Method for preparing reactive sealant resin

Patent metadata

Field	Value
Publication number	US-12122876-B2
Application number	US-201817413858-A
Country	US
Kind code	B2
Filing date	Dec 27, 2018
Priority date	Dec 27, 2018
Publication date	Oct 22, 2024
Grant date	Oct 22, 2024

Abstract

Disclosed by the present invention is a method for preparing a reactive sealant resin, the method comprising: (1) under the action of an alkali catalyst, polymerizing a hydroxyl-containing initiator with an epoxy compound to obtain a polyether polyol; (2) adding an alkoxide reagent and a halogenated end-capping agent containing a double bond to the polyether polyol obtained in step (1) for reaction, so as to obtain a crude double-bonded polyether product, and refining the crude product to obtain a modified polyether product; and (3) subjecting the modified polyether and hydrogen-containing silane to silane end-capping reaction under the action of a hydrosilylation catalyst, so as to obtain the target product, i.e., a reactive sealant resin. The resin has excellent properties as well as good adhesion and paintability.

First claim

What is claimed is:

1. A method for preparing a reactive sealant resin, comprising:
(1) preparation of a polyether polyol: under the action of an alkali catalyst, polymerizing a hydroxyl-containing initiator with an epoxide to obtain a first polyether polyol;
(2) polyether modification: adding an alkoxidation reagent and a halogenated end-capping agent containing a double bond to the first polyether polyol obtained in step (1) for reaction to obtain a crude product of double-bond-terminated polyether, and refining the obtained crude product to obtain a product of modified polyether;
(3) silane end-capping: subjecting the modified polyether obtained in step (2) as a raw material and hydrogen-containing silane to a silane end-capping reaction under the action of a hydrosilylation catalyst to obtain a target product of a reactive sealant resin;
wherein in step (2), when the crude product is refined, the crude product is first neutralized by using a neutralizing agent, then water and an organic solvent are added, and the water in the crude product is separated by using a coalescing separator, the organic solvent is evaporated, so as to obtain the product of modified polyether;
wherein in step (3), the hydrosilylation catalyst is a supported metal platinum catalyst with an amount of 0.1 ppm to 50 ppm, based on the platinum content; and
wherein the supported metal platinum catalyst is obtained by subjecting a chloroplatinic acid solution to impregnation and reduction with a polyurethane flexible foam as a carrier; the polyurethane flexible foam is prepared by subjecting a raw material comprising a second polyether polyol to a foaming reaction, wherein a polymerized monomer for preparing the second polyether polyol comprises an epoxide containing a C═C double bond in the molecule, and the content of the epoxide in the polymerized monomer is 1 wt % to 40 wt %.

2. The preparation method according to claim 1 , wherein in step (1), the first polyether polyol has a molecular weight of 3000 g/mol to 50000 g/mol and a functionality of 2 to 8.

3. The preparation method according to claim 1 , wherein in step (1), the first polyether polyol is obtained by a n-stage polymerization, wherein n≥2; when the target molecular weights of each polymerization stage are sequentially set to M1, . . . , Mi, . . . , and Mn, M1≤1000 g/mol, and Mi−M(i−1)≤12000 g/mol, wherein i is an integer between 1 and n, and when i=1, M0 is the molecular weight of the hydroxyl-containing initiator.

4. The preparation method according to claim 3 , wherein when Mi≤10000 g/mol, Mi−M(i−1)≤5000 g/mol.

5. The preparation method according to claim 1 , wherein in step (1), the epoxide is ethylene oxide, propylene oxide or a mixture of any proportion thereof.

6. The preparation method according to claim 1 , wherein in step (1), the hydroxyl-containing initiator is a small-molecule polyol having a molecular weight of not greater than 400.

7. The preparation method according to claim 6 , wherein in step (1), the hydroxyl-containing initiator is one or more of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, mannitol, glucose, sucrose or xylitol.

8. The preparation method according to claim 1 , wherein the content of the alkali catalyst in the reaction system of step (1) is 10 ppm to 100 ppm; the alkali catalyst is one or more of an alkali metal, an alkali metal hydride, an alkali metal hydroxide, an alkali metal alkoxide, a composite metal cyanide or a phosphazene catalyst.

