Monovinylidene aromatic polymers comprising sulfanylsilane functionalized elastomeric polymers
View Patent ↗The present invention is a rubber modified monovinylidene aromatic polymer composition where the rubber is a sulfanylsilane chain end modified elastomeric polymer. In the present invention the functionalized rubber provides sufficient grafting levels in standard graft polymerization process technologies to prepare desired rubber particle size distributions and morphologies. Across a range of rubber modified monovinylidene aromatic polymers, it has been found that the use of the modified elastomeric polymers according to the present invention can improve the combinations of resin properties, particularly clarity, surface and physical properties, including both rubber modified monovinylidene aromatic homopolymers (e.g., high impact polystyrene and copolymers (e.g., ABS). The functionalized rubbers have sulfanyl functional groups that provide an optimized reactive grafting site. This ensures that under graft polymerization conditions a monovinylidene aromatic polymer block is formed grafted to the butadiene polymer block. This is particularly desirable to enable the use of polybutadiene homopolymer rubbers which are more cost effectively used in rubber-modified monovinylidene aromatic polymers.
1. A rubber modified monovinylidene aromatic polymer composition comprising:
a) a monovinylidene aromatic polymer; and
b) from about 1 to about 40 percent by weight sulfanylsilane modified elastomeric polymer dispersed as particles grafted with monovinylidene aromatic polymer.
2. A polymer composition according to claim 1 comprising grafted sulfanylsilane modified elastomeric polymer as represented by the following formula:
(D) z (RO) x (R) y Si—R′—S-Polymer
wherein:
D is an elastomeric polymer chain,
x is an integer selected from 0, 1 and 2;
y is an integer selected from 0, 1, and 2;
z is an integer selected from 1, 2 and 3,
x+y+z= 3,
Si is silicon; S is sulfur; O is oxygen;
R is the same or different and is (C 1 -C 16 ) alkyl;
R′ is aryl, and alkyl aryl, or (C 1 -C 16 ) alkyl; and
Polymer is graft polymerized monovinylidene aromatic polymer.
3. A polymer composition according to claim 1 wherein D in the elastomeric polymer is a conjugated diene polymer chain.
4. A polymer composition according to claim 3 wherein D in the elastomeric polymer is a conjugated diene homopolymer rubber chain.
5. A polymer composition according to claim 4 wherein D in the elastomeric polymer is a polybutadiene chain.
6. A polymer composition according to claim 3 wherein D in the elastomeric polymer is a styrene-butadiene copolymer chain.
7. A polymer composition according to claim 1 where at least about 70 percent of the elastomeric polymer particles have a core/shell morphology.
8. A polymer composition according to claim 1 wherein the volume average particle size of the dispersed elastomeric polymer particles is from about 0.05 to about 10 microns.
9. A polymer composition according to claim 1 where the monovinylidene aromatic matrix polymer is polystyrene.
10. A polymer composition according to claim 9 comprising from about 3 to about 15 percent by weight elastomeric polymer.
11. A polymer composition according to claim 9 wherein the volume average particle size is from about 0.4 to about 1.5 microns.
12. A polymer composition according to claim 1 wherein the monovinylidene aromatic matrix polymer is poly(styrene-acrylonitrile).
13. A polymer composition according to claim 12 comprising from about 5 to about 20 percent by weight elastomeric polymer.
14. A polymer composition according to claim 12 wherein the volume average particle size is from about 0.3μ to about 4 microns.
15. A process for preparing a rubber modified monovinylidene aromatic polymer composition comprising polymerizing the monovinylidene aromatic polymer in the presence of from about 1 to about 40 percent by weight sulfanylsilane modified elastomeric polymer.
16. The process according to claim 15 wherein the sulfanylsilane modified elastomeric polymer is represented by the formulae:
(D) z (RO) x (R) y Si—R′—S—SiR 3 and (D) z (RO) x (R) y Si—R′—S—H
wherein:
D is an elastomeric polymer chain,
x is an integer selected from 0, 1 and 2;
y is an integer selected from 0, 1, and 2;
z is an integer selected from 1, 2 and 3,
x+y+z= 3,
Si is silicon; S is sulfur; O is oxygen;
R is the same or different and is (C 1 -C 16 ) alkyl; and
R′ is aryl, and alkyl aryl, or (C 1 -C 16 ) alkyl.
17. The process according to claim 16 where, in the elastomeric polymer, D is a polybutadiene chain.
18. A thermoformed article prepared from a polymer composition according to claim 1 .
19. An injection molded article prepared from a polymer composition according to claim 1 .
20. A sheet or film prepared from a polymer composition according to claim 1 .