Silane modified polyether-polybutadiene, transparent hydrolysis-resistant silane modified polyether sealant and preparation method thereof

Abstract

The invention relates to silane modified polyether-polybutadiene, a transparent hydrolysis-resistant silane modified polyether sealant and a preparation method thereof. The silane modified polyether-polybutadiene is obtained by reaction of silane modified polybutadiene and polyether amine, and the silane modified polybutadiene is obtained by reaction of hydroxyl-terminated epoxidized polybutadiene and isocyanate silane. The preparation raw materials of the silane modified polyether sealant comprise the silane modified polyether-polybutadiene disclosed by the invention. The silane modified polyether sealant disclosed by the invention has very low water permeability and excellent hydrolysis resistance and mechanical properties.

Description

Technical Field

[0001] The invention belongs to the technical field of sealants, and in particular relates to a silane-modified polyether-polybutadiene, transparent, hydrolysis-resistant silane-modified polyether sealant and a preparation method thereof. Background Art

[0002] Silane modified polyether sealant (MS sealant) is a high-performance environmentally friendly sealant developed on the basis of silicone sealant. Since MS sealant is a polyether-based structure with siloxane end caps at both ends, it has the characteristics of both polyether and silicone, and has excellent elongation, flexibility, weather resistance, aging resistance, etc. In addition, it overcomes the shortcomings of traditional silicone sealants such as poor surface finish and bonding limitations, and is widely used in the field of prefabricated buildings.

[0003] With the continuous development of MS glue, its application field is becoming more and more extensive. Among them, transparent silane-modified polyether sealants are widely used in some special scenarios, such as weather-resistant sealing of glass curtain walls and skylights, bonding and sealing of acrylic panels, and waterproof bonding and sealing of medical equipment. However, due to the characteristics of the ether bond groups in the polymer structure itself, traditional silane-modified polyether glue has poor hydrolysis resistance. During long-term use, problems such as shedding of the interface layer after water absorption and swelling due to high water permeability and poor hydrolysis stability may occur, which are not conducive to the long-term use of silane-modified polyether glue.

[0004] Therefore, it is necessary to prepare a transparent silane-modified polyether sealant with hydrolysis resistance to ensure its long-term use effect in a humid environment. Summary of the invention

[0005] Based on this, the object of the present invention is to provide a hydrolysis-resistant transparent silane-modified polyether sealant.

[0006] The technical solutions for achieving the above-mentioned purpose include the following.

[0007] In the first aspect, the present invention provides a silane-modified polyether-polybutadiene, the structural formula of which is as follows:

[0008]

[0009] Wherein, n and m are positive integers, and the ratio of n to m is (2-5):1, and R is a methyl group or an ethyl group.

[0010] The silane-modified polyether-polybutadiene of the present invention is obtained by reacting silane-modified polybutadiene and polyetheramine, and the silane-modified polybutadiene is obtained by reacting terminal hydroxyl epoxidized polybutadiene and isocyanate silane;

[0011] The structural formula of the hydroxy-terminated epoxidized polybutadiene is:

[0012]

[0013] The structural formula of the polyetheramine is:

[0014]

[0015] Wherein, n and m are positive integers, and the ratio of n to m is (2-5):1.

[0016] In a second aspect, the present invention provides a method for preparing the silane-modified polyether-polybutadiene, comprising the following steps:

[0017] Under the protection of inert gas, the terminal hydroxyl epoxidized polybutadiene and isocyanate silane react under the action of a catalyst to obtain silane-modified polybutadiene, which is then added with the polyether amine for reaction to obtain the silane-modified polyether-polybutadiene.

[0018] In a third aspect, the present invention provides a silane-modified polyether sealant, the raw materials for preparing the sealant include the silane-modified polyether-polybutadiene described in the present invention.

[0019] For example, the silane-modified polyether sealant is prepared from raw materials including the following components:

[0020]

[0021]

[0022] In a fourth aspect, the present invention provides a method for preparing the silane-modified polyether sealant, comprising the following steps:

[0023] The silane-modified polyether resin, silane-modified polyether-polybutadiene, part of the plasticizer, fumed silica and the stabilizer are uniformly mixed, and then a dehydrating agent, the remaining plasticizer and the coupling agent are added in sequence, and the mixture is stirred and degassed under vacuum conditions to obtain the product.

[0024] The present invention has the following beneficial effects:

[0025] The invention uses terminal hydroxyl epoxidized polybutadiene to react with isocyanate silane and polyether amine in sequence to prepare a silane-modified polyether-polybutadiene. The silane-modified polyether-polybutadiene is combined with silane-modified polyether resin and other raw materials to prepare a transparent silane-modified polyether sealant with excellent hydrolysis resistance.

[0026] On the one hand, the silane-modified polyether-polybutadiene prepared by the present invention has strong hydrophobicity, and its terminal siloxane group can well react with the hydroxyl group on the surface of the substrate to undergo hydrolysis and condensation reaction, further forming a synergistic effect with its own good hydrophobic properties, thereby significantly enhancing the water resistance of the polyether sealant. After mixing and curing it with the silane-modified polyether resin, the sealant has excellent hydrolysis resistance and air tightness, so that the prepared silane-modified polyether sealant can effectively block the penetration of water at the interface, avoid the shedding of the interface layer caused by the sealant swelling due to water absorption, and improve the water-resistant adhesion of the adhesive. On the other hand, the hydrolyzable and condensable siloxane group grafted on the modified polybutadiene structure can also participate in the reaction when the colloid is cured, thereby ensuring its stability under long-term use without the problem of precipitation failure, so that the sealant can maintain a very low water permeability for a long time, and can maintain good hydrolysis resistance for long-term use, and can also increase the cross-linking density of the sealant, thereby improving the long-term use effect of the sealant. On the other hand, the silane-modified polyether-polybutadiene prepared by the present invention has the same polyoxyalkyl ether chain structure as the silane-modified polyether resin, and the two have good compatibility, thereby further improving the effect of the modified polyether-polybutadiene on the hydrolysis resistance of the polyether sealant. Under the synergistic effect of the above-mentioned multiple structural units, the obtained silane-modified polyether sealant has very low water permeability, excellent hydrolysis resistance and mechanical properties, thereby expanding its scope of use in humid environments.

