Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
  • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
• • 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
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/04—Nickel compounds
• • 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
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/04—Nickel compounds
  • C07F15/045—Nickel compounds without a metal-carbon linkage
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
  • C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not

Definitions

• This invention is directed to a method of copolymerizing ethylene with cycloolefin monomers, often referred to as norbornene-type, or NB-type. More specifically, the method employs neutral nickel catalysts and the polymers obtained by the method of this invention are amorphous addition copolymers which may be random or alternating in character.
• Addition copolymers of ethylene and norbornene-type monomers are well known and can be prepared using a variety of catalysts disclosed in the prior art.
• This general type of copolymers can be prepared using free radical catalysts disclosed in U.S. Patent 3,494,897 (Reding et al.); titanium tetrachloride and diethylaluminum chloride as disclosed in East German Patents 109,224 and 222,317 (VEB Leuna); or a variety of vanadium compounds, usually in combination with organoaluminum compounds, as disclosed in European Patent Application No. 156464 (Kajiura et al.). The copolymers obtained with these catalysts are random copolymers.
• U.S. Patent 3,494,897 Reding et al.
• titanium tetrachloride and diethylaluminum chloride as disclosed in East German Patents 109,224 and 222,317
• VB Leuna vanadium compounds, usually in combination with organ
• Patent 4,948,856 issued to Minchak et al. discloses preparing generally alternating copolymers by the use of vanadium catalysts which are soluble in the norbornene-type monomer and a co- catalyst which may be any alkyl aluminum halide or alkylalkoxy aluminum halide.
• European Patent Application No. 0 504 418 Al discloses copolymerization of said monomers in the presence of catalysts such as transition metal compounds, including nickel compounds, and a compound which forms an ionic complex with the transition metal compound or a catalyst comprising said two compounds and an organoaluminum compound.
• metallocene catalysts were used to prepare copolymers of cycloolefins and ⁇ -olefins as disclosed in EP 283,164 (1987) issued to Mitsui Petrochemicals and EP 407,870 (1989), EP 485,893 (1990) and EP 503,422 (1991) issued to Hoechst AG.
• Most recently PCT published application WO96/23010 discloses processes of polymerizing ethylene, ⁇ -olefins and/or selected cyclic olefins which are catalyzed by selected transition metal compounds, including nickel complexes of diimine ligands, and sometimes also a cocatalyst. This disclosure provides, however, that when norbornene or a substituted norbornene is used, no other olefin can be present.
• This method comprises polymerizing said monomers in a diluent or in bulk in the presence of a neutral nickel catalyst which may be represented by the formula
• Y may be a saturated or unsaturated hydrocarbyl chain
• X may be oxygen or sulfur
• E may be phosphorus, arsenic, antimony, oxygen or nitrogen
• R and R' independently each is hydrogen or a hydrocarbyl group
• L is a ligand containing a heteroatom P, N or O or L and R together with L may form part of a chelating structure in which case L is an ethylenic double bond.
• This invention is directed to a new method of preparing substantially amorphous copolymers of ethylene and one or more norbornene (NB)- type comonomers.
• the resulting copolymers may be alternating or random, depending on the relative proportion of each type of monomer used.
• This method comprises copolymerizing said monomers in the presence of a catalyst which is a neutral nickel compound bearing a bidentate ligand which chelates the nickel via two hetero-atoms (which may be the same or different) and a hydrocarbyl group (R) or a hydride.
• Catalysts employed in the method of this invention may be represented by the formula
• Y is a saturated or unsaturated hydrocarbyl chain containing 1 to 3 carbon atoms which may be unsubstituted or substituted with hydrocarbyl groups having up to 20 carbon atoms or functional groups or two adjoining carbon atoms of said hydrocarbyl chain may form part of a cyclic structure, or said hydrocarbyl group may contain a hetero atom;
• X is O or S;
• E is P, As, Sb, N or O;
• R and R independently is H or Q, 2 ⁇ hydrocarbyl group; n is 0, 1 or 2, and
• L is a ligand bearing the heteroatom P, N or O or alternatively L together with R form part of a chelating structure containing a nickel-carbon bond and a neutral two-electron donor moiety.
• E is phosphorus (P)
• X is oxygen (O)
• Y is a hydrocarbyl chain containing 2 or 3 carbon atoms.
