CA2166193A1 - A new catalyst for ring-opening metathesis polymerization - Google Patents
A new catalyst for ring-opening metathesis polymerizationInfo
- Publication number
- CA2166193A1 CA2166193A1 CA 2166193 CA2166193A CA2166193A1 CA 2166193 A1 CA2166193 A1 CA 2166193A1 CA 2166193 CA2166193 CA 2166193 CA 2166193 A CA2166193 A CA 2166193A CA 2166193 A1 CA2166193 A1 CA 2166193A1
- Authority
- CA
- Canada
- Prior art keywords
- substituted
- hydrocarbyl
- group
- halocarbyl
- radical
- 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.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
Abstract
This invention relates to ring-opening metathesis polymerizations of cyclic olefins utilizing a transition metal catalyst system comprising a cyclopentadienyl transition metal compound and a non-coordinating anion.
Description
PCTUS9407433 ~
r r r r ~
r
r r r r ~
r
2 1 6 ~ 1~ 3 ~ ~ ~
r r ~ r r ~ r r Title: A New Catalyst for Ring-Opening Metathesis Polymerization Inventor: Bruce Harrington Field of the Invention This invention relates to ring-opening metathesis - polymerizations of cyclic olefins utilizing a transition metal catalyst system comprising a cyclopentadienyl transition metal complex and a non-coordinating anion.
Backqround of the Invention li In the early 1980's, new classes of olefin catalysts based on group 4 transition metals having one or two cyclopentadienyl groups or derivatives thereof attached to a metal center combined with an alumoxane activator were disclosed by Welborn. These catalysts were found useful for the polymerization of many olefins and created new polymers with controllable molecular weight and composition distributiQns. A next class of catalysts based on the cyclopentadienyl group 2~ 4 metal complexes was developed by Turner and Hlatky in the mid 1980's. These catalyst systems used a non-coordinating anion as the activator in place of the alumoxanes used in the above catalysts. These systems were also found useful for polymerizing a wide variety ,0 of olefins. In particular these catalysts polymerized not only typical alpha-olefins but they also polymerized and copolymerized cyclic olefins without ring-opening the cyclic monomers. For example, Eu-ropean patent application 0 504 418 published
r r ~ r r ~ r r Title: A New Catalyst for Ring-Opening Metathesis Polymerization Inventor: Bruce Harrington Field of the Invention This invention relates to ring-opening metathesis - polymerizations of cyclic olefins utilizing a transition metal catalyst system comprising a cyclopentadienyl transition metal complex and a non-coordinating anion.
Backqround of the Invention li In the early 1980's, new classes of olefin catalysts based on group 4 transition metals having one or two cyclopentadienyl groups or derivatives thereof attached to a metal center combined with an alumoxane activator were disclosed by Welborn. These catalysts were found useful for the polymerization of many olefins and created new polymers with controllable molecular weight and composition distributiQns. A next class of catalysts based on the cyclopentadienyl group 2~ 4 metal complexes was developed by Turner and Hlatky in the mid 1980's. These catalyst systems used a non-coordinating anion as the activator in place of the alumoxanes used in the above catalysts. These systems were also found useful for polymerizing a wide variety ,0 of olefins. In particular these catalysts polymerized not only typical alpha-olefins but they also polymerized and copolymerized cyclic olefins without ring-opening the cyclic monomers. For example, Eu-ropean patent application 0 504 418 published
3~ September 23, 1992, discloses an efficient process for AMENDED SH~
PCTUS9407433, 2 2 1-6 6 i ~ 3 r r r producing cycloolefin polymer and cyclo-olefin copolymer without causing any ring-opening of the cycloolefin utilizing cyclopentadienyl transitlon metal complexes activated by non-coordinating anions. The above catalysts and catalyst systems have hëretofore not been used as ring-opening,metathesis polymerization catalysts (hereinafter referred to as ROMP catalysts or ROM polymerizations).
Other catalysts containing a metal carbene have been used to ring open cyclic olefins and although these metathesize alpha olefins quite well, they suffer from the inability to polymerize alpha olefins. Thus, it has been difficult to make copolymers of alpha olefins and ring-opened cyclic monomers.
One answer to this problem has been to use an active alpha olefin catalyst in conjunction with or sequentially with a ring-opening metathesis polymerization catalyst. For example Japanese Kokia Jo 4020-Sl0-A published January 24, 1990 discloses a catalyst system using Ziegler-Natta catalyst and a metathesis catalyst which claims to form an alpha olerin polymer and a metathesis polymer in the same 2j particle. The catalyst system comprises contacting a solid which contains Ti, Mg and halogen and a transition metal (groups 5-7) compound having a metal metathesis catalyst function. In essence, two separate catalysts are used at the same time to produce an 3~ intimate blend of the two polymer products. However, some catalyst components in this system contain metal halides which can initiate the cationic polymerization of many cyclic olefins in the prese~ce of trace amounts of a proton'sou-rce. Alumoxane activated catalyst 3j suffer from the same problems since alumoxanes are strong Lewis acids that typically have trace amounts of AhlEI\lDEo SHEET
PCTUS9407433- _ 3 _ r ,, r r ~ ~
r ~ r ~ ~ r r ~ ~
2 1 fi 6 1 5 3 ~ ~ ~
water that can act as the proton source. U.S. Patent 5,015,710 discloses a similar process for preparing a blend of metathesis polymer and a radical polymer utilizing a redox catalyst. Thus, there exist in the art a need for developing a method to produc.e an intimate blend of alpha olefin polymer and ring-opening polymerized polymer or even a copolymer of alpha olefin and ring-opened cyclic monomer with a catalyst systems that is essentially free of metal halides.
SummarY of the Invention This invention relates in part to the discovery that cyclopentadienyl transition metal complexes activated by ion exchange non-coordinating anions are capable of performing ring-opening metathesis po.lymerizations. This invention relates to methods utilizing these catalyst systems for ring opening metathesis polymerizations alone, sequentially or in ~0 conjunction with using these catalyst systems in olefin and alpha olefin coordination ("Ziegler-Natta") type polymerizations.
DescriPtion of Preferred Embodiments In a preferred embodiment, this invention utilizes a catalyst system to ring-open metathesis polymerize cyclic olefins and utilizes the same catalyst system to polymerize any olefin without ring-opening. A unique ,0 aspect of this invention is that under certain conditions when the catalyst system is present with non-cyclic olefins and cyclic olefins, the cyclic olefins generally incor~orate into the ~rowing polymer cha-in without ring-opening. However, when only cyclic ,5 monomers are present or when the monomer feed contains predominantly cyclic olefins, the cyclic monomers do AMENDED SHEET
PCTUS 9407433~ ~ 4 ~ r ~
~_ ~ r ~ r r ~ r - ~ -2 1 6 6 1 9 ~
ring-open and form ring-opening metathesis polymerized polymers. Because the catalysts systems are essentially free of metal halides and or strong Lewis - acids and essentially free of a proton containing Lewis base, the potential for cationicly polymerizing the cyclic olefins is significantly limited. This simplifies the overall polymerization mechanism and limits the cyclic olefins to either Ziegler-Natta or metathesis polymerization. Thus, from a single catalyst/cocatalyst system there exists the ability to form Ziegler/Natta polyolefins and/or ring-open metathesis polymers in a single reaction by adjusting reaction conditions.
CATALYST
This invention is practiced with the class of catalysts referred to, disclosed, and described in the following publications EPA 277 ~ 003 ~ published 1988; EPA
277 ~ 004 ~ published 1988; EPA S20732 ~ published 1992; WO
9403506 ~ published 1994 and WO 9200333 ~ published 1992 and U.S. Patents 5 ~ 153 ~ 157 and 5, 278 ~ 119 ~ all of which are incorporated by reference herein. Preferred ionic catalysts used in this invention can be represented by 25 one of the following general formulae (all references to groups being the new group notation of the Period Table of the Elements as described by Chemical and Enqineering News, 63 (5), 21~ 1985) 1. [([(A-CP)MXl]+~d]~[B']d-~
;0 2 . ~[(A-CP)MxlL]+)d]~[B']d-}
wherein:
(A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from-zero to-five substituent groups i~ S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-AMENûED SHEEI
_ PCTUS940743_ - 4a -- 21~6l93 ^ :
hydrocarbyl, halocarbyl, substituted-halocarbyl, AMENOED SHEET
- PCTUS9407433 _ 5 _ r ~ r r 2 16 6 1 9 ~ ~ ` r r hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl 5 rings in which any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings;
M is a transition metal, preferably a group 4, 5, 6, 7 or 8 transition metal, even more preferably group
PCTUS9407433, 2 2 1-6 6 i ~ 3 r r r producing cycloolefin polymer and cyclo-olefin copolymer without causing any ring-opening of the cycloolefin utilizing cyclopentadienyl transitlon metal complexes activated by non-coordinating anions. The above catalysts and catalyst systems have hëretofore not been used as ring-opening,metathesis polymerization catalysts (hereinafter referred to as ROMP catalysts or ROM polymerizations).
Other catalysts containing a metal carbene have been used to ring open cyclic olefins and although these metathesize alpha olefins quite well, they suffer from the inability to polymerize alpha olefins. Thus, it has been difficult to make copolymers of alpha olefins and ring-opened cyclic monomers.
One answer to this problem has been to use an active alpha olefin catalyst in conjunction with or sequentially with a ring-opening metathesis polymerization catalyst. For example Japanese Kokia Jo 4020-Sl0-A published January 24, 1990 discloses a catalyst system using Ziegler-Natta catalyst and a metathesis catalyst which claims to form an alpha olerin polymer and a metathesis polymer in the same 2j particle. The catalyst system comprises contacting a solid which contains Ti, Mg and halogen and a transition metal (groups 5-7) compound having a metal metathesis catalyst function. In essence, two separate catalysts are used at the same time to produce an 3~ intimate blend of the two polymer products. However, some catalyst components in this system contain metal halides which can initiate the cationic polymerization of many cyclic olefins in the prese~ce of trace amounts of a proton'sou-rce. Alumoxane activated catalyst 3j suffer from the same problems since alumoxanes are strong Lewis acids that typically have trace amounts of AhlEI\lDEo SHEET
PCTUS9407433- _ 3 _ r ,, r r ~ ~
r ~ r ~ ~ r r ~ ~
2 1 fi 6 1 5 3 ~ ~ ~
water that can act as the proton source. U.S. Patent 5,015,710 discloses a similar process for preparing a blend of metathesis polymer and a radical polymer utilizing a redox catalyst. Thus, there exist in the art a need for developing a method to produc.e an intimate blend of alpha olefin polymer and ring-opening polymerized polymer or even a copolymer of alpha olefin and ring-opened cyclic monomer with a catalyst systems that is essentially free of metal halides.
SummarY of the Invention This invention relates in part to the discovery that cyclopentadienyl transition metal complexes activated by ion exchange non-coordinating anions are capable of performing ring-opening metathesis po.lymerizations. This invention relates to methods utilizing these catalyst systems for ring opening metathesis polymerizations alone, sequentially or in ~0 conjunction with using these catalyst systems in olefin and alpha olefin coordination ("Ziegler-Natta") type polymerizations.
DescriPtion of Preferred Embodiments In a preferred embodiment, this invention utilizes a catalyst system to ring-open metathesis polymerize cyclic olefins and utilizes the same catalyst system to polymerize any olefin without ring-opening. A unique ,0 aspect of this invention is that under certain conditions when the catalyst system is present with non-cyclic olefins and cyclic olefins, the cyclic olefins generally incor~orate into the ~rowing polymer cha-in without ring-opening. However, when only cyclic ,5 monomers are present or when the monomer feed contains predominantly cyclic olefins, the cyclic monomers do AMENDED SHEET
PCTUS 9407433~ ~ 4 ~ r ~
~_ ~ r ~ r r ~ r - ~ -2 1 6 6 1 9 ~
ring-open and form ring-opening metathesis polymerized polymers. Because the catalysts systems are essentially free of metal halides and or strong Lewis - acids and essentially free of a proton containing Lewis base, the potential for cationicly polymerizing the cyclic olefins is significantly limited. This simplifies the overall polymerization mechanism and limits the cyclic olefins to either Ziegler-Natta or metathesis polymerization. Thus, from a single catalyst/cocatalyst system there exists the ability to form Ziegler/Natta polyolefins and/or ring-open metathesis polymers in a single reaction by adjusting reaction conditions.
CATALYST
This invention is practiced with the class of catalysts referred to, disclosed, and described in the following publications EPA 277 ~ 003 ~ published 1988; EPA
277 ~ 004 ~ published 1988; EPA S20732 ~ published 1992; WO
9403506 ~ published 1994 and WO 9200333 ~ published 1992 and U.S. Patents 5 ~ 153 ~ 157 and 5, 278 ~ 119 ~ all of which are incorporated by reference herein. Preferred ionic catalysts used in this invention can be represented by 25 one of the following general formulae (all references to groups being the new group notation of the Period Table of the Elements as described by Chemical and Enqineering News, 63 (5), 21~ 1985) 1. [([(A-CP)MXl]+~d]~[B']d-~
;0 2 . ~[(A-CP)MxlL]+)d]~[B']d-}
wherein:
(A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from-zero to-five substituent groups i~ S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-AMENûED SHEEI
_ PCTUS940743_ - 4a -- 21~6l93 ^ :
hydrocarbyl, halocarbyl, substituted-halocarbyl, AMENOED SHEET
- PCTUS9407433 _ 5 _ r ~ r r 2 16 6 1 9 ~ ~ ` r r hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl 5 rings in which any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings;
M is a transition metal, preferably a group 4, 5, 6, 7 or 8 transition metal, even more preferably group
4 or 6 transition metal, even more preferably titanium, zirconium or hafnium;
X1 is a hydride radical, hydrocarbyl radical, 1~ substituted-hydrocarbyl radical, hydrocarbyl-- substituted organometalloid radical or halocarbyl-substituted organometalloid radical which radical may optionally be covalently bonded to both or either M and L or all or any M, S or S';
L is an olefin, diolefin or aryne ligand;
B is a chemically stable, non-nucleophilic anionic complex having a molecular diameter of 4 angstroms or greater or an anionic Lewis-acid activator resulting from the reaction of a Lewis-acid activator with the 2~ precursor to the cationic portion of the catalyst system described in formulae l or 2. When B' is a Lewis-acid activator, Xl can also be an alkyl group donated by the Lewis-acid activator; and d is an integer representing the charge of B.
Another class of preferred catalysts includes systems represented by the formulae (all references to groups being the new group notation of the Periodic Table of the Elements as described by Chemical and ;~ Enqineerinq News, 63(5), 27, 1985):
p~E~ED S~
. PCTUS9407433 - 6 - ~' r~r~
' ~ ' ~ ' .
2 1 6 6~L 9 ~
(CsHs-~xSx) L
' / \ ~
(A~)y X1 [B~]d / \X
Js(z1-y) - - d wherein:
A' is a bridging group;
(C5H5_y_XSx) is a cyclopentadienyl ring substituted with from zero to five S radicals each S
being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalIoid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or - any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
l~ x is from 0 to 5 denoting the degree of substitution;
M is titanium, zirconium or hafnium;
X1 and X2 are independently a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, ~o hydrocarbyl-substituted organometalloid radical or halocarbyl-substituted organometalloid radical which radical may optionally be covalently bonded to both or either M, S or S';
JS'(z-l-y) is a heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of.3 or an element from Group 16 w-ith a coordination number.of 2; S' is a radical group wh-ich is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, A~E~l~E~ SHE~T
PCTUS9407433 - 6 a ~ 9 3 ~ ' ~ r ~
hydrocarbyl-substituted organometalloid, or halocarbyl-A~E,I~nEr'~ S',tE-wo 95,0~88 C A 2 1 6 6 1 ~ 3 PCT~S94/07433 substituted organometalloid; and z is the coordination number of the element J;
y is 0 or l;
L is an olefin, diolefin or aryne ligand, or a neutral Lewis base; L can also be a second transition metal compound of the same type such that the two metal center M and M* are bridged by Xl and X'l, wherein M~
has the same m~ing as N, X'l has the same me~ni nq as Xl and X'2 has the same me~ing as X2 where such dimeric compounds which are precursors to the cationic portion of the catalyst are ~e~l2sented by the formula:
(C5H5~XS~ Js~(z-y) X~1 ~ / ~
(A~)y M--X~ - M (A')y / \ "~ / \ /
JS'(z~y) X2 ~ x~2 (C5H5~S,d wherein B' is a chemically stable, non-nucleophilic anionic complex having a molecular diameter of 4 a~ L.~ms or greater or an anionic Lewis-acid activator resulting from the reaction of a Lewis-acid activator with the ~L e~u~ aor to the cationic portion of the catalyst system described in the formulae. When B' is a Lewis-acid activator, Xl can also be an alkyl group donated by the Lewis-acid activator; and d is an integer e~le_cnting the charge of B'.
