POLYESTERCARBONATE COPOLYMERS WITH HIGH SCRATCH RESISTANCE

• US 20100130700A1
• Filed: 11/21/2008
• Published: 05/27/2010
• Est. Priority Date: 11/21/2008
• Status: Active Grant

• Current Assignee: SHPP Global Technologies BV
• Original Assignee: Sabic Innovative Plastics IP BV (Government of Saudi Arabia)
• Inventors: Kusters, Adrianus Alphonsus Maria, Hoover, James F., van Zyl, Andries Jakobus Petrus, de Brouwer, Hans, Lens, Jan-Pleun, van Grampel, Robert Dirk
• Granted Patent: US 9,260,561 B2
• Time in Patent Office: Days
• US Class Current: 525/418
• CPC Class Codes: C08G 63/64 Polyesters containing both carboxylic ester groups and carbonate groups

Abstract

Disclosed are polyestercarbonate copolymers comprising a carbonate unit of Formula (I), an ITR ester unit of Formula (V), and optionally a different carbonate unit of Formula (VI):

wherein R^a, R^b, p, q, A, h, j, k, R^c, r, and R¹ are as described herein. The polyestercarbonate copolymers have a combination of scratch resistance, good flow, and good weatherability.

Claims

1. A polyestercarbonate copolymer comprising:

a carbonate unit of Formula (I);

wherein each R^a and R^b is independently halogen or hydrocarbon;

p and q are independently integers from 1 to 4; and

A is selected from C₁-C₁₂ alkyl, C₆-C₂₀ aromatic, and C₆-C₂₀ cycloaliphatic; and

an ITR ester unit of Formula (V);

wherein h corresponds to the molar percentage of the isophthalate, j corresponds to the molar percentage of the resorcinolate, and k corresponds to the molar percentage of the terephthalate;

h, j, and k add up to 100 mole percent of the ester unit;

each R^c is independently selected from C_1-12 alkyl and halogen; and

r is an integer from zero to 3.

2. The polyestercarbonate copolymer of claim 1, wherein the carbonate unit of Formula (I) is a DMBPC unit having the structure of Formula (III):

3. The polyestercarbonate copolymer of claim 1, wherein:

the carbonate unit of Formula (I) is present in the amount of from about 20 to about 90 mole percent; and

the ITR ester unit of Formula (V) is present in the amount of from about 5 to about 80 mole percent.

4. The polyestercarbonate copolymer of claim 1, wherein:

the carbonate unit of Formula (I) is present in the amount of from about 25 to about 60 mole percent;

the ITR ester unit of Formula (V) is present in the amount of from about 5 to about 30 mole percent.

5. The polyestercarbonate copolymer of claim 1, wherein the copolymer further comprises a carbonate unit of Formula (VI):

wherein R¹ is a divalent organic radical; and

the carbonate unit of Formula (VI) is different from the carbonate unit of Formula (I).

6. The polyestercarbonate copolymer of claim 5, wherein the carbonate unit of Formula (VI) is a bisphenol-A unit having the structure of Formula (VII):

7. The polyestercarbonate copolymer of claim 5, wherein the carbonate unit of Formula (VI) is present in the amount of from about 5 to about 50 mole percent.

8. The polyestercarbonate copolymer of claim 5, wherein the carbonate unit of Formula (VI) is present in the amount of from about 20 to about 50 mole percent.

9. The polyestercarbonate copolymer of claim 1, wherein the polyestercarbonate copolymer has a scratch resistance of 15 micrometers or less, when measured using the Erichson Scratch Test with a 6N load.

10. The polyestercarbonate copolymer of claim 1, wherein the polyestercarbonate copolymer has a haze level below 5, as measured by ASTM D1003.

11. The polyestercarbonate copolymer of claim 1, wherein the polyestercarbonate copolymer has a light transmittance greater than 75%, as measured by ASTM D1003.

12. The polyestercarbonate copolymer of claim 1, wherein the polyestercarbonate copolymer has a total color shift dE* of 12 or less after 500 hours exposure, according to ASTM D2244.

