IP Library Granted Patent US 10,731,031
Granted Patent B2
US 10,731,031 · App. 15/780,353 · Granted Aug 4, 2020

Method for producing ABS plastics having improved properties

Inventors: Gisbert Michels (Leverkusen, DE); Norbert Niessner (Friedelsheim, DE)
Assignee: INEOS STYROLUTION GROUP GMBH
C08L25/12C08F6/005C08F6/008C08L55/02C08L2205/03
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Quick Facts
Patent No.
US 10,731,031
App. No.
15/780,353
Granted
Aug 4, 2020
Kind
B2
Abstract

The invention relates to a method for producing thermoplastic molding materials based on acrylonitrile-butadiene-styrene copolymers (ABS) having improved surface properties, in particular improved resistance of the surface quality to storage in a warm, humid environment, and having a reduced content of residual monomers. The invention further relates to the use of a fluid bed dryer and/or a flash dryer in the production of thermoplastic ABS molding materials in order to improve the surface quality. The invention further relates to the use of a fluid bed dryer and/or a flash dryer in the production of thermoplastic ABS molding materials having a reduced content of residual monomers. The invention further relates to ABS molding materials that can be produced by means of the method according to the invention and to molded parts (e.g., molded bodies, films, and coatings) that can be produced from the thermoplastic molding materials according to the invention.

Claims (40)

1. A process for the production of a thermoplastic molding composition comprising:

A: from 5 to 95% by weight of at least one thermoplastic copolymer A produced from:

A1: from 50 to 95% by weight, based on the copolymer A, of a monomer A1 selected from styrene, α-methylstyrene, and mixtures of styrene and at least one other monomer selected from α-methylstyrene, p-methylstyrene, and C 1 -C 8 -alkyl (meth)acrylate,

A2: from 5 to 50% by weight, based on the copolymer A, of a monomer A2 selected from acrylonitrile and mixtures of acrylonitrile and at least one other monomer selected from methacrylonitrile, anhydrides of unsaturated carboxylic acids, and imides of unsaturated carboxylic acids,

B: from 5 to 95% by weight of at least one graft copolymer B comprising:

B1: from 40 to 85% by weight, based on the graft copolymer B, of at least one graft base B1 which is obtained via emulsion polymerization of:

B11: from 50 to 100% by weight, based on the graft base B1, of butadiene,

B12: from 0 to 50% by weight, based on the graft base B1, of at least one other monomer B12 selected from styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, isoprene, chloroprene, C 1 -C 4 -alkylstyrene, C 1 -C 8 -alkyl (meth)acrylate, alkylene glycol di(meth)acrylate, and divinylbenzene;

where the total quantity of B11+B12 is exactly 100% by weight; and

B2: from 15 to 60% by weight, based on the graft copolymer B, of a graft shell B2 which is obtained via emulsion polymerization in the presence of the at least one graft base B1 of:

B21: from 50 to 95% by weight, based on the graft shell B2, of a monomer B21 selected from styrene and mixtures of styrene and at least one other monomer selected from α-methylstyrene, p-methylstyrene, and C 1 -C 8 -alkyl (meth)acrylate,

B22: from 5 to 50% by weight, based on the graft shell B2, of a monomer B22 selected from acrylonitrile and mixtures of acrylonitrile and at least one other monomer selected from methacrylonitrile, anhydrides of unsaturated carboxylic acids, and imides of unsaturated carboxylic acids;

where the total quantity of graft base B1 and graft shell B2 is exactly 100% by weight; and

K: from 0 to 90% by weight of at least one other component K,

comprising the following steps:

a) precipitation of the at least one graft copolymer B after the emulsion polymerization reaction via addition of a precipitation solution comprising at least one salt and/or at least one inorganic acid;

b) mechanical dewatering of the precipitated graft copolymer B, where a graft copolymer B with water content smaller than or equal to 50% by weight is obtained;

c) drying of the dewatered graft copolymer B with use of a drying gas, where the graft copolymer B is caused to move in the drying gas and the temperature of the drying gas is in the range from 50 to 160° C.; and

d) mixing of the thermoplastic copolymer A, of the at least one dried graft copolymer B, and optionally of the other component(s) K.

2. The process of claim 1 , wherein the drying of the dewatered graft copolymer B in step c) takes place with use of a fluidized-bed drier and/or of a pneumatic drier.

3. The process of claim 1 , wherein the median particle diameter d 50 of the graft base B1 is in the range from 100 to 1000 nm.

