发明涉及从单烯基芳烃和共轭二烯烃的新颖阴离子嵌段共聚物制备的凝胶。嵌段共聚物被选择性氢化和具有单烯基芳烃端嵌段及单烯基芳烃和共轭二烯烃的受控分布嵌段。嵌段共聚物可以与油和其它组分结合以形成本发明的凝胶。

Description

来自受控分布嵌段共聚物的凝胶
发明领域
本发明涉及从单烯基芳烃和共轭二烯烃的新颖阴离子嵌段共聚物制备的凝胶。
技术背景
单烯基芳烃和共轭二烯烃嵌段共聚物的制备是公知的。采用苯乙烯和丁二烯制备线性ABA嵌段共聚物的最早专利之一是U.S.Pat.3149182。这些聚合物依次可以氢化以形成更稳定的嵌段共聚物，如在U.S.Pat.3595942和U.S.Re.27145中描述的那些。这样的聚合物宽广地称为苯乙烯类嵌段共聚物或SBC。
SBC长期以来用作粘合剂、密封剂和凝胶。凝胶的近来例子发现于US专利No.5879694。随着油凝胶的增加使用，该油凝胶变成作为蜡烛的流行礼物，需要增加的性能(按照更高拉伸强度和更高伸长率表达)。本发明包括新类别的SBC，其中聚合物制造商可改变橡胶链段的相容性特性，导致改进的油凝胶。例如，这样的凝胶也可以用作电子件中的防水封装剂/密封剂和用于电线和电缆应用。
现在已经发现基于单烯基芳烃端嵌段和单烯基芳烃和共轭二烯烃受控分布中间嵌段的新颖阴离子嵌段共聚物和该新颖阴离子嵌段共聚物描述于在先未决，通常受让的U.S.专利申请系列号60/355210，题目为“新颖嵌段共聚物及其制备方法”。制备这样聚合物的方法详细描述于上述专利申请中。专利权人发现这些新聚合物可以制备改进的油凝胶。
发明概述
在本发明的一个方面，我们发现一种新颖油凝胶组合物，该组合物包括100重量份至少一种具有单烯基芳烃和共轭二烯烃受控分布嵌段的氢化嵌段共聚物，和350-2000重量份填充油，其中该氢化嵌段共聚物含有至少一个聚合物嵌段A和至少一个聚合物嵌段B，和其中(a.)在氢化之前，每个A嵌段独立地是单烯基芳烃均聚物嵌段和每个B嵌段独立地是至少一种共轭二烯烃和至少一种单烯基芳烃的受控分布共聚物嵌段；(b.)在氢化之后已减少0-10％的芳烃双键，和已减少至少90％的共轭二烯烃双键；(c.)每个A嵌段的数均分子量为3,000-60,000和每个B嵌段的数均分子量为30,000-300,000；(d.)每个B嵌段包括邻近A嵌段、富含共轭二烯烃单元的末端区域和一个或多个不邻近A嵌段、富含单烯基芳烃单元的区域；(e.)氢化嵌段共聚物中单烯基芳烃的总数量是20-80wt％；和(f.)每个B嵌段中单烯基芳烃的重量百分比是10-75％。
嵌段共聚物的通常构型优选是如下一种：A-B、A-B-A、(A-B)n、(A-B)n-A、(A-B-A)nX或(A-B)nX，其中n是2-30，优选2-15，更优选2-6的整数，和X是偶合剂残基。
优选实施方案的详细描述
本发明的关键组分是新颖嵌段共聚物，该共聚物包含单烯基芳烃端嵌段和单烯基芳烃和共轭二烯烃的独特中间嵌段。令人惊奇地，(1)单体加入的独特控制和(2)乙醚或其它改性剂作为溶剂组分(它以下称为“分布剂”)的使用的结合导致两种单体(在此称为“受控分布”聚合，导致“受控分布”结构的聚合)的某些特性分布，和也在聚合物嵌段中导致某些单烯基芳烃富集区域和某些共轭二烯烃富集区域的存在。对于在此的目的，“受控分布”定义为表示具有如下属性的分子结构：(1)邻近单烯基芳烃均聚物(“A”)嵌段的末端区域，该区域富含(即含有大于平均数量的)共轭二烯烃单元；(2)一个或多个不邻近A嵌段的区域，该区域富含(即含有大于平均数量的)单烯基芳烃单元；和(3)具有相对低嵌段度的总体结构。对于在此的目的，“富含”定义为大于平均数量，优选大于平均数量5％。此相对低嵌段度可以仅仅由受控分布嵌段中间体的单一玻璃化转变温度(Tg)的存在显示，当使用差示扫描量热法(“DSC”)热方法或通过机械方法分析时，该单一玻璃化转变温度在单独的任一单体的Tg之间，或如通过质子核磁共振(“H-NMR”)方法显示。也可以在B嵌段聚合期间适于聚苯乙烯基锂端基检测的波长范围内，从UV-可见吸光度的测量推断嵌段度的可能性。此数值的急剧和显著增加指示聚苯乙烯基锂链端的显著增加。在此方法中，这仅在共轭二烯烃浓度下降到临界水平以下才发生，以保持受控分布聚合。在此点存在的任何苯乙烯单体以嵌段的形式加入。由本领域技术人员使用质子NMR测量的术语“苯乙烯嵌段度”定义为在聚合物链上含有两个S最近邻接部分的聚合物中S单元的比例。在使用H-1 NMR测量两个试验数量之后测量苯乙烯嵌段如下：
首先，通过在7.5-6.2ppm的H-1 NMR光谱中积分总苯乙烯芳族信号和将此数量除以5以解释每个苯乙烯芳族环上的5个芳族氢，测定苯乙烯单元(即当成比例时任意仪器单位被抵消)的总数目。
其次，通过从6.88和6.80之间的信号最小值到6.2ppm的H-1 NMR光谱中积分芳族信号部分和将此数量除以2以解释每个嵌段苯乙烯芳族环上的2个邻位氢，测定嵌段苯乙烯单元。此信号对那些苯乙烯单元的环上两个邻位氢的指定报导于F.A.Bovey，大分子的高分辩率NMR(AcademicPress，纽约和伦敦，1972)，第6章，该苯乙烯单元含有两个苯乙烯最近邻接部分。
苯乙烯嵌段度简单地是嵌段苯乙烯对总苯乙烯单元的百分比：
嵌段％＝100乘(嵌段苯乙烯单元/总苯乙烯单元)
这样表达的聚合物-Bd-S-(S)n-Bd-聚合物，其中n大于零，定义为嵌段苯乙烯。例如，如果在以上例子中n等于8，则嵌段度指数是80％。优选嵌段度指数小于40。对于苯乙烯含量为10wt％-40wt％的一些聚合物，优选嵌段度指数小于10。
此受控分布结构在控制获得共聚物的结构和Tg中非常重要，这是由于受控分布结构保证实质上没有两种单体的相分离，即与如下嵌段共聚物形成对照：其中单体实际保持为具有不同Tg的单独“微相”，但实际上化学结合在一起。此受控分布结构保证仅存在一个Tg和，因此，所得共聚物的热性能是可预测的和事实上是可预先确定的。此外，当具有这样受控分布结构的共聚物然后用作二嵌段、三嵌段或多嵌段共聚物中的一个嵌段时，通过适当构成的受控分布共聚物区域的存在变成可能的相对更高Tg倾向于改进流动和加工性能。也可以达到某些其它性能的改进。
在本发明的优选实施方案中，主题受控分布共聚物嵌段含有三个不同的区域-在嵌段端部的共轭二烯烃富集区域和靠近嵌段中间或中心的单烯基芳烃富集区域。希望的是单烯基芳烃/共轭二烯烃受控分布共聚物嵌段，其中单烯基芳烃单元的比例逐渐增加到靠近嵌段中间或中心的最大值和然后逐渐降低，直到聚合物嵌段完全聚合。此结构是显著的和不同于现有技术中讨论的渐变和/或无规结构。
制备本发明新颖受控分布共聚物的开始材料包括初始单体。烯基芳烃可以选自苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、乙烯基甲苯、乙烯基萘、和对丁基苯乙烯或其混合物。在这些物质中，苯乙烯是最优选的和可购自各个制造商和相对便宜。在此使用的共轭二烯烃是1，3-丁二烯和取代丁二烯如异戊二烯、戊间二烯、2，3-二甲基-2，3-丁二烯、和1-苯基-1，3-丁二烯、或其混合物。在这些物质中，最优选是1，3-丁二烯。在此使用的和在权利要求中使用的“丁二烯”具体地表示“1，3-丁二烯”。
如上所讨论的那样，受控分布聚合物嵌段含有邻近A嵌段的二烯烃富集区域和不邻近A嵌段和典型地靠近B嵌段中心的芳烃富集区域。典型地邻近A嵌段的区域包括嵌段的前15-25％和包括二烯烃富集区域，和剩余部分被认为富集芳烃。术语“二烯烃富集”表示与芳烃富集区域相比，该区域具有可测量的较高的二烯烃对芳烃比例。表达此的另一种方式是单烯基芳烃单元的比例沿聚合物链逐渐增加到靠近嵌段中间或中心的最大值(如果我们描述ABA结构)和然后逐渐降低直到聚合物嵌段完全聚合。对于受控分布嵌段B，单烯基芳烃的重量百分比是约10％-约75。
在此使用的“热塑性嵌段共聚物”定义为含有如下嵌段的嵌段共聚物：至少单烯基芳烃，如苯乙烯的第一嵌段及二烯烃和单烯基芳烃受控分布共聚物的第二嵌段。制备此热塑性嵌段共聚物的方法是通过嵌段聚合一般已知的任何方法。本发明包括作为实施方案的热塑性共聚物组合物，它们可以是二嵌段、三嵌段共聚物或多嵌段组合物。在二嵌段共聚物组合物的情况下，一个嵌段是烯基芳烃基均聚物嵌段和与其聚合的是二烯烃和烯基芳烃受控分布共聚物的第二嵌段。在三嵌段组合物的情况下，它包括作为端嵌段的玻璃性烯基芳烃基均聚物和作为中间嵌段的二烯烃和烯基芳烃受控分布共聚物。在制备三嵌段共聚物组合物的情况下，受控分布二烯烃/烯基芳烃共聚物可以在此指定为“B”和烯基芳烃基均聚物指定为“A”。A-B-A型三嵌段组合物可以由顺序聚合或偶合制备。在顺序溶液聚合技术中，首先将单烯基芳烃引入以生产相对硬的芳族嵌段，随后引入受控分布二烯烃/烯基芳烃混合物以形成中间嵌段，和然后随后引入单烯基芳烃以形成末端嵌段。除线性的A-B-A构型以外，可以构造嵌段以形成星形(支化)聚合物(A-B)nX，或可以在混合物中结合两种类型的结构。一些A-B二嵌段聚合物可以存在，但优选至少约30wt％嵌段共聚物是A-B-A或星形的(或另外支化的以每个分子含有2个或更多末端树脂性嵌段)以赋予强度。
也重要的是控制各个嵌段的分子量。对于AB二嵌段，所需的嵌段重量对于单烯基芳烃A嵌段为3,000-60,000，和对于受控分布共轭二烯烃/单烯基芳烃B嵌段为30,000-300,000。优选的范围是对于A嵌段为5000-45,000和对于B嵌段为50,000-250,000。对于可以是顺序ABA或偶合(AB)2X嵌段共聚物的三嵌段，A嵌段应当是3,000-60,000，优选5000-45,000，而顺序嵌段的B嵌段应当是约30,000-300,000，和偶合聚合物的B嵌段(两个)为该数量的一半。三嵌段共聚物的总平均分子量应当为40,000-400,000，和对于星形共聚物为60,000-600,000。这些分子量最精确地由光散射测量测定，和表达为数均分子量。
