MXPA06007479A - Ltmc polymerization of unsaturated monomers - Google Patents

Abstract

A process for polymerizing unsaturated monomers is disclosed. The process comprises polymerizing, in the presence of a late transition metal catalyst (LTMC), a variety of unsaturated monomers which are traditionally, some of which are exclusively, made by free radical polymerizations. The LTMC polymerization provides the polymer with improved properties such as no free radical residue and narrow molecular weight distribution.

Description

POLYMERIZATION OF SINGLE BATTERIES INSATURAPOS WITH LTMC FIELD OF THE INVENTION The invention relates to polymerization of unsaturated monomers. More particularly, the invention relates to the polymerization of unsaturated monomers with late transition metal catalysts (LTMC).

BACKGROUND OF THE INVENTION The chain polymerization of unsaturated monomers can be divided into free radical, ionic, and coordination polymerizations. The ionic polymerization includes anionic and cationic polymerizations. Cationic polymerization is usually initiated by means of Lewis acids, such as BF3. Polyisobutylene rubber is the important polymer commercially made by cationic polymerization. The anionic polymerization is usually initiated by alkyl trio such as n-BuLi. Many anionic polymerizations lack any termination reaction, and therefore are called "living" polymerization. The living anionic polymerization has led to the creation of thermoplastic elastomers such as SBS (styrene-butadiene-styrene block copolymers). Coordination polymerization includes the Ziegler-Natta polymerization and the metallocene polymerization in a single site. The Ziegler-Natta polymerization is carried out with zirconium or titanium salts, such as TiCl 4, ZrCl 4 > and VCI4, as catalysts, and aluminum and alkyl compounds, such as trimethyl aluminum, as co-catalysts. The metallocene catalyst was discovered by Kaminski at the beginning of the 1980s (see U.S. Patent Nos. 4,404,344 and 4,431,788). The metallocene catalyst comprises a transition metal complex having one or more cyclopentadienyl ligands (Cp). Unlike the Ziegler-Natta catalysts, which have multiple active polymerization sites, the metallocene catalysts have a single polymerization site, and are therefore called "single-site" catalysts. Many non-metallocene single-site catalysts have also been developed in the past decade. Among the chain polymerizations, polymerization by free radical is the most widely used in the polymer industry. Commonly used free radical initiators include peroxides, azo compounds, and persulfates. Unlike ionic initiators or coordination catalysts, which require restricted conditions such as reaction systems free of moisture and impurities, free-radical polymerization can tolerate functional monomers such as hydroxyl, carboxyl and amino monomers. Thus, free radical polymerizations are used exclusively to make acrylic hydroxyl resins, polyacrylic acid, olefin-acrylic copolymers, and many other functional polymers. Since the late 1990s, catalysts for the polymerization of olefins incorporating late transition metals (especially iron, nickel or cobalt) and bulky α-diimino ligands (or "bis (imines)") have been investigated. These late transition metal catalysts (LTMC) are of interest because, unlike the early transition metal metallocenes or Ziegler catalysts, the LTMC may incorporate alkyl acrylate co-monomers in polyolefins. See U.S. Patent Nos. 5,866,663 and 5,955,555. However, the LTMC is considered to be a coordination catalyst, and therefore the study of the LTMC has been limited to olefin-related polymerizations. No prior art describes the use of LTMC to make acrylic hydroxyl resins, styrene-allyl alcohol copolymers, and many other important functional polymers. No previous act describes the use of LTMC for the polymerization of unsaturated monomers in the absence of olefins. Compared to free radical polymerization, LTMC have great potential to adjust to the critical properties of polymers: molecular weight, crystallinity or melting point, and poly dispersion. Therefore, LTMCs can provide better product quality and production consistency. Also, LTMCs do not require high temperature and high pressure for polymerization. This avoids the use of explosive peroxides or azo compounds. Thus, polymerization with LTMC can provide a more cost-effective alternative to existing technology with free radicals. In summary, it is obviously important to explore the use of LTMC for the polymerization of unsaturated monomers that have been traditionally polymerized, and some exclusively, by free radical polymerizations.

