Preparation method of silane modified polyether resin

Abstract

The invention belongs to the technical field of sealants, and discloses a preparation method of silane modified polyether resin. The preparation method comprises the following steps: carrying out alkalization reaction on polyether polyol and an alkalization reagent, then adding a halogenated end-capping reagent containing double bonds, and carrying out end-capping reaction to prepare a double-bond end-capped polyether crude product; adding acid liquor into the double-bond end-capped polyether crude product for washing and neutralizing, and then adding an antioxidant and an adsorbent for adsorption treatment to prepare double-bond end-capped polyether; and finally, carrying out a silane end-capping reaction with alkoxy silane under the action of a hydrosilylation catalyst. The preparation method provided by the invention comprises the following steps: firstly, carrying out water washing neutralization treatment on a double-bond end-capped polyether crude product by adopting acid liquor; the preparation method comprises the following steps: adding an antioxidant and an adsorbent for adsorption treatment, and controlling the variety, dosage and adding time of the antioxidant, so that double bonds can be effectively protected, and the silane modified polyether resin with high end capping rate, light color and strong storage stability is prepared.

Description

Technical Field

[0001] The invention belongs to the technical field of sealants, and particularly relates to a preparation method of a silane-modified polyether resin. Background Art

[0002] Silane-modified polyether resin is a polymer sealant first developed by Kaneka Chemical in Japan. It combines the advantages of silicone sealants and polyurethane sealants, avoiding their shortcomings, such as low tear strength, high-temperature resistance, and the release of harmful gases. It is also environmentally friendly: low VOC, pollution-free, solvent-free, and MDI- and TDI-free. Unlike Kaneka Chemical's dichloromethane chain extension method, Asahi Glass in Japan first uses small-molecule alcohols as initiators to undergo a ring-opening addition polymerization with ethylene oxide (EO) or propylene oxide (PO) in the presence of a double metal cyanide complex catalyst (DMC) to produce a hydroxyl-terminated high-molecular-weight polyether polyol. The polyether polyol is then double-terminated with allyl chloride in the presence of an alkoxide (sodium methoxide) to produce a high-molecular-weight bisallyl polyether polyol. Finally, methyldimethoxysilane and the high-molecular-weight bisallyl polyether polyol are subjected to a platinum-catalyzed hydrosilylation reaction to produce the silane-modified polyether (MS) resin.

[0003] The difficulty of this process is the use of a hydrosilane addition reaction to terminate the bisallyl polyether polyol with siloxane. Commonly used end-capping agents, alkoxysilanes, include dimethoxyhydrosilane, trimethoxyhydrosilane, methyldimethoxysilane, triethoxyhydrosilane, diethoxyhydrosilane, methyldiethoxyhydrosilane, and the like. The smaller the molecular weight of the silane side chain (such as dimethoxyhydrosilane), the higher its reactivity and the easier it is to undergo a hydrosilane addition reaction; however, compared to triethoxyhydrosilane and diethoxyhydrosilane with larger molecular weights, the storage stability of the resulting silane-modified polyether (MS) resin is poor. The larger the molecular weight of the silane side chain (such as triethoxyhydrosilane), the greater the steric hindrance when reacting with the bisallyl polyether polyol, the more difficult the reaction is to proceed, and the lower the end-capping rate of the product. To improve the end-capping rate of the product, the most common approach is to increase the amount of end-capping agent alkoxysilane. However, unreacted alkoxysilane can also affect the storage stability of the final silane-modified polyether (MS) resin. Therefore, improving the storage stability of the final silane-modified polyether (MS) resin is one of the technical difficulties in this field.

[0004] Furthermore, the synthesis of bisallyl polyether polyols generates byproducts such as chloride salts and residual catalyst. These byproducts, residual catalysts, and various factors affecting double bonds can affect subsequent reactions, testing, and characterization of the terminal allyl polyethers, further impacting final product properties such as color. Dark-colored products are detrimental to the preparation of transparent or lighter-colored sealants, a key concern in the market.