本发明的另一个重要方面是控制受控分布共聚物嵌段中共轭二烯烃的微结构或乙烯基含量。术语“乙烯基含量”表示通过1，2-加成(在丁二烯的情况下-在异戊二烯的情况下它是3，4-加成)聚合的共轭二烯烃。尽管纯“乙烯基”仅在1，3-丁二烯的1，2-加聚情况下形成，异戊二烯的3，4-加聚(和对于其它共轭二烯烃的相似加成)对嵌段共聚物最终性能的效果相似。术语“乙烯基”表示聚合物链上侧乙烯基的存在。当表示丁二烯作为共轭二烯烃的用途时，优选共聚物嵌段中20-80mol％的缩合丁二烯单元具有由质子NMR分析测定的1，2乙烯基构型，优选30-70mol％的缩合丁二烯单元应当具有1，2乙烯基构型。这有效地通过改变分布剂的相对数量而控制。如将会理解的那样，分布剂起两个目的-它产生单烯基芳烃和共轭二烯烃的受控分布，和也控制共轭二烯烃的微结构。分布剂对锂的合适比例公开和教导于US Pat.Re27145，它的公开内容引入作为参考。
本发明热塑性弹性体二嵌段和三嵌段聚合物的重要特征在于它们具有至少两个Tg，低值是受控共聚物嵌段的结合Tg，该Tg是它的组成单体Tg的中间，该聚合物包括一个或多个受控分布二烯烃/烯基芳烃共聚物嵌段和一个或多个单烯基芳烃嵌段。这样的Tg优选是至少-60℃，更优选-40～+30℃，和更优选-40～+10℃。第二Tg，即单烯基芳烃“玻璃性”嵌段的Tg优选大于80℃，更优选80-110℃。两个Tg的存在，说明嵌段的微相分离，在很多种应用中引起材料显著的弹性和强度，和它的加工容易和所需的熔体流动特性。
选择性氢化嵌段共聚物。氢化可以通过现有技术已知的任何氢化或选择性氢化工艺进行。例如，已经使用方法如在如下文献中教导的那些完成这样的氢化：例如，U.S.专利3494942、3634594、3670054、3700633、和Re.27145。氢化可以在一定的条件下进行使得已减少至少90％的共轭二烯烃双键，和已减少0-10％的芳烃双键。优选的范围是减少至少95％的共轭二烯烃双键，和更优选减少98％的共轭二烯烃双键。或者，可以氢化聚合物使得芳族不饱和也减少超过上述10％水平。在该情况下，共轭二烯烃和芳烃两者的双键可以减少90％或更多。
另外，可以采用许多方式官能化本发明的嵌段共聚物。一种方式是采用含有一个或多个官能团或它们的衍生物，如羧酸基团和它们的盐、酸酐、酯、酰亚胺基团、酰胺基团、和酰氯的不饱和单体进行处理。要接枝到嵌段共聚物上的优选单体是马来酸酐、马来酸、富马酸、和它们的衍生物。官能化这样嵌段共聚物的进一步描述可以发现于Gergen等人，U.S.Pat.No.4578429和发现于U.S.Pat.No.5506299。在另一种方式中，可以通过将含硅或硼化合物接枝到聚合物上官能化本发明的选择性氢化嵌段共聚物，如在U.S.Pat.No.4882384中教导的那样。在仍然另一种方式中，可以将本发明的嵌段共聚物与烷氧基硅烷化合物接触，以形成硅烷改性的嵌段共聚物。在仍然另一种方式中，可以通过反应至少一个环氧乙烷分子到聚合物上，如在U.S.Pat.No.4898914中教导的那样，或通过聚合物与二氧化碳反应，如在U.S.Pat.No.4970265中教导的那样官能化本发明的嵌段共聚物。更进一步地，可以金属化本发明的嵌段共聚物，如在U.S.Pat.Nos.5206300和5276101中教导的那样，其中将聚合物与烷基碱金属，如烷基锂接触。和更进一步地，可以通过将磺酸类基团接枝到聚合物上官能化本发明的嵌段共聚物，如在U.S.5516831中教导的那样。
用于本发明油凝胶的组分之一是聚合物填充油或增塑剂。特别优选是与嵌段共聚物弹性体链段相容类型的油。尽管更高芳族物质含量的油是令人满意的，但优选是具有低挥发性和小于50％芳族物质含量的那些石油基白油。这样的油包括链烷油和环烷油两者。油应当另外具有低挥发性，优选具有大于260℃(500°F)的初始沸点。
可用于本发明的另外增塑剂的例子是无规或顺序聚合的苯乙烯和共轭二烯烃的低聚物、共轭二烯烃如丁二烯或异戊二烯的低聚物、液体聚丁烯-1、和乙烯-丙烯-二烯烃橡胶，所有的分子量都为300-35,000，优选小于25,000mol重量。
采用的油或增塑剂数量从350到2000重量份变化，相对于每一百重量份橡胶，或嵌段共聚物，优选400-1000重量份。
各种类型的填料和颜料可以包括在油凝胶配制剂中以着色油凝胶和降低成本。合适的填料包括碳酸钙、粘土、滑石、二氧化硅、氧化锌、二氧化钛等。依赖于使用的填料类型和油凝胶要用于的应用，填料的数量通常为0-30wt％，基于配制剂。
本发明的组合物可以由其它聚合物、增强剂、抗氧剂、稳定剂、阻燃剂、防粘连剂、润滑剂和其它橡胶和塑料混炼成分的加入进一步改性而不背离本发明的范围。这样的组分描述于包括US Pat.No.3239478和USPat.No5777043的各种专利，其公开内容引入作为参考。
可以设计本发明的组合物用于很多种用途和应用。它们可以应用为电子件的防水封装剂/密封剂和用于电线和电缆应用，而且也用于蜡烛的制备等。
关于各种成分的相对数量，这会部分依赖于特定的最终用途和依赖于选择用于特定最终用途的特定嵌段共聚物。下表A显示包括在本发明中的一些想象组合物。“CD聚合物”表示本发明的受控分布聚合物：
表A：应用，组合物和范围
应用 成分 组成，重量份
油凝胶 CD聚合物填充油 100300-2000
实施例
提供如下实施例以说明本发明。实施例不用于限制本发明的范围和它们不应当这样解释。除非另外说明，数量为重量份或重量百分比。用于实施例的测试方法是美国材料试验学会(ASTM)测试方法，和使用如下具体方法：
    环球软化点     ASTM D-36
    熔体粘度     ASTM D-3236
    拉伸性能     ASTM D-412
实施例1
根据以上提及的在先未决专利申请系列号60/355210中公开的方法制备本发明的各种受控分布嵌段共聚物，该在先未决专利申请包括同时提交的它的连续申请。所有的聚合物是选择性氢化AB或ABA嵌段共聚物，其中A嵌段是聚乙烯嵌段和在氢化之前的B嵌段是苯乙烯丁二烯受控分布嵌段，该受控分布嵌段含有富含丁二烯单元的末端区域和富含苯乙烯单元的中心区域。在下表1中显示各种聚合物。这些聚合物然后用于其它实施例中描述的各种应用。步骤I MW是第一A嵌段的分子量，步骤II MW是AB嵌段的分子量和步骤III MW是ABA嵌段的分子量。将聚合物氢化使得减少大于约95％的二烯烃双键。
表1.受控分布聚合物
聚合物序号 步骤IMW(k)  步骤IIMW(k) 步骤IIIMW(k)   步骤II中的％苯乙烯   苯乙烯嵌段度   1，2-BD   PSC
   (％)   (％)
    25     9.1     89     97     25     0     36     39
    27     7.5     70     77     25     3     36.1     40
    28     7.8     39     -     25     16     36     39
    26     7.3     43     50     37     0     36.7     47
其中“MW(k)”＝以千计的分子量和“PSC(％)”＝最终聚合物中苯乙烯的wt％。“苯乙烯嵌段度”仅用于B嵌段。
因此，聚合物#25是数均嵌段摩尔重量为9500-80,000-9500的线性ABA三嵌段共聚物；聚合物#27是嵌段摩尔重量为7500-62,600-7300的线性ABA三嵌段共聚物；聚合物#28是嵌段摩尔重量为7800-31,500的AB二嵌段共聚物；和聚合物#26是嵌段摩尔重量为7300-35,800-7300的线性ABA三嵌段共聚物。
实施例2
实施例2显示新颖CD聚合物#25在油凝胶中的用途。样品#2-1,202和2-3显示基于常规氢化SBC，SEBS#1的凝胶的性能。SEBS#1是聚苯乙烯端嵌段为约10,000和氢化聚丁二烯中间嵌段为约50,000的选择性氢化SBS嵌段共聚物。结果显示聚合物含量增加，软化点和拉伸性能改进及熔体粘度增加。样品#2-4，2-5和2-6显示使用CD聚合物#25发现相同的倾向。然而令人惊奇地，与常规氢化聚合物相比，CD聚合物#25向凝胶提供更高的拉伸强度和更高的伸长率。DRAKEOL 34购自Penreco和是Tg为-64℃的链烷类加工油。
表2
组成，％w  #2-1  #2-2   #2-3  #2-4   #2-5  #2-6
 DRAKEOL 34  90  85   80  90   85  80
 SEBS#1  10  15   20
 CD聚合物#25  10   15  20
 熔体粘度149℃，mpa.s(cps)  185  750   3,870  235   2210  17,500
 环球软化点，℃  85  96   106  89   104  117
 拉伸强度，kPa(psi)  太软  117(17)   352(51)  太软   124(18.5)  545(79)
 断裂伸长率，％  280  280   540   460  760