BRIEF DESCRIPTION OF THE INVENTION The process of the invention contains unsaturated monomers in the presence of a late transition metal catalyst (LTMC). The LTMC contains a late transition metal complex of group 8-10 and an activator. By "complex" we mean compounds that contain a group of metals 8-10 and at least one stable ligand for polymerization, which remains attached to the metal during the course of the polymerization process. the process includes polymerization of one of the groups of monomers (a) through (f): (a) a vinyl monomer selected from the group consisting of vinyl aromatics, vinyl ethers, vinyl esters, and vinyl halides; (b) a vinyl monomer selected from the group consisting of vinyl ethers, vinyl esters, and vinyl halides, and at least one olefin; (c) a hydroxy functional monomer selected from the group consisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates, allyl alcohols, and alkoxylated allylic alcohols, and at least one alkyl or aryl acrylate, or at least one alkyl or methacrylate aril; (d) a hydroxy functional monomer selected from the group consisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates, allyl alcohols, and alkoxylated allyl alcohols, at least one alkyl or aryl acrylate or at least one alkyl or aryl methacrylate, and at least one olefin; (e) a hydroxy functional monomer selected from the group consisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates, allyl alcohols, and alkoxylated allyl alcohols, and at least one aromatic vinyl monomer; or (f) a hydroxy functional monomer selected from the group consisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates, allyl alcohols, and alkoxylated allyl alcohols, at least one vinyl aromatic monomer, and at least one olefin.

DETAILED DESCRIPTION OF THE INVENTION The process of the invention is to polymerize unsaturated monomers with a late transition metal catalyst (LTMC). The LTMC contains a complex of late transition metals of group 8-10 and an activator. The LTMCs include those that are known in the art. Late transition metal complexes have the general structure: LM (X) n M is a late transition metal of group 8-10.

