Method for preparing a multi-layered polymeric composite and a multi-layered composite produced thereby

• US 20020054996A1
• Filed: 09/13/2001
• Published: 05/09/2002
• Est. Priority Date: 09/14/2000
• Status: Active Grant

• Current Assignee: Rohm and Haas Company (Dow, Inc.)
• Original Assignee: Rohm and Haas Company (Dow, Inc.)
• Inventors: Rheenen, Paul Ralph Van
• Granted Patent: US 6,682,809 B2
• Time in Patent Office: Days
• US Class Current: 428/420
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: C08F 257/02 on to polymers of styrene or alkyl-substituted styrenes
• CPC Class Codes: C08F 265/04 on to polymers of esters
• CPC Class Codes: C08F 265/06 Polymerisation of acrylate or methacrylate esters on to polymers thereof
• CPC Class Codes: C08F 290/00 Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
• CPC Class Codes: C08F 290/04 Polymers provided for in subclasses C08C or C08F
• CPC Class Codes: C08F 290/046 Polymers of unsaturated carboxylic acids or derivatives thereof
• CPC Class Codes: C08F 290/06 Polymers provided for in subclass C08G
• CPC Class Codes: C08F 290/061 Polyesters; Polycarbonates
• CPC Class Codes: C08F 291/00 Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• CPC Class Codes: C08L 101/00 Compositions of unspecified macromolecular compounds
• CPC Class Codes: C08L 23/0815 Copolymers of ethene with aliphatic 1-olefins
• CPC Class Codes: C08L 23/10 Homopolymers or copolymers of propene
• CPC Class Codes: C08L 23/16 Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
• CPC Class Codes: C08L 23/20 having four to nine carbon atoms
• CPC Class Codes: C08L 23/22 Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
• CPC Class Codes: C08L 2314/06 Metallocene or single site catalysts
• CPC Class Codes: C08L 25/12 with unsaturated nitriles
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/04 : Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 2666/14 : Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• 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 27/06 : Homopolymers or copolymers of vinyl chloride
• CPC Class Codes: C08L 27/24 : halogenated
• CPC Class Codes: C08L 33/00 : Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 33/06 : of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• CPC Class Codes: C08L 33/10 : Homopolymers or copolymers of methacrylic acid esters
• 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: C08L 51/003 : grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C08L51/04, C08L51/06 take precedence
• CPC Class Codes: C08L 53/00 : Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 53/02 : of vinyl-aromatic monomers and conjugated dienes
• CPC Class Codes: C08L 55/02 : ABS [Acrylonitrile-Butadiene-Styrene] polymers
• CPC Class Codes: C08L 67/02 : Polyesters derived from dicarboxylic acids and dihydroxy compounds C08L67/06 takes precedence
• CPC Class Codes: C08L 67/06 : Unsaturated polyesters
• CPC Class Codes: C08L 69/00 : Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• CPC Class Codes: C08L 77/00 : Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 77/02 : Polyamides derived from omega-amino carboxylic acids or from lactams thereof C08L77/10 takes precedence
• CPC Class Codes: C08L 77/06 : Polyamides derived from polyamines and polycarboxylic acids C08L77/10 takes precedence
• CPC Class Codes: C09D 151/003 : grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C09D151/04, C09D151/06 take precedence
• CPC Class Codes: C09D 153/00 : Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
• CPC Class Codes: C09J 133/00 : Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
• CPC Class Codes: C09J 133/10 : Homopolymers or copolymers of methacrylic acid esters
• CPC Class Codes: C09J 151/003 : grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C09J151/04, C09J151/06 take precedence
• CPC Class Codes: C09J 2301/302 : the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
• CPC Class Codes: Y10T 428/31536 : Including interfacial reaction product of adjacent layers
• CPC Class Codes: Y10T 428/3175 : Next to addition polymer from unsaturated monomer[s]
• CPC Class Codes: Y10T 428/31797 : Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31913 : Monoolefin polymer
• CPC Class Codes: Y10T 428/31917 : Next to polyene polymer
• CPC Class Codes: Y10T 428/3192 : Next to vinyl or vinylidene chloride polymer
• CPC Class Codes: Y10T 428/31928 : Ester, halide or nitrile of addition polymer
• CPC Class Codes: Y10T 428/31931 : Polyene monomer-containing
• CPC Class Codes: Y10T 428/31935 : Ester, halide or nitrile of addition polymer

Abstract

The present invention relates to: a method of preparing a capstock layer that includes a comb copolymer; a method of preparing a multi-layered polymeric composite, one layer of which is a capstock layer; and a capstock layer and a multi-layered composite formed, respectively, thereby.