Claims (7)

1.一种油凝胶组合物，包括100重量份至少一种具有单烯基芳烃和共轭二烯烃受控分布嵌段的氢化嵌段共聚物，350-2000重量份填充油，其中该氢化嵌段共聚物含有至少一个聚合物嵌段A和至少一个聚合物嵌段B，和其中(a.)在氢化之前，每个A嵌段独立地是单烯基芳烃均聚物嵌段和每个B嵌段独立地是至少一种共轭二烯烃和至少一种单烯基芳烃的受控分布共聚物嵌段；(b.)在氢化之后减少了0-10％的芳烃双键，和减少了至少90％的共轭二烯烃双键；(c.)每个A嵌段的数均分子量为3,000-60,000和每个B嵌段的数均分子量为30,000-300,000；(d.)每个B嵌段包括邻近A嵌段、富含共轭二烯烃单元的末端区域和一个或多个不邻近A嵌段、富含单烯基芳烃单元的区域；(e.)氢化嵌段共聚物中单烯基芳烃的总数量是20-80wt％；和(f.)每个B嵌段中单烯基芳烃的重量百分比是10-75％。
2.根据权利要求1的油凝胶组合物，其中该单烯基芳烃是苯乙烯和该共轭二烯烃选自异戊二烯和丁二烯。
3.根据权利要求1或2的油凝胶组合物，其中该共轭二烯烃是丁二烯，和其中嵌段B中20-80mol％的缩合丁二烯单元具有1，2-构型。
4.根据权利要求1-3任意一项的油凝胶组合物，其中嵌段B的苯乙烯嵌段度小于40mol％，该苯乙烯嵌段度指数定义为在聚合物链上含有两个苯乙烯邻接部分的嵌段B中苯乙烯单元的比例。
5.根据权利要求1-4任意一项的油凝胶组合物，其中每个B嵌段中苯乙烯的重量百分比是10％-30％，和每个嵌段B的苯乙烯嵌段度指数小于10。
6.根据权利要求1-5任意一项的油凝胶组合物，其中该氢化嵌段共聚物是ABA、(A-B)n、(A-B)nA、或(A-B)nX嵌段共聚物，其中n是2-30的整数，X是偶合剂残基，该嵌段共聚物总分子量是40,000-140,000和其中每个B嵌段含有10-30wt％苯乙烯。
7.根据权利要求1-6任意一项的油凝胶组合物，其中该填充油是具有低挥发性和小于50％芳族物质含量的石油基白油。
CNB03807477XA 2002-02-07 2003-02-07 来自受控分布嵌段共聚物的凝胶 Expired - Lifetime CN1288209C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US35521002P 2002-02-07 2002-02-07
US60/355,210 2002-02-07

Publications (2)

Publication Number Publication Date
CN1643067A true CN1643067A (zh) 2005-07-20
CN1288209C CN1288209C (zh) 2006-12-06

Family

ID=27734482

Family Applications (4)

Application Number Title Priority Date Filing Date
CNB03807477XA Expired - Lifetime CN1288209C (zh) 2002-02-07 2003-02-07 来自受控分布嵌段共聚物的凝胶
CN038074842A Expired - Lifetime CN1643016B (zh) 2002-02-07 2003-02-07 新型嵌段共聚物及其制备方法
CNB038075040A Expired - Fee Related CN1315948C (zh) 2002-02-07 2003-02-07 聚合物改性沥青组合物
CNB038074834A Expired - Lifetime CN1280323C (zh) 2002-02-07 2003-02-07 来自受控分布嵌段共聚物的粘合剂

Family Applications After (3)

Application Number Title Priority Date Filing Date
CN038074842A Expired - Lifetime CN1643016B (zh) 2002-02-07 2003-02-07 新型嵌段共聚物及其制备方法
CNB038075040A Expired - Fee Related CN1315948C (zh) 2002-02-07 2003-02-07 聚合物改性沥青组合物
CNB038074834A Expired - Lifetime CN1280323C (zh) 2002-02-07 2003-02-07 来自受控分布嵌段共聚物的粘合剂

Country Status (10)

Country Link
US (11) US6759454B2 (zh)
EP (4) EP1474482A1 (zh)
CN (4) CN1288209C (zh)
AT (2) ATE427988T1 (zh)
AU (4) AU2003208666A1 (zh)
DE (3) DE60327051D1 (zh)
EA (1) EA007542B1 (zh)
ES (1) ES2291615T3 (zh)
TW (4) TWI301845B (zh)
WO (4) WO2003066770A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110050035A (zh) * 2016-12-07 2019-07-23 道达尔销售服务公司 固体油质组合物
CN110408220A (zh) * 2018-04-30 2019-11-05 科腾聚合物有限责任公司 具有改进功效的凝胶组合物用嵌段共聚物