The catalysts are preferably prepared by combining at least two components. In one preferred method, the first component is a cyclopentadienyl derivative of a transition metal compound cont~in;ng at least one ligand which will combine with the second component or at least a portion thereof such as a cation portion SUBSTITUTE SHEET (RULE 26) wo 95,0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 thereof. The second component is an ion-eY~h~n~e compound comprising a cation which will irreversibly react with at least one ligand cont~in~ in said transition metal compound (first component) and a non-s coordinating anion which is either a singlecoordination complex comprising a plurality of lipo~hilic radicals covalently coordinated to and shielding a central formally charge-bearing metal or metalloid atom or an anion comprising a plurality of boron atoms such as polyhedral boranes, carboranes and metallacarboranes.
The cation portion of the -sPcon~ component may comprise Bronsted acids such as protons or protonated Lewis bases or may comprise reducible Lewis acids such as ferricinum, tropylium, triphenylcarbenium or silver cations.
In another preferred method, the se~on~ component is a Lewis-acid complex which will react with at least one ligand of the first component, thereby forming an ionic species described in the formulae above with the ligand abstracted from the first component now bound to the ~Pcon~ comronPnt.
In general, suitable anions for the second component may be any stable and bulky anionic complex having the following molpc~ r attributes: 1) the anion should have a molecular diameter greater than 4 A; 2) the ~nion should form stable ammonium salts; 3) the negative charge on the anion should be delocalized over the framework of the anion or be localized within the core of the anion; 4) the anion should be a relatively poor nucleophile; and 5) the anion should not be a powerful reducing to oxidizing agent. Anions meeting these criteria - such as polynuclear boranes, SUBSmUTE SHEET ~RULE 26) PCTUS9407433 _ 9~~ ~ r~
2 1 6 6 1 g 3 carboranes, metallacarboranes, polyoxoanions (including alumoxane anions), and anionic coordination complexes are well described in the chemical literature. Upon combination of the first and second components, the second component reacts with one of the ligands of the first component, thereby generating an anion pair consisting of a Group 4 metal cation and the aforementioned anion, which anion is compatible with and non-coordinating towards the Group 4 metal cation formed from the first component. The anion of the second compound must be capable of stabilizing the Group 4 metal cation's ability to function as a catalyst and must be sufficiently labile to permit displacement by an olefin, diolefin or an acetylenically unsaturated monomér during polymerization. The catalysts of this invention may be supported. U.S. Patents 4,808,561, issued 2-28-89;
4,897,455 issued 1-3-90; and 5,057,47S issued 10-15-91 disclose such supported catalysts and the methods to produce such and are herein incorporated by reference.
A. The Transition Metal ComPonent The transition metal compounds useful as first 2~ compounds in the preparation of the improved catalyst of this invention are cyclopentadienyl derivatives of group 4, 5, 6, 7 or 8 transition metals, preferably titanium, zirconium and hafnium. In general, useful cyclopentadienyl compounds may be represented by the0 following general formulae:
(A-cp)Mxlx2 (Cp*) (CpR)MX
..
AMENDED S~EET
PCTU5940743~ - 15~ r ~
21~193 - ` -(C5H5-~xSX) L
X
(A'h M
X
JS (z1y wherein:
(A-Cp) is either (Cp)(Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or Cp.and Cp~ are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
R is ~ substituent on one of the cyclopentadienyl radical~s whiGh is also bonded to the metal atom;
A' is~a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings;
L is an olefin, diolefin or aryne ligand; and Xl and X2 are, independently, hydride radicals, hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, 2~ and hydrocarbyl- and halocarbyl-substituted organometalloid radicals, substituted pnicogen radicals, or substituted chalcogen radicals; or X1 and X2 are joined and bound to the metal atom to form a ~etallacycle ring containing from 3 to 20 carbon atoms;
-or Xl and X2 together can be an olefin, diol.efin or .
aryne ligand; (C5H5_y_XSx) is a cyclopentadienyl ring substituted with from zero to five S radicals, each AME~!DE~ SHEET
PCTUS9407~ ~J~
-- ~21 86 1~ ~
.. ... .
substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or any two adjacent S groups which are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
x is from 0 to 5 denoting the degree of substitution;
M is titani~m, zirconium or hafnium;
X1 and X2 are independently a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, hydrocarbyl-substituted organometalloid radical or halocarbyl-substituted organometalloid radical which radical may optionally be covalently bonded to both or either M and L or all or any M, S or S';
(JSz_l_y) is a heteroatom ligand in which J is an 20 element from Group 15 of the Periodic Table of Elements with a coordinatioIl number of 3 or an element from Group 16 with.a coordination number of 2; and z is the coordination number of the element J;
y is 0 or 1;
2~ L is an olefin, diolefin or aryne ligand, or a neutral Le~is base.
A number of final components may be formed by permutin~ all possible combinations of the constituent ;0 moieties with each other. Illustrative compounds include: bis(cyclopentadienyl)hafnium dimethyl, ethylenebis(tetrahydroindenyl)zirconium dihydride, bis(pentamethyl)zirconium ethylidene, dimethyisilyl(1-fluorenyl)(cyclopentadienyl)zirconium dimethyl and the .j like; bis(cyclopentadienyl) (1,3-butadiene(zirconium), bis(cyclopentadienyl) (2,3-dimethyl-1,3-butadiene) AME.'`~DEr' S''E~
PCTUS9~07433 ~ 1 6 6 ~ 9~ -zirconium, bis(pentamethylcyclopentadienyl) (benzene) zirconium, bis(pentamethylcyclopentadienyl) titanium ethylene and the like; (pentamethylcyclopentadienyl) (tetramethylcyclopentadienylmethylene) zirconium hydride, (pentamethylcyclopentadienyl) (tetramethylcyclopentadienyl)-(tetramethylcyclopentadienylmethylene) zirconium phenyl - and the like.
B. The Activator ComPonent Preferred ionic catalysts can be prepared by reacting the transition metal compound with some neutral ~ewis acids, such as B(C6F6)3, which upon li reaction with the hydrolyzable ligand (x) of the transition metal compound forms an anion, such as (tB(C6F5)3(X)] ), which stabilizes the cationic transition metal species generated by the reaction.
Ionic catalysts can be, and preferably aré, prepared with activator components which are ionic compounds or compositions. The above ionic compounds may comprise non-coordinating counter cations such as Bronsted acids(, for example R3NH+), carbonium ions (for example Ph3C+), reducible cations (for example Cp2Fe+) and the 2j like.
Two classes of compatible non-coordinating anions have been disclosed in U.S. Patent 5,278,119: 1) anionic coordination complexes comprising a plurality ~0 of lipophilic radicals covalently coordinated to and shielding a central charge-bearing metal or metalloid core, and 2) anions comprising a plurality of boron atoms s~ch as carboranes, metallacarboranes and boranes-. -3~
;,, ., ~ . ., . . .... _ W095/0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 In general, the activator compounds cont~in;ng single anionic coordination complexes which are useful in this invention may be represented by the following general formula:
t(L~-H)+]d~(M')m+Ql~Qn]d wherein:
H is a hydrogen atom;
tL"-H] is a Bronsted acid;
M' is a metal or metalloid:
Ql to Qn are, i~epen~pntly~ bridged or unbridged hydride radicals, dialkylamido radicals, ~lkoYide and aryloxide radicals, ~lydLocarbyl and substituted-hyd ~arbyl radicals, halocarbyl and substituted-halocarbyl rA~ir~ls and hydrocarbyl and halocarbyl-substituted organometalloid radicals and any one, but not more than one, of Ql to Qn may be a halide radical;
m is an integer representing the formal valence charge of M; and n is the total number of ligands q.
As indicated above, any metal or metalloid capable of forming an anionic complex which is stable in water may be used or contained in the anion of the second compound. Suitable metals, then, include, but are not limited to , aluminum, gold, platinum and the like.
Suitable metalloids include, but are not limited to, boron, phosphorus, silicon and the like. Compounds cont~in;n~ anions which comprise coordination complexes cont~ining a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially. In light of this, salts cont~ining anions comprising a coordination complex containing a single boron atom are preferred.
SUBSTITUTE SHEET (RULE 26) PCTUS940743' - l~ _ r r ~ r r < ~
~21~36193- ` r The preferred activator compounds comprising boron may be represented by the following general formula:
[L''-H]+[BArlAr2X3x4]
wherein:
B is a boron in a valence state of 3;
Arl and Ar2 are the same or different aromatic or substituted-aromatic hydrocarbon radicals containing from 6 to 20 carbon atoms and may be linked to each other through a stable bridging group; and X3 and X4 are, independently, hydride radicals, hydrocarbyl a~d substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals, hydrocarbyl- and halocarbyl-substituted organometalloid radicals, disubstituted pnicogen radicals, substituted chalcogen radicals and halide radicals, with the provision that X3 and X4 will not be halide at the same time.
In general, Arl and Ar2 may, independently, be any aromatic of substituted-aromatic hydrocarbon radical.
Suitable aromatic radicals include, but are not limited to, phenyl, naphthyl and anthracenyl radicals.
Suitable substituents on the substituted-aromatic hydrocarbon radicals, include, but are not necessarily 2~ limited to, hydrocarbyl radicals, organometalloid radicals, alkoxy and aryloxy radicals, alkylamido radicals, fluorocarbyl and fluorohydrocarbyl radicals and the like such as those useful as X3 and X4. The substituent may be ortho, meta or para, relative to the carbon atoms bonded to the boron atom. When either or both X3 and X4 are a hydrocarbyl radical, each may be the same or a different aromatic or substituted-aromatic radical as are Arl and Ar2, or the same may be - a straight or branched alkyl, alkenyl o~ alkenyl-3j radical, a cyclic hydrocarbon radical or an alkyl-substituted cyclic hydrocarbon radical. X3 and X4 may AMENDED ~HFFT
wo 95/0~88 C A ~. f; ~ 6 ~ ~ 3 PCT~S94/07433 also, ;nA~n~ently be alkoxy or dialkylamido radicals wherein the alkyl portion of said alkoxy and -dialkylamido radicals, hydrocarbyl radicals and organometalloid radicals and the like. As indicated above, Arl and Ar2 could be linked to either X3 or X4.
Finally, X3 and X4 may also be linked to each other through a suitable bridging group.
Illustrative, but not limiting, examples of boron compo~lnAc which may be used as an acti~ator component in the preparation of the imp~uv~d catalysts of this invention are trialkyl-substituted ammonium salts such as triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-lS butyl)ammonium tetra(phenyl)boron, trimethylammoniumtetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropyla onium tetra(o,p-dimethylphenyl)boron, tributylammonium te-tra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-tri-fluoromethylphenyl)boron, tri(., L~Lyl)ammonium tetra(o-tolyl)boron and the like: N,N-dialkyl anilinium salts such as N,N-dimethylanilinium tetra(pentafluorophenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, N,N-2,4,5 ~e.,Lamethylanilinium tetra(phenyl)boron and the like: dialkyl ammonium salts such as di(i p-~yl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron and the like; and triaryl F~nc~nnium salts such as triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron and the like.
35Similar lists of suitable compounds cont~inin~
other metals and metalloids which are useful as SUBSTITUTE SHEET (RULE 26) WO95/0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 - 16 - :
activator components may be made, but such lists are not deemed n~ceCc~ry to a complete disclosure. In this regard, it should be noted that the foregoing list is not inten~ to be exhaustive and that other useful boron compounds as well as useful compounds cont~; n; nq other metals or metalloids would be readily apparent to those skilled in the art from the foregoing general equations.
The most preferred activator compounds comprising boron may be represented by the following general formula:
~ L''-H]+tB(C6F5)3Q]
wherein:
F is fluorine, C is carbon and B, L', and Q are defined her~ h~ve. Illustrative but not limiting, examples of most preferred activator com~G~.ds comprising boron which may be used in the preparation of the improved catalysts of this invention include N,N-dialkylanilinium salts (L~ = N,N-dialkylaniline) where Q is a simple hydrocarbyl such as methyl, butyl, cyclohexyl, or phenyl or where Q is a polymeric hydrocarbyl of indefinite chain length such as poly~ LYL ~,.e, polyisoprene, or poly-paramethylstyrene.
Polymeric Q substituents on the most preferred anion offer the advantage of providing a highly soluble ion-~Y~nge activator component and final ionic catalyst.
Soluble catalysts and/or precursors are often preferred over insoluble waxes, oils, phases, or solids because 30 they can be diluted to a desired con~e..LLation and can be transferred easily using simple equipment in commercial processes.
Activator components based on anions which contain a plurality of boron atoms may be represented by the following general formulae:
SUBSmUTE SHEET (RULE 26) WO95/0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 [L~-H]C~(CX)a(Bx)mxb]c- or [L~-H]d~ t [ [ (cx6)a~ (BX7)m~ (X8)b. ]C -]2Mn'~]d'-wherein [L"-H] is either H+ or a Bronsted acid derived from the protonation of a neutral Lewis base;
X, X', X", X6, X7 and X8 are, in~Pp~ nt hydride rA~icAls~ halide radicals, hydrocarbyl radicals, substituted-hydrocarbyl radicals, halocarbyl radicals, substituted-halocarbyl radicals~ or lo hydrocarbyl- or halocarbyl-substituted organometalloid radicals;
M is a transition metal;
a and b are integers ~ 0; c is an integer > 1:
a + b + c = an even-numbered integer from 2 to 8; and m is an integer ranging from 5 to 22;
a and b are the same or a different integer or 0;
c is an integer > 2; a + b + c = an even-numbered integer from 4 to 8; m is an integer from 6 to 12; n is an integer such that 2c - n = d; and d is an integer >
1.
Preferred anions of this invention comprising a plurality of boron atoms comprise:
(1) A trisubstituted ammonium salt of a borane or carborane anion satisfying the general formula:
[ (CH) a~C (BH) bX] CX-wherein: `
ax is either 0 or 1; cx is either 1 or 2; ax ~ cx z 2; and bx is an integer ranging from 10 to 12;
(2) A trisubstituted ammonium salt of a borane or carborane or a neutral borane or carborane compound satisfying the general formula:
[ (CH) ay (BH) my (H) by] cy-wherein:
SUBSTITUTE SHEET (RULE 26) *rB
W095/0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 ay is an integer from 0 to 2; by is an integer from 0 to 3; cy is an integer from 0 to 3; ay +
by + cy = 4; and my is an integer from 9 to 18; or S (3) A trisubstituted ammonium salt of a metallaborane or metallacarborane anion satisfying the following general formula:
t t ~ (CH) az (BH) mz tH) ~z] cz- ] 2MnZ+ ~ dz-wherein:
az is an integer from 0 to 2; bz is an integer from 0 to 2; cz is either 2 or 3; mz is an integer from 9 to 11; az + bz + cz = 4; and nz and dz are, respectively, 2 and 2 or 3 and 1.
Illustrative, but not limiting, examples of second components which can be used in preparing catalyst systems utilized in the ~LG~ess of this invention wherein the anion of the CpcQn~ component contains a plurality of boron atoms are mono-, di-, trialkylammonium and phosphonium and dialkylarylammonium and -phosphonium salts such as bis[tri(n-butyl)ammonium] ~o~ec~horate, bis[tri(n-butyl)ammonium]~Pc~ohloro~ç~horate, tri(n-butyl)ammonium ~o~c~rhloro~o~PcAhorate, tri(n-butyl)ammonium l-carh~Pc~horate, tri(n-butyl)ammonium l-carba~Pc~orate, tri(n-butyl)ammonium 1-c~rP,Ado~c~horate, tri(,l L~Lyl)ammonium 1-trimethylsilyl-l-c~rh~c~horate, tri(n-butyl)ammonium dibromo-l-c~rh~o~c~horate: borane and carborane 30 complexes and salts of borane and carborane anions such as decaborane(14), 7,8-dicarbaudecaborane(13), 2,7-~ir~rh~lln~Pc~horane(13), 1~Pc~hydrido-7~8-dimethyl-7,8-dicarbal~dPc~horane, tri(n-butyl)ammonium 6-carb~APc~horate(12), tri(n-butyl)ammonium 7-carbal~n~c~horate, tri(n-butyl)ammonium 7,8-dicarballn~ec~horate and metallaborane anions such as SUBSmUTE SHEET (RULE 26) PCTUS9407~33 - lQ.- r r~ - -- 2'`1'6 6 1 9 3 " '` , ^ ' , ' -tri(n-butyl)ammonium bis(nonahydrido-1,3-dicarbanonabo-rato)cobaltate(III), tri(n-butyl)ammonium bis(undecahydrido-7,8-dicarbaundecaborato) ferrate(III), tri(n-butyl)ammonium bis(undecahydrido-7,8-dicarbaundecaborato) cobaltate(III), tri(n-butyl)ammonium bis(undecahydrido-7,8-dicarbaunaborato) nikelate(III), tri(n-butyl)amm~nium bis(nonahydrido-7,8-dimethyl-7,8-dicarbaundecaborato)ferrate(III), tri(n-butyl)ammonium bis(tribromooctahydrido-7,8-dicarbaundecaborato)cobaltate(III), tri(n-butyl) ammonium bis(undecahydridodicarbadodecaborato) cobaltate(III) and bis[tri(n-butyl)ammonium]
bis(undecahydrido-7-carbaundecaborato) cobaltate(III).