Preferably, the M is selected from the group consisting of Ni, Co and Fe. More preferably, the M is Ni or Fe. Much more preferably, the M is Fe. The L is a stable ligand in the polymerization. By "stable ligand in the polymerization" we mean that the ligand remains attached to the metal during the course of the polymerization process. Preferably, the L is an isoindoline or bis (imine). Suitable ligands L also include those mentioned in U.S. Patent Nos. 5,714,556 and 6,620,759. X is a labile ligand. By "labile ligand" we mean that the ligand is easily displaceable during polymerization. Preferably, L is independently selected from the group consisting of hydrogen and halides, and n the amount of ligands X, is greater than or equal to 1. Suitable isoindoline ligands include those presented by the copending patent application together with this, number 09 / 947,745, presented on September 6, 2001. Preferably, the isoindoline ligands have the general structure: When a late transition metal complex is being formed, the hydrogen of the N-H group can be removed to form an ionic bond between the nitrogen and the late transition metal. Optionally, the hydrogen atoms of the aromatic ring of the above structure are independently replaced. Suitable substitute groups in the ring include alkyl, aryl, aralkyl, alkylaryl, silyl, halogen, alkoxy, aryloxy, siloxy, nitro, dialkylamino, diarylamino groups, and the like. A is an aryl or heteroaryl group. When A is aryl, it is preferably substituted with phenyl or with alkyl, such as 4-methylphenyl or 2,4,6-trimethylphenyl (2-mesityl). When A is heteroaryl, it is preferably 2-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl, 2-imidazolyl, 2-thiazolyl, or 2-oxazolyl. The aryl and heteroaryl groups can be fused with other rings, such as a 2-naphthyl, 2-benzothiazolyl or 2-benzimidazolyl group. A few examples of isoindolines appear below: Bis (imine) ligands include those shown in U.S. Patent No. 5,866,663. Suitable bis (imine) ligands include those having the general structure: wherein R1 and R4 are each independently hydrocarbyl or substituted hydrocarbyl. R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R2 and R3 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring. Suitable bis (imine) ligands include those having the general structure R6 is hydrocarbyl or substituted hydrocarbyl, and R6 is hydrogen, hydrocarbyl or substituted hydrocarbyl, or R5 and R6 taken together form a ring. R9 is hydrocarbyl or substituted hydrocarbyl, and R8 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R9 and R8 taken together form a ring. Each R7 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R7 taken together form a ring; n is 2 or 3. Suitable bis (imine) ligands include bis (imines) of 2,6-pyridinecarboxaldehyde and bis (2,6-diacylpyridine imines, which are mentioned, for example, in U.S. Patent No. 5,955,555. Suitable bis (imine) ligands also include bis-N, N '- (2,6-diisopropylphenyl) imines of acenaphthene, which are presented, for example, in U.S. Patent No. 6,127,497. Suitable activators include alumoxane and alkylaluminum compounds Examples of alumoxane compounds include methyl alumoxane (MAO), polymeric MAO (PMAO), ethyl alumoxane, diisobutyl alumoxane, and the like Examples of suitable alkylaluminum compounds include triethylaluminum, diethylaluminum chloride, trimethylaluminum, triisobutyl aluminum, and the like. Suitable alumoxane compounds also include those that are modified The methods for the modification of alumoxanes are known, for example, U.S. Patent No. 4,990.6 40 teaches the modification of alumoxanes with active compounds containing hydrogen, such as ethylene glycol. U.S. Patent Number, 340, 771 teaches the modification of MAO with sugar to make "sweet" MAO. Also, U.S. Patent No. 6,340,771 teaches the modification of alumoxanes with cetyl alcohols and β-diketones. Suitable activators also include acid salts that contain non-nucleophilic anions. These compounds generally consist of bulked ligands bound to boron or aluminum. Examples include lithium tetracis (pentafluorophenyl) borate, tetracis-pentafluorophenyl) lithium aluminate, anilinium tetracis (pentafluorophenyl) borate, and the like. Suitable activators further include organoboranes, which are boron compounds and one or more alkyl, aryl or aralkyl groups. Suitable organoborans include substituted and unsubstituted trialkyl and triaryl boranes, such as tris (pentafluorophenyl) borane, triphenylborane, tri-n-octylborane, and the like. Suitable organoborane activators are described in U.S. Patent Nos. 5,153,157, 5,198,401, and 5,241,025. Suitable activators also include aluminoboronates, which are the reaction products of alkyl and aluminum compounds and organoboronic acids. These activators are described in U.S. Patent Nos. 5,414,180 and 5,648,440. The late transition metal complex, the activator or both, are supported on a solid or organic inorganic polymeric support. Suitable supports include silica, alumina, silica-aluminas, magnesiums, titaniums, clays, zeolites, or the like. The support is preferably heat treated, chemically or both before use to reduce the concentration of surface hydroxyl groups. The heat treatment consists of heating (or "calcination") the support in a dry atmosphere at an elevated temperature, preferably greater than about 100 ° C, and more preferably from about 150 ° C to about 600 ° C., Before its use. A variety of different chemical treatments can be used, including reaction with organoaluminum, magnesium, silicon or boron compounds. See, for example, the techniques described in U.S. Patent No. 6,211,311. The invention includes a process for polymerization, in the presence of LTMC, a vinyl monomer selected from the group consisting of aromatic vinyls, vinyl ethers, vinyl esters, vinyl halides, and the like, and mixtures thereof. Surprisingly, we find that those vinyl monomers, which are traditionally polymerized by free radical polymerization, can be easily polymerized by the LTBC without the presence of some olefin co-monomer. Suitable vinyl aromatic monomers preferably have a group -CR '= CH2 connected to an aromatic group. R 'is hydrogen or an alkyl group of 1 to 10 carbon atoms. Examples of suitable vinyl aromatic monomers are styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene. , pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl-methyl-styrene, 4-fluoro-3-trifluoromethylstyrene, 9-vinylanthracene, 2-vinylnaphthalene, the like and mixtures thereof. Styrene is particularly preferred. Suitable vinyl