Families Citing this family (211)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7226484B2 (en) * 1994-04-19 2007-06-05 Applied Elastomerics, Inc. Tear resistant gels and articles for every uses
US7179860B2 (en) * 2001-03-13 2007-02-20 Liwei Cao Crosslinked polymer electrolyte membranes for heat, ion and moisture exchange devices
US6759454B2 (en) 2002-02-07 2004-07-06 Kraton Polymers U.S. Llc Polymer modified bitumen compositions
US7012118B2 (en) * 2002-02-07 2006-03-14 Kraton Polymers U.S. Llc Photopolymerizable compositions and flexographic plates prepared from controlled distribution block copolymers
US20030181584A1 (en) * 2002-02-07 2003-09-25 Kraton Polymers U.S. Llc Elastomeric articles prepared from controlled distribution block copolymers
JP4530669B2 (ja) * 2002-04-25 2010-08-25 旭化成ケミカルズ株式会社 ブロック共重合体及びその組成物
EP1431348A1 (en) * 2002-12-16 2004-06-23 KRATON Polymers Research B.V. Block copolymer modified bitumen felts
EP1605002A4 (en) * 2003-03-14 2009-10-21 Jsr Corp HYDROGENIC DIENE COPOLYMER, POLYMER COMPOSITION AND MOLDED OBJECT
US7795347B2 (en) * 2003-03-14 2010-09-14 Mitsui Chemicals, Inc. Multi-branched polymer, process for producing the same, and applications thereof
US7517932B2 (en) * 2003-03-24 2009-04-14 Kraton Polymers U.S. Llc Poly(styrene-butadiene-styrene)polymers having a high vinyl content in the butadiene block and hot melt adhesive composition comprising said polymers
JP2006525398A (ja) * 2003-05-01 2006-11-09 クレイトン・ポリマーズ・リサーチ・ベー・ベー 着色可能な組成物
US20070026175A1 (en) * 2003-07-15 2007-02-01 Denki Kagaku Kogyo Kabushiki Kaisha Heat-shrinkable foam films
JP2007506842A (ja) * 2003-09-23 2007-03-22 デイス−アナリティック コーポレーション 新規なブロックコポリマー及びその製造方法
JP4776155B2 (ja) * 2003-10-21 2011-09-21 旭化成ケミカルズ株式会社 水添共重合体
US7037980B2 (en) * 2003-11-10 2006-05-02 Chevron Phillips Chemical Company, Lp Monovinylarene/conjugated diene copolymers having lower glass transition temperatures
US20050119403A1 (en) * 2003-12-01 2005-06-02 St. Clair David J. Solvent based, elastomeric coatings with lower VOC
DE602004005568T2 (de) * 2004-02-19 2007-08-09 Kraton Polymers Research B.V. Gefärbte Filzprodukte als Dachabdeckung
JP5080967B2 (ja) * 2004-03-03 2012-11-21 クレイトン・ポリマーズ・リサーチ・ベー・ベー 高い流動及び高い弾性を有するブロック共重合体
US7799854B2 (en) * 2004-04-01 2010-09-21 Sabic Innovative Plastics Ip B.V. Flame retardant thermoplastic composition and articles comprising the same
US7417083B2 (en) 2004-04-01 2008-08-26 Sabic Innovative Plastics Ip B.V. Flame retardant composition
US7582692B2 (en) * 2004-04-01 2009-09-01 Sabic Innovative Plastics Ip B.V. Flame retardant thermoplastic composition and articles comprising the same
US7348076B2 (en) 2004-04-08 2008-03-25 Saint-Gobain Ceramics & Plastics, Inc. Single crystals and methods for fabricating same
US7717893B2 (en) 2004-06-04 2010-05-18 The Procter & Gamble Company Absorbent articles comprising a slow recovery elastomer
US7905872B2 (en) 2004-06-04 2011-03-15 The Procter & Gamble Company Absorbent articles comprising a slow recovery stretch laminate
KR20070049149A (ko) * 2004-08-05 2007-05-10 화이어스톤 폴리머스, 엘엘씨 관능성 다-블록 폴리머의 단일단계 합성
FR2876141B1 (fr) * 2004-10-06 2006-12-08 Sandvik Tamrock Secoma Sas Soc Dispositif de foration par rotopercussion
US20060115613A1 (en) * 2004-12-01 2006-06-01 Cryovac, Inc. Patch bag and barrier bag
US7473473B2 (en) * 2004-12-01 2009-01-06 Cryovac, Inc. Tear resistant shrink film
US20060135695A1 (en) * 2004-12-17 2006-06-22 Hua Guo Flexible poly(arylene ether) composition and articles thereof
US7776441B2 (en) * 2004-12-17 2010-08-17 Sabic Innovative Plastics Ip B.V. Flexible poly(arylene ether) composition and articles thereof
US8419701B2 (en) 2005-01-10 2013-04-16 The Procter & Gamble Company Absorbent articles with stretch zones comprising slow recovery elastic materials
WO2006081068A1 (en) 2005-01-26 2006-08-03 The Procter & Gamble Company Disposable pull-on diaper having a low force, slow recovery elastic waist
US7772322B2 (en) * 2005-02-17 2010-08-10 Sabic Innovative Plastics Ip B.V. Poly(arylene ether) composition and articles
US7531209B2 (en) * 2005-02-24 2009-05-12 Michael Raymond Ayers Porous films and bodies with enhanced mechanical strength
EP1858974B1 (en) * 2005-03-11 2012-08-22 KRATON Polymers Research B.V. Oil gels of controlled distribution block copolymers and ester oils
US20060205904A1 (en) * 2005-03-11 2006-09-14 St Clair David J Oil gels of controlled distribution block copolymers and ester oils
EP1707596A1 (en) * 2005-03-14 2006-10-04 Kraton Polymers Research B.V. Hydrogenated block copolymer composition for overmoulding onto thermoplastics
US20060251890A1 (en) * 2005-05-06 2006-11-09 Richard Lane Pressure sensitive adhesive (PSA) laminates
US20060263596A1 (en) * 2005-05-06 2006-11-23 Bamborough Derek W Pressure sensitive adhesives (PSA) laminates
TWI326691B (en) * 2005-07-22 2010-07-01 Kraton Polymers Res Bv Sulfonated block copolymers, method for making same, and various uses for such block copolymers
US20070026251A1 (en) * 2005-07-26 2007-02-01 Kraton Polymers U.S. Llc Flexible packaging laminate films including a block copolymer layer
US20070055015A1 (en) * 2005-09-02 2007-03-08 Kraton Polymers U.S. Llc Elastomeric fibers comprising controlled distribution block copolymers
US20070066753A1 (en) * 2005-09-16 2007-03-22 Ehrlich Martin L Highly processible compounds of high MW conventional block copolymers and controlled distribution block copolymers
US20070078194A1 (en) * 2005-10-04 2007-04-05 St Clair David J Flexographic printing plate and flexographic printing plate precursor composition for preparing same
KR100969106B1 (ko) 2005-11-14 2010-07-09 크레이튼 폴리머즈 리서치 비.브이. 역청질 결합제 조성물의 제조방법
CA2631160C (en) 2005-11-28 2013-10-15 Gala Industries, Inc. Apparatus and method for controlled pelletization processing
US20070130863A1 (en) * 2005-12-01 2007-06-14 Jones David R Iv Roofing adhesive
US7737216B2 (en) * 2006-01-26 2010-06-15 Chevron Phillips Chemical Company Lp Monovinylarene conjugated diene block copolymer compositions for shrinkable films
US7662528B2 (en) * 2006-02-17 2010-02-16 Xerox Corporation Charge generating composition
US7625851B2 (en) * 2006-03-10 2009-12-01 Kraton Polymers Us Llc Viscosity index improver for lubricating oils
ES2397099T3 (es) * 2006-03-24 2013-03-04 Kraton Polymers U.S. Llc Copolímeros de bloque para altas temperaturas y procedimientos para su producción
US7585916B2 (en) 2006-03-24 2009-09-08 Kraton Polymers Us Llc Block copolymer compositions
US7582702B2 (en) 2006-03-24 2009-09-01 Kraton Polymers U.S. Llc Block copolymer compositons
US7592390B2 (en) * 2006-03-24 2009-09-22 Kraton Polymers U.S. Llc Hydrogenated block copolymer compositions
US7858693B2 (en) * 2006-03-24 2010-12-28 Kratonpolymers U.S. Llc Unhydrogenated block copolymer compositions
WO2007127155A2 (en) * 2006-04-24 2007-11-08 Kraton Polymers U.S Llc Polymeric compositions and films formed therefrom
US7990679B2 (en) * 2006-07-14 2011-08-02 Dais Analytic Corporation Nanoparticle ultracapacitor
DE102006037627A1 (de) * 2006-08-10 2008-02-14 Tesa Ag Selbstklebemasse aus hydrierten Blockcopolymeren und daraus hergestellte Schutzfolie für glatte und raue Oberflächen
US7685784B2 (en) * 2006-08-25 2010-03-30 Tremco Incorporated Cool roof covering and adhesive therefor
US8470071B2 (en) * 2006-09-25 2013-06-25 Dais Analytic Corporation Enhanced HVAC system and method
CA2669383C (en) * 2006-11-13 2013-02-26 Kraton Polymers Us Llc Bituminous emulsions
US20100075132A1 (en) * 2006-12-07 2010-03-25 3M Innovative Properties Company Blends of block copolymer and acrylic adhesives
EP2094801B2 (en) * 2006-12-07 2017-02-22 3M Innovative Properties Company Block copolymer blend adhesives with multiple tackifiers
US20080153970A1 (en) * 2006-12-21 2008-06-26 Kraton Polymers U.S. Llc Solvent sprayable contact adhesive formulations from functionalized/controlled distribution block copolymers
US7977432B2 (en) * 2007-01-12 2011-07-12 Kraton Polymers U.S. Llc Functionalized block copolymers, method for making same, and various uses for such block copolymers
WO2008089332A2 (en) 2007-01-19 2008-07-24 Stepan Company Method of sulfonation of block polymers
US8500960B2 (en) * 2007-01-20 2013-08-06 Dais Analytic Corporation Multi-phase selective mass transfer through a membrane
US20080193755A1 (en) * 2007-02-09 2008-08-14 Olivier Guise Extrusion die, methods of coating a wire core, and a coated wire by the extrusion die and methods
MX2009011561A (es) * 2007-05-01 2009-11-10 Kraton Polymers Us Llc Composicion aglutinante bituminosa y proceso para preparar la misma.
