Thermoplastic moulding compositions with appropriately designed graft shell

Patent metadata

Field	Value
Publication number	US-10072145-B2
Application number	US-201415038510-A
Country	US
Kind code	B2
Filing date	Nov 19, 2014
Priority date	Nov 26, 2013
Publication date	Sep 11, 2018
Grant date	Sep 11, 2018

Abstract

The invention relates to a thermoplastic molding composition which comprises at least one copolymer component made of styrene monomers and nitrile monomers, and also at least one graft copolymer based on an acrylate rubber. The invention also relates to thermoplastic moldings produced from the thermoplastic molding composition, and the use thereof.

First claim

What is claimed is:

1. A thermoplastic molding composition comprising:
from 55 to 85% by weight of at least one copolymer A composed of 66 to 68% by weight of styrene and/or α-methylstyrene A1 and of 32 to 34% by weight of acrylonitrile A2,
from 10 to 40% by weight of at least one graft copolymer B composed of
B1: from 50 to 80% by weight, based on B, of an elastomeric, crosslinked acrylate polymer B1 with average particle diameter (weight average) in the range from 300 to 700 nm as graft base B1,
B2: a first graft shell B2 made of from 5 to 30% by weight, based on B, of a vinylaromatic monomer B21, and
B3: a second graft shell B3 made of from 15 to 40% by weight, based on B, of a mixture of vinylaromatic monomers B31 and nitrile monomers B32, and wherein the graft shell B3 is composed of styrene as vinylaromatic monomer B31 and acrylonitrile as nitrile monomer B32 in a ratio by weight of from 76:24 to 74:26,

from 0 to 30% by weight of at least one small-particle graft copolymer B′ with average particle diameter (weight average) from 80 to 200 nm,
from 0 to 5% by weight of additives and/or auxiliaries C,
where the content of nitrile monomer (unit) in copolymer component A of the thermoplastic molding composition is at least 8% by weight higher than the content of nitrile monomer (unit) in the graft shell B3 and
where the acrylonitrile content in the graft shell B3 exhibits a distribution, wherein that part of the graft shell B3 that is further from the graft base B1 has higher acrylonitrile content, and that part of the graft shell B3 that is closer to the graft base B1 has lower acrylonitrile content.

2. The molding composition as claimed in claim 1 , wherein the at least one graft polymer B is composed of
B1: from 60 to 70% by weight, based on B, of an elastomeric, crosslinked acrylate polymer B1 with average particle diameter (weight average) in the range from 300 to 700 nm as graft base B1,
B2: a first graft shell B2 made of from 10 to 20% by weight, based on B, of a vinylaromatic monomer B21, and
B3: a second graft shell B3 made of from 20 to 30% by weight, based on B, of a mixture of vinylaromatic monomers B31 and nitrile monomers B32, where the ratio by weight of these monomers B31 to B32 in the graft shell B3 is from 76:24 to 74:26.

3. The molding composition as claimed in claim 1 , characterized in that the graft copolymer B is produced by starting from a graft base B1 with average particle diameter (weight average) in the range from 400 to 600 nm.

4. The molding composition as claimed in claim 1 , characterized in that the graft copolymer B is produced by starting from a graft base B1 with average particle diameter (weight average) in the range from 440 to 520 nm.

5. The molding composition as claimed in claim 1 , characterized in that the graft copolymer B is produced from:
from 60 to 70% by weight of the graft base B1, and
from 10 to 20% by weight of the graft shell B2 made of styrene, and also
from 20 to 30% by weight of a graft shell B3 composed of B31 and B32 in a ratio by weight of from 76:24 to 74:26.

6. The molding composition as claimed in claim 1 , characterized in that the graft copolymer B is produced by starting from a graft base B1 with butyl acrylate content >90% by weight, based on B1.

7. The molding composition as claimed in claim 1 , characterized in that the graft copolymer B is produced by starting from a graft base B1 with butyl acrylate content from 92 to 99% by weight, based on B1.