ethers include alkyl vinyl ethers, aryl vinyl ethers and mixtures thereof. Examples of suitable alkylvinyl ethers are methyl vinyl ether, ethyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropylvinyl ether, 2-ethylbutylvinyl ether, hydroxyethyl vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetahydrofufuryl vinyl ether, and the like, and mixtures thereof. Examples of suitable vinyl amyl ethers are vinylphenyl ether, vinyl tolyl ether, vinylchlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, and the like, and mixtures thereof. Suitable vinyl halides include ethylene substituted by halogen. Examples are vinyl chloride, vinyl fluoride, vinylidene chloride, chlorotrifluoroethylene, the like and mixtures thereof. The invention includes a process for polymerizing an olefin and a vinyl monomer selected from the group consisting of vinyl ethers, vinyl ethers, vinyl halides, the like and mixtures thereof. Suitable vinyl ethers, vinyl esters and vinyl halides are described above. Suitable olefins include α-olefins, cyclic olefins, and mixtures thereof. Preferred are α-olefins of 2 to 10 carbon atoms, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and mixtures thereof, are particularly preferred. Ethylene and propylene are most preferred. The invention includes a process for polymerizing a hydroxy functional monomer selected from the group consisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylate, allyl alcohols, alkoxylated allyl alcohols, and mixtures thereof, and an alkyl or aryl acrylate or a methacrylate alkylaryl ,. Suitable hydroxyalkyl acrylates and methacrylates include acrylate and hydroxyethyl methacrylate. Suitable allyl alcohols are alkoxylated allylic alcohols including allyl alcohol, metal alcohol, ethoxylated allyl alcohol, ethoxylated methallyl alcohol, propoxylated allyl alcohol, and propoxylated methallyl alcohol. Suitable alkyl or aryl acrylates and methacrylates include alkyl acrylates and methacrylates of 1 to 20 carbon atoms, aryl acrylates and methacrylates of 6 to 20 carbon atoms, similar and mixtures thereof. Examples are n-butyl acrylate, n-butyl methacrylate, methyl methacrylate, t-butyl methacrylate, butyl butyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, the like and mixtures thereof. The invention includes a process for polymerizing an aromatic vinyl and a hydroxy functional monomer selected from the group consisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates, allyl alcohols, alkoxylated allyl alcohols and mixtures thereof. The hydroxyalkyl acrylates and methacrylates, allyl alcohols, alkoxylated allyl alcohols and appropriate aromatic vinyls were described above. The invention also includes a process for polymerizing an olefin, an aromatic vinyl, and a hydroxy functional monomer selected from the group consisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates, allyl alcohols, alkoxylated allyl alcohols, and mixtures thereof. The olefins, acrylates and hydroxyalkyl methacrylates, allyl alcohols, alkoxylated allyl alcohols and appropriate aromatic vinyls were described above. The polymerization of the invention is preferably carried out at a temperature in the range from about 0 ° C to about 200 ° C. The polymerization temperature varies depending on the polymers to be processed. For example, to make acrylic hydroxyl resins or styrene-allyl alcohol copolymers, a relatively high temperature is required (from about 80 ° C to about 150 ° C is preferred). High polymerization temperatures lead to low molecular weight resins, which are suitable for high or low solid coatings in VOC (volatile organic compounds). The polymerization can be carried out in bulk, in solution, suspension or in any other appropriate forms, depending on the polymers to be made. For example, when a styrene-allyl alcohol copolymer is made, a bulk polymerization is preferred because the allyl alcohol is slowly polymerized, and the allyl alcohol in excess functions as a solvent to control the polymerization. When a hydroxyl acrylic resin is made from a hydroxyalkyl acrylate and alkyl acrylate, the polymerization is preferably carried out in solution wherein the solvent is used as a chain transfer agent to decrease the molecular weight of the polymer and to control the polymerization rate. The polymerization can be carried out in a batch process, semi-batches or continuous, depending on the monomers used and the polymers produced. For example, a semi-batch process is preferred when a styrene-allyl alcohol copolymer is made. In the semi-batch process, the allylic alcohol is initially charged to the reactor, and the styrene is fed gradually into the reactor during the polymerization. The gradual addition of styrene ensures a uniform distribution of the groups as a function of the OH along the polymer chain. The invention includes polymers made by the process of the invention. Particularly interesting polymers include hydroxyl acrylic resins (ie, the copolymers include hydroxyl functional monomers, alkyl or aryl acrylates, or alkyl or aryl methacrylates, and optionally aromatic vinyls), olefin-acrylic copolymers, olefin copolymers -vinyl, and vinyl aromatic-allyl alcohol copolymers. The polymers made by the invention differ from the polymers made by the free radical polymerization, in that the polymers of the invention do not contain residual free radical initiators, or fragments of decomposition of the initiator. Polymers made by polymerization with free radical are thermally, chemically or photochemically unstable, due to the residual initiator or fragments of the initiator. Thus, it is expected that the polymers of the invention have improved thermal, chemical and photochemical resistance. The invention also includes articles made from the polymers of the invention. Examples of useful articles that can be made from the polymers of the invention include films, sheets, containers, tubes, fibers, coatings, adhesives, elastomers, sealants and the like. An advantage of the invention is that the LTMC provides better fit than radical polymerization to control polymer properties such as density, molecular weight, and molecular weight distribution. For example, polymerization with LTMC can provide hydroxyl acrylic resins with narrow molecular weight distribution. The narrow molecular weight distribution results in low or high VOC solid coatings. The following examples merely illustrate the invention. Those skilled in the art will recognize many variations that are within the spirit of the invention and the scope of the claims.

