CN1259147A - 支化烯烃共聚物的热塑性弹性体组合物 - Google Patents

支化烯烃共聚物的热塑性弹性体组合物 Download PDF

Info

Publication number
CN1259147A
CN1259147A CN98802252.4A CN98802252A CN1259147A CN 1259147 A CN1259147 A CN 1259147A CN 98802252 A CN98802252 A CN 98802252A CN 1259147 A CN1259147 A CN 1259147A
Authority
CN
China
Prior art keywords
ethene
thermoplastic elastomer
composition
equal
branched olefin
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
CN98802252.4A
Other languages
English (en)
Other versions
CN1113915C (zh
Inventor
E·J·马克尔
翁卫青
A·H·德克梅兹安
A·J·皮科克
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.)
ExxonMobil Chemical Patents Inc
Original Assignee
Exxon Chemical Patents Inc
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 Exxon Chemical Patents Inc filed Critical Exxon Chemical Patents Inc
Publication of CN1259147A publication Critical patent/CN1259147A/zh
Application granted granted Critical
Publication of CN1113915C publication Critical patent/CN1113915C/zh
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/005—Homopolymers or copolymers obtained by polymerisation of macromolecular compounds terminated by a carbon-to-carbon double bond
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • C08F2/08—Organic solvent with the aid of dispersing agents for the polymer
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/34—Polymerisation in gaseous state
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/042—Polymers of hydrocarbons as defined in group C08F10/00
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/044—Polymers of aromatic monomers as defined in group C08F12/00
    • 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
    • C08F297/06—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 coordination type
    • C08F297/08—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 coordination type polymerising mono-olefins
    • 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
    • C08F297/06—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 coordination type
    • C08F297/08—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 coordination type polymerising mono-olefins
    • C08F297/083—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 coordination type polymerising mono-olefins the monomers being ethylene or propylene
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/63908—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/63912—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/63922—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • 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
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00

Abstract

本发明涉及一种含有由可插入聚合的烯属不饱和单体得到的支化烯烃共聚物的热塑性弹性体组合物,其中该支化烯烃共聚物A)由DSC测定的Tg,小于或等于10℃;B)Tm大于80℃;C)断裂伸长率大于或等于300%;D)拉伸强度大于或等于1500磅/平方英寸(10300kPa);以及E)弹性回复大于或等于50%。本发明还涉及制备该组合物的方法,该方法包括:A)在一聚合反应中使乙烯或丙烯,以及任选地一种或多种可共聚合的单体进行聚合,聚合条件应足以形成具有大于40%链端基不饱和度的共聚物;B)使A)的产物与乙烯和一种或多种共聚单体进行共聚,以制备所述的支化烯烃共聚物。本发明的支化烯烃共聚物组合物适用于替代苯乙烯嵌段共聚物组合物,并适用于其它传统的热塑性弹性体应用领域。

