A kind of silane-terminated polyether polymer resin and preparation method thereof

Abstract

The present invention relates to the technical field of silane-modified polymers, specifically to a silane-terminated polyether polymer resin and a preparation method thereof, comprising the following processes: step 1, mixing a polyether polyol with a solvent, heating to 60-70° C. under nitrogen gas protection, adding diisocyanate and catalyst A, reacting for 12-24 hours, and obtaining an isocyanate-terminated polyether; step 2, mixing epoxysiloxane, an isocyanate-terminated polyether, a catalyst B and imidazole, heating to 150-160° C. under nitrogen gas protection, and keeping the temperature for 8-10 hours to obtain a silane-terminated polyether polymer resin. The present invention obtains a silane-modified polyether having a carbamate and oxazolidinone five-membered heterocyclic structure by reacting diisocyanate with polyether polyol and epoxysiloxane, which can effectively enhance its cohesion and improve the mechanical properties, bonding properties and high-temperature adhesion stability of the silane-terminated polyether polymer resin.

Description

Technical Field

[0001] The invention relates to the technical field of silane-modified polymers, in particular to a silane-terminated polyether polymer resin and a preparation method thereof. Background Art

[0002] Silane-modified polymer resin is referred to as STP resin. In the presence of room temperature moisture and an appropriate catalyst, the alkoxy groups in the silane-modified terminal silane groups are rapidly hydrolyzed to form silanol groups, which undergo polycondensation reactions to form an elastomer with a three-dimensional network structure. As a sealant component, it can achieve the effects of sealing and bonding. However, some existing silane-modified polymers have insufficient strength, and the strength and bonding strength of the sealants produced after curing are poor. Therefore, we propose a silane-terminated polyether polymer resin and a preparation method thereof. Summary of the invention

[0003] The object of the present invention is to provide a silane-terminated polyether polymer resin and a preparation method thereof to solve the problems raised in the above background technology.

[0004] In order to solve the above technical problems, the present invention provides the following technical solution: a method for preparing a silane-terminated polyether polymer resin, comprising the following process:

[0005] Step 1: Mix the polyether polyol with the solvent, raise the temperature to 60-70° C. under nitrogen protection, add diisocyanate and catalyst A, and react for 12-24 hours to obtain an isocyanate-terminated polyether;

[0006] Step 2: Mix epoxysiloxane, isocyanate-terminated polyether, catalyst B and imidazole, raise the temperature to 150-160° C. under nitrogen protection, and keep the temperature for reaction for 8-10 hours; add distilled water, precipitate, filter, wash and dry to obtain a silane-terminated polyether polymer resin.

[0007] Furthermore, in step 1, the solvent is a mixed solvent of ethyl acetate / methyl ethyl ketone, and the volume ratio of ethyl acetate to methyl ethyl ketone is (1-3):1;

[0008] The ratio of polyether polyol to solvent is (10-25) g / 100 mL.

[0009] Furthermore, in the step 1, the molar ratio of -NCO / -OH in the polyether polyol and the diisocyanate is 2:(1.0-1.5);

[0010] The diisocyanate is one of toluene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0011] Furthermore, in the step 1, the catalyst A is dibutyltin dilaurate or stannous octoate, and the amount used is 0.8-0.1% of the total mass of the polyether polyol and the diisocyanate.

[0012] Furthermore, in the step 2, the ratio of the terminal isocyanate polyether to the imidazole is (10-25) g / 100 mL.

[0013] Furthermore, in the step 2, the molar ratio of -NCO / -CH(O)CH- in the epoxysiloxane and the isocyanate-terminated polyether is 1:(1.0-1.5).

[0014] Furthermore, in the step 2, the catalyst B is aluminum chloride·hexamethylphosphoric triamide, and the amount used is 0.02-0.05% of the total mass of the epoxysiloxane and the terminal isocyanate polyether.

[0015] In the above technical scheme, polyether polyol and diisocyanate are mixed and reacted. Under the action of catalyst A, the hydroxyl group (-OH) at the end of the polyether polyol reacts with the isocyanate group (-NCO) in the diisocyanate to generate a carbamate group (-NHCOO-), and a polyether compound with an isocyanate group end is obtained, which is recorded as an isocyanate-terminated polyether. The introduction of the carbamate flexible chain segment enables the prepared polymer resin to have the high strength and high elongation characteristics of polyurethane to a certain extent. The rigid group in the diisocyanate structure can also give the polymer resin more excellent mechanical properties, and its tear resistance is improved.

