Polymerization using late transition metal catalyst...

Details Polymerization using late transition metal catalyst... Polymerization using late transition metal catalyst...

2000-08-18

2003-01-14

Wu, David W. (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S348000, C526S328000, C526S319000, C526S161000, C502S155000, C502S165000, C502S167000, C502S162000

Reexamination Certificate

active

06506859

ABSTRACT:

FIELD OF THE INVENTION
The invention is directed towards the formation of polymers and copolymers using late transition metal polymerization catalyst complexes which are formed in situ.
BACKGROUND
Polymers and copolymers may be formed from olefinic monomers by using organometallic catalyst technology. Commonly used organometallic catalysts include Ziegler-Natta catalysts and metallocene catalysts. Despite the technological and commercial success of Group 4 (Ti and Zr) Ziegler-Natta and metallocene catalysts for polyolefins, the search for new catalysts and polymerization techniques continue. More specifically, the chemical industry strives to obtain even greater control over product properties and extend the family of products to new monomer combinations. Catalysts that tolerate a variety of functional groups are of particular interest because they not only open up new product possibilities, but also allow the use of cheaper, less pure monomer feeds. To this end, late transition metals are generally more tolerant of polar groups than the early transition metals.
Late transition metal catalysts have been used to a limited degree in polymerization processes. Many of these processes use free radical techniques and preformed catalyst complexes. Other techniques such as atom transfer radical polymerization (“ATRP”) utilize an initiator such as an alkyl halide, a Group 11 metal compound such as CuCl, and an amine such as 2,2′-dipyridine as taught by Matyjaszewski in WO96/30421, herein incorporated by reference. The ATRP process uses an initiator in lieu of a cocatalyst (e.g., methyl alumoxane, a.k.a. “MAO”). The amine in ATRP is used to solubilize the metal compound in media. Furthermore, ATRP is known to polymerize only styrene and acrylates and is not known to polymerize other monomers such as ethylene.
Recently, novel late transition organometallic catalysts have been developed which are useful in forming polymers and copolymers having hydrocarbyl polar functionality. More specifically, U.S. Pat. No. 6,037,297 to Stibrany et al., herein incorporated by reference, details group 11 (Cu, Ag and Au) containing catalyst compositions having a pseudotetrahedral geometry. The polymerization technique disclosed in U.S. Pat. No. 6,037,297 teaches the preparation of a solid and isolated complex. The complex is a single compound that can be put in the container and stored on the bench top. Such a complex would not yet be considered an active catalyst by one skilled in the art. For the complex to be used as a catalyst for polymerization, the complex must be mixed with an activating cocatalyst, such as MAO, to create an activated catalyst which can be used to polymerize monomers. Thus, there are two discrete steps which are undertaken to create the active polymerization catalyst which makes the production of polymers and copolymers less efficient and more expensive.
Hence, there is still a need to improve the efficiency of processes for catalyst formation and polymerization. Additionally, processes which allow the incorporation of polar monomer groups are advantageous.
SUMMARY OF THE INVENTION
The instant invention provides a novel olefin polymerization process based on the use of a group 11 transition metal halide, a nitrogen containing ligand such as a bis-benzimidazole, and an activating cocatalyst (e.g., MAO) which form an activated catalyst composition in situ. This activated catalyst composition is then used to polymerize olefins and copolymerize olefins with polar monomers. Unlike ATRP, the instant invention does not use an alkyl halide initiator but instead uses a cocatalyst. Further, unlike U.S. Pat. No. 6,037,297, the invention teaches that use of a preformed metal complex is not a prerequisite. More specifically, the metal complex may be formed in-situ by adding the metal compound with a ligand at the same time cocatalyst is added. Hence, the advantages of the instant invention include an in situ method for forming an active catalyst composition which is a step-saving, cost-saving process. The invention also provides a method for polymerizing olefins as well as copolymers having polar monomers incorporated therein.
In one embodiment, the invention provides a method for producing an activated catalyst composition in situ and producing polymers therefrom comprising the steps of: (a) simultaneously contacting a composition having the formula MXZ
n
with L and an activating cocatalyst; wherein M is selected from the group consisting of Cu, Ag, and Au; X is selected from the group consisting of halides, hydride, triflate, acetates, borates, C
1
through C
12
alkyl, C
1
through C
12
alkoxy, C
3
through C
12
cycloalkyl, C
3
through C
12
cycloalkoxy, aryl, thiolates, carbon monoxide, cyanate, olefins, and any other moiety into which a monomer can insert; Z is selected from the group consisting of halides, hydride, triflate, acetates, borates, C
1
through C
12
alkyl, C
1
through C
12
alkoxy, C
3
through C
12
cycloalkyl, C
3
through C
12
cycloalkoxy, aryl, thiolates, carbon monoxide, cyanate, olefins, a neutral coordinating ligand, and any other moiety into which a monomer can insert; n equals 0, 1 or 2; L is selected from the group consisting of monodentate nitrogen-containing ligands and bidentate nitrogen-containing ligands; and, (b) contacting olefinic monomers under polymerization conditions; wherein said olefinic monomers are selected from the group consisting of acyclic aliphatic olefins, olefins having a hydrocarbyl polar functionality, mixtures of olefins having at least one olefin with a hydrocarbyl functionality and at least one acyclic aliphatic olefin; whereby polymers or copolymers are formed.
These and other features, aspects and advantages of the present invention will become better understood in view of the following description and claims.
DESCRIPTION
In one embodiment, the invention provides a method for producing an activated catalyst composition in situ and producing polymers or copolymers therefrom. It should be appreciated by those skilled in the art that use of the general term “copolymers” includes terpolymers and other polymers having various combinations of different monomer units.
In the first process step of the instant invention, a composition having the formula MXZ
n
is simultaneously contacted with L and an activating cocatalyst. Referring to the formula, M is selected from the group consisting of Cu, Ag, and Au; X is selected from the group consisting of halides, hydride, triflate, acetates, borates, C
1
through C
12
alkyl, C
1
through C
12
alkoxy, C
3
through C
12
cycloalkyl, C
3
through C
12
cycloalkoxy, aryl, thiolates, carbon monoxide, cyanate, olefins, and any other moiety into which a monomer can insert; Z is selected from the group consisting of halides, hydride, triflate, acetates, borates, C
1
through C
12
alkyl, C
1
through C
12
alkoxy, C
3
through C
12
cycloalkyl, C
3
through C
12
cycloalkoxy, aryl, thiolates, carbon monoxide, cyanate, olefins, a neutral coordinating ligand, and any other moiety into which a monomer can insert; n equals 0, 1 or 2; and L is selected from the group consisting of monodentate nitrogen-containing ligands and bidentate nitrogen-containing ligands.
In a subsequent process step of the instant invention, olefinic monomers are contacted with the activated catalyst composition under polymerization conditions. The olefinic monomers are selected from the group consisting of acyclic aliphatic olefins, olefins having a hydrocarbyl polar functionality, mixtures of olefins having at least one olefin with a hydrocarbyl polar functionality and at least one acyclic aliphatic olefin. Polymers and copolymers are thereby formed.
Examples of the activating cocatalysts used above include, but are not limited to, aluminum compounds containing an Al—O bond such as the alkylalumoxanes such as methylalumoxane (“MAO”) and isobutyl modified methylalumoxane; aluminum alkyls; aluminum halides; alkylaluminum halides; Lewis acids other than any of the foregoing list; and mixtures of the foregoing can also be use

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