[0027] The hydroxy-terminated epoxidized polybutadiene of the present invention has good transparency itself, and the silane-modified polyether-polybutadiene also has good transparency, so that the obtained sealant maintains good transparency.

[0028] The α-silane-terminated silane-modified polyether resin and silane-modified polybutadiene in the sealant system of the present invention can be rapidly hydrolyzed, cross-linked and cured under the action of only an aminosilane coupling agent without the need for additional organic tin catalysts, thereby reducing the use and harm of organic tin catalysts and greatly improving the environmental performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is the infrared spectrum of the silane-modified polyether-polybutadiene prepared in Example 1. DETAILED DESCRIPTION

[0030] In order to facilitate the understanding of the present invention, the present invention will be described more fully below. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0031] The experimental methods in the following examples without specifying specific conditions are usually carried out under conventional conditions or conditions recommended by the manufacturers. The various commonly used chemical reagents used in the examples are all commercially available products.

[0032] Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used in the present invention includes any and all combinations of one or more of the related listed items.

[0033] In addition, as used in the present invention, the term "or" is an inclusive "or" symbol and is equivalent to the term "and / or", unless the context clearly dictates otherwise. The term "based on" is not exclusive and allows for being based on other factors not described, unless the context clearly dictates otherwise. In addition, throughout the specification, the meanings of "a", "an", and "the" include plural referents. The meaning of "in..." includes "in..." and "on...".

[0034] Some of the embodiments involve a silane-modified polyether-polybutadiene, the structural formula of which is as follows:

[0035]

[0036] Wherein, n and m are positive integers, and the ratio of n to m is (2-5):1, and R is a methyl group or an ethyl group.

[0037] In some preferred embodiments, a=0.6-0.7, b=0.18-0.22, c=0.1-0.15.

[0038] In some preferred embodiments, a=0.68, b=0.2, c=0.12.

[0039] The silane-modified polyether-polybutadiene of the present invention is obtained by reacting silane-modified polybutadiene and polyetheramine, and the silane-modified polybutadiene is obtained by reacting terminal hydroxyl epoxidized polybutadiene and isocyanate silane;

[0040] The structural formula of the hydroxy-terminated epoxidized polybutadiene is:

[0041]

[0042] The structural formula of the polyetheramine is:

[0043]

[0044] Wherein, n and m are positive integers, and the ratio of n to m is (2-5):1.

[0045] In some preferred embodiments, the molar ratio of the terminal hydroxyl epoxidized polybutadiene to the isocyanate silane is 1:1-2, more preferably 1:1.5-2, such as 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8 or 1:2, preferably 1:2.

[0046] In some preferred embodiments, the molar ratio of the epoxy group in the silane-modified polybutadiene to the amino group in the polyetheramine is 1:1-2, more preferably 1:1.8-2, such as 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8 or 1:2, preferably 1:2.

[0047] In some preferred embodiments, the hydroxyl value of the hydroxy-terminated epoxidized polybutadiene is 0.17-0.20 mol / 100 g, such as 0.17 mol / 100 g, 0.175 mol / 100 g, 0.18 mol / 100 g, 0.185 mol / 100 g, 0.186 mol / 100 g, 0.19 mol / 100 g, 0.195 mol / 100 g or 0.20 mol / 100 g.

[0048] In some preferred embodiments, the epoxide value of the hydroxy-terminated epoxidized polybutadiene is 0.20-0.30 mol / 100 g, such as 0.20 mol / 100 g, 0.22 mol / 100 g, 0.24 mol / 100 g, 0.26 mol / 100 g, 0.28 mol / 100 g or 0.30 mol / 100 g.

[0049] In some preferred embodiments, a=0.6-0.7, b=0.18-0.22, c=0.1-0.15.

[0050] In some preferred embodiments, a=0.68, b=0.2, c=0.12.

[0051] In some preferred embodiments, the molecular weight of the polyetheramine is 400-3000, preferably 400-2000, more preferably 400-1000, such as 400, 800, 1000, 1500, 2000, 2500 or 3000, etc. For example, the polyetheramine can be polyetheramine D400, polyetheramine D800, polyetheramine D1000, etc.

[0052] In some preferred embodiments, the isocyanate silane is 3-isocyanate propyl alkoxy silane, preferably at least one of 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane and 3-isocyanate propyl methyl dimethoxy silane. It can also be a combination of at least two, such as a combination of 3-isocyanate propyl trimethoxy silane and 3-isocyanate propyl triethoxy silane, a combination of 3-isocyanate propyl triethoxy silane and 3-isocyanate propyl methyl dimethoxy silane, and more preferably isocyanate propyl trimethoxy silane.

[0053] In the present invention, the silane-modified polyether-polybutadiene has the same polyoxyalkyl ether chain structure as the silane-modified polyether resin, thus enhancing the compatibility of the two resins, thereby maintaining the transparency of the polymer itself, and the siloxane group participates in the reaction during the curing process of the base resin, thereby ensuring its water-resistant stability under long-term use without precipitation failure. In addition, the α-silane-terminated silane-modified polyether resin and the silane-modified polyether-polybutadiene with a structure similar to that of the aminosilane coupling agent used in the system of the present invention can be rapidly hydrolyzed, cross-linked and cured under the catalytic action of aminosilane alone without the need for additional addition of an organotin catalyst, thereby reducing the use and harm of organotin, thereby improving its environmental performance.