DE102007027156A1 (de) 2007-06-13 2008-12-24 Kraiburg Tpe Gmbh & Co. Kg Transparente, thermoplastisch verarbeitbare, elastomere Polymerzusammensetzung mit UV-Stabilität und guten Haftungseigenschaften
WO2009002984A2 (en) * 2007-06-26 2008-12-31 Aegis Biosciences Llp Stable and compatible polymer blends
US20090062457A1 (en) * 2007-09-04 2009-03-05 Kraton Polymers U.S. Llc Styrenic block copolymers and compositions containing the same
US7923391B2 (en) * 2007-10-16 2011-04-12 Kimberly-Clark Worldwide, Inc. Nonwoven web material containing crosslinked elastic component formed from a pentablock copolymer
US8399368B2 (en) * 2007-10-16 2013-03-19 Kimberly-Clark Worldwide, Inc. Nonwoven web material containing a crosslinked elastic component formed from a linear block copolymer
US8349963B2 (en) * 2007-10-16 2013-01-08 Kimberly-Clark Worldwide, Inc. Crosslinked elastic material formed from a linear block copolymer
US7923392B2 (en) * 2007-10-16 2011-04-12 Kimberly-Clark Worldwide, Inc. Crosslinked elastic material formed from a branched block copolymer
US8323257B2 (en) 2007-11-21 2012-12-04 The Procter & Gamble Company Absorbent articles comprising a slow recovery stretch laminate and method for making the same
US8883927B2 (en) * 2007-11-28 2014-11-11 Dynasol Elastómeros, S.A. De C.V. Radial multi-block copolymers
BRPI0820134A2 (pt) * 2007-12-21 2015-05-12 Kraton Polymers Us Llc Películas elastoméricas macias
US9453606B2 (en) * 2007-12-26 2016-09-27 Smart Pipe Company, Inc. Movable factory for simultaneous mobile field manufacturing and installation of non-metallic pipe
US8084521B2 (en) 2008-04-30 2011-12-27 Wright Advanced Asphalt Systems System and method for the pre-treatment of rubber-modified asphalt cement, and emulsions thereof
ES2569076T3 (es) * 2008-04-30 2016-05-06 Trinseo Europe Gmbh Polímeros de estireno-butadieno con gradiente de estireno y métodos para preparar los mismos
US8012539B2 (en) 2008-05-09 2011-09-06 Kraton Polymers U.S. Llc Method for making sulfonated block copolymers, method for making membranes from such block copolymers and membrane structures
US9017791B2 (en) 2008-05-13 2015-04-28 Owens Corning Intellectual Capital, Llc Shingle blank having formation of individual hip and ridge roofing shingles
CN102099381B (zh) * 2008-06-18 2013-10-02 思迪隆欧洲有限公司 低氯化物聚丁二烯
US20100010147A1 (en) * 2008-07-08 2010-01-14 Kraton Polymer U.S. Llc Adhesives prepared from diphenylethylene containing block copolymers
US20100010154A1 (en) * 2008-07-08 2010-01-14 Kraton Polymers U.S. Llc Gels prepared from dpe containing block copolymers
US20100010171A1 (en) * 2008-07-11 2010-01-14 Ruidong Ding Thermoplastic polyurethane/block copolymer compositions
US9732178B1 (en) 2008-07-24 2017-08-15 Bridgestone Corporation Block copolymers including high vinyl segments
CN102159607B (zh) * 2008-08-05 2014-03-12 费尔斯通聚合物有限责任公司 不是附聚体的含有苯乙烯/丁二烯二嵌段共聚物的共混物及其制备方法
US20100056721A1 (en) * 2008-09-03 2010-03-04 Kathryn Wright Articles prepared from certain hydrogenated block copolymers
US8202923B2 (en) 2008-09-24 2012-06-19 Wright Asphalt Products Company System and method for high throughput preparation of rubber-modified asphalt cement
WO2010042668A1 (en) 2008-10-07 2010-04-15 Ross Technology Corporation Spill resistant surfaces having hydrophobic and oleophobic borders
US20100130670A1 (en) * 2008-11-21 2010-05-27 Kraton Polymers Us Llc End use applications prepared from certain block copolymers
US9151055B2 (en) 2009-02-25 2015-10-06 Owens Corning Intellectual Capital, Llc Hip and ridge roofing material
US11313127B2 (en) 2009-02-25 2022-04-26 Owens Corning Intellectual Capital, Llc Hip and ridge roofing material
US20100222467A1 (en) * 2009-02-27 2010-09-02 Semmaterials, L.P. crack resistent layer with good mixture fracture energy made from an emulsion of a polymer modified bituminous binder and method of selecting same
US20100222465A1 (en) * 2009-02-27 2010-09-02 Semmaterials, L.P. Crack resistant layer with good mixture fracture energy and method of selecting same
US20100222464A1 (en) * 2009-02-27 2010-09-02 Semmaterials, L.P. Emulsion of a polymer modified asphalt
US20100222469A1 (en) 2009-02-27 2010-09-02 Semmaterials, L.P. A crack resistant layer with good binder fracture energy properties and method of selecting same
US20100222466A1 (en) * 2009-02-27 2010-09-02 Semmaterials, L.P. Crack resistant layer with good beam fatigue properties made from an emulsion of a polymer modified bituminous binder and method of selecting same
CN101508811A (zh) * 2009-03-10 2009-08-19 叶孙勇 可注射可硫化苯乙烯系橡胶粒子及制备工艺
US20100239807A1 (en) * 2009-03-20 2010-09-23 Grubka Lawrence J Flexible laminated hip and ridge shingle
US8263713B2 (en) * 2009-10-13 2012-09-11 Kraton Polymers U.S. Llc Amine neutralized sulfonated block copolymers and method for making same
US8445631B2 (en) * 2009-10-13 2013-05-21 Kraton Polymers U.S. Llc Metal-neutralized sulfonated block copolymers, process for making them and their use
BR112012011124A2 (pt) * 2009-11-12 2016-07-05 Kraton Polymers Us Llc composicao de copolímero em bloco
US9013155B2 (en) 2010-01-09 2015-04-21 Dais Analytic Corporation Energy storage devices including a solid multilayer electrolyte
US9393557B2 (en) 2010-01-09 2016-07-19 Dais Analytic Corporation Anionic exchange electrolyte polymer membranes
BR112012017173A2 (pt) * 2010-01-27 2016-04-19 Kraton Polymers Us Llc composição de copolímero em bloco
KR101434517B1 (ko) 2010-01-29 2014-08-29 크레이튼 폴리머즈 유.에스. 엘엘씨 슬러쉬 성형용 열용융성 조성물
US20140141233A1 (en) 2012-07-03 2014-05-22 Peterson Chemical Technology, Inc. Surface Infusion of Flexible Cellular Foams With Novel Liquid Gel Mixture
US9097020B2 (en) * 2010-03-04 2015-08-04 Owens Corning Intellectual Capital, Llc Hip and ridge roofing shingle
EP2547832A4 (en) 2010-03-15 2016-03-16 Ross Technology Corp PISTON AND METHODS FOR PRODUCING HYDROPHOBIC SURFACES
US20110262686A1 (en) * 2010-04-22 2011-10-27 Kathryn Wright High Tensile Strength Article with Elastomeric Layer
CN101870744A (zh) * 2010-06-11 2010-10-27 北京化工大学 一种丁腈酯橡胶的加氢方法
US9429366B2 (en) 2010-09-29 2016-08-30 Kraton Polymers U.S. Llc Energy recovery ventilation sulfonated block copolymer laminate membrane
US9394414B2 (en) 2010-09-29 2016-07-19 Kraton Polymers U.S. Llc Elastic, moisture-vapor permeable films, their preparation and their use
CN103201298B (zh) 2010-10-18 2015-06-24 科腾聚合物美国有限责任公司 生产磺化的嵌段共聚物组合物的方法
US9017305B2 (en) 2010-11-12 2015-04-28 The Procter Gamble Company Elastomeric compositions that resist force loss and disintegration
US20130260069A1 (en) 2010-12-06 2013-10-03 Colgate-Palmolive Company Laminate Tube Having a Resilent Copolymer Coating
JP5859563B2 (ja) 2010-12-23 2016-02-10 スタイロリューション・ヨーロッパ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング 熱可塑性エラストマー組成物及びその製造方法
CN108559288B (zh) * 2011-01-30 2020-10-27 戴纳索尔伊莱斯托米罗斯公司 递变三嵌段共聚物
JP2014511411A (ja) 2011-02-18 2014-05-15 クレイトン・ポリマーズ・ユー・エス・エル・エル・シー ケーブル充填用硬化性ポリマー組成物
PE20140834A1 (es) 2011-02-21 2014-07-10 Ross Technology Corp Revestimiento superhidrofos y oleofobos con sistema aglutinantes con bajo contenido de cov
CN102190957B (zh) * 2011-03-21 2013-04-24 武汉理工大学 一种镁铝基层状双氢氧化物耐老化弹性体改性沥青涂盖料及其制备方法
CA2831339A1 (en) * 2011-04-07 2012-10-11 David Strickland Bituminous composition
TWI512060B (zh) * 2011-04-26 2015-12-11 Chi Mei Corp 防濕絕緣塗料及其應用
US8378453B2 (en) 2011-04-29 2013-02-19 Georgia Tech Research Corporation Devices including composite thermal capacitors
CN102277112B (zh) * 2011-05-23 2014-11-05 波士胶芬得利（中国）粘合剂有限公司 含蜡热熔胶和一次性吸收制品
US9861941B2 (en) 2011-07-12 2018-01-09 Kraton Polymers U.S. Llc Modified sulfonated block copolymers and the preparation thereof
US20130101767A1 (en) 2011-10-25 2013-04-25 Kraton Polymers U.S. Llc Method for melt processing sulfonated block copolymers and articles comprising optionally amine modified sulfonated block copolymers
US11021559B2 (en) 2011-10-31 2021-06-01 Kraton Polymers Llc Sulfonated block copolymer laminates with polar or active metal substrates
US20130310492A1 (en) * 2011-11-17 2013-11-21 Baker Hughes Incorporated Process for improving the physical properties of bitumen
WO2013090939A1 (en) 2011-12-15 2013-06-20 Ross Technology Corporation Composition and coating for superhydrophobic performance
US9290943B2 (en) 2012-01-05 2016-03-22 Owens Corning Intellectual Capital, Llc Hip and ridge roofing shingle
US9293269B2 (en) 2012-02-08 2016-03-22 Dais Analytic Corporation Ultracapacitor tolerating electric field of sufficient strength
US20130225020A1 (en) 2012-02-24 2013-08-29 Kraton Polymers Us Llc High flow, hydrogenated styrene-butadiene-styrene block copolymer and applications
US9771473B2 (en) 2012-02-24 2017-09-26 Kraton Polymers U.S. Llc High flow, hydrogenated styrene-butadiene-styrene block copolymers and applications