A similar list of representative phosphonium compounds lj can be recited as illustrative second compounds, but for the sake of brevity, it is simply noted that the phosphonium and substituted-phosphonium salts corresponding to the listed ammonium and substituted-ammonium salts could be used as second compounds in the present invention.
The monomers that may be ring-opening metathesis polymerized with the above catalyst system include any cyclic or multicyclic olefin, cyclic diolefin or cyclic 2~ polyene. Preferred cyclics include strained olefins and diolefins, preferably norbornene, dicyclopentadiene, ethylidene norbornene, vinyl norbnene, cyclopentene, cyclobutene, tetracyclododecene and their substituted isomers. Especially preferred io cyclics include norbornene and cyclopentene.
Olefin and alpha olefin monomers that may be - polymerized by-the above catalyst system include monoenes, dienes, and polyenes in linear branched or 3~ cyclic structures. Preferred monomers include alpha olefins, particularly alpha olefins having 2 to 40 A~EN~ED SHEEr PCTUS9407433 - 2~
2i~6193 - - -carbon atoms. Especially preferred monomers include the alpha-olefins, ethylene and propylene.
The C~cloolefins In general, any cycloolefin can be copolymerized-with an olefin in the present process. The cycloolefin includes cyclized ethylenic or acetylenic unsaturation which polymerizes in the presence of the metallocene catalyst substantially by insertion polymerization, generally without ring opening, so that the ring structure in which the unsaturation is present is incorporated into the polymer bac~bone. However when an alpha olefin is not present or is present in very 1~ limited concentrations, the cyclo-olefin including cyclized ethylenically or acetylenically unsaturated cyclics, are ring-open polymerized in the presence of the activated transition metal catalyst substantially without insertion so that the ring structure containing ~0 the unsaturation is opened and becomes a part of the linear polymer bac~bone. Suitable cycloolefins generally correspond to one of the formulae:
A~J~ !C,,7~
W095/0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 A.
ll (Ra-c-Rb)ac ,J
B.
IC Fi rm /\ ~~; <~P
Ra--Rb R9 ---Rh Rk--R l Rr ~/ ~Rs R~ Rf Rd Ri ~In ~i ~
/\ ~
R~--Rb R9__Rh Rk~Rl ~RP-C-Qq) dc \/--~R~--/
Re Rf cc l,d ki Rn wherein each Ra through Rs is inApF~nA~ntly hydrogen, halogen, hyd~ucarbyl, or halohydrocarbyl; ac and dc are integers of 2 or more, and bc and cc are integers of 0 or more.
Specific representative cycloolefins according to formula A are cyclobutene, cyclopentene, - 10 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene, 4-methylcyclohPY~np~ 3,4-dimethylcyclohexene, 3-chlorocycl~P~Pne, cycloheptene, cyclodoAecP~e and the like. Preferred monocycloolefins according to SUBSmUTE SHEET tRULE 26) W095/0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 formula A have from 4 to 12 carbon atoms, more preferably 4 to 5 or 7 to 8 carbon atoms.
Cycloolefins according to formulae B and C can be prepared by co~P~cing cyclopentadienes with the oo ~ L,o..~in~ olefins and/or cycloolefins in a Diels-Alder reaction. Specific representative cycloolefins according to formula B are as follows:
bicyclo(2.2.1)hept-2-ene;
6-methylbicyclo(2.2.1)hept-2-ene;
X1 is a hydride radical, hydrocarbyl radical, 1~ substituted-hydrocarbyl radical, hydrocarbyl-- substituted organometalloid radical or halocarbyl-substituted organometalloid radical which radical may optionally be covalently bonded to both or either M and L or all or any M, S or S';
L is an olefin, diolefin or aryne ligand;
B is a chemically stable, non-nucleophilic anionic complex having a molecular diameter of 4 angstroms or greater or an anionic Lewis-acid activator resulting from the reaction of a Lewis-acid activator with the 2~ precursor to the cationic portion of the catalyst system described in formulae l or 2. When B' is a Lewis-acid activator, Xl can also be an alkyl group donated by the Lewis-acid activator; and d is an integer representing the charge of B.
Another class of preferred catalysts includes systems represented by the formulae (all references to groups being the new group notation of the Periodic Table of the Elements as described by Chemical and ;~ Enqineerinq News, 63(5), 27, 1985):
p~E~ED S~
. PCTUS9407433 - 6 - ~' r~r~
' ~ ' ~ ' .
2 1 6 6~L 9 ~
(CsHs-~xSx) L
' / \ ~
(A~)y X1 [B~]d / \X
Js(z1-y) - - d wherein:
A' is a bridging group;
(C5H5_y_XSx) is a cyclopentadienyl ring substituted with from zero to five S radicals each S
being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalIoid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or - any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
l~ x is from 0 to 5 denoting the degree of substitution;
M is titanium, zirconium or hafnium;
X1 and X2 are independently a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, ~o hydrocarbyl-substituted organometalloid radical or halocarbyl-substituted organometalloid radical which radical may optionally be covalently bonded to both or either M, S or S';
JS'(z-l-y) is a heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of.3 or an element from Group 16 w-ith a coordination number.of 2; S' is a radical group wh-ich is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, A~E~l~E~ SHE~T
PCTUS9407433 - 6 a ~ 9 3 ~ ' ~ r ~
hydrocarbyl-substituted organometalloid, or halocarbyl-A~E,I~nEr'~ S',tE-wo 95,0~88 C A 2 1 6 6 1 ~ 3 PCT~S94/07433 substituted organometalloid; and z is the coordination number of the element J;
y is 0 or l;
L is an olefin, diolefin or aryne ligand, or a neutral Lewis base; L can also be a second transition metal compound of the same type such that the two metal center M and M* are bridged by Xl and X'l, wherein M~
has the same m~ing as N, X'l has the same me~ni nq as Xl and X'2 has the same me~ing as X2 where such dimeric compounds which are precursors to the cationic portion of the catalyst are ~e~l2sented by the formula:
(C5H5~XS~ Js~(z-y) X~1 ~ / ~
(A~)y M--X~ - M (A')y / \ "~ / \ /
JS'(z~y) X2 ~ x~2 (C5H5~S,d wherein B' is a chemically stable, non-nucleophilic anionic complex having a molecular diameter of 4 a~ L.~ms or greater or an anionic Lewis-acid activator resulting from the reaction of a Lewis-acid activator with the ~L e~u~ aor to the cationic portion of the catalyst system described in the formulae. When B' is a Lewis-acid activator, Xl can also be an alkyl group donated by the Lewis-acid activator; and d is an integer e~le_cnting the charge of B'.
The catalysts are preferably prepared by combining at least two components. In one preferred method, the first component is a cyclopentadienyl derivative of a transition metal compound cont~in;ng at least one ligand which will combine with the second component or at least a portion thereof such as a cation portion SUBSTITUTE SHEET (RULE 26) wo 95,0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 thereof. The second component is an ion-eY~h~n~e compound comprising a cation which will irreversibly react with at least one ligand cont~in~ in said transition metal compound (first component) and a non-s coordinating anion which is either a singlecoordination complex comprising a plurality of lipo~hilic radicals covalently coordinated to and shielding a central formally charge-bearing metal or metalloid atom or an anion comprising a plurality of boron atoms such as polyhedral boranes, carboranes and metallacarboranes.
The cation portion of the -sPcon~ component may comprise Bronsted acids such as protons or protonated Lewis bases or may comprise reducible Lewis acids such as ferricinum, tropylium, triphenylcarbenium or silver cations.
In another preferred method, the se~on~ component is a Lewis-acid complex which will react with at least one ligand of the first component, thereby forming an ionic species described in the formulae above with the ligand abstracted from the first component now bound to the ~Pcon~ comronPnt.
In general, suitable anions for the second component may be any stable and bulky anionic complex having the following molpc~ r attributes: 1) the anion should have a molecular diameter greater than 4 A; 2) the ~nion should form stable ammonium salts; 3) the negative charge on the anion should be delocalized over the framework of the anion or be localized within the core of the anion; 4) the anion should be a relatively poor nucleophile; and 5) the anion should not be a powerful reducing to oxidizing agent. Anions meeting these criteria - such as polynuclear boranes, SUBSmUTE SHEET ~RULE 26) PCTUS9407433 _ 9~~ ~ r~
2 1 6 6 1 g 3 carboranes, metallacarboranes, polyoxoanions (including alumoxane anions), and anionic coordination complexes are well described in the chemical literature. Upon combination of the first and second components, the second component reacts with one of the ligands of the first component, thereby generating an anion pair consisting of a Group 4 metal cation and the aforementioned anion, which anion is compatible with and non-coordinating towards the Group 4 metal cation formed from the first component. The anion of the second compound must be capable of stabilizing the Group 4 metal cation's ability to function as a catalyst and must be sufficiently labile to permit displacement by an olefin, diolefin or an acetylenically unsaturated monomér during polymerization. The catalysts of this invention may be supported. U.S. Patents 4,808,561, issued 2-28-89;
4,897,455 issued 1-3-90; and 5,057,47S issued 10-15-91 disclose such supported catalysts and the methods to produce such and are herein incorporated by reference.
A. The Transition Metal ComPonent The transition metal compounds useful as first 2~ compounds in the preparation of the improved catalyst of this invention are cyclopentadienyl derivatives of group 4, 5, 6, 7 or 8 transition metals, preferably titanium, zirconium and hafnium. In general, useful cyclopentadienyl compounds may be represented by the0 following general formulae:
(A-cp)Mxlx2 (Cp*) (CpR)MX
..
AMENDED S~EET
PCTU5940743~ - 15~ r ~
21~193 - ` -(C5H5-~xSX) L
X
(A'h M
X
JS (z1y wherein:
(A-Cp) is either (Cp)(Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or Cp.and Cp~ are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
R is ~ substituent on one of the cyclopentadienyl radical~s whiGh is also bonded to the metal atom;
A' is~a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings;
L is an olefin, diolefin or aryne ligand; and Xl and X2 are, independently, hydride radicals, hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, 2~ and hydrocarbyl- and halocarbyl-substituted organometalloid radicals, substituted pnicogen radicals, or substituted chalcogen radicals; or X1 and X2 are joined and bound to the metal atom to form a ~etallacycle ring containing from 3 to 20 carbon atoms;
-or Xl and X2 together can be an olefin, diol.efin or .
aryne ligand; (C5H5_y_XSx) is a cyclopentadienyl ring substituted with from zero to five S radicals, each AME~!DE~ SHEET
PCTUS9407~ ~J~
-- ~21 86 1~ ~
.. ... .
substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or any two adjacent S groups which are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
x is from 0 to 5 denoting the degree of substitution;
M is titani~m, zirconium or hafnium;
X1 and X2 are independently a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, hydrocarbyl-substituted organometalloid radical or halocarbyl-substituted organometalloid radical which radical may optionally be covalently bonded to both or either M and L or all or any M, S or S';
(JSz_l_y) is a heteroatom ligand in which J is an 20 element from Group 15 of the Periodic Table of Elements with a coordinatioIl number of 3 or an element from Group 16 with.a coordination number of 2; and z is the coordination number of the element J;
y is 0 or 1;
2~ L is an olefin, diolefin or aryne ligand, or a neutral Le~is base.
A number of final components may be formed by permutin~ all possible combinations of the constituent ;0 moieties with each other. Illustrative compounds include: bis(cyclopentadienyl)hafnium dimethyl, ethylenebis(tetrahydroindenyl)zirconium dihydride, bis(pentamethyl)zirconium ethylidene, dimethyisilyl(1-fluorenyl)(cyclopentadienyl)zirconium dimethyl and the .j like; bis(cyclopentadienyl) (1,3-butadiene(zirconium), bis(cyclopentadienyl) (2,3-dimethyl-1,3-butadiene) AME.'`~DEr' S''E~
PCTUS9~07433 ~ 1 6 6 ~ 9~ -zirconium, bis(pentamethylcyclopentadienyl) (benzene) zirconium, bis(pentamethylcyclopentadienyl) titanium ethylene and the like; (pentamethylcyclopentadienyl) (tetramethylcyclopentadienylmethylene) zirconium hydride, (pentamethylcyclopentadienyl) (tetramethylcyclopentadienyl)-(tetramethylcyclopentadienylmethylene) zirconium phenyl - and the like.
B. The Activator ComPonent Preferred ionic catalysts can be prepared by reacting the transition metal compound with some neutral ~ewis acids, such as B(C6F6)3, which upon li reaction with the hydrolyzable ligand (x) of the transition metal compound forms an anion, such as (tB(C6F5)3(X)] ), which stabilizes the cationic transition metal species generated by the reaction.
Ionic catalysts can be, and preferably aré, prepared with activator components which are ionic compounds or compositions. The above ionic compounds may comprise non-coordinating counter cations such as Bronsted acids(, for example R3NH+), carbonium ions (for example Ph3C+), reducible cations (for example Cp2Fe+) and the 2j like.
Two classes of compatible non-coordinating anions have been disclosed in U.S. Patent 5,278,119: 1) anionic coordination complexes comprising a plurality ~0 of lipophilic radicals covalently coordinated to and shielding a central charge-bearing metal or metalloid core, and 2) anions comprising a plurality of boron atoms s~ch as carboranes, metallacarboranes and boranes-. -3~
;,, ., ~ . ., . . .... _ W095/0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 In general, the activator compounds cont~in;ng single anionic coordination complexes which are useful in this invention may be represented by the following general formula:
t(L~-H)+]d~(M')m+Ql~Qn]d wherein:
H is a hydrogen atom;
tL"-H] is a Bronsted acid;
M' is a metal or metalloid:
Ql to Qn are, i~epen~pntly~ bridged or unbridged hydride radicals, dialkylamido radicals, ~lkoYide and aryloxide radicals, ~lydLocarbyl and substituted-hyd ~arbyl radicals, halocarbyl and substituted-halocarbyl rA~ir~ls and hydrocarbyl and halocarbyl-substituted organometalloid radicals and any one, but not more than one, of Ql to Qn may be a halide radical;
m is an integer representing the formal valence charge of M; and n is the total number of ligands q.
As indicated above, any metal or metalloid capable of forming an anionic complex which is stable in water may be used or contained in the anion of the second compound. Suitable metals, then, include, but are not limited to , aluminum, gold, platinum and the like.
Suitable metalloids include, but are not limited to, boron, phosphorus, silicon and the like. Compounds cont~in;n~ anions which comprise coordination complexes cont~ining a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially. In light of this, salts cont~ining anions comprising a coordination complex containing a single boron atom are preferred.
SUBSTITUTE SHEET (RULE 26) PCTUS940743' - l~ _ r r ~ r r < ~
~21~36193- ` r The preferred activator compounds comprising boron may be represented by the following general formula:
[L''-H]+[BArlAr2X3x4]
wherein:
B is a boron in a valence state of 3;
Arl and Ar2 are the same or different aromatic or substituted-aromatic hydrocarbon radicals containing from 6 to 20 carbon atoms and may be linked to each other through a stable bridging group; and X3 and X4 are, independently, hydride radicals, hydrocarbyl a~d substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals, hydrocarbyl- and halocarbyl-substituted organometalloid radicals, disubstituted pnicogen radicals, substituted chalcogen radicals and halide radicals, with the provision that X3 and X4 will not be halide at the same time.
In general, Arl and Ar2 may, independently, be any aromatic of substituted-aromatic hydrocarbon radical.
Suitable aromatic radicals include, but are not limited to, phenyl, naphthyl and anthracenyl radicals.
Suitable substituents on the substituted-aromatic hydrocarbon radicals, include, but are not necessarily 2~ limited to, hydrocarbyl radicals, organometalloid radicals, alkoxy and aryloxy radicals, alkylamido radicals, fluorocarbyl and fluorohydrocarbyl radicals and the like such as those useful as X3 and X4. The substituent may be ortho, meta or para, relative to the carbon atoms bonded to the boron atom. When either or both X3 and X4 are a hydrocarbyl radical, each may be the same or a different aromatic or substituted-aromatic radical as are Arl and Ar2, or the same may be - a straight or branched alkyl, alkenyl o~ alkenyl-3j radical, a cyclic hydrocarbon radical or an alkyl-substituted cyclic hydrocarbon radical. X3 and X4 may AMENDED ~HFFT
wo 95/0~88 C A ~. f; ~ 6 ~ ~ 3 PCT~S94/07433 also, ;nA~n~ently be alkoxy or dialkylamido radicals wherein the alkyl portion of said alkoxy and -dialkylamido radicals, hydrocarbyl radicals and organometalloid radicals and the like. As indicated above, Arl and Ar2 could be linked to either X3 or X4.
Finally, X3 and X4 may also be linked to each other through a suitable bridging group.
Illustrative, but not limiting, examples of boron compo~lnAc which may be used as an acti~ator component in the preparation of the imp~uv~d catalysts of this invention are trialkyl-substituted ammonium salts such as triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-lS butyl)ammonium tetra(phenyl)boron, trimethylammoniumtetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropyla onium tetra(o,p-dimethylphenyl)boron, tributylammonium te-tra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-tri-fluoromethylphenyl)boron, tri(., L~Lyl)ammonium tetra(o-tolyl)boron and the like: N,N-dialkyl anilinium salts such as N,N-dimethylanilinium tetra(pentafluorophenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, N,N-2,4,5 ~e.,Lamethylanilinium tetra(phenyl)boron and the like: dialkyl ammonium salts such as di(i p-~yl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron and the like; and triaryl F~nc~nnium salts such as triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron and the like.
