CN112029088A - Silane-modified polyether based on Michael addition reaction and its synthesis method - Google Patents

Abstract

The invention relates to silane modified polyether based on Michael addition reaction and a synthesis method thereof. The polyether amine is synthesized from 1.00 part of polyether amine and 4.00-6.00 parts of acryloyloxy silane by a Michael addition reaction according to equivalent parts. Polyether amine, ether amine and acryloyloxy silane are adopted to successfully synthesize silane terminated polyether through Michael addition reaction. The synthetic route has the advantages of mild reaction conditions, simple and convenient process, no need of catalyst and no by-product. The synthesized product contains abundant siloxane, is compounded with a crosslinking silane coupling agent, and can realize quick surface drying. The molecular chain of the product does not contain urethane bond and free urethane, and simultaneously, the product is crosslinked through Si-O-Si bond, so that the advantages of polyurethane sealant and silicone adhesive can be integrated, and the product is expected to be applied to preparation of high-performance MS sealant.

Description

Silane-modified polyether based on Michael addition reaction and its synthesis method

technical field

The invention relates to a silane-modified polyether based on Michael addition reaction and a synthesis method thereof, and belongs to the field of polymer materials.

Background technique

The molecular structure of silane-modified polyether sealant (MS sealant) does not contain urethane, free isocyanate and organic solvent, and it is chemically cross-linked through the hydrolysis-dehydration condensation of siloxane, so it is also a polyurethane sealant. It has the advantages of silicone sealant, that is, excellent mechanical properties, workability, and adhesion, but there is no silicone rubber and silicone oil oozing out to contaminate the substrate, and polyurethane sealant has poor weather resistance characteristics. Therefore, MS sealant is the development trend of today's new elastic sealing materials.

The technical difficulty of MS sealants is the silane-terminated polyether. The synthetic route pioneered by Japan's Zhongyuan Chemical, that is, a general-purpose polyether polyol and allyl chloride undergo Williamson reaction in the presence of an alkali catalyst to obtain an allyl-terminated polyether, and then use Pt or chloroplatinic acid as a catalyst , and reacted with dimethoxymethylsilane to obtain silane-terminated polyether. The route has been industrialized and has intellectual property protection. Switzerland's WACKER and US Dow Chemical each also have unique technology routes and commercialized products. Subject to the protection of intellectual property rights and the advantages of first-mover industrialization, there is no real commercial silane-terminated polyether in China. Domestic sealant manufacturers usually use the above three raw materials to produce MS sealants.

It can be seen that breaking through the existing synthetic route is the key to promoting the development of MS sealants in China. The invention uses polyetheramine and acryloxysilane through Michael addition reaction to successfully synthesize silane-terminated polyether under mild reaction conditions. MS sealant with excellent comprehensive properties can be prepared by using the polyether.

SUMMARY OF THE INVENTION

In order to solve the above problems, the present invention provides a silane-modified polyether based on Michael addition reaction and a synthesis method thereof.

The synthesis of the silane-modified polyether based on the Michael addition reaction involved in the present invention comprises the formula of the following molar equivalents:

1.00 equivalent parts of polyetheramine;

Acryloyloxysilane 4.00-6.00 equivalent parts.

Preferably, for the silane-modified polyether based on Michael addition reaction, acryloxysilane has an electro-absorbing conjugated double bond, and the reaction principle with polyetheramine is as follows:

Preferably, in the synthesis of the silane-modified polyether based on Michael addition reaction, the polyetheramine has a number-average molecular weight of 400-6000 g/mol, a functionality of 2.0-3.0, and an amine value of 0.40-7.00 meq/g.

Preferably, in the synthesis of the silane-modified polyether based on Michael addition reaction, the acryloyloxysilane is 3-(methacryloyloxy)propyltrimethoxysilane (CAS No.: 2530-85-0 ), 3-(diethoxymethylsilyl)propyl acrylate (CAS number: 13732-00-8), 3-trimethoxysilane propyl acrylate (CAS number: 4369-14-6 ), Acryloyloxymethyltrimethoxysilane (CAS No.: 21134-38-3), Methacryloxypropyltriethoxysilane (CAS No.: 21142-29-0), (Acrylic Oxygen methyl) dimethylmethoxysilane (CAS number: 130771-16-3), 1-methyl-2-(trimethoxysilyl)ethyl methacrylate (CAS number: 51749-70- 3), methacrylate propoxytriacetoxysilane (CAS number: 51772-85-1), 2-hydroxy-3-[3-(trimethoxysilyl)propoxy]methacrylate propylene Esters (CAS No: 59214-63-0), 2-Hydroxy-3-[3-(trimethoxysilyl)propoxy]propylacrylate (CAS No: 93858-44-7), Methpropylene Acyloxymethyltriethoxysilane (CAS No.: 5577-72-0), Methacryloxymethyltrimethoxysilane (CAS No.: 54586-78-6), Tris(methoxyethoxy) (CAS No. 57069-48-4), 3-[Tris(1-methylethoxy)silyl]propyl methacrylate (CAS No. 80750-05-6 ), (triethoxysilyl)-2-methyl acrylate (CAS number: 78884-71-6), (2-acetoxyethyl) trimethoxysilane (CAS number: 66280-77-1) 、2-Propenoic acid,2-methyl-,6-(trimethoxysilyl)hexyl ester(CAS No.: 132251-59-3), 2-Propenoic acid-3-(tributoxysilyl)propyl ester(CAS No.: 66469-83-8 ), 2-Propenoic acid-2-[tris(1-methylethoxy)silyl]ethyl ester(CAS No.: 189194-82-9), 2-Propenoic acid-2-methyl-4-(trimethoxysilyl)butyl ester(CAS No. : 129721-34-2), 3-[bis(2-methoxyethoxy)methylsilyl]propyl methacrylate (CAS No.: 93804-26-3), 2-(trimethoxy)si One or more mixtures of lylpropyl metacrylate (CAS number: 72537-60-1), preferably 3-(methacryloyloxy)propyltrimethoxysilane (CAS number: 2530-85-0).

