Interfacial processes for preparing photoactive additives
View Patent ↗Different interfacial processes for producing photoactive additives are disclosed. Generally, the photoactive additives are cross-linkable polycarbonate resins formed from a dihydroxybenzophenone, a first linker moiety, a diol chain extender, and an end-capping agent. The resulting additives can be crosslinked with other polymers upon exposure to UV radiation.
1. A process for preparing a photoactive additive from a dihydroxybenzophenone, a diol chain extender, an end-capping agent, a carbonate precursor, a base, a tertiary amine catalyst, water, and a water-immiscible organic solvent, comprising:
combining the dihydroxybenzophenone, diol chain extender, tertiary amine catalyst, water, and water-immiscible solvent to form a reaction mixture;
adding the carbonate precursor to the reaction mixture over a first time period while co-adding the base to regulate the reaction pH;
adding the end-capping agent to the reaction mixture for a second time period while continuing to add the carbonate precursor and the base; and
continuing to add the carbonate precursor and the base to the reaction mixture for a third time period after addition of the end-capping agent is complete to obtain the photoactive additive.
2. The process of claim 1 , wherein the carbonate precursor is phosgene, the diol chain extender is bisphenol-A, the base is an alkali metal hydroxide, and the water-immiscible organic solvent is methylene chloride.
3. The process of claim 1 , wherein the dihydroxybenzophenone is 4,4′-dihydroxybenzophenone.
4. The process of claim 1 , wherein the end-capping agent is dissolved in a solvent prior to being added to the reaction mixture, the solvent being either the water-immiscible organic solvent or water containing a base.
5. The process of claim 4 , wherein the end-capping agent is dissolved in a dilute aqueous sodium hydroxide solution.
6. The process of claim 5 , wherein the solution contains from about 1 to about 2 moles of NaOH per mole of the end-capping agent, and contains from about 5 wt % to about 20 wt % of the end-capping agent compound.
7. The process of claim 1 , wherein a total time period is defined by the sum of the first time period, the second time period, and the third time period; and the second time period in which the end-capping agent is added to the reaction mixture begins at a point from 10% to about 40% of the total time period.
8. The process of claim 1 , wherein the reaction pH is regulated to remain between about 8.5 and about 10.
9. The process of claim 1 , wherein the end-capping agent is selected from the group consisting of phenol, p-t-butylphenol, p-cumylphenol, octylphenol, and p-cyanophenol.
10. The process of claim 1 , wherein the resulting photoactive additive contains less than 2% of low molecular weight molecules.
11. The process of claim 1 , wherein the resulting photoactive additive comprises about 0.5 mole % to 50 mole % of the dihydroxybenzophenone.
12. The process of claim 1 , wherein the resulting photoactive additive has a weight-average molecular weight of between 17,000 and 80,000 Daltons, as measured by GPC using a UV detector and polycarbonate molecular weight standards.
13. The process of claim 1 , wherein the ratio of the PDI measured using a UV detector to the PDI measured using an RI detector is 1.4 or less when using a GPC method and polycarbonate molecular weight standards.
14. The process of claim 1 , wherein the resulting photoactive additive has a MFR of 1 to 40 g/10 min measured according to ASTM D1238 at 300° C./1.2 kg/360 sec dwell.
15. The process of claim 1 , wherein the resulting photoactive additive maintains a PDI between 2.0 and 3.5 when made into powder, pellet, and tensile bar forms.
16. A process for preparing a photoactive additive from a dihydroxybenzophenone, a diol chain extender, an end-capping agent, a carbonate precursor, a base, a tertiary amine catalyst, water, and a water-immiscible organic solvent, comprising:
combining the dihydroxybenzophenone, diol chain extender, end-capping agent, tertiary amine catalyst, water, and water-immiscible solvent to form a reaction mixture; and
adding the carbonate precursor to the reaction mixture while co-adding the base to regulate the reaction pH to obtain the photoactive additive.
17. The process of claim 16 , wherein the carbonate precursor is phosgene, the diol chain extender is bisphenol-A, the base is an alkali metal hydroxide, and the water-immiscible organic solvent is methylene chloride.
18. The process of claim 16 , wherein the dihydroxybenzophenone is 4,4′-dihydroxybenzophenone.
19. The process of claim 16 , wherein the end-capping agent is selected from the group consisting of phenol, p-t-butylphenol, p-cumylphenol, octylphenol, and p-cyanophenol.