35Similar lists of suitable compounds cont~inin~
other metals and metalloids which are useful as SUBSTITUTE SHEET (RULE 26) WO95/0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 - 16 - :
activator components may be made, but such lists are not deemed n~ceCc~ry to a complete disclosure. In this regard, it should be noted that the foregoing list is not inten~ to be exhaustive and that other useful boron compounds as well as useful compounds cont~; n; nq other metals or metalloids would be readily apparent to those skilled in the art from the foregoing general equations.
The most preferred activator compounds comprising boron may be represented by the following general formula:
~ L''-H]+tB(C6F5)3Q]
wherein:
F is fluorine, C is carbon and B, L', and Q are defined her~ h~ve. Illustrative but not limiting, examples of most preferred activator com~G~.ds comprising boron which may be used in the preparation of the improved catalysts of this invention include N,N-dialkylanilinium salts (L~ = N,N-dialkylaniline) where Q is a simple hydrocarbyl such as methyl, butyl, cyclohexyl, or phenyl or where Q is a polymeric hydrocarbyl of indefinite chain length such as poly~ LYL ~,.e, polyisoprene, or poly-paramethylstyrene.
Polymeric Q substituents on the most preferred anion offer the advantage of providing a highly soluble ion-~Y~nge activator component and final ionic catalyst.
Soluble catalysts and/or precursors are often preferred over insoluble waxes, oils, phases, or solids because 30 they can be diluted to a desired con~e..LLation and can be transferred easily using simple equipment in commercial processes.
Activator components based on anions which contain a plurality of boron atoms may be represented by the following general formulae:
SUBSmUTE SHEET (RULE 26) WO95/0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 [L~-H]C~(CX)a(Bx)mxb]c- or [L~-H]d~ t [ [ (cx6)a~ (BX7)m~ (X8)b. ]C -]2Mn'~]d'-wherein [L"-H] is either H+ or a Bronsted acid derived from the protonation of a neutral Lewis base;
X, X', X", X6, X7 and X8 are, in~Pp~ nt hydride rA~icAls~ halide radicals, hydrocarbyl radicals, substituted-hydrocarbyl radicals, halocarbyl radicals, substituted-halocarbyl radicals~ or lo hydrocarbyl- or halocarbyl-substituted organometalloid radicals;
M is a transition metal;
a and b are integers ~ 0; c is an integer > 1:
a + b + c = an even-numbered integer from 2 to 8; and m is an integer ranging from 5 to 22;
a and b are the same or a different integer or 0;
c is an integer > 2; a + b + c = an even-numbered integer from 4 to 8; m is an integer from 6 to 12; n is an integer such that 2c - n = d; and d is an integer >
1.
Preferred anions of this invention comprising a plurality of boron atoms comprise:
(1) A trisubstituted ammonium salt of a borane or carborane anion satisfying the general formula:
[ (CH) a~C (BH) bX] CX-wherein: `
ax is either 0 or 1; cx is either 1 or 2; ax ~ cx z 2; and bx is an integer ranging from 10 to 12;
(2) A trisubstituted ammonium salt of a borane or carborane or a neutral borane or carborane compound satisfying the general formula:
[ (CH) ay (BH) my (H) by] cy-wherein:
SUBSTITUTE SHEET (RULE 26) *rB
W095/0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 ay is an integer from 0 to 2; by is an integer from 0 to 3; cy is an integer from 0 to 3; ay +
by + cy = 4; and my is an integer from 9 to 18; or S (3) A trisubstituted ammonium salt of a metallaborane or metallacarborane anion satisfying the following general formula:
t t ~ (CH) az (BH) mz tH) ~z] cz- ] 2MnZ+ ~ dz-wherein:
az is an integer from 0 to 2; bz is an integer from 0 to 2; cz is either 2 or 3; mz is an integer from 9 to 11; az + bz + cz = 4; and nz and dz are, respectively, 2 and 2 or 3 and 1.
Illustrative, but not limiting, examples of second components which can be used in preparing catalyst systems utilized in the ~LG~ess of this invention wherein the anion of the CpcQn~ component contains a plurality of boron atoms are mono-, di-, trialkylammonium and phosphonium and dialkylarylammonium and -phosphonium salts such as bis[tri(n-butyl)ammonium] ~o~ec~horate, bis[tri(n-butyl)ammonium]~Pc~ohloro~ç~horate, tri(n-butyl)ammonium ~o~c~rhloro~o~PcAhorate, tri(n-butyl)ammonium l-carh~Pc~horate, tri(n-butyl)ammonium l-carba~Pc~orate, tri(n-butyl)ammonium 1-c~rP,Ado~c~horate, tri(,l L~Lyl)ammonium 1-trimethylsilyl-l-c~rh~c~horate, tri(n-butyl)ammonium dibromo-l-c~rh~o~c~horate: borane and carborane 30 complexes and salts of borane and carborane anions such as decaborane(14), 7,8-dicarbaudecaborane(13), 2,7-~ir~rh~lln~Pc~horane(13), 1~Pc~hydrido-7~8-dimethyl-7,8-dicarbal~dPc~horane, tri(n-butyl)ammonium 6-carb~APc~horate(12), tri(n-butyl)ammonium 7-carbal~n~c~horate, tri(n-butyl)ammonium 7,8-dicarballn~ec~horate and metallaborane anions such as SUBSmUTE SHEET (RULE 26) PCTUS9407~33 - lQ.- r r~ - -- 2'`1'6 6 1 9 3 " '` , ^ ' , ' -tri(n-butyl)ammonium bis(nonahydrido-1,3-dicarbanonabo-rato)cobaltate(III), tri(n-butyl)ammonium bis(undecahydrido-7,8-dicarbaundecaborato) ferrate(III), tri(n-butyl)ammonium bis(undecahydrido-7,8-dicarbaundecaborato) cobaltate(III), tri(n-butyl)ammonium bis(undecahydrido-7,8-dicarbaunaborato) nikelate(III), tri(n-butyl)amm~nium bis(nonahydrido-7,8-dimethyl-7,8-dicarbaundecaborato)ferrate(III), tri(n-butyl)ammonium bis(tribromooctahydrido-7,8-dicarbaundecaborato)cobaltate(III), tri(n-butyl) ammonium bis(undecahydridodicarbadodecaborato) cobaltate(III) and bis[tri(n-butyl)ammonium]
bis(undecahydrido-7-carbaundecaborato) cobaltate(III).
A similar list of representative phosphonium compounds lj can be recited as illustrative second compounds, but for the sake of brevity, it is simply noted that the phosphonium and substituted-phosphonium salts corresponding to the listed ammonium and substituted-ammonium salts could be used as second compounds in the present invention.
The monomers that may be ring-opening metathesis polymerized with the above catalyst system include any cyclic or multicyclic olefin, cyclic diolefin or cyclic 2~ polyene. Preferred cyclics include strained olefins and diolefins, preferably norbornene, dicyclopentadiene, ethylidene norbornene, vinyl norbnene, cyclopentene, cyclobutene, tetracyclododecene and their substituted isomers. Especially preferred io cyclics include norbornene and cyclopentene.
Olefin and alpha olefin monomers that may be - polymerized by-the above catalyst system include monoenes, dienes, and polyenes in linear branched or 3~ cyclic structures. Preferred monomers include alpha olefins, particularly alpha olefins having 2 to 40 A~EN~ED SHEEr PCTUS9407433 - 2~
2i~6193 - - -carbon atoms. Especially preferred monomers include the alpha-olefins, ethylene and propylene.
The C~cloolefins In general, any cycloolefin can be copolymerized-with an olefin in the present process. The cycloolefin includes cyclized ethylenic or acetylenic unsaturation which polymerizes in the presence of the metallocene catalyst substantially by insertion polymerization, generally without ring opening, so that the ring structure in which the unsaturation is present is incorporated into the polymer bac~bone. However when an alpha olefin is not present or is present in very 1~ limited concentrations, the cyclo-olefin including cyclized ethylenically or acetylenically unsaturated cyclics, are ring-open polymerized in the presence of the activated transition metal catalyst substantially without insertion so that the ring structure containing ~0 the unsaturation is opened and becomes a part of the linear polymer bac~bone. Suitable cycloolefins generally correspond to one of the formulae:
A~J~ !C,,7~
W095/0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 A.
ll (Ra-c-Rb)ac ,J
B.
IC Fi rm /\ ~~; <~P
Ra--Rb R9 ---Rh Rk--R l Rr ~/ ~Rs R~ Rf Rd Ri ~In ~i ~
/\ ~
R~--Rb R9__Rh Rk~Rl ~RP-C-Qq) dc \/--~R~--/
Re Rf cc l,d ki Rn wherein each Ra through Rs is inApF~nA~ntly hydrogen, halogen, hyd~ucarbyl, or halohydrocarbyl; ac and dc are integers of 2 or more, and bc and cc are integers of 0 or more.
Specific representative cycloolefins according to formula A are cyclobutene, cyclopentene, - 10 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene, 4-methylcyclohPY~np~ 3,4-dimethylcyclohexene, 3-chlorocycl~P~Pne, cycloheptene, cyclodoAecP~e and the like. Preferred monocycloolefins according to SUBSmUTE SHEET tRULE 26) W095/0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 formula A have from 4 to 12 carbon atoms, more preferably 4 to 5 or 7 to 8 carbon atoms.
Cycloolefins according to formulae B and C can be prepared by co~P~cing cyclopentadienes with the oo ~ L,o..~in~ olefins and/or cycloolefins in a Diels-Alder reaction. Specific representative cycloolefins according to formula B are as follows:
bicyclo(2.2.1)hept-2-ene;
6-methylbicyclo(2.2.1)hept-2-ene;
5,6-dimethylbicyclo(2.2.1)hept-2-ene;
l-methylbicyclo (2.2.1)hept-2-ene;
l-methylbicyclo (2.2.1)hept-2-ene;
6-ethylbicyclo(2.2.1)hept-2-ene:
6-n-butylbicyclo(2.2.1)hept-2-ene;
6-isobutylbicyclo(2.2.1)hept-2-ene;
6-n-butylbicyclo(2.2.1)hept-2-ene;
6-isobutylbicyclo(2.2.1)hept-2-ene;
7-methylbicyclo(2.2.1)hept-2-ene;
5-phenylbicyclo(2.2.1)hept-2-ene;
5-methyl-5-phenylbicyclo(2.2.1)hept-2-ene;
5-benzylbicyclo(2.2.1)hept-2-ene;
5-tolylbicyclo(2.2.1)hept-2-ene;
5-ethylphenylbicyclo(2.2.1)hept-2-ene;
5-isu~Lu~ylphenylbicyclo(2.2.l)hept-2-ene;
5-alpha-naphthylbicyclo(2.2.1)hept-2-ene;
5-acetoracenylbicyclo(2.2.1)hept-2-ene;
tetracyclo(4.4.o.l2~5.l7~lo)-3 -~o~Pc~e;
2-methyltetracyclo(4.4.o.l2~5.l7~lo)-3-doApcpn~;
2-ethyltetracyclo(4.4Ø12~5.17~10)-3 -~o~ecP~;
2-propyltetracyclo(4.4Ø12,5.17,10)-3-Ao~cPnP;
2-hexyltetracyclo(4.4Ø12,5.17,10)-3-dodecene;
2-stearyltetracyclo(4.4Ø12,5.17,10)-3-~s~ec~n~;
2,10-dimethyltetracyclo(4.4Ø12,5.17,10)-3-dodecene;
2-methyl-lO-ethyltetracyclo(4.4Ø12~5.17~l0)-3-~o~1Pcerl~;
2-chlorotetracyclo(4.4Ø12,5.17,10)-3-~o~Pce~e;
2-bromotetracyclo(4.4Ø12,5.17,10)-3-~o~PcPne:
2,10-dichlorotetracyclo(4.4Ø12,5.17,10)-3-dodecene;
SUBSmUTE SHEET ~RULE 26) W095/0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 2-cyclohexyltetracyclo(4.4Ø12,5.17,10)-3-AoAPc~ne;
2-n-butyltetracyclo(4.4Ø12,~.17,l0)-3-~oAecenp;
2-isobutyltetracyclo(4.4Ø12~5.17,10)-3-dOA~cDnO
5~lo-dimethyltetracyclo(4.4.o.l2~5.l7~lo)-3-dodecene;
2~lo-dimethyltetracyclo(4.4.o.l2~5.l7~lo)-3-Ao~c~n~;
11,12-dimethyltetracyclo(4.4Ø12,5.1,7,1)-3-AoA~c~ne;
2,7,9-trimethyltetracyclo(4.4Ø12,5.17,10)-3-~oA~cer~;
9-ethyl-2~7-dimethyltetracyclo(4.4.o.l2~5.l7~lo) AoAPc~e;
9-isobutyl-2,7-dimethyltetracyclo(4.4Ø12,5.17,10)-3-AoA~PnD;
9~ l2-trimethyltetracyclo(4.4.o.l2~5.l7~lo) doAPc~n ;
9-ethy~ l2-dimethyltetracyclo(4.4.o.l2~5.l7~lo)-3 ~o~cene;
9-isobutyl-11,12-dimethyltetracyclo (4.4Ø12~5.17~10)-3_AnAPc~n~;
5,8,9,10-tetramethyltetracyclo(4.4Ø12~5.17~1)-3-AgAPc~nP;
5-phenylbicyclo(2.2.1)hept-2-ene;
5-methyl-5-phenylbicyclo(2.2.1)hept-2-ene;
5-benzylbicyclo(2.2.1)hept-2-ene;
5-tolylbicyclo(2.2.1)hept-2-ene;
5-ethylphenylbicyclo(2.2.1)hept-2-ene;
5-isu~Lu~ylphenylbicyclo(2.2.l)hept-2-ene;
5-alpha-naphthylbicyclo(2.2.1)hept-2-ene;
5-acetoracenylbicyclo(2.2.1)hept-2-ene;
tetracyclo(4.4.o.l2~5.l7~lo)-3 -~o~Pc~e;
2-methyltetracyclo(4.4.o.l2~5.l7~lo)-3-doApcpn~;
2-ethyltetracyclo(4.4Ø12~5.17~10)-3 -~o~ecP~;
2-propyltetracyclo(4.4Ø12,5.17,10)-3-Ao~cPnP;
2-hexyltetracyclo(4.4Ø12,5.17,10)-3-dodecene;
2-stearyltetracyclo(4.4Ø12,5.17,10)-3-~s~ec~n~;
2,10-dimethyltetracyclo(4.4Ø12,5.17,10)-3-dodecene;
2-methyl-lO-ethyltetracyclo(4.4Ø12~5.17~l0)-3-~o~1Pcerl~;
2-chlorotetracyclo(4.4Ø12,5.17,10)-3-~o~Pce~e;
2-bromotetracyclo(4.4Ø12,5.17,10)-3-~o~PcPne:
2,10-dichlorotetracyclo(4.4Ø12,5.17,10)-3-dodecene;
SUBSmUTE SHEET ~RULE 26) W095/0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 2-cyclohexyltetracyclo(4.4Ø12,5.17,10)-3-AoAPc~ne;
2-n-butyltetracyclo(4.4Ø12,~.17,l0)-3-~oAecenp;
2-isobutyltetracyclo(4.4Ø12~5.17,10)-3-dOA~cDnO
5~lo-dimethyltetracyclo(4.4.o.l2~5.l7~lo)-3-dodecene;
2~lo-dimethyltetracyclo(4.4.o.l2~5.l7~lo)-3-Ao~c~n~;
11,12-dimethyltetracyclo(4.4Ø12,5.1,7,1)-3-AoA~c~ne;
2,7,9-trimethyltetracyclo(4.4Ø12,5.17,10)-3-~oA~cer~;
9-ethyl-2~7-dimethyltetracyclo(4.4.o.l2~5.l7~lo) AoAPc~e;
9-isobutyl-2,7-dimethyltetracyclo(4.4Ø12,5.17,10)-3-AoA~PnD;
9~ l2-trimethyltetracyclo(4.4.o.l2~5.l7~lo) doAPc~n ;
9-ethy~ l2-dimethyltetracyclo(4.4.o.l2~5.l7~lo)-3 ~o~cene;
9-isobutyl-11,12-dimethyltetracyclo (4.4Ø12~5.17~10)-3_AnAPc~n~;
5,8,9,10-tetramethyltetracyclo(4.4Ø12~5.17~1)-3-AgAPc~nP;
8-methyltetracyclo(4.4Ø12~5.17,10)-3 -~oA P~Pn~
8-ethyltetracyclo(4.4Ø12,5.17,10)-3-AoA~ce~;
8-propyltetracyclo(~.4Ø12,5.17,10)-3-dodecene;
8-hexyltetracyclo(4.4Ø12,5.17,10)-3-dodecene;
8-stearyltetracyclo(4.4Ø12,5.17,10)-3-AoA~c~ne;
8~9-dimethyltetracyclo(4.4.o.l2~5.l7~lo)-3-dodecene;
8-methyl-9-ethyltetracyclo(4.4Ø12,5.17,10)-3-A~APc~n~;
8-chlorotetracyclo(4.4Ø12,5.17,10)-3-dodecene;
8-bromotetracyclo(4.4~0.12~5.17~l0)-3-AsApcDne;
8-fluorotetr~cyclo (4 . 4 . O .12, 5 .17 ,10) -3-~oA~c~ e;
8,9-dichlorotetracyclo(4.4Ø12,5.17,10)-3-dodecene;
8-cyclohexyltetracyclo(4.4Ø12,5.17,10)-3-dodecene;
8-iso~utyltetracyclo(4.4Ø12,5.17,10)-3-dOA~n~;
8-butyltetracyclo(4.4Ø12,5.17,l0)-3-doApc~ne;
8-ethylidenetetracyclo(4.4Ø12,5.17,10)-3-dodecene;
SUBSmUTE SHEET tRULE 26) wo 95,0~88 C A 2 1 6 6 1 9 3 PCT~S94tO7433 8-ethylidene-9-methyltetracyclo(4.4.o~l2r5.l7 Ao~rPn~;
8-ethylidene-9-ethyltetracyclo(4.4.o.l2~5.l7~lo) ~oAecPI
S 8-ethylidene-9-isopropyltetracyclo(4.4.o.l2~5. 17~10) 3 _~3oAp~ne;
8-ethylidene-9-butyltetracyclo(4.4Ø12~5.17~10)-3-Ao~P~Pn - ;
8-l~ ylidenetetracyclo(4.4Ø12,5.17,10)-3 -dodecene;
8-n-propylidene-9-methyltetracyclO (4.4.o.l2~5.l7~ln)-3-~oAPcP~e;
8-ll ~o~ylidene-9-ethyltetracyclo(4.4Ø12,5.17,10)-3-~o~ec~nP;
8-n-propylidene-9-iso~o~yltetracyclo (4.4.o.l2~5.17~lO)-3-~o~pc~p;
8-n-propylidene-9-butyltetracyclo(4.4Ø12~5.17~10)-3-~9~PcPne;
8-isu~r~,~ylidenetetracyclo(4.4.o.l2~5.l7~lo)-3 P~pr~p 8-is~G~lidene-s-methyltetracyclo(4.4.o.l2~5. 17,10)-3--~1o-3PCPn~;
8-iso~v~lidene-9-ethyltetracyclo(4.4Ø12,5. 17,10)-3 -~9~p~en~;
8-is~ro~ylidene-9-isopropyltetracyclo(4.4Ø12,5.