[0005] Therefore, there is an urgent need to provide a method for preparing a silane-modified polyether resin, which can prepare a silane-modified polyether resin with a high end-capping rate, light color, and strong storage stability. Summary of the Invention

[0006] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides a method for preparing a silane-modified polyether resin. The method provided by the present invention can produce a silane-modified polyether resin with a high end-capping rate, light color, and strong storage stability.

[0007] The invention provides a method for preparing a silane-modified polyether resin.

[0008] Specifically, a method for preparing a silane-modified polyether resin comprises the following steps:

[0009] S1, performing an alcoholization reaction on a polyether polyol and an alcoholization reagent, and after the reaction is completed, adding a halogenated end-capping agent containing a double bond to perform an end-capping reaction to obtain a crude double-bond end-capped polyether;

[0010] S2, adding acid solution to the crude double-bond terminated polyether prepared in step S1 for washing and neutralization, then adding an antioxidant and an adsorbent for adsorption treatment, and then dehydrating and solid-liquid separation to remove the filtrate to obtain the double-bond terminated polyether;

[0011] S3, performing a silane-terminated reaction on the double-bond terminated polyether prepared in step S2 and an alkoxysilane in the presence of a hydrosilylation catalyst to obtain a silane-modified polyether resin;

[0012] In step S2, the antioxidant is selected from at least one of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol, di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate]triethylene glycol, triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl alcohol.

[0013] In some embodiments of the present invention, in step S2, the antioxidant is selected from at least two of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate]triethylene glycol, triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, and octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. In some embodiments of the present invention, the antioxidant is selected from at least three of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate]triethylene glycol, triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0014] In some embodiments of the present invention, the antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate] triethylene glycol, and triethylene glycol ether-bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate. In some embodiments of the present invention, the mass ratio of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate] triethylene glycol, and triethylene glycol ether-bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate is 1:(0.5-3):(0.5-2), such as 1:1:1, 1:2:1, 1:2:2, etc.

[0015] In some embodiments of the present invention, in step S2, the amount of the antioxidant added is 0.4%-3% of the mass of the crude double-bond terminated polyether. In some embodiments of the present invention, the amount of the antioxidant added is 0.5%-1.5% of the mass of the crude double-bond terminated polyether. In some embodiments of the present invention, the amount of the antioxidant added is 0.6%-1.2% of the mass of the crude double-bond terminated polyether.

[0016] In some embodiments of the present invention, in step S1, the polyether polyol is prepared as follows: a hydroxyl-containing initiator and an epoxy compound are subjected to a polymerization reaction in the presence of an alkaline catalyst to produce the polyether polyol. In some embodiments of the present invention, in step S1, the polyether polyol can be prepared in multiple steps, such as first preparing a low molecular weight polyether polyol, then preparing a medium molecular weight polyether polyol, and finally preparing a high molecular weight polyether polyol. This multi-step process can produce a high molecular weight polyether polyol product with a narrow molecular weight distribution and low viscosity. In some embodiments of the present invention, the hydroxyl-containing initiator includes propylene glycol, glycerol, glycerol, n-butanol, etc. The epoxy compound can be ethylene oxide and / or propylene oxide. The alkaline catalyst includes an alkali metal, alkali metal hydride, or alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide.

[0017] In some embodiments of the present invention, in step S1, the alkoxide reagent is sodium methoxide. The halogenated capping agent containing a double bond includes allyl chloride or methylallyl chloride.

[0018] In some embodiments of the present invention, in step S1, the ratio of the alcohol salt reagent to the polyether polyol is (1-8): 1. The ratio of the halogenated end-capping agent containing a double bond to the polyether polyol is 1-8: 1.

[0019] In some embodiments of the present invention, in step S1, the alkoxide reaction temperature is 110-120° C., and the alkoxide reaction time is 3-8 hours, such as 4 hours, 5 hours, 6 hours, etc.

[0020] In some embodiments of the present invention, in step S1, the temperature of the end-capping reaction is 80-90° C., and the time of the end-capping reaction is 10-24 hours, such as 12, 15, 18, 20, 22, 24 hours, etc.