Description

支化烯烃共聚物的热塑性弹性体组合物
发明领域
本发明涉及含有支化烯烃共聚物的热塑性弹性体组合物，该支化烯烃共聚物具有并入低结晶性聚乙烯主链的结晶性聚烯烃侧链。
背景技术
由于连接“硬”(可结晶的或玻璃态的)嵌段的“软”(弹性的)嵌段的存在，三嵌段和多嵌段共聚物在用作热塑性弹性体(“TPE”)组合物的弹性体聚合物领域是公知的。在典型的使用温度下，硬嵌段将聚合物网络连接在一起。然而，当加热至硬嵌段的熔融温度或玻璃化转变温度以上时，聚合物便易于流动，表现出热塑性行为。例如参见G.Holden和N.R.Legge，热塑性弹性体：综述(Thermoplastic Elastomers：A Comprehensive Review)，Oxford University Press(1987)。
商业上最常见的一类TPE聚合物为苯乙烯嵌段共聚物(SBC)，典型地为线性三嵌段聚合物，如苯乙烯-异戊二烯-苯乙烯和苯乙烯-丁二烯-苯乙烯，后者当氢化时实质上变为苯乙烯-(乙烯-丁烯)-苯乙烯嵌段共聚物。辐射型和星型支化的SBC共聚物也是公知的。典型地，这些共聚物是通过顺序阴离子聚合或线性二嵌段共聚物的化学偶联制备的。典型的SBC TPE的玻璃化转变温度(Tg)等于或低于约80～90℃，因此限制了这些共聚物在高温使用条件下的应用。例如参见，“嵌段聚合物及多相聚合物体系的结构和性能：目前态势及未来潜力纵览”(“Structure and Properties of Block Polymers and MultiphasePolymer System：An Overview of Present Status and FuturePotential”，)S.L.Aggarwal，Sixth Biennial Manchester PolymerSymposium(UMIST Manchester，March 1976)。
由于方法效率和原料成本的差异，烯烃的插入或配位聚合可经济性地提供更有效的制备共聚物产品的方式。因此已经发展了由烯属不饱和单体，如乙烯和C3～C8α烯烃得到的适用的TPE聚合物，并且这些聚合物也是公知的。其例子包括热塑性烯烃(“TPO”)如聚丙烯与乙烯-丙烯共聚物的物理共混物，以及类似的共混物，其中乙烯-丙烯，或乙烯-丙烯-二烯烃相被动态硫化，以使其在聚丙烯基质中保持良好分散的、呈分离的软相粒子的形式。例如参见，N.R.Legge，“热塑性弹性体等级：物理性能对比”(“Thermoplastic elastomercategories：a comparison of physical properties”)  ，ELASTOMERICS，14-20页(Sept.，1991)，这里将其引为参考。
金属茂催化剂在烯烃聚合中的使用在这一领域中带来了其它一些贡献。U.S.P.5391629公开了含有由乙烯和α-烯烃得到的递变和嵌段线性聚合物的热塑性弹性体配混料。据报道，可以用既可以制备硬片断又可以制备软片断的单点金属茂催化剂制备具有硬和软片断的聚合物。所提供的例子为具有高密度聚乙烯或全同立构聚丙烯的硬嵌段和乙丙橡胶软嵌段的线性热塑性弹性体。日本早期公开说明书H4-337308(1992)公开了称为聚烯烃共聚物的产物，该产物的制备是首先聚合丙烯形成全同立构聚丙烯，然后使聚丙烯与乙烯和丙烯共聚合，这两步聚合均是在有机铝化合物和硅桥连的双环戊二烯基二卤化锆化合物的存在下进行的。
Datta等(D.J.Lohse，S.Datta，and E.N.Kresge，大分子(Macromolecules)24，561(1991))公开了通过乙烯、丙烯和二烯烃的三元共聚合而用环二烯烃官能化的EP主链。然后在制备全同立构聚丙烯的催化剂的存在下，使统计官能化的EP“软嵌段”与丙烯进行共聚合。以这种方式，“硬”嵌段聚丙烯链中的一些在其形成时通过残余的烯属不饱和部分接枝到EP“软”嵌段上。例如参见EP-A-0366411。其中多官能度聚合物链用于随后反应中的这一类反应的缺点是，形成了不期望的高分子量物质，典型地，本领域中称其为凝胶。U.S.P.4999403公开了类似的接枝共聚物配混料，其中EPR主链中的官能团用于接枝具有反应性基团的全同立构聚丙烯。在这两种情况下，据称接枝共聚物适用作全同立构聚丙烯和乙丙橡胶共混物的相容剂配混料。
发明概述
本发明涉及含有由可插入聚合的烯属不饱和单体得到的支化烯烃共聚物的热塑性弹性体组合物，其中该支化烯烃共聚物A)由DSC测定的Tg小于或等于10℃；B)熔融温度(Tm)大于80℃；C)断裂伸长率大于或等于300％，优选大于500％；D)拉伸强度大于或等于1500磅/平方英寸(10300kPa)，优选大于2000磅/平方英寸(13800kPa)；以及E)弹性回复大于或等于50％。更特别地，该支化烯烃共聚物含有由烯烃，以及任选地一种或多种可共聚合的单体得到的结晶性侧链，使得其Tm大于80℃，并且数均分子量(Mn)大于1500，小于45000。本发明的热塑性弹性体组合物可通过含有下述步骤的方法制得：A)在一聚合反应中使一种烯烃，以及任选地一种或多种可共聚合的单体进行共聚合，聚合条件应足以形成具有大于40％链端基不饱和度的结晶性或玻璃态共聚物；B)使A)的产物与乙烯和一种或多种可共聚合的单体进行共聚，以制备所述的支化烯烃共聚物。该热塑性弹性体组合物具有与传统的重要的SBC共聚物可比的、或超过它们的弹性性能，因此对于这一重要类别的商业产品来说，提供了可供选择的原料来源和工业生产。
附图说明
图1说明的是本发明的支化烯烃共聚物与商品可得的苯乙烯嵌段共聚物热塑性弹性体，其测得的物理性能的比较。
发明详述
本发明的热塑性弹性体组合物含有支化的共聚物，其中共聚物主链和聚合物侧链均是使用活化的过渡金属有机金属催化剂，在配位或插入条件下，由单烯烃聚合得到。侧链是共聚合得到的，以使其具有适合于硬相区的结晶、半结晶或玻璃态性能，所谓“硬相区”是按照本领域对该术语的理解，并且侧链连接于结晶性或玻璃化状态低于侧链，优选基本上为无定形的，以使其适合于互补的热塑性弹性体组合物的软相区特性的聚合物主链。
结晶性侧链含有可在插入聚合条件下形成结晶或玻璃态聚合物片断的化学单元。符合该要求的公知单体为乙烯，丙烯，3-甲基-1-戊烯，以及它们的共聚物，包括乙烯与α-烯烃、环烯烃或苯乙烯系共聚单体的共聚物。优选的乙烯或丙烯共聚物侧链为，共聚单体的量不足以破坏结晶性使其Tm降至低于80℃。适宜的共聚单体包括C3～C20α-烯烃或偕二取代的单体，C5～C25环烯烃，苯乙烯系烯烃，及低碳数(C3～C8)烷基取代的环烯烃或苯乙烯系烯烃的同型物。因此典型地，侧链可含有85～100摩尔％的乙烯，0～15摩尔％的共聚单体，优选90～99摩尔％的乙烯和1～10摩尔％的共聚单体，最优选94～98摩尔％的乙烯和2～6摩尔％的共聚单体。或者是，侧链可含有90～100摩尔％的丙烯，0～10摩尔％的共聚单体，优选92～99摩尔％的丙烯和1～8摩尔％的共聚单体，最优选95～98摩尔％的丙烯和2～5摩尔％的共聚单体。特别地，当侧链Mn增至高于约3000时，优选引入少量的共聚单体以使脆性最小化，例如约0.2～4.0摩尔％的共聚单体。该共聚单体的选择可基于非结晶性破坏能力的其它一些性能，例如为提高聚乙烯膜的撕裂性，相对于短链的烯烃如1-丁烯，可优选长链烯烃共聚单体如1-辛烯。为提高聚乙烯膜的弹性或阻隔性能，相对于α-烯烃，可优选环状共聚单体，如降冰片烯或烷基取代的降冰片烯。
侧链可具有窄或宽的分子量分布(Mw/Mn)，例如1.1～30，典型地为2～8。此外，侧链可具有不同的共聚单体组成，例如包括公开于U.S.P.5382630(CDBI＞50％)的正交组成分布，这里将其引为参考。任选地，可使用具有不同分子量和/或组成的侧链的混合物。
侧链Mn的范围为大于或等于1500，小于或等于45000。优选侧链的Mn为1500～30000，更优选Mn为1500～25000。侧链的数目与侧链的Mn有关，使得侧链的重量与介于及出于并入的侧链的聚合物主链片断的总重量的总重量比为小于60％，优选40～50％。分子量这里是由凝胶渗透色谱(GPC)和差示折光指数(DRI)测量仪测定的。这一类别的优选支化烯烃共聚物，其由差示扫描量热法测定的熔融焓(ΔHf)为≤90cal/g(在≥80℃，≥5℃/min的扫描速度下，由记录的热流进行积分测定)。
当考虑侧链对主链结构的影响时，主链或主链聚合物片断的Tm(或者是Tg，若无Tm时)应低于侧链的。因此主链将优选含有测不出结晶性的化学单元的片断，或者Tg低于-10℃的化学单元的片断。结合起来，典型地，主链片断的Tm低于或等于80℃，Tg低于或等于-10℃。弹性主链将是特别适宜的，典型地，这样的主链将含有乙烯以及一种或多种C3～C12α-烯烃或二烯烃，特别是丙烯和1-丁烯。其它的共聚合单体包括偕二取代的烯烃如异丁烯，环烯烃如环戊烯，降冰片烯和烷基取代的降冰片烯，以及苯乙烯系单体如苯乙烯和烷基取代的苯乙烯。低结晶性的主链是适宜的，其例子为高共聚单体含量的乙烯共聚物(如前所述)，例如共聚单体含量大于8摩尔％。
如上所指出的，典型地，主链重量至少为聚合物总重量，即主链和侧链的总重量的40重量％。典型地，主链的公称重均分子量(Mw)至少等于或大于约50000。术语“公称”是指直接测定主链的Mn是基本不可能的，但共聚物产物的表征将显示与聚合物主链的非常近似的重量相关联的Mw测定值，该聚合物主链仅包括单烯烃单体单元衍生物和侧链的插入部分。
典型地，由实施例说明的通过GPC/DRI测定的、含有上述侧链和主链的支化烯烃共聚物的Mw等于或大于50000。典型地，Mw可超过300000，优选200000，上至500000或更大。
本发明的热塑性弹性体组合物可通过含有下述步骤的方法制得：A)在一聚合反应中使乙烯或丙烯，以及任选地一种或多种可共聚合的单体进行共聚合，聚合条件应足以形成具有大于40％链端基不饱和度的共聚物，其Tm≥80℃，Tg≤-10℃；B)使A)的产物与乙烯和一种或多种可共聚合的单体进行共聚，以制备所述的支化烯烃共聚物。对于步骤A)中制备的基于乙烯的大单体，优选其Tg低于-5℃，更优选低于-10℃。
有利地，方法中的步骤A)可以溶液法进行，其中所述的乙烯和任选地一种或多种可共聚合的单体，与被烷基铝氧烷助催化剂活化的过渡金属烯烃聚合催化剂相接触，铝与过渡金属的摩尔比小于约220∶1。如此形成的端不饱和共聚物，在从仅具有饱和端基的共聚物产物中分离或不分离的情况下，然后可与乙烯和可共聚合的单体在另一单独的反应中进行共聚合，该反应可以用活化的过渡金属插入聚合催化剂，特别是可以在所述支化烯烃共聚物中并入乙烯共聚物的催化剂，通过溶液、淤浆或气相乙烯聚合法进行。
或者是，方法步骤A)可以溶液法进行，其中使丙烯和任选地一种或多种可共聚合的单体，与由任何适宜的助催化剂活化的、立构严格的过渡金属烯烃聚合催化剂，即可以制得立构规整聚丙烯的催化剂相接触，反应保持在足够高的温度，以获得明显量的端不饱和聚合物链，反应温度例如高于约85℃，优选高于约90℃。如此形成的端不饱和共聚物，在从仅具有饱和端基的共聚物产物中分离或不分离的情况下，然后可与乙烯和可共聚合的单体，或者其它选择的适于制备低结晶性聚合物的单体，在另一单独的反应中进行共聚合，该反应使用活化的过渡金属插入聚合催化剂，特别是可以在所述具有低结晶性主链的支化烯烃共聚物中并入丙烯共聚物的催化剂，通过溶液、淤浆或气相乙烯聚合法进行。
足以形成侧链乙烯共聚物的条件包括，使用适宜的乙烯和共聚单体反应物摩尔比，以保证所述的侧链的衍生自烯烃的单元组成，以及可操作的催化剂和方法条件，以形成不饱和的链端。02/07/97提交的共同待审的临时申请U.S.系列No.60/037323的教导内容，特别适用于催化剂的选择，以及以高乙烯基不饱和度产率制备大单体共聚物链。在步骤A)中用于制备含不饱和部分的大单体的金属茂催化剂，实质上可以是任何可以进行乙烯的插入聚合的催化剂，它可以是具有高共聚单体并入能力的催化剂(见下述)，或者是低共聚单体并入能力的催化剂。典型地，低并入能力的催化剂为那些在金属配位位置上更加立构聚积的催化剂，因此特别适宜的为非桥连的和取代的非桥连的金属茂催化剂。还有在U.S.P.5498809、国际申请WO 94/19436和WO94/13715中公开了以高产率制备端亚乙烯基乙烯-1-丁烯共聚物的方式。还有1996.5.21提交的共同待审申请U.S.系列No.08/651030，其教导内容涉及制备具有高含量的亚乙烯基链端不饱和度的乙烯-异丁烯共聚物。在上述和下述部分中的短语“链端”或“端基”，当指不饱和度时，是指适于插入聚合的烯属不饱和度，而不论其是否精确地位于链端。还有U.S.P.5324801和5621054公开了结晶熔点为235℃和更高的交替乙烯-环烯烃共聚物，由这些公开内容的适宜的催化剂制得的大单体，将对用作本发明热塑性弹性体的硬相组分，具有玻璃态贡献作用。这一段中的所有文献并入本申请以作参考。
在一特别的实施方案中，可以在溶液聚合条件下，以优选的铝在烷基铝氧烷活化剂中的摩尔比，例如甲基铝氧烷(MAO)与过渡金属的摩尔比，制备适用作随后共聚合反应支链的含乙烯基、含乙烯的大单体聚合产物。优选的铝与烷基铝氧烷活化剂的摩尔比为≥20并≤175；更优选≥20并≤140；最优选≥20并≤100。温度、压力和反应时间与所选的方法有关，但通常它们在溶液法的正常范围内。因此温度的范围可为20～200℃，优选30～150℃，更优选50～140℃。反应压力通常为大气压至345MPa，优选至182MPa。对于典型溶液反应来说，温度范围为室温至190℃，压力为大气压至3.45MPa。反应可以间歇进行。适宜的淤浆型反应条件类似于溶液反应条件，不同的是反应温度受限在低于聚合物的熔融温度之下。此外还可以使用其它的反应方式，例如超临界液体介质法，其温度上至250℃，压力上至345MPa。在高温和高压反应条件下，典型地，生成低分子量，例如Mn为约1500的大单体产物。
在另一可选择的实施方案中，可以用适合于制备或者全同或者间同聚丙烯的金属茂催化剂，在溶液聚合条件下制备适用作随后共聚合反应支链的、含乙烯基含丙烯的大单体聚合产物。具有高含量端乙烯基不饱和度的丙烯大单体的优选反应方法，公开于Attorney DocketNo.97B075，1997.12.10提交的共同待审的美国申请60/067783。典型使用的催化剂为立构严格、手性或非对称的、桥连金属茂。例如参见U.S.P4892851、U.S.P.5017714、U.S.P.5132281、U.S.P.5155080、U.S.P.5296434、U.S.P.5278264、U.S.P.5318935、WO-A-(PCT/US92/10066)、WO-A-93/19103、EP-A2-0577581、EP-A1-0578838，以及科技文献“芳族取代基对桥连锆茂催化剂聚合特性的影响”(“The Influence of Aromatic Substituents on thePolymerization Behavior of Bridged Zirconocene Catalysts”)，Spaoeck，W.，等，有机金属(Organometallics)1994，13，954-963，和“ansa-Zirconocene Polymerization Catalysts withAnnelated Ring Ligands-Effects on Catalytic Activity andPolymer Chain Lengths”″对催化活性具有增环反应环配体作用的柄型锆茂聚合催化剂和聚合物链长″，Brinzinger，H.，等，有机金属(Organometallics)1994，13，964-970，这里将这些文献引为参考。
优选地，对于全同聚丙烯来说，立构严格的过渡金属催化剂化合物选自桥连的双(茚基)锆茂或铪茂。在一优选的实施方案中，过渡金属催化剂化合物为二甲基甲硅烷基桥连的双(茚基)锆茂或铪茂。更优选地，过渡金属催化剂化合物为二甲基甲硅烷基(2-甲基-4-苯基茚基)二氯合锆、二氯合铪或二甲基锆、二甲基铪。在另一优选的实施方案中，过渡金属催化剂为二甲基甲硅烷基桥连的双(茚基)铪茂，如二甲基甲硅烷基双(茚基)二甲基铪或二氯合铪。制备高百分含量端乙烯基键合的、基于丙烯的大单体的方法包括：
a)约90～120℃下，于溶液中，使丙烯以及任选地少量可共聚合的单体，与含有立构严格的活化的过渡金属催化剂化合物的催化剂组合物相接触；和
b)回收数均分子量为约2000～50000的全同或间同聚丙烯链。
优选地，溶液中含有一种烃类溶剂。更优选地，烃类溶剂为芳香族的。同样，优选地，丙烯单体在95～115℃下接触。更优选地，所用温度为100～110℃。最优选地，丙烯单体在105～110℃下接触。通常反应压力可以为大气压至345MPa，优选至182MPa。反应可间歇或连续进行。适合于淤浆型反应的条件也同样适用，并且类似于溶液反应条件，典型地，聚合在适合的压力下于液态丙烯中进行。这里将所有文献引为参考。
此外，本发明的支化烯烃共聚物热塑性弹性体组合物，还可以在混合的催化剂体系存在下，由选定的烯烃直接同时制备，该混合的催化剂体系含有至少一种第一过渡金属烯烃聚合催化剂，该催化剂可制备链端基不饱和度大于40％的乙烯或丙烯共聚物，以及至少一种第二过渡金属烯烃聚合催化剂，该催化剂可在所述的支化烯烃共聚物中并入乙烯或丙烯均聚物或共聚物侧链。这种就地制备方法可以通过任何方法来进行，只要它能够制备具有结晶、半结晶或玻璃态性能的不饱和大单体，又能够使该大单体与构成低结晶性主链的共聚单体共聚合，从而制备支化的共聚物即可。可以在公知的适用于所述方法的温度和压力条件下，使用气相、淤浆和溶液法。