EXAMPLE 1 COPOLYMERIZATION OF ETHYLENE. N-BUTYL ACRYLATE. Y ALYLO MONOPROPOXYLATE WITH IRON COMPLEX NI) AND 1.3-BIS- (2-MESITILIMINO) ISOINDOLINE. AND ACTIVATOR MAO PREPARATION OF THE CATALYST COMPLEX A 100 mL round bottom flask equipped with a nitrogen inlet and an internally adjusted glass filter is charged with phthalimide (2.94 g, 20.0 mmol) and ethyl acetate (60 mL). 2.4.6-Trimethylaniline (5.41 g, 40.0 mmol, 2.0 eq.) And iron (II) chloride (2.54 g, 20.0 mmol) are added to the flask, and the mixture is stirred under nitrogen at room temperature for 1 hour. The yellow mixture is heated by reflux (77 ° C) for 10 h, and then stirred at room temperature for 32 h. A brown precipitate forms. The reaction mixture is concentrated by removing the ethyl acetate under a stream of nitrogen. Cold diethyl ether (30 mL) is added to the residue, and the mixture is stirred to wash the residue. The glass filter is immersed in the liquid phase, which is then removed under reduced pressure by the internal filter. The solids are dried under vacuum for 2 h to give a brown powder.

POLYMERIZATION The polymerization is carried out in an Endeavor chemical process workstation (Advantage ™ 3400 Series, developed by Argonaut Technologies, Inc.). The Endeavor contains eight pressure reactor tubes, each with individual temperature, pressure, agitation and injection controls. The Endeavor is placed in a box with gloves for manual manipulation and in an atmosphere of inert nitrogen. A pre-programmed computer monitors and collects data on pressure, temperature, ethylene consumption, in each reactor tube as a function of reaction time. A reactor tube (10 mL) is charged with n-butyl acrylate (2 mL), allyl monopropoxylate (2 mL), tri-isobutyl aluminum (0.1 mL, hexanol.OM solution), MAO (0.08 mL, toluene 1.0 M), and the catalyst complex (0.2 mL, 1.0 mg / mL toluene solution), and the catalyst complex (0.2 mL, 1.0 mg / mL toluene solution). Then the reactor tube is sealed. The reactor is pressurized with ethylene up to 28.1 kg / cm2 (400 psig) and heated to 100 ° C. Polymerization continues at these temperature and pressure readings for about 1 hr with continuous ethylene feed. The ethylene consumption is approximately 0.02 g. After polymerization, monomers that did not react are removed by vacuum, yielding 0.4 g of polymer. The polymer has a MW of 5650; NM: 3220 and PM / NM: 1.75.

