Melt reaction process for crosslinkable polycarbonates

Patent metadata

Field	Value
Publication number	US-10131742-B2
Application number	US-201515320151-A
Country	US
Kind code	B2
Filing date	Jun 19, 2015
Priority date	Jun 20, 2014
Publication date	Nov 20, 2018
Grant date	Nov 20, 2018

Abstract

Melt polymerization processes for producing photoactive additives are disclosed. The photoactive additives are cross-linkable polycarbonate resins formed from a benzophenone, a dihydroxy chain extender, a carbonate precursor, and a catalyst. The additives can be produced without the use of phosgene or dichloromethane, and can be cross-linked with other polymers upon exposure to UV radiation.

First claim

The invention claimed is:

1. A process for making a cross-linkable polycarbonate resin, comprising:
combining a first dihydroxy chain extender, a diaryl carbonate, and a transesterification catalyst to form a polycarbonate reaction mixture;
melt polymerizing the polycarbonate reaction mixture with a hydroxybenzophenone to form the cross-linkable polycarbonate resin; and
isolating the cross-linkable polycarbonate resin,
wherein the hydroxbenzophenone is a monohydroxybenzophenone.

2. The process of claim 1 , wherein the hydroxybenzophenone is added to the polycarbonate mixture prior to melt polymerization, such that the process is a batch process, or is added continuously to the polycarbonate reaction mixture during the melt polymerization process.

3. The process of claim 1 , further comprising adding a quenching agent to the polycarbonate reaction mixture prior to isolating the cross-linkable polycarbonate resin.

4. The process of claim 3 , wherein the quenching agent is a Bronsted acid.

5. A process for making a cross-linkable polycarbonate resin, comprising:
combining a first dihydroxy chain extender, a diaryl carbonate, and a transesterification catalyst to form a polycarbonate reaction mixture;
melt polymerizing the polycarbonate reaction mixture with a hydroxybenzophenone to form the cross-linkable polycarbonate resin;
isolating the cross-linkable polycarbonate resin; and
adding a quenching agent to the polycarbonate reaction mixture prior to isolating the cross-linkable polycarbonate resin,
wherein the quenching agent is added at a pressure of greater than or equal to 2 bars and is mixed with the cross-linkable polycarbonate resin for a period of time of greater than or equal to 5 seconds prior to the addition of any additives having a reactive OH group or reactive ester group to the cross-linkable polycarbonate resin.

6. The process of claim 5 , wherein the hydroxybenzophenone is a dihydroxybenzophenone.

7. A process for making a cross-linkable polycarbonate resin, comprising:
combining a first dihydroxy chain extender, a diaryl carbonate, and a transesterification catalyst to form a polycarbonate reaction mixture;
melt polymerizing the polycarbonate reaction mixture with a hydroxybenzophenone to form the cross-linkable polycarbonate resin; and
isolating the cross-linkable polycarbonate resin;
wherein the hydroxybenzophenone is a dihydroxybenzophenone, and wherein the cross-linkable polycarbonate resin contains from about 50 mole % to about 99.5% of repeating units derived from the first dihydroxy chain extender, and contains from about 0.5 mole % to about 50 mole % of repeating units derived from the dihydroxybenzophenone.

8. The process of claim 5 , wherein the hydroxbenzophenone is a monohydroxybenzophenone.

9. The process of claim 1 , wherein the cross-linkable polycarbonate resin contains from about 0.5 mole % to about 5 mole % of endcap groups derived from the monohydroxybenzophenone.

10. A process for making a cross-linkable polycarbonate resin, comprising:
combining a first dihydroxy chain extender, a diaryl carbonate, and a transesterification catalyst to form a polycarbonate reaction mixture;
melt polymerizing the polycarbonate reaction mixture with a hydroxybenzophenone to form the cross-linkable polycarbonate resin; and
isolating the cross-linkable polycarbonate resin;
wherein the hydroxybenzophenone is the bis-carbonate of 4-hydroxybenzophenone, and is used as the diaryl carbonate.

11. The process of claim 1 , wherein the transesterification catalyst comprises an alkali catalyst and a quaternary catalyst;
wherein the alkali catalyst is an alkali and/or alkaline earth metal hydroxide, an alkali and/or alkaline earth metal salt of a carboxylic acid, or an alkali and/or alkaline earth metal salt of a non-volatile inorganic acid; and
wherein the quaternary catalyst is a quaternary ammonium compound or a quaternary phosphonium compound.

12. The process of claim 7 , wherein the transesterification catalyst is a quaternary catalyst and does not contain an alkali catalyst; wherein the quaternary catalyst is a quaternary phosphonium compound.

13. The process of claim 11 , wherein the melt polymerization occurs at an elevated temperature of 120° C. to 350° C.

14. The process of claim 11 , wherein the melt polymerization occurs at a pressure of about 0.1 millibar to about 920 millibar.

15. A process comprising:
combining a first dihydroxy chain extender, a diaryl carbonate, and a transesterification catalyst to form a polycarbonate reaction mixture;
melt polymerizing the polycarbonate reaction mixture with a hydroxybenzophenone to form the cross-linkable polycarbonate resin; and
isolating the cross-linkable polycarbonate resin;
wherein the process further comprises
forming an article from a polymeric composition comprising the melt-formed cross-linkable polycarbonate resin; and
exposing the article to an effective dosage of ultraviolet radiation to cause crosslinking of the cross-linkable polycarbonate resin.

16. The process of claim 15 , wherein the effective dosage is form about 1 J/cm 2 to about 60 J/cm 2 of UVA radiation.

17. The process of claim 15 , wherein the ultraviolet radiation has a wavelength between 280 nm and 380 nm.

18. The process of claim 15 , wherein the polymeric composition comprises a second polymer that does not comprise units derived from the hydroxybenzophenone.

19. The process of claim 18 , wherein the second polymer comprises a polyester, a homopolycarbonate, a polycarbonate copolymer, a polyester, a polyesteramide, a polyimide, a polyetherimide, a polyamideimide, a polyether, a polyethersulfone, a polyepoxide, a polyactide, a polylactic acid, or a combination comprising one or more of the foregoing.

20. An article formed from the process of claim 15 .

21. The process of claim 7 , wherein the polycarbonate resin contains from about 50 mole % to about 99.5% of repeating units derived from bisphenol A.

22. The process of claim 1 , wherein the diaryl carbonate is bis(methyl salicyl) carbonate.

23. The process of claim 7 , wherein the diaryl carbonate is bis(methyl salicyl) carbonate.

24. The process of claim 15 , wherein the diaryl carbonate is bis(methyl salicyl) carbonate.

Assignees

• Sabic Global Technologies Bv

Inventors

• Lyakhovych Mykhaylo
• Fernandez Ignacio Vic
• Hoover James Franklin
• Flores Amanda Marie
• Pal Jaykisor

Classifications

• C08G64/14

  containing a chain-terminating or -crosslinking agent · CPC title

• C08J3/28

  Treatment by wave energy or particle radiation · CPC title

• C08J2369/00

  Characterised by the use of polycarbonates; Derivatives of polycarbonates · CPC title

• C08G64/04

  Aromatic polycarbonates · CPC title

• C08G64/307 Primary

  and phenols · CPC title