9. The preparation method according to claim 1 , wherein in step (1), the reaction temperature for preparing the first polyether polyol is 90° C. to 180° C.; the reaction pressure is 0.05 MPa to 0.8 MPa.

10. The preparation method according to claim 1 , wherein the alkoxidation reagent in step (2) is one or more of an alkali metal sodium, a sodium hydride or a sodium methoxide; a halide containing a double bond used is allyl chloride or methallyl chloride.

11. The preparation method according to claim 1 , wherein in step (2), the molar ratio of the amount of the alkoxidation reagent to the hydroxyl equivalent of the polyether polyol is 1:1 to 3:1; the molar ratio of the amount of the halide containing a double bond to the hydroxyl equivalent of the polyether polyol is 1:1 to 3:1.

12. The preparation method according to claim 1 , wherein in step (2), the reaction temperature for modifying the polyether polyol to prepare the double-bond-terminated polyether is 80° C. to 160° C.; the reaction time is 3 hours to 18 hours.

13. The preparation method according to claim 1 , wherein the mass ratio of the organic solvent, water and polyether crude product is (0.1 to 3): (0.1 to 2): 1.

14. The preparation method according to claim 1 , wherein the neutralizing agent is one or more of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid or lactic acid, and the amount of the neutralizing agent is 0.1 wt % to 5 wt % of the mass of the polyether crude product;
the organic solvent is an alkane, a benzene compound or a nitrile compound.

15. The preparation method according to claim 1 , wherein in step (3), the hydrogen-containing silane is one selected from the group consisting of trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, and a mixture of more than one selected therefrom.

16. The preparation method according to claim 15 , wherein the molar ratio of the amount of the hydrogen-containing silane to the double bond equivalent of the modified polyether is 0.9:1 to 2:1; the reaction temperature is 50° C. to 140° C.; the reaction time is 1 hour to 8 hours.

17. The preparation method according to claim 1 , wherein the epoxide containing a C═C double bond is one or more of allyl glycidyl ether

methallyl glycidyl ether, glycidyl acrylate or glycidyl methacrylate

18. The preparation method according to claim 1 , wherein the second polyether polyol is obtained by polymerizing the hydroxyl-containing initiator with the polymerized monomer comprising the epoxide containing a C═C double bond in the molecule under the action of an alkali catalyst; the second polyether polyol has a molecular weight of 700 g/mol to 10000 g/mol and a nominal functionality of 1 to 6.

19. The preparation method according to claim 1 , wherein the polymerized monomer consists of at least one of ethylene oxide or propylene oxide and the epoxide containing a C═C double bond in the molecule.

20. The preparation method according to claim 19 , wherein the epoxide containing a C═C double bond in the molecule is first added during the addition of the polymerized monomer.

21. The preparation method of claim 1 , wherein during the impregnation, the polyurethane flexible foam is added to the chloroplatinic acid solution, the impregnation is carried out at a reaction temperature of 10° C. to 80° C., then a reducing agent is added and reacted for 10 hours to 30 hours, and after the reaction, the polyurethane flexible foam is taken out, washed and dried to obtain the supported metal platinum catalyst.

22. The preparation method according to claim 1 , wherein the amount of substance of chloroplatinic acid in the impregnation solution is 0.01*n to 0.6*n, wherein n is the amount of substance of double bonds contained i

Assignees

• Wanhua Chemical Group Co Ltd
• Wanhua Chemical Ningbo Co Ltd

Inventors

• Ju Changxun
• Liu Bin
• Wang Mingyong
• Ye Tian
• Shi Zhengyang
• Li Yuan
• Hua Weiqi

Classifications

• C09D171/02

  Polyalkylene oxides · CPC title

• B01J2231/323

  Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation · CPC title

• B01J31/1658

  immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins · CPC title

• C09J171/02

  Polyalkylene oxides · CPC title

• C08L75/04

  Polyurethanes · CPC title