8. The molding composition as claimed in claim 1 , characterized in that the graft copolymer B is produced by starting from:
from 60 to 70% by weight of the graft base B1,
from 10 to 20% by weight of styrene B2, and
from 20 to 30% by weight of a mixture B3 of styrene and acrylonitrile in a ratio by weight of 75:25.

9. The molding composition as claimed in claim 1 , characterized in that the at least one copolymer A is composed of styrene A1 and acrylonitrile A2 in the ratio by weight 67:33, and that the molding composition comprises components A and B in a ratio by weight of from 85:15 to 60:35.

10. The molding composition as claimed in claim 1 , characterized in that it comprises: from 55 to 80% by weight of copolymers A, from 10 to 40% by weight of graft copolymer B, and also from 0.2 to 5% by weight of additives and/or auxiliaries C.

11. The molding composition as claimed in claim 1 , characterized in that the particle size distribution of the graft base B1 is narrow (Q being from 0.14 to 0.2) and the particle size distribution of the graft copolymer B is also narrow (Q being from 0.14 to 0.2).

12. The molding composition as claimed in claim 1 , characterized in that the average particle diameter (weight average) of the graft copolymer B equipped with two graft shells (B2 and B3) is in the range from 400 to 600 nm.

13. The molding composition as claimed in claim 1 , characterized in that the average particle diameter (weight average) of the graft copolymer B equipped with two graft shells (B2 and B3) is in the range from 500 to 580 nm.

14. A molding, film, or coating comprising a molding composition as claimed in claim 1 .

15. A process for the production of a thermoplastic styrene copolymer molding composition, characterized in that it includes the following steps:
a) a graft copolymer B is produced by using the following steps:
a1) an elastomeric, crosslinked acrylate polymer with average particle diameter (weight average) in the range from 300 to 700 nm is used as graft base B1,
a2) a first graft shell B2 made of a vinylaromatic monomer B21 is applied by polymerization to said graft base B1, where this reaction takes place via continuous addition of the monomer B21at a temperature below 65° C., and where this step takes place within a period of from 45 to 90minutes and continued polymerization within a period of less than 30 minutes,
wherein the copolymer product obtained in step a2) also comprises from 0.1 to 10% by weight of styrene monomer which is available for the polymerization for the second graft shell B3,

a3) a second graft shell B3 made of a mixture of vinylaromatic monomers B31 and nitrile monomers B32 is applied by polymerization on the copolymer product obtained from step a2), where the monomers B31 and B32 are present in a ratio by weight of about 3:1 in the graft shell B3, where this reaction takes place via continuous addition of the monomer mixture at a temperature of from 60 to 68° C., and where this step takes place within a period of from 120 to 240 minutes,

b) the graft copolymer B obtained is isolated by precipitation and subjected to a drying step,
c) a quantity of from 10 to 40% by weight of the graft copolymer B obtained is mixed with from 55to 85% by weight of at least one copolymer A composed of styrene and/or α-methylstyrene A1and of acrylonitrile A2, where A1 and A2 are present in a ratio by weight of about 2:1 in the copolymer A, and optionally with from 0 to 5% by weight of other additives and/or auxiliaries C.

16. The process for the production of a thermoplastic styrene copolymer molding composition as claimed in claim 15 , characterized in that the graft copolymer B is produced by starting from a graft base B1 made of butyl acrylate and tricyclodecenyl acrylate with average particle diameter (weight average) in the range from 440 to 520 nm, that the graft shell B2 is composed of styrene, and the graft shell B3 is composed of styrene and acrylonitrile in a ratio by weight of from 76:24 to 74:26, and that the copolymer A is composed of styrene and acrylonitrile in a ratio by weight of 67:33.

Assignees

• Ineos Styrolution Group Gmbh

Inventors

• Boeckmann Philipp
• Fischer Wolfgang
• Staal Maarten

Classifications

• C08L25/12 Primary

  with unsaturated nitriles · CPC title

• C08J2451/00

  Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers · CPC title

• C08J2325/12

  with unsaturated nitriles · CPC title

• C08L51/04

  grafted on to rubbers · CPC title

• C08F220/44

  Acrylonitrile · CPC title