4. The process of claim 1 , wherein the graft copolymer B is a mixture of at least two graft copolymers B-I and B-II, where:

graft copolymer B-I is obtained via emulsion polymerization of a mixture of the monomers B21 and B22 in the presence of a graft base B1-A which has a median particle diameter d 50 in the range from 230 to 330 nm and of a graft base B1-B which has a median particle diameter d 50 in the range from 340 to 480 nm; and

graft copolymer B-II is obtained via emulsion polymerization of a mixture of the monomers B21 and B22 in the presence of a graft base B1-C which has a median particle diameter d 50 in the range from 10 to 220 nm.

5. The process of claim 4 , wherein in step a) the graft copolymers B-I and B-II are mixed and the mixture of the graft copolymers is precipitated via addition of the precipitation solution comprising at least one salt.

6. The process of claim 1 , wherein the drying in step c) is carried out by means of a drying gas selected from air and/or nitrogen, where:

the drying is carried out with use of a fluidized-bed drier and the temperature of the drying gas is in the range from 50 to 100° C.; or

the drying is carried out with use of a pneumatic drier and the temperature of the drying gas is in the range from 100 to 160° C.

7. The process of claim 1 , wherein the drying in step c) is carried out by means of a drying gas selected from air and/or nitrogen, where:

the drying is carried out with use of a fluidized-bed drier, the temperature of the drying gas is in the range from 50 to 100° C., and the average residence time of the graft copolymer B in the fluidized-bed drier is from 10 to 60 min; or

the drying is carried out with use of a pneumatic drier, the temperature of the drying gas is in the range from 100 to 160° C., and the average residence time of the graft copolymer B in the pneumatic drier is from 1 to 300 seconds.

8. The process of claim 1 , wherein the drying in step c) is carried out by means of a drying gas selected from air and/or nitrogen, where:

the drying is carried out with use of a fluidized-bed drier which has one or more heat exchangers integrated into the fluidized bed, the temperature of the drying gas is in the range from 50 to 100° C., and the heat exchanger is operated at a temperature in the range from 50 to 100° C.

9. The process of claim 1 , wherein the dried graft copolymer B obtained in step c) has water content in the range from 0.05 to 0.8% by weight and total residual monomer content smaller than or equal to 2,000 ppm.

10. The process of claim 1 , wherein a fluidized-bed drier and/or of a pneumatic drier is used in the production of a thermoplastic molding composition for the drying of the graft copolymer B, the water content of which is less than or equal to 50% by weight, after the emulsion polymerization reaction, precipitation, and mechanical dewater of the graft copolymer B, in order to improve the surface quality of the thermoplastic molding composition.

11. The process of claim 9 , wherein the drying of the graft copolymer B is carried out in a fluidized-bed drier and/or a pneumatic drier by means of a drying gas selected from air and/or nitrogen, and the temperature of the drying gas is in the range from 50 to 160° C.

12. The process of claim 9 , wherein the improvement of the surface quality of the thermoplastic molding composition comprises a reduced number of surface defects after storage of the molding composition at a temperature in the range from 30 to 100° C. and relative humidity in the range from 65 to 100% and/or direct action of liquid water at a temperature in the range from 30 to 100° C. on the surface of the molding composition.

13. The process of claim 1 , wherein a fluidized-bed drier and/or of a pneumatic drier is used in the production of a thermoplastic molding composition for the drying of the graft copolymer B, the water content of which is smaller than or equal to 50% by weight, after emulsion polymerization, precipitation, and mechanical dewatering of the graft copolymer B, in order to reduce total residual monomer content in the graft copolymer B.

14. A thermoplastic molding composition obtained by a process of claim 1 , where the thermoplastic molding composition comprises salt inclusions and where the size of at least 80% of the salt inclusions, based on the total number of the salt inclusions, is smaller than 0.3 mm.

15. A molding produced from a thermoplastic molding composition of claim 14 .

Assignments (2)
FIRST LIEN INTELLECTUAL PROPERTY SECURITY AGREEMENT Recorded Apr 30, 2021
From: INEOS STYROLUTION GROUP GMBH
To: HSBC CORPORATE TRUSTEE COMPANY (UK) LIMITED
Reel/Frame 056103/0236 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 21, 2018
From: MICHELS, GISBERT; NIESSNER, NORBERT
To: INEOS STYROLUTION GROUP GMBH
Reel/Frame 046643/0349 →
Priority Claims (2)
EP 15197523 · Dec 2, 2015 · regional
EP 16190743 · Sep 27, 2016 · regional
Continuity (1)
Related Publication 20180355160A1 · Dec 13, 2018
Cited By (1)
US 12,698,351