Functionalized diene oligomers
AssigneeE. I. Du Pont de Nemours and Company
InventorsAlexei Alexeyevich Gridnev, Steven Dale Ittel
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Abstract
This invention relates to the controlled molecular weight production of macromonomers and polymers with terminal conjugated double bonds from starting monomers including, but not limited to substituted butadienes. The terminal diene end thus produced is also a potential reaction site for further polymerization or functionalization. The molecular weight is controlled by use of Co chain transfer catalysts and appropriate process conditions.
Claims13
A process for polymerizing substituted butadienes to substituted polybutadienes having controlled molecular weight and end-group functionality;
- wherein the process consists of:
- contacting a substituted butadiene, in the optional presence of a comonomer, with a chain transfer catalyst comprising a cobalt (II) or cobalt (III) compound and a free radical initiator, said substituted butadienes having a structure
- CHR.sup.1 .dbd.CX--CY.dbd.CR.sup.2 R.sup.3
- where X and Y are each independently selected from the group consisting of H, alkyl, substituted alkyl, COO(Metal), --COOR, CN, OR, --COR, --CONR.sub.2, --OCOR,
- halogen, aryl, and substituted aryl;
- where R is selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, and hydrogen;
- said alkyl and substituted alkyl groups having one or more carbon atoms;
- said aryl groups having six or more carbon atoms;
- and
- provided that both X and Y cannot both be H;
- wherein the Metal is selected from the group consisting of lithium, sodium, potassium, magnesium, cadmium and zinc;
- wherein R.sup.1, R.sup.2 and R.sup.3 are each selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, halide, nitrile, ester, ether, CN and hydrogen;
- said alkyl and substituted alkyl groups having one or more carbon atoms;
- said aryl groups having six or more carbon atoms;
- and
- wherein any two of R.sup.1 or R.sup.2 and R.sup.3 are optionally arranged in a cyclic structure;
- said reaction carried out at a temperature from about room temperature to about 240.degree. C., in the optional presence of a solvent.
A terminally functionalized oligomer or polymer having the structure:
- ##STR7## wherein I is an initiating group derived from an initiator for said polymerization process, or a hydrogen atom derived from a cobalt (II) or cobalt (III) chain transfer catalyst;
- where X and Y are each independently selected from the group consisting of H, alkyl, substituted alkyl, COO(Metal),COOR, CN, OR, COR, COOR, CONR.sub.2, OCOR, halogen, aryl, and substituted aryl;
- where R is selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, and hydrogen;
- said alkyl and substituted alkyl groups having one or more carbon atoms;
- said aryl groups having six or more carbon atoms;
- and
- provided that both X and Y cannot both be H;
- wherein the Metal is selected from the group consisting of lithium, sodium, potassium, magnesium, cadmium and zinc;
- n is greater than 2;
- m is zero or greater;
- and
- wherein R.sup.1, R.sup.2, and R.sup.3 are selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, halide, nitrile, ester, ether, CN and hydrogen;
- said alkyl and substituted alkyl groups having one or more carbon atoms;
- said aryl groups having six or more carbon atoms.
Dependencies are inferred from the claim text.