阅读说明：本技术 用酸官能化二氧化硅和金属硅酸盐提纯粗聚环氧烷聚合物 (Purification of crude polyalkylene oxide polymers with acid-functionalized silica and metal silicates ) 是由 A.巴格里夫 G.E.希克斯 于 2018-03-13 设计创作，主要内容包括：一种提纯含有催化剂,如氢氧化钾的粗聚环氧烷聚合物的方法。该方法包含使粗聚环氧烷聚合物与从聚环氧烷聚合物中有效除去催化剂的量的包含酸官能化硅酸盐,如含有至少一种酸的酸官能化硅酸镁吸附剂的组合物接触。这种方法实现改进的聚环氧烷聚合物中除去催化剂。(A process for purifying a crude polyalkylene oxide polymer containing a catalyst, such as potassium hydroxide. The process comprises contacting a crude polyalkylene oxide polymer with an amount of a composition comprising an acid-functionalized silicate, such as an acid-functionalized magnesium silicate adsorbent comprising at least one acid, effective to remove catalyst from the polyalkylene oxide polymer. This process achieves improved catalyst removal from the polyalkylene oxide polymer.)

1. A process for purifying a crude polyalkylene oxide polymer containing a catalyst, the process comprising:

contacting the crude polyalkylene oxide polymer with a composition comprising an acid-functionalized silicate adsorbent comprising at least one acid, wherein the crude polyalkylene oxide polymer is contacted with the composition in an amount effective to remove the catalyst from the crude polyalkylene oxide polymer.

2. The method of claim 1, wherein the acid-functionalized silicate is an acid-functionalized metallosilicate.

3. The method of claim 2, wherein said acid-functionalized metal silicate is an acid-functionalized magnesium silicate.

4. The method of claim 3 wherein said acid-functionalized magnesium silicate is acid-functionalized by contacting the magnesium silicate with at least one acid.

5. The method of claim 4, wherein the at least one acid is at least one polyprotic acid.

6. The method of claim 5, wherein the at least one polyprotic acid is selected from H₂SO₄、H₂SO₃、H₂S₂O₃、H₃PO₄、H₄P₂O₇、H₂PO₂、H₃PO₃、H₂CO₃And mixtures thereof.

7. The method of claim 6, wherein the at least one polyprotic acid is sulfuric acid.

8. The method of claim 6, wherein the at least one polyprotic acid is phosphoric acid.

9. The method of claim 3 wherein said at least one acid is present in said acid-functionalized magnesium silicate in an amount in the range of from about 0.2 weight percent to about 40 weight percent.

10. The method of claim 9 wherein said at least one acid is present in said acid-functionalized magnesium silicate in an amount in the range of from about 0.2 weight percent to about 25 weight percent.

11. The method of claim 10 wherein said at least one acid is present in said acid-functionalized magnesium silicate in an amount in the range of from about 1 weight percent to about 15 weight percent.

12. The method of claim 3 wherein said acid-functionalized magnesium silicate has MgO and SiO in the range of about 1:1.0 to about 1:4.0₂In a molar ratio of (a).

13. The method of claim 12 wherein said acid-functionalized magnesium silicate has MgO and SiO in the range of about 1:1.4 to about 1:4.0₂In a molar ratio of (a).

14. The method of claim 13 wherein said acid-functionalized magnesium silicate has a MgO and SiO ratio of from about 1:2.5 to about 1:3.6₂In a molar ratio of (a).

15. The method of claim 3 wherein said acid-functionalized magnesium silicate has a pH in a 5% slurry of from about 3.0 to about 10.8.

16. The method of claim 15 wherein said acid-functionalized magnesium silicate has a pH in a 5% slurry of from about 7.5 to about 10.5.

17. The method of claim 7 wherein said sulfuric acid-functionalized magnesium silicate has a pH in a 5% slurry of from about 8.0 to about 10.5.

18. The method of claim 17 wherein said sulfuric acid-functionalized magnesium silicate has a pH in a 5% slurry of from about 8.0 to about 9.7 and MgO and SiO in the range of from about 2.5 to about 2.8₂In a molar ratio of (a).

19. The method of claim 17 wherein said sulfuric acid-functionalized magnesium silicate has a pH in a 5% slurry of from about 8.0 to about 10.5 and MgO and SiO of from about 3.2 to about 3.6₂In a molar ratio of (a).

20. The method of claim 3 wherein said acid-functionalized magnesium silicate has a conductivity in a 1.0% slurry of from about 0.2 mS/cm to about 5.0 mS/cm.

21. The method of claim 7 wherein said sulfuric acid-functionalized magnesium silicate has a conductivity in a 1.0% slurry of from about 0.2 mS/cm to about 2.6 mS/cm.

22. The method of claim 8 wherein said phosphoric acid functionalized magnesium silicate has a conductivity in a 1.0% slurry of from about 0.2 mS/cm to about 1.5 mS/cm.

23. The method of claim 3 wherein said acid-functionalized magnesium silicate has a loss on ignition of from about 10.0% to about 15.0%.

24. The method of claim 3 wherein said acid-functionalized magnesium silicate has a surface area of at least 30 square meters per gram.