[0054] Some of the embodiments also involve a method for preparing the silane-modified polyether-polybutadiene, comprising the following steps:

[0055] Under the protection of inert gas, the terminal hydroxyl epoxidized polybutadiene and isocyanate silane react under the action of a catalyst to obtain silane-modified polybutadiene, which is then added with the polyether amine for reaction to obtain the silane-modified polyether-polybutadiene.

[0056] In some preferred embodiments, the catalyst is dibutyltin dilaurate.

[0057] In some preferred embodiments, the added amount of the catalyst is 0.02-0.5% of the total mass of the terminal hydroxyl epoxidized polybutadiene and isocyanate silane; for example, 0.02%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4% or 0.5%, etc.

[0058] In some preferred embodiments, the reaction time of the hydroxyl-terminated epoxidized polybutadiene and the isocyanate silane is 2 h to 6 h, such as 2 h, 3 h, 4 h, 5 h or 6 h.

[0059] In some preferred embodiments, the reaction temperature of the silane-modified polybutadiene and the polyetheramine is 50° C. to 60° C. (eg, 50° C., 52° C., 54° C., 56° C., 58° C. or 60° C.), and the reaction time is 2 h to 6 h.

[0060] Some of the embodiments also involve a silane-modified polyether sealant, the raw materials for preparing the sealant include the silane-modified polyether-polybutadiene described in the present invention.

[0061] In some embodiments, the silane-modified polyether sealant is prepared from raw materials including the following components in parts by weight:

[0062]

[0063]

[0064] For example, the amount of the silane-modified polyether resin can be 30 parts, 32 parts, 35 parts, 40 parts, 45 parts or 50 parts, etc.; the amount of the silane-modified polyether-polybutadiene can be 5 parts, 8 parts, 11 parts, 13 parts or 15 parts, etc.; the amount of the plasticizer can be 20 parts, 25 parts, 30 parts, 35 parts, 40 parts or 45 parts, etc.; the amount of the fumed silica can be 5 parts, 6 parts, 7 parts, 8 parts, etc. The amount of the stabilizer can be 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts, etc.; the amount of the dehydrating agent can be 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts, etc.; the amount of the coupling agent can be 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts or 4 parts, etc.

[0065] In some embodiments, the silane-modified polyether sealant is prepared from raw materials including the following components in parts by weight:

[0066]

[0067] In some embodiments, the silane-modified polyether resin is an α-silane-terminated silane-modified polyether resin, and its structural formula is:

[0068]

[0069] Wherein, Polyol is a polyether segment, preferably selected from STP-E10, STP-E30 and It can also be a combination of at least two, such as a combination of STP-E10 resin and STP-XB502 resin, a combination of STP-E30 resin and STP-XB502 resin, or a combination of STP-E10 resin and STP-E30 resin.

[0070] In some embodiments, the plasticizer is a polyether polyol or phthalate plasticizer, preferably at least one selected from PPG2000, PPG3000, PPG5000, diisononyl phthalate and diisodecyl phthalate.

[0071] In some embodiments, the fumed silica is a hydrophobic fumed silica, preferably selected from Evonik Degussa R974, Evonik Degussa R972, At least one of Cabot TS620 and Cabot TS610.

[0072] In some embodiments, the stabilizer is selected from at least one of Tinuvin 326, Tinuvin 770, Tinuvin 328 and Tinuvin 540.

[0073] In some embodiments, the desiccant is a vinyl silane desiccant, preferably at least one selected from vinyl triethoxy silane, vinyl trimethoxy silane and vinyl methyl dimethoxy silane.

[0074] In some embodiments, the coupling agent is an aminosilane coupling agent, preferably at least one selected from 3-aminopropyltrimethoxysilane (KH540), 3-aminopropyltriethoxysilane (KH550) and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane (KH792).

[0075] The present invention uses α-silane-terminated silane-modified polyether resin as a base resin, adds a certain amount of silane-modified polyether-polybutadiene, and reasonably adjusts the specific gravity of each component to prepare a transparent single-component silane-modified polyether sealant with good water resistance. On the one hand, the prepared silane-modified polyether-polybutadiene and the silane-modified polyether resin have the same polyoxyalkyl ether chain structure, so the two have good compatibility, and the transparency of the base resin itself is maintained to the greatest extent. At the same time, due to the hydrophobic property of polybutadiene, the water resistance of the silane-modified polyether sealant is greatly improved; on the other hand, the silane-modified polyether-polybutadiene of the present invention contains an alkoxy group that can be hydrolyzed and condensed, which can participate in the curing reaction during the cross-linking process, which can not only solve the problem of small molecular substances precipitating out of the sealant after long-term use, but also increase the cross-linking density of the sealant, thereby improving the long-term use effect of the sealant.

[0076] Some of the embodiments also involve a method for preparing the silane-modified polyether sealant, comprising the following steps:

[0077] The silane-modified polyether resin, silane-modified polyether-polybutadiene, part of the plasticizer, fumed silica and the stabilizer are uniformly mixed, and then a dehydrating agent, the remaining plasticizer and the coupling agent are added in sequence, and the mixture is stirred and degassed under vacuum conditions to obtain the product.

[0078] In some preferred embodiments, the mixing speed is 20rpm~50rpm, for example, 20rpm, 25rpm, 30rpm, 35rpm, 40rpm, 45rpm or 50rpm; the mixing time is 30-60min, for example, 30min, 35min, 40min, 45min, 50min, 55min or 60min.

