Polar monomer grafted polypropylene resin, preparation method therefor and application thereof

Patent metadata

Field	Value
Publication number	US-11926687-B2
Application number	US-201917051069-A
Country	US
Kind code	B2
Filing date	Apr 26, 2019
Priority date	Apr 27, 2018
Publication date	Mar 12, 2024
Grant date	Mar 12, 2024

Abstract

A grafted polypropylene resin is prepared by a grafting reaction of a polar monomer capable of absorbing microwave so as to raise its temperature in a microwave field to more than 200° C. and a solid polypropylene resin using microwave irradiation without adding an initiator. The polar grafted polypropylene resin that does not contain initiator residues and does not have a significant reduction in molecular mass compared with a resin before grafting is obtained.

First claim

The invention claimed is:

1. A grafted polypropylene resin,
comprising a polypropylene backbone having a plurality of side groups, each side group being obtained by grafting a polar monomer on the polypropylene backbone, and a grafting ratio of the polar monomer is 0.01-8%,
wherein the grafted polypropylene resin does not contain a residue of an initiator,
wherein the polar monomer is selected from the group consisting of organic acids, anhydrides, esters, and salts thereof, and
wherein a melt index of the grafted polypropylene resin is less than or equal to a melt index of a grafting base of the grafted polypropylene resin.

2. The grafted polypropylene resin of claim 1 , wherein the polar monomer is selected from the group consisting of maleic anhydrides, acids and esters of maleic anhydride (meth)acrylic acids, anhydrides and esters of (meth)acrylic acid, vinyl acetates, alkenyl sulfonic acids and anhydrides and esters thereof, p-styryl formic acid, p-styryl acetic acid, itaconic acid, oleic acid, arachidonic acid and combinations thereof, and salt forms thereof.

3. The grafted polypropylene resin of claim 1 , wherein the grafting ratio is 0.01%-6%.

4. The grafted polypropylene resin of claim 1 , wherein the value of the water contact angle of the grafted polypropylene resin is less than 90°, as measured on a film prepared from the grafted polypropylene resin by a solution method.

5. The grafted polypropylene resin of claim 1 , wherein the polypropylene resin as the grafting base is selected from the group consisting of propylene homopolymers and propylene copolymers and mixtures thereof.

6. The grafted polypropylene resin of claim 5 , wherein the grafting base of the grafted polypropylene resin is an impact polypropylene resin comprising a propylene homopolymer and a rubber phase that is a copolymer formed by propylene and a comonomer selected from the group consisting of ethylene, C 4 , C 5 , C 6 to C 8 α-olefins, and mixtures thereof.

7. The grafted polypropylene resin of claim 1 , wherein the grafting base of the grafted polypropylene is in a solid form of powder, pellets, or articles.

8. The grafted polypropylene resin of claim 1 , wherein the grafted polypropylene resin is obtained by subjecting the polar monomer and the solid polypropylene resin to grafting reaction using microwave irradiation without the addition of an initiator.

9. A method for the preparation of a grafted polypropylene resin of claim 1 , comprising the step of subjecting the polar monomer and the solid polypropylene resin to grafting reaction using microwave irradiation without the addition of an initiator.

10. The method of claim 9 , wherein the amount of the polar monomer is 0.1-10% by weight based on the weight of the solid polypropylene resin.

11. The method of claim 9 , wherein the polar monomer is in liquid or solution form.

12. The method of claim 9 , wherein the irradiation power of the microwave irradiation is 100w-2000w; the irradiation time is 1s-120 min.

13. The method of claim 9 , wherein the method comprises the following steps:
1) sufficiently mixing the polar monomer with the solid polypropylene resin; and
2) subjecting the mixture obtained in step 1) to microwave irradiation.

14. The method of claim 13 , wherein in step 1), the polar monomer and the solid polypropylene resin are sufficiently mixed under vacuum condition.

15. The method of claim 13 , wherein the polar monomer is in the form of a solution dissolved in a solvent, and the mixture obtained in step 1) is dried to remove the solvent prior to step 2).

