High melting thermoplastic elastomeric alpha-olefin polymers (PRE/EPE effect) and catalysts therefor
This invention relates generally to processes for production of -olefin polymers using unbridged fluxional metallocenes, primarily substituted aryl indenyl metallocenes, and more particularly to use of unbridged, fluxional, cyclopentadienyl or indenyl metallocene catalysts and catalyst systems in me...
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| creator | Waymouth, Robert M Kravchenko, Raisa Bendig, Larry L Moore, Eric J Myers, Charles L Quan, Roger W Ernst, Andreas B |
| description | This invention relates generally to processes for production of -olefin polymers using unbridged fluxional metallocenes, primarily substituted aryl indenyl metallocenes, and more particularly to use of unbridged, fluxional, cyclopentadienyl or indenyl metallocene catalysts and catalyst systems in methods of production of high melting point olefin homo- and co-polymers, particularly elastomeric crystalline and amorphous block homo- and co-polymers of alpha olefins. More specifically, the invention is directed to: (1) the discovery and catalytic process use of a Polymerization Rate-Enhancement effect (PRE effect) in polymerization processes which involve the addition of minor amounts of ethylene to the polymerization system to produce polymers having properties ranging from crystalline thermoplastics to high melting point thermoplastic elastomers to amorphous gum elastomers, and methods for increasing polymerization production rates and polymer molecular weight; (2) the discovery and catalytic process use of an Elastomeric Property-Enhancement effect (EPE effect) in which small quantities of ethylene added to the polymerization system activates selected metallocene catalyst systems, which otherwise do not produce elastomeric polymers, to produce elastomeric polymers; and (3) novel substituted aryl indenyl metallocene catalysts.
This invention relates generally to low ethylene insertions into I-olefin polymers and processes for production of such polymers using unbridged fluxional metallocenes, primarily substituted aryl indenyl metallocenes, and more particularly to use of unbridged, fluxional, cyclopentadienyl or indenyl metallocene catalyst systems in methods of production of high melting point I-olefin homo- and co-polymers, particularly elastomeric crystalline and amorphous block homo- and co-polymers of I-olefins. The activity of fluxional unbridged metallocene polymerization catalysts containing at least one 2-arylindene ligand is increased 10× or more by the addition of small (typically 0.1-10 wt. %) amounts of ethylene to the polymerization system, which increase is termed the Polymerization Rate-Enhancement effect (PRE), which is measured in terms of an Ethylene Enhancement Factor (EEF) as a dimensionless ratio in the range of from about 1.1 to about 10 or above. The amount of ethylene included in the reaction system can be selected and controlled to be so small as to result in essentially minimal ( |
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| fullrecord | <record><control><sourceid>uspatents_EFH</sourceid><recordid>TN_cdi_uspatents_grants_06559262</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>06559262</sourcerecordid><originalsourceid>FETCH-uspatents_grants_065592623</originalsourceid><addsrcrecordid>eNqNzLEKwkAQBNA0FqL-w5ZaBCWSQGo5SRnEXpZkLznY3B23a5G_NxE_wOoNwzDbrG_cMMJErM4PoCOlKURGUdcBrYaJ0pKR44h5YLLOQww8L7XAsX2Ys2kNkLXU6QnQ99ChIs-i8r0jG9I-21hkocPPXQZ387w1-VsiKnmV15Bw5VKVZV1UxfWPyQdlDD9J</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>patent</recordtype></control><display><type>patent</type><title>High melting thermoplastic elastomeric alpha-olefin polymers (PRE/EPE effect) and catalysts therefor</title><source>USPTO Issued Patents</source><creator>Waymouth, Robert M ; Kravchenko, Raisa ; Bendig, Larry L ; Moore, Eric J ; Myers, Charles L ; Quan, Roger W ; Ernst, Andreas B</creator><creatorcontrib>Waymouth, Robert M ; Kravchenko, Raisa ; Bendig, Larry L ; Moore, Eric J ; Myers, Charles L ; Quan, Roger W ; Ernst, Andreas B ; The Board of Trustees of the Leland Stanford Jr. University</creatorcontrib><description>This invention relates generally to processes for production of -olefin polymers using unbridged fluxional metallocenes, primarily substituted aryl indenyl metallocenes, and more particularly to use of unbridged, fluxional, cyclopentadienyl or indenyl metallocene catalysts and catalyst systems in methods of production of high melting point olefin homo- and co-polymers, particularly elastomeric crystalline and amorphous block homo- and co-polymers of alpha olefins. More specifically, the invention is directed to: (1) the discovery and catalytic process use of a Polymerization Rate-Enhancement effect (PRE effect) in polymerization processes which involve the addition of minor amounts of ethylene to the polymerization system to produce polymers having properties ranging from crystalline thermoplastics to high melting point thermoplastic elastomers to amorphous gum elastomers, and methods for increasing polymerization production rates and polymer molecular weight; (2) the discovery and catalytic process use of an Elastomeric Property-Enhancement effect (EPE effect) in which small quantities of ethylene added to the polymerization system activates selected metallocene catalyst systems, which otherwise do not produce elastomeric polymers, to produce elastomeric polymers; and (3) novel substituted aryl indenyl metallocene catalysts.