对于含高乙烯基或亚乙烯基的大单体的制备，特别地，当活化时可获得高链端不饱和度的适宜的第一催化剂包括上述说明的那些。优选地，如上所述对乙烯的均聚合呈活性、但不明显地并入高碳原子数的单体，或者是并入高碳原子数的单体而仅伴随Mn的降低的催化剂，在本发明热塑性共聚物组合物的同时或就地制备法中，对于结晶性或玻璃态侧链的制备将是特别适宜的，只要Mn可保持或提高至高于侧链的最小值。
适宜的第二催化剂化合物包括那些在所用的温度和压力条件下可以很好地并入共聚单体，而不明显降低聚合物主链Mn的催化剂。02/07/97提交的共同待审的临时申请U.S.系列No.60/037323的教导内容，特别适用于催化剂的选择，以及用以制备支化烯烃共聚物，并指出了适合于高共聚单体和大单体并入的催化剂化合物。如该申请所指出的，由含乙烯基或亚乙烯基的大单体、乙烯和可共聚合的共聚单体制备支化烯烃共聚物的优选的催化剂化合物包括，U.S.P.5198401、5270393、5324801、5444145、5475075、5635573、国际申请WO92/00333和WO96/00244所公开的桥连的双环戊二烯基和单环戊二烯基第4族金属化合物；10/20/95提交的共同待审的美国专利申请08/545973所提出的非桥连的单环戊二烯基第4族金属化合物，U.S.P.5318935和2/24/97提交的共同待审的申请08/803687所公开或提出的二酰胺基和二丙烯酰胺基过渡金属催化剂，以及WO96/23010所公开的α-二亚胺镍催化剂配合物。按照这些教导，典型地，过渡金属催化剂化合物与所述的活化助催化剂组分一起使用，助催化剂组分例如为可提供稳定化的非配位阴离子的烷基铝氧烷和离子化化合物。这一段中的每一篇文献均被并入本申请作为参考。
工业实用性
本发明的热塑性弹性体组合物可用于其它热塑性弹性体组合物已应用的许多领域。这些应用包括但不限于苯乙烯嵌段共聚物，如苯乙烯-异戊二烯-苯乙烯和苯乙烯-丁二烯-苯乙烯共聚物，以及它们的加氢同系物的公知应用领域。这些应用包括许多，如粘合剂组合物和模塑制品的主链聚合物。这些应用将得益于提高的使用温度范围，典型地超过SBC共聚物组合物的80～90℃范围。本发明的组合物还适用作聚烯烃共混物的相容剂配料。此外，由于其固有的拉伸强度、弹性、和易于熔融加工的特性，本发明的热塑性弹性体组合物，任选地用通常的添加剂和辅助剂进行改性，可制备挤出膜、涂层和包装组合物。而且，由于优选的、使用易于得到的烯烃的插入聚合的制备方法，本发明的热塑性弹性体组合物可用低成本的石油化工原料，在低能量输入条件下制备(与低温阴离子聚合或者多步熔融加工条件相比，其中必须硫化以获得分离的热塑性弹性体形态)。
实施例
为进一步说明本发明，提供下列实施例。这些实施例不是以任何方式限制本发明，而仅仅是起到进一步说明的目的。
概述：所有的聚合反应在配有控温水夹套的1升密闭釜反应器中进行。用校正的视镜将液体计量注入到反应器中。首先经过高温下氮气中活化的碱性氧化铝，然后再经过高温下氮气中活化的13X分子筛，对高纯度(＞99.5％)己烷、甲苯和丁烯进料进行纯化。在氮气夹套管线中直接供应聚合级的乙烯，并且不用经进一步纯化使用。从Albemarle Inc.直接获得在不锈钢筒中的澄清的10％的甲基铝氧烷(在甲苯中)，将其分装入1升的玻璃容器中，室温下储存在实验室手套箱中。以所需量向反应器中加入乙烯，以维持总系统压力在所报道的水平上(半间歇操作)。用Matheson质量流量计(型号8272-0424)检测乙烯的流速。为确保反应介质混合良好，使用转速为750rpm的平浆搅拌器。
反应器的准备：首先用甲苯加热至150℃清洗反应器以溶解任何聚合物残余物，然后冷却并排掉。然后用110℃的夹套水对反应器进行加热，并用氮气流冲洗约30分钟。反应前，进一步将反应器用10氮气压力/出口循环(至100psi)和2乙烯压力/出口循环(至300psi)进行冲洗。该循环有三个目的：(1)彻底疏通所有的死点，如压力表，以冲洗掉不坚牢的污染物，(2)用乙烯置换体系中的氮气，(3)对反应器进行压力测试。
催化剂制备：所有的催化剂均是在水含量小于1.5ppm的惰性气氛下进行制备。为精确地计量少量的催化剂(常常低于1毫克)，在催化剂制备中使用新鲜制备的催化剂原液/稀释法。为使金属茂的溶解度最大化，使用甲苯作为溶剂。用MAO洗涤不锈钢转移管，以除去杂质，排掉，并用移液吸管加入活化剂和催化剂，首先加入MAO。
大单体合成：首先，在连续的氮气流下将催化剂转移管连接到反应器的一个端口上，以清除环境空气。然后如上所述清洗反应器并进行压力测试。接着向反应器中加入600ml溶剂并加热至所需的温度。然后加入共聚单体(若需要的话)，使温度达到平衡，并记录基本体系压力。除基本体系压力之外还要加上所需的乙烯的分压。使乙烯饱和体系(由0乙烯流率看出)后，用高压溶剂以脉冲形式注射入催化剂。通过从电子质量流量计上读取乙烯的摄入量来监视反应进程。当积累了所需量的大单体时，停止乙烯进料，并通过加热(～1分钟)至150℃30分钟使反应终止。在终止步骤的最后，将反应器冷却至LCB分段制备反应(下述)所需的温度，并取出大单体样品以作分析。
LCB分段结构的制备：在甲苯中用乙烯，100磅/平方英寸下，用MAO活化的(C5Me4SiMe2NC12H23)TiCl2催化剂，进行所有的长链支化(LCB)的烯烃共聚物的制备反应。在大多数的合成中用丁烯作共聚单体，但也使用降冰片烯作共聚单体进行选择性的反应，以制得用于使LCB含量定量化的样品。当生成所需量的聚合物(所有的聚积物)时，通过注入甲醇使反应终止。在约注入10秒钟内，观察到乙烯摄入量/反应器压力降停止。将产物倒入过量的异丙醇中，并使之蒸发以干燥。在另一实施例中(实施例3)，在一步法、混合金属茂的合成中，使用Cp2ZrCl2和(C5Me4SiMe2NC12H23)TiCl2催化剂，其中大单体与主链同时制备并并入到主链中。
催化剂匹配(配对)：对于混合金属茂的就地法实施例，选择金属茂催化剂配对，以使既使用具有良好并入性能的催化剂，又使用并入能力较差的催化剂。对该工艺来说，并入能力好的催化剂，其并入能力将是并入能力差的催化剂的3倍，更优选5倍。就本发明目的而言，对于每一催化剂化合物，使用如下定义的标准反应条件，通过并入的丁烯的重量百分数，来定义并测定共聚单体的并入能力。90℃下用高纯氮气冲洗1升高压釜2小时。接着用乙烯流冲洗体系的氮气。然后加入600ml甲苯和50ml液态丁烯。使体系在90℃平衡。然后以100磅/平方英寸加入乙烯，直至溶液饱和。在惰性气氛手套箱中，用不锈钢加料管将1毫克的催化剂加入到0.5毫升10重量％的MAO中。根据催化剂的活性，需要可多可少量的催化剂/MAO溶液，以保证实质水平的聚合反应而不产生过多的反应放热。用加压溶剂将催化剂注入到反应器中。通过加入所需量的乙烯将反应器压力保持在100磅/平方英寸。在反应器内的反应物组成有实质性改变之前(转化率＜20％，通过反应产物的分析确定)使反应终止。共聚单体并入量由1H NMR测定，并以每1000个碳原子的乙基数记。实施例1
催化剂制备：如上所述制备不锈钢催化剂加料管。加入一等分的1毫升10％甲基铝氧烷(MAO)的甲苯溶液，然后加入5毫升含16毫克(C5Me4SiMe2NC12H23)TiCl2的甲苯溶液。将密封管从手套箱中取出，并在连续的氮气流下连接到反应器的一个端口。在连续的氮气流下，将从反应器的供料管线引出的柔性不锈钢管线连接到加料管的另一端。
大单体合成：同时氮气清洗反应器中，并用两个乙烯充入/冲洗循环(至300磅/平方英寸)进行压力测试。然后将反应器的压力升至～40磅/平方英寸，以在初始操作过程中保持正反应器压力。夹套水温设定为90℃，并向反应器中加入600毫升甲苯和10毫升丁烯。搅拌器速率设定为750rpm。由于气相乙烯被吸收进溶液中，因此加入额外的乙烯以维持正反应器表压。反应器温度控制器设定为90℃，并使体系达到稳定状态。然后将乙烯压力控制器设定为100磅/平方英寸，并向体系中加入乙烯，直至乙烯摄入量测定为0，获得稳定状态为止。隔离反应器，用加压至300磅/平方英寸的甲苯迫使催化剂溶液从加料管中进入反应器。同时向反应器打开100磅/平方英寸的乙烯供料管线，目的是随着乙烯的反应消耗保持恒定的反应器压力。
反应进行15分钟后，将反应液迅速加热至150℃，保持30分钟，然后冷却至90℃。从反应器中取出预聚合的大单体样品。
LCB分段共聚物的合成：如上所述制备不锈钢催化剂加料管。加入一等分的0.5毫升10％甲基铝氧烷(MAO)的甲苯溶液，然后加入1毫升每毫升含0.5毫克(C5Me4SiMe2NC12H23)TiCl2的甲苯溶液。将密封管从手套箱中取出，并在连续的氮气流下连接到反应器的一个端口。在连续的氮气流下，将从反应器的供料管线引出的柔性不锈钢管线连接到加料管的另一端。
反应器温度控制器设定为90℃。然后向含有大单体的反应器中加入70毫升丁烯，并使体系达到热平衡。接着以100磅/平方英寸(总的)向体系中加入乙烯。使乙烯饱和体系(由0乙烯流率看出)后，用高压溶剂以脉冲形式注射入催化剂。通过从电子质量流量计上读取乙烯的摄入量来监视反应进程。15分钟后通过注射入甲醇使反应终止。将产物倒入过量的异丙醇中，并蒸发干燥。LCB分段共聚物的总产量为42.6克。实施例2
催化剂制备：如上所述制备不锈钢催化剂加料管。加入一等分的0.5毫升10％甲基铝氧烷(MAO)的甲苯溶液，然后加入5毫升含8毫克Cp2ZrCl2的甲苯溶液。将密封管从手套箱中取出，并在连续的氮气流下连接到反应器的一个端口。在连续的氮气流下，将从反应器的供料管线引出的柔性不锈钢管线连接到加料管的另一端。
大单体合成：同时清洗反应器中的氮气，并用两个乙烯充入/冲洗循环(至300磅/平方英寸)进行压力测试。然后将反应器的压力升至～20磅/平方英寸，以在初始操作过程中保持正反应器压力。夹套水温设定为90℃，并向反应器中加入600毫升甲苯和2毫升80.6重量％降冰片烯的甲苯溶液。搅拌器速率设定为750rpm。由于气相乙烯被吸收进溶液中，因此加入额外的乙烯以维持正反应器表压。反应器温度控制器设定为90℃，并使体系达到稳定状态。然后将乙烯压力控制器设定为30磅/平方英寸，并向体系中加入乙烯，直至乙烯摄入量测定为0，获得稳定状态为止。隔离反应器，用加压至300磅/平方英寸的甲苯迫使催化剂溶液从加料管中进入反应器。同时向反应器打开30磅/平方英寸的乙烯供料管线，目的是随着乙烯的反应消耗保持恒定的反应器压力。
反应进行15分钟后，将反应液迅速加热至150℃，保持30分钟，然后冷却至90℃。从反应器中取出预聚合的大单体样品。
LCB分段共聚物的合成：如上所述制备不锈钢催化剂加料管。加入一等分的0.5毫升10％甲基铝氧烷(MAO)的甲苯溶液，然后加入1毫升每毫升含1毫克(C5Me4SiMe2NC12H23)TiCl2的甲苯溶液。将密封管从手套箱中取出，并在连续的氮气流下连接到反应器的一个端口。在连续的氮气流下，将从反应器的供料管线引出的柔性不锈钢管线连接到加料管的另一端。
反应器温度控制器设定为60℃。然后加入60毫升80.6重量％降冰片烯的甲苯溶液，并使体系达到热平衡。接着以100磅/平方英寸(总的)向体系中加入乙烯。使乙烯饱和体系(由0乙烯流率看出)后，用高压溶剂以脉冲形式注射入催化剂。通过从电子质量流量计上读取乙烯的摄入量来监视反应进程。5分钟后通过注射入甲醇使反应终止。将产物倒入过量的异丙醇中，并蒸发干燥。LCB分段共聚物的总产量为91.9克。实施例3
催化剂制备：如上所述制备不锈钢催化剂加料管。加入一等分的1毫升10％甲基铝氧烷(MAO)的甲苯溶液，然后加入含0.25毫克(C5Me4SiMe2NC12H23)TiCl2和5微克Cp2ZrCl2的甲苯溶液。将密封管从手套箱中取出，并在连续的氮气流下连接到反应器的一个端口。在连续的氮气流下，将从反应器的供料管线引出的柔性不锈钢管线连接到加料管的另一端。
LCB分段共聚物的现场合成：同时氮气清洗反应器，并用两个乙烯充入/冲洗循环(至300磅/平方英寸)进行压力测试。然后将反应器的压力升至～40磅/平方英寸，以在初始操作过程中保持正反应器压力。夹套水温设定为90℃，并向反应器中加入600毫升甲苯和20毫升丁烯。搅拌器速率设定为750rpm。由于气相乙烯被吸收进溶液中，因此加入额外的乙烯以维持正反应器表压。反应器温度控制器设定为90℃，并使体系达到稳定状态。然后将乙烯压力控制器设定为100磅/平方英寸，并向体系中加入乙烯，直至乙烯摄入量测定为0，获得稳定状态为止。隔离反应器，用加压至300磅/平方英寸的甲苯迫使催化剂溶液从加料管中进入反应器。同时向反应器打开100磅/平方英寸的乙烯供料管线，目的是随着乙烯的反应消耗保持恒定的反应器压力。7分钟后通过注射入甲醇使反应终止。将产物倒入过量的异丙醇中，并蒸发干燥。LCB分段共聚物的总产量为18.5克。性能
表1中列出了选定物质的结构数据。头两个弹性体样品(1和2)中，将直接从反应器中取出的大单体作为样品，并用1H NMR和GPC表征，而对于实施例3(混合金属茂合成)，大单体和主链的性能是来自于相应的单一金属茂反应。
按照ASTM D-14的方法获得室温下和80℃的拉伸数据(图1中，室温下和80℃的断裂拉伸强度的单位是磅/平方英寸，断裂伸长率的单位是百分数)。使用与在ASTM D-14的测试方法中相同的样品在室温下测定回复率，所不同的是使样品伸长150％，然后释放10分钟，直接使用在试验样品上的参考标记测定相对于原始尺寸的回复百分率。选定样品的拉伸数据说明，统计支化的LCB分段共聚物配料，其拉伸强度等于或超过苯乙烯嵌段共聚物(Kraton)的拉伸强度，其弹性回复略微低于Kraton，但仍很好地保持在商业适用的范围内(见表1和图1)。降冰片烯LCB分段共聚物的断裂拉伸强度最大(4011磅/平方英寸)，而混合金属茂的丁烯LCB分段共聚物的弹性回复率最大(89％)。低分子量(10K，Cp2ZrCl2催化的)和高Mn(30-40K，(C5Me4SiMe2NC12H23)TiCl2催化的)的大单体，均使LCB分段共聚物具有适用的性能。
乙烯/丁烯LCB分段共聚物的弹性性能优于密度相近的EXACT4033(Exxon Chemical Company)乙烯/丁烯(E/B)无规共聚物，相当于或优于密度近似的ENGAGE 8100(Dow Chemical Company)乙烯/辛烯(E/O)无规共聚物(表2)。对应的乙烯/降冰片烯(E/NB)线性和E/NB LCB分段共聚物的比较显示出，LCB分段共聚物在多数情况下有一定程度的缺陷，这部分是由于其降冰片烯含量太低。当然，所有的LCB分段共聚物与其线性对应物相比，在更高的温度下熔融，这是由于结晶性低分子量支链组分所致。值得注意的是，即使是当加热至其无定形组分的熔融温度之上，LCB分段共聚物仍保持相当的拉伸强度(参见80℃的拉伸数据)。所观察到的高温强度可能是缘于多嵌段型网络，其中无定形部分通过侧链固定在高密度、高熔融区。
产物表征：用配有DRI检测器、Shodex AT-806MS柱的高温系统Waters 150C GPC仪，在系统温度145℃下操作，分析支化烯烃共聚物产物样品。使用的溶剂为1，2，4-三氯苯，由该溶剂制备注射入的浓度为0.1mg/ml的聚合物样品溶液。总的溶剂流速为1.0ml/min，注射量为300微升。用一系列窄分布的聚苯乙烯(由Tosoh Corporation，Tokyo，1989获得)对GPC柱进行校正。为控制质量，使用了基于线性PE样品NBS-1475的宽标准校准物。用每一带有16个管形瓶的转盘进行标准的操作。每一批次的第一个样品注射两次。聚合物样品流出后，用Waters Expert Ease程序对所得谱图进行分析，计算分子量分布和平均Mn、Mw和Mz。
聚合物分析：表2中列出了反应产物的分子量、共聚单体含量和不饱和基团结构的分布。发现不饱和基团浓度(每1000个碳原子的总烯烃)和乙烯基的选择性随铝：金属比的降低而增加，其它因素相当。可通过减少溶液中乙烯的浓度(通过降低乙烯分压或提高温度)进一步增加所报道的烯烃共聚单体的浓度。
表2  支化共聚物与代表性的LLDPE的性能比较
    性能  支化共聚物E/B(#1)   支化共聚物E/NB(#2)  支化共聚物E/B(#3)   ENGAGE8100 E/O   EXACT4033 E/B
密度(g/ml)ASTM D-1505     0.887     ＞0.935     0.887     0.870     0.880
共聚单体(摩尔％1HNMR)     15.5     5.65     12.6     12.1     11.7
熔点(℃，DSC)     119.2     115.5     123.5     60     63
断裂拉伸强度磅/平方英寸(kPa)ASTM D-412     2401(16500)     4011(27700)     3054(21000)     1030(7100)     1780(12300)
断裂伸长率(％)ASTM D-412     905     386     669     950     740
回复率(％)150％伸长     76     60     87     76     50
注：E＝乙烯，B＝丁烯，NB＝降冰片烯，O＝辛烯
表3  支化共聚物与商品三嵌段苯乙烯共聚物的性能比较(图1)
  实施例序号 反应器  拉伸嵌段(磅/平方英寸/kPa@25℃) 伸长率(％@25℃) 回复率(％@25℃) 拉伸强度(磅/平方英寸/kPa@80℃) 伸长率(％@80℃)
    1 二元   4011/27000     594     60   1544/10600     386
    2 单一   3054/21100     669     87   351/2400     505
KratonG 1652   4002/276000     580     95   220/13500     86