JP6022669B2 (ja) 2012-03-15 2016-11-09 クレイトン・ポリマーズ・ユー・エス・エル・エル・シー スルホン化ブロック共重合体および粒状炭素のブレンドならびにこれを含む膜、フィルムおよび被膜
CN103382241B (zh) * 2012-05-04 2016-06-08 中国石油天然气股份有限公司 星形异戊二烯-b-丁二烯苯乙烯三元共聚物及其制备方法
CA2878189C (en) * 2012-06-25 2021-07-13 Ross Technology Corporation Elastomeric coatings having hydrophobic and/or oleophobic properties
US20140100310A1 (en) 2012-10-08 2014-04-10 Teknor Apex Company Thermoplastic elastomer compositions having biorenewable content
EP2759572A1 (en) 2013-01-23 2014-07-30 Teknor Apex Company Thermoplastic elastomer compositions having biorenewable content
EP2904046B1 (en) 2012-10-08 2018-11-21 Teknor Apex Company Thermoplastic elastomer compositions having biorenewable content
JP2016503441A (ja) 2012-11-05 2016-02-04 クレイトン・ポリマーズ・ユー・エス・エル・エル・シー 可撓性および強度を可能とするポリマー用難燃剤系
CN103804603B (zh) * 2012-11-07 2016-03-02 中国石油化工股份有限公司 一种溶聚丁苯橡胶及其合成方法和酸酐的应用
EP2938666A4 (en) * 2012-12-27 2016-06-29 Peterson Chemical Technology Inc SURFACE INFUSION OF FLEXIBLE CELLULAR FOAMS WITH A NOVEL LIQUID MIXTURE
US9061254B2 (en) * 2013-01-14 2015-06-23 Kraton Polymers U.S. Llc Block copolymers, their manufacture and their use
CN107056971B (zh) 2013-01-14 2019-08-13 科腾聚合物美国有限责任公司 阴离子交换嵌段共聚物，其制造及其用途
US20140202357A1 (en) * 2013-01-18 2014-07-24 Special Materials Company Asphalt cutback formulations
KR20150005424A (ko) * 2013-07-05 2015-01-14 주식회사 엘지화학 혼련성이 개선된 아스팔트 개질제 및 이를 포함하는 아스팔트 조성물
US9127132B2 (en) 2013-10-08 2015-09-08 Katon Polymers U.S. LLC Process for coagulating sulfonated block copolymers
US10843401B2 (en) 2013-11-01 2020-11-24 Kraton Polymers U.S. Llc Fuse molded three dimensional article and a method for making the same
TWI512062B (zh) * 2013-11-21 2015-12-11 Chi Mei Corp 防濕絕緣塗料及其應用
US20150148488A1 (en) * 2013-11-25 2015-05-28 Kraton Polymers U.S. Llc Impact Resistant Compositions Of Thermoplastic Polyamides And Modified Block Copolymers For Use In Tubes, Pipes, And Hoses
US11130276B2 (en) * 2013-12-18 2021-09-28 Ineos Styrolution Group Gmbh Use of molding materials based on vinyl aromatic/diene block copolymers for 3-D-printing
MY192325A (en) * 2014-01-17 2022-08-17 Asahi Chemical Ind Polymer and asphalt composition
WO2015108139A1 (ja) 2014-01-17 2015-07-23 旭化成ケミカルズ株式会社 重合体及びアスファルト組成物
US10072140B2 (en) 2014-02-11 2018-09-11 Ineos Styrolution Group Gmbh Blends of thermoplastic elastomers based on styrene (S-TPE) and polyolefins
US9758970B2 (en) 2014-02-25 2017-09-12 Owens Corning Intellectual Capital, Llc Laminated hip and ridge shingle
USD755997S1 (en) 2014-02-27 2016-05-10 Owens Corning Intellectual Capital, Llc Shingle
EP3112431B1 (en) * 2014-02-28 2020-06-17 Zeon Corporation Transparent adhesive sheet
US9988500B2 (en) 2014-04-02 2018-06-05 Kraton Polymers U.S. Llc Process for the preparation of an aqueous emulsion of a midblock sulfonated block copolymer
US10053603B2 (en) 2014-04-02 2018-08-21 Kraton Polymers U.S. Llc Block copolymers containing a copolymer myrcene block
EP3126438B1 (en) 2014-04-02 2018-09-26 Kraton Polymers U.S. LLC Process for the preparation of an aqueous emulsion of a midblock sulfonated block copolymer
US10047477B2 (en) 2014-04-02 2018-08-14 Kraton Polymers U.S. Llc Textile coating composition
TWI616491B (zh) 2014-05-08 2018-03-01 Asahi Kasei Chemicals Corp Asphalt composition
JP6557326B2 (ja) 2014-05-16 2019-08-07 クレイトン・ポリマーズ・ユー・エス・エル・エル・シー 分岐した広いｍｗｄの共役ジエンポリマー
US9156978B1 (en) * 2014-06-06 2015-10-13 Teknor Apex Company Low softener halogen free flame retardant styrenic block copolymer-based thermoplastic elastomer compositions
US9216405B1 (en) 2014-06-26 2015-12-22 Kraton Polymers U.S. Llc Rotary enthalpy exchange wheel having sulfonated block copolymer
CN105273204B (zh) 2014-07-16 2020-10-16 科腾聚合物美国有限责任公司 嵌段共聚物、其制备及其用途
US9902884B2 (en) 2014-12-17 2018-02-27 H.B. Fuller Company Hot melt adhesive composition for bonding packs of plastic containers
CA2967861C (en) 2014-12-17 2021-11-30 H.B. Fuller Company Hot melt adhesive composition for bonding packs of metal containers
US9598524B1 (en) 2015-09-18 2017-03-21 Chevron Phillips Chemical Company Lp Styrene-butadiene block copolymers with a terminal butadiene block for tubing applications
US9441090B1 (en) 2015-03-12 2016-09-13 Chevron Phillips Chemical Company Lp Methods for controlling hardness of styrene-butadiene block copolymers
US9540475B2 (en) 2015-03-12 2017-01-10 Chevron Phillips Chemical Company Lp Styrene-butadiene block copolymers for tubing applications
BR112017022689B1 (pt) * 2015-04-24 2021-06-15 Pirelli Tyre S.P.A. Pneu para rodas de veículo, copolímero, e processo de copolimerização de estireno e butadieno com um ou mais monômeros diênicos
WO2016200783A1 (en) 2015-06-12 2016-12-15 Kraton Polymers U.S. Llc A composition for soft skins and uses thereof
CN107735413B (zh) 2015-07-16 2020-11-06 旭化成株式会社 部分氢化嵌段共聚物、粘着粘结组合物、粘着粘结性胶带、标签、改性沥青组合物、改性沥青混合物和铺装用粘结剂组合物
US9738781B2 (en) 2015-09-03 2017-08-22 Ineos Styrolution Group Gmbh Blends of styrene-butadiene block copolymer with styrenic thermoplastic elastomers for tubing applications
US10066100B2 (en) * 2015-09-08 2018-09-04 Kraton Polymers U.S. Llc Copolyester/controlled distribution styrenic block copolymer blends and methods of making and using same
CN108602990B (zh) 2016-01-26 2021-03-30 戴纳索尔伊莱斯托米罗斯公司 逆向递变热塑性弹性体
US10023676B2 (en) 2016-02-24 2018-07-17 Ineos Styrolution Group Gmbh Styrene-butadiene block copolymers with an internal butadiene block for tubing applications
US9828455B2 (en) 2016-02-24 2017-11-28 Ineos Styrolution Group Gmbh Styrene-butadiene block copolymers with an internal butadiene block for tubing applications
EP3436490B1 (en) 2016-03-24 2023-08-16 Kraton Polymers U.S. LLC Semi-crystalline block copolymers and compositions therefrom
US10539649B2 (en) 2016-03-28 2020-01-21 Michael L. Howard System and methods for detecting a position using differential attenuation
EP3445833B8 (en) 2016-05-09 2021-05-26 Kraton Polymers U.S. LLC Foam adhesion promotion
US10839979B2 (en) 2016-07-08 2020-11-17 Teknor Apex Company Cable with flame retardant multi-layer covering
CN106398618A (zh) * 2016-08-27 2017-02-15 安徽天瞳智能科技有限公司 一种高密度树脂胶粘剂
US11124644B2 (en) * 2016-09-01 2021-09-21 University Of Florida Research Foundation, Inc. Organic microgel system for 3D printing of silicone structures
WO2019009836A2 (en) * 2016-12-30 2019-01-10 Turkiye Petrol Rafinerileri Anonim Sirketi Tupras BITUMINOUS MIXTURE COMPRISING POLYURETHANE OBTAINED BY A POLYMERIZATION REACTION AND PROCESS FOR PREPARING THE MIXTURE
US20220411637A1 (en) 2017-01-26 2022-12-29 Dynasol Elastómeros, S.A. De C.V. Counter Tapered Thermoplastic Elastomers
US11891503B2 (en) * 2017-03-16 2024-02-06 Ineos Styrolution Group Gmbh Non-sticky, soft and transparent styrenic thermoplastic elastomers
EP3635021A4 (en) * 2017-06-09 2021-04-07 Kraton Polymers LLC HIGHLY ASYMMETRIC TRIBLOCK POLYMER COMPOSITIONS AND METHOD FOR MANUFACTURING THEREOF
CN110997803B (zh) 2017-06-19 2023-03-28 英力士苯领集团股份公司 具有良好感官特性的乙烯基芳族/二烯嵌段共聚物
JP2020536139A (ja) 2017-09-29 2020-12-10 クレイトン・ポリマーズ・エル・エル・シー 湿潤状態での握り心地が改善されたエラストマー組成物
TW201936770A (zh) 2018-01-31 2019-09-16 日商積水富樂股份有限公司 伸縮性熱熔組成物
DE102018109269A1 (de) 2018-04-18 2019-10-24 Clariant Plastics & Coatings Ltd Dauerklebrige Haftklebstoffe mit verbesserter Umweltverträglichkeit
US11524150B2 (en) 2018-09-10 2022-12-13 Kraton Polymers Llc Medical tubing and compositions and methods for making therefor
EP3623417B1 (en) 2018-09-10 2021-06-23 Kraton Polymers Research B.V. Rubber composition and method for making thereof
US11454623B2 (en) 2018-10-11 2022-09-27 Baker Hughes Holdings Llc Method for quantitatively assessing stability additive performance at field dosages
US11760826B2 (en) 2018-12-14 2023-09-19 Kraton Corporation Block copolymers and uses thereof
US11629215B2 (en) * 2019-04-02 2023-04-18 Kraton Corporation Sulfonated block copolymers and uses thereof
US11613619B2 (en) 2019-05-29 2023-03-28 Kraton Corporation Molding compositions and foam molded articles made thereof
FR3099766B1 (fr) * 2019-08-07 2021-07-30 Michelin & Cie Polymère bloc diénique riche en éthylène ayant un bloc statistique et un bloc polyéthylène.
BR112022007667A2 (pt) * 2019-11-07 2022-08-09 Dynasol Elastomeros Sa De Cv Copolímeros de dieno modificados e uso dos mesmos
US11739208B2 (en) 2020-08-14 2023-08-29 Kraton Corporation Block copolymers and uses thereof
KR20240009382A (ko) 2021-01-24 2024-01-22 크레이튼 코포레이션 배터리용 전극 바인더
WO2022268957A1 (en) 2021-06-24 2022-12-29 Borealis Ag Method for determining compressive character of olefin polymerisation catalysts
CN117881707A (zh) 2021-06-24 2024-04-12 博里利斯股份公司 生产聚乙烯聚合物的方法
CN115948121B (zh) * 2023-01-05 2023-10-20 江苏凯伦建材股份有限公司 一种基于单环氧封端二嵌段共聚物的改性沥青涂料及其制备方法和应用