17,10) -3-~o~p~Dn~;
8-isu~o~ylidene-s-butyltetracyclo(4.4.o.l2~5. 17,10)-3~~c~n~;
hexacyclo(6.6.1.13,6.110,13.o2,7.09,14)-4-heptadecene;
l2-methylhexacyclo(6.6.l.l3~6.llo~l3.o2~7.o9~l4) hept~e~n~;
l2-ethylhexacyclo(6.6.l.l3~6.llo~l3.o2~7.o9~l4) hept~Pcene;
12-isobutylhexacyclo(6.6.l.l3,6.l10,13.02~7.o9~l4) hept~Pcen~;
1,6,10-trimethyl-12-isobutylhexacyclo (6.6.l.l3~6.llo~l3.o2~7.o9~l4)-4-heptadecene;
SUBSTITUTE SHEET (RULE ~6) WO95l0~88 C A 2 1 6 6 1 q 3 PCT~S94/07433 octacyclo(8.8Ø12,9.14,7.111,18,l13,16.o3~8~ ol2,17)_ 5-~ococ~ne;
15-methyloctacyclo(8.8Ø12,9.14,7.111,18.113,16.
o3~8.ol2~l7)-5-~G~ocellp; and 15-ethyloctacyclo(8.8Ø12,9.14,7.111,18.113,16.
o3,8.ol2,17)_5_~ "~, pentacyclo(4.7Ø12,~. Os ~ 13.19,12)-3-pentAd~c~n~;
methyl-substituted pentacyclo(4.7.o.l2~s.o8~l3~ 19,12)_ 3-pen~
Specific representative cycloolefins according to formula C are as follows:
tricyclo(4.3Ø12,5)-3-~ec~
tricyclo(4.3Ø12,5)-3, 7-~CD~; ene;
IS 2-methyltricyclo(4.3Ø12,5)-3-decene;
5-methyltricyclo(4.3.o.l2~5) tricyclo(4.4Ø12,5)-3-~n~Pc~ne;
10-methyltricyclo(4.4Ø12,5)-3-1lnA~ e;
pentacyclo(6.5.l.l3,6.o2,7.o9,13)_4_pen~A~eç~n~;
1,3-dimethylpentacyclo(6.s.l.13,6.o2,7.o9,13)-4-penta~ec~ne;
l~6-dimethylpentacyclo(6.s.l.l3~6.o2~7.o9~l3) pentA~ec n~;
14,15-dimethylpentacyclo(6.5.1.13,6.o2,7.o9,13)_4-pentA~ec~D;
pentacyclo(6.6.1.13~6.02~7.09~14)-4-h~A~c~ne:
1,3-dimethylpentacyclo(6.6.1.13,6.o2,7.o9,14)_4_ hPyA~c~ne;
1,6-dimethylpentacyclo(6.6.1.13,6.o2,7.o9,14)_4-30 h~Y;~d~-en~;
15,16-dimethylpentacyclo(6.6.l.l3,6.o2,7.o9~l4) hPxA~ce~e;
heptacyclo(8.7.o.12,9.14,7.l11,17.o3~8.ol2~l6) eicosene;
3~ heptacyclo(7.8Ø13,6.o2,7.110,17.oll,16.112,13)_4_ eicosene;
SUBSmVTE SHEET (RULE 26) . PCTUS9407433 - 26 - ; ~ ~
2i6~193 ^
heptacyclo(8.8.o.l2,9.14,7.111,18.o3,8.ol2,17)_s_ heneicosene;
nonacyclo(9.10.1.14,7.o3,8.o2,18.ol2,21.113,20.
ol4,19.115,18)-S-pentacosene;
1,4-methano-l,la,4,4a-tetrahydrofluorene;
1,4-methano-l,la,4,4a,5,10a-hexahydroanthracene; and cyclopentadiene-acenaphthylene adduct.
.
With the catalysts described above it is often the case that one olefin of a polyene is substantially more reactive for polyermization than another. This enables - one to use dienes and polyenes as a major component of the polymer without obtaining substantial crosslinking.
For example, dicyclopentadiene or ethylidene norbornene 1~ can be polymerized exclusively through the nor~ornene-like olefin in an addition polymerization. However, polyenes having two or more double bonds can optionally be used in a relatively minor proportion to impart higher molecular weight to the copolymer and/or provide residual pendant side chain unsaturation for functionalization or crosslinking. Where the polyenes can participate in polymerization at two (or more) sites, these monomers tend to promote chain extension which can double or quadruple the molecular weight at low incorporation. Ideally the polyene is not present in such high amounts which might result in excessive crosslinking and produce insoluble gel formation.
Preferably, the molecular weight is suitably increased by including the optional polyene in the copolymer at from O.S to 3 mole percent.
Suitable chain-extending, molecular-weight-- increas~ng polyenes incl-ude, for example, alpha-omega dienes having from S to 18 carbon atoms, such as lr4~
3~ pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-C A 2 1 6 6 1 9 3 PCT~S94/07433 W095/0~88 ,~^.
n~ecA~;ene, ~ o~cA~iene, 1,12-tri~c~A~;ene, 1,13-tetrA~cA~iene, 1,14-pentAA~ca~;ene, 1,15-hPYAA~cA~iene, 1,16-hepta~cA~;ene, 1,17-oc~A~PcA~iene, or the like.
When two (or more) of the double bonds are sufficiently reactive under the particular reaction conditions to participate in the polymerization reaction, or when the QDcQn~ olefin on a given monomer or polyene is not polymerizable in an addition reaction (such as a tri-substituted olefin), but can be used to crosslink in post-polymerization, free-radical, crosslinking reactions, then suitable polyenes generally also include other ~;n~Ar or brAn~h~
aliphatic dienes and trienes, mo~ y~lic dienes and trienes, bicyclic dienes and trienes, polycyclic dienes and trienes, aromatic dienes, and the like.
Specific rep~e~cntative examples of nGl, _G.Ijugated brAn~h~A aliphatic ~ie~s and polyenes include 1,4-- hPYA~iene, 6-methyl-1,4-heptadiene, 4-isopropyl-1,4-h~YA~i~n~, 4-methyl-1,4 -h ~YA~iene, 5-methyl-1,4hPY~iene, 4-ethyl-1,4-h~A~iene, 1-phenyl-4propyl-1,4-h~Y~iene, 4, 5-dimethyl-1, 4-h~XAA i ene, 6-phenyl-1,4-h~Y~iene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 6-methyl-1,5-heptadiene, 5,7-dimethyl-1,5-octadiene, 4,5-dipropyl-1,4-octadiene, 5-~opyl-6-methyl-1,5-heptadiene, 5-ethyl-7-methyl-1,6-octadiene, 4,7-dimethyl-1,4,7-nonatriene, and 5,8-dimethyl-1,4,7-nonatriene.
Specific representative examples of non-conjugated monocyclic dienes and polyenes include 4-vinylcyclohexene, 4-propenylcyclohexene, 1,4-cyclnh~YA~iene, l-vinyl-4-1(1-propenyl)-cyclnh~YAne, 4-methyl-1,4-cyclooctadiene, 4-methyl 1-5-propyl-1,4-SUBSTITUTE SHEET (RULE 26) *rB
wo ssto~ss r A 2 1 6 6 1 9 3 PCT~S94/07433 cyclooctadiene, 5-methylcyclopentadiene, 1,5,9-cyclododecatriene, trans-1,2-divinylcyclobutane, and 1,4-divinylcyclo~eYAne.
Specific representative examples of non-conjugated bicyclic dienes including:
no~bGL..adiene, 5-ethylirl~nPnQrbornene-2, 5 ~.o~yli~PnP~orbornene-2, 10 5-butyli ~PnenG~boll-ene-2, 5-iso~ ~ylide--e ..v bornene-2, l-methyl-2,5-norbornadiene, l-ethyl-2,5-norbornadiene, 1 ~1o~yl-2,5-norbornadiene, 1-butyl-2,5-no~bGL--adiene, l-chloro-2,5-norhornadiene, l-bromo-2,5-l-GlboL-.adiene, 2-methyl-2,5-norbornadiene, 2-ethyl-2,5-nGL~oL..adiene, 2-propyl-2,5--.u~LoL.ladiene, 2-butyl-2,5-no~Lul-~adiene, 2-pentyl-2.5-norbornadiene, 2-hexy1-2,5-norbornadiene, 2-chloro-2,5-norbornadiene, 2S 2-bromo-2,5-,-o~boL--adiene, 2-fluoro-2,5-norbornadiene, 7-methyl-2,5-norbornadiene, 7-ethyl-2,5-.,o~o~l.adiene, 7-propyl-2,5-norbornadiene, 7-butyl-2,5-norbornadiene, 7-chloro-2,5-norbornadiene, 7,7-dimethyl-2,5-norbornadiene, 7,7-diethyl-2,5-norbornadiene, 7,7-methylethyl-2,5-norbornadiene, 3~ 7,7-dichloro-2,5-norbornadiene, 5-methylene-2-norborene, SUBSTITUTE SHEET (RULE 26) W09s/0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 5-(2-butenyl)-2-norbornene, 3-heptyl-2,5-norbornadiene, 2,3-dimethyl-2,5-norbornA~iene, 1,4-dimethyl-2,5-norbornadiene, 1,2,3,4-tetramethyl-2,5-norbornadiene, 1,2,3,4,7-pentamethyl-2,5-norbornadiene, 2-ethyl-3-propyl-1,2,5-norbornadiene, bicyclo(2.2.2)octadiene-2,5 5-isopropylidene-bicyclo(2.2.2)octene-2, 5,ethylidenebicyclo(2.2.2)octene-2, 5-butyli~n~hicyclo(2.2.2)octene-2, 2-ethylbicyclo(2.2.2)octadiene-2,5, 2-methyl-3-ethyl-bicyclo(2.2.2)octadiene-2,5, 2-hexylbicyclo(2.2.2)oct~iP~-2,5 2-(1',5'-dimethylh~Y~yl-4)bicyclo(2.2.2)octadiene-2,5, l-isopropyli~n hicyclo(4.4.0) APC~; ene-2.6, 2-ethylidene-bicyclo(4.4.0)~e~-c~.~ G, 3-ethyli~D~hicyclo(3.2.0)heptadiene-2,6, 3-methylbicyclo(3.3.0)octadiene-2,6, tetrahydro~ ne, 3-methyltetrahydroin~ P,
8-ethyltetracyclo(4.4Ø12,5.17,10)-3-AoA~ce~;
8-propyltetracyclo(~.4Ø12,5.17,10)-3-dodecene;
8-hexyltetracyclo(4.4Ø12,5.17,10)-3-dodecene;
8-stearyltetracyclo(4.4Ø12,5.17,10)-3-AoA~c~ne;
8~9-dimethyltetracyclo(4.4.o.l2~5.l7~lo)-3-dodecene;
8-methyl-9-ethyltetracyclo(4.4Ø12,5.17,10)-3-A~APc~n~;
8-chlorotetracyclo(4.4Ø12,5.17,10)-3-dodecene;
8-bromotetracyclo(4.4~0.12~5.17~l0)-3-AsApcDne;
8-fluorotetr~cyclo (4 . 4 . O .12, 5 .17 ,10) -3-~oA~c~ e;
8,9-dichlorotetracyclo(4.4Ø12,5.17,10)-3-dodecene;
8-cyclohexyltetracyclo(4.4Ø12,5.17,10)-3-dodecene;
8-iso~utyltetracyclo(4.4Ø12,5.17,10)-3-dOA~n~;
8-butyltetracyclo(4.4Ø12,5.17,l0)-3-doApc~ne;
8-ethylidenetetracyclo(4.4Ø12,5.17,10)-3-dodecene;
SUBSmUTE SHEET tRULE 26) wo 95,0~88 C A 2 1 6 6 1 9 3 PCT~S94tO7433 8-ethylidene-9-methyltetracyclo(4.4.o~l2r5.l7 Ao~rPn~;
8-ethylidene-9-ethyltetracyclo(4.4.o.l2~5.l7~lo) ~oAecPI
S 8-ethylidene-9-isopropyltetracyclo(4.4.o.l2~5. 17~10) 3 _~3oAp~ne;
8-ethylidene-9-butyltetracyclo(4.4Ø12~5.17~10)-3-Ao~P~Pn - ;
8-l~ ylidenetetracyclo(4.4Ø12,5.17,10)-3 -dodecene;
8-n-propylidene-9-methyltetracyclO (4.4.o.l2~5.l7~ln)-3-~oAPcP~e;
8-ll ~o~ylidene-9-ethyltetracyclo(4.4Ø12,5.17,10)-3-~o~ec~nP;
8-n-propylidene-9-iso~o~yltetracyclo (4.4.o.l2~5.17~lO)-3-~o~pc~p;
8-n-propylidene-9-butyltetracyclo(4.4Ø12~5.17~10)-3-~9~PcPne;
8-isu~r~,~ylidenetetracyclo(4.4.o.l2~5.l7~lo)-3 P~pr~p 8-is~G~lidene-s-methyltetracyclo(4.4.o.l2~5. 17,10)-3--~1o-3PCPn~;
8-iso~v~lidene-9-ethyltetracyclo(4.4Ø12,5. 17,10)-3 -~9~p~en~;
8-is~ro~ylidene-9-isopropyltetracyclo(4.4Ø12,5.