Claims (7)

1.一种含有由可插入聚合的烯属不饱和单体得到的支化烯烃共聚物的热塑性弹性体组合物，其中该支化烯烃共聚物A)由DSC测定的Tg小于或等于10℃；B)Tm大于80℃；C)断裂伸长率大于或等于300％；D)拉伸强度大于或等于1500磅/平方英寸(10300kPa)；以及E)弹性回复大于或等于50％。
2.权利要求1的热塑性弹性体组合物，其中所述的支化烯烃共聚物含有由乙烯及任选地一种或多种可共聚合的单体得到的侧链，以使该侧链的Tg小于-10℃，Tm大于或等于80℃，数均分子量大于1500，小于45000。
3.权利要求1的热塑性弹性体组合物，其中所述的支化烯烃共聚物含有由丙烯及任选地一种或多种可共聚合的单体得到的侧链，以使该侧链的Tg小于10℃，Tm大于或等于110℃，数均分子量大于1500，小于45000。
4.权利要求1的热塑性弹性体组合物，该组合物由包含下述步骤的方法制备：A)在一聚合反应中使乙烯，以及任选地一种或多种可共聚合的单体进行共聚合，聚合条件应足以形成具有大于40％链端基不饱和度的共聚物；B)使A)的产物与乙烯和一种或多种可共聚合的单体进行共聚，以制备所述的支化烯烃共聚物。
5.权利要求4的热塑性弹性体组合物，其中步骤A)以溶液法进行，其中所述的乙烯和一种或多种可共聚合的单体，与被铝氧烷助催化剂活化的过渡金属烯烃聚合催化剂相接触，铝与过渡金属的摩尔比小于约220∶1。
6.权利要求5的热塑性弹性体组合物，其中步骤B)用活化的过渡金属插入聚合催化剂，通过溶液、淤浆或气相乙烯聚合法，在一分离的反应中进行。
7.权利要求4的热塑性弹性体组合物，其中步骤A)和B)在混合的催化剂体系存在下同时进行，该混合的催化剂体系含有至少一种过渡金属烯烃聚合催化剂，该催化剂可制备链端基不饱和度大于40％的乙烯共聚物，以及至少一种过渡金属烯烃聚合催化剂，该催化剂可在所述的支化烯烃共聚物中并入乙烯共聚物。
CN98802252.4A 1997-02-07 1998-02-06 支化烯烃共聚物的热塑性弹性体组合物 Expired - Lifetime CN1113915C (zh)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US3732397P 1997-02-07 1997-02-07
US60/037,323 1997-02-07
US4681297P 1997-05-02 1997-05-02
US60/046,812 1997-05-02
US6778297P 1997-12-10 1997-12-10
US60/067,782 1997-12-10

Publications (2)

Publication Number Publication Date
CN1259147A true CN1259147A (zh) 2000-07-05
CN1113915C CN1113915C (zh) 2003-07-09

Family

ID=27365194

Family Applications (2)

Application Number Title Priority Date Filing Date
CN98802252.4A Expired - Lifetime CN1113915C (zh) 1997-02-07 1998-02-06 支化烯烃共聚物的热塑性弹性体组合物
CN98802303A Expired - Fee Related CN1130406C (zh) 1997-02-07 1998-02-06 结合有聚乙烯大分子单体的丙烯聚合物

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN98802303A Expired - Fee Related CN1130406C (zh) 1997-02-07 1998-02-06 结合有聚乙烯大分子单体的丙烯聚合物

Country Status (10)

Country Link
US (4) US6660809B1 (zh)
EP (2) EP0958313B1 (zh)
JP (2) JP2001511215A (zh)
KR (2) KR100564500B1 (zh)
CN (2) CN1113915C (zh)
BR (2) BR9807672A (zh)
CA (2) CA2277111A1 (zh)
DE (2) DE69809192T2 (zh)
ES (2) ES2181173T3 (zh)
WO (2) WO1998034970A1 (zh)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102245696A (zh) * 2008-12-15 2011-11-16 埃克森美孚化学专利公司 热塑性弹性体聚烯烃反应器内共混物和由此得到的模塑制品
CN101578307B (zh) * 2005-03-17 2013-06-19 陶氏环球技术有限责任公司 乙烯/α-烯烃嵌段共聚体
CN103339187A (zh) * 2011-02-15 2013-10-02 埃克森美孚化学专利公司 热塑性聚烯烃共混物
CN103890023A (zh) * 2011-10-24 2014-06-25 三菱化学株式会社 热塑性弹性体组合物及其制造方法
CN101018815B (zh) * 2004-04-15 2016-11-30 埃克森美孚化学专利公司 烯烃聚合用多催化剂和反应器系统及所生产的聚合物