[0079] In some preferred embodiments, the stirring and degassing speed is 10rpm to 30rpm, such as 10rpm, 15rpm, 20rpm, 25rpm or 30rpm; the time is 20min to 40min; such as 20min, 25min, 30min, 35min or 40min.

[0080] In some preferred embodiments, the vacuum degree of the vacuum condition is -0.09 MPa to -0.1 MPa, such as -0.09 MPa, -0.092 MPa, -0.094 MPa, -0.096 MPa, -0.098 MPa or -0.1 MPa.

[0081] The present invention is further described in detail below with reference to specific embodiments.

[0082] In the following examples, unless otherwise specified, "parts" refer to parts by weight.

[0083] In the following examples, the general structural formula of the silane-modified polyether resin is:

[0084]

[0085] Among them, Polyol is a polyether segment.

[0086] The general structural formula of hydroxyl-terminated epoxidized polybutadiene is:

[0087]

[0088] The general structural formula of polyetheramine is:

[0089]

[0090] The general structure formula of silane-modified polyether-polybutadiene and its reaction principle are as follows:

[0091] (1) The hydroxyl group in the hydroxyl-terminated epoxidized polybutadiene reacts with the isocyanate group in the isocyanate silane to obtain a silane-modified polybutadiene intermediate product:

[0092]

[0093] (2) The amino group in the polyetheramine reacts with the epoxy group in the silane-modified polybutadiene intermediate to obtain silane-modified polyether-polybutadiene:

[0094]

[0095] Wherein, R is methyl or ethyl.

[0096] Example 1

[0097] The raw materials for preparing the transparent hydrolysis-resistant silane-modified polyether adhesive provided in this embodiment are as follows:

[0098] Silane modified polyether resin (Wacker, Germany) STP-E10) 43 copies

[0099]

[0100] Among them, the structural formula of silane-modified polyether-polybutadiene is as follows:

[0101]

[0102] Among them, a=0.68, b=0.2, c=0.12, n:m=5:1.

[0103] Silane-modified polyether-polybutadiene is prepared by the following method:

[0104] (1) According to the molar ratio of terminal hydroxyl epoxidized polybutadiene to isocyanate propyl trimethoxy silane being 1:1.5, isocyanate propyl trimethoxy silane is slowly added dropwise to terminal hydroxyl epoxidized polybutadiene (Crayville Polybd 600E, a=0.68, b=0.2, c=0.12, hydroxyl value of 0.186 mol / 100 g, epoxy value of 0.22 mol / 100 g), and a catalyst dibutyltin dilaurate is added, and the reaction is stirred under nitrogen protection for about 5 hours (until the reaction is stopped after no isocyanate group is found in the system by back titration of di-n-butylamine), to obtain a silane-modified polybutadiene intermediate product.

[0105] The added amount of dibutyltin dilaurate is 0.05% of the total mass of the terminal hydroxyl epoxidized polybutadiene and isocyanate propyltrimethoxysilane.

[0106] (2) According to the ratio of the molar number of amino groups in the polyetheramine to the molar number of epoxy groups in the intermediate product of 2:1, polyetheramine D400 was added to the intermediate product of step (1), the temperature was raised to 50° C., and the reaction was carried out for 4 hours to obtain a silane-modified polyether-polybutadiene.

[0107] FT-IR spectroscopy analysis (see Figure 1 ) found that: at 3362cm -1 (NH), 1739cm -1 There are characteristic peaks at 2268cm -1 No characteristic absorption peak was found at (-NCO), indicating that the isocyanate silane had been grafted onto the polybutadiene main chain. -1 and 1080cm -1 The stretching vibration absorption peaks attributed to Si-O and CO are shown, proving that the silane-modified polyether-polybutadiene of the above structural formula has been synthesized.

[0108] The preparation method of the transparent hydrolysis-resistant silane-modified polyether adhesive provided in this embodiment is as follows:

[0109] The silane-modified polyether resin, silane-modified polyether-polybutadiene, fumed silica, stabilizer and part of the plasticizer were mixed at 30 rpm for 50 minutes until uniformly stirred, a dehydrating agent was added, and the mixture was stirred at a low speed of 20 rpm for 20 minutes. Finally, the remaining plasticizer and coupling agent were added, and the mixture was stirred and degassed at a speed of 10 rpm for 30 minutes under a vacuum condition of -0.092 MPa to obtain the transparent hydrolysis-resistant silane-modified polyether adhesive.

[0110] Example 2

[0111] The raw materials for preparing the transparent hydrolysis-resistant silane-modified polyether adhesive provided in this embodiment are as follows:

[0112]

[0113] Among them, the structural formula of silane-modified polyether-polybutadiene is as follows:

[0114]

[0115] Among them, a=0.68, b=0.2, c=0.12, n:m=3:1.

[0116] Silane-modified polyether-polybutadiene is prepared by the following method:

[0117] (1) According to the molar ratio of terminal hydroxyl epoxidized polybutadiene to isocyanate propyl triethoxy silane being 1:1.8, isocyanate propyl triethoxy silane is slowly added dropwise to terminal hydroxyl epoxidized polybutadiene (Crayville Polybd 600E, a=0.68, b=0.2, c=0.12, hydroxyl value of 0.186 mol / 100 g, epoxy value of 0.22 mol / 100 g), and a catalyst dibutyltin dilaurate is added, and the reaction is stirred under nitrogen protection for about 5 hours (until the reaction is stopped after no isocyanate group is found in the system by back titration of di-n-butylamine), to obtain a silane-modified polybutadiene intermediate product.

[0118] The added amount of dibutyltin dilaurate is 0.05% of the total mass of the terminal hydroxyl epoxidized polybutadiene and isocyanate propyltriethoxysilane.