EXAMPLE 2 COPOLYMERIZATION OF ETHYLENE. N-BUTYL ACRYLATE. Y HYDROXYETHYL ACRYLATE WITH IRON COMPLEX 1,3-BISÍ2-MESITILIMINO) ISOINDOLINE, AND ACTIVATOR MAO The general procedure of Example 1 is followed. A reactor tube (10 mL) is charged with n-butyl acrylate (2 mL), hydroxyethyl acrylate (2 mL), tri-isobutyl aluminum (0.1 mL, 1.0 M hexane solution). ), MAO (0.08 mL, 1.0 M toluene solution), and the catalyst complex (0.2 mL, 1.0 mg / mL toluene solution). The reactor tube is then sealed. The reactor is pressurized with ethylene up to 28.1 kg / cm2 (400 psig) and heated to 100 ° C. Polymerization continues at these temperature and pressure readings for about 1 hr with continuous ethylene feed.

The ethylene consumption is approximately 0.2 g. After polymerization, monomers that did not react are removed by vacuum, yielding 2.2 g of polymer.

EXAMPLE 3 COPOLYMERIZATION OF N-BUTYL ACRYLATE AND ALYLO MONOPROPOXYLATE WITH IRON COMPLEX (11) AND 1,3-BIS (2-MESlTILIMINO) ISOINDOLINE, AND ACTIVATOR MAO The general procedure of Example 1 is followed. A reactor tube (10 mL) is charged with n-butyl acrylate (2 mL), allyl monopropoxylate (2 mL), tri-isobutyl aluminum (0.1 mL, 1.0 M hexane solution). ), MAO (0.08 mL, 1.0 M toluene solution), and the catalyst complex (0.2 mL, 1.0 mg / mL toluene solution). The reactor tube is then sealed. The reactor content is heated to 100 ° C. The polymerization continues at this temperature reading for about 1 h. After polymerization, monomers that did not react are removed by vacuum, yielding 2.1 g of polymer.

EXAMPLE 4 COPOLYMERIZATION OF ETHYLENE. STYRENE AND MONOPROPOXYLATE OF ALYLO WITH IRON COMPLEX (II) 1,3-BIS (2-MESITILIMINO) ISOINDOLINE AND ACTIVATOR MAO The general procedure of Example 1 is followed. A reactor tube (10 mL) is charged with styrene (2 mL), allyl monopropoxylate (2 mL), tri-isobutyl aluminum (0.1 mL, 1.0 M hexane solution), MAO (0.08 mL, 1.0 M toluene solution), and the catalyst complex (0.2 mL, 1.0 mg / mL toluene solution). The reactor tube is then sealed. The reactor is pressurized with ethylene up to 28.1 kg / cm2 (400 psig) and heated to 100 ° C. Polymerization continues at these temperature and pressure readings for about 1 hr with continuous ethylene feed. The ethylene consumption is approximately 0.01 g. After polymerization, monomers that did not react are removed by vacuum, yielding 0.23 g of polymer.