[0021] In some embodiments of the present invention, in step S2, the acidic solution is one or more of phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, or lactic acid. Preferably, the acidic solution is a phosphoric acid solution, and the mass percentage of the phosphoric acid solution is 0.05%-1%, such as 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, etc. Preferably, the mass percentage of the phosphoric acid solution is 0.1%-0.5%. The mass of the phosphoric acid solution is 5%-50% of the mass of the crude double-bond-terminated polyether; preferably, the mass of the phosphoric acid solution is 10%-30% of the mass of the crude double-bond-terminated polyether, such as 15%, 18%, 20%, 25%, etc.

[0022] In some embodiments of the present invention, in step S2, the temperature of the water washing and neutralization is 80-90°C, and the time of the water washing and neutralization is 10-60 minutes, preferably 20-40 minutes.

[0023] In some embodiments of the present invention, in step S2, the adsorbent includes silicates with a porous structure such as magnesium silicate and aluminum silicate, as well as acidic clay or activated carbon; the amount (mass) of the adsorbent is 30%-60% of the mass of the antioxidant, such as 35%, 40%, 42%, 45%, 50%, 55%, 58%, etc.

[0024] In some embodiments of the present invention, in step S2, a filter aid is also added during the adsorption treatment to facilitate the subsequent solid-liquid separation step.

[0025] In some embodiments of the present invention, in step S2, the temperature of the adsorption treatment is 80-90°C, and the time of the adsorption treatment is 10-60 minutes, preferably 20-40 minutes.

[0026] In some embodiments of the present invention, in step S2, the dehydration process is to control the dehydration temperature to 75-95°C, slowly dehydrate at -0.099 to -0.095 MPa, and after the dehydration is completed, raise the temperature to 100-150°C and continue dehydration for 0.5-3 hours.

[0027] In some embodiments of the present invention, in step S3, the alkoxysilane is selected from dimethoxysilane, trimethoxysilane, methyldimethoxysilane, triethoxysilane, diethoxysilane, and methyldiethoxysilane. In some embodiments of the present invention, in step S3, the hydrosilylation catalyst comprises chloroplatinic acid.

[0028] In some embodiments of the present invention, in step S3, the ratio of the alkoxysilane to the double-bond terminated polyether is 0.7-1.05: 1. The amount of the catalyst is 500-2000 ppm.

[0029] In some embodiments of the present invention, in step S3, the silane capping reaction is carried out under closed reaction conditions with a pressure of less than 0.2 MPa and a reaction temperature of 80-90° C. for 2-5 hours. In some embodiments of the present invention, in step S3, the silane capping reaction is carried out under closed reaction conditions with a pressure of less than 0.2 MPa and a reaction temperature of 80-85° C. for 3-4 hours.

[0030] The present invention also provides a silane-modified polyether resin.

[0031] Specifically, a silane-modified polyether resin is prepared by the above preparation method, wherein the silane-terminated polyether resin has a silane-terminated ratio greater than 98.0%. Preferably, the silane-terminated ratio of the silane-modified polyether resin is greater than or equal to 99.0%. More preferably, the silane-terminated ratio of the silane-modified polyether resin is greater than or equal to 99.3%.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The preparation method of the silane-modified polyether resin provided by the present invention is to wash and neutralize the double-bond terminated polyether crude product with acid solution first; then add an antioxidant and an adsorbent for adsorption treatment, and control the type, amount and timing of addition of the antioxidant, so that the double bonds in the double-bond terminated polyether are all stable during the adsorption treatment process and in the silane-terminated reaction; and it has a synergistic effect with a hydrosilane addition catalyst (with reducing property), can promote the hydrosilane addition reaction efficiency, and greatly improve the reaction speed and conversion rate. The preparation method provided by the present invention can protect the double bond to the greatest extent, is beneficial to the hydrosilane addition reaction, and when reducing the ratio of the double-bond terminated polyether to the silane-terminated polyether, improves the end-capping rate; and the silane-modified polyether resin prepared has a light color and strong storage stability. DETAILED DESCRIPTION

[0034] In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the following examples are given for illustration. It should be noted that the following examples do not limit the scope of protection claimed by the present invention.