Families Citing this family (176)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7919561B2 (en) * 1996-09-04 2011-04-05 Exxonmobil Chemical Patents Inc. Process of producing thermoplastic polymer blends
US6573352B1 (en) * 1997-06-06 2003-06-03 Idemitsu Petrochemical Co., Ltd. Olefinic polymer
US6184327B1 (en) * 1997-12-10 2001-02-06 Exxon Chemical Patents, Inc. Elastomeric propylene polymers
US6197910B1 (en) 1997-12-10 2001-03-06 Exxon Chemical Patents, Inc. Propylene polymers incorporating macromers
US6117962A (en) * 1997-12-10 2000-09-12 Exxon Chemical Patents Inc. Vinyl-containing stereospecific polypropylene macromers
KR100699623B1 (ko) * 1999-07-26 2007-03-23 이데미쓰 고산 가부시키가이샤 올레핀계 분지상 매크로모노머, 올레핀계 그래프트공중합체 및 올레핀계 수지 조성물
SG82087A1 (en) * 1999-09-10 2001-07-24 Sumitomo Chemical Co Pressure sensitive adhesive
JP4748908B2 (ja) * 1999-09-10 2011-08-17 ザ・ユニバーシティ・オブ・シドニー ジペプチジルペプチダーゼ
US6803422B2 (en) * 1999-09-13 2004-10-12 Denki Kagaku Kogyo Kabushiki Kaisha Cross-copolymerized olefin/aromatic vinyl compound/diene copolymer and process for its production
MY137183A (en) 2001-03-16 2009-01-30 Dow Global Technologies Inc Method of making interpolymers and products made therefrom
US7022794B2 (en) * 2001-05-15 2006-04-04 Denki Kagaku Kogyo Kabushiki Kaisha Process for producing olefin/aromatic vinyl copolymer
US20030050411A1 (en) * 2001-06-12 2003-03-13 Dow Global Technologies Inc. Use of polar monomers in olefin polymerization and polymers thereof
EP1419183B2 (en) * 2002-01-15 2011-02-02 Advanced Elastomer Systems, L.P. Thermoplastic elastomers and process for making the same
JP2005528501A (ja) * 2002-06-04 2005-09-22 ユニオン・カーバイド・ケミカルズ・アンド・プラスティックス・テクノロジー・コーポレイション ポリマー組成物およびそれらからパイプ類を製造する方法
US7271209B2 (en) 2002-08-12 2007-09-18 Exxonmobil Chemical Patents Inc. Fibers and nonwovens from plasticized polyolefin compositions
US7998579B2 (en) 2002-08-12 2011-08-16 Exxonmobil Chemical Patents Inc. Polypropylene based fibers and nonwovens
US7531594B2 (en) 2002-08-12 2009-05-12 Exxonmobil Chemical Patents Inc. Articles from plasticized polyolefin compositions
WO2004014997A2 (en) 2002-08-12 2004-02-19 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US8003725B2 (en) 2002-08-12 2011-08-23 Exxonmobil Chemical Patents Inc. Plasticized hetero-phase polyolefin blends
US8653169B2 (en) 2002-10-15 2014-02-18 Exxonmobil Chemical Patents Inc. Propylene copolymers for adhesive applications
US7700707B2 (en) 2002-10-15 2010-04-20 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions and articles made therefrom
US7223822B2 (en) * 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
KR101113341B1 (ko) 2002-10-15 2012-09-27 엑손모빌 케미칼 패턴츠 인코포레이티드 올레핀 중합용 다중 촉매 시스템 및 이로부터 제조된중합체
US8618219B2 (en) 2002-10-15 2013-12-31 Exxonmobil Chemical Patents Inc. Propylene copolymers for adhesive applications
US7550528B2 (en) * 2002-10-15 2009-06-23 Exxonmobil Chemical Patents Inc. Functionalized olefin polymers
US7439312B2 (en) 2002-10-24 2008-10-21 Exxonmobil Chemical Patents Inc. Branched crystalline polypropylene
AU2003284027A1 (en) * 2002-10-24 2004-05-13 Exxonmobil Chemical Patents Inc. Branched crystalline polypropylene
EP1422250A1 (en) * 2002-11-20 2004-05-26 ATOFINA Research Branched polypropylene
JP2004175953A (ja) * 2002-11-28 2004-06-24 Kanegafuchi Chem Ind Co Ltd ポリイソブチレン−ポリオレフィン共重合体とその製造方法
US8192813B2 (en) 2003-08-12 2012-06-05 Exxonmobil Chemical Patents, Inc. Crosslinked polyethylene articles and processes to produce same
JP4902099B2 (ja) 2003-10-09 2012-03-21 出光興産株式会社 極性基含有高級オレフィン重合体及びその製造方法
RU2386646C2 (ru) * 2004-01-22 2010-04-20 Дау Глобал Текнолоджиз Инк. Функционализированные эластомерные композиции
US7803728B2 (en) 2004-03-17 2010-09-28 Dow Global Technologies Inc. Fibers made from copolymers of ethylene/α-olefins
US7582716B2 (en) 2004-03-17 2009-09-01 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for blown films with high hot tack
US7514517B2 (en) 2004-03-17 2009-04-07 Dow Global Technologies Inc. Anti-blocking compositions comprising interpolymers of ethylene/α-olefins
US7504347B2 (en) * 2004-03-17 2009-03-17 Dow Global Technologies Inc. Fibers made from copolymers of propylene/α-olefins
US7608668B2 (en) 2004-03-17 2009-10-27 Dow Global Technologies Inc. Ethylene/α-olefins block interpolymers
US7863379B2 (en) 2004-03-17 2011-01-04 Dow Global Technologies Inc. Impact modification of thermoplastics with ethylene/alpha-olefin interpolymers
RU2375381C2 (ru) 2004-03-17 2009-12-10 Дау Глобал Текнолоджиз Инк. Состав катализатора, содержащий челночный агент, для формирования мульти-блок-сополимера высшего олефина
US7687442B2 (en) * 2004-03-17 2010-03-30 Dow Global Technologies Inc. Low molecular weight ethylene/α-olefin interpolymer as base lubricant oils
US7662881B2 (en) 2004-03-17 2010-02-16 Dow Global Technologies Inc. Viscosity index improver for lubricant compositions
US7355089B2 (en) 2004-03-17 2008-04-08 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates
US7671131B2 (en) 2004-03-17 2010-03-02 Dow Global Technologies Inc. Interpolymers of ethylene/α-olefins blends and profiles and gaskets made therefrom
US7714071B2 (en) 2004-03-17 2010-05-11 Dow Global Technologies Inc. Polymer blends from interpolymers of ethylene/α-olefins and flexible molded articles made therefrom
US7671106B2 (en) 2004-03-17 2010-03-02 Dow Global Technologies Inc. Cap liners, closures and gaskets from multi-block polymers
US7897689B2 (en) 2004-03-17 2011-03-01 Dow Global Technologies Inc. Functionalized ethylene/α-olefin interpolymer compositions
US7622179B2 (en) 2004-03-17 2009-11-24 Dow Global Technologies Inc. Three dimensional random looped structures made from interpolymers of ethylene/α-olefins and uses thereof
US7741397B2 (en) 2004-03-17 2010-06-22 Dow Global Technologies, Inc. Filled polymer compositions made from interpolymers of ethylene/α-olefins and uses thereof
WO2005090427A2 (en) * 2004-03-17 2005-09-29 Dow Global Technologies Inc. Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation
US8273838B2 (en) 2004-03-17 2012-09-25 Dow Global Technologies Llc Propylene/α-olefins block interpolymers
US7557147B2 (en) 2004-03-17 2009-07-07 Dow Global Technologies Inc. Soft foams made from interpolymers of ethylene/alpha-olefins
US7579408B2 (en) 2004-03-17 2009-08-25 Dow Global Technologies Inc. Thermoplastic vulcanizate comprising interpolymers of ethylene/α-olefins
US7666918B2 (en) 2004-03-17 2010-02-23 Dow Global Technologies, Inc. Foams made from interpolymers of ethylene/α-olefins
US7622529B2 (en) 2004-03-17 2009-11-24 Dow Global Technologies Inc. Polymer blends from interpolymers of ethylene/alpha-olefin with improved compatibility
US7795321B2 (en) * 2004-03-17 2010-09-14 Dow Global Technologies Inc. Rheology modification of interpolymers of ethylene/α-olefins and articles made therefrom
EP1727840B1 (en) 2004-03-17 2012-10-24 Dow Global Technologies LLC Catalyst composition comprising shuttling agent for higher olefin multi-block copolymer formation
US7524911B2 (en) 2004-03-17 2009-04-28 Dow Global Technologies Inc. Adhesive and marking compositions made from interpolymers of ethylene/α-olefins
AR053693A1 (es) 2004-03-17 2007-05-16 Dow Global Technologies Inc Composiciones de interpolimero de etileno/alfa-olefina multibloque adecuado para peliculas
US7645829B2 (en) * 2004-04-15 2010-01-12 Exxonmobil Chemical Patents Inc. Plasticized functionalized propylene copolymer adhesive composition
US8389615B2 (en) 2004-12-17 2013-03-05 Exxonmobil Chemical Patents Inc. Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin
JP4975730B2 (ja) * 2005-03-17 2012-07-11 ダウ グローバル テクノロジーズ エルエルシー エチレン／α−オレフィンのコポリマーから製造される繊維
RU2007138504A (ru) 2005-03-17 2009-04-27 Дау Глобал Текнолоджиз Инк. (Us) Композиция катализатора, содержащая челночный агент передачи кинетической цепи, предназначенная для получения регионерегулярного многоблочного сополимера
US7910658B2 (en) 2005-03-17 2011-03-22 Dow Global Technologies Llc Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates
US8084537B2 (en) 2005-03-17 2011-12-27 Dow Global Technologies Llc Polymer blends from interpolymers of ethylene/α-olefin with improved compatibility
EP1869095B1 (en) 2005-03-17 2011-04-27 Dow Global Technologies LLC Compositions of ethylene/alpha-olefin multi-block interpolymer for elastic films and laminates
US9410009B2 (en) 2005-03-17 2016-08-09 Dow Global Technologies Llc Catalyst composition comprising shuttling agent for tactic/ atactic multi-block copolymer formation
JP5231987B2 (ja) * 2005-03-17 2013-07-10 ダウ グローバル テクノロジーズ エルエルシー エチレン／α−オレフィン共重合体から製造される接着剤およびマーキング用組成物
JP5231984B2 (ja) * 2005-03-17 2013-07-10 ダウ グローバル テクノロジーズ エルエルシー 向上した相溶性を有するエチレン／α−オレフィンの共重合体から製造されるポリマーブレンド
US7786216B2 (en) * 2005-03-17 2010-08-31 Dow Global Technologies Inc. Oil based blends of interpolymers of ethylene/α-olefins
WO2006113000A2 (en) * 2005-03-17 2006-10-26 Dow Global Technologies Inc. Cap liners, closures and gaskets from multi-block polymers
EP3424966B1 (en) 2005-03-17 2020-05-27 Dow Global Technologies Llc Catalyst composition comprising shuttling agent for tactic/ atactic multi-block copolymer formation
US7737215B2 (en) * 2005-03-17 2010-06-15 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates
BRPI0609825B1 (pt) 2005-03-17 2023-05-16 Dow Global Technologies Inc Composição e artigo
JP5318567B2 (ja) * 2005-05-12 2013-10-16 ダウ グローバル テクノロジーズ エルエルシー 光沢の少ない熱成形押出しシート材
GB0511320D0 (en) 2005-06-03 2005-07-13 Exxonmobil Chem Patents Inc Elastomeric structures
US9644092B2 (en) 2005-06-22 2017-05-09 Exxonmobil Chemical Patents Inc. Heterogeneous in-situ polymer blend
US7951872B2 (en) * 2005-06-22 2011-05-31 Exxonmobil Chemical Patents Inc. Heterogeneous polymer blend with continuous elastomeric phase and process of making the same
US9745461B2 (en) 2005-06-22 2017-08-29 Exxonmobil Chemical Patents Inc. Vulcanized polymer blends
US7928164B2 (en) 2005-06-22 2011-04-19 Exxonmobil Chemical Patents Inc. Homogeneous polymer blend and process of making the same
US20060293462A1 (en) * 2005-06-22 2006-12-28 Sunny Jacob Heterogeneous polymer blend and process of making the same
US8288480B2 (en) * 2005-06-22 2012-10-16 Exxonmobil Chemical Patents Inc. In-reactor polymer blends
EP1896537B1 (en) * 2005-06-24 2017-10-11 ExxonMobil Chemical Patents Inc. Functionalized propylene copolymer adheside composition
WO2007011541A1 (en) 2005-07-15 2007-01-25 Exxonmobil Chemical Patents Inc. Elastomeric compositions
KR20080055838A (ko) 2005-09-15 2008-06-19 다우 글로벌 테크놀로지스 인크. 다중심 셔틀링제를 통한 중합체 구성 및 분자량 분포의제어
BRPI0617042B1 (pt) * 2005-09-15 2018-05-15 Dow Global Technologies Inc. Processo para preparar um polímero ramificado, processo para preparar um copolímero em pseudo-bloco multi-ramificado e polímero em pseudo-bloco ramificado
US7906587B2 (en) 2005-09-16 2011-03-15 Dow Global Technologies Llc Polymer blends from interpolymer of ethylene/α olefin with improved compatibility
US7695812B2 (en) * 2005-09-16 2010-04-13 Dow Global Technologies, Inc. Fibers made from copolymers of ethylene/α-olefins
US7498282B2 (en) * 2005-10-26 2009-03-03 Dow Global Technology Inc. Multi-layer, elastic articles
EP1954730B2 (en) 2005-11-23 2019-10-23 Dow Global Technologies LLC Heterogeneous, compositionally phase separated, ethylene alpha-olefin interpolymers
US8153243B2 (en) 2005-12-09 2012-04-10 Dow Global Technologies Llc Interpolymers suitable for multilayer films
EP1963383B1 (en) 2005-12-09 2019-06-19 Dow Global Technologies LLC Processes of controlling molecular weight distribution in ethylene/alpha-olefin compositions
US20070255026A1 (en) * 2006-04-28 2007-11-01 Fina Technology, Inc. Process for polyolefin production using fluorinated transition metal catalysts having a low pH
US8110518B2 (en) * 2006-04-28 2012-02-07 Fina Technology, Inc. Fluorinated transition metal catalysts and formation thereof
US20070255022A1 (en) * 2006-04-28 2007-11-01 Fina Technology, Inc. Fluorinated transition metal catalysts and formation thereof
EP2079863A1 (en) * 2006-09-06 2009-07-22 Dow Global Technologies Inc. Knit fabrics comprising olefin block interpolymers
EP1908814B1 (en) * 2006-10-05 2009-11-11 Chisso Corporation Liquid crystal compositon and liquid crystal display device
AU2007325008A1 (en) 2006-11-30 2008-06-05 Dow Global Technologies Inc. Stretch fabrics with wrinkle resistance and garment
US7928022B2 (en) * 2006-11-30 2011-04-19 Dow Global Technologies Llc Olefin block compositions for heavy weight stretch fabrics
TW200837234A (en) * 2006-11-30 2008-09-16 Dow Global Technologies Inc Molded fabric articles of olefin block interpolymers
US7745544B2 (en) * 2006-11-30 2010-06-29 Exxonmobil Chemical Patents Inc. Catalytic epoxidation and hydroxylation of olefin/diene copolymers
CA2671703A1 (en) * 2006-12-07 2008-06-12 Grace Gmbh & Co. Kg Matting agent
AU2008206340A1 (en) * 2007-01-16 2008-07-24 Dow Global Technologies Inc. Cone dyed yarns of olefin block compositions
EP2102396B1 (en) * 2007-01-16 2011-05-04 Dow Global Technologies LLC Colorfast fabrics and garments of olefin block compositions
US7615589B2 (en) * 2007-02-02 2009-11-10 Exxonmobil Chemical Patents Inc. Properties of peroxide-cured elastomer compositions
KR20090121285A (ko) * 2007-02-20 2009-11-25 디에스엠 아이피 어셋츠 비.브이. 그래프트 공중합체
US20080287614A1 (en) * 2007-05-15 2008-11-20 Sonoco Development, Inc. Polypropylene-Based Polymer Blend of Enhanced Melt Strength
US8241753B2 (en) * 2007-06-04 2012-08-14 Exxonmobil Chemical Patents Inc. Composite thermoplastic elastomer structures with high adhesion performance and uses for the same
US20080306215A1 (en) * 2007-06-06 2008-12-11 Abhimanyu Onkar Patil Functionalization of olefin/diene copolymers
EP2167574A2 (en) * 2007-07-09 2010-03-31 Dow Global Technologies Inc. Olefin block interpolymer composition suitable for fibers
US20090105374A1 (en) * 2007-09-28 2009-04-23 Dow Global Technologies Inc. Thermoplastic olefin composition with improved heat distortion temperature
EP2052857A1 (en) 2007-10-22 2009-04-29 Dow Global Technologies Inc. Multilayer films
US8138285B2 (en) * 2007-10-26 2012-03-20 Fina Technology, Inc. Fluorinated impregnated catalyst systems and methods of forming the same
US8143353B2 (en) 2008-01-18 2012-03-27 Exxonmobil Chemical Patents Inc. Polymerization process and adhesives therefrom
CA2717417A1 (en) 2008-03-13 2009-03-12 Dow Global Technologies Inc. Long chain branched (lcb), block, or interconnected copolymers of ethylene in combination with one other polymer
US8404773B2 (en) 2008-03-17 2013-03-26 Dow Global Technologies Llc Coating composition, method of producing the same, articles made therefrom, and method of making such articles
US8283419B2 (en) 2008-06-20 2012-10-09 Exxonmobil Chemical Patents Inc. Olefin functionalization by metathesis reaction
US8283428B2 (en) 2008-06-20 2012-10-09 Exxonmobil Chemical Patents Inc. Polymacromonomer and process for production thereof
US8372930B2 (en) 2008-06-20 2013-02-12 Exxonmobil Chemical Patents Inc. High vinyl terminated propylene based oligomers
US8399725B2 (en) 2008-06-20 2013-03-19 Exxonmobil Chemical Patents Inc. Functionalized high vinyl terminated propylene based oligomers
US8802797B2 (en) 2008-06-20 2014-08-12 Exxonmobil Chemical Patents Inc. Vinyl-terminated macromonomer oligomerization
US8093335B2 (en) * 2008-12-15 2012-01-10 Exxonmobil Chemical Patents Inc. Thermoplastic polyolefin in-reactor blends and molded articles therefrom
US8410217B2 (en) * 2008-12-15 2013-04-02 Exxonmobil Chemical Patents Inc. Thermoplastic polyolefin blends
US8227547B2 (en) * 2008-12-15 2012-07-24 Exxonmobil Chemical Patents Inc. Foamable thermoplastic reactor blends and foam article therefrom
US8106127B2 (en) * 2008-12-15 2012-01-31 Exxonmobil Chemical Patents Inc. Heterogeneous in-reactor polymer blends
US8497325B2 (en) 2008-12-15 2013-07-30 Exxonmobil Chemical Patents Inc. Thermoplastic polyolefin blends and films therefrom
US8101685B2 (en) * 2008-12-15 2012-01-24 Exxonmobil Chemical Patents Inc. Thermoplastic elastomer polyolefin in-reactor blends and molded articles therefrom
US8431651B2 (en) 2009-07-14 2013-04-30 Dow Global Technologies Llc Vacuum thermoformed, extruded sheeting with improved reduced gloss
ES2858349T3 (es) 2009-07-29 2021-09-30 Dow Global Technologies Llc Agentes de transporte de cadena de múltiples cabezas y su uso para la preparación de copolímeros de bloques
WO2011025587A1 (en) * 2009-08-27 2011-03-03 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions and method of making thereof
US9458310B2 (en) 2009-10-16 2016-10-04 Exxonmobil Chemical Patents Inc. Modified polyethylene film compositions
US9103966B2 (en) * 2009-12-18 2015-08-11 Dow Global Technologies Llc Plastic optical fiber comprising cyclic block copolymer
US8907034B2 (en) 2010-09-30 2014-12-09 Dow Global Technologies Llc Comb architecture olefin block copolymers
US8501894B2 (en) 2011-03-25 2013-08-06 Exxonmobil Chemical Patents Inc. Hydrosilyation of vinyl macromers with metallocenes
US8835563B2 (en) 2011-03-25 2014-09-16 Exxonmobil Chemical Patents Inc. Block copolymers from silylated vinyl terminated macromers
US8669330B2 (en) 2011-03-25 2014-03-11 Exxonmobil Chemical Patents Inc. Olefin triblock polymers via ring-opening metathesis polymerization
US8623974B2 (en) 2011-03-25 2014-01-07 Exxonmobil Chemical Patents Inc. Branched vinyl terminated polymers and methods for production thereof
WO2012134713A2 (en) * 2011-03-25 2012-10-04 Exxonmobil Chemical Patents Inc. Olefin triblock polymers via ring-opening metathesis polymerization
US8426659B2 (en) 2011-03-25 2013-04-23 Exxonmobil Chemical Patents Inc. Vinyl terminated higher olefin polymers and methods to produce thereof
US8940839B2 (en) 2011-03-25 2015-01-27 Exxonmobil Chemical Patents Inc. Diblock copolymers prepared by cross metathesis
US8841397B2 (en) 2011-03-25 2014-09-23 Exxonmobil Chemical Patents Inc. Vinyl terminated higher olefin polymers and methods to produce thereof
US8455597B2 (en) 2011-03-25 2013-06-04 Exxonmobil Chemical Patents Inc. Catalysts and methods of use thereof to produce vinyl terminated polymers
US8399724B2 (en) 2011-03-25 2013-03-19 Exxonmobil Chemical Patents Inc. Vinyl terminated higher olefin copolymers and methods to produce thereof
US8669326B2 (en) 2011-03-25 2014-03-11 Exxonmobil Chemical Patents Inc. Amine functionalized polyolefin and methods for preparation thereof
US8785562B2 (en) 2011-03-25 2014-07-22 Exxonmobil Chemical Patents Inc. Amphiphilic block polymers prepared by alkene metathesis
US9340664B2 (en) 2011-09-23 2016-05-17 Exxonmobil Chemical Patents Inc. Modified polyethylene compositions for blown film
US9321911B2 (en) 2011-09-23 2016-04-26 Exxonmobil Chemical Patents Inc. Modified polyethylene compositions for cast film
US20160272798A1 (en) 2011-09-23 2016-09-22 Exxonmobil Chemical Patents Inc. Modified Polyethylene Compositions with Enhanced Melt Strength
JP5960831B2 (ja) 2011-09-23 2016-08-02 エクソンモービル ケミカル パテンツ インコーポレイテッド 改質ポリエチレン組成物
US8629217B2 (en) 2011-11-22 2014-01-14 Exxonmobil Chemical Patents Inc. Modified polyethylene blown film compositions having excellent bubble stability
US8604148B2 (en) 2011-11-29 2013-12-10 Exxonmobil Chemical Patents Inc. Functionalization of vinyl terminated polymers by ring opening cross metathesis
IN2014CN04856A (zh) 2011-12-29 2015-09-18 Dow Global Technologies Llc
US8796376B2 (en) 2012-03-26 2014-08-05 Exxonmobil Chemical Patents Inc. Functionalized polymers and oligomers
US10836853B2 (en) 2012-09-20 2020-11-17 Exxonmobil Chemical Patents Inc. Crack-resistant polyethylene compositions
US10822479B2 (en) 2012-09-20 2020-11-03 Exxonmobil Chemical Patents Inc. Foamed polyethylene compositions
EP2928958B1 (en) 2012-12-05 2019-08-21 ExxonMobil Chemical Patents Inc. Hdpe modified polyethylene blown film compositions having excellent bubble stability
JP6439280B2 (ja) * 2013-08-09 2018-12-19 三菱ケミカル株式会社 熱可塑性エラストマー組成物の製造方法
US9321856B2 (en) 2013-12-19 2016-04-26 Exxonmobil Chemical Patents Inc. Process to produce functionalized polymer
EP3110885B1 (en) 2014-02-24 2018-10-03 Dow Global Technologies LLC Thermoplastic polyolefin with reduced gloss for non-carpeted flooring
JP6017089B2 (ja) 2014-03-28 2016-10-26 三井化学株式会社 オレフィン系樹脂、その製造方法およびプロピレン系樹脂組成物
WO2015183577A1 (en) 2014-05-29 2015-12-03 Exxonmobil Chemical Patents Inc. Cyclic-diene additives in polyethylene films and enhanced film orientation balance in production thereof
CN106414568B (zh) 2014-05-29 2019-08-06 埃克森美孚化学专利公司 聚乙烯薄膜及其生产
US10125247B2 (en) 2014-05-29 2018-11-13 Exxonmobil Chemical Patents Inc. Polyethylene compositions
KR101792171B1 (ko) 2014-12-08 2017-10-31 주식회사 엘지화학 우수한 용융 강도를 갖는 올레핀계 중합체 및 이를 포함하는 필름
WO2016093266A1 (ja) 2014-12-09 2016-06-16 三井化学株式会社 プロピレン系樹脂組成物
US10246542B2 (en) 2015-09-14 2019-04-02 Exxonmobil Chemical Patents Inc. Atactic polypropylene comb block polyolefins useful as modifiers in polyolefins and hydrocarbons
CN110582536A (zh) 2017-03-29 2019-12-17 埃克森美孚化学专利公司 聚乙烯组合物
CN109748988B (zh) * 2017-11-04 2021-12-03 天津大学 一种丙烯共聚物及其制备方法
US11028196B2 (en) * 2017-12-22 2021-06-08 Exxonmobil Chemical Patents Inc. Polyolefin compositions
CN111138575B (zh) * 2018-11-05 2021-06-11 中国科学院化学研究所 有机硅烷化合物、聚烯烃树脂及其制备方法和应用
KR20200065147A (ko) * 2018-11-29 2020-06-09 롯데케미칼 주식회사 우수한 용융 특성을 지닌 폴리프로필렌 수지 및 그 제조 방법
WO2020131311A1 (en) 2018-12-18 2020-06-25 Exxonmobil Research And Engineering Company Modified asphalts and methods for producing the same
JP7370191B2 (ja) * 2019-08-15 2023-10-27 三井化学株式会社 オレフィン系樹脂、その製造方法および組成物
WO2021051103A1 (en) * 2019-09-13 2021-03-18 Cornell University Graft copolymers for compatibilization of polyethylene and polypropylene
FR3105225B1 (fr) * 2019-12-18 2021-12-03 Michelin & Cie Copolymère d’éthylène et d’un 1,3-diène
CN113861348B (zh) * 2021-10-09 2022-07-26 天津大学 一种pmp共聚物及其制备方法
WO2023101004A1 (ja) * 2021-12-02 2023-06-08 三井化学株式会社 オレフィン系樹脂、その製造方法および用途