[0016] The isocyanate-terminated polyether is reacted with epoxysiloxane, and under the action of catalyst B and high temperature, the isocyanate group reacts with the epoxy group to form an oxazolidone group; the polyether segment is grafted with siloxane to achieve the preparation of a silane-modified polyether compound, which is recorded as a silane-modified polyether polymer resin (hereinafter referred to as polymer resin). The introduction of the oxazolidone five-membered heterocyclic ring into the polymer resin can form a hydrogen bond interaction with the carbamate, thereby enhancing its cohesive force, effectively improving its thermal stability and toughness, and improving the mechanical properties and high-temperature adhesion stability of the polymer resin.

[0017] When the prepared polymer resin is used as a sealant component, it has good compatibility with silane-modified polyether. When compounded with silane-modified polyether, it reacts with moisture at room temperature to hydrolyze the siloxane (-Si(OR) or -SiR(OR)-) in the polymer resin chain segment and cross-link to form an elastomer with a Si-O-Si network structure, thereby improving the mechanical properties, bonding properties and high-temperature adhesion stability of the sealant and achieving sealing and bonding effects.

[0018] By reacting the polyhydroxyl groups of polyether polyols with appropriate amounts of diisocyanates and epoxysiloxanes, terminal branching is achieved, the content of siloxane in the polymer resin is increased, the surface penetration of the colloid into the bonded substrate is promoted, the bonding strength of the joints is increased, the cross-linking density of the system is increased, and the mechanical properties and high-temperature adhesion stability of the sealant are further improved.

[0019] Further, the polyether polyol is prepared by the following process:

[0020] Take a polyhydroxy compound, an epoxy compound and a catalyst C and mix them. Under the protection of a nitrogen atmosphere, stir and heat to 100-120° C. for 6-10 hours. Cool to room temperature, dialyze and rotary evaporate to obtain a polyether polyol.

[0021] Further, the polyether polyol is prepared from the following components by mass: 1 part of a polyhydroxy compound, 10 to 20 parts of an epoxy compound, and 50 to 100 ppm of a catalyst C;

[0022] The polyol is one of 1,3,5-tris(2-hydroxyethyl)cyanuric acid (CAS No.839-90-7), N,N,N',N',N'-penta(2-hydroxypropyl)diethylenetriamine (CAS No.17121-34-5), and tannic acid (CAS No.1401-55-4);

[0023] The epoxy compound is a mixture of two or more of epoxy ester compounds, bisphenol A diglycidyl ether, propylene oxide, and glycidol;

[0024] Catalyst C is double metal cyanide (DMC).

[0025] In the above technical scheme, the polyether polyol is obtained by reacting a polyhydroxy compound with an epoxy compound and etherifying. During the reaction, the epoxy compound is ring-opened and etherified with a hydroxyl group, and a new hydroxyl group is generated at the same time. The new hydroxyl group is etherified with an epoxy group to form a new hydroxyl group until the epoxy group in the system reacts completely, thereby forming a polyether segment of the polyether polyol. The polyhydroxy compound is selected from one of 1,3,5-tris(2-hydroxyethyl)cyanuric acid, N,N,N',N',N'-penta(2-hydroxypropyl)diethylenetriamine, and tannic acid. One of the above substances is used as an initiator to react with an epoxy compound. The prepared polyether polyol has multiple groups of ether segments, which is helpful for obtaining a branched structure of the prepared polymer resin.

[0026] When tannic acid is used as an initiator, a rigid benzene ring structure is added to the polymer resin structure, which helps to improve its strength, bonding performance and high-temperature adhesion stability. Epoxy compounds include epoxy ester compounds, bisphenol A diglycidyl ether, propylene oxide, glycidol, etc. Propylene oxide has a high reactivity. While participating in the formation of polyether segments, it also helps to activate the reaction system and promote the reaction of other epoxy compound components. Glycidol also contains a hydroxyl group, which can increase the hydroxyl content in the system and increase the branching degree of polyether polyols. The use of bisphenol A diglycidyl ether introduces a bisphenol A polyether structure into the polyether polyol segment, which helps to significantly improve the hardness and strength of the polymer resin and improve the bonding performance and high-temperature adhesion stability.

[0027] Further, the epoxy ester compound is prepared by the following process:

[0028] 1.1. Mix propylene oxide, abietic acid, tetrabutylammonium bromide and propylene glycol methyl ether acetate, stir and heat to 120-125°C, keep warm for 3-6 hours until the acid value of the system is less than 5mg / KOH; wash and dry to obtain epoxy ester;

[0029] 1.2. Mix epoxy ester and tetrahydrofuran, add potassium metal, stir, and react at 20-35°C for 8-10 hours;

[0030] Add epichlorohydrin, stir and react for 3-4 hours; let stand, filter, distill under reduced pressure, wash and dry to obtain an epoxy ester compound.