25. The method of claim 24 wherein said acid-functionalized magnesium silicate has a surface area of at least 50 square meters per gram.

26. The method of claim 25 wherein said acid-functionalized magnesium silicate has a surface area of from about 50 square meters per gram to about 700 square meters per gram.

27. The method of claim 3 wherein said acid-functionalized magnesium silicate has a total pore volume of at least 0.1 ml/g.

28. The method of claim 27 wherein said acid-functionalized magnesium silicate has a total pore volume of from about 0.1 ml/g to about 1.2 ml/g.

29. The method of claim 3 wherein said acid-functionalized magnesium silicate has an average particle size of from about 10 microns to about 1,000 microns.

30. The method of claim 29 wherein said acid-functionalized magnesium silicate has an average particle size of from about 10 microns to about 500 microns.

31. The method of claim 30 wherein said acid-functionalized magnesium silicate has an average particle size of from about 10 microns to about 250 microns.

32. The method of claim 31 wherein said acid-functionalized magnesium silicate has an average particle size of from about 10 microns to about 175 microns.

33. The method of claim 32 wherein said acid-functionalized magnesium silicate has an average particle size of from about 10 microns to about 125 microns.

34. The method of claim 33 wherein said acid-functionalized magnesium silicate has an average particle size of from about 30 microns to about 100 microns.

35. The method of claim 3 wherein said acid-functionalized magnesium silicate has a bulk density of from about 0.2 g/cc to about 0.8 g/cc.

36. The process of claim 3 wherein the crude polyalkylene oxide polymer is contacted with the acid-functionalized magnesium silicate in an amount of from about 0.1 wt.% to about 3.0 wt.%, based on the weight of the crude polyalkylene oxide polymer.

37. The process of claim 36 wherein the crude polyalkylene oxide polymer is contacted with the acid-functionalized magnesium silicate in an amount of from about 0.5 wt.% to about 3.0 wt.%, based on the weight of the crude polyalkylene oxide polymer.

38. The process of claim 3, wherein the catalyst is an alkali metal catalyst.

39. The process of claim 38, wherein the alkali metal catalyst is potassium hydroxide.

40. The method of claim 3, further comprising:

contacting the crude polyalkylene oxide polymer with the acid-functionalized magnesium silicate after contacting the crude polyalkylene oxide polymer with an aqueous liquid.

41. The process of claim 40, wherein the crude polyalkylene oxide polymer is contacted with the aqueous liquid in an amount of from about 0.5 wt.% to about 4.0 wt.%, based on the weight of the crude polyalkylene oxide polymer.

42. The method of claim 40, wherein the aqueous liquid further comprises at least one alcohol.

43. The method of claim 42, wherein the at least one alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, and mixtures thereof.

44. The method of claim 3, further comprising:

contacting the crude polyalkylene oxide polymer with at least one alcohol after contacting the crude polyalkylene oxide polymer with the acid-functionalized magnesium silicate.

45. The method of claim 44, wherein the at least one alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, and mixtures thereof.

46. The process of claim 44, wherein the crude polyalkylene oxide polymer is contacted with the at least one alcohol in an amount of from about 0.5 wt.% to about 4.0 wt.%, based on the weight of the crude polyalkylene oxide polymer.

47. The process of claim 1, wherein the crude polyalkylene oxide polymer is a polyether monol.

48. The process of claim 1, wherein the crude polyalkylene oxide polymer is a polyether polyol.

49. The method of claim 2, wherein the acid-functionalized metal silicate is an acid-functionalized calcium silicate.

Brief Description of Drawings

The invention will now be described with reference to the accompanying drawings, in which:

FIG. 1 is a graph showing the residual potassium hydroxide (KOH) concentration (in ppm) in a polyol treated with a sulfuric acid-functionalized magnesium silicate alone or in combination with the addition of 2 wt.% water;

FIG. 2 is a graph showing the KOH adsorption capacity (mg/g) of a sulfuric acid-functionalized magnesium silicate used to treat a crude polyol containing a KOH catalyst, alone or in combination with the addition of 2 wt.% water;

FIG. 3 is a graph showing the partition constant (Kd) for sulfuric acid concentration in sulfuric acid-functionalized magnesium silicate used to treat crude polyols containing KOH catalysts, alone or in combination with the addition of 2 weight percent water;

FIG. 4 is a graph showing the effect of water addition on KOH adsorption (mg/g) on sulfuric acid-functionalized magnesium silicate with 4 wt% sulfuric acid when treating crude polyol containing KOH catalyst;

FIGS. 5A and 5B are graphs showing KOH adsorption isotherms from dipropylene glycol (DPG) samples treated with non-acid-functionalized magnesium silicate (sample S0) or acid-functionalized magnesium silicate treated with 5.3% sulfuric acid (sample S9) at 95 ℃ for 40 minutes;

FIG. 6 is a graph showing the effect of sorbent metering on the residual potassium content in commercial high molecular weight polyols treated with sample S0 or sample S9; and

FIG. 7 is a graph showing the effect of water addition on KOH adsorption from DPG samples treated with sample S0 or sample S9.

Examples

The invention will now be described with reference to the following examples. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended.