IP Library Granted Patent US 8,389,664
Granted Patent B2
US 8,389,664 · App. 13/235,046 · Granted Mar 5, 2013

High molecular weight, random, bisphenol based copoly(phosphonate carbonate)s

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Quick Facts
Patent No.
US 8,389,664
App. No.
13/235,046
Granted
Mar 5, 2013
Kind
B2
Abstract

Disclosed are random copoly(phosphonate carbonate)s with the high molecular weight and narrow molecular weight distribution exhibiting a superior combination of properties compared to prior art.

Claims (38)

1. A random copoly(phosphonate carbonate) comprising randomly distributed monomeric units derived from carbonate and phosphonate monomers and having a phosphorous content of about 2% to about 10% by weight of the total random copoly(phosphonate carbonate) and total acidic components derived from phosphonate monomers of less than about 0.15% by weight.

2. The random copoly(phosphonate carbonate) of claim 1 , wherein the random copoly(phosphonate carbonate) comprises a weight average molecular weight of from about 10,000 g/mole to about 100,000 g/mole as determined by gel permeation chromatography.

3. The random copoly(phosphonate carbonate) of claim 1 , wherein the random copoly(phosphonate carbonate) comprises a number average molecular weight of from about 5,000 g/mole to about 50,000 g/mole as determined by gel permeation chromatography.

4. The random copoly(phosphonate carbonate) of claim 1 , wherein the random copoly(phosphonate carbonate) comprises a polydisperisty of from about 2 to about 7.

5. The random copoly(phosphonate carbonate) of claim 1 , wherein the random copoly(phosphonate carbonate) comprises a polydispersity of from about 2 to about 4.

6. The random copoly(phosphonate carbonate) of claim 1 , comprising monomeric units derived from diphenylmethyl phosphonate, diphenyl carbonate, and 2,2-bis(4-hydroxyphenyl)propane.

7. The random copoly(phosphonate carbonate) of claim 1 , wherein the random copolyphosphonate comprises no monomeric units derived from a branching agent.

8. The random copoly(phosphonate carbonate) of claim 1 , further comprising at least one other polymer, oligomer, or combination thereof to make a blend or mixture.

9. The random copoly(phosphonate carbonate) of claim 8 , wherein the other polymer, oligomer, or combination thereof comprises carbonates, epoxies, benzoxazine, acrylates, acrylonitriles, esters, terephthalates, or combinations thereof.

10. The random copoly(phosphonate carbonate) of claim 8 , wherein the other polymer, oligomer, or combination thereof comprises unsaturated polyester, polyamide, polystyrene (including high impact strength polystyrene), polyurea, polyurethane, polyphosphonate, poly(acrylonitrile butadiene styrene), polyimide, polyarylate, poly(arylene ether), poly(ethylene terephthalate), poly(trimethylene terephthalate), poly(butylene terephthalate), polyethylene, polypropylene, polyphenylene sulfide, poly(vinyl ester), polyvinyl chloride, bismaleimide polymer, polyanhydride, liquid crystalline polymer, cellulose polymer, or combinations thereof.

11. The random copoly(phosphonate carbonate) of claim 1 , further comprising fillers, fibers, surfactants, organic binders, polymeric binders, crosslinking agents, coupling agents, anti-dripping agents, lubricants, mould release agents, nucleating agents, anti-static agents, catalysts, colorants, inks, dyes, antioxidants, stabilizers, or combinations thereof.

12. A method for preparing a random copoly(phosphonate carbonate) comprising:

combining one or more diaryl alkylphosphonate or optionally substituted diaryl alkylphosphonate, one or more optionally substituted diaryl carbonate, aromatic dihydroxide, and one or more transesterification catalyst, wherein the diaryl alkylphosphonate comprises 20 mole % based on the total diaryl alkylphosphonate and diaryl carbonate; and

wherein acidic components in the diaryl alkylphosphonate comprise less than about 0.15% by weight; and

covalently linking the one or more diaryl alkylphosphonate or optionally substituted diaryl alkylphosphonate, one or more diaryl carbonate, one or more aromatic dihydroxide, and transesterification catalyst by transesterification to form a random copoly(phosphonate carbonate).

13. The method of claim 12 , wherein the step of covalently linking comprises:

heating the one or more diaryl alkylphosphonate or optionally substituted diaryl alkylphosphonate, one or more diaryl carbonate, one or more aromatic dihydroxide, and transesterification catalyst under vacuum to form a melt; and

reacting the one or more diaryl alkylphosphonate or optionally substituted diaryl alkylphosphonate, one or more diaryl carbonate, and one or more aromatic dihydroxide.

14. The method of claim 12 , wherein the transesterification catalyst is of the general formula (I):

wherein,

R 1 , R 2 , R 3 and R 4 , each independently are selected from C 1 - to C 18 -alkylenes, C 6 - to C 10 -aryls or C 5 - to C 6 -cycloalkyls; and

X − comprises an anion where having a pKb of greater than about 11.

15. The method of claim 12 , wherein the transesterification catalyst comprises tetraphenylphosphonium phenolate.

16. The method of claim 12 , wherein the transesterification catalysts comprised about 10 −2 to about 10 −8 mole per moles aromatic dihydroxide.

17. The method of claim 12 , wherein the method is carried out continuously and comprises at least two reaction steps.

18. The method of claim 12 , wherein no branching agent is used in any step of the method.

19. An article of manufacture comprising random copoly(phosphonate carbonate) comprising randomly distributed monomeric units derived from carbonate and phosphonate monomers and having a phosphorous content of about 2% to about 10% by weight of the total random copoly(phosphonate carbonate) and total acidic components derived from phosphonate monomers of less than about 0.15% by weight.

20. The article of manufacture of claim 19 , wherein the random copoly(phosphonate carbonate) comprises a weight average molecular weight of from about 10,000 to about 100,000 grams/mole as determined by gel permeation chromatography.

21. The article of manufacture of claim 19 , wherein the random copoly(phosphonate carbonate) comprises a polydisperisty of from about 2 to about 7.

22. The article of manufacture of claim 19 , wherein the random copoly(phosphonate carbonate) comprises a polydispersity of from about 2 to about 5.

23. The article of manufacture of claim 19 , comprising monomeric units derived from diphenylmethyl phosphonate, diphenyl carbonate, and 2,2-bis(4-hydroxyphenyl)propane.

24. The article of manufacture of claim 19 , wherein the random copoly(phosphonate carbonate) comprises no monomeric units derived from a branching agent.

25. The article of manufacture of claim 19 , further comprising at least one other polymer, oligomer, or combination thereof to make a blend or mixture.

26. The article of manufacture of claim 25 , wherein the other polymer, oligomer, or combination thereof comprises carbonates, epoxies, benzoxazine, acrylates, acrylonitriles, esters, terephthalates, or combinations thereof.

27. The article of manufacture of claim 25 , wherein the other polymer, oligomer, or combination thereof comprises unsaturated polyester, polyamide, polystyrene (including high impact strength polystyrene), polyurea, polyurethane, polyphosphonate, poly(acrylonitrile butadiene styrene), polyimide, polyarylate, poly(arylene ether), poly(ethylene terephthalate), poly(trimethylene terephthalate), poly(butylene terephthalate), polyethylene, polypropylene, polyphenylene sulfide, poly(vinyl ester), polyvinyl chloride, bismaleimide polymer, polyanhydride, liquid crystalline polymer, cellulose polymer, or combinations thereof.

28. The article of manufacture of claim 19 , further comprising fillers, fibers, surfactants, organic binders, polymeric binders, crosslinking agents, coupling agents, anti-dripping agents, lubricants, mould release agents, nucleating agents, anti-static agents, catalysts, colorants, inks, dyes, antioxidants, stabilizers, or combinations thereof.

29. The article of manufacture of claim 19 , wherein the random copoly(phosphonate carbonate) comprises a coating, adhesive, prepreg, foam, film, fiber, molding, fiber reinforced laminate, or combination thereof.

30. The article of manufacture of claim 19 , wherein the article of manufacture comprises a consumer product or component or portion thereof.

Assignments (5)
CHANGE OF NAME Recorded Apr 5, 2016
From: BAYER MATERIALSCIENCE AG
To: COVESTRO DEUTSCHLAND AG
Reel/Frame 038353/0325 →
CORRECTIVE ASSIGNMENT TO CORRECT THE APPLICATION NO. 13/253,046, PREVIOUSLY RECORDED ON REEL 027300 FRAME 0025. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Jan 10, 2012
From: FREITAG, DIETER; GO, PIN; KAGUMBA, LAWINO
To: FRX POLYMERS, INC.
Reel/Frame 027572/0094 →
CORRECTIVE ASSIGNMENT TO CORRECT THE APPLICATION NO. 13253046 SHOULD BE APPLICATION NO. 13235046 PREVIOUSLY RECORDED ON REEL 027299 FRAME 0687. ASSIGNOR(S) HEREBY CONFIRMS THE STEPHAN KONRAD, HELMUT-WERNER HEUER, BERIT KRAUTER, PIETER OOMS, MICHAEL PREIN AND JOHANN RECHNER TO BAYER MATERIAL SCIENCE AG Recorded Jan 10, 2012
From: KONRAD, STEPHAN; HEUER, HELMUT-WERNER; KRAUTER, BERIT; OOMS, PIETER; PREIN, MICHAEL; RECHNER, JOHANN
To: BAYER MATERIAL SCIENCE AG
Reel/Frame 027572/0124 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 30, 2011
From: KONRAD, STEPHAN; HEUER, HELMUT-WERNER; KRAUTER, BERIT; OOMS, PIETER; PREIN, MICHAEL; RECHNER, JOHANN
To: BAYER MATERIAL SCIENCE AG
Reel/Frame 027299/0687 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 30, 2011
From: FREITAG, DIETER; GO, PIN; KAGUMBA, LAWINO
To: FRX POLYMERS, INC.
Reel/Frame 027300/0025 →