Method of producing ABS polyblends having a low residual monomer content

• US 3,991,136 A
• Filed: 04/02/1975
• Issued: 11/09/1976
• Est. Priority Date: 04/02/1975
• Status: Expired due to Term

• Current Assignee: Monsanto Company (Bayer AG)
• Original Assignee: Monsanto Company (Bayer AG)
• Inventors: Dalton, William O., Peng, Fred M.
• Primary Examiner(s): Michl, Paul R.
• Application Number:
  US05/564,516
• Time in Patent Office: 587 Days
• Field of Search: 260/880 R
• US Class Current: 525/261
• CPC Class Codes: C08F 218/08 Vinyl acetate
• CPC Class Codes: C08F 220/14 Methyl esters , e.g. methyl (meth)acrylate
• CPC Class Codes: C08F 279/04 Vinyl aromatic monomers and nitriles as the only monomers
• CPC Class Codes: C08F 285/00 Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers

Abstract

An improved process for preparing ABS polyblends, the steps comprising, polymerizing a polymerizable mixture of a monomer formulation and a diene rubber forming a grafted copolymer and a matrix interpolymer, the improvement comprising, polymerizing said monomer formulation to at least about 90% conversion, charging a third monomer and further polymerizing said monomer formulation in the presence of said third monomer to convert essentially all of said monomer formulation to interpolymer followed by recovering said polyblend having a low residual monomer content.

Claims

1. In an improved process for preparing an ABS polyblend having a low residual monomer content, the steps comprising:

A. polymerizing a polymerizable mixture comprising a monomer formulation, a molecular weight regulator and a prepolymerized graftable rubber containing a diene monomer component, to graft at least a portion of the polymerizing monomers as superstrate interpolymer on said rubber as a rubber substrate to provide a graft copolymer, said monomer formulation consisting essentially of from about 60 to 85 percent by weight of styrene and from about 15 to 40 percent by weight of acrylonitrile, forming during polymerization thereof, an ABS polyblend of said graft copolymer and a matrix interpolymer, the improvement comprising;

B. charging a third monomer selected from the group consisting of vinyl acetate and methyl methacrylate and mixtures thereof to said polymerizable mixture in step (A) after polymerizing about 90 to 98% by weight of said monomer formulation, said third monomer being charged in an amount equivalent to about 2 to 10 percent by weight of the monomer formulation.

C. further polymerizing said monomer formulation in the presence of said third monomer so as to convert essentially all of said monomer formulation to interpolymer, reducing said monomers of said monomer formulation to less than about 1.0% by weight as residual monomers in said interpolymer, and

D. recovering said polyblend from said polymerizing mixture and drying said polyblend to remove essentially all residual monomers.

2. A process of claim 1, wherein said third monomer is methyl methacrylate.

3. A process of claim 1, wherein a molecular weight regulator selected from the group consisting of normal alkyl mercaptans and tertiary alkyl mercaptans or mixtures thereof, is present in said polymerizable mixture.

4. A process of claim 3, wherein said molecular weight regulator is n-dodecyl mercaptan.

5. A process of claim 3, wherein said molecular weight regulator is tert-dodecyl mercaptan.

6. A process of claim 3, wherein said molecular weight regulator is present in said polymerizable mixture in an amount of from about 0.001 to 2.5 percent by weight of said monomer formulation.

7. A process of claim 1, wherein a free radical generating catalyst is present in said polymerizable mixture during the polymerization thereof.

8. A process of claim 7, wherein said catalyst is present in an amount of from about 0.001 to 2.0 percent by weight of said monomer formulation.

9. A process of claim 7, wherein said catalyst is selected from the group consisting of water soluble and oil soluble catalysts and mixtures thereof.

10. A process of claim 9, wherein said water soluble catalyst is selected from the group consisting of alkali metal peroxides, persulfates, perborates, peracetates, percarbonates and hydrogen peroxide or mixtures thereof.

11. A process of claim 9, wherein said catalyst is activated forming a redox catalyst system.

12. A process of claim 10, wherein said catalyst is potassium persulfate.

13. A process of claim 10, wherein said catalyst is added to said polymerizable mixture continuously during the polymerization thereof in step (A).

14. A process of claim 10, wherein said catalyst is added to said polymerizable mixture incrementally with said monomer formulation.

15. A process of claim 1, wherein said polymerization of step (A) is carried out in an aqueous emulsion having said polymerizable mixture dispersed therein, said graftable diene rubber being dispersed as rubber particles having a weight average particle size diameter of from about 0.03 to 1.0 microns.

16. A process of claim 1, wherein the rubber substrate is a diene rubber polymer having at least about 75 percent by weight of a conjugated 1,3 diene monomer.

17. A process of claim 1, wherein said ABS polyblend formed has present about 10 to 50 percent by weight of said graft copolymer.

18. A process of claim 1, wherein said monovinylidene aromatic hydrocarbon and said ethylenically unsaturated nitrile comprises at least about 75 percent by weight of said monomer formulation.

19. A process of claim 1, wherein said monomer formulation has a weight ratio to said graftable rubber of from about 20-250:

100 in said polymerizable mixture.

20. A process of claim 1, wherein said graft copolymer has about 0.7 to 70.0 ×

10^-7 grams of superstrate for square centimeter of substrate surface, said substrate rubber having a weight average particle size of from about 0.03 to 1.0 microns.

21. A process of claim 1, wherein said polymerization of step (A) is carried out by mass-suspension polymerization in combination with steps (B), (C) and (D).