[0035] Unless otherwise specified, the raw materials, reagents, or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0036] Example 1

[0037] A method for preparing a silane-modified polyether resin comprises the following steps:

[0038] (1) Synthesis of polypropylene glycol oligomers

[0039] Add 24g of potassium hydroxide catalyst to the condensation reactor, and 1520g of propylene glycol initiator is pumped from a storage tank into the reactor via a metering pump. Nitrogen is purged once, and the reactor is sealed. Heat to 110°C and begin adding propylene oxide (a total of 10480g). During this process, the pressure is controlled at ≤0.25Mpa. After the reaction is normal, control the pressure to ≤0.30Mpa and the temperature to 115°C. Add propylene oxide at a uniform rate. After the propylene oxide is added, close the propylene oxide discharge valve and the reactor feed valve and check the quantity. Ripen for 120 minutes until the pressure does not drop. After aging is complete, cool to about 100°C, turn on the vacuum pump, and slowly open the vacuum valve to degas. Vacuum -0.096Mpa and degas normally for 30 minutes. Transfer the material to a post-processing reactor, add 16g of phosphoric acid to neutralize the potassium hydroxide, and after adsorption and vacuum dehydration, obtain polypropylene glycol oligomers.

[0040] (2) Synthesis of medium molecular weight polypropylene glycol

[0041] A condensation reactor was charged with 0.7 g of DMC catalyst and 2392 g of the polypropylene glycol oligomer prepared in step (1). After nitrogen substitution, the reactor was sealed, heated to 125° C., and propylene oxide (9600 g in total) was added. When the pressure in the reactor reached 0.25 MPa and the temperature was 130° C., the reaction was allowed to proceed. After the reaction was normal, the normal feeding temperature was 135° C., the pressure was controlled at <0.3 MPa, and propylene oxide was added at a constant rate. After the addition of propylene oxide was completed, the reaction was aged for 1 hour, then cooled to 100° C. for degassing for 30 minutes, and then cooled to 70° C. to discharge the mixture to obtain a medium molecular weight polypropylene glycol.

[0042] (3) Synthesis of high molecular weight polypropylene glycol

[0043] A condensation reactor was added with 0.35 g of catalyst and 749.54 g of the medium molecular weight polypropylene glycol prepared in step (2). After nitrogen substitution, the reactor was sealed and heated to 125° C. to begin trial addition of propylene oxide (2250 g in total). When the pressure in the reactor was 0.25 MPa and the temperature was 135° C., the reaction was carried out. After the reaction was normal, the normal feeding temperature was 140° C., the pressure was controlled at <0.3 MPa, and propylene oxide was passed at a uniform rate. After the addition of propylene oxide was completed, the reactor was aged for 1 hour, then cooled to 100° C. for degassing for 30 minutes, and then cooled to 70° C. to discharge the material to obtain a high molecular weight polypropylene glycol.

[0044] (4) Preparation of Diallyl Polypropylene Glycol

[0045] 6000.51g of the high molecular weight polypropylene glycol prepared in step (3) was transferred to a dealcoholization kettle, 58g of sodium methoxide and 113g of n-hexane were added, and after nitrogen replacement three times, the temperature was raised to 120°C for alcoholization reaction and the reaction was carried out for 5 hours. After the reaction was completed, the vacuum pump was turned on to remove low boiling points, the temperature was controlled at about 115°C, the vacuum degree was above -0.100MPa, and the mixture was kept warm and degassed for 2 hours. After degassed, the mixture was cooled to 80°C and pressed into a capping kettle, the temperature was controlled at 80-90°C, 81g of allyl chloride was added dropwise, and after the addition was completed, the mixture was kept warm at 85°C for 18 hours. After the heat preservation was completed, the mixture was degassed and the vacuum degree was above -0.099MPa for 2 hours. After degassed, a crude bisallyl polypropylene glycol was obtained.