Family Cites Families (117)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3350778A (en) 1966-05-04 1967-11-07 Joseph F Perry Onion peeler
US3989768A (en) * 1971-02-22 1976-11-02 Cpc International Inc. Chemically joined phase separated thermoplastic graft copolymers
BE793639A (fr) 1972-01-03 1973-07-03 Xerox Corp Revelateur electrostatographique
JPS52141888A (en) 1976-05-21 1977-11-26 Nippon I P Rubber Kk Ethyleneepropylene copolymers rubber
US4335225A (en) 1978-06-20 1982-06-15 E. I. Du Pont De Nemours And Company Elastomeric polypropylene
DE3127133A1 (de) 1981-07-09 1983-01-27 Hoechst Ag, 6000 Frankfurt Verfahren zur herstellung von polyolefinen und deren copolymerisaten
US4588790A (en) 1982-03-24 1986-05-13 Union Carbide Corporation Method for fluidized bed polymerization
US4543399A (en) 1982-03-24 1985-09-24 Union Carbide Corporation Fluidized bed reaction systems
US4937299A (en) 1983-06-06 1990-06-26 Exxon Research & Engineering Company Process and catalyst for producing reactor blend polyolefins
US5324800A (en) 1983-06-06 1994-06-28 Exxon Chemical Patents Inc. Process and catalyst for polyolefin density and molecular weight control
US4530914A (en) 1983-06-06 1985-07-23 Exxon Research & Engineering Co. Process and catalyst for producing polyethylene having a broad molecular weight distribution
ATE88196T1 (de) 1985-01-31 1993-04-15 Himont Inc Polypropylen mit freier langkettenverzweigung, verfahren zur herstellung und verwendung davon.
DE3508887A1 (de) 1985-03-13 1986-09-25 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von optisch aktiven polyolefinen
US4808561A (en) 1985-06-21 1989-02-28 Exxon Chemical Patents Inc. Supported polymerization catalyst
US4665208A (en) 1985-07-11 1987-05-12 Exxon Chemical Patents Inc. Process for the preparation of alumoxanes
US4701432A (en) 1985-11-15 1987-10-20 Exxon Chemical Patents Inc. Supported polymerization catalyst
US4752597A (en) * 1985-12-12 1988-06-21 Exxon Chemical Patents Inc. New polymerization catalyst
IL80888A (en) * 1985-12-12 1991-12-12 Exxon Chemical Patents Inc Olefin polymerization catalysts,their preparation and use thereof
DE3782243T2 (de) 1986-08-26 1993-03-04 Mitsui Petrochemical Ind Katalysator zur polymerisierung von alpha-olefin und verfahren.
ATE177759T1 (de) 1986-09-24 1999-04-15 Mitsui Chemicals Inc Verfahren zur olefinpolymerisation
JPH0780933B2 (ja) 1986-11-20 1995-08-30 三井石油化学工業株式会社 オレフインの重合方法
JP2618384B2 (ja) 1986-12-27 1997-06-11 三井石油化学工業株式会社 オレフイン重合用固体触媒およびその製法
US4921825A (en) 1986-12-30 1990-05-01 Mitsui Petrochemical Industries, Ltd. Solid catalyst for olefin polymerization and processes for its production
US5391629A (en) * 1987-01-30 1995-02-21 Exxon Chemical Patents Inc. Block copolymers from ionic catalysts
US5198401A (en) 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
PL276385A1 (en) 1987-01-30 1989-07-24 Exxon Chemical Patents Inc Method for polymerization of olefines,diolefins and acetylene unsaturated compounds
IL85097A (en) 1987-01-30 1992-02-16 Exxon Chemical Patents Inc Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes
JPH0742301B2 (ja) 1987-02-14 1995-05-10 三井石油化学工業株式会社 微粒子状アルミノオキサン、その製法およびその用途
US4769910A (en) 1987-03-30 1988-09-13 Northern Telecom Limited Cutting tool for cylindrical articles
JP2538588B2 (ja) 1987-04-03 1996-09-25 三井石油化学工業株式会社 オレフイン重合用固体触媒の製法
US5206199A (en) 1987-04-20 1993-04-27 Mitsui Petrochemical Industries, Ltd. Catalyst for polymerizing an olefin and process for polymerizing an olefin
DE3742934A1 (de) 1987-12-18 1989-06-29 Hoechst Ag Verfahren zur herstellung einer chiralen, stereorigiden metallocen-verbindung
US5120867A (en) 1988-03-21 1992-06-09 Welborn Jr Howard C Silicon-bridged transition metal compounds
US5017714A (en) 1988-03-21 1991-05-21 Exxon Chemical Patents Inc. Silicon-bridged transition metal compounds
US5149819A (en) 1988-04-28 1992-09-22 Ricoh Company, Ltd. Squarylium compounds and optical information recording medium using the same
US4871705A (en) 1988-06-16 1989-10-03 Exxon Chemical Patents Inc. Process for production of a high molecular weight ethylene a-olefin elastomer with a metallocene alumoxane catalyst
FR2634212B1 (fr) 1988-07-15 1991-04-19 Bp Chimie Sa Appareillage et procede de polymerisation d'olefines en phase gazeuse dans un reacteur a lit fluidise
US5155080A (en) 1988-07-15 1992-10-13 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
US4892851A (en) 1988-07-15 1990-01-09 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
EP0354893B2 (en) 1988-08-05 2002-03-13 Fina Technology, Inc. Process for producing large symmetrical polymer particles
US5091352A (en) 1988-09-14 1992-02-25 Mitsui Petrochemical Industries, Ltd. Olefin polymerization catalyst component, olefin polymerization catalyst and process for the polymerization of olefins
US5382630A (en) 1988-09-30 1995-01-17 Exxon Chemical Patents Inc. Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distribution
US4999403A (en) * 1988-10-28 1991-03-12 Exxon Chemical Patents Inc. Graft polymers of functionalized ethylene-alpha-olefin copolymer with polypropylene, methods of preparation, and use in polypropylene compositions
EP0366411A3 (en) * 1988-10-28 1991-04-24 Exxon Chemical Patents Inc. Graft polymers of ethylene-propylene-diene monomer polymers with propylene, means of preparation, and use of polypropylene compositions
US4908463A (en) 1988-12-05 1990-03-13 Ethyl Corporation Aluminoxane process
CA2008315C (en) 1989-01-24 1995-03-21 Toshiyuki Tsutsui Olefin copolymers and processes for preparing same
US5047485A (en) 1989-02-21 1991-09-10 Himont Incorporated Process for making a propylene polymer with free-end long chain branching and use thereof
US5103031A (en) 1989-02-21 1992-04-07 Ethyl Corporation Falling film aluminoxane process
DE3907964A1 (de) 1989-03-11 1990-09-13 Hoechst Ag Verfahren zur herstellung eines syndiotaktischen polyolefins
US4968827A (en) 1989-06-06 1990-11-06 Ethyl Corporation Alkylaluminoxane process
US4924018A (en) 1989-06-26 1990-05-08 Ethyl Corporation Alkylaluminoxane process
US5057475A (en) 1989-09-13 1991-10-15 Exxon Chemical Patents Inc. Mono-Cp heteroatom containing group IVB transition metal complexes with MAO: supported catalyst for olefin polymerization
US5026798A (en) 1989-09-13 1991-06-25 Exxon Chemical Patents Inc. Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system
US5763549A (en) 1989-10-10 1998-06-09 Fina Technology, Inc. Cationic metallocene catalysts based on organoaluminum anions
DE69018376T3 (de) 1989-10-30 2002-05-16 Fina Technology Herstellung von Metallocenkatalysatoren für Olefinpolymerisation.
ATE186918T1 (de) 1990-01-02 1999-12-15 Exxon Chemical Patents Inc Ionische metallocenkatalysatoren auf träger für olefinpolymerisation
GB2241244B (en) * 1990-02-22 1994-07-06 James C W Chien Thermoplastic elastomers
WO1991015523A1 (fr) 1990-04-09 1991-10-17 Mitsui Toatsu Chemicals, Incorporated Copolymere de propylene
AU7875791A (en) 1990-05-07 1991-11-27 Exxon Chemical Patents Inc. Unsaturated alpha-olefin copolymers and method for preparation thereof
BR9106589A (pt) 1990-06-22 1993-06-01 Exxon Chemical Patents Inc Catalisadores de monociclopentadienil metaloceno isentos de aluminio para a polimerizacao de olefinas
US5272236A (en) * 1991-10-15 1993-12-21 The Dow Chemical Company Elastic substantially linear olefin polymers
WO1992001723A1 (en) 1990-07-24 1992-02-06 Mitsui Toatsu Chemicals, Incorporated CATALYST FOR α-OLEFIN POLYMERIZATION AND PRODUCTION OF POLY-α-OLEFIN THEREWITH
US5239022A (en) 1990-11-12 1993-08-24 Hoechst Aktiengesellschaft Process for the preparation of a syndiotactic polyolefin
US5243001A (en) 1990-11-12 1993-09-07 Hoechst Aktiengesellschaft Process for the preparation of a high molecular weight olefin polymer
EP0485821B1 (de) 1990-11-12 1996-06-12 Hoechst Aktiengesellschaft Metallocene mit Liganden aus 2-substituierten Indenylderivaten, Verfahren zu ihrer Herstellung und ihre Verwendung als Katalysatoren
ATE135358T1 (de) 1990-12-27 1996-03-15 Exxon Chemical Patents Inc Übergangsmetall-amidoverbindung und katalysatorsystem zur herstellung von isotaktischem propylen
US5189192A (en) 1991-01-16 1993-02-23 The Dow Chemical Company Process for preparing addition polymerization catalysts via metal center oxidation
JP3076619B2 (ja) * 1991-05-14 2000-08-14 三井化学株式会社 ブロック共重合体の製造方法
DE4120009A1 (de) 1991-06-18 1992-12-24 Basf Ag Loesliche katalysatorsysteme zur herstellung von polyalk-1-enen mit hohen molmassen
US5721185A (en) 1991-06-24 1998-02-24 The Dow Chemical Company Homogeneous olefin polymerization catalyst by abstraction with lewis acids
US5157137A (en) 1991-07-26 1992-10-20 Ethyl Corporation Method of making gel free alkylaluminoxane solutions
US5235081A (en) 1992-03-18 1993-08-10 Ethyl Corporation Method of removing gel forming materials from methylaluminoxanes
US5308815A (en) 1991-07-26 1994-05-03 Ethyl Corporation Heterogeneous methylaluminoxane catalyst system
DE4130299A1 (de) 1991-09-12 1993-03-18 Basf Ag Verfahren zur herstellung von polypropylen unter hochdruck
JP3394997B2 (ja) 1991-10-15 2003-04-07 バーゼル・ポリオレフィン・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 特異的に置換されたインデニル配位子を持つメタロセンを用いてオレフィンポリマーを製造する方法
JPH07501845A (ja) * 1991-12-13 1995-02-23 エクソン・ケミカル・パテンツ・インク エチレンとより長いアルファーオレフィンのコポリマー
US5329032A (en) 1992-03-18 1994-07-12 Akzo Chemicals Inc. Polymethylaluminoxane of enhanced solution stability
US5436304A (en) 1992-03-19 1995-07-25 Exxon Chemical Patents Inc. Process for polymerizing monomers in fluidized beds
US5352749A (en) 1992-03-19 1994-10-04 Exxon Chemical Patents, Inc. Process for polymerizing monomers in fluidized beds
US5310794A (en) * 1992-03-31 1994-05-10 Himont Incorporated Theromoplastic blends containing graft copolymers of polyacrylates as impact modifiers
EP0641362B1 (en) * 1992-04-20 1998-11-11 Exxon Chemical Patents Inc. Ethylene/branched olefin copolymers
EP0578838A1 (en) 1992-04-29 1994-01-19 Hoechst Aktiengesellschaft Olefin polymerization catalyst, process for its preparation, and its use
US5350723A (en) 1992-05-15 1994-09-27 The Dow Chemical Company Process for preparation of monocyclopentadienyl metal complex compounds and method of use
US5240894A (en) 1992-05-18 1993-08-31 Exxon Chemical Patents Inc. Method for making and using a supported metallocene catalyst system
US5434115A (en) 1992-05-22 1995-07-18 Tosoh Corporation Process for producing olefin polymer
EP0572034A2 (en) * 1992-05-29 1993-12-01 Idemitsu Kosan Company Limited Ethylenic copolymer and ethylenic copolymer composition
ES2113900T3 (es) 1992-06-13 1998-05-16 Targor Gmbh Proceso para la preparacion de catalizadores de metalocenos quirales, puenteados del tipo bisindenilo.
US5710222A (en) 1992-06-22 1998-01-20 Fina Technology, Inc. Method for controlling the melting points and molecular weights of syndiotactic polyolefins using metallocene catalyst systems
CA2141814A1 (en) 1992-08-05 1994-02-17 David Jonathan Upton Supported ionic transition metal catalysts for olefin polymerization
US5248801A (en) 1992-08-27 1993-09-28 Ethyl Corporation Preparation of methylaluminoxanes
WO1994007930A1 (en) * 1992-09-29 1994-04-14 Exxon Chemical Patents Inc. Long chain branched polymers and a process to make long chain branched polymers
WO1994007928A1 (en) 1992-10-02 1994-04-14 The Dow Chemical Company Supported homogeneous catalyst complexes for olefin polymerization
US5608009A (en) 1992-10-28 1997-03-04 Idemitsu Kosan Co., Ltd. Olefin copolymer and process for preparing same
US5939346A (en) 1992-11-02 1999-08-17 Akzo Nobel N.V. Catalyst system comprising an aryloxyaluminoxane containing an electron withdrawing group
US5635573A (en) 1992-12-01 1997-06-03 Exxon Chemical Patents Inc. Method for preparing alpha-olefin/cycloolefin copolymers
CA2110654C (en) 1992-12-17 2006-03-21 Albert Rossi Dilute process for the polymerization of ethylene/alpha-olefin copolymer using metallocene catalyst systems
IL107927A0 (en) 1992-12-17 1994-04-12 Exxon Chemical Patents Inc Oil soluble ethylene/1-butene copolymers and lubricating oils containing the same
US5747620A (en) * 1993-02-22 1998-05-05 Idemitsu Kosan Co., Ltd. Ethylene copolymer, thermoplastic resin composition containing same, and process for preparing ethylene copolymer
KR100190268B1 (ko) 1993-04-26 1999-06-01 에인혼 해롤드 유동상에서 단량체를 중합시키는 방법
ATE174945T1 (de) * 1993-04-28 1999-01-15 Dow Chemical Co Produkte aus ethylenenpolymergemischen
AU683899B2 (en) 1993-05-25 1997-11-27 Exxon Chemical Patents Inc. Supported metallocene catalyst systems for the polymerization of olefins, preparation and use thereof
US5414027A (en) 1993-07-15 1995-05-09 Himont Incorporated High melt strength, propylene polymer, process for making it, and use thereof
JPH081575B2 (ja) * 1993-07-26 1996-01-10 工業技術院長 機器構成用多機能モジュール
KR0126658B1 (ko) * 1993-10-05 1997-12-29 구자홍 비표준 텔레비젼 신호처리를 위한 샘플률 변환장치
US5955557A (en) * 1993-10-26 1999-09-21 Idemitsu Kosan Co., Ltd. Branched ethylenic macromonomer and its polymer
US5594080A (en) 1994-03-24 1997-01-14 Leland Stanford, Jr. University Thermoplastic elastomeric olefin polymers, method of production and catalysts therefor
PL182074B1 (en) 1994-06-24 2001-11-30 Exxon Chemical Patents Inc Catalytic systems for polymerisation processes, their production and application
ATE207085T1 (de) 1994-06-24 2001-11-15 Exxonmobil Chem Patents Inc Polymerisationskatalysatorsystem, ihre herstellung und verwendung
US5643847A (en) 1994-08-03 1997-07-01 Exxon Chemical Patents Inc. Supported ionic catalyst composition
ATE208404T1 (de) 1994-08-03 2001-11-15 Exxonmobil Chem Patents Inc Ionische katalysatorzusammensetzung auf träger
EP0805826B1 (en) 1995-01-24 2003-04-23 E.I. Du Pont De Nemours And Company Olefin polymers
US5539056A (en) 1995-01-31 1996-07-23 Exxon Chemical Patents Inc. Thermoplastic elastomers
EP0836624B1 (en) 1995-07-06 2002-04-17 ExxonMobil Chemical Patents Inc. Method for producing prepolymerized, supported metallocene catalyst systems
US6084030A (en) * 1995-08-04 2000-07-04 Dsm Copolymer, Inc. Branched polymers with polyolefin arms
KR100455230B1 (ko) * 1995-09-11 2005-04-06 미쓰이 가가쿠 가부시키가이샤 수지조성물의제조방법
US5914372A (en) 1997-01-23 1999-06-22 Jsr Corporation Ethylene copolymer rubber composition
US6184327B1 (en) 1997-12-10 2001-02-06 Exxon Chemical Patents, Inc. Elastomeric propylene polymers