EXAMPLE 6 COPOLYMERIZATION OF STYRENE AND MONOPROPOXYLATE OF ALYLO WITH IRON COMPLEX (II) AND 1.3-BISÍ2- MESITILIMINOISOINDOLINA AND ACTIVATOR MAO The general procedure of Example 1 is followed. A reactor tube (10 mL) is charged with styrene (2 mL), allyl monopropoxylate (2 mL), tri-isobutyl aluminum (0.1 mL, 1.0 M hexane solution), MAO ( 0.08 mL, 1.0 M toluene solution), and the catalyst complex (0.2 mL, 1.0 mg / mL toluene solution). The reactor tube is then sealed. The reactor content is heated to 100 ° C. The polymerization continues at this temperature reading for about 1 h. After polymerization, monomers that did not react are removed by vacuum, yielding 0.1 g of polymer.

EXAMPLE 7 COPOLYMERIZATION OF ETHYLENE. N-BUTYL ACRYLATE AND ALYLO MONOPROPOXYLATE WITH IRON COMPLEX (II) AND 1,3-BIS (2-PIR DIL1MIN0) IS0INDQLINA, AND ACTIVATOR MAO PREPARATION OF THE CATALYST A 100 mL round bottom flask equipped with a nitrogen inlet and an internally adjusted glass filter is charged with phthalimide (2.94 g, 20.0 mmol) and ethyl acetate (50 mL). To the flask is added 2-aminopyridine (3.77 g, 40.0 mmol, 2.1 eq.) And iron (II) chloride (2.54 g, 20.0 mmol), and the mixture is stirred under nitrogen at room temperature for 1 hour. The mixture is stirred at room temperature for 120 h, producing a white precipitate. After washing with cold diethyl ether (3 x 20 mL), the white solids are dried under vacuum for 1 h.

POLYMERIZATION The polymerization process of Example 1 is followed, but the catalyst complex prepared in the previous point is used. The ethylene consumption is 0.01 g, and 0.15 g of polymer is collected.

EXAMPLE 8 COPOLYMERIZATION OF ETHYLENE. N-BUTYL ACRYLATE, ALYLO MONOPROPOXYLATE WITH COMPLEX OF IRON (II) AND BIS (IMINA) An iron (II) complex is prepared with bis-imine according to example 1 of US Pat. No. 6,562,973. A 100 mL round bottom flask with a nitrogen inlet and an internally adjusted glass filter is charged with 2,6-diacetylpyridine (2.00 g, 12.2 mmol) and ethyl acetate (50 mL). 2,4,6-Trimethylaniline (3.52 g, 26.0 mmol, 2.13 eq.) Is added to the stirred solution. Iron (II) chloride (1.55 g, 12.2 mmol) is added to the flask and the mixture is stirred under nitrogen at room temperature for 42 hours. The reaction mixture is concentrated by removing the solvents under reduced pressure. Cold diethyl ether (30 mL) is added to the residue, and the mixture is stirred to wash the residue. The glass filter is immersed in the liquid phase, which is then removed under reduced pressure through the internal filter. The complex solids are dried under vacuum for 1 hour.

POLYMERIZATION The polymerization procedure of Example 1 is followed, but the catalyst complex prepared in the previous point is used. The ethylene consumption is 0.01 g and 0.1 7 g of polymer is collected. The polymer has MW: 6000 and NM: 2170; and PM / NM: 2.76.

Claims (26)

1. A process comprising polymerizing, in the presence of a metal complex of group 8-10 and an activator, one of the monomer groups (a) through (f): (a) a vinyl monomer selected from the group consisting of aromatic vinyls , vinyl ethers, vinyl esters, and vinyl halides thereof; (b) a vinyl monomer selected from the group consisting of vinyl ethers, vinyl esters, and vinyl halides, and at least one olefin; (c) a hydroxy functional monomer selected from the group consisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates, allyl alcohols, and alkoxylated allylic alcohols, and at least one alkyl or aryl acrylate, or at least one alkyl or methacrylate aril; (d) a hydroxy functional monomer selected from the group consisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates, allyl alcohols, and alkoxylated allyl alcohols, at least one alkyl or aryl acrylate or at least one alkyl or aryl methacrylate, and at least one olefin; (e) a hydroxy functional monomer selected from the group consisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates, allyl alcohols, and alkoxylated allyl alcohols, and at least one aromatic vinyl monomer; or (f) a hydroxy functional monomer selected from the group consisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates, allyl alcohols, and alkoxylated allyl alcohols, at least one vinyl aromatic monomer, and at least one olefin. 2. The process of claim 1, further characterized in that the complex has the general structure