13. The polyestercarbonate copolymer of claim 1, wherein the polyestercarbonate copolymer has a gloss of 40 or higher when measured according to ASTM D523 after 1000 hours weathering according to SAE J1885.

14. The polyestercarbonate copolymer of claim 1, wherein the polyestercarbonate copolymer has a gloss of 90 or higher when measured according to ASTM D523 after 1000 hours weathering according to SAE J1960.

15. The polyestercarbonate copolymer of claim 1, wherein the polyestercarbonate copolymer has a scratch resistance of 15 micrometers or less, when measured using the Erichson Scratch Test with a 6N load;

and a haze level below 5 and a percent transmittance higher than 75, both as measured by ASTM D1003.

16. The polyestercarbonate copolymer of claim 1, wherein the polyestercarbonate copolymer has a scratch resistance of 15 micrometers or less, when measured using the Erichson Scratch Test with a 6N load;

and a melt volume rate of 25 cc/10 minutes or less, according to ASTM D1238.

17. A polyestercarbonate copolymer comprising:

a DMBPC unit of Formula (III);

and

an ITR ester unit of Formula (V);

wherein h corresponds to the molar percentage of the isophthalate, j corresponds to the molar percentage of the resorcinolate, and k corresponds to the molar percentage of the terephthalate;

h, j, and k add up to 100 mole percent of the ester unit;

each R^c is independently selected from C_1-12 alkyl and halogen; and

r is an integer from zero to 3;

wherein the polyestercarbonate copolymer has a scratch resistance of 15 micrometers or less, when measured using the Erichson Scratch Test with a 6N load.

18. A polyestercarbonate copolymer comprising:

a DMBPC unit of Formula (III);

and

an ITR ester unit of Formula (V);

wherein h corresponds to the molar percentage of the isophthalate, j corresponds to the molar percentage of the resorcinolate, and k corresponds to the molar percentage of the terephthalate;

h, j, and k add up to 100 mole percent of the ester unit;

each R^c is independently selected from C_1-12 alkyl and halogen; and

r is an integer from zero to 3;

wherein the polyestercarbonate copolymer has a scratch resistance of 15 micrometers or less, when measured using the Erichson Scratch Test with a 6N load; and

a haze level below 5 and a percent transmittance higher than 75, both as measured by ASTM D1003.

19. A method of preparing a polyestercarbonate copolymer, comprising:

providing a polycarbonate polymer of Formula (IX) and a polyestercarbonate polymer of Formula (X);

wherein each R^a and R^b is independently halogen or hydrocarbon;

p and q are independently integers from 1 to 4;

A is selected from C₁-C₁₂ alkyl, C₆-C₂₀ aromatic, and C₆-C₂₀ cycloaliphatic; and

w is the degree of polymerization;

wherein R¹, R², and T are independently divalent organic radicals;

m is the molar percentage of carbonate units; and

n is the molar percentage of ester units;

mixing the polycarbonate polymer, the polyestercarbonate polymer, and a chain transfer catalyst to form a mixture; and

reacting the mixture to form the polyestercarbonate copolymer.

20. A method for making a polyestercarbonate copolymer, comprising:

forming an initial mixture comprising a dihydroxyaromatic moiety, a catalyst, water, and a substantially water-immiscible organic solvent;

reacting the initial mixture by adding a first dicarboxylic acid moiety and a second dicarboxylic acid moiety to the initial mixture while maintaining the pH at from about 4 to about 5 to form an intermediate mixture;

adding a first dihydroxy compound and a second dihydroxy compound to the intermediate mixture; and

reacting the intermediate mixture by adding a carbonate precursor to the intermediate mixture while maintaining the pH at from about 8 to about 9 to form the polyestercarbonate copolymer.

21. The method of claim 20, wherein the first dicarboxylic acid moiety is a terephthalate moiety and the second dicarboxylic acid moiety is an isophthalate moiety.

22. The method of claim 20, wherein the first dihydroxy compound is DMBPC and the second dihydroxy compound is bisphenol-A.

23. The method of claim 20, wherein the carbonate precursor is phosgene.

24. The method of claim 20, wherein the dihydroxyaromatic moiety is resorcinol.