17,10) -3-~o~p~Dn~;
8-isu~o~ylidene-s-butyltetracyclo(4.4.o.l2~5. 17,10)-3~~c~n~;
hexacyclo(6.6.1.13,6.110,13.o2,7.09,14)-4-heptadecene;
l2-methylhexacyclo(6.6.l.l3~6.llo~l3.o2~7.o9~l4) hept~e~n~;
l2-ethylhexacyclo(6.6.l.l3~6.llo~l3.o2~7.o9~l4) hept~Pcene;
12-isobutylhexacyclo(6.6.l.l3,6.l10,13.02~7.o9~l4) hept~Pcen~;
1,6,10-trimethyl-12-isobutylhexacyclo (6.6.l.l3~6.llo~l3.o2~7.o9~l4)-4-heptadecene;
SUBSTITUTE SHEET (RULE ~6) WO95l0~88 C A 2 1 6 6 1 q 3 PCT~S94/07433 octacyclo(8.8Ø12,9.14,7.111,18,l13,16.o3~8~ ol2,17)_ 5-~ococ~ne;
15-methyloctacyclo(8.8Ø12,9.14,7.111,18.113,16.
o3~8.ol2~l7)-5-~G~ocellp; and 15-ethyloctacyclo(8.8Ø12,9.14,7.111,18.113,16.
o3,8.ol2,17)_5_~ "~, pentacyclo(4.7Ø12,~. Os ~ 13.19,12)-3-pentAd~c~n~;
methyl-substituted pentacyclo(4.7.o.l2~s.o8~l3~ 19,12)_ 3-pen~
Specific representative cycloolefins according to formula C are as follows:
tricyclo(4.3Ø12,5)-3-~ec~
tricyclo(4.3Ø12,5)-3, 7-~CD~; ene;
IS 2-methyltricyclo(4.3Ø12,5)-3-decene;
5-methyltricyclo(4.3.o.l2~5) tricyclo(4.4Ø12,5)-3-~n~Pc~ne;
10-methyltricyclo(4.4Ø12,5)-3-1lnA~ e;
pentacyclo(6.5.l.l3,6.o2,7.o9,13)_4_pen~A~eç~n~;
1,3-dimethylpentacyclo(6.s.l.13,6.o2,7.o9,13)-4-penta~ec~ne;
l~6-dimethylpentacyclo(6.s.l.l3~6.o2~7.o9~l3) pentA~ec n~;
14,15-dimethylpentacyclo(6.5.1.13,6.o2,7.o9,13)_4-pentA~ec~D;
pentacyclo(6.6.1.13~6.02~7.09~14)-4-h~A~c~ne:
1,3-dimethylpentacyclo(6.6.1.13,6.o2,7.o9,14)_4_ hPyA~c~ne;
1,6-dimethylpentacyclo(6.6.1.13,6.o2,7.o9,14)_4-30 h~Y;~d~-en~;
15,16-dimethylpentacyclo(6.6.l.l3,6.o2,7.o9~l4) hPxA~ce~e;
heptacyclo(8.7.o.12,9.14,7.l11,17.o3~8.ol2~l6) eicosene;
3~ heptacyclo(7.8Ø13,6.o2,7.110,17.oll,16.112,13)_4_ eicosene;
SUBSmVTE SHEET (RULE 26) . PCTUS9407433 - 26 - ; ~ ~
2i6~193 ^
heptacyclo(8.8.o.l2,9.14,7.111,18.o3,8.ol2,17)_s_ heneicosene;
nonacyclo(9.10.1.14,7.o3,8.o2,18.ol2,21.113,20.
ol4,19.115,18)-S-pentacosene;
1,4-methano-l,la,4,4a-tetrahydrofluorene;
1,4-methano-l,la,4,4a,5,10a-hexahydroanthracene; and cyclopentadiene-acenaphthylene adduct.
.
With the catalysts described above it is often the case that one olefin of a polyene is substantially more reactive for polyermization than another. This enables - one to use dienes and polyenes as a major component of the polymer without obtaining substantial crosslinking.
For example, dicyclopentadiene or ethylidene norbornene 1~ can be polymerized exclusively through the nor~ornene-like olefin in an addition polymerization. However, polyenes having two or more double bonds can optionally be used in a relatively minor proportion to impart higher molecular weight to the copolymer and/or provide residual pendant side chain unsaturation for functionalization or crosslinking. Where the polyenes can participate in polymerization at two (or more) sites, these monomers tend to promote chain extension which can double or quadruple the molecular weight at low incorporation. Ideally the polyene is not present in such high amounts which might result in excessive crosslinking and produce insoluble gel formation.
Preferably, the molecular weight is suitably increased by including the optional polyene in the copolymer at from O.S to 3 mole percent.
Suitable chain-extending, molecular-weight-- increas~ng polyenes incl-ude, for example, alpha-omega dienes having from S to 18 carbon atoms, such as lr4~
3~ pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-C A 2 1 6 6 1 9 3 PCT~S94/07433 W095/0~88 ,~^.
n~ecA~;ene, ~ o~cA~iene, 1,12-tri~c~A~;ene, 1,13-tetrA~cA~iene, 1,14-pentAA~ca~;ene, 1,15-hPYAA~cA~iene, 1,16-hepta~cA~;ene, 1,17-oc~A~PcA~iene, or the like.
When two (or more) of the double bonds are sufficiently reactive under the particular reaction conditions to participate in the polymerization reaction, or when the QDcQn~ olefin on a given monomer or polyene is not polymerizable in an addition reaction (such as a tri-substituted olefin), but can be used to crosslink in post-polymerization, free-radical, crosslinking reactions, then suitable polyenes generally also include other ~;n~Ar or brAn~h~
aliphatic dienes and trienes, mo~ y~lic dienes and trienes, bicyclic dienes and trienes, polycyclic dienes and trienes, aromatic dienes, and the like.
Specific rep~e~cntative examples of nGl, _G.Ijugated brAn~h~A aliphatic ~ie~s and polyenes include 1,4-- hPYA~iene, 6-methyl-1,4-heptadiene, 4-isopropyl-1,4-h~YA~i~n~, 4-methyl-1,4 -h ~YA~iene, 5-methyl-1,4hPY~iene, 4-ethyl-1,4-h~A~iene, 1-phenyl-4propyl-1,4-h~Y~iene, 4, 5-dimethyl-1, 4-h~XAA i ene, 6-phenyl-1,4-h~Y~iene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 6-methyl-1,5-heptadiene, 5,7-dimethyl-1,5-octadiene, 4,5-dipropyl-1,4-octadiene, 5-~opyl-6-methyl-1,5-heptadiene, 5-ethyl-7-methyl-1,6-octadiene, 4,7-dimethyl-1,4,7-nonatriene, and 5,8-dimethyl-1,4,7-nonatriene.
Specific representative examples of non-conjugated monocyclic dienes and polyenes include 4-vinylcyclohexene, 4-propenylcyclohexene, 1,4-cyclnh~YA~iene, l-vinyl-4-1(1-propenyl)-cyclnh~YAne, 4-methyl-1,4-cyclooctadiene, 4-methyl 1-5-propyl-1,4-SUBSTITUTE SHEET (RULE 26) *rB
wo ssto~ss r A 2 1 6 6 1 9 3 PCT~S94/07433 cyclooctadiene, 5-methylcyclopentadiene, 1,5,9-cyclododecatriene, trans-1,2-divinylcyclobutane, and 1,4-divinylcyclo~eYAne.
Specific representative examples of non-conjugated bicyclic dienes including:
no~bGL..adiene, 5-ethylirl~nPnQrbornene-2, 5 ~.o~yli~PnP~orbornene-2, 10 5-butyli ~PnenG~boll-ene-2, 5-iso~ ~ylide--e ..v bornene-2, l-methyl-2,5-norbornadiene, l-ethyl-2,5-norbornadiene, 1 ~1o~yl-2,5-norbornadiene, 1-butyl-2,5-no~bGL--adiene, l-chloro-2,5-norhornadiene, l-bromo-2,5-l-GlboL-.adiene, 2-methyl-2,5-norbornadiene, 2-ethyl-2,5-nGL~oL..adiene, 2-propyl-2,5--.u~LoL.ladiene, 2-butyl-2,5-no~Lul-~adiene, 2-pentyl-2.5-norbornadiene, 2-hexy1-2,5-norbornadiene, 2-chloro-2,5-norbornadiene, 2S 2-bromo-2,5-,-o~boL--adiene, 2-fluoro-2,5-norbornadiene, 7-methyl-2,5-norbornadiene, 7-ethyl-2,5-.,o~o~l.adiene, 7-propyl-2,5-norbornadiene, 7-butyl-2,5-norbornadiene, 7-chloro-2,5-norbornadiene, 7,7-dimethyl-2,5-norbornadiene, 7,7-diethyl-2,5-norbornadiene, 7,7-methylethyl-2,5-norbornadiene, 3~ 7,7-dichloro-2,5-norbornadiene, 5-methylene-2-norborene, SUBSTITUTE SHEET (RULE 26) W09s/0~88 C A 2 1 6 6 1 9 3 PCT~S94/07433 5-(2-butenyl)-2-norbornene, 3-heptyl-2,5-norbornadiene, 2,3-dimethyl-2,5-norbornA~iene, 1,4-dimethyl-2,5-norbornadiene, 1,2,3,4-tetramethyl-2,5-norbornadiene, 1,2,3,4,7-pentamethyl-2,5-norbornadiene, 2-ethyl-3-propyl-1,2,5-norbornadiene, bicyclo(2.2.2)octadiene-2,5 5-isopropylidene-bicyclo(2.2.2)octene-2, 5,ethylidenebicyclo(2.2.2)octene-2, 5-butyli~n~hicyclo(2.2.2)octene-2, 2-ethylbicyclo(2.2.2)octadiene-2,5, 2-methyl-3-ethyl-bicyclo(2.2.2)octadiene-2,5, 2-hexylbicyclo(2.2.2)oct~iP~-2,5 2-(1',5'-dimethylh~Y~yl-4)bicyclo(2.2.2)octadiene-2,5, l-isopropyli~n hicyclo(4.4.0) APC~; ene-2.6, 2-ethylidene-bicyclo(4.4.0)~e~-c~.~ G, 3-ethyli~D~hicyclo(3.2.0)heptadiene-2,6, 3-methylbicyclo(3.3.0)octadiene-2,6, tetrahydro~ ne, 3-methyltetrahydroin~ P,
9-methyltetrahydroinAPne, 7-propyltetrahydroindene, 7-isopropyltetrahydroindene and the like.
Specific representative examples of non-conjugated polycyclic dienes include:
dicyclopentadiene, methyl substituted dicyclopentadienes, dimethyl substituted dicyclopentadienes, 4-methyl-5-ethyldicyclopentadiene, 5-iS~l u~yldicyclopentadiene, 8-iSG~ opyldicyclopentadiene, tetracyclo~o~c~;ene, methyl substituted tetracyclododecadienes, dimethyl substituted tetracycloAo~ec~ienes~
SUBSTITUTE 5HEET ~RULE 26) W095/0~88 C A 2 1 6 6 1 q 3 PCT~S94107433 trimethyl substituted tetracycloAoA~cA~ienes, hexacycloheptaA~cA~iene, methyl substituted hexacyclohept~A~cA~ienes, dimethyl substituted hexacycloheptA~c~ienes, trimethyl substituted hexacycloheptAA~cAA;enes, pentacyclot6.5.13~6.02~7.09~13)-4,10-pen~AAocAAiene (tricylopentadiene), methyl substituted pentacyclo(6.5.1.1-3~6. o2, 7.o9,13)-4,10-pent~Ao~ienes, dimethyl substituted pentacyclo(6.5.1.1=3~60.2~7.09~13)-4 10-pen~A~ocA~ienes, pentacyclo(7.4Ø13~6.02~7.11,13)-4,11-pentAAocA~iene, ll-methyl-pentacyclo(7.4.o.l3~6. o2, 7.110,13)_4 11-lS pen~a~oc~iene~
12-methyl-pentacyclo(7.4.o.l3~6.o2~7.llo~l3) pentAAoc~;ene, 11-12-dimethyl pentacyclo(7.4.o.13~6102~7.11~~13)-4,11-pen~A~sc~iene, and other alkyl substituted 20 pentacyclo(7.4.013~6.o2~7.llo~13(-4~ll pentadocadienes.
Specific representative examples of no-- ~o.ljugated aromatic dienes include alkyl styrenes and the like.
2S When dicyclopentadiene (or a similar cyclopolyene) is employed, it may be used in either the endo or exo form or both. In a preferred embodiment the exo form is used.
Pol~merization Conditions The polymèrization may be conducted at any suitable temperature known to those of ordinary skill in the art. In a preferred P~hoAiment the temperature may range from -100 degrees C to 250 degrees C, preferably from -50 to 200 degrees C. Further, the SUBSTITUTE SHEET (RULE 26) PCTUS9407433 - 31 -- ~
1 r catalyst is preferably used in an amount to provide a starting monomer to catalyst ratio of from 1 to 109, preferably 100 to 107. The polymerization time may usually range from less than one minute to 10 hours or more. The reaction pressure may range from sub-atmospheric to atmospheric to 1000 MPa, preferably from atmospheric to 500 MPa. Polymerization methods are not particularly limited and include bulk polymerization, gas phase polymerization, solution polymerization and suspension polymerization. When utilizing solvents for polymerization, suitable solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; alicyclic hydrocarbons such as cyclopentane; cyclohexane and methylcyclohexane;
aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; and halogenated hydrocarbons such as chloroform and di-chloromethane. These solvents can be used alone or in combination. Monomers such as alpha olefins and cyclic olefins can also be used as solvents. The polymerization may be conducted in any vessel suitable for the chosen reaction conditions.
Furthermore, two or more vessels may be run in series or parallel to produce intimate blends of different polymers or blends of varieties of the "same" polymer, i.e. a 1000 Mw homopolyethylene blended with a 100,000 Mw homopolyethylene.
Products The polymers produced by this invention can range from plastics, thermoplastic olefins (TPO's), thermoplastic elastomers(TPE's), thermosets and elastomers. -By varying the monomer feed(s) and - reaction conditions many different polymers and polymer 3~ blends, specifically intimate polymer blends, and interpenetrating networks can be produced. For AMENDED SHEET
PCTUS940743. - 32 -~
19~
r ~ -purposes of this invention and any claims thereto intimate blend is defined to be a mixed combination of at least two polymers neither of which are necessarily in network form provided tnat at least one of which is synthesized in the immediate presence of the other(s) such that the mixture does not significantly phase separate. Likewise for the purposes of this invention and any claims thereto interpenetrating network is defined to be an intimate combination of at least two polymers, at least one of which is in network form and at least one of which is synthesized ln the immediate presence of the other(s). Network is herein defined to include polymers having intra-chain associations, aggregations, or other interactions between segments of the same polymer chain or chain type as well as covalently crosslinked polymers For example, if a reactor was charged with cyclic monomer first, ring-open metathesis polymerization of the monomer would occur and produce ring-opened polymer chains. Then an alpha olefin could be introduced into the reactor and allowed to polymerize. This sequence would produce an intimate blend of ring-opened polymer and alpha-olefin polymer. Likewise, it is also possible to produce multiple polymer blends and intimate blends of many 2j olefins and cyclic olefins. Furthermore the ring-opened cyclic polymer could be a polymer of one or more cyclic monomers and the olefin polymer could be a polymer of one or more olefins. Furthermore, the ring-open metathesis polymerization of cyclic dienes and alpha olefins could produce a network of ring-opened metathesis polymerization thermoset interdispersed with Ziegler-Natta thermoplastic olefin in an ~ interpenetrating network or intimate blend. Likewise, an intimate blend or interpenetrating network of two or 3j more ring-opening metathesis polymerizations can also AM~ EDS~E~
PCTUS9407433 - 32a ~
r 2i66~l93 be produced, preferably by sequential addition of -- different cyclic monomers.
U `~ ~ lc ~ ~ `
PCTUS9407433 _ 33 _, r ~ r r 6 6 i-93~
As ring-opened metathesis polymerization results in unsaturated chains, it is occasionally desirable to hydrogenate the resulting copolymers and/or polymer mixtures to make a predominantly saturated polymer mixture. Hydrogenation can improve oxidative and thermal stability.
It is also envisioned that block copolymers and tapered bloc~ copolymers could be made by varying monomer addition, concentrations and other reaction conditions such as temperature and pressure. For example, the catalyst described above can be used to create vinyl terminated polymers or macromonomers.
Such a vinyl terminated polymer could then be combined with cyclic monomers to produce block copolymers and/or long chain branches, depending on the reaction conditions and monomers chosen. There are many combinations of the ring-opened metathesis polymerized monomers and the olefin polymerized monomers that will occur to those of ordinary skill in the art. These combinations are within the scope of this invention and intended to be covered hereby. In particular, intimate blends of 3 to 50 weight percent ring-opening metathesis polymerized polymer with 97 to 50 weight '5 percent Ziegler-Natta polymer are preferred.
It is believed that a hydrogen abstraction, loss, shift or transfer from the alpha carbon of the metal al~yl, or some other occurrence causes the formation of ,0 a metal carbene in the above catalyst systems.
Carbenes produced in this way and present in the system could possibly react with the alpha olefin monomers in non-pol~vmerizing olefin ~etathesis reactions, but these reactions will not adversely affect the ongoing " Zeigler/Natta polymerization. An olefin could cause a chain transfer of a growing ring-opening metathesis A~EN~ S~EEr PCTUS9407433 - 33a r~ ~~
~ 1 6 ~; 1 9 3 polymerization chain leaving an olefin terminated ring-opening metathesis polymerized polymer that could thereafter potentially insert into a growing Ziegler-Natta chain.
, SHE~
- PCTUS9407433 2 ~ ~ 6 1 9 3 `
On the other hand, a growing Ziegler-Natta chain could chain terminate in a terminal olefin that could metathesize with a metal carbene to act as an active ring-opening metathesis polymerization catalyst to yield block copolymers with one block from a ring-opening metathesis polymerization and one block from a Ziegler-Natta polymerization. Thus, this invention also provides for new species~of carbenes based on Ti, Zr and Hf, particularly Zr and Hf. These carbenes may be represented by the formulae: (A-Cp)M=CR(R'), wherein (A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, - disubstituted pnicogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are jolned forming ~ C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
A' is a bridging group, which group may serve to 2j restrict rotation of the Cp and Cp* rings;
M is any group 4, 5, 6, 7 or 8 metal, preferably Ti, Zr of Hf;
R and R' are independently a hydrogen or a C1 to 40 linear, cyclic or branched alkyl, preferably a C
,0 to C20 linear, cyclic or branched alkyl, even more preferably hydrogen, R and R' may be the same or different alkyl groups, although in a preferred - embodiment R and R' are the same alkyl group .
