Silane-modified polyether-polybutadiene, clear hydrolysis-resistant silane-modified polyether sealant, and method for preparing the same

Abstract

The present application relates to a kind of silane modified polyether-polybutadiene, transparent hydrolysis-resistant silane modified polyether sealant and its preparation method.The silane modified polyether-polybutadiene is obtained by the reaction of silane modified polybutadiene and polyetheramine, and the silane modified polybutadiene is obtained by the reaction of terminal hydroxyl epoxidized polybutadiene and isocyanate silane.The preparation raw material of the silane modified polyether sealant includes the silane modified polyether-polybutadiene described in the present application.The silane modified polyether sealant of the present application has very low water permeability, excellent hydrolysis resistance and mechanical properties.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of sealant, and particularly relates to a silane-modified polyether-polybutadiene, a transparent hydrolysis-resistant silane-modified polyether sealant and a preparation method thereof. BACKGROUND

[0002] The silane-modified polyether sealant (MS sealant) is a high-performance environment-friendly sealant developed on the basis of silicone sealant. Since the MS sealant has a structure in which polyether is used as a main chain and siloxane is used for end capping, the MS sealant has the characteristics of both polyether and silicone, and has excellent properties such as elongation, flexibility, weather resistance and aging resistance. In addition, the MS sealant overcomes the defects of poor surface finishing and bonding limitations of traditional silicone sealant, and is widely used in the field of fabricated buildings.

[0003] With the continuous development of the MS sealant, the application field of the MS sealant is becoming more and more extensive. The transparent silane-modified polyether sealant is widely used in some special scenarios, such as weather-resistant sealing of glass curtain walls and awnings, bonding and sealing of acrylic plates, and waterproof bonding and sealing of medical devices. However, due to the characteristics of the ether bond group in the structure of the polymer, the traditional silane-modified polyether sealant has poor hydrolysis resistance. In the long-term use process, the interface layer may be detached due to high water permeability and poor hydrolysis stability, which is not conducive to the long-term use effect of the silane-modified polyether sealant.

[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

[0005] Based on this, the purpose of the present application is to provide a transparent silane-modified polyether sealant with hydrolysis resistance.

[0006] The technical solution for achieving the above-mentioned purpose comprises the following.

[0007] In a first aspect, the present application 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 methyl or ethyl.

[0010] The silane-modified polyether-polybutadiene of the present application is obtained by the reaction of silane-modified polybutadiene and polyether amine, and the silane-modified polybutadiene is obtained by the reaction of hydroxyl-terminated epoxidized polybutadiene and isocyanate silane.

[0011] The structural formula of the hydroxyl-terminated epoxidized polybutadiene is as follows:

[0012]

[0013] The structural formula of the polyether amine is:

[0014]

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

[0016] In a second aspect, the present application provides a preparation method of the silane-modified polyether-polybutadiene, comprising the following steps:

[0017] Under the protection of inert gas, the hydroxyl-terminated epoxidized polybutadiene and isocyanate silane are reacted under the action of a catalyst to obtain silane-modified polybutadiene, and then the polyether amine is added to react, thereby obtaining the silane-modified polyether-polybutadiene.

[0018] In a third aspect, the present application provides a silane-modified polyether sealant, and the preparation raw materials thereof comprise the silane-modified polyether-polybutadiene of the present application.

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

[0020]

[0021]

[0022] In a fourth aspect, the present application provides a preparation method of the silane-modified polyether sealant, comprising the following steps:

[0023] The silane-modified polyether resin, the silane-modified polyether-polybutadiene, part of the plasticizer, fumed white carbon black and the stabilizer are mixed uniformly, and then the water-removing agent, the remaining plasticizer and the coupling agent are sequentially added, and then the stirring and defoaming are carried out under vacuum, thereby obtaining the silane-modified polyether sealant.

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

[0025] The present application uses the hydroxyl-terminated epoxidized polybutadiene to sequentially react with isocyanate silane and polyether amine to obtain a silane-modified polyether-polybutadiene, and the silane-modified polyether-polybutadiene is combined with raw materials such as silane-modified polyether resin to prepare a transparent silane-modified polyether sealant with excellent hydrolysis resistance.

