Back to results
US 12,747,315 B2Granted
Process and catalysts for hydrogen mediated anionic polymerization of conjugated dienes and liquid polymers thereof
AssigneeAlbemarle Corporation
InventorWilliam J. Layman, Jr.
Life of this patent
Estimating the term…
Abstract
The disclosure relates to hydrogen mediated anionically polymerized conjugated diene compositions, including homopolymers and copolymers of isoprene and/or butadiene, and processes and compositions for preparing them.
Claims29
A process for polymerizing conjugated dienes in a hydrocarbon reaction medium within a reactor, comprising
- a) chemically adding a lithium alkoxide complexed saline hydride (LOXSH) catalyst to a low boiling conjugated diene (CD) to form a polymerization initiating species in the reaction medium,
- b) co-feeding at least two gaseous and/or volatile compounds to the reaction medium forming a polymerization reaction mixture, wherein the at least two gaseous and/or volatile compounds comprise hydrogen and the low boiling CD, and wherein the at least two gaseous and/or volatile compounds are co-fed at a pre-set molar ratio to the polymerization reaction mixture over the course of at least a portion of the entire co-feed wherein the reactor pressure adjusts autogenously to the condensed phase activity of hydrogen and of the CD at a relative steady state pressure and temperature, and
- c) polymerizing at least a portion of the CD,
- wherein the LOXSH catalyst comprises one or more σ-μ polar modifiers.
1 more element
A LOXSH catalyst or reagent composition comprising:
- a) at least one tertiary amino alcohol σ-μ or amino-ether-alcohol polar modifier;
- b) at least one separate ether-alcohol σ-μ polar modifier;
- c) an organo lithium compound;
- and d) elemental hydrogen and/or an organo silicon hydride, wherein the σ-μ polar modifiers of the composition comprise about 50 mole % or more, but less than 100 mole %, of a tertiary amino-alcohol or a tertiary amine-ether-alcohol σ-μ polar modifier selected from one or more of:
- N,N-dimethylethanolamine, 1-(dimethylamino)-2-propanol, 1-(dimethylamino)-2-butanol, trans-2-(dimethylamino) cyclohexanol;
- 2-piperidinoethanol;
- 1-piperidino-2-propanol;
- 1-piperidino-2-butanol, trans-2-piperidinocyclohexan-1-ol, 1-pyrrolidinoethanol, pyrrolidinylpropan-2-ol, 1-(1-pyrolidinyl)-2-butanol, 2-pyrolidinocyclohexanol, 4-methyl-1-piperazineethanol, 1-(4-methyl-1-piperazinyl)-2-propanol;
- 1-(4-methyl-1-piperazinyl)-2-butanol;
- trans-2-(4-methyl-1-piperazinyl)-cyclohexanol, 2-morpholinoethanol, 1-(4-morpholinyl)-2-propanol, 1-(4-morpholinyl)-2-butanol, trans-2-morpholin-4-ylcyclohexanol, 1-methyl-2-piperidinemethanol, 1-methyl-2-pyrrolidinemethanol, N-methyl-diethanolamine, 3-dimethylamino-1-propanol, 1,3-bis(dimethylamino)-2-propanol, 2-{[2-dimethylamino)ethyl]methylamino}ethanol, 2-[2-(dimethylamino)ethoxy]ethanol, 2-(2-(piperidyl)ethoxy) ethanol, 2-[2-(4-morpholinyl)ethoxy]ethanol, 2-[2-(1-pyrrolidinyl)ethoxy]ethanol, and 2-[2-(4-methyl-1-piperazinyl)ethoxy]ethanol;
- and from about 50 mole % to greater than 0 mole % of an ether-alcohol σ-μ polar modifier selected from one or more of 2-methoxyethanol, 1-methoxypropan-2-ol, 1-methoxybutan-2-ol, 2-methoxycyclohexan-1-ol, tetrahydrofurfuryl alcohol, tetrahydropyran-2-methanol, and diethylene glycol monomethyl ether.
8 more elements
A composition comprising a hydrogen mediated polyisoprene (HMPIP) distribution, wherein the HMPIP is characterized as having a number average (Mn,) molecular weight from about 500 to about 2600 Daltons and having one of the following:
- 1) from about 73 wt. % to about 80 wt. % 1,4-IP contents with a Brookfield viscosity (@ 25° C.) that varies as a function of Mn from about 30 cP at about 500 Daltons to about 5000 cP at about 2600 Daltons;
- or 2) from about 40 wt. % to about 73 wt. % 1,4-IP contents content with a Brookfield viscosity (@ 25° C.) that varies as a function of Mn over the range of about 200 cP at about 500 Daltons to about 40,000 cP at about 2600 Daltons;
- or 3) from about 30 wt. % to about 54 wt. % 1,4-IP contents and a Brookfield viscosity (@ 25° C.) that varies as a function of Mn over the range of about 100 cP at about 500 Daltons to about 200,000 cP at about 2600 Daltons;
- wherein the 1,4-IP contents is determined by 1HNMR analyses.
1 more element
A composition comprising a hydrogen mediated polybutadiene (HMPBD) distribution having a number average (Mn,) molecular weight from about 500 to about 2600 Daltons and having one of the following:
- 1) from about 74 wt. % to about 84 wt. % total vinyl content with a Brookfield viscosity (@ 25° C.) that varies as a function of Mn over the range of about 45 cP at about 500 Daltons to about 30,000 cP at about 2600 Daltons;
- or 2) from about 55 wt. % to about 73 wt. % total vinyl content with a Brookfield viscosity (@ 25° C.) that varies as a function of Mn over the range of about 50 cP at about 500 Daltons to about 8000 cP at about 2600 Daltons;
- or 3) from about 30 wt. % to about 54 wt. % total vinyl content and a Brookfield viscosity (@ 25° C.) that varies as a function of Mn over the range of about 20 cP at about 500 Daltons to about 3000 cP at about 2600 Daltons;
- wherein the total vinyl content is determined by C-13 NMR analyses having glass transition temperatures Tg from less than −120° C. to about −45° C. over the range of Mn=500 to Mn=2600.
1 more element
A hydrogen mediated anionic poly (conjugated diene) composition characterized by high vinyl content from about 74 wt. % to about 82 wt. % (as determined by C-13 NMR analyses) wherein the:
- 1) number average molecular weight distribution (Mn) is from about 500 to about 2600 Daltons;
- 2) Brookfield viscosity (@ 25° C.) is from about 50 to about 32,000 cP;
- 3) glass transition temperature Tg is from about −95° C. to about −45° C.;
- and 4) molar ratio of vinyl-1,2-BD:VCP is from about 7:1 to about 15:1 (based on 1HNMR analysis).
1 more element
Dependencies are inferred from the claim text.