[0031] Furthermore, in step 1.1, the ratio of abietic acid to propylene glycol methyl ether acetate is (10-20) g / 10 mL;

[0032] The molar ratio of abietic acid to propylene oxide is 1:(1.0-1.2);

[0033] The dosage of tetrabutylammonium bromide is 0.3-1.0% of the mass of abietic acid.

[0034] Further, in step 1.2, the ratio of epoxy ester to tetrahydrofuran is 5 g / 10 mL;

[0035] The mass ratio of epoxy ester, epichlorohydrin and metallic potassium is 10: (2.8-3.8): (0.4-0.6).

[0036] In the above technical scheme, the epoxy compound can also be selected from epoxy ester compounds obtained by reacting abietic acid with propylene oxide and epichlorohydrin. In the preparation of epoxy ester compounds, the carboxyl group in abietic acid reacts with propylene oxide to generate epoxy esters. The epoxy ester molecular chain contains hydroxyl groups, which are reacted with epichlorohydrin to obtain epoxy esters with epoxy groups, which are recorded as epoxy ester compounds. When it participates in the preparation of polyether polyols, the side chains of the prepared polyether polyols have abietic acid and epoxy ester structures, which can effectively improve the mechanical properties and high temperature adhesion stability of polymer resins and sealants prepared therefrom.

[0037] Furthermore, the epoxysiloxane is γ-glycidyloxypropyltrimethoxysilane.

[0038] The invention discloses an application of a silane-terminated polyether polymer resin in a sealant, comprising the following processes: mixing the silane-terminated polyether polymer resin, silane-modified polyether, a plasticizer, calcium carbonate and an auxiliary agent, heating the mixture to 100-120° C. and removing water in a vacuum; cooling the mixture to room temperature, adding a coupling agent, a catalyst and a dehydrating agent, and obtaining the sealant.

[0039] Further, the sealant includes the following components by mass: 1 to 100 parts of silane-modified polyether, 1 to 100 parts of silane-terminated polyether polymer resin, 1 to 60 parts of plasticizer, 80 to 140 parts of calcium carbonate, 1 to 10 parts of coupling agent, 0.5 to 2.0 parts of catalyst and 3 to 10 parts of auxiliary agent;

[0040] Calcium carbonate is a mixture of 80-100% nano calcium carbonate and 0-20% heavy calcium carbonate;

[0041] The coupling agents are two of A171, KH-550, and KH792;

[0042] The auxiliary agent is one or more of a dewatering agent, a leveling agent, a diluent, a colorant, a thixotropic agent, an antioxidant, a light stabilizer, and a UV absorber.

[0043] Furthermore, the sealant includes the following components by mass: 10 to 30 parts of silane-terminated polyether polymer resin, 70 to 90 parts of silane-modified polyether, 1 to 20 parts of plasticizer, 64 to 112 parts of nano calcium carbonate, 16 to 28 parts of heavy calcium carbonate, 2 to 5 parts of coupling agent A171, 2 to 5 parts of coupling agent KH792, 1 to 2 parts of catalyst, 1 to 5 parts of thixotropic agent, 0.5 to 1.5 parts of light stabilizer, 0.5 to 1.5 parts of ultraviolet absorber and 1 to 2 parts of dewatering agent.

[0044] Compared with the prior art, the present invention has the following beneficial effects:

[0045] 1. The present invention describes a silane-terminated polyether polymer resin, which is obtained by reacting diisocyanate with polyether polyol and epoxysiloxane to obtain a silane-modified polyether having a five-membered heterocyclic structure of carbamate and oxazolidinone, which can effectively enhance its cohesive force and improve the mechanical properties, bonding properties and high-temperature adhesion stability of the silane-terminated polyether polymer resin.

[0046] 2. The present invention describes a silane-terminated polyether polymer resin, which is prepared by etherification through the reaction of polyhydroxy compounds with epoxy compounds, wherein the epoxy compounds contain epoxy ester compounds obtained by the reaction of abietic acid, propylene oxide and epichlorohydrin, and the side chains of the prepared polyether polyol have abietic acid and epoxy ester structures, which can effectively improve the mechanical properties, bonding properties and high-temperature adhesion stability of the polymer resin and the sealant prepared therefrom. DETAILED DESCRIPTION

[0047] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0048] The following specific implementation methods are laboratory tests, and the composition ratio can be expanded in equal proportions; all materials are dehydrated before use; the "parts" mentioned are parts by mass;

[0049] Catalyst B is aluminum chloride·hexamethylphosphoric triamide;

[0050] Catalyst C is double metal cyanide (DMC), which is sourced from Jiangsu Bader Polyurethane Co., Ltd.;

[0051] In the sealant components,

[0052] Silane modified polyether: from Jiangsu Ruiyang Antai New Material Technology Co., Ltd.;

[0053] The plasticizer is didecyl phthalate, which comes from ExxonMobil Oil Company in the United States;

[0054] The light stabilizer was Tinuvin 326, and the UV absorber was Tinuvin 770, both from BASF AG;

[0055] Thixotropic agent: D680, from Guangdong Core New Materials Co., Ltd.;

[0056] Catalyst: Neostann U-220, from Nitto (China) New Materials Co., Ltd.;

[0057] Dewatering agent: Zoldine MS-PLus, from Angus Chemical Company, USA;

[0058] Nano calcium carbonate: CCS-25, particle size 60-80nm, from Guangzhou Warner New Materials Co., Ltd.

