Polyalkenyl coupling agent and conjugated diene polymers prepared therefrom
View Patent ↗A process is provided for preparing a coupled polymer by anionic polymerization wherein the coupled polymer is a conjugated diene polymer comprising the following reaction steps: a) polymerizing a monomer or a mixture of monomers comprising at least one conjugated diene optionally one or more monoalkenyl arene compounds in the presence of an anionic initiator to form a living polymer arm or mixture of arms with an average apparent molecular weight greater than 2000; b) reacting the living polymer arm or arms with a polyalkenyl coupling agent; c) terminating the polymerization if any living polymers remain after step b); and d) optionally functionalizing and/or hydrogenating the coupled polymer so produced, wherein the polyalkenyl coupling agent is an alpha,omega-bis(vinylphenyl)alkane. Also provided is the polymer so prepared and its use in concentrates, aqueous emulsions and products made from aqueous emulsions.
1. A process for preparing a coupled polymer by anionic polymerization wherein the coupled polymer is a conjugated diene polymer comprising the following reaction steps:
a) polymerizing a monomer or a mixture of monomers comprising at least one conjugated diene and optionally one or more monoalkenyl arene compounds in the presence of an anionic initiator to form a living polymer arm or mixture of arms, with an average apparent molecular weight greater than 2000, measured with gel permeation chromatography (GPC) using polystyrene calibration standards, in accordance with ASTM D5296-11;
b) reacting the living polymer arm or arms with a polyalkenyl coupling agent;
c) terminating the polymerization if any living polymers remaining after step b); and
d) optionally functionalizing and/or hydrogenating the coupled polymer so produced,
wherein the polyalkenyl coupling agent is an alpha,omega-bis(vinylphenyl)alkane, and
wherein the living polymer arm or mixture of arms is capped with one or more styrene monomer molecules before step b); and
wherein a hydrocarbon lithium based initiator is used to prepare the living polymer in a concentration of from 10 to 2000 ppm Li based on the weight of the monomer or the mixture of monomers in step a).
2. The process of claim 1 , wherein the polyalkenyl coupling agent is 1,2-bis(vinylphenyl)ethane.
3. The process of claim 1 , wherein the amount of coupling agent added is at least 0.2 mole per mole of living polymer.
4. The process of claim 1 , wherein the coupling agent is added in a single shot or more stages.
5. The process of claim 1 , wherein more than the stoichiometric amount of coupling agent is used, and wherein the coupling agent molecules polymerize to form a core or nucleus of polymerized or even cross-linked coupling agent molecules.
6. The process of claim 1 , wherein in step c) a deactivator is selected from the group consisting of water, alcohols, carboxylic acids, compounds with one active halogen atom, compounds with one ester group and carbon dioxide.
7. The process of claim 1 , wherein, prior to step c), the living polymer is reacted with further amounts of monomers.
8. The process of claim 1 , wherein at least 50%, of the original olefinic unsaturation of the polymer is hydrogenated in step d).
9. The process of claim 8 wherein less than 10% of aromatic unsaturation is hydrogenated.
10. The process of claim 1 , wherein the isomer mixture in the coupling agent is varied to control the amount of star-shaped versus linear coupled polymer made in the coupling step b).
11. A conjugated diene polymer obtainable by the process of claim 1 comprising at least two arms with an average apparent molecular weight greater than 2000, measured with gel permeation chromatography (GPC) using polystyrene calibration standards, in accordance with ASTM D5296-11, attached to the residue of a coupling agent, wherein the polyalkenyl coupling agent is an alpha, omega-bis(vinylphenyl)alkane.
12. The conjugated diene polymer of claim 11 , wherein the polyalkenyl coupling agent is 1,2-bis(vinylphenyl)ethane.
13. The conjugated diene polymer of claim 11 , wherein the conjugated diene polymer is a homopolymer of isoprene or butadiene or a copolymer of isoprene and butadiene.
14. The conjugated diene polymer of claim 11 , wherein the conjugated diene polymer is a block copolymer with at least one block of a monoalkenyl arene compound and at least one block of a conjugated diene selected from the group consisting of isoprene, butadiene, a mixture of isoprene/styrene, a mixture of butadiene/styrene, a mixture of isoprene/butadiene or a mixture of i soprene/butadiene/styrene.
15. A viscosity index improver comprising the conjugated diene polymer of claim 11 in a hydrocarbon solvent.
16. An aqueous emulsion of the conjugated diene polymer of claim 11 .
17. An article made from the aqueous emulsion of the conjugated diene polymer of claim 16 and wherein said article is made by dipping.