Weather-resistant, high-impact strength acrylic compositions

• US 7,294,399 B2
• Filed: 03/24/2003
• Issued: 11/13/2007
• Est. Priority Date: 04/02/2002
• Status: Expired due to Term

• Current Assignee: Trinseo Europe Gmbh
• Original Assignee: Arkema France (Arkema)
• Inventors: Wanat, Robert A., Crabb, Charles C., Labanoski, Dennis J.
• Primary Examiner(s): MULLIS, JEFFREY C
• Application Number:
  US10/395,643
• Publication Number:
  US 20030216510A1
• Time in Patent Office: 1,695 Days
• Field of Search: 428/412, 428/483, 428/500, 428/522, 525/64, 525/67, 525/85, 525/87
• US Class Current: 428/412
• CPC Class Codes: C08L 2666/24 Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• CPC Class Codes: C08L 33/12 Homopolymers or copolymers of methyl methacrylate
• CPC Class Codes: C08L 51/00 Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds for ABS polymers C08L55/02; Compositions of derivatives of such polymers
• CPC Class Codes: Y10T 428/31507 Of polycarbonate
• CPC Class Codes: Y10T 428/31797 Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers

Abstract

Disclosed is an improved weatherable thermoplastic composition. The composition is comprised of a copolymer of an alkyl acrylate or alkyl methacrylate and (methyl)methacrylate and a multi-stage, sequentially-polymerized impact modifier polymer. The copolymer is characterized by greater than 15 weight percent alkyl acrylate content. The multi-stage, sequentially-polymerized impact modifier is characterized by an elastomer stage, which is 55 percent by weight or greater of the impact modifier composition and is minimally crosslinked. The thermoplastic composition can be used in a wide range of film, sheet, or molded applications.

Claims

1. A thermoplastic composition comprised of

a. about 40-90 weight percent of a rigid thermoplastic copolymer matrix consisting of 50-85 weight percent methyl methacrylate, and 15-50 weight percent of an alkyl acrylate selected from the group consisting of ethyl acrylate, methyl acrylate, and mixtures thereof;

and

b. about 10-60 weight percent of a multi-stage, sequentially-produced polymer characterized by;

(A) a first stage which is optionally non-elastomeric, relatively hard, and has a glass transition temperature of greater than 25°

C., and which is polymerized from a monomer mixture consisting of 50-85 weight percent of methyl methacrylate, and 15-50 weight percent of an alkyl acrylate selected from the group consisting of ethyl acrylate, methyl acrylate, and mixtures thereof, 0 to 10 weight percent of a copolymerizable polyfunctional crosslinking monomer, and 0 to 10 weight percent of a copolymerizable graftlinking monomer having two or more addition polymerizable unsaturated reactive groups which participate in the polymerization reaction at substantially different rates said percentages of said alkyl acrylate, methyl methacrylate, polyfunctional crosslinking monomer and graftlinking monomer adding up to 100 percent;

(B) an intermediate stage which is elastomeric and which is polymerized in the presence of the first stage, from a monomer mixture comprising 50 to 99.9 weight percent of an alkyl acrylate and/or alkyl methacrylate mixtures thereof wherein the alkyl groups contain 1 to 8 carbon atoms, 0 to 49.9 weight percent of a copolymerizable monoethylenically unsaturated monomer, 0 to 5.0 weight percent of a copolymerizable polyfunctional crosslinking monomer, and 0.05 to 5.0 weight percent of a copolymerizable graftlinking monomer as described above, said intermediate stage further characterized in that it would exhibit a glass transition temperature of 25°

C. or less if the monomers were polymerized in the absence of the first stage; and

(C) at least one final stage which is relatively hard and which is polymerized in the presence the first and intermediate stages from a monomer mixture of the monomers described above for the rigid thermoplastic polymer, the final stage further characterized in that it would exhibit a glass transition temperature of greater than 50°

C. if the monomers were polymerized in the absence of first and intermediate stages, the graft linking monomer having two or more addition polymerizable unsaturated reactive groups which participate in the polymerization reaction at substantially different rates and the cross-linking monomer having a plurality of addition polymerizable unsaturated groups all of which participate in the polymerization reaction at about the same rate as one another.

2. The composition of claim 1 wherein the multi-stage polymer is a three stage composition wherein the stages are present in ranges of 10 to 40 percent by weight of the first stage (A), 45 to 70 percent of the second intermediate stage (B), and 10 to 50 percent of the final stage (C), all percentages based on the total weight of the three-stage polymer.

3. The composition of claim 1 wherein the multi-stage polymer is a three stage composition wherein the stages are present in ranges of 10 to 20 percent of the first stage (A), 50 to 60 percent of the second intermediate stage (B), and 20 to 40 percent of the final stage (C), all percentages based on the total weight of the three-stage polymer.