[0119] (2) According to the ratio of the molar number of amino groups in the polyetheramine to the molar number of epoxy groups in the intermediate product of 2:1, polyetheramine D800 was added to the intermediate product of step (1), the temperature was slowly raised to 50° C., and the reaction was carried out for 4 hours to obtain a silane-modified polyether-polybutadiene.

[0120] The preparation method of the transparent hydrolysis-resistant silane-modified polyether adhesive provided in this embodiment is as follows:

[0121] The silane-modified polyether resin, silane-modified polyether-polybutadiene, fumed silica, stabilizer and part of the plasticizer were mixed at 35 rpm for 45 minutes until they were uniformly stirred, a dehydrating agent was added, and the mixture was stirred at a low speed of 25 rpm for 30 minutes. Finally, the remaining plasticizer and coupling agent were added, and the mixture was stirred and degassed at a speed of 10 rpm for 20 minutes under a vacuum condition of -0.092 MPa to obtain the transparent, hydrolysis-resistant silane-modified polyether adhesive.

[0122] Example 3

[0123] The raw materials for preparing the transparent hydrolysis-resistant silane-modified polyether adhesive provided in this embodiment are as follows:

[0124]

[0125] Among them, the structural formula of silane-modified polyether-polybutadiene is as follows:

[0126]

[0127] Among them, a=0.68, b=0.2, c=0.12, n:m=2.5:1.

[0128] Silane-modified polyether-polybutadiene is prepared by the following method:

[0129] (1) According to the molar ratio of terminal hydroxyl epoxidized polybutadiene to isocyanate propyl trimethoxy silane being 1:1.6, isocyanate propyl trimethoxy silane is slowly added dropwise to terminal hydroxyl epoxidized polybutadiene (Crayville Polybd 600E, a=0.68, b=0.2, c=0.12, hydroxyl value of 0.186 mol / 100 g, epoxy value of 0.22 mol / 100 g), and a catalyst dibutyltin dilaurate is added, and the reaction is stirred under nitrogen protection for about 4 hours (until the reaction is stopped after no isocyanate group is found in the system by back titration of di-n-butylamine), to obtain a silane-modified polybutadiene intermediate product.

[0130] The added amount of dibutyltin dilaurate is 0.05% of the total mass of the terminal hydroxyl epoxidized polybutadiene and isocyanate propyltrimethoxysilane.

[0131] (2) According to the ratio of the molar number of amino groups in the polyetheramine to the molar number of epoxy groups in the intermediate product of 2:1, polyetheramine D1000 was added to the intermediate product of step (1), the temperature was slowly raised to 50° C., and the reaction was carried out for 4 hours to obtain a silane-modified polyether-polybutadiene.

[0132] The preparation method of the transparent hydrolysis-resistant silane-modified polyether adhesive provided in this embodiment is as follows:

[0133] The silane-modified polyether resin, silane-modified polyether-polybutadiene, fumed silica, stabilizer and part of the plasticizer were mixed at 30 rpm for 50 minutes until uniformly stirred, a dehydrating agent was added, and the mixture was stirred at a low speed of 20 rpm for 20 minutes. Finally, the remaining plasticizer and coupling agent were added, and the mixture was stirred and degassed at a speed of 15 rpm for 25 minutes under a vacuum condition of -0.092 MPa to obtain the transparent hydrolysis-resistant silane-modified polyether adhesive.

[0134] Example 4

[0135] The raw materials for preparing the transparent hydrolysis-resistant silane-modified polyether adhesive provided in this embodiment are as follows:

[0136] Silane modified polyether resin (STP-E30:XB502=3:2 (mass ratio)) 45 parts

[0137] Silane modified polyether-polybutadiene 11 parts

[0138] Plasticizer (Diisononyl Phthalate, DINP) 34 parts

[0139] Fumed silica (Evonik Degussa R972, Germany) 6 parts

[0140] Stabilizer (BASF light stabilizer Tinuvin 770) 1 part

[0141] Dewatering agent (vinyl triethoxysilane) 1 part

[0142] 2 parts of coupling agent (N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, KH792).

[0143] Among them, the structural formula of silane-modified polyether-polybutadiene is as follows:

[0144]

[0145] Among them, a=0.68, b=0.2, c=0.12, n:m=3:1.

[0146] Silane-modified polyether-polybutadiene is prepared by the following method:

[0147] (1) According to the molar ratio of terminal hydroxyl epoxidized polybutadiene to isocyanate propyl trimethoxy silane being 1:2, isocyanate propyl trimethoxy silane is slowly added dropwise to terminal hydroxyl epoxidized polybutadiene (Crayville Polybd 600E, a=0.68, b=0.2, c=0.12, hydroxyl value of 0.186 mol / 100 g, epoxy value of 0.22 mol / 100 g), and a catalyst dibutyltin dilaurate is added, and the reaction is stirred under nitrogen protection for about 4 hours (until the reaction is stopped after no isocyanate group is found in the system by back titration of di-n-butylamine), to obtain a silane-modified polybutadiene intermediate product.

[0148] The added amount of dibutyltin dilaurate is 0.05% of the total mass of the terminal hydroxyl epoxidized polybutadiene and isocyanate propyltrimethoxysilane.

[0149] (2) According to the ratio of the molar number of amino groups in the polyetheramine to the molar number of epoxy groups in the intermediate product of 2:1, polyetheramine D800 was added to the intermediate product of step (1), the temperature was slowly raised to 50° C., and the reaction was carried out for 4 hours to obtain a silane-modified polyether-polybutadiene.

