Silane functionalized olefin interpolymer derivatives

Details Silane functionalized olefin interpolymer derivatives Silane functionalized olefin interpolymer derivatives

2000-06-14

2003-09-23

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Mixing of two or more solid polymers; mixing of solid...

C525S474000, C526S279000

Reexamination Certificate

active

06624254

ABSTRACT:

BACKGROUND OF THE INVENTION
The present invention relates to olefin interpolymers having uniform incorporation of silane functionality therein and to derivatives thereof formed by post polymerization reaction of such silane functionality. The interpolymers and derivatives thereof may be usefully employed in the preparation of solid objects and articles such as moldings, films, sheets and foamed objects by molding, extruding or the like process.
In EP-A-321259, silicon containing polymers prepared by polymerizing a vinyl silane compound or copolymerizing the same with an olefin monomer using as a catalyst a titanium compound supported on a magnesium halide carrier and an organic aluminum halide compound were disclosed. In WO 97/42234, there is disclosed a process for the preparation of polymers of vinylidene aromatic monomers having a stereoregular structure of high syndiotacticity, by the use of Group 4 metal coordination catalysts and a hydrocarbylsilane or dihydrocarbylsilane adjuvant. In
Journal of the American Chemical Society
(
JACS
), (1995), 117, 10747-10748 and in EP-A-739,910, the use of silanes as chain transfer agents in metallocene-mediated olefin polymerizations was described. The products formed included silyl terminated polyolefins. Additional disclosures of interest include: U.S. Pat. No. 5,741,858; EP-A-702 032; EP-A-325 573; WO 97/24023; WO 98/56835; WO 095/29197; and
JACS
(1998), 120, 4019-4020. For the teachings contained therein, the foregoing patents, publications and equivalent United States patent applications are hereby incorporated by reference.
SUMMARY OF THE INVENTION
According to the present invention there is now provided:
A) A process for preparing silane functionalized interpolymers of one or more addition polymerizable monomers, the process comprising contacting one or more addition polymerizable monomers lacking silane functionality and one or more alkenylsilane compounds corresponding to the formula: A
n
J
j
SiH
4-(n+j)
wherein:
J is C
1-40
hydrocarbyl,
A is a C
2-20
alkenyl group,
n is 1 or 2, preferably 1, and
j is 0, 1 or 2;
with a catalyst composition comprising a Group 3-10 metal complex under addition polymerization conditions, wherein the interpolymer comprises from 0.01 to 100 long chain branches per 10,000 carbons. Preferably such interpolymers comprise from 0.01 to 1000 silane groups derived from the alkenylsilane compound per 10,000 carbons. Also claimed are the resulting interpolymers containing in polymerized form one or more addition polymerizable monomers and the interpolymerized derivative of the foregoing alkenylsilane compound, including the preferred embodiments of such interpolymers.
In a further embodiment of the present invention there is provided:
B) A process for preparing silane functionalized interpolymers of one or more addition polymerizable monomers, the process comprising contacting one or more addition polymerizable monomers lacking silane functionality and one or more alkenylsilane compounds corresponding to the formula: A
n
J
j
SiH
4-(n+j)
wherein:
J is C
1-40
hydrocarbyl,
A is a C
2-20
alkenyl group,
n is 1 or 2, preferably 1, and
j is 0, 1 or 2;
with a catalyst composition comprising a Group 3-10 metal complex under addition polymerization conditions, wherein the interpolymer comprises randomly distributed silane functionality within the interpolymer, preferably uniformly and randomly distributed silane functionality within the interpolymer. Preferably the interpolymer contains from 0.01 to 100 long chain branches per 10 ,000 carbons. More preferably, the interpolymer contains from 0.01 to 1000 silane groups derived from the alkenylsilane compound per 10,000 carbons, most preferably from 0.05 to 50 silane groups derived from the alkenylsilane compound per 10,000 carbons. Also claimed are the resulting interpolymers, including the preferred and most preferred embodiments of such interpolymers.
In yet another embodiment of the present invention there is provided:
C) A process for preparing silane functionalized interpolymers of one or more addition polymerizable monomers, the process comprising contacting one or more addition polymerizable monomers lacking silane functionality and one or more alkenylsilane compounds corresponding to the formula: AJ
2
SiH wherein:
J is C
1-40
hydrocarbyl, and
A is a C
2-20
alkenyl group,
with a catalyst composition comprising a Group 3-10 metal complex under addition polymerization conditions, wherein the interpolymer comprises silane functionality derived from the alkenylsilane compound within the interpolymer, preferably randomly distributed silane functionality within the interpolymer, and most preferably uniformly and randomly distributed silane functionality within the interpolymer. Preferably the interpolymer contains from 0.01 to 100 long chain branches per 10,000 carbons. Also preferably, the interpolymer contains from 0.01 to 1000 silane groups derived from the alkenylsilane compound per 10,000 carbons, more preferably from 0.05 to 50 silane groups derived from the alkenylsilane compound per 10,000 carbons. Also claimed are the resulting interpolymers, including the preferred and most preferred embodiments of such interpolymers.
Finally, according to the present invention there are provided a process for preparing further derivatives of interpolymers of an addition polymerizable monomer and an alkenylsilane compound corresponding to the formula: A
n
J
j
SiH
4-(n+j)
wherein:
J is C
1-40
hydrocarbyl,
A is a C
2-20
alkenyl group,
n is 1 or 2, preferably 1, and
j is 0, 1 or 2;
said derivative being formed by one or more subsequent silane conversion processes. Also claimed are the resulting derivatives of silane functional interpolymers resulting from such one or more silane conversion processes.
DETAILED DESCRIPTION OF THE INVENTION
All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1995. Also, any reference to a Group or Series shall be to the Group or Series as reflected in this Periodic Table of the Elements, utilizing the IUPAC system for numbering groups. Where any reference is made herein to any publication, patent application or provisional patent application, the contents thereof are incorporated herein in its entirety by reference. By the term “interpolymer” herein is meant any form of polymer, including graft or block polymers, that includes in polymerized form two or more monomers. By the term “random distribution” as used herein, is meant that the silane functionality resulting from polymerization of the alkenylsilane group is distributed within each polymer chain in a random or nearly random, e.g., non-block, manner (intrachain distribution). By the term “uniform distribution” is meant that the forgoing silane functionality is equally or nearly equally distributed among different polymer chains (interchain distribution). When subsequent derivatives of the silane groups of such random or of such uniform, random interpolymers are performed, for example coupling, the resulting converted polymer's physical properties are improved and are more homogeneous because none of the polymer populations are systematically included or excluded from the reaction. Advantageously therefor, highly efficient post reactor functionalization of the present interpolymers may be obtained.
Quantification of silane content in the interpolymers of the invention may be achieved by the use of any suitable analytical technique, including
13
C NMR-,
29
Si NMR- and IR-spectroscopic analysis of the interpolymer. Such techniques may also be employed to monitor and measure the degree of conversion of silane functionality in subsequent derivative formation.
Interchain distribution of silane within the interpolymers may be measured by a polymer fractionation technique, followed by silane analysis of the various polymer fractions, using one of the foregoing techniques. Examples of suitable fractionation techniques include Temperature Rising Elution Fractiona

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