US 2019/0161566 A1 · PROCESS AND HYDROCARBON SOLUBLE SALINE HYDRIDE CATALYST FOR HYDROGEN MEDIATED SALINE HYDRIDE INIATED ANIONIC CHAIN TRANSFER POLYMERIZATION AND POLYMER DISTRIBUTION COMPOSITIONS PRODUCED THEREFROM

Abstract

This invention relates to processes for forming hydrogen mediated saline hydride initiated anionic polymer distributions via novel polymerization conditions in which molecular hydrogen is a chain transfer agent and a Lithium Aminoalkoxide Complexed Saline Hydride (LOXSH) forms an anionic polymer chain initiating species by addition of saline hydride to an anionically polymerizable hydrocarbon monomer. This invention further relates to polystyrene compositions having greatly improved microstructures free of co-product polymer chain distributions. This invention also relates to novel hydrocarbon soluble saline hydride catalyst and reagent compositions useful in conducting the hydrogen mediated saline hydride initiated polymerizations of this invention. This invention further relates to hydrocarbon soluble lithium hydride catalysts and reagent compositions formed from dimethylaminoethanol, an alkyllithium reagent and molecular hydrogen. It also relates to the catalyst forming processes, the use of the catalyst in hydrogen mediated anionic polymerization of styrene (HMAPS) and the resulting low molecular weight polystyrene distributions of low asymmetry and high “head to tail” microstructure.

Claims32

Dependent claims

1-57. (canceled)

A process of conducting hydrogen mediated saline hydride initiated polymerizations which features feeding one or more anionically polymerizable hydrocarbon monomers to a reaction medium containing a solvent, a soluble saline hydride catalyst, and optionally a polytertiaryamine compound under an atmosphere comprising molecular hydrogen.

A hydrocarbon soluble catalyst or reagent composition formed from (i) an organolithium compound optionally with an organomagnesium compound;

(ii) an optional polytertiaryamine promoter compound;
(iii) a polarizing complexing agent selected from a tertiary amino alcohol, a tertiary amino ether-alcohol, an ether-alcohol or combinations thereof;
(iv) optionally an aromatic hydrocarbon having at least one C—H covalent bond pKa within the range of 2.75 pKa units above that of the pKa of toluene to −4.30 pKa units below the pKa of toluene;
(v) an optional solid alkali or magnesium hydride;
or an alkali metal or alkali metal alloy;
or a alkali metal or magnesium amide;
(vi) a hydrocarbon solvent having a pKa greater than H2, wherein the aromatic hydrocarbon and hydrocarbon solvent may be the same or different;
and (vii) molecular hydrogen.

5 more elements

A process for forming a hydrocarbon soluble LOXSH catalyst, wherein (i) an organolithium compound with or without an organomagnesium compound;

(ii) an optional polytertiaryamine promoter compound;
(iii) a polarizing complexing agent selected from a tertiary amino alcohol, a tertiary amino ether-alcohol an ether-alcohol or combinations thereof;
(iv) optionally an aromatic hydrocarbon having at least one C—H covalent bond pKa within the range of 2.75 pKa units above that of the pKa of toluene to −4.30 pKa units below the pKa of toluene;
(v) an optional solid alkali or magnesium metal hydride or an alkali metal or alkali metal alloy or a alkali or magnesium amide;
(vi) a hydrocarbon solvent having a pKa greater than H2, wherein the aromatic hydrocarbon and hydrocarbon solvent may be the same or different;
and (vii) molecular hydrogen are contacted or otherwise combined.

3 more elements

A hydrogen mediated anionic polymerization of styrene (HMAPS) polystyrene having a polymer microstructure that is greater than 99 wt % head to tail microstructure as depicted by the following polymeric structure:

and having a polymer chain length distributions wherein less than 1.0% of the polymer chains have one or more quaternary carbons in the polymer microstructure and comprising less than 1.0% to an amount below the detection limit of the chain length distribution(s) as a coproduct distribution(s) arising from a fragmentation polymerization processes where the microstructure and purity of the chain length distribution is determined vide infra from gas chromatographic analyses of the lowest molecular weight chains obtained from the HMAPS distributions where n=0 to n=2.

Dependencies are inferred from the claim text.

Process and hydrocarbon soluble saline hydride catalyst for hydrogen mediated saline hydride iniated anionic chain transfer polymerization and polymer distribution compositions produced therefrom

Life of this patent

Process and hydrocarbon soluble saline hydride catalyst for hydrogen mediated saline hydride iniated anionic chain transfer polymerization and polymer distribution compositions produced therefrom

Life of this patent

Abstract

Claims32