[0150] The preparation method of the transparent hydrolysis-resistant silane-modified polyether adhesive provided in this embodiment is as follows:

[0151] The silane-modified polyether resin, silane-modified polyether-polybutadiene, fumed silica, stabilizer and part of the plasticizer were mixed at 30 rpm for 45 minutes until uniformly stirred, a dehydrating agent was added, and the mixture was stirred at a low speed of 20 rpm for 20 minutes. Finally, the remaining plasticizer and coupling agent were added, and the mixture was stirred and degassed at a speed of 15 rpm for 30 minutes under a vacuum condition of -0.092 MPa to obtain the transparent hydrolysis-resistant silane-modified polyether adhesive.

[0152] Example 5

[0153] The raw materials for preparing the transparent hydrolysis-resistant silane-modified polyether adhesive provided in this embodiment are as follows:

[0154]

[0155] Among them, the structural formula of silane-modified polyether-polybutadiene is as follows:

[0156]

[0157] Among them, a=0.68, b=0.2, c=0.12, n:m=5:1.

[0158] Silane-modified polyether-polybutadiene is prepared by the following method:

[0159] (1) In a molar ratio of hydroxyl-terminated epoxidized polybutadiene to isocyanate propyl triethoxysilane of 1:2, isocyanate propyl triethoxysilane is slowly added dropwise to hydroxyl-terminated epoxidized polybutadiene (Crayville Polybd 600E, a=0.68, b=0.2, c=0.12, hydroxyl value of 0.186 mol / 100 g, epoxy value of 0.22 mol / 100 g), and a catalyst dibutyltin dilaurate is added, and the reaction is stirred under nitrogen protection for about 4 hours (until the reaction is stopped after no isocyanate group is found in the system by back titration of di-n-butylamine), to obtain a silane-modified polybutadiene intermediate product.

[0160] The added amount of dibutyltin dilaurate is 0.05% of the total mass of the terminal hydroxyl epoxidized polybutadiene and isocyanate propyltriethoxysilane.

[0161] (2) According to the ratio of the molar number of amino groups in the polyetheramine to the molar number of epoxy groups in the intermediate product of 2:1, polyetheramine D400 was added to the intermediate product of step (1), the temperature was slowly raised to 50° C., and the reaction was carried out for 4 hours to obtain a silane-modified polyether-polybutadiene.

[0162] The preparation method of the transparent hydrolysis-resistant silane-modified polyether adhesive provided in this embodiment is as follows:

[0163] The silane-modified polyether resin, silane-modified polyether-polybutadiene, fumed silica, stabilizer and part of the plasticizer were mixed at 25 rpm for 40 minutes until uniformly stirred, a dehydrating agent was added, and the mixture was stirred at a low speed of 20 rpm for 20 minutes. Finally, the remaining plasticizer and coupling agent were added, and the mixture was stirred and degassed at a speed of 15 rpm for 25 minutes under a vacuum condition of -0.092 MPa to obtain the transparent hydrolysis-resistant silane-modified polyether adhesive.

[0164] Comparative Example 1:

[0165] The transparent hydrolysis-resistant silane-modified polyether sealant provided in this comparative example has a preparation method different from that of Example 1 in that no silane-modified polyether-polybutadiene is added, the weight portion of the silane-modified polyether resin (STP-E10) is 50 parts, and the rest is the same as that of Example 1.

[0166] Comparative Example 2:

[0167] The transparent, hydrolysis-resistant silane-modified polyether sealant provided in this comparative example has a preparation method that is different from that of Example 1 in that the silane-modified polyether-polybutadiene is replaced by terminal hydroxyl epoxidized polybutadiene (Crayville Poly bd 600E, a=0.68, b=0.2, c=0.12, hydroxyl value of 0.186 mol / 100 g, epoxy value of 0.22 mol / 100 g), and the rest is the same as that of Example 1.

[0168] Comparative Example 3

[0169] The transparent hydrolysis-resistant silane-modified polyether sealant provided in this comparative example has a preparation method different from that of Example 1 in that the silane-modified polyether-polybutadiene is replaced by the silane-modified polybutadiene intermediate product prepared in step (1) of Example 1, and the rest is the same as that of Example 1. The details are as follows:

[0170] The raw materials for preparing the transparent hydrolysis-resistant silane-modified polyether adhesive provided in this comparative example are as follows:

[0171]

[0172] Wherein, the silane-modified polybutadiene intermediate product is prepared by the following method:

[0173] According to the molar ratio of terminal hydroxyl epoxidized polybutadiene and isocyanate propyl trimethoxy silane being 1:1.5, isocyanate propyl trimethoxy silane is slowly added dropwise to terminal hydroxyl epoxidized polybutadiene (Crayville Polybd 600E, a=0.68, b=0.2, c=0.12, hydroxyl value of 0.186 mol / 100 g, epoxy value of 0.22 mol / 100 g), and catalyst dibutyltin dilaurate is added, and the reaction is stirred for about 5 hours under nitrogen protection (until the reaction is stopped after the di-n-butylamine back titration method determines that there is no isocyanate group in the system), to obtain a silane-modified polybutadiene intermediate product.

[0174] The added amount of dibutyltin dilaurate is 0.05% of the total mass of the terminal hydroxyl epoxidized polybutadiene and isocyanate propyltrimethoxysilane.

[0175] The preparation method of the transparent hydrolysis-resistant silane-modified polyether adhesive provided in this comparative example is as follows:

[0176] The silane-modified polyether resin, the silane-modified polybutadiene intermediate product, the fumed silica, the stabilizer and part of the plasticizer were mixed at 30 rpm for 50 min until they were uniformly stirred, a dehydrating agent was added, and the mixture was stirred at a low speed of 20 rpm for 20 min. Finally, the remaining plasticizer and coupling agent were added, and the mixture was stirred and degassed at a speed of 10 rpm for 30 min under a vacuum condition of -0.092 to obtain the transparent, hydrolysis-resistant silane-modified polyether adhesive.

