Oligomeric chain extenders for processing, post-processing and recycling of condensation polymers, synthesis, compositions and applications

• US 6,984,694 B2
• Filed: 01/15/2003
• Issued: 01/10/2006
• Est. Priority Date: 02/01/2002
• Status: Expired due to Term

• Current Assignee: BASF Corporation (BASF SE), Clariant International AG (Clariant AG)
• Original Assignee: Johnson Polymers LLC
• Inventors: Villalobos, Marco A., Deeter, Gary A., Blasius, William George Jr.
• Primary Examiner(s): Robertson, Jeffrey B.
• Application Number:
  US10/342,502
• Publication Number:
  US 20040138381A1
• Time in Patent Office: 1,091 Days
• Field of Search: 525/123, 525/131, 525/132, 525/148, 525/153, 525/154, 525/163, 525/165, 525/178, 526/273, 526/317.1, 526/319, 526/328, 526/328.5, 526/329.7, 526/346
• US Class Current: 525/148
• CPC Class Codes: C08F 220/325 containing glycidyl radical, e.g. glycidyl (meth)acrylate
• CPC Class Codes: C08F 283/06 on to polyethers, polyoxymethylenes or polyacetals C08F283/004 takes precedence
• CPC Class Codes: C08F 283/10 on to polymers containing more than one epoxy radical per molecule C08F283/004 takes precedence
• 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 290/06 Polymers provided for in subclass C08G
• CPC Class Codes: C08G 18/831 by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides by aldehydes C08G18/84, by peroxides C08G18/86
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• 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 35/06 Copolymers with vinyl aromatic monomers
• 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 51/08 grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: C08L 59/00 Compositions of polyacetals; Compositions of derivatives of polyacetals of polyvinyl acetals C08L29/14
• CPC Class Codes: C08L 61/00 Compositions of condensation polymers of aldehydes or ketones with polyalcohols C08L59/00; with polynitriles C08L77/00; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 63/10 Epoxy resins modified by unsaturated compounds
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 69/00 Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• CPC Class Codes: C08L 71/12 Polyphenylene oxides
• CPC Class Codes: C08L 75/04 Polyurethanes
• 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 79/08 : Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C08L 81/00 : Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 81/06 : Polysulfones; Polyethersulfones
• CPC Class Codes: C09D 133/06 : of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
• CPC Class Codes: C09D 135/06 : Copolymers with vinyl aromatic monomers
• CPC Class Codes: C09D 151/00 : Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds based on ABS polymers C09D155/02; Coating compositions based on derivatives of such polymers
• 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

Abstract

The invention provides chain extenders made from epoxy-functional (meth)acrylic monomers and styrenic and/or (meth)acrylic monomers. The invention further provides polymeric compositions made from the chain extenders and plastic articles made from the compositions. Finally, the invention provides methods of using the chain extenders to improve the properties of virgin, recycled, and reprocessed condensation polymers.

Claims

1. A chain-extended polymeric composition comprising:

(a) a chain extender comprising a polymerization product of;

(i) at least one epoxy-functional (meth)acrylic monomer; and

(ii) at least one styrenic and/or (meth)acrylic monomer;

(b) at least one condensation polymer;

wherein the chain extender has an epoxy equivalent weight of from about 180 to about 2800, a number-average epoxy functionality (Efn) value of less than about 30, a weight-average epoxy functionality (Efw) value of up to about 140, and a number-average molecular weight (M_n) value of less than 6000 and wherein at least a portion of the chain extender has reacted with at least a portion of the at least one condensation polymer to produce a chain-extended condensation polymer wherein the polymeric composition is substantially free of gel particles.

2. The polymeric composition of claim 1, wherein the chain extender has a polydispersity index of from about 1.5 to about 5.

3. The polymeric composition of claim 1, wherein the chain extender comprises about 50 to about 80 weight percent of the at least one epoxy-functional (meth)acrylic monomer and about 20 to about 50 weight percent of the at least one styrenic and/or (meth)acrylic monomer.

4. The polymeric composition of claim 1, wherein the chain extender comprises about 25 to about 50 weight percent of the at least one epoxy-functional (meth)acrylic monomer and about 50 to about 75 weight percent of the at least one styrenic and/or (meth)acrylic monomer.

5. The polymeric composition of claim 1, wherein the chain extender comprises about 5 to about 25 weight percent of the at least one epoxy-functional (meth)acrylic monomer and about 75 to about 95 weight percent of the at least one styrenic and/or (meth)acrylic monomer.

6. The polymeric composition of claim 1, wherein the chain extender has a weight average molecular weight of less than about 25,000.

7. The polymeric composition of claim 1, wherein the chain extender is made in a reactor by a continuous polymerization process at a polymerization temperature of from about 180°

C. to about 350°

C. with a residence time in the reactor of less than about 60 minutes.

8. The polymeric composition of claim 1, wherein the chain extender is present in an amount of less than about 5 weight percent based on the total weight of the at least one condensation polymer and the chain extender.

9. The polymeric composition of claim 1, wherein the at least one condensation polymer is selected from the group consisting of polyesters, polyamides, polycarbonates, polyurethanes, polyacetals, polysulfones, polyphenylene ethers, polyether sulfones, polyimides, polyether imides, polyether ketones, polyether-ether ketones, polyarylether ketones, polyarylates, polyphenylene sulfides and polyalkyls.

10. The polymeric composition of claim 1, wherein the at least one condensation polymer is a condensation polymer that has been recycled or reprocessed.