[0046] The mixture was placed in a post-treatment kettle and the temperature was controlled at 85°C. 1000 g of water and 2 g of phosphoric acid were added, followed by water washing and neutralization for 30 min. Then, 25 g of adsorbent, 60 g of antioxidant (including 20 g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 20 g of triethylene glycol di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate], and 20 g of triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate), and 6 g of filter aid were added. Adsorption was allowed to proceed for 30 min. The vacuum pump was then turned on for slow dehydration. The dehydration temperature was controlled at approximately 85°C, the Roots pump was turned on at -0.095 MPa, and the vacuum level was maintained at -0.099 MPa. After the primary dehydration, the temperature was raised to 105°C and dehydration was continued for 1.5 h. After dehydration, bisallyl polypropylene glycol was obtained by filtration.

[0047] (5) Preparation of silane-terminated polyether

[0048] Add 5980.03 g of bisallyl polypropylene glycol prepared in step (4) and 118.5 g of dimethoxysilane into the reactor. After replacing nitrogen once, heat to 85° C., add 3 g of chloroplatinic acid, seal the reactor, keep the pressure below 0.2 MPa, and react at 83° C. for 3 h to terminate the reaction. Cool and discharge the mixture to obtain a silane-modified polyether resin.

[0049] Example 2

[0050] A method for preparing a silane-modified polyether resin comprises the following steps:

[0051] (1) Synthesis of polypropylene glycol oligomers

[0052] Add 24g of potassium hydroxide catalyst to the condensation reactor, and 1520g of propylene glycol initiator is pumped from a storage tank into the reactor via a metering pump. Nitrogen is purged once, and the reactor is sealed. Heat to 110°C and begin adding propylene oxide (a total of 10480g). During this process, the pressure is controlled at ≤0.25Mpa. After the reaction is normal, control the pressure to ≤0.30Mpa and the temperature to 120°C, and add propylene oxide at a uniform rate. After the propylene oxide is added, close the propylene oxide discharge valve and the reactor feed valve and check the quantity. Ripen for about 120 minutes until the pressure does not drop. After aging is complete, cool to about 100°C, turn on the vacuum pump, and slowly open the vacuum valve to degas. Vacuum -0.096Mpa and degas normally for 30 minutes. The material is transferred to a post-processing reactor, 16g of phosphoric acid is added to neutralize the potassium hydroxide, and after adsorption and vacuum dehydration, polypropylene glycol oligomers are obtained.

[0053] (2) Synthesis of medium molecular weight polypropylene glycol

[0054] A condensation reactor was charged with 0.7 g of DMC catalyst and 2392 g of the polypropylene glycol oligomer prepared in step (1). After nitrogen substitution, the reactor was sealed, heated to 125° C., and propylene oxide (9600 g in total) was added. When the pressure in the reactor reached 0.25 MPa and the temperature was 135° C., the reaction was allowed to proceed. After the reaction was normal, the normal feeding temperature was 145° C., the pressure was controlled at <0.3 MPa, and propylene oxide was added at a constant rate. After the addition of propylene oxide was completed, the reaction was aged for 1 hour, then cooled to 100° C. for degassing for 30 minutes, and then cooled to 70° C. to discharge the mixture to obtain a medium molecular weight polypropylene glycol.

[0055] (3) Synthesis of high molecular weight polypropylene glycol

[0056] A condensation reactor was added with 0.35 g of catalyst and 749.54 g of the medium molecular weight polypropylene glycol prepared in step (2). After nitrogen substitution, the reactor was sealed and heated to 125° C. to begin trial addition of propylene oxide (a total of 2250 g). When the pressure in the reactor was 0.25 MPa and the temperature was 135° C., the reaction was carried out. After the reaction was normal, the normal feeding temperature was 145° C., the pressure was controlled at <0.3 MPa, and propylene oxide was passed at a uniform rate. After the addition of propylene oxide was completed, the reactor was aged for 1 hour, then cooled to 100° C. for degassing for 30 minutes, and then cooled to 70° C. to discharge the mixture to obtain a high molecular weight polypropylene glycol.