[0177] Comparative Example 4

[0178] The transparent hydrolysis-resistant silane-modified polyether sealant provided in this comparative example has a preparation method different from that of Example 1 in that the silane-modified polyether-polybutadiene is replaced by polyether-polybutadiene, and the rest is the same as that of Example 1. The details are as follows:

[0179] The raw materials for preparing the transparent hydrolysis-resistant silane-modified polyether adhesive provided in this comparative example are as follows:

[0180]

[0181] Polyether-polybutadiene is prepared by the following method:

[0182] According to the ratio of the molar number of amino groups in the polyetheramine to the molar number of epoxy groups in the terminal hydroxyl epoxidized polybutadiene of 2:1, polyetheramine D400 was added to the terminal hydroxyl epoxidized polybutadiene (Crayville Polybd 600E, a=0.68, b=0.2, c=0.12, hydroxyl value of 0.186 mol / 100 g, epoxy value of 0.22 mol / 100 g), the temperature was raised to 50°C, and the reaction was carried out for 4 hours to obtain polyether-polybutadiene.

[0183] The preparation method of the transparent hydrolysis-resistant silane-modified polyether adhesive provided in this embodiment is as follows:

[0184] The silane-modified polyether resin, polyether-polybutadiene, fumed silica, stabilizer and part of the plasticizer were mixed at 30 rpm for 50 minutes until uniformly stirred, a dehydrating agent was added, and the mixture was stirred at a low speed of 20 rpm for 20 minutes. Finally, the remaining plasticizer and coupling agent were added, and the mixture was stirred and degassed at a speed of 10 rpm for 30 minutes under a vacuum condition of -0.092 to obtain the transparent, hydrolysis-resistant silane-modified polyether adhesive.

[0185] Comparative Example 5:

[0186] The transparent hydrolysis-resistant silane-modified polyether sealant provided in this comparative example has a preparation method which is different from that of Example 2 in that the silane-modified polybutadiene is replaced with a silane-modified polyether resin (STP-E30) of the same mass fraction, and the rest is the same as that of Example 2.

[0187] Comparative Example 6:

[0188] Commercially available transparent silane-modified polyether adhesive MS751 was selected.

[0189] The transparent silane-modified polyether sealants of Examples 1-5 and Comparative Examples 1-6 were subjected to the following performance tests:

[0190] Surface drying time: tested according to GB / T 13477.5-2003 standard.

[0191] Tensile strength and elongation at break: tested according to GB / T 528-2009 standard.

[0192] Water vapor permeability: tested according to GB / T 1037-2021 standard.

[0193] Light transmittance: Tested according to GB / T2410-2008 standard. Prepare a 2mm thick sealant film and use SM-2 light transmittance tester to test its light transmittance.

[0194] Waterproof sealing: According to the GB / T 4208-2017 standard test, color-changing silica gel is placed inside the cubic aluminum cavity with a skirt to prepare a waterproof sealing model, and the glass and the skirt are bonded with the sealant to be tested. After curing, the glass plate is bonded to the aluminum model to observe the water absorption of the internal color-changing silica gel to test the sealing inside the cubic cavity. The result of waterproof sealing is mainly based on whether the color-changing silica gel in the waterproof sealing model changes color. If the silica gel turns red, the waterproof sealing performance fails, and if the silica gel remains blue, the waterproof sealing performance is good.

[0195] The test results are shown in Table 1.

[0196] Table 1

[0197]

[0198]

[0199] It can be seen from the experimental results in Table 1 that the transparent hydrolysis-resistant silane-modified polyether sealant prepared by the present invention, after adding silane-modified polyether-polybutadiene, has a low water vapor permeability while maintaining good transparency, and after the sealant is prepared into a waterproof sealing model and immersed in water for 12 months, the internal color-changing silica gel still remains blue, indicating that its waterproof sealing effect is very good; while the silane-modified polyether sealant prepared without adding silane-modified polyether-polybutadiene (Comparative Examples 1 and 5) and the silane-modified polyether sealant prepared by directly adding terminal hydroxyl epoxidized polybutadiene (Comparative Example 2) have a higher water vapor permeability, and after they are made into waterproof sealing models and immersed in water for 3 months, the silica gel inside the model changes color, indicating that their long-term water-resistant bonding effect is not good. The results also indicate that unmodified hydroxy-terminated epoxidized polybutadiene can only act as a partial plasticizer in the sealant. As time goes by, the hydroxy-terminated epoxidized polybutadiene will precipitate from the sealant, which will not provide good water resistance, causing the sealant to absorb water and swell during long-term immersion in water, leading to the shedding of the interface layer. However, by adding the silane-modified polyether-polybutadiene prepared by the present invention, the siloxane group therein can participate in the reaction when the colloid is solidified, thereby ensuring its stability under long-term use without causing the problem of precipitation failure, thereby effectively reducing the water permeability of the sealant and improving its hydrolysis resistance.

[0200] Moreover, the unmodified hydroxy-terminated epoxidized polybutadiene has poor compatibility with the silane-modified polyether resin. Therefore, the silane-modified polyether adhesive prepared in Comparative Example 2 by directly adding hydroxy-terminated epoxidized polybutadiene not only has poorer hydrolysis resistance than Example 1, but also has significantly worse mechanical properties and light transmittance than Example 1.

[0201] The waterproof sealing model prepared by the commercially available transparent silane-modified polyether adhesive of the hydrolyzable and condensable comparative example 6 also showed the phenomenon of silicone discoloration after being immersed in water for 3 months, and the waterproof sealing performance failed.