This invention relates generally to low ethylene insertions into I-olefin polymers and processes for production of such polymers using unbridged fluxional metallocenes, primarily substituted aryl indenyl metallocenes, and more particularly to use of unbridged, fluxional, cyclopentadienyl or indenyl metallocene catalyst systems in methods of production of high melting point I-olefin homo- and co-polymers, particularly elastomeric crystalline and amorphous block homo- and co-polymers of I-olefins. The activity of fluxional unbridged metallocene polymerization catalysts containing at least one 2-arylindene ligand is increased 10× or more by the addition of small (typically 0.1-10 wt. %) amounts of ethylene to the polymerization system, which increase is termed the Polymerization Rate-Enhancement effect (PRE), which is measured in terms of an Ethylene Enhancement Factor (EEF) as a dimensionless ratio in the range of from about 1.1 to about 10 or above. The amount of ethylene included in the reaction system can be selected and controlled to be so small as to result in essentially minimal (<2 mole %) incorporation of ethylene units into the resulting elastomeric polymer and the molecular weight may be increased. Amounts of ethylene to generate the PRE effect may be greater than 0.1 wt. % and preferably range up to about 2 wt. %. However, if a polymer with more ethylene is desired, additional ethylene may be incorporated into the polymerization feed, including up to 10 to about 50 mole % based on olefin units. A second important aspect of this invention is the ability to use a PRE activity-enhancing amount of ethylene in an olefin polymerization without substantially affecting the physical properties of the elastomer. In a third important aspect of this invention, I-olefin elastomers are produced through incorporation of ethylene using unbridged fluxional catalyst systems which may not otherwise produce acceptable elastomeric homopolymers. This effect is termed the EPE effect, for Elastomeric Property-Enhancing effect. The EPE amount of ethylene required to produce such elastomers typically overlaps the PRE activity-enhancing amount. Incorporation of up to about 5 mole % or more of ethylene typically will produce an elastomeric polymer using such catalyst systems. Typical useful amounts of incorporated ethylene include about 1 to 3 mole %. Preferred polymers of this invention retain sufficient crystallinity to provide a high melting point (by DSC) of about 80° C., preferably above 100° C., including in the range of from about 120° C. to about 140° C. and above. Novel flexible -olefin homo and copolymers having elongation in excess of 600% and substantially no retained force are disclosed.</description><language>eng</language><creationdate>2003</creationdate><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://image-ppubs.uspto.gov/dirsearch-public/print/downloadPdf/6559262$$EPDF$$P50$$Guspatents$$Hfree_for_read</linktopdf><link.rule.ids>230,308,776,798,881,64016</link.rule.ids><linktorsrc>$$Uhttps://image-ppubs.uspto.gov/dirsearch-public/print/downloadPdf/6559262$$EView_record_in_USPTO$$FView_record_in_$$GUSPTO$$Hfree_for_read</linktorsrc></links><search><creatorcontrib>Waymouth, Robert M</creatorcontrib><creatorcontrib>Kravchenko, Raisa</creatorcontrib><creatorcontrib>Bendig, Larry L</creatorcontrib><creatorcontrib>Moore, Eric J</creatorcontrib><creatorcontrib>Myers, Charles L</creatorcontrib><creatorcontrib>Quan, Roger W</creatorcontrib><creatorcontrib>Ernst, Andreas B</creatorcontrib><creatorcontrib>The Board of Trustees of the Leland Stanford Jr. University</creatorcontrib><title>High melting thermoplastic elastomeric alpha-olefin polymers (PRE/EPE effect) and catalysts therefor</title><description>This invention relates generally to processes for production of -olefin polymers using unbridged fluxional metallocenes, primarily substituted aryl indenyl metallocenes, and more particularly to use of unbridged, fluxional, cyclopentadienyl or indenyl metallocene catalysts and catalyst systems in methods of production of high melting point olefin homo- and co-polymers, particularly elastomeric crystalline and amorphous block homo- and co-polymers of alpha olefins. More specifically, the invention is directed to: (1) the discovery and catalytic process use of a Polymerization Rate-Enhancement effect (PRE effect) in polymerization processes which involve the addition of minor amounts of ethylene to the polymerization system to produce polymers having properties ranging from crystalline thermoplastics to high melting point thermoplastic elastomers to amorphous gum elastomers, and methods for increasing polymerization production rates and polymer molecular weight; (2) the discovery and catalytic process use of an Elastomeric Property-Enhancement effect (EPE effect) in which small quantities of ethylene added to the polymerization system activates selected metallocene catalyst systems, which otherwise do not produce elastomeric polymers, to produce elastomeric polymers; and (3) novel substituted aryl indenyl metallocene catalysts.