11. The polymeric composition of claim 10, wherein the chain-extended condensation polymer has a molecular weight that is equal to or greater than the initial molecular weight of the at least one condensation polymer prior to recycling or reprocessing.

12. The polymeric composition of claim 10, wherein the chain-extended condensation polymer has an intrinsic viscosity that is equal to or greater than the initial intrinsic viscosity of the at least one condensation polymer prior to recycling or reprocessing.

13. The polymeric composition of claim 1, wherein the at least one condensation polymer is not pre-dried prior to the reaction of at least a portion of the chain extender with at least a portion of the at least one condensation polymer.

14. The polymeric composition of claim 1, wherein the reaction of at least a portion of the chain extender with at least a portion of the at least one condensation polymer is carried out in the absence of a catalyst.

15. A plastic article made from the polymeric composition of claim 1.

16. The plastic article of claim 14, wherein the plastic article is made using a process selected from the group consisting of blow molding, injection molding, extrusion, compression molding, rotational molding, calendaring, and fiber spinning.

17. The plastic article of claim 14, wherein the article is selected from the group consisting of food containers, non-food containers, films, coatings, tapes, moldings, fibers, extrusion profiles, and strapping.

18. A method for increasing the molecular weight of a condensation polymer comprising reacting a chain extender comprising a polymerization product of:

(i) at least one epoxy-functional (meth)acrylic monomer; and

(ii) at least one styrenic and/or (meth)acrylic monomer;

with at least one condensation polymer wherein the chain extender has an epoxy equivalent weight of from about 180 to about 2800, a number-average epoxy functionality (Efn) value of less than about 30, a weight-average epoxy functionality (Efw) value of up to about 140, and a number-average molecular weight (M_n) value of less than 6000 and wherein condensation polymer with increased molecular weight is substantially free of gel particles.

19. The method of claim 18, wherein the chain extender has a polydispersity index of from about 1.5 to about 5.

20. The method of claim 18, wherein the chain extender comprises about 50 to about 80 weight percent of the at least one epoxy-functional (meth)acrylic monomer and about 20 to about 50 weight percent of the at least one styrenic and/or (meth)acrylic monomer.

21. The method of claim 18, wherein the chain extender comprises about 25 to about 50 weight percent of the at least one epoxy-functional (meth)acrylic monomer and about 50 to about 75 weight percent of the at least one styrenic and/or (meth)acrylic monomer.

22. The method of claim 18, wherein the chain extender comprises about 5 to about 25 weight percent of the at least one epoxy-functional (meth)acrylic monomer and about 75 to about 95 weight percent of the at least one styrenic and/or (meth)acrylic monomer.

23. The method of claim 18, wherein the chain extender is made in a reactor by a continuous polymerization process at a polymerization temperature of from about 180°

C. to about 350°

C. with a residence time in the reactor of less than about 60 minutes.

24. The method of claim 18, wherein the chain extender has a weight average molecular weight of less than about 25,000.

25. The method of claim 18, wherein the chain extender is present in an amount of less than about 5 weight percent based on the total weight of the at least one condensation polymer and the chain extender.

26. The method of claim 18, wherein the at least one condensation polymer is selected from the group consisting of polyesters, polyamides, polycarbonates, polyurethanes, polyacetals, polysulfones, polyphenylene ethers, polyether sulfones, polyimides, polyether imides, polyether ketones, polyether-ether ketones, polyarylether ketones, polyarylates, polyphenylene sulfides and polyalkyls.

27. The method of claim 18, wherein the at least one condensation polymer is a condensation polymer that has been recycled or reprocessed.

28. The method of claim 27, wherein the chain-extended condensation polymer has a molecular weight that is equal to or greater than the initial molecular weight of the at least one condensation polymer prior to recycling or reprocessing.

29. The method of claim 27, wherein the chain-extended condensation polymer has an intrinsic viscosity that is equal to or greater than the initial intrinsic viscosity of the at least one condensation polymer prior to recycling or reprocessing.

30. The method of claim 18, wherein the at least one condensation polymer is not pre-dried prior to reacting with the chain extender.

31. The method of claim 18, wherein reaction between the chain extender and the at least one condensation polymer is carried out in the absence of a catalyst.

32. The method of claim 18, wherein the chain extended polycondensation polymer is substantially free of gel particles.

33. The method of claim 18, wherein reacting the chain extender with the at least one condensation polymer is carried out, at least in part, by melt blending the chain extender and the at least one condensation polymer at a temperature above the glass transition temperature of the chain extender and above either the glass transition temperature of the condensation polymer or above both the melting temperature and the glass transition temperature of the condensation polymer.

34. The method of claim 33, wherein the melt blending takes place in a reactor selected from the group consisting of a single screw extruder, a twin screw extruder, a Banbury mixer, a Farrell continuous mixer, a Buss co-kneader, and a roll mill.

35. The method of claim 33, wherein the melt blending takes place in a reactor and the chain extender and the at least one condensation polymer have an average residence time in the reactor of less than about 15 minutes.

36. The method of claim 33, wherein the chain extender and the at least one condensation polymer are pre-compounded prior to melt blending.

37. The method of claim 18, wherein reacting the chain extender with the at least one condensation polymer is carried out, at least in part, through solid state polymerization of the chain extender with the at least one condensation polymer at a temperature above the glass transition temperature of the chain extender and between the glass transition temperature and the melting temperature of the condensation polymer.

38. The method of claim 37, wherein the solid state polymerization takes place in a reactor and the chain extender and the at least one condensation polymer reactants have an average residence time of less than about 24 hours.