• These catalysts can be prepared in advance or may be generated in situ by mixing the ligand with a suitable nickel complex such as bis (cyclooctadiene) nickel.
• a suitable nickel complex such as bis (cyclooctadiene) nickel.
• the above formula I which broadly represents the catalysts useful in the method of this invention, includes the below identified sub-categories of such catalysts.
• These neutral nickel-containing catalysts consist essentially of one or more of the following: 1(a) A dinickel compound of the formula
• R 3 and each R 4 independently, is H or C,. 20 hydrocarbyl; X 1 is O or S; E 1 is P, As or Sb; and
• R 5 and R 6 independently, is H, C,. 20 hydrocarbyl or a functional group selected from -OR 2 , -Cl, -CO 2 R 2 , -CO 2 M, -C(O)N(R 1 ) 2 , -C(O)R 2 , -SR 2 , -SO 2 R 2 , - SOR 2 , -O-SO 2 R 2 , -P(O)(OR 2 ) 2 .
• y (R') v , -CN, -NHR 2 , -N(R 2 ) 2 , -CH— CH 2
• R 5 and R 6 taken together with the carbon atoms to which they are attached, is a substituted or unsubstituted C 5 . 8 alicyclic, C 5 . g heterocyclic or C 6 . 14 aromatic ring, the heteroatom of the heterocyclic ring being selected from O, N and S.
• R 3 , R 4 , R 5 , R 6 , X 1 and E 1 are defined as above and L 1 is a weakly coordinating ligand, or R 3 and L 1 taken together form a group having the structure
• R" is H, C ⁇ . 20 hydrocarbyl or oxyhydrocarbyl or N(R 2 ) 2 wherein each R 2 , independently, is C ⁇ . 20 hydrocarbyl;
• R 1 , R 4 , R 5 , R 6 ' X 1 and E 1 are as defined above; each R 7 , independently, is H, -OSi(R'") 3 , C,. M alkyl or oxyalkyl, C ⁇ aryl, alkaryl, aralkyl or oxyaryl, -N(R 2 ) 2 wherein R 2 is as defined above, or halogen, or both R 7 groups, taken together, form a 5 to 8-membered heterocyclic ring wherein the heteroatom is selected from O, N and S; and each R" ⁇ independently, is C 2Q alkyl or oxyalkyl, C M0 aryl, alkaryl, aralkyl or oxyaryl;
• R 3 , R 4 , R 5 , R 6 , X 1 and E 1 are defined as above and L 2 is a strongly coordinating ligand;
• R 4 , R 5 , R 6 ' X 1 and E 1 are defined as above;
• E, X, R, L and n are as defined above, Z is a double bond or a carbon atom containing one hydrogen or fluorine or one or two C,.
• 20 hydrocarbyl groups provided that one or both hydrocarbyl groups can form a cyclic structure with the carbon atom adjacent to Z, and each of R 5 and R 6 , independently, is H, C,. 20 hydrocarbyl or a functional group selected from -OR 2 , -Cl, -CO 2 R 2 , -CO 2 M, -
• R 5 and R 6 taken together with the carbon atoms to which they are attached, is a substituted or unsubstituted C 5 . 8 alicyclic, C 5 . g heterocyclic or C 4 . 14 aromatic ring, the heteroatom of the heterocyclic ring being selected from O, N and S.
• C- may have the following structures
• hydrocarbyl is meant an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic monovalent radical, optionally containing one or more "polar substituents" and/or one or more in-chain heteroatoms which are inert under polymerizing conditions.
• hydrocarbyl groups may contain one or more straight chain or branched alkyl substituents having 1 to 12 carbons and more practically 1 to 6 carbons; or one or more halogen substituents, more practical of which are chlorine and fluorine; or one or more other type of substituents such as -CN, -CO 2 R 2 , -R 2 OR 2 , -OR 2 , -CON(R 2) 2 , and the like.
• the heterocyclic groups may also contain one or more of the above mentioned substituents.