[0026] On one hand, the prepared silane modified polyether-polybutadiene has strong hydrophobicity, and the terminal siloxane group thereof can well hydrolyze and condense with the hydroxyl group on the surface of a substrate, and further form a synergistic effect with the good hydrophobicity of itself, thereby significantly enhancing the water resistance of the polyether sealant. After mixing and curing 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 peeling of the interface layer caused by the swelling of the sealant after water absorption, and improve the water-resistant bonding property 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 during the curing of the glue, thereby ensuring the stability of the sealant during long-term use without the problem of precipitation failure, so that the sealant can maintain very low water permeability for a long time, and has good hydrolysis resistance during long-term use. Moreover, the crosslinking density of the sealant can be increased, thereby improving the long-term use effect of the sealant. On the other hand, the prepared silane modified polyether-polybutadiene 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 improving the hydrolysis resistance of the polyether sealant. Under the synergistic effect of the above-mentioned various structural units, the obtained silane modified polyether sealant has very low water permeability, excellent hydrolysis resistance and mechanical properties, thereby expanding its use range in humid environments.

[0027] The hydroxyl-terminated epoxidized polybutadiene of the present application has good transparency itself, and the polyether-polybutadiene after silane modification also has good transparency, so that the obtained sealant maintains good transparency.

[0028] The alpha-silane terminated silane modified polyether resin and the silane modified polybutadiene in the sealant system of the present application can be rapidly hydrolyzed and crosslinked and cured without additional addition of organic tin catalyst under the action of only amino silane coupling agent, thereby reducing the use and harm of organic tin catalyst and greatly improving the environmental protection performance. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 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 application, the present application will be described more fully below. The present application can be realized 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 disclosed content of the present application more thorough and comprehensive.

[0031] The experimental methods in the following examples, unless otherwise specified, are generally in accordance with conventional conditions or as suggested by the manufacturer. The various common chemical reagents used in the examples are commercially available.

[0032] Unless otherwise defined, all technical and scientific terms used in the application have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety.

[0033] In addition, as used in this application, the term "or" is the inclusive "or" and not the

[0034] In some embodiments, a silane-modified polyether-polybutadiene is involved, which has the following structural formula:

[0035]

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

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

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

[0039] The silane-modified polyether-polybutadiene of the present application is obtained by the reaction of a silane-modified polybutadiene and a polyether amine, wherein the silane-modified polybutadiene is obtained by the reaction of a hydroxyl-terminated epoxidized polybutadiene and an isocyanate silane.

[0040] The hydroxyl-terminated epoxidized polybutadiene has the following structural formula:

[0041]

[0042] The polyether amine has the following structural formula:

[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 hydroxyl-terminated epoxidized polybutadiene to the isocyanate silane is 1 : 1-2, more preferably 1 : 1.5-2. For example, 1 : 1, 1 : 1.2, 1 : 1.4, 1 : 1.6, 1 : 1.8, or 1 : 2, and the like, preferably 1 : 2.

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

[0047] In some preferred embodiments, the hydroxyl value of the hydroxyl-terminated epoxidized polybutadiene is 0.17-0.20 mol / 100 g. For example, 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, and the like.

[0048] In some preferred embodiments, the epoxy value of the hydroxyl-terminated epoxidized polybutadiene is 0.20-0.30 mol / 100 g. For example, 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, and the like.

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

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

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

[0052] In some preferred embodiments, the isocyanate silane is at least one of 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropylmethyldimethoxysilane. It can also be a combination of at least two, such as a combination of 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane, a combination of 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropylmethyldimethoxysilane, etc., and more preferably isocyanatopropyltrimethoxysilane.

[0053] In the present application, the silane-modified polyether-polybutadiene enhances the compatibility of the two resins due to having the same polyoxyalkyl ether chain structure as the silane-modified polyether resin, thereby maintaining the transparency of the polymer itself, while the siloxane group participates in the reaction during the curing of the base resin, thereby ensuring the water resistance stability during long-term use without precipitation failure. In addition, the α-silane-terminated silane-modified polyether resin and the silane-modified polyether-polybutadiene having a similar structure to the amino silane coupling agent used in the system of the present application can be rapidly hydrolyzed and cross-linked and cured without the need for additional addition of an organic tin catalyst under the catalysis of only the amino silane, thereby reducing the use and harm of organic tin and improving the environmental performance thereof.