[0057] (4) Preparation of Diallyl Polypropylene Glycol

[0058] 6000.51g of the high molecular weight polypropylene glycol prepared in step (3) was transferred to a dealcoholization kettle, 58g of sodium methoxide and 113g of n-hexane were added, and after nitrogen replacement three times, the temperature was raised to 120°C for alcoholization reaction and the reaction was carried out for 5 hours. After the reaction was completed, the vacuum pump was turned on to remove low boiling points, the temperature was controlled at about 110°C, the vacuum degree was above -0.100MPa, and the mixture was kept warm and degassed for 2 hours. After degassed, the mixture was cooled to 80°C and pressed into a capping kettle, the temperature was controlled at about 85°C, 81g of allyl chloride was added dropwise, and after the addition was completed, the mixture was kept warm at 85°C for 18 hours. After the heat preservation was completed, the mixture was degassed and the vacuum degree was kept warm at above -0.099MPa for 2 hours. After degassed, a crude bisallyl polypropylene glycol was obtained.

[0059] The mixture was placed in a post-treatment kettle and the temperature was controlled at 90°C. 1000 g of water and 2 g of phosphoric acid were added, followed by water washing and neutralization for 30 min. Then, 25 g of adsorbent, 60 g of antioxidant (including 15 g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 30 g of triethylene glycol di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate], and 15 g of triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate), and 6 g of filter aid were added. Adsorption was allowed to proceed for 30 min. The vacuum pump was then turned on for slow dehydration. The dehydration temperature was controlled at approximately 80°C, the Roots pump was turned on at -0.095 MPa, and the vacuum level was maintained at -0.099 MPa. After the primary dehydration, the temperature was raised to 110°C and dehydration was continued for 2.0 h. After dehydration, bisallyl polypropylene glycol was obtained by filtration.

[0060] (5) Preparation of silane-terminated polyether

[0061] Add 5980.03 g of bisallyl polypropylene glycol prepared in step (4) and 135 g of trimethoxysilane into the reactor. After replacing nitrogen once, heat to 85° C., add 3 g of chloroplatinic acid, seal the reactor, keep the pressure below 0.2 MPa, and react at 85° C. for 3 h to terminate the reaction. Cool and discharge the mixture to obtain a silane-modified polyether resin.

[0062] Example 3

[0063] Example 3 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the difference is that in step (4) of Example 3, the amount of antioxidant added is 30 g, specifically comprising 10 g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 10 g of triethylene glycol di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate], and 10 g of triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate. The remaining preparation steps are the same as those of Example 1.

[0064] Example 4

[0065] Example 4 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the difference is that in step (4), the amount of antioxidant added in Example 4 is 120 g, specifically comprising 40 g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 40 g of triethylene glycol di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate], and 40 g of triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate. The remaining preparation steps are the same as those in Example 1.

[0066] Example 5

[0067] Example 5 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the difference is that in step (4), the amount of antioxidant added in Example 5 is 40 g, specifically comprising 20 g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 20 g of triethylene glycol di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate]. The remaining preparation steps are the same as those in Example 1.

[0068] Example 6

[0069] Example 6 provides a method for preparing a silane-modified polyether resin. Compared to Example 1, Example 6 differs in that, in step (4), 20 g of an antioxidant, specifically pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, is added. The remaining preparation steps are the same as in Example 1.

[0070] Example 7

[0071] Example 7 provides a method for preparing a silane-modified polyether resin. Compared to Example 1, the difference is that in step (4), the amount of antioxidant added in Example 7 is 20 g, specifically bis[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionic acid]triethylene glycol. The remaining preparation steps are the same as in Example 1.

[0072] Example 8

[0073] Example 8 provides a method for preparing a silane-modified polyether resin. Compared to Example 1, the difference is that in step (4), the amount of antioxidant added in Example 8 is 20 g, specifically triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate. The remaining preparation steps are the same as in Example 1.