• hydrocarbyl groups are various simple straight chain and branched alkyl groups as well as the alkyl groups substituted with the above mentioned substituents which may be exemplified by chloroethyl group, fluoromethyl, perfluoroethyl, 6-fluorohexyl, pentafluorophenyl, tris(trifluoromethyl)phenyl and the like; f ⁇ iranyl, pyrrolyl, thiophenyl, dihydrofuranyl, pyrrolinyl, tetrahydrofuranyl, pyrrolidinyl, mono or dimethylpyrrolyl as well as such and similar heterocyclic groups which are substituted by the above mentioned substituents.
• polar substituents is meant polar radicals or groups which are unreactive under polymerizing conditions.
• Functional substituents include, but are not limited to, such groups as -OH, OR 2 , -Cl, -CO 2 R 2 , -CO 2 M, -C(O)N(R 1 ) 2 , - C(O)R 2 , -SR 2 , -SOR 2 , -SO 2 R 2 , -OSO 2 R 2 , -P(O)(OR 2 ) 2 .
• y (R') y -CN, -NHR 2 , - N(R 2 ) 2 , -CH— CHR 1 O
• in-chain is intended to include both the main (backbone) chain and any side chain.
• Preferred in-chain heteroatoms are -O-, -N- and -S-.
• weakly coordinating ligand (L 1 ) is meant a compound which can bond to nickel, but is readily displaced therefrom by the olefin which is being polymerized.
• Weakly coordinating ligands (L 1 ) include, but are not limited to pyridine, piperidine, dialkyl ethers, tetrahydrofuran, alkyl and aryl nitriles and dinitriles, alcohols, amides, aliphatic esters and tertiary amines.
• the chain length of the alkyl groups are not critical and usually will have 1 to 20 atoms and the aryl groups will usually have 6 to 14 carbon atoms.
• strongly coordinating ligand (L 2 ) is means a compound which can bond to nickel sufficiently strongly to displace therefrom part or all of the olefin which is being polymerized.
• Strongly coordinating ligands (L 2 ) include, but are not limited to, compounds of the formula E'(R') 3 wherein E 1 and R 1 are as defined above.
• acceptor compound is meant a compound which reacts with or competitively bonds (complexes) with ligand L 1 or L 2 .
• Acceptor compounds include, but are not limited to organic oxidants, such as amine oxides, peroxides, hydroperoxides, and alkylating compounds which oxidize the ligand rendering it less effective in complexing the catalytic metal. Such oxidants can be used effectively, for example, with phosphines which are oxidized to the corresponding phosphine oxides which are less effective complexants.
• Further acceptor compounds include and Group VIII metal complexes and Lewis acids. These compounds can bond reversibly or irreversibly with a ligand.
• oxidants include trimethylamine oxide, di-t-butylperoxide, cyclohexylhydroperoxide, methyl iodide, trimethylsilyl iodide and the like.
• Group VIII metals and Lewis acids are bis(benzonitrile)- palladium dichloride, bis(l,5-cyclooctadiene)nickel(0), nickel tetracarbonyl, 2,4- pentanedionatobis(ethylene)rhodium(I), methylaluminumbis(2,6-di-tert-butyl-4- methylphenoxide) and ethylene pentacarbonylchromium(O).
• alkylating or arylating compound is meant a compound which is capable of chemically transferring alkyl and/or aryl groups, as the case may be, to nickel.
• Alkylating and arylating compounds include, but are not limited to, alkyl and aryl iodides, aluminum alkyls and aryls, transition metal alkyl- and aryl- containing compounds, such as dimethyl(l,5-cyclooctadiene)-platinum(II) and dimethylbis(phosphine)nickel, and other conventional reagents capable of transferring alkyl and/or aryl groups.
• Additional nickel-containing compounds that may be used as catalysts in the method of this invention may be represented by the formula: O
• Ph is a phenyl group which may be unsubstituted or substituted with up to three alkyl groups having 1 to 8 carbon atoms.
• This class of compounds is disclosed in GB Patent 1,364,870 which is incorporated herein by reference.
• Also useful compounds are nickel compounds containing chelating ligands bearing nitrogen and oxygen, such ligands being exemplified by 8- hydroxyquinoline, o-aminophenol and o-aminobenzoic acid.
• auxiliary ligand L are: triphenylphosphine; triphenylphosphine methylene ylid; triphenylphosphite; tris(2,4-di-t-butylphenyl)phosphite; pyridine; triphenylphosphine oxide; tris(o- tolyl)phosphine, and the like.
• L can also be the "complex itself in which X acts as the heteroatom, i.e., a dimer.
• X acts as the heteroatom
• a dimer a dimer of the nickel catalysts
• the catalysts of this invention can be conveniently prepared by methods well-documented in the literature.
• the catalysts can be prepared in situ by reacting a suitable nickel compound with the desired ligand, optionally in the presence of a metal alkyl (e.g. triethylaluminum and the like) or a metal hydride (e.g. sodium borohydride and the like).
• a preferred method of generating an active catalyst in situ is to react bis(cyclooctadiene)nickel with an active hydrogen containing chelate ligand such as hexafluoroacetylacetone or (o- C 6 H 4 COOH)diphenylphos ⁇ hine.
• Catalysts G and J can be prepared by addition of chelating ligands containing phosphine and ketonic functionality to a stable bis(pentafluorophenyl)nickel complex, either the toluene, bis(tetrahydrofuran), or the bis(diethylether) complex.
• the intermediate bis(pentafluorophenyl)nickel chelate complex undergoes proton transfer (either inter- or intramolecular) from the chelate ligand to the pentafluorophenyl ligand thus forming pentafluorobenzene and the expected dimers G and J .
• the nickel catalyst is suitably employed as an unsupported material.
• the nickel catalyst can be supported on an inorganic, solid catalyst carrier which is normally solid under reaction conditions and is heterogeneous, i.e., is substantially insoluble in the reaction medium.
• suitable inorganic, solid catalyst carriers are inorganic acidic oxides such as alumina and inorganic materials known as refractory oxides.
• Suitable refractory oxides include synthetic components as well as acid treated clays and similar materials such as kieselguhr or crystalline macroreticular aluminosilicates known in the art as molecular sieves.
• synthetic catalyst carriers are preferred over natural occurring materials or molecular sieves.
• Exemplary synthetic catalyst carriers include alumina, silica-alumina, silica-magnesia, silica-alumina-titania, silica-alumina-zirconia, silica-titania-zirconia, silica-magnesia-alumina, and the like.
• Particularly preferred catalyst carriers are siliceous refractory oxides containing up to 90% by weight of alumina, especially silica and silica-alumina.
• the proportion of catalyst composition to carrier is not critical. In general, proportions of catalyst composition from 0.01% to 70% by weight, based on the catalyst carrier are satisfactory, with amounts of from 0.1% to 20% by weight, calculated on the same basis, being preferred.
• the catalyst composition is introduced onto the carrier in any suitable manner.
• the supported catalyst composition is prepared by intimately contacting the preformed catalyst composition and the carrier in an inert diluent, preferably the same inert diluent employed for preparing the catalyst composition.
• the catalyst composition can be prepared directly on the catalyst carrier support surface by contacting the catalyst composition precursors in the presence of the catalyst carrier in a suitable inert diluent.
• the copolymers of the present invention are essentially amorphous and may be alternating or random, depending on the choice of catalyst and/or the ratio or the relative concentration of the monomers used.
• the monomers may be incorporated into the polymer in an amount of from about 1 mole % to about 80 mole % of at least one NB- type monomer, preferably from about 4 to about 65 mol per cent and most preferably from about 40 to about 60 mole per cent of the NB-type monomer.
• the corresponding balance of the monomer, to make up 100 percent, is ethylene.
• the amount of each comonomer may be selected depending on the desired properties of the resulting copolymer. For example, if a polymer having a higher glass transition temperature is desired, such as between 120°C to
• alkylnorbornenes all give lower Tg's than does norbornene itself at a given level of incorporation, with longer alkyl chains giving successively lower Tg's.
• polycyclic norbornene-type monomers give higher Tg's than does norbornene for a given level of incorporation.
• tetracyclododecene gives a Tg in the range of 120 to 160°C at only 25 to 35 mole
• % incorporation (compared to 40 to 60 mole % in the case of norbornene). Furthermore, it is possible to control the glass transition temperature by using a mixture of different NB-type monomers. More specifically, by replacing some norbornene with a substituted norbornene, such as alkyl norbornene, a lower Tg polymer results as compared to the copolymer if only norbornene were used. Catalysts of formula I where E is phosphorus and X is oxygen have been found to preferably yield essentially alternating copolymers of norbornene and ethylene. Nevertheless at extremely high ratio of either one monomer over the other deviations from this alternating compositions are observed. When substituted norbornenes are employed, higher concentrations of the norbornenes are required to obtain the alternating compositions.
• the polymerizations of this invention may be carried out in bulk or in a diluent. If the catalyst is soluble in the NB-type monomer being copolymerized, it may be convenient to carry out the polymerization in bulk. More often, however, it is preferable to carry out the copolymerization in a diluent. Any organic diluent or solvent which does not adversely interfere with the catalyst and is a solvent for the monomers may be employed.
• organic solvents examples include aliphatic (non- polar) hydrocarbons such as pentane, hexane, heptane, octane, decane and the like; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and the like; halogenated (polar) hydrocarbons such as methylene chloride, ethyl chloride, 1,1-dichloroethane, 1,2- dichloroethane, 1 ,2-dichloroethylene,
• the instant method is unique in that it makes it possible to prepare copolymers of ethylene with NB-type monomers containing functional substituents such as esters, ethers or silyl groups as disclosed below in greater detail.
• the catalysts employed in the prior art in the polymerization of cyclic olefins were deactivated if such monomers contained functional substituents.
• the copolymers may be prepared from 0 to 100 per cent of functional NB- type monomers or the NB-type monomers may contain 1 to 99 per cent of nonfunctional and 1 to 99 per cent of functional NB-type monomers. Practical categories of terpolymers are those containing 1 to 10 per cent of functional NB- type monomers or those containing 20 to 50 percent of functional NB-type monomers.
• copolymers which contain 100 percent of one or more functional NB-type monomer(s). Due to the presence of functionality such copolymers possess exceptionally good adhesion and paintability properties.
• the copolymers of the present invention are essentially amorphous and include those that are substantially alternating as well as those that are largely random. Those copolymers which contain close to 50:50 mole ratio of each category of monomers will tend to be largely alternating.
• These copolymers are essentially amorphous in nature and exhibit glass transition temperatures in the range of approximately 0° C to 200° C, preferably 80 °C to 180°C and most preferably 100°C to 150°C.
• the copolymers range in molecular weight (Mw) from about 1,000 to about 250,000, often from about 2,000 to about 150,000 and preferably from about 5,000 to about 125,000. Furthermore, essentially every copolymer chain is terminated with a vinyl end group originating from ⁇ -hydride elimination from the ultimate ethylene unit.
• copolymers prepared according to the method of this invention are generally amorphous, with low crystallinity. Consequently, they are transparent. Additionally, these copolymers have relatively low density, low birefringence and low water absorption. Furthermore, they have very desirable vapor barrier properties and good resistance to hydrolysis, acids and alkali and to weathering; very good electrical insulating properties, thermoplastic processing characteristics, high stiffness, modulus, hardness and melt flow. Accordingly, these copolymers may be used for optical storage media applications such as CD and CD-ROM, in optical uses such as lenses and lighting articles, in medical applications where gamma or steam sterilization is required, as films and in electronic and electrical applications.
• NB-Type Monomers are generally amorphous, with low crystallinity. Consequently, they are transparent. Additionally, these copolymers have relatively low density, low birefringence and low water absorption. Furthermore, they have very desirable vapor barrier properties and good resistance to hydrolysis, acids and alkali and to weathering; very good electrical insulating
• This category of monomers are the NB-type monomers which are polycyclic and contain at least one norbornene-moiety and may be selected from those represented by the formula below:
• R 1 to R 4 independently represents hydrogen, linear or branched (C, to C 10 ) alkyl, aromatic or saturated or unsaturated cyclic groups; a functional substituent selected from the group -(CH 2 ) n -C(O)OR, -(CH 2 ) n -OR, -(CH 2 ) n - OC(O)R, -(CH 2 ) n -C(O)R and -(CH 2 ) n -OC(O)OR, -(CH 2 ) n C(R) 2 CH(R)(C(O)OR),
• R represents hydrogen, or linear and branched (C, to C ⁇ 0 ) alkyl; or a silyl substituent represented as follows:
• R 5 independently represents hydrogen, methyl, or ethyl
• R 6 , R 7 , and R 8 independently represent halogen selected from bromine, chlorine, fluorine, and iodine, linear or branched (C, to C 20 ) alkyl, linear or branched (C, to C 20 ) alkoxy, linear or branched (C, to C 20 ) alkyl carbonyloxy (e.g., acetoxy), linear or branched
• (C, to C 20 ) alkyl peroxy e.g., t-butyl peroxy
• any of R 1 and R 2 or R 3 and R 4 can be taken together to form a (C, to C 10 ) alkylidenyl group
• m is an integer from 0 to 5
• n is an integer from 0 to 10, preferably n is 0.