16. The method of claim 13 , wherein the irradiated mixture obtained in step 2) is washed to remove the unreacted polar monomers, and is dried, the solvent used for washing is at least one selected from the group of alcohols, ketones, esters and water.

17. The method of claim 9 , wherein the solid polypropylene resin used is free of an antioxidant.

18. The method of claim 9 , wherein the polar monomer is an organic acid or its anhydride or ester, the product obtained after the grafting reaction under microwave irradiation is further reacted with a base.

19. The method as claimed in claim 18 , wherein the base is selected from the group consisting of ammonia and metal hydroxides.

20. The method of claim 18 , wherein the amount of the base is 0.1-10% by weight, based on the weight of the polypropylene resin used.

21. The method of claim 9 , wherein during the grafting reaction, no auxiliary grafting monomers are used.

22. The method of claim 9 , wherein an inorganic microwave absorbing medium is added.

23. The method of claim 22 , wherein the amount of the inorganic microwave absorbing medium is 0.1-10% by weight, based on the weight of the solid polypropylene resin.

24. The method of claim 22 , wherein the inorganic microwave absorbing medium is selected from the group consisting of metal hydroxides; metal salts; metal oxides; graphite materials; ferroelectrics materials; electrolysis stone; chalcopyrite; and their combinations.

25. The method of claim 22 , wherein prior to microwave radiation, a polar monomer, an inorganic microwave absorbing medium and a solid polypropylene resin are sufficiently mixed.

26. The method of claim 25 , wherein the polypropylene resin is first mixed with a polar monomer, and then the resulting mixture is mixed with an inorganic microwave absorbing medium.

27. The method of claim 22 , wherein the mixture after irradiation is washed to remove unreacted polar monomers, and dried.

28. Pellets or articles, obtained from the grafted polypropylene resin of claim 1 , through melt extrusion pelletization or a further molding process.

29. Composite materials, coatable film materials or bonding materials, prepared by blending the grafted polypropylene resin of claim 1 with other polymers.

30. A method for modification of plastics by using the grafted polypropylene resin of claim 1 in the plastics, comprising
blending the grafted polypropylene resin with other polymers to prepare composite materials, coatable film materials or bonding materials; or
adding the grafted polypropylene resin as a compatibilizer when polypropylene is blended and composited with other polymers.

31. The grafted polypropylene resin of claim 2 , wherein the ester of (meth)acrylic acid is glycidyl methacrylate.

32. The grafted polypropylene resin of claim 4 , wherein the value of the water contact angle of the grafted polypropylene resin is less than 65°, as measured on a film prepared from the grafted polypropylene resin by a solution method.

33. The grafted polypropylene resin of claim 4 , wherein the value of the water contact angle of the grafted polypropylene resin is 50°-0°, as measured on a film prepared from the grafted polypropylene resin by a solution method.

34. The grafted polypropylene resin of claim 5 , wherein the polypropylene resin as the grafting base is selected from random copolymers of propylene with the comonomer selected from the group consisting of ethylene, C 4 , C 5 , C 6 to C 8 -α-olefins, and combinations thereof.

35. The grafted polypropylene resin of claim 7 , wherein the polypropylene resin used as the grafting base is polypropylene powder obtained by polymerization using a spherical catal

Assignees

• China Petroleum & Chem Corp
• Beijing Res Inst Chemical Ind China Petroleum & Chemical Corp

Inventors

• Qiao Jinliang
• Wang Songhe
• Zhang Xiaohong
• Qi Guicun
• Song Zhihai
• Cai Chuanlun
• Wang Xiang
• Lai Jinmei
• Li Binghai
• Jiang Haibin
• Ru yue
• Zhang Jiangru
• Gao Jianming
• Zhang Hongbin
• Han Peng
• Liu Wenlu

Classifications

• C08F255/02 Primary

  on to polymers of olefins having two or three carbon atoms · CPC title

• B01J19/0066 Primary

  Stirrers (mixing per se B01F) · CPC title

• B01J19/126

  Microwaves · CPC title

• B01J2219/00166

  controlling the residence time inside the reactor vessel · CPC title