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 in particular relates to a method for preparing a silane-modified polyether resin. Background Art

[0002] Silane-modified polyether resin is a polymer sealant first developed by Japan's Kaneka Chemical. It has the advantages of both silicone sealants and polyurethane sealants, avoiding the defects of the two, such as low tear strength, high temperature resistance, and release of harmful gases; and it has green environmental protection characteristics: low VOC, no pollution, no solvent, no MDI, TDI, etc. Unlike the dichloromethane chain extension method used by Kaneka Chemical, Japan's Asahi Glass Co., Ltd. first uses small molecular alcohol substances as initiators, and reacts with ethylene oxide (EO) or propylene oxide (PO) under the action of double metal cyanide complex catalyst (DMC) to produce hydroxyl-terminated high molecular weight polyether polyols by ring-opening addition polymerization; then, the polyether polyols are double-bonded with allyl chloride under the action of alcohol salt reagent (sodium methoxide) to prepare high molecular weight bisallyl polyether polyols; finally, methyl dimethoxysilane and high molecular weight bisallyl polyether polyols are reacted with platinum catalysts to prepare silane-modified polyether (MS) resins through hydrosilylation.

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

[0004] In addition, during the synthesis of bisallyl polyether polyols, byproducts such as chloride salts and residual catalysts are generated. The residual byproducts and catalysts and the effects of various factors on double bonds will also affect the subsequent reactions, testing and characterization of terminal allyl polyethers, and thus affect the performance of the final product, such as color. Products with dark colors are not conducive to the preparation of transparent or lighter-colored sealants, which is also the focus of market attention.

[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 prepare 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: S1, subjecting a polyether polyol to an alcohol salting reaction with an alcohol salting agent, and after the reaction is completed, adding a halogenated end-capping agent containing a double bond to carry out 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 water 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, subjecting the double-bond terminated polyether prepared in step S2 to a silane termination reaction with 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 ester, 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 ester.

[0009] 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, triethylene glycol di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate], triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, and 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 tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol ester, 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 ester.

[0010] In some embodiments of the present invention, the antioxidant is tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol ester, di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate] triethylene glycol and triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate. In some embodiments of the present invention, the mass ratio of the tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, the di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate] triethylene glycol and the triethylene glycol ether-di(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.

[0011] 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-capped 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-capped 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-capped polyether.

[0012] In some embodiments of the present invention, in step S1, the preparation process of the polyether polyol is as follows: a hydroxyl-containing initiator and an epoxy compound are subjected to a polymerization reaction under the action of an alkali catalyst to obtain 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 then preparing a high molecular weight polyether polyol. A narrow molecular weight distribution, low viscosity, high molecular weight polyether polyol product can be prepared through multiple steps. 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 alkali catalyst includes an alkali metal, an alkali metal hydride or an alkali metal hydroxide, such as sodium hydroxide, potassium hydroxide, etc.

[0013] 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 methyl allyl chloride.

[0014] 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 In some embodiments of the present invention, in step S1, the temperature of the alkoxide reaction is 110-120° C., and the time of the alkoxide reaction is 3-8 hours, such as 4 hours, 5 hours, 6 hours, etc.

[0015] 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.

[0016] In some embodiments of the present invention, in step S2, the acid solution is one or more of phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid or lactic acid. Preferably, the acid 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.

[0017] 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.

[0018] 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, and acidic white 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.

[0019] 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.

[0020] 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.

[0021] 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, heat up to 100-150°C and continue dehydration for 0.5-3 hours.

[0022] In some embodiments of the present invention, in step S3, the alkoxysilane is selected from one of dimethoxyhydrogensilane, trimethoxyhydrogensilane, methyldimethoxysilane, triethoxyhydrogensilane, diethoxyhydrogensilane, and methyldiethoxyhydrogensilane. In some embodiments of the present invention, in step S3, the hydrosilylation catalyst includes chloroplatinic acid.

[0023] 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.

[0024] In some embodiments of the present invention, in step S3, the process of the silane end-capping reaction is to control the pressure to be less than 0.2Mpa under closed reaction conditions, and the reaction temperature is 80-90°C for 2-5h. In some embodiments of the present invention, in step S3, the process of the silane end-capping reaction is to control the pressure to be less than 0.2Mpa under closed reaction conditions, and the reaction temperature is 80-85°C for 3-4h.

[0025] The invention also provides a silane-modified polyether resin.

[0026] Specifically, a silane-modified polyether resin is prepared by the above preparation method, wherein the silane end-capping rate of the silane-modified polyether resin is greater than 98.0%. Preferably, the silane end-capping rate of the silane-modified polyether resin is greater than or equal to 99.0%; further preferably, the silane end-capping rate of the silane-modified polyether resin is greater than or equal to 99.3%.

[0027] Compared with the prior art, the present invention has the following beneficial effects: The preparation method of the silane-modified polyether resin provided by the present invention is to first use acid solution to wash and neutralize the crude double-bond terminated polyether; then add an antioxidant and an adsorbent for adsorption treatment, and control the type, amount and timing of the antioxidant, so that the double bonds in the double-bond terminated polyether are highly stable during the adsorption treatment process and the silane termination reaction; and it has a synergistic effect with the hydrosilylation catalyst (with reducing properties), which can promote the efficiency of the hydrosilylation reaction, and greatly improve the reaction speed and conversion rate. The preparation method provided by the present invention can protect the double bonds to the greatest extent, is conducive to the hydrosilylation reaction, and improves the termination rate when reducing the ratio of the double-bond terminated polyether to the silane termination; and the prepared silane-modified polyether resin has a light color and strong storage stability. DETAILED DESCRIPTION

[0028] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be noted that the following embodiments do not limit the protection scope of the present invention.

[0029] 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.

[0030] Example 1 A method for preparing a silane-modified polyether resin comprises the following steps: (1) Synthesis of polypropylene glycol oligomers Add 24g of potassium hydroxide catalyst to the condensation reactor, and 1520g of propylene glycol initiator is pumped from the storage tank to the reactor through a metering pump. Nitrogen is replaced once and the reactor is sealed. Heat to 110℃ and start to add propylene oxide (a total of 10480g). The pressure in this process is controlled at ≤0.25Mpa. After the reaction is normal, control the pressure to ≤0.30Mpa, the temperature is 115℃, and propylene oxide is added at a uniform rate. After propylene oxide is added, close the propylene oxide discharge valve and the reactor feed valve and check the quantity, and mature for 120 minutes until the pressure does not drop. After the aging is completed, cool down to about 100℃, turn on the vacuum pump, and slowly open the vacuum valve for degassing, vacuum -0.096Mpa, normal degassing for 30 minutes. The material is transferred to the post-treatment kettle, 16g of phosphoric acid is added to neutralize potassium hydroxide, and after adsorption and vacuum dehydration, polypropylene glycol oligomers are obtained.

[0031] (2) Synthesis of medium molecular weight polypropylene glycol The condensation reactor was added with 0.7 g of DMC catalyst and 2392 g of polypropylene glycol 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 was 0.25 MPa and the temperature was 130°C, the reaction was carried out. 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 uniform rate. After the addition of propylene oxide was completed, it was aged for 1 hour, then cooled to 100°C for degassing for 30 minutes, cooled to 70°C and discharged to obtain medium molecular weight polypropylene glycol.

[0032] (3) Synthesis of high molecular weight polypropylene glycol The 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, heated to 125°C and propylene oxide (2250 g in total) was added. 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 constant speed. After the addition of propylene oxide, it was aged for 1 hour, then cooled to 100°C for degassing for 30 minutes, cooled to 70°C and discharged to obtain high molecular weight polypropylene glycol.

[0033] (4) Preparation of diallyl polypropylene glycol 6000.51g of high molecular weight polypropylene glycol prepared in step (3) was transported to the 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 5h. After the reaction, 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 temperature was kept for degassing for 2h. After degassing, it was cooled to 80°C, pressed into the end-capping kettle, the temperature was controlled at 80-90°C, 81g of allyl chloride was added dropwise, and after the addition was completed, it was kept at 85°C for 18h, and after the heat preservation, it was degassed, and the vacuum degree was kept above -0.099MPa for degassing for 2h. After degassing, the crude product of bis-allyl polypropylene glycol was obtained.

[0034] Press into the post-treatment kettle, control the temperature at 85℃, add 1000g of water and 2g of phosphoric acid, wash and neutralize for 30min, then add 25g of adsorbent, 60g of antioxidant (including 20g of tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, 20g of di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate] triethylene glycol and 20g of triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate), 6g of filter aid, adsorb for 30min, then turn on the vacuum pump, slowly dehydrate, control the dehydration temperature at about 85℃, turn on the Roots pump at -0.095MPa, and the vacuum degree is -0.099MPa. After the first dehydration, heat to 105℃ and continue dehydration for 1.5h. After dehydration, bisallyl polypropylene glycol is obtained by filtration.

[0035] (5) Preparation of silane-terminated polyether Add 5980.03 g of the bisallyl polypropylene glycol prepared in step (4) and 118.5 g of dimethoxysilane into the reaction kettle. After replacing the nitrogen once, raise the temperature to 85°C, add 3 g of chloroplatinic acid, seal the reaction kettle, keep the pressure less than 0.2 MPa, and react at 83°C for 3 h to terminate the reaction. Then cool and discharge the material to obtain a silane-modified polyether resin.

[0036] Example 2 A method for preparing a silane-modified polyether resin comprises the following steps: (1) Synthesis of polypropylene glycol oligomers Add 24g of potassium hydroxide catalyst to the condensation reactor, and 1520g of propylene glycol initiator is pumped from the storage tank to the reactor through a metering pump. Nitrogen is replaced once and the reactor is sealed. Heat to 110℃ and start to add propylene oxide (a total of 10480g). The pressure in this process is controlled at ≤0.25Mpa. After the reaction is normal, control the pressure to ≤0.30Mpa, the temperature is 120℃, and propylene oxide is added at a uniform rate. After 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, cool to about 100℃, turn on the vacuum pump, and slowly open the vacuum valve for degassing. The vacuum is -0.096Mpa, and normal degassing is 30 minutes. The material is transferred to the post-treatment kettle, 16g of phosphoric acid is added to neutralize potassium hydroxide, and polypropylene glycol oligomers are obtained after adsorption and vacuum dehydration.

[0037] (2) Synthesis of medium molecular weight polypropylene glycol The condensation reactor was added 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, the temperature was raised to 125°C, and propylene oxide (a total of 9600 g) was added. 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 added at a uniform rate. After the addition of propylene oxide was completed, it was aged for 1 hour, then cooled to 100°C for degassing for 30 minutes, cooled to 70°C and discharged to obtain medium molecular weight polypropylene glycol.

[0038] (3) Synthesis of high molecular weight polypropylene glycol The 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, heated to 125°C and propylene oxide (2250 g in total) was added. 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 constant speed. After the addition of propylene oxide, it was aged for 1 hour, then cooled to 100°C for degassing for 30 minutes, cooled to 70°C and discharged to obtain high molecular weight polypropylene glycol.

[0039] (4) Preparation of diallyl polypropylene glycol 6000.51g of high molecular weight polypropylene glycol prepared in step (3) was transported to the 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 5h. After the reaction, 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 temperature was kept for degassing for 2h. After degassing, it was cooled to 80°C, pressed into the end-capping kettle, the temperature was controlled at about 85°C, 81g of allyl chloride was added dropwise, and after the addition was completed, it was kept at 85°C for 18h, and after the heat preservation, it was degassed, and the vacuum degree was kept above -0.099MPa for degassing for 2h. After degassing, the crude product of bis-allyl polypropylene glycol was obtained.

[0040] Press into the post-treatment kettle, control the temperature at 90℃, add 1000g of water and 2g of phosphoric acid, wash and neutralize with water for 30min, then add 25g of adsorbent, 60g of antioxidant (including 15g of tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, 30g of di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate] triethylene glycol and 15g of triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate), 6g of filter aid, adsorb for 30min, then turn on the vacuum pump, slowly dehydrate, control the dehydration temperature at about 80℃, turn on the Roots pump at -0.095MPa, and the vacuum degree is -0.099MPa. After the first dehydration, heat to 110℃ and continue dehydration for 2.0h. After dehydration, bisallyl polypropylene glycol is obtained by filtration.

[0041] (5) Preparation of silane-terminated polyether Add 5980.03 g of the bisallyl polypropylene glycol prepared in step (4) and 135 g of trimethoxysilane into the reaction kettle. After replacing the nitrogen once, raise the temperature to 85°C, add 3 g of chloroplatinic acid, seal the reaction kettle, keep the pressure less than 0.2 MPa, and react at 85°C for 3 h to terminate the reaction. Then cool and discharge the material to obtain a silane-modified polyether resin.

[0042] Example 3 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 including 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, and the remaining preparation steps are the same as those of Example 1.

[0043] Example 4 Example 4 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the difference is that in step (4) of Example 4, the amount of antioxidant added is 120 g, specifically including 40 g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 40 g of di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate]triethylene glycol and 40 g of triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, and the remaining preparation steps are the same as those of Example 1.