[0059] Heavy calcium carbonate: TC8, particle size 3-5μm, sourced from Guangxi Hezhou Kelong Powder Co., Ltd.

[0060] Example 1: A method for preparing a silane-terminated polyether polymer resin, comprising the following process:

[0061] Step 1, 5.5g of propylene oxide, 10g of abietic acid, 0.03g of tetrabutylammonium bromide, and 10mL of propylene glycol methyl ether acetate are mixed, stirred and heated to 120°C, and kept warm to react until the acid value of the system is less than 5mg / KOH; washed and dried to obtain epoxy ester;

[0062] Mix 10g of epoxy ester and 20mL of tetrahydrofuran, add 0.4g of potassium metal, stir, and react at 20°C for 8h; add 2.8g of epichlorohydrin, stir and react for 3h; let stand, filter, distill under reduced pressure, wash, and dry to obtain an epoxy ester compound;

[0063] Step 2, taking a polyhydroxy compound, an epoxy compound and a catalyst C, mixing them, stirring and heating to 100° C. under a nitrogen atmosphere, and reacting for 10 hours; cooling to room temperature, dialyzing, and rotary evaporation to obtain a polyether polyol; the polyether polyol is prepared from the following mass components: 1.0 parts of a polyhydroxy compound, 12.1 parts of an epoxy compound and 50 ppm of a catalyst C; the polyhydroxy compound is 1,3,5-tris(2-hydroxyethyl)cyanuric acid; the epoxy compound is a mixture of an epoxy ester compound, bisphenol A diglycidyl ether, glycidol, and propylene oxide, and the mass ratio is 9.0:7.3:1.6:50;

[0064] Step 3, 10g of polyether polyol was mixed with 100mL of solvent, and the temperature was raised to 70°C under nitrogen protection, 4.3g of isophorone diisocyanate and 0.8% of catalyst A dibutyltin dilaurate were added, and the reaction was carried out for 12h to obtain an isocyanate-terminated polyether; the solvent was a mixed solvent of ethyl acetate / methyl ethyl ketone, and the volume ratio of ethyl acetate to methyl ethyl ketone was 2:1; the mass ratio of polyether polyol to isophorone diisocyanate was 10:2.0;

[0065] Step 4: 1.8 g of γ-glycidyloxypropyltrimethoxysilane, 10 g of terminal isocyanate polyether, 0.02% of catalyst B and 100 mL of imidazole were mixed, and the mixture was heated to 150° C. and kept for 10 h under nitrogen protection; the mixture was added into distilled water, precipitated, filtered, washed and dried to obtain a silane-terminated polyether polymer resin;

[0066] The invention discloses an application of a silane-terminated polyether polymer resin in a sealant, comprising the following process: mixing 10 parts of a silane-terminated polyether polymer resin, 90 parts of a silane-modified polyether, 20 parts of a plasticizer, 80 parts of nano calcium carbonate, 20 parts of heavy calcium carbonate, 2 parts of a thixotropic agent, 1 part of a light stabilizer and 1 part of an ultraviolet absorber, heating the mixture to 100°C and removing water in vacuo; cooling the mixture to room temperature, adding 3 parts of a coupling agent A171, 3 parts of a coupling agent KH792, 1 part of a catalyst and 2 parts of a dehydrating agent to obtain a sealant.

[0067] Example 2: A method for preparing a silane-terminated polyether polymer resin, comprising the following process:

[0068] Step 1, 5.4 g of propylene oxide, 10 g of abietic acid, and 0.06 g of tetrabutylammonium bromide are mixed with 10 mL of propylene glycol methyl ether acetate, stirred and heated to 122° C., and kept warm to react until the acid value of the system is less than 5 mg / KOH; washed and dried to obtain epoxy ester;

[0069] Mix 10g of epoxy ester and 20mL of tetrahydrofuran, add 0.5g of potassium metal, stir, and react at 27°C for 9h; add 3.2g of epichlorohydrin, stir and react for 3.5h; let stand, filter, distill under reduced pressure, wash, and dry to obtain an epoxy ester compound;