M (X) n

Where M is a metal of group 8-10; L is a stable ligand in the polymerization selected from isoindolines or bis (imines); X is a labile ligand and is greater than or equal to 1. 3. The process of claim 2, further characterized in that L is an isoindoline ligand having the general structure: wherein A and A 'are the same or different aryl or heteroaryl groups.

4. The process of claim 3, further characterized in that A and A 'are identical aryl groups.

5. The process of claim 3, further characterized in that A and A 'are identical heteroaryl groups.

6. The process of claim 2, further characterized in that M is Fe and L is a 1,3-bis (2-mesitylimino) isoindoline or a 1,3-bis (2-pyridylimino) isoindoline. The process of claim 1, further characterized in that the activator is selected from the group consisting of alkyl alumoxanes, alkylaluminium compounds, aluminioboronates, organoboranes, ionic borates, and ionic aluminates. 8. A polymer made by the process of claim 1. 9. An article containing the polymer of claim 8. 10. A process comprising polymerizing, in the presence of a Group 8-10 metal complex and an activator, a hydroxy functional monomer selected from the group consisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates, allyl alcohols, and alkoxylated allyl alcohols, at least one alkyl or aryl acrylate, or at least one alkyl or aryl methacrylate, optionally a vinyl aromatic monomer, and optionally an α-olefin of 2 to 10 carbon atoms. The process of claim 10, further characterized in that the hydroxy functional monomer is selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, allyl alcohol , metal alcohol, allyl alcohol propoxylated allyl alcohol ethoxylate. The process of claim 10, further characterized in that at least one of the alkyl or aryl acrylate, or the alkyl or aryl methacrylate, is selected from the group consisting of n-butyl acrylate, n-butyl methacrylate. , 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, methyl acrylate, methyl methacrylate, t-butyl acrylate, t-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, iso-bornyl acrylate, and iso-bornyl methacrylate. 13. The process of claim 10, further characterized in that the hydroxy-functional monomer is allyl monopropylate and the alkyl acrylate or methacrylate is n-butyl acrylate or n-butyl methacrylate. The process of claim 10, further characterized in that the aromatic vinyl monomer is selected from the group consisting of styrene, α-methyl styrene, p-methyl styrene and p-t-butyl styrene. 15. The process of claim 10, further characterized in that the α-olefin is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene. The process of claim 10, further characterized in that the late transition metal complex contains Fe and a 1,3-bis (2-mesitylimino) isoindoline or a 1,3-bis (2-pyridylimino) isoindoline ligand, and wherein the activator is an alkyl alumoxane. 1

7. A polymer made by the process of claim 10. 1

8. An article containing the polymer of claim 10. 1

9. A process comprising polymerizing, in the presence of a Group 8-10 metal complex and an activator, at least one vinyl ester and at least one α-olefin of 2 to 10 carbon atoms. 20. The process of claim 19, further characterized in that the vinyl ester is vinyl acetate and the α-olefin is ethylene. 21. A polymer made by the process of claim 19. 22. An article containing the polymer of claim 21. 23. A process comprising polymerizing, in the presence of a Group 8-10 metal complex and an activator, a hydroxy functional monomer selected from the group consisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates, allyl alcohols, and alkoxylated allylic alcohols, at least one aromatic vinyl monomer and optionally at least one α-olefin of 2 to 10 carbon atoms. 24. The process of claim 23, further characterized in that the aromatic vinyl monomer is styrene and the hydroxy functional monomer is selected from the group q. consists of allyl alcohol, metal alcohol, alkoxylated allyl alcohol, and alkoxylated metal alcohol. 25. A polymer made by the process of claim 23. 26. An article containing the polymer of claim 25.