Preferably, the synthesis process of the silane-modified polyether based on Michael addition reaction is as follows: put polyetheramine into the reaction kettle according to the set ratio, heat up to 100-120°C, and vacuumize to no more than -0.095MPa , mechanically stir for 1 to 3 hours to remove traces of moisture, cool down to 25 to 60 ° C and continue to feed nitrogen, put in acryloxysilane, mechanically stir for 3 to 6 hours, put in diluent to adjust the viscosity, and continue to mechanically stir for 12 to For 36 hours, the diluent is removed by heating under reduced pressure, metering and discharging, and sealing and packaging to obtain a silane-modified polyether.

Preferably, in the process of synthesizing the silane-modified polyether based on the Michael addition reaction, adding a diluent is an unnecessary step, and when a diluent needs to be added, the diluent is tetrahydrofuran (THF), N,N-dimethyl One or more mixtures of methylformamide (DMF), N,N-dimethylacetamide (DMAc), toluene, xylene, dichloromethane, chloroform, petroleum ether.

The beneficial effects of the silane-modified polyether based on the Michael addition reaction of the present invention: adopting the Michael addition reaction between amino groups and electricity-absorbing conjugated double bonds, and grafting siloxane at the end, the reaction conditions are mild, the process is simple, and the energy consumption is low. Low; (2) Silane-modified polyether can be used to prepare MS sealant, and through the hydrolysis and cross-linking of siloxane, rapid curing under moisture conditions can be achieved.

Specific implementation example

In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below with reference to specific embodiments.

The raw materials used in the experiments in the examples and comparative examples of the present invention are as follows, but are not limited to the following raw materials. The present invention only uses the following raw materials as specific examples to further illustrate the effect of the silane-modified polyether based on the Michael addition reaction described in this application. :

Polyetheramine: Jeffamine D-400, functionality 2.0, number average molecular weight 430g/mol, amine value 4.10～4.70meq/g; Jeffamine D-2000, functionality 2.0, number average molecular weight 2000g/mol, amine value 0.98～1.05 meq/g; Jeffamine D-4000, functionality 2.0, number average molecular weight 4000g/mol, amine value 0.44～0.52meq/g; Jeffamine T-403, functionality 3.0, number average molecular weight 440g/mol, amine value 6.10～6.60meq /g; Jeffamine T-5000, functionality 3.0, number average molecular weight 5000g/mol, amine value 0.50～0.54meq/g; Huntsman.

Acryloyloxysilane: 3-(methacryloyloxy)propyltrimethoxysilane, CG-571, Nanjing Chengong.

Diluent: THF, Jinan Renyuan Chemical Co., Ltd.

Vinyltrimethoxysilane: JH-V171, Hubei Jinleda Chemical Industry.

Cross-linked silane coupling agent: methyltrimethoxysilane, CG-8030, Nanjing Chengong.

In the present invention, Examples 1 to 7 and Comparative Examples 1 to 3 are set, and formulas are designed according to the combination of high and low molecular weights.

The examples and comparative examples were synthesized according to the same method to obtain silane-modified polyether based on Michael addition reaction. -0.100MPa, mechanically stirred for 1 hour to remove traces of moisture, cooled to 35°C, continuously fed with nitrogen, put in acryloxysilane CG-571 or vinyltrimethoxysilane JH-V171, mechanically stirred for 3 hours, put in The diluent THF was used to adjust the viscosity, and the mechanical stirring was continued for 24 hours.

The formulas and properties of the silane-modified polyethers based on Michael addition reaction of Examples 1 to 7 and Comparative Examples 1 to 3 are shown in Table 1.

The above product was blended with 0.1 equivalent (relative to polyetheramine) cross-linking silane coupling agent CG-8030 for 30 minutes, and the sample was prepared by laying a film. Refer to the method A specified in GB/T 13477.5-2002 to test the surface dry time. GB/T 14683-2017 stipulates that the tack-free time is ≤24 hours to test whether the polyetheramine is successfully terminated by silane.