20. The process of claim 16 , wherein the reaction mixture further comprises a phase transfer catalyst.
21. The process of claim 20 , wherein the phase transfer catalyst is methyltributylammonium chloride.
22. The process of claim 16 , wherein the pH of the reaction mixture is maintained from about 8.5 to about 10 while the carbonate precursor is added to the reaction mixture.
23. The process of claim 16 , wherein the carbonate precursor is added to the reaction mixture over a time period of about 15 minutes to about 45 minutes.
24. The process of claim 16 , wherein the resulting photoactive additive contains less than 2% of low molecular weight molecules.
25. The process of claim 16 , wherein the resulting photoactive additive does not contain residual pyridine.
26. The process of claim 16 , wherein the resulting photoactive additive comprises from about 0.5 mole % to 50 mole % of repeating units derived from the dihydroxybenzophenone.
27. The process of claim 16 , wherein the resulting photoactive additive has a weight-average molecular weight of between 17,000 and 80,000 Daltons, as measured by GPC using a UV detector and polycarbonate molecular weight standards.
28. The process of claim 16 , wherein the resulting photoactive additive has a MFR of about 1 to about 40 g/10 min measured according to ASTM D1238 at 300° C./1.2 kg/360 sec dwell.
29. A process for preparing a photoactive additive from a dihydroxybenzophenone, a diol chain extender, an end-capping agent, a carbonate precursor, a tertiary amine catalyst, water, and a water-immiscible organic solvent, comprising:
combining the dihydroxybenzophenone, diol chain extender, water, and water-immiscible solvent to form a reaction mixture;
adding the carbonate precursor to the reaction mixture to form chloroformate in the reaction mixture while co-adding the base to regulate the reaction pH;
adding the end-capping agent to the reaction mixture and reacting the reaction mixture; and
adding the tertiary amine catalyst to the reaction mixture and reacting the reaction mixture to obtain the photoactive additive.
30. The process of claim 29 , wherein the carbonate precursor is phosgene, the diol chain extender is bisphenol-A, the base is an alkali metal hydroxide, and the water-immiscible organic solvent is methylene chloride.
31. The process of claim 29 , wherein the dihydroxybenzophenone is 4,4′-dihydroxybenzophenone.
32. The process of claim 29 , wherein the end-capping agent is selected from the group consisting of phenol, p-t-butylphenol, p-cumylphenol, octylphenol, and p-cyanophenol.
33. The process of claim 29 , wherein the resulting photoactive additive contains less than 2% of low molecular weight molecules.
34. The process of claim 29 , wherein the resulting photoactive additive comprises about 0.5 mole % to 50 mole % repeating units derived from the dihydroxybenzophenone.
35. The process of claim 29 , wherein the resulting photoactive additive has a weight-average molecular weight of between 17,000 and 80,000 Daltons, as measured by GPC using a UV detector and polycarbonate molecular weight standards.
36. A process for preparing a photoactive additive from a dihydroxybenzophenone, a diol chain extender, an end-capping agent, a carbonate precursor, a tertiary amine catalyst, water, and a water-immiscible organic solvent, comprising:
pre-reacting the end-capping agent with the carbonate precursor in a tubular reactor to convert the end-capping agent into a monochloroformate;
combining the dihydroxybenzophenone, diol chain extender, tertiary amine catalyst, water, and water-immiscible solvent in a reaction mixture;
adding the carbonate precursor to the reaction mixture over a first time period; and
adding the monochloroformate compound to the reaction mixture throughout the first time period while co-adding the base to regulate the reaction pH to obtain the photoactive additive.
37. The process of claim 36 , wherein the carbonate precursor is phosgene, the diol chain extender is bisphenol-A, the base is an alkali metal hydroxide, and the water-immiscible organic solvent is methylene chloride.
38. The process of claim 36 , wherein the dihydroxybenzophenone is 4,4′-dihydroxybenzophenone.
39. The process of claim 36 , wherein the end-capping agent is selected from the group consisting of phenol, p-t-butylphenol, p-cumylphenol, octylphenol, and p-cyanophenol.
40. The process of claim 36 , wherein the resulting photoactive additive comprises about 0.5 mole % to 50 mole % repeating units derived from the dihydroxybenzophenone.
41. The process of claim 36 , wherein the resulting photoactive additive has a weight-average molecular weight of between 17,000 and 80,000 Daltons, as measured by GPC using a UV detector and polycarbonate molecular weight standards.