[0054] In some embodiments, a method for preparing the silane-modified polyether-polybutadiene is also involved, comprising the following steps:

[0055] Under the protection of inert gas, the hydroxyl-terminated epoxidized polybutadiene and the isocyanate silane are reacted in the presence of a catalyst to obtain a silane-modified polybutadiene, and then the polyether amine is added to react, thereby obtaining the silane-modified polyether-polybutadiene.

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

[0057] In some preferred embodiments, 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; 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 2-6h; for example, 2h, 3h, 4h, 5h or 6h, etc.

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

[0060] Also involved in some embodiments is a silane-modified polyether sealant prepared from raw materials including the silane-modified polyether-polybutadiene described herein.

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

[0062]

[0063]

[0064] For example, the silane-modified polyether resin can be used in an amount of 30 parts, 32 parts, 35 parts, 40 parts, 45 parts, or 50 parts, etc.; the silane-modified polyether-polybutadiene can be used in an amount of 5 parts, 8 parts, 11 parts, 13 parts, or 15 parts, etc.; the plasticizer can be used in an amount of 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, or 45 parts, etc.; the fumed white carbon black can be used in an amount of 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, or 15 parts, etc.; the stabilizer can be used in an amount of 1 part, 1.5 parts, 2 parts, 2.5 parts, or 3 parts, etc.; the water scavenger can be used in an amount of 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, or 3 parts, etc.; and the coupling agent can be used in an amount of 0.5 parts, 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 by weight:

[0066]

[0067] In some embodiments, the silane-modified polyether resin is an alpha-silane terminated silane-modified polyether resin having the structure:

[0068]

[0069] wherein Polyol is a polyether segment, preferably selected from at least one of STP-E10, STP-E30, and STP-XB502. 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 of PPG2000, PPG3000, PPG5000, diisononyl phthalate and diisodecyl phthalate.

[0071] In some embodiments, the fumed white carbon black is a hydrophobic fumed white carbon black, preferably at least one of Wacker DeGussa R974, Wacker DeGussa R972, at least one of Cabot TS620 and Cabot TS610.

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

[0073] In some embodiments, the water-removing agent is a vinyl silane water-removing agent, preferably at least one of vinyl triethoxysilane, vinyl trimethoxysilane and vinyl methyl dimethoxysilane.

[0074] In some embodiments, the coupling agent is an amino silane coupling agent, preferably at least one of 3-aminopropyl trimethoxysilane (KH540), 3-aminopropyl triethoxysilane (KH550) and N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane (KH792).

[0075] The present application uses α-silane-terminated silane-modified polyether resin as the base resin, by adding a certain amount of silane-modified polyether-polybutadiene and reasonably adjusting the specific gravity of each component, a one-component silane-modified polyether sealant with good transparency and water resistance is prepared. On the one hand, the prepared silane-modified polyether-polybutadiene and the silane-modified polyether resin have good compatibility due to the same polyoxyalkyl ether chain structure, thus the transparency of the base resin itself is maintained to the greatest extent. On the other hand, the silane-modified polyether-polybutadiene of the present application contains hydrolyzable condensation alkoxyl groups, which can participate in the curing reaction in the crosslinking process, not only solving the problem of small molecule substance precipitation of the sealant after long-term use, but also increasing the crosslinking density of the sealant, thereby improving the long-term use effect of the sealant.

[0076] In some embodiments, a preparation method of the silane-modified polyether sealant is also involved, comprising the following steps:

[0077] The silane-modified polyether resin, silane-modified polyether-polybutadiene, partial plasticizer, fumed white carbon black and stabilizer are mixed uniformly, and then the water-removing agent, residual plasticizer and coupling agent are added in sequence, and stirred and defoamed under vacuum condition, to obtain the product.

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

[0079] In some preferred embodiments, the stirring and defoaming speed is 10-30 rpm, for example 10 rpm, 15 rpm, 20 rpm, 25 rpm or 30 rpm, etc.; and the time is 20-40 min, for example 20 min, 25 min, 30 min, 35 min or 40 min, etc.