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101018815B (zh) * 2004-04-15 2016-11-30 埃克森美孚化学专利公司 烯烃聚合用多催化剂和反应器系统及所生产的聚合物
CN101578307B (zh) * 2005-03-17 2013-06-19 陶氏环球技术有限责任公司 乙烯/α-烯烃嵌段共聚体
CN102245696A (zh) * 2008-12-15 2011-11-16 埃克森美孚化学专利公司 热塑性弹性体聚烯烃反应器内共混物和由此得到的模塑制品
CN102245696B (zh) * 2008-12-15 2013-06-19 埃克森美孚化学专利公司 热塑性弹性体聚烯烃反应器内共混物和由此得到的模塑制品
CN103339187A (zh) * 2011-02-15 2013-10-02 埃克森美孚化学专利公司 热塑性聚烯烃共混物
CN103339187B (zh) * 2011-02-15 2016-01-20 埃克森美孚化学专利公司 热塑性聚烯烃共混物
CN103890023A (zh) * 2011-10-24 2014-06-25 三菱化学株式会社 热塑性弹性体组合物及其制造方法
US9139679B2 (en) 2011-10-24 2015-09-22 Mitsubishi Chemical Corporation Thermoplastic elastomer composition and process for manufacturing the same
CN103890023B (zh) * 2011-10-24 2016-11-16 三菱化学株式会社 热塑性弹性体组合物及其制造方法