• the silyl substituent could also be -(CH 2 ) n -O-SiR 6 R 7 R 8 where n and the R groups are as defined above.
• R 1 and R 4 taken together with the two ring carbon atoms to which they are attached represent a saturated cyclic group of 4 to 8 carbon atoms.
• the cyclic group formed by R 1 and R 4 can be substituted by at least one of R 2 and R 3 , the definition of which is set forth above.
• the NB-type monomers which contain one or more functional substituents are referred to as functional NB-type monomers.
• B is a -CH 2 - group and q is a number from 2 to 6. It should be apparent that when the carbon atom in the -CH 2 - group represented by B is substituted by R 2 or R 3 (i.e., R 2 and R 3 are other than hydrogen), the -CH 2 - group will have one less hydrogen atom attached thereto.
• Polycyclic monomers of the above formula with a substituent selected from the group -(CH 2 ) n C(R) 2 CH(R)(C(O)OR) or -(CH 2 ) n C(R) 2 CH(C(O)OR) 2 can be represented as follows:
• m is preferably 0 or 1, more preferably m is 0.
• m is 0 the preferred structure is represented as follows:
• R 1 to R 4 are previously defined.
• suitable monomers include 2-norbornene, 5-butyl-2-norbornene, 5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2- norbomene, 5-phenyl-2-norbornene, 5-naphthyl-2-norbornene 5-ethylidene-2- norbornene, vinylnorbornene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, methyltetracyclododecene, tetracyclododecadiene, dimethyltetracyclododecene, ethyltetracyclododecene, ethylidenyl tetracyclododecene, phenyltetracyclododecene, trimers of cyclopentadiene (e.g., 2-nor
• Catalyst D This catalyst was synthesized using a procedure published previously in Angew. Chem., Int. Ed Engl. 1985, 24, 599.
• Synthesis of Catalyst E This catalyst was synthesized by reacting catalyst I (0.76 g) with Rh(acetylacetonate)(C 2 H 4 ) 2 (0.14 g) in a minimum amount of toluene (about 25 mL). After stirring the mixture for 4 hours, the precipitated solid was filtered and dried overnight in vacuo to yield 0.48 g of a yellow-brown solid.
• the terpolymer product precipitated from solution and was filtered and washed with excess methanol. After drying to constant weight (overnight in a vacuum oven at ambient temperature) the yield of terpolymer amounted to 24.0 grams. GPC showed the terpolymer to have an Mw of 41,500 and an Mn of 18,600.
• NMR revealed the composition to be ethylene, 57.6 mole percent, norbornene, 40.6 mole percent and triethoxysilylnorbornene, 1.8 % mol.
• the incorporation of ethylene was determined to be 51 mole percent by NMR spectroscopy. Glass transition temperature was determined to be l23°C by DSC.
• Polymerization Example 14 To a clean, dry 500 mL stainless steel reactor 40.0 g of norbornene in 150 mL of dry, deoxygenated toluene was added under nitrogen. The reactor was allowed to remain at ambient temperature. To the reactor was added a solution of catalyst E (0.047 g, 0.053 mmol) and methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (0.047 g, 0.1 1 mmol) in a minimum amount of toluene. The reactor was then pressurized to 50 psig with ethylene.
• catalyst E 0.047 g, 0.053 mmol
• methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) 0.047 g, 0.1 1 mmol
• Polymerization Example 18 To a clean, dry 500 mL stainless steel reactor 20.0 g of norbornene in 150 mL of dry, deoxygenated toluene was added under nitrogen.