[0070] Step 2, take a polyhydroxy compound, an epoxy compound and a catalyst C double metal cyanide (DMC) and mix them, under the protection of a nitrogen atmosphere, stir and heat to 110°C, and the reaction time is 8 hours; cool to room temperature, dialyze, and rotary evaporate to obtain a polyether polyol; the polyether polyol is prepared from the following mass components: 1.0 parts of a polyhydroxy compound, 13.3 parts of an epoxy compound and 80 ppm of a catalyst C; the polyhydroxy compound is N,N,N',N',N'-penta(2-hydroxypropyl)diethylenetriamine; the epoxy compound is a mixture of an epoxy ester compound, bisphenol A diglycidyl ether, glycidol, and propylene oxide, and the mass ratio is 9.0:7.3:1.6:50;

[0071] Step 3, 10g of polyether polyol was mixed with 100mL of solvent, and the temperature was raised to 65°C under nitrogen gas protection, and isophorone diisocyanate and 0.9% catalyst A stannous octoate were added, and the reaction was carried out for 18h to obtain an isocyanate-terminated polyether; the solvent was ethyl acetate / methyl ethyl ketone mixed solvent, and the volume ratio of ethyl acetate to methyl ethyl ketone was 2:1; the mass ratio of polyether polyol to isophorone diisocyanate was 10:2.0;

[0072] Step 4: 1.8 g of γ-glycidyloxypropyltrimethoxysilane, 10 g of terminal isocyanate polyether, 0.03% of catalyst B and 100 mL of imidazole were mixed, and the mixture was heated to 155° C. under nitrogen gas protection, and kept warm for 9 hours; the mixture was added into distilled water, precipitated, filtered, washed and dried to obtain a silane-terminated polyether polymer resin;

[0073] The invention discloses an application of a silane-terminated polyether polymer resin in a sealant, comprising the following process: mixing 20 parts of a silane-terminated polyether polymer resin, 80 parts of a silane-modified polyether, 20 parts of a plasticizer, 90 parts of nano calcium carbonate, 10 parts of heavy calcium carbonate, 2 parts of a thixotropic agent, 1 part of a light stabilizer, and 1 part of an ultraviolet absorber, heating the mixture to 110° C. and removing water in vacuo; cooling the mixture to room temperature, adding 3 parts of a coupling agent A171, 3 parts of a coupling agent KH792, 1 part of a catalyst, and 2 parts of a dehydrating agent, to obtain the sealant.

[0074] Example 3: A method for preparing a silane-terminated polyether polymer resin, comprising the following process:

[0075] Step 1, 5.7g of propylene oxide, 10g of abietic acid, 0.10g of tetrabutylammonium bromide, and 10mL of propylene glycol methyl ether acetate are mixed, stirred and heated to 125°C, and kept warm to react until the acid value of the system is less than 5mg / KOH; washed and dried to obtain epoxy ester;

[0076] Mix 10g of epoxy ester and 20mL of tetrahydrofuran, add 0.6g of potassium metal, stir, and react at 35°C for 8h; add 3.8g of epichlorohydrin, stir and react for 3h; let stand, filter, distill under reduced pressure, wash, and dry to obtain an epoxy ester compound;

[0077] Step 2, taking a polyhydroxy compound, an epoxy compound and a catalyst C, mixing them, stirring and heating to 120° C. under a nitrogen atmosphere, and reacting for 6 hours; cooling to room temperature, dialyzing, and rotary evaporation to obtain a polyether polyol; the polyether polyol is prepared from the following components by mass: 1.0 part of a polyhydroxy compound, 9.3 parts of an epoxy compound and 100 ppm of a catalyst C; the polyhydroxy compound is tannic acid; the epoxy compound is a mixture of an epoxy ester compound, bisphenol A diglycidyl ether, glycidol, and propylene oxide, and the mass ratio is 9.0:7.3:1.6:50;

[0078] Step 3, 10g of polyether polyol was mixed with 100mL of solvent, and the temperature was raised to 60°C under nitrogen protection, and diisocyanate isophorone diisocyanate and 0.1% catalyst A were added, and the reaction was carried out for 24h to obtain an isocyanate-terminated polyether; the solvent was a mixed solvent of ethyl acetate / methyl ethyl ketone, and the volume ratio of ethyl acetate to methyl ethyl ketone was 2:1; the mass ratio of polyether polyol to isophorone diisocyanate was 10:2.0;

[0079] Step 4: 1.8 g of γ-glycidyloxypropyltrimethoxysilane, 10 g of isocyanate-terminated polyether, 0.05% of catalyst B and 100 mL of imidazole were mixed, and the mixture was heated to 160° C. under nitrogen gas protection, and kept warm for 8 h; the mixture was added into distilled water, precipitated, filtered, washed and dried to obtain a silane-terminated polyether polymer resin;