Claims

1. A composition comprising a comb copolymer:

wherein said comb copolymer comprises a backbone and at least one graft segment; and

wherein;

(i) said graft segment and said backbone are in a weight ratio from 30;

70 to 60;

40;

(ii) said backbone is immiscible with said graft segment at room temperature;

(iii) said backbone has a glass transition temperature of −

65°

C. to 10°

C.; and

(iv) said graft segment has a glass transition temperature of 60 to 180°

C.

2. The composition of claim 1, wherein said composition is a capstock layer having a thickness of 10 microns to 1,000 microns.

3. The composition of claim 1, wherein said comb copolymer has a weight average molecular weight of 80,000 to 2,000,000.

4. The composition of claim 1, wherein said graft segment has a degree of polymerization of 10 to 1,000.

5. The composition of claim 1:

wherein said composition is an impact resistant capstock layer having a composition which is the same as the composition of Dropping Dart Impact specimens prepared and tested according to ASTM method D-446 with impact head configuration H.25; and

wherein said Dropping Dart Impact specimens have a dart impact energy of at least 2.0 joules.

6. A process comprising the steps of:

(a) forming a capstock composition;

(b) feeding said capstock composition into an extruder comprising a feed section and a metering section;

(c) metering and melting said capstock composition to form a capstock melt;

(d) forming said capstock melt into a capstock melt layer;

(e) extruding said capstock melt layer; and

(f) cooling said capstock melt layer to form a solid capstock layer;

wherein said capstock composition comprises a comb copolymer comprising a backbone and at least one graft segment; and

wherein;

(i) said graft segment and said backbone are in a weight ratio from 30;

70 to 60;

40;

(ii) said backbone is immiscible with said graft segment at room temperature;

(iii) said backbone has a glass transition temperature of −

65°

C. to 10°

C.; and

(iv) said graft segment has a glass transition temperature of 60 to 180°

C.

7. A coextrusion process comprising the steps of:

(A) forming a capstock melt layer by a process comprising the steps of;

(a) forming a capstock composition;

(b) feeding said capstock composition into a first extruder comprising a feed section and a metering section;

(c) metering and melting said capstock composition to form a capstock melt;

(d) forming said capstock melt into a capstock melt layer; and

(e) extruding said capstock melt layer;

wherein said capstock composition comprises a comb copolymer comprising a backbone and at least one graft segment; and

wherein;

(i) said graft segment and said backbone are in a weight ratio from 30;

70 to 60;

40;

(ii) said backbone is immiscible with said graft segment at room temperature;

(iii) said backbone has a glass transition temperature of −

65°

C. to 10°

C.; and

(iv) said graft segment has a glass transition temperature of 60 to 180°

C.

(B) forming a substrate melt layer by a process comprising the steps of;

(a) forming a substrate composition;

(b) feeding said substrate composition into a second extruder comprising a feed section and a metering section;

(c) metering and melting said substrate composition to form a substrate melt;

(d) forming said substrate melt into a substrate melt layer;

(e) extruding said substrate melt layer; and

wherein said substrate composition comprises a thermoplastic polymer;

(C) causing said capstock melt layer to contact said substrate melt layer to form a multi-layered melt composite; and

(D) cooling said multi-layered melt composite to form said multi-layered polymeric composite, comprising a solid capstock layer disposed upon a solid substrate layer.

8. The method of claim 7, wherein said thermoplastic polymer is a polymer selected from the group consisting of poly(vinyl halide), chlorinated poly(vinyl chloride), ABS terpolymer, polyaromatics, polyamides, polyesters, polyolefins, and combinations thereof.

9. The method of claim 7, wherein said thermoplastic polymer is a polymer selected from the group consisting of poly(vinyl chloride) and ABS terpolymer.

10. A multi-layered polymeric composite comprising:

(a) at least one solid substrate layer comprising a thermoplastic resin; and

(b) at least one solid capstock layer disposed thereon, wherein said solid capstock layer comprises a comb copolymer;

wherein said comb copolymer comprises a backbone and at least one graft segment; and

wherein;

(i) said graft segment and said backbone are in a weight ratio from 30;

70 to 60;

40;

(ii) said backbone is immiscible with said graft segment at room temperature;

(iii) said backbone has a glass transition temperature of −

65°

C. to 10°

C.; and

(iv) said graft segment has a glass transition temperature of 60 to 180°

C.

11. The composite of claim 10:

wherein said capstock layer is an impact resistant capstock layer having a composition which is the same as the composition of Dropping Dart Impact specimens prepared and tested according to ASTM method D-446 with impact head configuration H.25; and

wherein said Dropping Dart Impact specimens have a dart impact energy of at least 2.0 joules.