4. A coextruded sheet or profile where at least one layer consists of the thermoplastic composition of claim 1.

5. The coextruded sheet or profile of claim 4 wherein a layer of the coextruded sheet is selected from the group consisting of (meth)acrylic polymers and copolymers;

polycarbonate;

polyesters and copolyesters;

vinyl polymers and copolymers, and styrene polymers and copolymers.

6. The coextruded sheet or profile of claim 5 where the claimed resin is used in an outer layer as a weather resistant capstock.

7. The thermoplastic composition of claim 1, wherein said rigid thermoplastic matrix copolymer consists of 50-75 weight percent methyl methacrylate, and about 25 weight percent of ethyl acrylate.

8. The thermoplastic composition of claim 1 wherein said composition has the characteristic of being die-cut without cracking or undergoing brittle fracture.

9. An extruded sheet or profile made from a weatherable thermoplastic composition comprising a matrix copolymer of an alkyl acrylate and methylmethacrylate and a multi-stage, sequentially-polymerized impact modifier polymer, the copolymer characterized by greater than 15 weight percent alkyl acrylate content, wherein the alkyl group consists of 1 to 4 carbon atoms, and the multi-stage, sequentially-polymerized impact modifier characterized by a core polymer consisting of 50-85 weight percent of methyl methacrylate, and 15-50 weight percent of an alkyl acrylate selected from the group consisting of ethyl acrylate, methyl acrylate, and mixtures thereon 0 to 10 weight percent of a copolymerizable polyfunctional crosslinking monomer, and 0 to 10 weight percent of a copolymerizable graftlinking monomer;

said percentages of said alkyl acrylate, methyl methacrylate, polyfunctional crosslinking monomer and graftlinking monomer adding up to 100 percent and an elastomer stage which is 55 percent by weight or greater of the impact modifier polymer and said elastomer stage containing from 0 to 5 weight percent of polyfunctional crosslinking monomer units.

10. The extruded sheet or profile of claim 9, wherein said matrix copolymer consists of about 25 weight percent alkyl acrylate content.

11. An embossed sheet made from a weatherable thermoplastic composition comprising a matrix copolymer of an alkyl acrylate and methylmethacrylate and a multi-stage, sequentially-polymerized impact modifier polymer, the copolymer characterized by greater than 15 weight percent alkyl acrylate content, wherein the alkyl group consists of 1 to 4 carbon atoms, and the multi-stage, sequentially-polymerized impact modifier characterized by a core polymer consisting of 50-85 weight percent of methyl methacrylate, and 15-50 weight percent of an alkyl acrylate selected from the group consisting of ethyl acrylate, methyl acrylate, and mixtures thereof, 0 to 10 weight percent of a copolymerizable polyfunctional crosslinking monomer, and 0 to 10 weight percent of a copolymerizable graftlinking monomer;

said percentages of said alkyl acrylate, methyl methacrylate, polyfunctional crosslinking monomer and graftlinking monomer adding up to 100 percent and an elastomer stage which is 55 percent by weight or greater of the impact modifier polymer and said elastomer stage containing from 0 to 5 weight percent of polyfunctional crosslinking monomer units.

12. The embossed sheet of claim 11, wherein said matrix copolymer consists of about 25 weight percent alkyl acrylate content.

13. A film comprising a weatherable thermoplastic composition comprising a matrix copolymer of an alkyl acrylate and methylmethacrylate and a multi-stage, sequentially-polymerized impact modifier polymer, the matrix copolymer characterized by 50 to 85 weight percent methyl methacrylate and 15-50 weight percent alkyl acrylate content, selected from the group consisting of ethyl acrylate, methyl acrylate, and mixtures thereof, and the multi-stage, sequentially-polymerized impact modifier characterized by a core polymer consisting of 50-85 weight percent of methyl methacrylate, and 15-50 weight percent of an alkyl acrylate selected from the group consisting of ethyl acrylate, methyl acrylate, and mixtures thereof, 0 to 10 weight percent of a copolymerizable polyfunctional crosslinking monomer, and 0 to 10 weight percent of a copolymerizable graftlinking monomer;

said percentages of said alkyl acrylate, methyl methacrylate, polyfunctional crosslinking monomer and graftlinking monomer adding up to 100 percent and an elastomer stage which is 55 percent by weight or greater of the impact modifier polymer and said elastomer stage containing from 0 to 5 weight percent of polyfunctional crosslinking monomer units.

14. The film of claim 13 made into a multilayer film.

15. The film of claim 13 used for in-mold decorating.

16. The film of claim 13 laminated to a plastic sheet or profile.

17. The film of claim 13 used as a protective layer in a sign or reflective sign.

18. The film of claim 13, wherein said matrix copolymer consists of about 25 percent alkyl acrylate content.