The properties of Examples 1 to 7 and Comparative Examples 1 to 3 are shown in Table 2

Examples 1 to 7 in Table 2 show that no matter how the polyetheramine is matched, the final product can achieve fast surface drying, indicating that the synthesis route can successfully realize the silane end capping of the polyetheramine. In contrast, the product of silane coupling agent without electro-absorbing conjugated structure could not be cured, indicating that polyetheramine failed to realize the end-capping of silane coupling agent.

The above descriptions are merely embodiments of the present invention, and are not intended to limit the present invention. Various suitable modifications and variations of the present invention are possible. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (6)

1. The silane modified polyether based on the Michael addition reaction and the synthesis method thereof are characterized in that the silane modified polyether based on the Michael addition reaction is synthesized by 1.00 equivalent parts of polyetheramine and 4.00-6.00 equivalent parts of acryloyloxysilane through the Michael addition reaction.

2. The silane modified polyether based on Michael addition reaction and the synthesis method thereof according to claim 1, wherein the acryloxysilane has an electroabsorption conjugated double bond and reacts with polyetheramine according to the following principle:

3. the silane modified polyether based on Michael addition reaction and the synthesis method thereof according to claims 1-2, wherein the polyether amine has a number average molecular weight of 400-6000 g/mol, a functionality of 2.0-3.0, and an amine value of 0.40-7.00 meq/g.

4. The silane-modified polyether based on Michael addition reaction and the synthesis method thereof as claimed in claims 1 to 3, wherein the acryloxysilane is 3- (methacryloyloxy) propyltrimethoxysilane (CAS number: 2530-85-0), 3- (diethoxymethylsilyl) propyl 2-acrylate (CAS number: 13732-00-8), 3-trimethoxysilylacrylate (CAS number: 4369-14-6), acryloxymethyltrimethoxysilane (CAS number: 21134-38-3), methacryloxypropyltriethoxysilane (CAS number: 21142-29-0), (acryloxymethyl) dimethylmethoxysilane (CAS number: 130771-16-3), 1-methyl-2- (trimethoxysilyl) ethyl methacrylate (CAS number: 51749-70-3) Methacrylic acid propoxytriethoxysilane (CAS No.: 51772-85-1), 2-hydroxy-3- [3- (trimethoxysilyl) propoxy ] propyl methacrylate (CAS No.: 59214-63-0), 2-hydroxy-3- [3- (trimethoxysilyl) propoxy ] propyl acrylate (CAS No.: 93858-44-7), methacryloxymethyltriethoxysilane (CAS No.: 5577-72-0), methacryloxymethyltrimethoxysilane (CAS No.: 54586-78-6), tris (methoxyethoxy) propylacyloxysilane (CAS No.: 57069-48-4), 3- [ tris (1-methylethoxy) silyl ] propyl methacrylate (CAS No.: 80750-05-6), (triethoxysilyl) -2-propenoic acid methyl ester (CAS number: 78884-71-6), (2-acetoxyethyl) trimethoxysilane (CAS No.: 66280-77-1), 2-Propenoic acid,2-methyl-,6- (trimethyoxyslyl) hexyl ester (CAS number: 132251-59-3), 2-Propenoic acid-3- (tributoxysilyl) propyl ester (CAS number: 66469-83-8), 2-Propenoic acid-2- [ tris (1-methyothoxy) lysine ] ethyl ester (CAS number: 189194-82-9), 2-Propenoic acid-2-methyl-4- (trimethylysilyl) butyl ester (CAS number: 129721-34-2), 3- [ bis (2-methoxylethyloxy) methylsilyl ] propyl methacrylate (CAS No.: 93804-26-3), 2- (trimethoxy) silylpropylate (CAS No.: 72537-60-1), preferably 3- (methacryloyloxy) propyltrimethoxysilane (CAS No.: 2530-85-0).

5. The silane modified polyether based on Michael addition reaction and the synthesis method thereof according to claims 1 to 4, wherein the synthesis method is as follows: adding polyetheramine into a reaction kettle according to a set proportion, heating to 100-120 ℃, vacuumizing to be not more than-0.095 MPa, mechanically stirring for 1-3 hours to remove trace moisture, cooling to 25-60 ℃, continuously introducing nitrogen, adding acryloyloxysilane, mechanically stirring for 3-6 hours, adding a diluent to adjust viscosity, continuously mechanically stirring for 12-36 hours, heating and decompressing to remove the diluent, metering, discharging, sealing and packaging to obtain the silane modified polyether.

6. The silane modified polyether based on Michael addition reaction and its synthesis method according to claims 1 to 5, wherein the step of adding a diluent is an optional step in the synthesis process, and when the diluent is needed, the diluent is one or more of Tetrahydrofuran (THF), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), toluene, xylene, dichloromethane, chloroform, and petroleum ether.