" or n~J SHE~
PCTUS9407433. _ ~5 _ r ~
r r ~ r 216~6193 r ~ --(C5H5yXsx) (A'h M: CR(R') /
JS'(Z1y) wherein A' is a bridging group;
(C5H5_y_XSxj is a cyclopentadienyl ring substituted with from zero to five S radicals each S
being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated o.r unsaturated polycyclic cyclopentadienyl ligand;
x is from 0 to 5 denoting the degree of substitution;
M is any ~roup 4, 5, 6, 7 or 8 metal, preferably titanium, zirconium or hafnium;
JS'(z--1-y) is a heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S' is a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl-substituted organometalloid; and z is the coordination number of the element J;
y ls o or 1;
30 R and R' are independently a hydrogen or a Cl to .
- C40 linear, cyclic or branched alkyl, preferably a C
to C20 linear, cyclic or branched alkyl, even more A~ L,;~II)L~
PCTUS9407~33 - ~6 ~r ,~
2f6~19~ -~ preferably-hydrogen. R and R' may be the same or different alkyl groups, although in a preferred embodiment R and R' are the same alkyl group. Carbenes which are useful in the pr~ctice of this invention, however, include those which can be represented by the formula above where M is any group 4, 5, 6, 7 or 8 metal. Metal carbenes complex with olefins to form metalocycles that are possibly intermediates in metathesis reactions. Metalocycle structures are discussed in detail in "Olefin Metathesis" K.J. Ivin, Academic Press, New York (1989).
For purposes of this invention a Ziegler-Natta polymer is a polymer that has incorporated a 1~ substantial amount of the cyclic monomers into the growing polymer chain resulting in a saturated chain, while maintaining the cyclic aspect of the monomer's - structure. A ring-opening metathesis polymerized polymer is a polymer that has incorporated the cyclic monomers into the growing polymer chain resulting in an unsaturated chain without maintaining the cyclic aspect on the monomer's structure.
ExamPles 2~
Molecular weight (Mw and Mn) were measured by Gel Permeation Chromotography using a Waters 150 gel - permeation chromatograph equipped with a differential refractive index (DRI) detector. The numerical io analyses were performed using the commercially available standard Gel Permeation software package.
- Proton NMR was used to-detect ring-open metathesis ~ polymer and Ziegler-Natta polymer in the same sample.
Procedure:
~4 PCTUS 9 4 0 7 4 3 3 ~ 1 9 3 In general, to demonstrate the ring-opening metathesis p~lymerization using catalyst discussed above, a vial containing 30 to 50 mg dicyclopentadienyl zirconium dimethyl(Cp2ZrMe2) or dicyclopentadienyl S ha~nium dimethyl (Cp2HfMe2), 30 to 60 mg of N,N-dimethylanilinium (DMAH)B(pfp)4 was stirred in 3 ml of toluene until gas evolution has stopped. The catalyst system was then added to 10 to 20 g of freshly sublimed norbornene dissolved in 300 to 400 ml of toluene (freshly distilled from sodium/benzophenone) in a one liter flask in the dry box at room temperature to 80C.
The polymerization was allowed to proceed for 10 to 120 minutes or until the viscosity was such that the mixture flowed slowly or not at all. The 1~ polymerization was killed by adding isopropyl alcohol.
White precipitate was filtered and dried. The proton NMR of the product matched that of commercially available ring-opening metathesis polymerization polynorbornene and the integration of the Qlefinic region indicated that there was o~e olefin per monomer unit. - ~
To demonstrate both Ziegler-Natta and ring-opening metathesis polymerization products from the same catalyst system and reaction pot, the procedure above was repeated except that the reaction was allowed to proceed for O.S to 15 minutes and then transferred to a preheated (40-60 degrees C) two liter autoclave reactor via cannula. The reaction was sealed and propylene was ,0 added (10 to 50 psi) and the reactor was stirred. The polymerization was continued for 1 to 240 minutes and the polymer was precipitated into isopropyl alcohol.
- NMR showed the expected resonances for propylene/norbornene(Zeigler-Natta) copolymer and there 3j were olefinic resonances, not from residual monomer, as well.
AMENDED SHEET
- PCTUS9407433 - 38 - ,~
'2~661g3 The examples are reported in table 1.
Sample Catalyst Activator M ratio Yiel Product (mmole) (mmole) cat/ d Descrip.
act (mg) 1* Cp2ZrMe2 DMAH NB 1 230ROMP
(0.090) B(pfp)4 polymer (0.090) 2* Cp2ZrMe2 DMAH NB .7 682ROMP
(0.090) B(pfp)4 polymer (0.129) 3* Cp2ZrMe2 DMAH NB 2 974ROMP
(0-096) B(pfp)4 polymer (0.047) 4* Cp2HfMe2 DMAH NB 1.5 570ROMP
(-0-15) B(pfp)4 polymer ( 0.10) 5*** Cp2HfMe2 DMAH P/ 1.5 300/mix/ROMP
** B(pfP)4 NB 570 polymer ( 0.08) (~0.05) M = Monomer; NB = norbornene; P = propylene *Runs were at room temperature using 4-~ of norbornene in 10 ml toluene.
**Run was at room temperature using 10g of norbornene in 300 ml of toluene.
***Half was transferred to an autoclave by cannula and run at 40C with 30 psi of propylene and 10g norbornene.
1 mix/ROMP polymer = 300g of a mixture of addition polymer and ROMP polymer and 570 g of ROMP polymer.
The ~MR indicated the presence of propylene/norbornene copolymer with some small - resonances in the olefinic region attributed to the presence of ROMP polynorbornene.
AMENC`ED SHEE~
Specific representative examples of non-conjugated polycyclic dienes include:
dicyclopentadiene, methyl substituted dicyclopentadienes, dimethyl substituted dicyclopentadienes, 4-methyl-5-ethyldicyclopentadiene, 5-iS~l u~yldicyclopentadiene, 8-iSG~ opyldicyclopentadiene, tetracyclo~o~c~;ene, methyl substituted tetracyclododecadienes, dimethyl substituted tetracycloAo~ec~ienes~
SUBSTITUTE 5HEET ~RULE 26) W095/0~88 C A 2 1 6 6 1 q 3 PCT~S94107433 trimethyl substituted tetracycloAoA~cA~ienes, hexacycloheptaA~cA~iene, methyl substituted hexacyclohept~A~cA~ienes, dimethyl substituted hexacycloheptA~c~ienes, trimethyl substituted hexacycloheptAA~cAA;enes, pentacyclot6.5.13~6.02~7.09~13)-4,10-pen~AAocAAiene (tricylopentadiene), methyl substituted pentacyclo(6.5.1.1-3~6. o2, 7.o9,13)-4,10-pent~Ao~ienes, dimethyl substituted pentacyclo(6.5.1.1=3~60.2~7.09~13)-4 10-pen~A~ocA~ienes, pentacyclo(7.4Ø13~6.02~7.11,13)-4,11-pentAAocA~iene, ll-methyl-pentacyclo(7.4.o.l3~6. o2, 7.110,13)_4 11-lS pen~a~oc~iene~
12-methyl-pentacyclo(7.4.o.l3~6.o2~7.llo~l3) pentAAoc~;ene, 11-12-dimethyl pentacyclo(7.4.o.13~6102~7.11~~13)-4,11-pen~A~sc~iene, and other alkyl substituted 20 pentacyclo(7.4.013~6.o2~7.llo~13(-4~ll pentadocadienes.
Specific representative examples of no-- ~o.ljugated aromatic dienes include alkyl styrenes and the like.
2S When dicyclopentadiene (or a similar cyclopolyene) is employed, it may be used in either the endo or exo form or both. In a preferred embodiment the exo form is used.
Pol~merization Conditions The polymèrization may be conducted at any suitable temperature known to those of ordinary skill in the art. In a preferred P~hoAiment the temperature may range from -100 degrees C to 250 degrees C, preferably from -50 to 200 degrees C. Further, the SUBSTITUTE SHEET (RULE 26) PCTUS9407433 - 31 -- ~
1 r catalyst is preferably used in an amount to provide a starting monomer to catalyst ratio of from 1 to 109, preferably 100 to 107. The polymerization time may usually range from less than one minute to 10 hours or more. The reaction pressure may range from sub-atmospheric to atmospheric to 1000 MPa, preferably from atmospheric to 500 MPa. Polymerization methods are not particularly limited and include bulk polymerization, gas phase polymerization, solution polymerization and suspension polymerization. When utilizing solvents for polymerization, suitable solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; alicyclic hydrocarbons such as cyclopentane; cyclohexane and methylcyclohexane;
aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; and halogenated hydrocarbons such as chloroform and di-chloromethane. These solvents can be used alone or in combination. Monomers such as alpha olefins and cyclic olefins can also be used as solvents. The polymerization may be conducted in any vessel suitable for the chosen reaction conditions.
Furthermore, two or more vessels may be run in series or parallel to produce intimate blends of different polymers or blends of varieties of the "same" polymer, i.e. a 1000 Mw homopolyethylene blended with a 100,000 Mw homopolyethylene.
Products The polymers produced by this invention can range from plastics, thermoplastic olefins (TPO's), thermoplastic elastomers(TPE's), thermosets and elastomers. -By varying the monomer feed(s) and - reaction conditions many different polymers and polymer 3~ blends, specifically intimate polymer blends, and interpenetrating networks can be produced. For AMENDED SHEET
PCTUS940743. - 32 -~
19~
r ~ -purposes of this invention and any claims thereto intimate blend is defined to be a mixed combination of at least two polymers neither of which are necessarily in network form provided tnat at least one of which is synthesized in the immediate presence of the other(s) such that the mixture does not significantly phase separate. Likewise for the purposes of this invention and any claims thereto interpenetrating network is defined to be an intimate combination of at least two polymers, at least one of which is in network form and at least one of which is synthesized ln the immediate presence of the other(s). Network is herein defined to include polymers having intra-chain associations, aggregations, or other interactions between segments of the same polymer chain or chain type as well as covalently crosslinked polymers For example, if a reactor was charged with cyclic monomer first, ring-open metathesis polymerization of the monomer would occur and produce ring-opened polymer chains. Then an alpha olefin could be introduced into the reactor and allowed to polymerize. This sequence would produce an intimate blend of ring-opened polymer and alpha-olefin polymer. Likewise, it is also possible to produce multiple polymer blends and intimate blends of many 2j olefins and cyclic olefins. Furthermore the ring-opened cyclic polymer could be a polymer of one or more cyclic monomers and the olefin polymer could be a polymer of one or more olefins. Furthermore, the ring-open metathesis polymerization of cyclic dienes and alpha olefins could produce a network of ring-opened metathesis polymerization thermoset interdispersed with Ziegler-Natta thermoplastic olefin in an ~ interpenetrating network or intimate blend. Likewise, an intimate blend or interpenetrating network of two or 3j more ring-opening metathesis polymerizations can also AM~ EDS~E~
PCTUS9407433 - 32a ~
r 2i66~l93 be produced, preferably by sequential addition of -- different cyclic monomers.
U `~ ~ lc ~ ~ `
PCTUS9407433 _ 33 _, r ~ r r 6 6 i-93~
As ring-opened metathesis polymerization results in unsaturated chains, it is occasionally desirable to hydrogenate the resulting copolymers and/or polymer mixtures to make a predominantly saturated polymer mixture. Hydrogenation can improve oxidative and thermal stability.
It is also envisioned that block copolymers and tapered bloc~ copolymers could be made by varying monomer addition, concentrations and other reaction conditions such as temperature and pressure. For example, the catalyst described above can be used to create vinyl terminated polymers or macromonomers.
Such a vinyl terminated polymer could then be combined with cyclic monomers to produce block copolymers and/or long chain branches, depending on the reaction conditions and monomers chosen. There are many combinations of the ring-opened metathesis polymerized monomers and the olefin polymerized monomers that will occur to those of ordinary skill in the art. These combinations are within the scope of this invention and intended to be covered hereby. In particular, intimate blends of 3 to 50 weight percent ring-opening metathesis polymerized polymer with 97 to 50 weight '5 percent Ziegler-Natta polymer are preferred.
It is believed that a hydrogen abstraction, loss, shift or transfer from the alpha carbon of the metal al~yl, or some other occurrence causes the formation of ,0 a metal carbene in the above catalyst systems.
Carbenes produced in this way and present in the system could possibly react with the alpha olefin monomers in non-pol~vmerizing olefin ~etathesis reactions, but these reactions will not adversely affect the ongoing " Zeigler/Natta polymerization. An olefin could cause a chain transfer of a growing ring-opening metathesis A~EN~ S~EEr PCTUS9407433 - 33a r~ ~~
~ 1 6 ~; 1 9 3 polymerization chain leaving an olefin terminated ring-opening metathesis polymerized polymer that could thereafter potentially insert into a growing Ziegler-Natta chain.
, SHE~
- PCTUS9407433 2 ~ ~ 6 1 9 3 `
On the other hand, a growing Ziegler-Natta chain could chain terminate in a terminal olefin that could metathesize with a metal carbene to act as an active ring-opening metathesis polymerization catalyst to yield block copolymers with one block from a ring-opening metathesis polymerization and one block from a Ziegler-Natta polymerization. Thus, this invention also provides for new species~of carbenes based on Ti, Zr and Hf, particularly Zr and Hf. These carbenes may be represented by the formulae: (A-Cp)M=CR(R'), wherein (A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, - disubstituted pnicogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are jolned forming ~ C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
A' is a bridging group, which group may serve to 2j restrict rotation of the Cp and Cp* rings;
M is any group 4, 5, 6, 7 or 8 metal, preferably Ti, Zr of Hf;
R and R' are independently a hydrogen or a C1 to 40 linear, cyclic or branched alkyl, preferably a C
,0 to C20 linear, cyclic or branched alkyl, even more preferably hydrogen, R and R' may be the same or different alkyl groups, although in a preferred - embodiment R and R' are the same alkyl group .
" or n~J SHE~
PCTUS9407433. _ ~5 _ r ~
r r ~ r 216~6193 r ~ --(C5H5yXsx) (A'h M: CR(R') /
JS'(Z1y) wherein A' is a bridging group;
(C5H5_y_XSxj is a cyclopentadienyl ring substituted with from zero to five S radicals each S
being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated o.r unsaturated polycyclic cyclopentadienyl ligand;
x is from 0 to 5 denoting the degree of substitution;
M is any ~roup 4, 5, 6, 7 or 8 metal, preferably titanium, zirconium or hafnium;
JS'(z--1-y) is a heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S' is a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl-substituted organometalloid; and z is the coordination number of the element J;
y ls o or 1;
30 R and R' are independently a hydrogen or a Cl to .
- C40 linear, cyclic or branched alkyl, preferably a C
to C20 linear, cyclic or branched alkyl, even more A~ L,;~II)L~
PCTUS9407~33 - ~6 ~r ,~
2f6~19~ -~ preferably-hydrogen. R and R' may be the same or different alkyl groups, although in a preferred embodiment R and R' are the same alkyl group. Carbenes which are useful in the pr~ctice of this invention, however, include those which can be represented by the formula above where M is any group 4, 5, 6, 7 or 8 metal. Metal carbenes complex with olefins to form metalocycles that are possibly intermediates in metathesis reactions. Metalocycle structures are discussed in detail in "Olefin Metathesis" K.J. Ivin, Academic Press, New York (1989).
For purposes of this invention a Ziegler-Natta polymer is a polymer that has incorporated a 1~ substantial amount of the cyclic monomers into the growing polymer chain resulting in a saturated chain, while maintaining the cyclic aspect of the monomer's - structure. A ring-opening metathesis polymerized polymer is a polymer that has incorporated the cyclic monomers into the growing polymer chain resulting in an unsaturated chain without maintaining the cyclic aspect on the monomer's structure.
ExamPles 2~
Molecular weight (Mw and Mn) were measured by Gel Permeation Chromotography using a Waters 150 gel - permeation chromatograph equipped with a differential refractive index (DRI) detector. The numerical io analyses were performed using the commercially available standard Gel Permeation software package.
- Proton NMR was used to-detect ring-open metathesis ~ polymer and Ziegler-Natta polymer in the same sample.
Procedure:
~4 PCTUS 9 4 0 7 4 3 3 ~ 1 9 3 In general, to demonstrate the ring-opening metathesis p~lymerization using catalyst discussed above, a vial containing 30 to 50 mg dicyclopentadienyl zirconium dimethyl(Cp2ZrMe2) or dicyclopentadienyl S ha~nium dimethyl (Cp2HfMe2), 30 to 60 mg of N,N-dimethylanilinium (DMAH)B(pfp)4 was stirred in 3 ml of toluene until gas evolution has stopped. The catalyst system was then added to 10 to 20 g of freshly sublimed norbornene dissolved in 300 to 400 ml of toluene (freshly distilled from sodium/benzophenone) in a one liter flask in the dry box at room temperature to 80C.