Family Cites Families (113)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA716645A (en) 1965-08-24 Shell Oil Company Block polymers and process for preparing them
US3149182A (en) 1957-10-28 1964-09-15 Shell Oil Co Process for preparing block copolymers utilizing organolithium catalysts
BE637376A (zh) 1958-05-23
NL254508A (zh) * 1960-08-03
US3239478A (en) 1963-06-26 1966-03-08 Shell Oil Co Block copolymer adhesive compositions and articles prepared therefrom
US3600250A (en) 1968-09-12 1971-08-17 Shell Oil Co Stretching and laminating thermoplastic elastomers
US3595942A (en) 1968-12-24 1971-07-27 Shell Oil Co Partially hydrogenated block copolymers
USRE27145E (en) 1969-05-20 1971-06-22 Side-chain
US3634549A (en) 1969-08-04 1972-01-11 Shell Oil Co Conjugated diene block copolymers having a random copolymer elastomeric block and their hydrogenated counterparts
US3670054A (en) 1969-10-29 1972-06-13 Shell Oil Co Block copolymers having reduced solvent sensitivity
US3700633A (en) 1971-05-05 1972-10-24 Shell Oil Co Selectively hydrogenated block copolymers
US4039593A (en) 1973-05-18 1977-08-02 Lithium Corporation Of America Preparation of hydroxy-terminated conjugated diene polymers
US3821148A (en) * 1973-09-28 1974-06-28 Exxon Research Engineering Co Plasticized thermoplastic block copolymers
US3821149A (en) * 1973-09-28 1974-06-28 Exxon Research Engineering Co Plasticized thermoplastic semicrystalline block copolymers
US4089913A (en) 1974-01-10 1978-05-16 Sumitomo Chemical Company, Limited Process for producing transparent block copolymer resin
JPS5232774B2 (zh) 1974-02-02 1977-08-24
US4122134A (en) 1974-02-13 1978-10-24 Sumitomo Chemical Company, Limited Method for producing transparent block copolymer resin
US3985830B1 (en) 1974-07-15 1998-03-03 Univ Akron Star polymers and process for the preparation thereof
DE2550546A1 (de) * 1975-11-11 1977-05-18 Basf Ag Schmelzhaftkleber auf der basis von blockcopolymerisaten
US4107131A (en) 1976-06-07 1978-08-15 Shell Oil Company Multicomponent polyurethane-block copolymer-polymer blends
FR2376188A1 (fr) 1976-12-28 1978-07-28 Elf Union Procede de preparation de compositions de bitumes polymeres
US4267284A (en) * 1977-01-07 1981-05-12 Phillips Petroleum Company Tough, transparent articles from styrene polymers blended with certain block-random copolymers
US4122434A (en) * 1977-09-26 1978-10-24 O.E.M. Technical Sales, Inc. Test system for trailer brake mechanism
US4129541A (en) 1977-10-26 1978-12-12 Phillips Petroleum Company Asphaltic compositions containing conjugated diene-monovinyl-substituted aromatic hydrocarbon copolymers of particular structures
US4248981A (en) * 1979-04-30 1981-02-03 Arco Polymers, Inc. Clear impact resistant thermoplastic star-block copolymers
JPS56149413A (en) 1980-04-22 1981-11-19 Japan Synthetic Rubber Co Ltd Production of styrene/butadiene copolymer
JPS57100112A (en) 1980-12-16 1982-06-22 Asahi Chem Ind Co Ltd Perfectly random styrene-butadiene copolymer rubber
US4444953A (en) 1981-11-12 1984-04-24 Shell Oil Company Assymetric block copolymers and corresponding adhesive formulations
US4391949A (en) 1981-11-12 1983-07-05 Shell Oil Company Asymmetric block copolymers and corresponding adhesive formulations
US4412087A (en) 1981-12-16 1983-10-25 Phillips Petroleum Company Viscosity index improver with high thickening power
US4603155A (en) 1983-03-10 1986-07-29 Japan Synthetic Rubber Co., Ltd. Alkenyl aromatic compound-conjugated diene block copolymer and process for the production thereof
US4530652A (en) 1984-01-12 1985-07-23 Buck Ollie G Asphalt composition
JPH0615595B2 (ja) 1984-02-07 1994-03-02 シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー ブロツク共重合体
JPS6129162A (ja) 1984-07-20 1986-02-10 Hitachi Ltd 半導体装置
US4578429A (en) 1984-08-31 1986-03-25 Shell Oil Company Selectively hydrogenated block copolymers modified with acid compounds or derivatives
DE3521597A1 (de) * 1985-06-15 1986-12-18 Rütgerswerke AG, 6000 Frankfurt Bituminoese masse und ihre verwendung
JPS61291610A (ja) 1985-06-18 1986-12-22 Japan Synthetic Rubber Co Ltd ブロツク共重合体およびその組成物
US5371141A (en) 1985-07-31 1994-12-06 Shell Oil Company High impact resistant blends of thermoplastic polyamides and modified block copolymers
JPS6241213A (ja) 1985-08-16 1987-02-23 シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ 変性ブロツクコポリマ−、該コポリマ−を含有する耐衝撃性組成物、及び該コポリマ−の製造法
GB8714817D0 (en) * 1987-06-24 1987-07-29 Flymo Ltd Grass trimmer
US4788361A (en) 1987-10-30 1988-11-29 Shell Oil Company Polymeric viscosity index improver and oil composition comprising the same
US4882384A (en) 1988-02-01 1989-11-21 Shell Oil Company Modified block copolymers
US5239010A (en) * 1988-05-24 1993-08-24 Shell Oil Company Sulfonated block copolymers
US4970265A (en) 1989-03-27 1990-11-13 Shell Oil Company Functionalized polymers and process for modifying unsaturated polymers
DE69032963T2 (de) 1989-05-19 1999-08-19 Japan Synthetic Rubber Co Ltd (Modifiziertes) hydriertes Dien-Blockcopolymer und dieses enthaltende Zusammensetzung
JPH0798890B2 (ja) 1989-06-23 1995-10-25 日本ゼオン株式会社 粘着剤用ブロック共重合体組成物及び粘着剤組成物
GB8918702D0 (en) * 1989-08-16 1989-09-27 Shell Int Research Process for the preparation of random solution copolymers of conjugated dienes and vinyl aromatic compounds
US5206300A (en) 1990-03-30 1993-04-27 Shell Oil Company Functionalized elastomeric polymers
KR0185671B1 (ko) 1990-08-23 1999-05-15 요하네스 아르트 반 주트펜 블록 공중합체의 용융 금속화 방법
US5227419A (en) 1990-12-20 1993-07-13 Phillips Petroleum Company Tapered block styrene/butadiene copolymers
US5516831A (en) 1991-01-30 1996-05-14 Shell Oil Company Selectively sulfonated block copolymers/extender oils
CA2068154C (en) * 1992-05-07 1997-01-14 Janice C. Halligan Programmable call progress tones for a switching system
US5290875A (en) 1992-11-30 1994-03-01 Phillips Petroleum Company Conjugated diene/monovinylarene block copolymers with multiple tapered blocks
US5905097A (en) * 1993-01-08 1999-05-18 The Dow Chemical Company High-strength breathable films of block copolymer lattices
JP3367136B2 (ja) 1993-03-22 2003-01-14 ジェイエスアール株式会社 熱可塑性樹脂組成物
GB9306517D0 (en) 1993-03-29 1993-05-19 Polyphalt Inc Stabilized bitumen compositions
JP3203399B2 (ja) * 1993-05-13 2001-08-27 松下電器産業株式会社 経路探索装置
US5331028A (en) 1993-06-30 1994-07-19 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Polymer-modified asphalt composition and process for the preparation thereof
JPH07123696A (ja) 1993-10-22 1995-05-12 Oriental Motor Co Ltd 多相リニアモータの鉄心製造方法
US6265484B1 (en) 1993-11-15 2001-07-24 Phillips Petroleum Company Tapered block copolymers of monovinylarenes and conjugated dienes
CA2134026C (en) 1993-11-15 1998-06-09 William J. Trepka Tapered block copolymers of monovinylarenes and conjugated dienes
JPH07149952A (ja) 1993-11-30 1995-06-13 Toray Ind Inc 熱硬化性樹脂組成物、樹脂硬化物、プリプレグおよび繊維強化プラスチック
US7226484B2 (en) * 1994-04-19 2007-06-05 Applied Elastomerics, Inc. Tear resistant gels and articles for every uses
US7234560B2 (en) * 1994-04-19 2007-06-26 Applied Elastomerics, Inc. Inflatable restraint cushions and other uses
US7290367B2 (en) * 1994-04-19 2007-11-06 Applied Elastomerics, Inc. Tear resistant gel articles for various uses
US5468574A (en) * 1994-05-23 1995-11-21 Dais Corporation Fuel cell incorporating novel ion-conducting membrane
DE4420952A1 (de) 1994-06-17 1995-12-21 Basf Ag Thermoplastisches Elastomer
US5451619A (en) 1994-08-19 1995-09-19 Shell Oil Company Asphalt composition containing epoxidized polymers
DE19503944A1 (de) 1995-02-07 1996-08-08 Basf Ag Medizintechnisches Formteil, insbesondere Bauteil für ein Übertragungssystem für Infusions- oder Transfusionszwecke
ZA961141B (en) 1995-02-20 1996-08-23 Shell Int Research Bituminous composition
DE19523585A1 (de) * 1995-06-29 1997-01-02 Basf Ag Schlagzähe Formmasse aus Styrolpolymeren
AU708193B2 (en) 1995-08-29 1999-07-29 Pennzoil Products Company Transparent gel candles
GB2305667A (en) * 1995-09-27 1997-04-16 Lawrence Lester Bitumen-polymer compositions
US6797765B2 (en) 1996-02-14 2004-09-28 Edizone, Lc Gelatinous elastomer
US5994450A (en) 1996-07-01 1999-11-30 Teksource, Lc Gelatinous elastomer and methods of making and using the same and articles made therefrom
US6865759B2 (en) 1996-02-14 2005-03-15 Edizone, Inc. Cushions with non-intersecting-columnar elastomeric members exhibiting compression instability
US5749111A (en) 1996-02-14 1998-05-12 Teksource, Lc Gelatinous cushions with buckling columns
US5795944A (en) 1996-03-18 1998-08-18 Shell Oil Company Programmed addition of heavy ethers for microstructure control of diene polymers
ZA972383B (en) * 1996-03-22 1997-09-25 Shell Int Research High temperature, low viscosity thermoplastic elastomer block copolymer compositions.
DE19615533A1 (de) * 1996-04-19 1997-10-23 Basf Ag Thermoplastische Formmasse
DE19621688A1 (de) 1996-05-30 1997-12-04 Basf Ag Transparente, nicht-blockende Folie
US5773496A (en) 1996-05-31 1998-06-30 Koch Industries, Inc. Polymer enhanced asphalt
TW416971B (en) 1996-07-31 2001-01-01 Shell Internattonale Res Mij B Oil gel formulations containing high vinyl content hydrogenated styrene-butadiene-styrene block copolymers
US5776234A (en) 1996-08-12 1998-07-07 Westvaco Corporation Anionic bituminous emulsions with improved adhesion
DE19638256A1 (de) * 1996-09-19 1998-03-26 Basf Ag Thermoplastische Formmassen
DE19638254A1 (de) 1996-09-19 1998-03-26 Basf Ag Thermoplastische Elastomere
DE19645732A1 (de) 1996-11-06 1998-05-07 Basf Ag Pulverförmige Polymerzusammensetzungen
US5973037A (en) 1996-11-27 1999-10-26 Fields; John R. Styrene ethylene butylene styrene (SEBS) copolymer rubber modified asphalt mixture
SG55445A1 (en) 1997-01-07 1998-12-21 Denki Kagaku Kogyo Kabushili K Block copolymer block copolymer compostion and heat shrinkable films made thereof
EP0853103A1 (en) 1997-01-08 1998-07-15 Fina Research S.A. Bituminous compositions containing linear copolymers
ATE229995T1 (de) 1997-04-04 2003-01-15 Polyphalt Inc Elastomermodifizierte bituminöse zusammensetzungen
US5886113A (en) 1997-04-28 1999-03-23 Taiwan Synthetic Rubber Corporation Process for preparing an elastomeric copolymer composition of mono-vinyl aromatic hydrocarbons and conjugated dienes
US6143832A (en) 1997-05-22 2000-11-07 Nippon Zeon Co., Ltd. Aromatic vinyl-conjugated diene block copolymer and production process thereof
US6423420B1 (en) * 1997-08-11 2002-07-23 Exxonmobil Chemical Patents Inc. Oriented coextruded films
US6110616A (en) * 1998-01-30 2000-08-29 Dais-Analytic Corporation Ion-conducting membrane for fuel cell
JP4599495B2 (ja) * 1998-08-03 2010-12-15 旭化成ケミカルズ株式会社 線状ブロック共重合体、及びそれを含む樹脂組成物
US5998514A (en) 1998-12-17 1999-12-07 Basf Corporation Random vinyl substituted aromatic/C4 -C6 conjugated diolefin polymer modified asphalt mixtures
WO2000049091A1 (es) * 1999-02-16 2000-08-24 Dynasol Elastomeros, S.A. Modificador para mejorar el comportamiento de las mezclas bituminosas usadas en la pavimentacion de carreteras
DK1169400T3 (da) * 1999-03-16 2003-11-24 Shell Int Research Rørovertræk
US6593430B1 (en) * 1999-03-27 2003-07-15 Basf Aktiengesellschaft Transparent, impact-resistant polystyrene on a styrene-butadiene block copolymer basis
DE19914075A1 (de) 1999-03-27 2000-09-28 Basf Ag Glasklares, schlagzähes Polystyrol auf Basis von Styrol-Butadien-Blockcopolymeren
US6391981B1 (en) 1999-04-23 2002-05-21 Kraton Polymers Us Llc Increased throughput in the manufacture of anionic polymers by reduction in polymer cement viscosity through the addition of metal alkyls
US6465557B1 (en) * 1999-06-25 2002-10-15 Kraton Polymers U.S. Llc Hot melt pressure sensitive positioning adhesive
US6310122B1 (en) 1999-09-03 2001-10-30 Fina Technology, Inc. Stable bitumen polymer compositions
US6395841B1 (en) * 2000-09-06 2002-05-28 The Dow Chemical Company Process for hydrogenating unsaturated polymers
CN1324895A (zh) * 2001-07-05 2001-12-05 上海交通大学 用于道路的改性沥青材料的生产工艺
US6759454B2 (en) * 2002-02-07 2004-07-06 Kraton Polymers U.S. Llc Polymer modified bitumen compositions
US7012118B2 (en) 2002-02-07 2006-03-14 Kraton Polymers U.S. Llc Photopolymerizable compositions and flexographic plates prepared from controlled distribution block copolymers
US20030181584A1 (en) * 2002-02-07 2003-09-25 Kraton Polymers U.S. Llc Elastomeric articles prepared from controlled distribution block copolymers
US20040138371A1 (en) 2002-02-07 2004-07-15 St. Clair David John Gels from controlled distribution block copolymers
US7001956B2 (en) * 2002-06-04 2006-02-21 Kraton Polymers U.S. Llc Articles prepared from hydrogenated block copolymers
EP1384768A1 (en) 2002-07-26 2004-01-28 KRATON Polymers Research B.V. Solvent-free hot melt adhesive, its use in bonding a polar leather layer to a non-polar substrate, and leather articles so produced
US20060205904A1 (en) 2005-03-11 2006-09-14 St Clair David J Oil gels of controlled distribution block copolymers and ester oils