[0080] The invention discloses an application of a silane-terminated polyether polymer resin in a sealant, comprising the following process: mixing 30 parts of a silane-terminated polyether polymer resin, 70 parts of a silane-modified polyether, 20 parts of a plasticizer, 100 parts of nano-calcium carbonate, 2 parts of a thixotropic agent, 1 part of a light stabilizer, and 1 part of an ultraviolet absorber, heating the mixture to 120°C and removing water in a vacuum; cooling the mixture to room temperature, adding 3 parts of a coupling agent A171, 3 parts of a coupling agent KH792, 1 part of a catalyst, and 2 parts of a dehydrating agent to obtain the sealant.

[0081] Comparative Example 1: A method for preparing a silane-terminated polyether polymer resin, comprising the following process:

[0082] Step 1, 2.2g propylene oxide, 10g n-hexanoic acid, 0.03g tetrabutylammonium bromide, 10mL propylene glycol methyl ether acetate are mixed, stirred and heated to 120°C, and kept warm to react until the acid value of the system is less than 5mg / KOH; washed and dried to obtain epoxy ester;

[0083] Mix 10g of epoxy ester and 20mL of tetrahydrofuran, add 0.8g of potassium metal, stir, and react at 20°C for 8h; add 5.6g of epichlorohydrin, stir and react for 3h; let stand, filter, distill under reduced pressure, wash, and dry to obtain an epoxy ester compound;

[0084] Step 2, taking a polyhydroxy compound, an epoxy compound and a catalyst C, mixing them, stirring and heating to 100° C. under a nitrogen atmosphere, and reacting for 10 hours; cooling to room temperature, dialyzing, and rotary evaporation to obtain a polyether polyol; the polyether polyol is prepared from the following components by mass: 1.0 parts of a polyhydroxy compound, 12.1 parts of an epoxy compound and 50 ppm of a catalyst C; the polyhydroxy compound is 1,3,5-tris(2-hydroxyethyl)cyanuric acid; the epoxy compound is a mixture of an epoxy ester compound, bisphenol A diglycidyl ether, glycidol, and propylene oxide, and the mass ratio is 4.5:7.3:1.6:50;

[0085] Step 3, 10g of polyether polyol was mixed with 100mL of solvent, and the temperature was raised to 70°C under nitrogen protection, 4.3g of isophorone diisocyanate and 0.8% of catalyst A dibutyltin dilaurate were added, and the reaction was carried out for 12h to obtain an isocyanate-terminated polyether; the solvent was a mixed solvent of ethyl acetate / methyl ethyl ketone, and the volume ratio of ethyl acetate to methyl ethyl ketone was 2:1; the mass ratio of polyether polyol to isophorone diisocyanate was 10:2.0;

[0086] Step 4: 1.8 g of γ-glycidyloxypropyltrimethoxysilane, 10 g of terminal isocyanate polyether, 0.02% of catalyst B and 100 mL of imidazole were mixed, and the mixture was heated to 150° C. and kept for 10 h under nitrogen protection; the mixture was added into distilled water, precipitated, filtered, washed and dried to obtain a silane-terminated polyether polymer resin;

[0087] An application of a silane-terminated polyether polymer resin in a sealant is the same as that in Example 1.

[0088] Comparative Example 2: A method for preparing a silane-terminated polyether polymer resin, comprising the following process:

[0089] Step 1, taking a polyhydroxy compound, an epoxy compound and a catalyst C, mixing them, stirring and heating to 100° C. under a nitrogen atmosphere, and reacting for 10 hours; cooling to room temperature, dialyzing, and rotary evaporation to obtain a polyether polyol; the polyether polyol is prepared from the following components by mass: 1.0 part of a polyhydroxy compound, 10.5 parts of an epoxy compound and 50 ppm of a catalyst C; the polyhydroxy compound is 1,3,5-tris(2-hydroxyethyl)cyanuric acid; the epoxy compound is a mixture of bisphenol A diglycidyl ether, glycidol, and propylene oxide, and the mass ratio is 7.3:1.6:50;

[0090] Step 2, 10g of polyether polyol was mixed with 100mL of solvent, and the temperature was raised to 70°C under nitrogen gas protection, 4.3g of isophorone diisocyanate and 0.8% of catalyst A dibutyltin dilaurate were added, and the reaction was carried out for 12h to obtain an isocyanate-terminated polyether; the solvent was a mixed solvent of ethyl acetate / methyl ethyl ketone, and the volume ratio of ethyl acetate to methyl ethyl ketone was 2:1; the mass ratio of polyether polyol to isophorone diisocyanate was 10:2.3;

[0091] Step 3, 2.0 g of γ-glycidyloxypropyltrimethoxysilane, 10 g of terminal isocyanate polyether, 0.02% of catalyst B and 100 mL of imidazole are mixed, and the mixture is heated to 150° C. under nitrogen gas protection, and kept warm for 10 hours; the mixture is added into distilled water, precipitated, filtered, washed and dried to obtain a silane-terminated polyether polymer resin;

[0092] An application of a silane-terminated polyether polymer resin in a sealant is the same as that in Example 1.