This invention relates generally to low ethylene insertions into I-olefin polymers and processes for production of such polymers using unbridged fluxional metallocenes, primarily substituted aryl indenyl metallocenes, and more particularly to use of unbridged, fluxional, cyclopentadienyl or indenyl metallocene catalyst systems in methods of production of high melting point I-olefin homo- and co-polymers, particularly elastomeric crystalline and amorphous block homo- and co-polymers of I-olefins. The activity of fluxional unbridged metallocene polymerization catalysts containing at least one 2-arylindene ligand is increased 10× or more by the addition of small (typically 0.1-10 wt. %) amounts of ethylene to the polymerization system, which increase is termed the Polymerization Rate-Enhancement effect (PRE), which is measured in terms of an Ethylene Enhancement Factor (EEF) as a dimensionless ratio in the range of from about 1.1 to about 10 or above. The amount of ethylene included in the reaction system can be selected and controlled to be so small as to result in essentially minimal (<2 mole %) incorporation of ethylene units into the resulting elastomeric polymer and the molecular weight may be increased. Amounts of ethylene to generate the PRE effect may be greater than 0.1 wt. % and preferably range up to about 2 wt. %. However, if a polymer with more ethylene is desired, additional ethylene may be incorporated into the polymerization feed, including up to 10 to about 50 mole % based on olefin units. A second important aspect of this invention is the ability to use a PRE activity-enhancing amount of ethylene in an olefin polymerization without substantially affecting the physical properties of the elastomer. In a third important aspect of this invention, I-olefin elastomers are produced through incorporation of ethylene using unbridged fluxional catalyst systems which may not otherwise produce acceptable elastomeric homopolymers. This effect is termed the EPE effect, for Elastomeric Property-Enhancing effect. The EPE amount of ethylene required to produce such elastomers typically overlaps the PRE activity-enhancing amount. Incorporation of up to about 5 mole % or more of ethylene typically will produce an elastomeric polymer using such catalyst systems. Typical useful amounts of incorporated ethylene include about 1 to 3 mole %. Preferred polymers of this invention retain sufficient crystallinity to provide a high melting point (by DSC) of about 80° C., preferably above 100° C., including in the range of from about 120° C. to about 140° C. and above. Novel flexible -olefin homo and copolymers having elongation in excess of 600% and substantially no retained force are disclosed.</description><fulltext>true</fulltext><rsrctype>patent</rsrctype><creationdate>2003</creationdate><recordtype>patent</recordtype><sourceid>EFH</sourceid><recordid>eNqNzLEKwkAQBNA0FqL-w5ZaBCWSQGo5SRnEXpZkLznY3B23a5G_NxE_wOoNwzDbrG_cMMJErM4PoCOlKURGUdcBrYaJ0pKR44h5YLLOQww8L7XAsX2Ys2kNkLXU6QnQ99ChIs-i8r0jG9I-21hkocPPXQZ387w1-VsiKnmV15Bw5VKVZV1UxfWPyQdlDD9J</recordid><startdate>20030506</startdate><enddate>20030506</enddate><creator>Waymouth, Robert M</creator><creator>Kravchenko, Raisa</creator><creator>Bendig, Larry L</creator><creator>Moore, Eric J</creator><creator>Myers, Charles L</creator><creator>Quan, Roger W</creator><creator>Ernst, Andreas B</creator><scope>EFH</scope></search><sort><creationdate>20030506</creationdate><title>High melting thermoplastic elastomeric alpha-olefin polymers (PRE/EPE effect) and catalysts therefor</title><author>Waymouth, Robert M ; Kravchenko, Raisa ; Bendig, Larry L ; Moore, Eric J ; Myers, Charles L ; Quan, Roger W ; Ernst, Andreas B</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-uspatents_grants_065592623</frbrgroupid><rsrctype>patents</rsrctype><prefilter>patents</prefilter><language>eng</language><creationdate>2003</creationdate><toplevel>online_resources</toplevel><creatorcontrib>Waymouth, Robert M</creatorcontrib><creatorcontrib>Kravchenko, Raisa</creatorcontrib><creatorcontrib>Bendig, Larry L</creatorcontrib><creatorcontrib>Moore, Eric J</creatorcontrib><creatorcontrib>Myers, Charles L</creatorcontrib><creatorcontrib>Quan, Roger W</creatorcontrib><creatorcontrib>Ernst, Andreas B</creatorcontrib><creatorcontrib>The Board of Trustees of the Leland Stanford Jr. University</creatorcontrib><collection>USPTO Issued Patents</collection></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext_linktorsrc</fulltext></delivery><addata><au>Waymouth, Robert M</au><au>Kravchenko, Raisa</au><au>Bendig, Larry L</au><au>Moore, Eric J</au><au>Myers, Charles L</au><au>Quan, Roger