[0074] Example 9

[0075] Example 9 provides a method for preparing a silane-modified polyether resin. Compared to Example 1, Example 9 differs in that, in step (5), the end-capping alkoxysilane used in Example 9 is diethoxyhydrogensilane, with an amount of 161.05 g. The remaining preparation steps are the same as in Example 1.

[0076] Example 10

[0077] Example 10 provides a method for preparing a silane-modified polyether resin. Compared to Example 1, Example 10 differs in that, in step (5), the end-capping alkoxysilane used in Example 10 is 145.84 g of methyldiethoxyhydrosilane. The remaining preparation steps are the same as in Example 1.

[0078] Example 11

[0079] Example 11 provides a method for preparing a silane-modified polyether resin. Compared to Example 1, Example 11 differs in that, in step (5), the end-capping alkoxysilane used in Example 11 is triethoxyhydrosilane, and the amount used is 178.43 g. The remaining preparation steps are the same as in Example 1.

[0080] Comparative Example 1

[0081] Comparative Example 1 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the difference is that no antioxidant is added in step (4) of Comparative Example 1, and the remaining preparation steps are the same as those of Example 1.

[0082] Comparative Example 2

[0083] Comparative Example 2 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the difference is that in step (4) of Comparative Example 2, the antioxidant and sodium methoxide are added simultaneously, and the amount added is the same as in Example 1. The remaining preparation steps are also the same as in Example 1.

[0084] Comparative Example 3

[0085] Comparative Example 3 provides a method for preparing a silane-modified polyether resin. Compared to Example 1, Comparative Example 3 differs in that no antioxidant is added in step (4). Instead, an equal amount of antioxidant (the type and amount of antioxidant are the same as in Example 1) is added simultaneously with the catalyst chloroplatinic acid in step (5). The remaining preparation steps are the same as in Example 1.

[0086] Comparative Example 4

[0087] Comparative Example 4 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the method differs in that, in step (4), an equal amount of butylated hydroxytoluene is used to replace pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, triethylene glycol di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate], and triethylene glycol ether di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate.

[0088] Product effect testing

[0089] The performance of the silane-modified polyether resins prepared in Examples 1-11 and Comparative Examples 1-4 was tested, mainly including the following performance indicators:

[0090] (1) Color test: Use platinum-cobalt colorimetry to test color;

[0091] (2) Silane capping rate: Instrument: Bruker NMR spectrometer (Ascend 600M); Solvent: deuterated acetone; Detection method: H NMR spectroscopy; Instrument parameters: Pulse sequence: zg30, Number of scans: 128, Relaxation delay time: 1 s, Number of sampling points: 64k, Spectral width = 19.83; Sample preparation: Weigh about 80 mg of sample, dissolve it in 0.55 mL of deuterated acetone and transfer it to a 5 mm NMR tube.

[0092] (3) Storage stability: The prepared sealant was placed in a 70°C environment and the appearance changes of the sealant were observed after storage for 168 hours.

[0093] After testing, the performance test results of Examples 1-11 and Comparative Examples 1-4 are shown in Table 1.

[0094] Table 1

[0095] Group Color Silane termination rate Appearance changes Example 1 6 99.8 No change Example 2 7 99.9 No change Example 3 9 99.0 No change Example 4 5 99.1 No change Example 5 11 99.2 No change Example 6 82 97.5 No change Example 7 68 98.0 No change Example 8 75 97.6 No change Example 9 8 99.7 No change Example 10 7 99.5 No change Example 11 5 99.3 No change Comparative Example 1 91 97.1 Severe yellow deepening Comparative Example 2 23 98.6 No change Comparative Example 3 57 98.3 The yellow color appears slightly darker Comparative Example 4 80 97.4 Yellow deepens

[0096] As shown in Table 1, the silane-modified polyether resins prepared in the examples of the present invention have a silane capping rate of 98.0% or higher, reaching as high as 99.9%. When the capping agent alkoxysilane is a relatively large molecular weight methyldiethoxyhydrosilane or triethoxyhydrosilane, the method provided by the present invention can also achieve a silane capping rate of 99.3% or higher. Furthermore, the silane-modified polyether resins prepared in the present invention have good color and are highly stable during storage.