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

[0081] The application will be further described in detail below with reference to specific embodiments.

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

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

[0084]

[0085] In the formula, Polyol is a polyether segment.

[0086] The general structure of the hydroxyl-terminated epoxidized polybutadiene is:

[0087]

[0088] The general structure of the polyether amine is:

[0089]

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

[0091] (1) the reaction of the hydroxyl groups in the hydroxyl-terminated epoxidized polybutadiene and the isocyanate groups in the isocyanate silane to obtain a silane-modified polybutadiene intermediate:

[0092]

[0093] (2) the reaction of the amino groups in the polyether amine and the epoxy groups in the silane-modified polybutadiene intermediate to obtain a 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 glue provided in this example are as follows:

[0098] Silane-modified polyether resin (Wacker's Silres® STP-E10) 43 parts

[0099]

[0100] wherein the structure of the silane-modified polyether-polybutadiene is as follows:

[0101]

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

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

[0104] (1) According to a molar ratio of 1:1.5 of the hydroxyl-terminated epoxidized polybutadiene (Krayt's Polybd 600E, a = 0.68, b = 0.2, c = 0.12, hydroxyl value = 0.186 mol / 100g, epoxy value = 0.22 mol / 100g) and the isocyanate propyl trimethoxysilane, the isocyanate propyl trimethoxysilane is slowly added dropwise in the hydroxyl-terminated epoxidized polybutadiene, and a catalyst dibutyltin dilaurate is added, and the system is stirred under nitrogen protection for about 5h (until no isocyanate groups are detected in the system by di-n-butylamine back titration method, the reaction is stopped), to obtain a silane-modified polybutadiene intermediate.

[0105] wherein the amount of the added dibutyltin dilaurate is 0.05% of the total mass of the hydroxyl-terminated epoxidized polybutadiene and the isocyanate propyl trimethoxysilane.

[0106] (2) According to the molar number of amino group in polyether amine and the molar number of epoxy group in intermediate product is 2:1, polyether amine D400 is added into the intermediate product of step (1), and the temperature is raised to 50℃, and the reaction is carried out for 4h to obtain silane modified polyether-polybutadiene.

[0107] FT-IR spectrum analysis (see Figure 1 ) shows that: it appears characteristic peaks at 3362cm -1 (-N-H), 1739cm -1 (-C=O), and no characteristic absorption peak is found at 2268cm -1 (-NCO), which indicates that isocyanate silane has been grafted to the polybutadiene main chain, and shows the stretching vibration absorption peaks belonging to Si-O and C-O at 1100cm -1 and 1080cm -1 , which proves that the silane modified polyether-polybutadiene with the above structural formula is synthesized.

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

[0109] The silane modified polyether resin, the silane modified polyether-polybutadiene, the fumed white carbon black, the stabilizer and part of the plasticizer are mixed at 30rpm for 50min to be stirred uniformly, the water removing agent is added, the low-speed stirring is carried out at 20rpm for 20min, finally the remaining plasticizer and the coupling agent are added, the defoaming is carried out under the vacuum condition of-0.092MPa at the stirring speed of 10rpm for 30min to obtain the transparent hydrolysis-resistant silane modified polyether glue.

[0110] Example 2

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

[0112]

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

[0114]

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

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

[0117] (1) According to the molar ratio of end hydroxyl epoxidized polybutadiene and isocyanate propyl triethoxysilane is 1:1.8, slowly drop isocyanate propyl triethoxysilane in end hydroxyl epoxidized polybutadiene (Krewel Polybd 600E, a=0.68, b=0.2, c=0.12, hydroxyl value is 0.186 mol / 100g, epoxy value is 0.22 mol / 100g), and add catalyst dibutyl tin dilaurate, stir under nitrogen protection for about 5h (stop the reaction until there is no isocyanate group in the system measured by di-n-butylamine back titration method), to obtain the silane modified polybutadiene intermediate product.

[0118] Wherein, the addition amount of dibutyl tin dilaurate is 0.05% of the total mass of end hydroxyl epoxidized polybutadiene and isocyanate propyl triethoxysilane.