[0093] Comparative Example 3: A method for preparing a silane-terminated polyether polymer resin, comprising the following process:

[0094] Step 1, taking a polyhydroxy compound, propylene oxide and a catalyst C, mixing them, stirring and heating to 100° C. under a nitrogen atmosphere, and reacting for 10 hours; cooling to room temperature, dialyzing, and rotary evaporation to obtain a polyether polyol; the polyether polyol is prepared from the following components by mass: 1.0 part of a polyhydroxy compound, 9.6 parts of propylene oxide and 50 ppm of a catalyst C; the polyhydroxy compound is 1,3,5-tris(2-hydroxyethyl)cyanuric acid;

[0095] Step 2, 10g of polyether polyol was mixed with 100mL of solvent, and the temperature was raised to 70°C under nitrogen protection, 4.3g of isophorone diisocyanate and 0.8% of catalyst A dibutyltin dilaurate were added, and the reaction was carried out for 12h to obtain an isocyanate-terminated polyether; the solvent was a mixed solvent of ethyl acetate / methyl ethyl ketone, and the volume ratio of ethyl acetate to methyl ethyl ketone was 2:1; the mass ratio of polyether polyol to isophorone diisocyanate was 10:2.5;

[0096] Step 3, 2.1 g of γ-glycidyloxypropyltrimethoxysilane, 10 g of terminal isocyanate polyether, 0.02% of catalyst B and 100 mL of imidazole were mixed, and the mixture was heated to 150° C. under nitrogen gas protection, and kept warm for 10 hours; the mixture was added into distilled water, precipitated, filtered, washed and dried to obtain a silane-terminated polyether polymer resin;

[0097] An application of a silane-terminated polyether polymer resin in a sealant is the same as that in Example 1.

[0098] Comparative Example 4: A method for preparing a silane-terminated polyether polymer resin, comprising the following process:

[0099] Step 1: 10 g of polyethylene glycol (PEG11000, from Sinopharm Chemical Reagent Co., Ltd.) was mixed with 100 mL of solvent, heated to 70 ° C under nitrogen protection, 4.3 g of isophorone diisocyanate and 0.8% of catalyst A dibutyltin dilaurate were added, and the reaction was carried out for 12 hours to obtain an isocyanate-terminated polyether; the solvent was a mixed solvent of ethyl acetate / methyl ethyl ketone, and the volume ratio of ethyl acetate to methyl ethyl ketone was 2:1; the mass ratio of polyether polyol to isophorone diisocyanate was 10:0.2;

[0100] Step 2: 0.45 g of γ-glycidyloxypropyltrimethoxysilane, 10 g of terminal isocyanate polyether, 0.02% of catalyst B and 100 mL of imidazole were mixed, and the mixture was heated to 150° C. and kept for 10 hours under nitrogen protection; the mixture was added into distilled water, precipitated, filtered, washed and dried to obtain a silane-terminated polyether polymer resin;

[0101] An application of a silane-terminated polyether polymer resin in a sealant is the same as that in Example 1.

[0102] Comparative Example 5: A method for preparing a silane-terminated polyether polymer resin, comprising the following process:

[0103] 10g of polyethylene glycol (PEG11000, from Sinopharm Chemical Reagent Co., Ltd.), 0.45g of isocyanatepropyltriethoxysilane and 0.8% of dibutyltin dilaurate catalyst were mixed, stirred and heated to 40°C under nitrogen atmosphere protection, and the reaction time was 48h; rotary evaporation, washing, and drying were performed to obtain a silane-terminated polyether polymer resin;

[0104] An application of a silane-terminated polyether polymer resin in a sealant is the same as that in Example 1.

[0105] Experiment: Take the silane-terminated polyether polymer resin and sealant obtained in Examples 1-3 and Comparative Examples 1-5, prepare samples, test their properties respectively and record the test results:

[0106] Mechanical properties test: Take cement mortar board as bonding substrate, take GB / T 13477.8 and GB / T 13477.10 as reference standards, and use electronic universal testing machine to test the mechanical properties of sealant samples to detect their 100% tensile strength (modulus);

[0107] Adhesion performance test: GB / T 13477.8 is used as the reference standard to test the fixed-extension adhesion of the sealant sample; the experimental temperature is 23±2℃;

[0108] High temperature adhesion stability test: Place the sample in an 80℃ oven for 120 minutes, take it out and air cool it to 23±2℃, and then test its bonding strength again.