The polymerization was allowed to proceed for 10 to 120 minutes or until the viscosity was such that the mixture flowed slowly or not at all. The 1~ polymerization was killed by adding isopropyl alcohol.
White precipitate was filtered and dried. The proton NMR of the product matched that of commercially available ring-opening metathesis polymerization polynorbornene and the integration of the Qlefinic region indicated that there was o~e olefin per monomer unit. - ~
To demonstrate both Ziegler-Natta and ring-opening metathesis polymerization products from the same catalyst system and reaction pot, the procedure above was repeated except that the reaction was allowed to proceed for O.S to 15 minutes and then transferred to a preheated (40-60 degrees C) two liter autoclave reactor via cannula. The reaction was sealed and propylene was ,0 added (10 to 50 psi) and the reactor was stirred. The polymerization was continued for 1 to 240 minutes and the polymer was precipitated into isopropyl alcohol.
- NMR showed the expected resonances for propylene/norbornene(Zeigler-Natta) copolymer and there 3j were olefinic resonances, not from residual monomer, as well.
AMENDED SHEET
- PCTUS9407433 - 38 - ,~
'2~661g3 The examples are reported in table 1.
Sample Catalyst Activator M ratio Yiel Product (mmole) (mmole) cat/ d Descrip.
act (mg) 1* Cp2ZrMe2 DMAH NB 1 230ROMP
(0.090) B(pfp)4 polymer (0.090) 2* Cp2ZrMe2 DMAH NB .7 682ROMP
(0.090) B(pfp)4 polymer (0.129) 3* Cp2ZrMe2 DMAH NB 2 974ROMP
(0-096) B(pfp)4 polymer (0.047) 4* Cp2HfMe2 DMAH NB 1.5 570ROMP
(-0-15) B(pfp)4 polymer ( 0.10) 5*** Cp2HfMe2 DMAH P/ 1.5 300/mix/ROMP
** B(pfP)4 NB 570 polymer ( 0.08) (~0.05) M = Monomer; NB = norbornene; P = propylene *Runs were at room temperature using 4-~ of norbornene in 10 ml toluene.
**Run was at room temperature using 10g of norbornene in 300 ml of toluene.
***Half was transferred to an autoclave by cannula and run at 40C with 30 psi of propylene and 10g norbornene.
1 mix/ROMP polymer = 300g of a mixture of addition polymer and ROMP polymer and 570 g of ROMP polymer.
The ~MR indicated the presence of propylene/norbornene copolymer with some small - resonances in the olefinic region attributed to the presence of ROMP polynorbornene.
AMENC`ED SHEE~
Claims (19)
1. A method of producing polymer by ring opening metathesis polymerization comprising:
contacting under polymerization conditions a feed consisting essentially of one or more unsaturated cyclic monomers having 5 or more carbon member rings with a catalyst system comprising a an unsubstituted or substituted cyclopentadienyl transition metal complex and a non-coordinating anion.
contacting under polymerization conditions a feed consisting essentially of one or more unsaturated cyclic monomers having 5 or more carbon member rings with a catalyst system comprising a an unsubstituted or substituted cyclopentadienyl transition metal complex and a non-coordinating anion.
2. A method of producing a polymer blend of Ziegler-Natta polymer and ring opening metathesis polymerization polymer comprising:
contacting under one or more cyclic olefin monomers with a catalyst system comprising a cyclopentadienyl transition metal complex and a non-coordinating anion; and contacting under polymerization conditions one or more linear or branched olefins and the same catalyst system or a catalyst system comprising a cyclopentadienyl transition metal complex and a non-coordinating anion.
contacting under one or more cyclic olefin monomers with a catalyst system comprising a cyclopentadienyl transition metal complex and a non-coordinating anion; and contacting under polymerization conditions one or more linear or branched olefins and the same catalyst system or a catalyst system comprising a cyclopentadienyl transition metal complex and a non-coordinating anion.
3. The method of claim 1 or 2 wherein the catalyst system is represented by one of the following formulae:
1. [{[(A-Cp)MX1]+}d]{[B']d-}
2. [{[(A-Cp)MX1L]+}d]{[B']d-}
wherein:
(A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings ;
M is a transition metal selected from the group consisting of Group 4, 5, 6, 7 or 8 transition metals;
X1 is a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, hydrocarbyl-substituted organometalloid radical or halocarbyl substituted organometalloid radical, when L is present said X1 radical may optionally be covalently bonded to all or any or M, S or L, and wherein L is not present, said X1 radical may optionally be bonded to M or S or both M and S;
L is an olefin, diolefin or aryne ligand;
B' is a chemically stable, non-nucleophilic anionic complex; and d is an integer representing the charge of B'.
1. [{[(A-Cp)MX1]+}d]{[B']d-}
2. [{[(A-Cp)MX1L]+}d]{[B']d-}
wherein:
(A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings ;
M is a transition metal selected from the group consisting of Group 4, 5, 6, 7 or 8 transition metals;
X1 is a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, hydrocarbyl-substituted organometalloid radical or halocarbyl substituted organometalloid radical, when L is present said X1 radical may optionally be covalently bonded to all or any or M, S or L, and wherein L is not present, said X1 radical may optionally be bonded to M or S or both M and S;
L is an olefin, diolefin or aryne ligand;
B' is a chemically stable, non-nucleophilic anionic complex; and d is an integer representing the charge of B'.
4. The method of claim 1 or 2 wherein the catalyst system is represented by the formula:
[B']d-wherein:
A' is a bridging group;
(C5H5-y-xSx) is a cyclopentadienyl ring substituted with from zero to five S radicals each S
being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
x is from 0 to 5 denoting the degree of substitution;
M is a transition metal selected from the group consisting of Group 4, 5, 6, 7 or 8 metals, preferably titanium, zirconium or hafnium;
X1 and X2 are independently a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, hydrocarbyl-substituted organometalloid radical or halocarbyl-substituted organometalloid radical, when L
is present said X1 radical may optionally be covalently bonded to all or any of M; S, or L, wherein L is not present said X1 radical my optionally be bonded to M or S or both M and S;
JS'(z-1-y) is a heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S' is a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl-substituted organometalloid; and z is the coordination number of the element J;
y is 0 or 1;
B' is a chemically stable, non-nucleophilic anionic complex; and d is an integer representing the charge of B'.
[B']d-wherein:
A' is a bridging group;
(C5H5-y-xSx) is a cyclopentadienyl ring substituted with from zero to five S radicals each S
being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
x is from 0 to 5 denoting the degree of substitution;
M is a transition metal selected from the group consisting of Group 4, 5, 6, 7 or 8 metals, preferably titanium, zirconium or hafnium;
X1 and X2 are independently a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, hydrocarbyl-substituted organometalloid radical or halocarbyl-substituted organometalloid radical, when L
is present said X1 radical may optionally be covalently bonded to all or any of M; S, or L, wherein L is not present said X1 radical my optionally be bonded to M or S or both M and S;
JS'(z-1-y) is a heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S' is a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl-substituted organometalloid; and z is the coordination number of the element J;
y is 0 or 1;
B' is a chemically stable, non-nucleophilic anionic complex; and d is an integer representing the charge of B'.
5. The method of claim 2 or 3, wherein the cyclic monomer is selected by the group consisting of formula A, B and C wherein:
A is B is C is wherein each Ra through Rs is independently hydrogen, halogen, hydrocarbyl, or halocarbyl: ac and dc are integers of 2 or more and bc and cc are integers of 0 or more.
A is B is C is wherein each Ra through Rs is independently hydrogen, halogen, hydrocarbyl, or halocarbyl: ac and dc are integers of 2 or more and bc and cc are integers of 0 or more.
6. The method of claim 1, 2, 3 or 4 wherein the cyclic monomer is a diene or a polyene.
7. The method of claim 1, 2, 3, or 4 wherein the cyclic monomer is norbornene.
8. The method of claim 1 or 2 wherein the catalyst system is a biscyclopentadienyl group 4 metal compound or a derivative thereof or a monocyclopentadienyl group 4 metal compound or derivative thereof activated by a non-coordinating anion wherein B' is B(C6F5)3Q wherein Q is a hydrocarbyl.
9. The method of claim 3 or 4, wherein B' is N,N- dimethylanilinium tetraperflourophenyl boron.
10. The method of claim 1 further comprising adding a second cyclic olefin after a first cyclic olefin and the catalyst system have been allowed to react.
11. The method of any of the above claims wherein the polymerizations are carried out in series reactors.
12. The method of any of the above claims wherein the polymerizations are carried out in the same reactor.
13. A carbene represented by the formulae:
(A-Cp) M=CR(R') wherein M is titanium, zirconium or hafnium;
(A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings;
R and R' are independently a hydrogen or a C1 to C40 linear, cyclic or branched alkyl;
or wherein A' is a bridging group;
(C5H5-y-xSx) is a cyclopentadienyl ring substituted with from zero to five S radicals each S
being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
x is from 0 to 5 denoting the degree of substitution;
M is titanium, zirconium or hafnium;
JS'(z-1-y) is a heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S' is a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl-substituted organometalloid; and z is the coordination number of the element J;
y is 0 or 1;
R and R' are independently hydrogen or a C1 to C40 linear, cyclic or branched alkyl.
(A-Cp) M=CR(R') wherein M is titanium, zirconium or hafnium;
(A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings;
R and R' are independently a hydrogen or a C1 to C40 linear, cyclic or branched alkyl;
or wherein A' is a bridging group;
(C5H5-y-xSx) is a cyclopentadienyl ring substituted with from zero to five S radicals each S
being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
x is from 0 to 5 denoting the degree of substitution;
M is titanium, zirconium or hafnium;
JS'(z-1-y) is a heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S' is a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl-substituted organometalloid; and z is the coordination number of the element J;
y is 0 or 1;
R and R' are independently hydrogen or a C1 to C40 linear, cyclic or branched alkyl.
14. The carbene of claim 13 wherein M is Hf.
15. The carbene of claim 13 wherein M is Zr.
16. The carbene of claim 13 wherein R and R' are the same or different hydrogen or alkyl groups having 1 to 20 carbon atoms, preferably hydrogen or methyl groups.
17. An intimate blend of ring opening metathesis polymerization polymer and Ziegler-Natta polymer comprising 3 to 50 weight percent ring opening metathesis polymerization polymer produced by any of the above claims.
18. A method of producing block copolymer comprising:
contacting a vinyl terminated macromonomer or vinyl terminated polymer chain with a compound represented by the formulae:
(A-Cp) M=CR(R') wherein M is a transition metal selected from the group consisting of Group 4, 5, 6, 7, or 8 transition metals;
(A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined-forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings;
R and R' are independently a hydrogen or a C1 to C40 linear, cyclic, branched or aromatic alkyl;
or wherein A' is a bridging group;
(C5H5-y-xSx) is a cyclopentadienyl ring substituted with from zero to five S radicals each S
being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
x is from 0 to 5 denoting the degree of substitution;
M is a transition metal selected from the group consisting of Group 4, 5, 6, 7, or 8 transition metals;
JS'(z-1-y) is a heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S' is a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl-substituted organometalloid; and z is the coordination number of the element J;
y is 0 or 1;
R and R' are independently a hydrogen or a C1 to C40 linear, cyclic, branched or aromatic alkyl, to produce a long chain metathesis active metal carbene, thereafter contacting said active metal carbene under ring opening metathesis polymerization conditions with one or more cyclic olefin monomers.
contacting a vinyl terminated macromonomer or vinyl terminated polymer chain with a compound represented by the formulae:
(A-Cp) M=CR(R') wherein M is a transition metal selected from the group consisting of Group 4, 5, 6, 7, or 8 transition metals;
(A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined-forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings;
R and R' are independently a hydrogen or a C1 to C40 linear, cyclic, branched or aromatic alkyl;
or wherein A' is a bridging group;
(C5H5-y-xSx) is a cyclopentadienyl ring substituted with from zero to five S radicals each S
being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
x is from 0 to 5 denoting the degree of substitution;
M is a transition metal selected from the group consisting of Group 4, 5, 6, 7, or 8 transition metals;
JS'(z-1-y) is a heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S' is a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl-substituted organometalloid; and z is the coordination number of the element J;
y is 0 or 1;
R and R' are independently a hydrogen or a C1 to C40 linear, cyclic, branched or aromatic alkyl, to produce a long chain metathesis active metal carbene, thereafter contacting said active metal carbene under ring opening metathesis polymerization conditions with one or more cyclic olefin monomers.
19. A method of producing block copolymer comprising:
contacting cyclic olefins with a compound represented by the formulae:
(A-Cp)M=CR(R') wherein M is a transition metal selected from the group consisting of Group 4, 5, 6, 7 or 8 metals;
(A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings;
R and R' are independently a hydrogen or a C1 to C40 linear, cyclic, branched or aromatic alkyl;
or wherein A' is a bridging group;
(C5H5-y-xSx) is a cyclopentadienyl ring substituted with from zero to five S radicals each S
being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
x is from 0 to 5 denoting the degree of substitution;
M is a transition metal selected from the group consisting of Group 4, 5, 6, 7 or 8 metals;
JS'(z-1-y) is a heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S' is a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl-substituted organometalloid; and z is the coordination number of the element J;
y is 0 or 1;
R and R' are independently a hydrogen or a C1 to C40 linear, cyclic, branched or aromatic alkyl, to produce ring opening metathesis polymerized polymers terminated with a metal carbene or a Zeigler active olefin, thereafter contacting said active olefin or carbene under addition polymerization conditions with one or more olefin monomers.
contacting cyclic olefins with a compound represented by the formulae:
(A-Cp)M=CR(R') wherein M is a transition metal selected from the group consisting of Group 4, 5, 6, 7 or 8 metals;
(A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings;
R and R' are independently a hydrogen or a C1 to C40 linear, cyclic, branched or aromatic alkyl;
or wherein A' is a bridging group;
(C5H5-y-xSx) is a cyclopentadienyl ring substituted with from zero to five S radicals each S
being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
x is from 0 to 5 denoting the degree of substitution;
M is a transition metal selected from the group consisting of Group 4, 5, 6, 7 or 8 metals;
JS'(z-1-y) is a heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S' is a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl-substituted organometalloid; and z is the coordination number of the element J;
y is 0 or 1;
R and R' are independently a hydrogen or a C1 to C40 linear, cyclic, branched or aromatic alkyl, to produce ring opening metathesis polymerized polymers terminated with a metal carbene or a Zeigler active olefin, thereafter contacting said active olefin or carbene under addition polymerization conditions with one or more olefin monomers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8521193A | 1993-06-30 | 1993-06-30 | |
| US085,211 | 1993-06-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2166193A1 true CA2166193A1 (en) | 1995-01-12 |
Family
ID=22190192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2166193 Abandoned CA2166193A1 (en) | 1993-06-30 | 1994-06-30 | A new catalyst for ring-opening metathesis polymerization |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0719294A1 (en) |
| JP (1) | JPH09501191A (en) |
| CA (1) | CA2166193A1 (en) |
| WO (1) | WO1995001388A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5466766A (en) * | 1991-05-09 | 1995-11-14 | Phillips Petroleum Company | Metallocenes and processes therefor and therewith |
| US5821278A (en) * | 1994-11-17 | 1998-10-13 | Ciba Specialty Chemicals Corporation | Process for polymerizing of cyclic olefins and a photopolymerizable composition |
| DE102010048970A1 (en) * | 2010-10-20 | 2012-04-26 | Deutsche Institute Für Textil- Und Faserforschung Denkendorf | Precatalysts for the production of polyolefins and their use |
| US9234985B2 (en) | 2012-08-01 | 2016-01-12 | California Institute Of Technology | Birefringent polymer brush structures formed by surface initiated ring-opening metathesis polymerization |
| WO2014022482A1 (en) * | 2012-08-01 | 2014-02-06 | California Institute Of Technology | Solvent-free enyne metathesis polymerization |
| CN112867741B (en) | 2018-09-20 | 2023-08-01 | 埃克森美孚化学专利公司 | Metathesis catalyst system for polymerizing cycloolefins |
| JPWO2023276873A1 (en) * | 2021-06-28 | 2023-01-05 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5198401A (en) * | 1987-01-30 | 1993-03-30 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
| BR9106589A (en) * | 1990-06-22 | 1993-06-01 | Exxon Chemical Patents Inc | ALUMINUM-FREE MONOCYCLOPENTADYLENE METAL CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
| CA2070654C (en) * | 1990-10-05 | 2003-06-03 | Takuji Okamoto | Process for producing cyclic olefin based polymers, cyclic olefin copolymers, compositions and molded articles comprising the copolymers |
-
1994
- 1994-06-30 JP JP7503660A patent/JPH09501191A/en active Pending
- 1994-06-30 WO PCT/US1994/007433 patent/WO1995001388A1/en not_active Application Discontinuation
- 1994-06-30 EP EP94921445A patent/EP0719294A1/en not_active Withdrawn
- 1994-06-30 CA CA 2166193 patent/CA2166193A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09501191A (en) | 1997-02-04 |
| WO1995001388A1 (en) | 1995-01-12 |
| EP0719294A1 (en) | 1996-07-03 |
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