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110050035A (zh) * 2016-12-07 2019-07-23 道达尔销售服务公司 固体油质组合物
CN110050035B (zh) * 2016-12-07 2022-05-13 道达尔销售服务公司 固体油质组合物
CN110408220A (zh) * 2018-04-30 2019-11-05 科腾聚合物有限责任公司 具有改进功效的凝胶组合物用嵌段共聚物
US11759758B2 (en) 2018-04-30 2023-09-19 Kraton Corporation Block copolymers for gel compositions with improved efficiency

Also Published As

Publication number Publication date
US7169850B2 (en) 2007-01-30
CN1315948C (zh) 2007-05-16
EA007542B1 (ru) 2006-10-27
US20030176582A1 (en) 2003-09-18
ES2291615T3 (es) 2008-03-01
US20050137349A1 (en) 2005-06-23
US6759454B2 (en) 2004-07-06
US7244785B2 (en) 2007-07-17
US7223816B2 (en) 2007-05-29
CN1643102A (zh) 2005-07-20
TW200307727A (en) 2003-12-16
US6987142B2 (en) 2006-01-17
US7067589B2 (en) 2006-06-27
DE60314843D1 (de) 2007-08-23
US7282536B2 (en) 2007-10-16
US20050137350A1 (en) 2005-06-23
TWI248964B (en) 2006-02-11
US7332542B2 (en) 2008-02-19
CN1646632A (zh) 2005-07-27
US20050137348A1 (en) 2005-06-23
CN1280323C (zh) 2006-10-18
EP1474458A1 (en) 2004-11-10
ATE427988T1 (de) 2009-04-15
DE60317044T2 (de) 2008-07-31
EP1474481B1 (en) 2007-07-11
DE60327051D1 (de) 2009-05-20
EP1474481A1 (en) 2004-11-10
EP1474496B1 (en) 2009-04-08
TWI248962B (en) 2006-02-11
AU2003208665A1 (en) 2003-09-02
DE60314843T2 (de) 2007-11-08
US20050137346A1 (en) 2005-06-23
US20030149140A1 (en) 2003-08-07
US20050137347A1 (en) 2005-06-23
ATE376563T1 (de) 2007-11-15
CN1288209C (zh) 2006-12-06
EP1474482A1 (en) 2004-11-10
US20050159547A1 (en) 2005-07-21
WO2003066738A1 (en) 2003-08-14
US7141621B2 (en) 2006-11-28
EP1474496A1 (en) 2004-11-10
WO2003066739A1 (en) 2003-08-14
CN1643016A (zh) 2005-07-20
TWI248447B (en) 2006-02-01
EP1474458B1 (en) 2007-10-24
AU2003207423A1 (en) 2003-09-02
US7138456B2 (en) 2006-11-21
US20050171290A1 (en) 2005-08-04
US7169848B2 (en) 2007-01-30
WO2003066696A1 (en) 2003-08-14
DE60317044D1 (de) 2007-12-06
TWI301845B (en) 2008-10-11
AU2003207422A1 (en) 2003-09-02
TW200303344A (en) 2003-09-01
EA200500184A1 (ru) 2005-06-30
CN1643016B (zh) 2011-07-27
WO2003066770A1 (en) 2003-08-14
TW200303320A (en) 2003-09-01
US20030176574A1 (en) 2003-09-18
US20030153681A1 (en) 2003-08-14
TW200307719A (en) 2003-12-16
AU2003208666A1 (en) 2003-09-02

Similar Documents

Publication Publication Date Title
CN1288209C (zh) 来自受控分布嵌段共聚物的凝胶
CN1139646C (zh) 密封胶组合物
CN1643058B (zh) 从受控分布嵌段共聚物制备的制品
US7297741B2 (en) Pressure sensitive adhesives from high molecular weight block copolymers having a high fraction of diblock copolymer
KR20080112282A (ko) 고온 블록 공중합체 및 이의 제조방법
TWI540169B (zh) 包含共聚月桂烯嵌段之嵌段共聚物
KR20090005328A (ko) 수소화된 블록 공중합체 조성물
JP2018527448A (ja) スチレン系ブロックコポリマー組成物
WO2004052989A9 (en) Styrenic block copolymer compositions to be used for the manufacture of transparent, gel free films
CN105980507A (zh) 含具有高乙烯基和高二-嵌段的苯乙烯-丁二烯聚合物的热熔压敏粘合剂和热固性树脂
WO2007044258A2 (en) Hot melt adhesive composition having improved stability
EP1266916B1 (en) Multiblock copolymer and the preparing method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term
CX01 Expiry of patent term

Granted publication date: 20061206