[0097] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A method for preparing a silane-modified polyether resin, characterized in that: The following steps are involved: S1, performing an alcoholization reaction on a polyether polyol and an alcoholization reagent, and after the reaction is completed, adding a halogenated end-capping agent containing a double bond to perform an end-capping reaction to obtain a crude double-bond end-capped polyether; S2, adding acid solution to the crude double-bond terminated polyether prepared in step S1 for washing and neutralization, then adding an antioxidant and an adsorbent for adsorption treatment, and then dehydrating and solid-liquid separation to remove the filtrate to obtain the double-bond terminated polyether; S3, performing a silane-terminated reaction on the double-bond terminated polyether prepared in step S2 and an alkoxysilane in the presence of a hydrosilylation catalyst to obtain a silane-modified polyether resin; In step S2, the antioxidant is selected from at least one of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol, di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate]triethylene glycol, triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl alcohol.

2. The preparation method according to claim 1, characterized in that In step S2, the antioxidant is selected from at least two of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol, di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate]triethylene glycol, triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl.

3. The preparation method according to claim 2, characterized in that The antioxidants are pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate]triethylene glycol and triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate.

4. The preparation method according to claim 3, characterized in that The mass ratio of the tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, the di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionic acid]triethylene glycol and the triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid ester is 1:(0.5-3):(0.5-2).

5. The preparation method according to any one of claims 1 to 4, characterized in that In step S2, the amount of the antioxidant added is 0.4%-3% of the mass of the crude double-bond terminated polyether.

6. The preparation method according to claim 5, characterized in that In step S1, the preparation process of the polyether polyol is as follows: a hydroxyl-containing initiator and an epoxy compound are polymerized in the presence of a base catalyst to obtain the polyether polyol.

7. The preparation method according to claim 6, characterized in that The hydroxyl-containing initiator includes one of propylene glycol, glycerol, and glycerol; the epoxy compound can be ethylene oxide and / or propylene oxide; and the base catalyst includes alkali metal, alkali metal hydride, or alkali metal hydroxide.

8. The preparation method according to any one of claims 1 to 4, characterized in that In step S2, the acid solution is one or more of phosphoric acid solution, sulfuric acid solution, hydrochloric acid solution, acetic acid solution or lactic acid solution.

9. The preparation method according to claim 8, characterized in that In step S2, the acid solution is a phosphoric acid solution, and the mass percentage of the phosphoric acid solution is 0.05%-1%; the mass of the phosphoric acid solution is 5%-50% of the mass of the crude double-bond terminated polyether.

10. The preparation method according to claim 9, characterized in that In step S2, the temperature of the water washing and neutralization is 80-90° C., and the time of the water washing and neutralization is 10-60 minutes.

11. The preparation method according to claim 9 or 10, characterized in that: In step S2, the adsorbent includes silicates, acid clay or activated carbon; the amount of the adsorbent is 30%-60% of the mass of the antioxidant.

12. The preparation method according to any one of claims 1-4, 6, 7, 9, and 10, characterized in that: In step S3, the end-capping agent alkoxysilane is selected from one of dimethoxyhydrogensilane, trimethoxyhydrogensilane, methyldimethoxysilane, triethoxyhydrogensilane, diethoxyhydrogensilane, and methyldiethoxyhydrogensilane.

13. The preparation method according to claim 12, characterized in that In step S3, the silane capping reaction is carried out under closed reaction conditions, with the pressure controlled to be less than 0.2 MPa and the reaction temperature being 80-90° C. for 2-5 hours.

14. A silane-modified polyether resin, characterized in that: The silane-modified polyether resin is prepared by the preparation method according to any one of claims 1 to 13, and the silane termination rate of the silane-modified polyether resin is greater than 98.0%.