• the reactor was allowed to remain at ambient temperature. To the reactor was added a solution of catalyst E (0.047 g, 0.053 mmol) and triethylaluminum (0.55 mL of a 1 M solution in cyclohexane) in a minimum amount of toluene. The reactor was then pressurized to 100 psig with ethylene. The reaction was allowed to proceed 2 h at which time the ethylene pressure was vented, the reactor was lowered and the solution was poured into an excess of MeOH to precipitate the polymer. The mixture was allowed to evaporate. Yield 0.22 g.
• the reactor temperature was allowed to remain at ambient temperature.
• Catalyst F (0.061 g) and Ni(COD) 2 (0.030 g) in a minimum amount of toluene were mixed and then added to the reactor.
• the reactor was then pressurized to 100 psig with ethylene.
• the reaction was allowed to proceed 2 h at which time the ethylene pressure was vented, the reactor was lowered and the solution was added to an excess of MeOH and then allowed to evaporate overnight. Yield 2.2 g. Polymerization Example 24.
• the terpolymer product precipitated from solution and was filtered and washed with excess methanol. After drying to constant weight (overnight in a vacuum oven at ambient temperature) the yield of terpolymer amounted to 5.0 grams. Proton NMR showed the terpolymer to comprise 52 mole percent ethylene, 44 mole percent norbornene and 4 mole percent triethoxysilylnorbornene.
• Mw 40,770 and the Mn 21,430.
• Catalyst C (0.11 g, 0.212 mmol)in a minimum amount of toluene was then added to the reactor.
• the reactor was then pressurized to 300 psig with ethylene.
• the reaction was allowed to proceed 2 h at which time the ethylene pressure was vented, the reactor was lowered and the solution was added to an excess of MeOH.
• the te ⁇ olymer product precipitated from solution and was filtered and washed with excess methanol. After drying to constant weight (overnight in a vacuum oven at 80°C) the yield of te ⁇ olymer amounted to 23.3 grams.
• Proton NMR confirmed the inco ⁇ oration of all three monomers and the GPC data revealed the Mw to be 39,000 and the Mn 19,350.
• the reaction was allowed to proceed 1 h at which time the ethylene pressure was vented, the reactor was lowered and the solution was added to an excess of MeOH.
• the copolymer product precipitated from solution and was filtered and washed with excess methanol. After drying to constant weight (overnight in a vacuum oven at 80°C) the yield of copolymer amounted to 6.5 grams.
• Proton NMR confirmed the product to be a copolymer of ethylene and norbornene and the GPC data revealed the Mw to be 15,200 and the Mn 9,500.
• the glass transition temperature was determined to be 210°C by DSC.
• the copolymer contained 59 mole percent of ethylene according to NMR spectroscopy. Glass transition temperature was determined to be 132°C by DSC.
• the reactor temperature was allowed to remain at ambient temperature and the reactor was saturated with ethylene.
• To the reactor was added bis(cyclooctadiene)nickel (0.244 g, 0.88 mmol) in toluene (4 mL.) followed by hexafluoroacetylacetone (0.14 mL, 1.0 mmol).
• the reactor was then pressurized to 250 psig with ethylene.
• the reaction was allowed to proceed 2 h at which time the ethylene pressure was vented, the reactor was lowered and the solution was poured into an excess of MeOH to precipitate the polymer which was subsequently filtered and dried in a vacuum oven overnight. The filtrate was allowed to evaporate and additional polymer was isolated. Yield 6.5 g.
• the reactor temperature was allowed to remain at ambient temperature and the reactor was saturated with ethylene.
• a mixture of bis(cyclooctadiene)nickel (0.244 g, 0.88 mmol) and hexafluoroacetylacetone (0.14 mL, 1.0 mmol) in toluene (2 mL.) which had first been allowed to stand at 10 minutes.
• the reactor was then pressurized to 400 psig with ethylene.
• the reaction was allowed to proceed 2 h at which time the ethylene pressure was vented, the reactor was lowered and the solution was poured into an excess of MeOH to precipitate the polymer which was subsequently filtered and dried in a vacuum oven overnight. The filtrate was allowed to evaporate and additional polymer was isolated.
• Example 47-69 Polymerization Examples 47-69. In the examples listed in the following table the procedure of Example 4 was followed. In every case catalyst C was employed. The amount of norbornene used is listed, and the norbornene was diluted to a total volume of 150 mL in the noted solvent. The molar ratio of norbornene to catalyst is listed as is the reaction temperature.

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