[0044] Example 5 Example 5 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the difference is that in step (4) of Example 5, the amount of antioxidant added is 40 g, specifically including 20 g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 20 g of di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate]triethylene glycol, and the remaining preparation steps are the same as those of Example 1.

[0045] Example 6 Example 6 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the difference is that in step (4) of Example 6, the amount of antioxidant added is 20 g, specifically pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and the remaining preparation steps are the same as those of Example 1.

[0046] Example 7 Example 7 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the difference is that in step (4) of Example 7, the amount of antioxidant added is 20 g, specifically di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionic acid]triethylene glycol, and the remaining preparation steps are the same as those of Example 1.

[0047] Example 8 Example 8 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the difference is that in step (4) of Example 8, the amount of antioxidant added is 20 g, specifically triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, and the remaining preparation steps are the same as those of Example 1.

[0048] Example 9 Example 9 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the difference is that in step (5), the end-capping agent alkoxysilane is diethoxyhydrogensilane, and the amount used is 161.05 g. The remaining preparation steps are the same as those in Example 1.

[0049] Example 10 Example 10 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the difference is that in step (5), the end-capping agent alkoxysilane is methyldiethoxyhydrosilane, and the amount used is 145.84 g. The remaining preparation steps are the same as in Example 1.

[0050] Embodiment 11 Example 11 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the difference is that in step (5), the end-capping agent alkoxysilane is triethoxyhydrogensilane, and the amount used is 178.43 g. The remaining preparation steps are the same as in Example 1.

[0051] Comparative Example 1 Comparative Example 1 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the difference is that in step (4), no antioxidant is added in Comparative Example 1, and the remaining preparation steps are the same as in Example 1.

[0052] Comparative Example 2 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, an antioxidant and sodium methoxide are added simultaneously, and the amount added is the same as that of Example 1, and the remaining preparation steps are also the same as those of Example 1.

[0053] Comparative Example 3 Comparative Example 3 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the difference is that in Comparative Example 3, no antioxidant is added in step (4), and an equal amount of antioxidant (the type and amount of antioxidant are the same as those in Example 1) is added simultaneously with the catalyst chloroplatinic acid in step (5). The remaining preparation steps are the same as those in Example 1.

[0054] Comparative Example 4 Comparative Example 4 provides a method for preparing a silane-modified polyether resin. Compared with Example 1, the difference is 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.

[0055] Product effect testing 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: (1) Color test: Use platinum-cobalt colorimetry to test color; (2) Silane capping rate: Instrument: Bruker NMR spectrometer (Ascend 600M); Solvent: deuterated acetone; Detection method: H NMR spectrum; Instrument parameters: Pulse sequence: zg30, number of scans: 128, relaxation delay time: 1 s, number of sampling points: 64k, spectrum 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.

[0056] (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.

[0057] After testing, the performance test results of Examples 1-11 and Comparative Examples 1-4 are shown in Table 1.

[0058] Table 1

[0059] As shown in Table 1, the silane-modified polyether resin prepared in the embodiment of the present invention has a silane end-capping rate of 98.0% or more, as high as 99.9%; when the end-capping agent alkoxysilane is methyldiethoxyhydrogensilane, triethoxyhydrogensilane, etc. with a large molecular weight, the method provided by the present invention can also make the silane end-capping rate reach 99.3% or more. In addition, the silane-modified polyether resin prepared in the present invention has good color and strong stability during storage.

[0060] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing a silane-modified polyether resin, characterized in that: The following steps are involved: S1, subjecting a polyether polyol to an alcohol salting agent for alcohol salting reaction, and after the reaction is completed, adding a halogenated end-capping agent containing a double bond to carry out 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 water 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, subjecting the double-bond terminated polyether prepared in step S2 to a silane termination reaction with 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 ester, 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 ester.

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 ester, 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 ester.

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, triethylene glycol di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate] 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)propionate] pentaerythritol ester, the di[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate] triethylene glycol and the triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate 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 under the action of an alkali 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 may 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 a phosphoric acid solution, a sulfuric acid solution, a hydrochloric acid solution, an acetic acid solution or a 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 process of the silane end-capping reaction is to control the pressure to be less than 0.2 MPa and the reaction temperature to be 80-90° C. for 2-5 hours under closed reaction conditions.

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

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