Also Published As

Publication number Publication date
US20040048984A1 (en) 2004-03-11
CA2277111A1 (en) 1998-08-13
CN1113915C (zh) 2003-07-09
EP0958314A1 (en) 1999-11-24
ES2187005T3 (es) 2003-05-16
ES2181173T3 (es) 2003-02-16
EP0958313A1 (en) 1999-11-24
KR100564500B1 (ko) 2006-03-29
US20030078350A1 (en) 2003-04-24
KR20000070780A (ko) 2000-11-25
US6774191B2 (en) 2004-08-10
BR9808578A (pt) 2000-05-30
KR20000070872A (ko) 2000-11-25
CN1130406C (zh) 2003-12-10
CA2277063A1 (en) 1998-08-13
BR9807672A (pt) 2000-02-15
US6660809B1 (en) 2003-12-09
WO1998034971A1 (en) 1998-08-13
WO1998034970A1 (en) 1998-08-13
EP0958313B1 (en) 2002-09-25
CA2277063C (en) 2007-03-20
US6147180A (en) 2000-11-14
KR100564499B1 (ko) 2006-03-29
CN1246871A (zh) 2000-03-08
US6750307B2 (en) 2004-06-15
DE69809192D1 (de) 2002-12-12
JP2001527589A (ja) 2001-12-25
JP4218988B2 (ja) 2009-02-04
JP2001511215A (ja) 2001-08-07
EP0958314B1 (en) 2002-11-06
DE69808243D1 (de) 2002-10-31
DE69809192T2 (de) 2003-07-24
DE69808243T2 (de) 2003-05-08

Similar Documents

Publication Publication Date Title
CN1113915C (zh) 支化烯烃共聚物的热塑性弹性体组合物
CA2304287C (en) Elastomeric propylene polymers
US6114457A (en) High melt strength polyethylene compositions
US6444773B1 (en) Preparation of vinyl-containing macromers
CN1111550C (zh) 改进的易于加工的线型低密度聚乙烯
US20070129490A1 (en) Proplyene polymer composition, molded object, and polyolefin copolymer
KR20020061634A (ko) 비정질 및 결정성 중합체의 가교결합 블렌드의 제조방법
KR20020061633A (ko) 비정질 및 결정성 중합체의 가교결합 블렌드 및 이들의 용도
MXPA05001171A (es) Copolimeros de bloque de poliolefinas.
CN1243528A (zh) 高熔体强度聚乙烯组合物
CA2286683A1 (en) Amorphous propylene-polyene copolymers and compositions thereof
JP3570809B2 (ja) ポリエチレンの製造方法
JP3803155B2 (ja) ポリエチレン製成形体
EP1312620B1 (en) Propylene homopolymer and propylene copolymer
MXPA99007265A (en) Thermoplastic elastomer compositions from branched olefin copolymers
JPH10251335A (ja) エチレン系重合体およびエチレン系重合体組成物
MXPA00005267A (es) Polimeros de propileno elastomericos
JPH10193379A (ja) ポリエチレン製射出成形体

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: 20030709