[0202] Comparative Examples 3 and 4 respectively used only isocyanate propyl trimethoxy silane and polyether amine alone to graft-modify terminal hydroxyl epoxidized polybutadiene. Although the waterproof performance of the obtained silane-modified polyether adhesive was improved compared with that of Comparative Example 1 without adding polybutadiene, its waterproof performance, mechanical properties and light transmittance were all worse than those of Example 1. This indicates that the graft-modification of polybutadiene with isocyanate propyl trimethoxy silane and polyether amine at the same time has a synergistic effect, which can more effectively improve the waterproof and water-resistant properties of the obtained polyether adhesive, while maintaining good light transmittance and mechanical properties.

[0203] In summary, the silane-modified polyether sealant prepared by the present invention has excellent water resistance and good mechanical properties while maintaining its transparency, thereby ensuring its long-term use effect in a humid environment.

[0204] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. 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, and these 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 silane-modified polyether-polybutadiene, characterized in that: Its structural formula is as follows: Wherein, n and m are positive integers, and the ratio of n to m is (2-5):1, and R is methyl or ethyl; Preferably, a=0.6-0.7, b=0.18-0.22, c=0.1-0.15; Preferably, a=0.68, b=0.2, c=0.

12.

2. A silane-modified polyether-polybutadiene, characterized in that: The silane-modified polybutadiene is obtained by reacting a silane-modified polybutadiene with a polyetheramine, wherein the silane-modified polybutadiene is obtained by reacting a terminal hydroxyl epoxidized polybutadiene with an isocyanate silane; The structural formula of the hydroxy-terminated epoxidized polybutadiene is: The structural formula of the polyetheramine is: Wherein, n and m are positive integers, and the ratio of n to m is (2-5):

1.

3. The silane-modified polyether-polybutadiene according to claim 2, characterized in that: The molar ratio of the terminal hydroxyl epoxidized polybutadiene to the isocyanate silane is 1:1-2, preferably 1:1.5-2; and / or, The molar ratio of the epoxy group in the silane-modified polybutadiene to the amino group in the polyetheramine is 1:1-2, preferably 1:1.8-2.

4. The silane-modified polyether-polybutadiene according to claim 2 or 3, characterized in that: The hydroxyl value of the hydroxyl-terminated epoxidized polybutadiene is 0.17 to 0.2 mol / 100 g; and / or, The epoxide value of the hydroxy-terminated epoxidized polybutadiene is 0.20 to 0.30 mol / 100 g; and / or, In the hydroxy-terminated epoxidized polybutadiene, a=0.6-0.7, b=0.18-0.22, c=0.1-0.15; and / or, The molecular weight of the polyetheramine is 400 to 3000, preferably 400 to 2000; and / or, The isocyanate silane is 3-isocyanate propyl alkoxy silane, preferably at least one of 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane and 3-isocyanate propyl methyl dimethoxy silane.

5. A method for preparing the silane-modified polyether-polybutadiene according to any one of claims 2 to 4, characterized in that: The steps include: Under the protection of inert gas, the terminal hydroxyl epoxidized polybutadiene and isocyanate silane react under the action of a catalyst to obtain silane-modified polybutadiene, which is then added with the polyether amine for reaction to obtain the silane-modified polyether-polybutadiene.

6. The method for preparing silane-modified polyether-polybutadiene according to claim 5, characterized in that: The catalyst is dibutyltin dilaurate; and / or, The amount of the catalyst added is 0.02-0.5% of the total mass of the hydroxyl-terminated epoxidized polybutadiene and the isocyanate silane; and / or, The reaction time of the hydroxyl-terminated epoxidized polybutadiene and the isocyanate silane is 2 hours to 6 hours; and / or, The temperature for the reaction of the silane-modified polybutadiene and the polyetheramine is 50° C. to 60° C., and the time is 2 h to 6 h.

7. A silane-modified polyether sealant, characterized in that: The raw materials for its preparation include the silane-modified polyether-polybutadiene described in any one of claims 1 to 4.

8. The silane-modified polyether sealant according to claim 7, characterized in that: The composition is prepared from the following raw materials in parts by weight: Preferably, the silane-modified polyether sealant is prepared from raw materials including the following components in parts by weight:

9. The silane-modified polyether sealant according to claim 8, characterized in that: The silane-modified polyether resin is an α-silane-terminated silane-modified polyether resin, and its structural formula is: Wherein, Polyol is a polyether segment, preferably selected from STP-E10, STP-E30 and At least one of STP-XB502; and / or, The plasticizer is a polyether polyol or phthalate plasticizer, preferably at least one selected from PPG2000, PPG3000, PPG5000, diisononyl phthalate and diisodecyl phthalate; and / or, The fumed silica is a hydrophobic fumed silica, preferably selected from Evonik Degussa R974, Evonik Degussa R972, H18, At least one of H20, Cabot TS620 and Cabot TS610; and / or, The stabilizer is selected from at least one of Tinuvin 326, Tinuvin 770, Tinuvin 328 and Tinuvin 540; and / or, The dewatering agent is a vinyl silane dewatering agent, preferably at least one selected from vinyl triethoxysilane, vinyl trimethoxysilane and vinyl methyl dimethoxysilane; and / or, The coupling agent is an aminosilane coupling agent, preferably at least one selected from 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane.

10. A method for preparing the silane-modified polyether sealant according to claim 8 or 9, characterized in that: The steps include: The silane-modified polyether resin, silane-modified polyether-polybutadiene, part of the plasticizer, fumed silica and the stabilizer are uniformly mixed, and then a dehydrating agent, the remaining plasticizer and the coupling agent are sequentially added, and the mixture is stirred and degassed under vacuum conditions to obtain a product; Preferably, the mixing speed is 20 rpm to 50 rpm, and the mixing time is 30 min to 60 min; Preferably, the stirring and degassing has a rotation speed of 10 rpm to 30 rpm and a time of 20 min to 40 min; Preferably, the vacuum degree of the vacuum condition is -0.09 MPa to -0.1 MPa.

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