[0109]

[0110] According to the data in the above table, we can clearly draw the following conclusions:

[0111] The silane-terminated polyether polymer resin obtained in Examples 1-3 is compared with the silane-terminated polyether polymer resin obtained in Comparative Examples 1-5. The test results show that:

[0112] Compared with the comparative example, the silane-terminated polyether polymer resin obtained in Examples 1-3, when used as a sealant component, has higher 100% modulus, bonding strength and high-temperature bonding strength data. This fully demonstrates that the silane-terminated polyether polymer resin in the present invention achieves improvements in the mechanical properties, bonding properties and high-temperature adhesion of the sealant produced therefrom.

[0113] Compared with Example 1, the preparation process of the epoxy ester compound and the components used in Comparative Example 1 are different; the epoxy ester compound component is not added in the preparation of the polyether polyol in Comparative Example 2; the polyether polyol in Comparative Example 3 is prepared from propylene oxide and 1,3,5-tris(2-hydroxyethyl)cyanuric acid; the polyether polyol in Comparative Example 4 is replaced with polyethylene glycol; the silane-terminated polyether polymer resin in Comparative Example 5 is prepared from polyethylene glycol and isocyanatepropyltriethoxysilane. When the silane-terminated polyether polymer resin obtained in Comparative Examples 1-3 is used as a sealant component, its 100% tensile strength, bonding strength and high-temperature bonding strength data are relatively lower. It can be seen that the setting of the preparation process of the silane-terminated polyether polymer resin and the components used in the present invention can promote the improvement of the mechanical properties, bonding properties and high-temperature adhesion of the sealant prepared therefrom.

[0114] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process method article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process method article or device.

[0115] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a silane-terminated polyether polymer resin, characterized in that: Including the following processes: Step 1: Mix the polyether polyol with the solvent, raise the temperature to 60-70° C. under nitrogen protection, add diisocyanate and catalyst A, and react for 12-24 hours to obtain an isocyanate-terminated polyether; Step 2: Mix epoxysiloxane, isocyanate-terminated polyether, catalyst B and imidazole, raise the temperature to 150-160° C. under nitrogen protection, and keep the temperature for reaction for 8-10 hours to obtain a silane-terminated polyether polymer resin; The polyether polyol is prepared by the following process: Take a polyhydroxy compound, an epoxy compound and a catalyst C, mix them, stir and heat to 100-120°C under a nitrogen atmosphere, and react for 6-10 hours; cool to room temperature, dialyze, and rotary evaporate to obtain a polyether polyol; The epoxy compound is a mixture of two or more of epoxy ester compounds, bisphenol A diglycidyl ether, propylene oxide, and glycidol; the epoxy compound includes an epoxy ester compound; The epoxy ester compound is prepared by the following process: Propylene oxide, abietic acid, tetrabutylammonium bromide, and propylene glycol methyl ether acetate are mixed, stirred, and heated to 120-125°C, and kept warm for 3-6 hours until the acid value of the system is less than 5 mg / KOH; washed, dried, and epoxy esters are obtained; Mix epoxy ester and tetrahydrofuran, add potassium metal, stir, and react at 20-35°C for 8-10 hours; Add epichlorohydrin, stir and react for 3-4 hours; let stand, filter, distill under reduced pressure, wash, and dry to obtain an epoxy ester compound; The polyhydroxy compound is one of 1,3,5-tris(2-hydroxyethyl)cyanuric acid, N,N,N',N',N'-penta(2-hydroxypropyl)diethylenetriamine and tannic acid.

2. The method for preparing a silane-terminated polyether polymer resin according to claim 1, characterized in that: The polyether polyol is prepared from the following components by mass: 1 part of a polyhydroxy compound, 10 to 20 parts of an epoxy compound and 50 to 100 ppm of a catalyst C.

3. The method for preparing a silane-terminated polyether polymer resin according to claim 1, characterized in that: The molar ratio of abietic acid to propylene oxide is 1:(1.0-1.2); The mass ratio of epoxy ester, epichlorohydrin and metallic potassium is 10:(2.8-3.8):(0.4-0.6).

4. The method for preparing a silane-terminated polyether polymer resin according to claim 1, characterized in that: The diisocyanate is one of toluene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

5. The method for preparing a silane-terminated polyether polymer resin according to claim 1, characterized in that: The epoxysiloxane is γ-glycidyloxypropyltrimethoxysilane.

6. A silane-terminated polyether polymer resin, characterized in that: The method is prepared by any one of claims 1 to 5.

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