W</au><au>Ernst, Andreas B</au><aucorp>The Board of Trustees of the Leland Stanford Jr. University</aucorp><format>patent</format><genre>patent</genre><ristype>GEN</ristype><title>High melting thermoplastic elastomeric alpha-olefin polymers (PRE/EPE effect) and catalysts therefor</title><date>2003-05-06</date><risdate>2003</risdate><abstract>This invention relates generally to processes for production of -olefin polymers using unbridged fluxional metallocenes, primarily substituted aryl indenyl metallocenes, and more particularly to use of unbridged, fluxional, cyclopentadienyl or indenyl metallocene catalysts and catalyst systems in methods of production of high melting point olefin homo- and co-polymers, particularly elastomeric crystalline and amorphous block homo- and co-polymers of alpha olefins. More specifically, the invention is directed to: (1) the discovery and catalytic process use of a Polymerization Rate-Enhancement effect (PRE effect) in polymerization processes which involve the addition of minor amounts of ethylene to the polymerization system to produce polymers having properties ranging from crystalline thermoplastics to high melting point thermoplastic elastomers to amorphous gum elastomers, and methods for increasing polymerization production rates and polymer molecular weight; (2) the discovery and catalytic process use of an Elastomeric Property-Enhancement effect (EPE effect) in which small quantities of ethylene added to the polymerization system activates selected metallocene catalyst systems, which otherwise do not produce elastomeric polymers, to produce elastomeric polymers; and (3) novel substituted aryl indenyl metallocene catalysts.
This invention relates generally to low ethylene insertions into I-olefin polymers and processes for production of such polymers using unbridged fluxional metallocenes, primarily substituted aryl indenyl metallocenes, and more particularly to use of unbridged, fluxional, cyclopentadienyl or indenyl metallocene catalyst systems in methods of production of high melting point I-olefin homo- and co-polymers, particularly elastomeric crystalline and amorphous block homo- and co-polymers of I-olefins. The activity of fluxional unbridged metallocene polymerization catalysts containing at least one 2-arylindene ligand is increased 10× or more by the addition of small (typically 0.1-10 wt. %) amounts of ethylene to the polymerization system, which increase is termed the Polymerization Rate-Enhancement effect (PRE), which is measured in terms of an Ethylene Enhancement Factor (EEF) as a dimensionless ratio in the range of from about 1.1 to about 10 or above. The amount of ethylene included in the reaction system can be selected and controlled to be so small as to result in essentially minimal (<2 mole %) incorporation of ethylene units into the resulting elastomeric polymer and the molecular weight may be increased. Amounts of ethylene to generate the PRE effect may be greater than 0.1 wt. % and preferably range up to about 2 wt. %. However, if a polymer with more ethylene is desired, additional ethylene may be incorporated into the polymerization feed, including up to 10 to about 50 mole % based on olefin units. A second important aspect of this invention is the ability to use a PRE activity-enhancing amount of ethylene in an olefin polymerization without substantially affecting the physical properties of the elastomer. In a third important aspect of this invention, I-olefin elastomers are produced through incorporation of ethylene using unbridged fluxional catalyst systems which may not otherwise produce acceptable elastomeric homopolymers. This effect is termed the EPE effect, for Elastomeric Property-Enhancing effect. The EPE amount of ethylene required to produce such elastomers typically overlaps the PRE activity-enhancing amount. Incorporation of up to about 5 mole % or more of ethylene typically will produce an elastomeric polymer using such catalyst systems. Typical useful amounts of incorporated ethylene include about 1 to 3 mole %. Preferred polymers of this invention retain sufficient crystallinity to provide a high melting point (by DSC) of about 80° C., preferably above 100° C., including in the range of from about 120° C. to about 140° C. and above. Novel flexible -olefin homo and copolymers having elongation in excess of 600% and substantially no retained force are disclosed.</abstract><oa>free_for_read</oa></addata></record> |
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| title | High melting thermoplastic elastomeric alpha-olefin polymers (PRE/EPE effect) and catalysts therefor |
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