[0119] (2) According to the molar ratio of amino group in polyether amine and epoxy group in intermediate product is 2:1, add polyether amine D800 to the intermediate product of step (1), slowly warm up to 50℃, and react for 4h to obtain the silane modified polyether-polybutadiene.

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

[0121] Mix the silane modified polyether resin, the silane modified polyether-polybutadiene, the fumed white carbon black, the stabilizer, and part of the plasticizer at 35rpm for 45min until they are stirred uniformly, add the water removing agent, stir at low speed of 25rpm for 30min, finally add the remaining plasticizer and the coupling agent, and stir under the vacuum condition of-0.092MPa at the stirring speed of 10rpm for 20min to remove bubbles, 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 by the embodiment are as follows:

[0124]

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

[0126]

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

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

[0129] (1) According to the molar ratio of end hydroxyl epoxidized polybutadiene and isocyanate propyl trimethoxysilane is 1:1.6, slowly drop isocyanate propyl trimethoxysilane in end hydroxyl epoxidized polybutadiene (Krewel Polybd 600E, a = 0.68, b = 0.2, c = 0.12, hydroxyl value is 0.186 mol / 100g, epoxy value is 0.22 mol / 100g) and add catalyst dibutyl tin dilaurate, stir under nitrogen protection for about 4h (stop the reaction until there is no isocyanate group in the system measured by di-n-butylamine back titration method), to obtain the silane modified polybutadiene intermediate product.

[0130] Among them, the addition amount of dibutyl tin dilaurate is 0.05% of the total mass of end hydroxyl epoxidized polybutadiene and isocyanate propyl trimethoxysilane.

[0131] (2) According to the molar number of amino group in polyetheramine and the molar number of epoxy group in the intermediate product is 2:1, polyetheramine D1000 is added to the intermediate product of step (1), slowly heated to 50℃, and reacted for 4h to obtain the silane modified polyether-polybutadiene.

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

[0133] The silane modified polyether resin, the silane modified polyether-polybutadiene, the fumed white carbon black, the stabilizer and part of the plasticizer are mixed at 30 rpm for 50 min to be stirred uniformly, the water removing agent is added, stirred at low speed of 20 rpm for 20 min, finally the remaining plasticizer and the coupling agent are added, and the defoaming is carried out under the vacuum condition of -0.092 MPa at the stirring speed of 15 rpm for 25 min 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 by the 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 white carbon black (Germany Wacker R972) 6 parts

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

[0141] Water removing agent (vinyl triethoxysilane) 1 part

[0142] Coupling agent (N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane, KH792) 2 parts.

[0143] wherein, the structure of silane modified polyether-polybutadiene is as follows:

[0144]

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

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

[0147] (1) According to the molar ratio of end hydroxyl epoxidized polybutadiene and isocyanate propyl trimethoxysilane is 1:2, slowly drop isocyanate propyl trimethoxysilane in end hydroxyl epoxidized polybutadiene (Krayville Polybd 600E, a = 0.68, b = 0.2, c = 0.12, hydroxyl value is 0.186 mol / 100g, epoxy value is 0.22 mol / 100g), and add catalyst dibutyl tin dilaurate, stir under nitrogen protection for about 4h (until there is no isocyanate group in the system measured by di-n-butylamine back titration method, stop the reaction), to obtain the silane modified polybutadiene intermediate product.

[0148] wherein, the addition amount of dibutyl tin dilaurate is 0.05% of the total mass of end hydroxyl epoxidized polybutadiene and isocyanate propyl trimethoxysilane.

[0149] (2) According to the molar number of amino group in polyether amine and the molar number of epoxy group in the intermediate product is 2:1, add polyether amine D800 to the intermediate product of step (1), slowly warm up to 50℃, react for 4h, to obtain the silane modified polyether-polybutadiene.

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

[0151] Mix the silane modified polyether resin, the silane modified polyether-polybutadiene, the fumed white carbon black, the stabilizer and part of the plasticizer at 30rpm for 45min to stir uniformly, add the water removing agent, stir at low speed of 20rpm for 20min, finally add the remaining plasticizer and the coupling agent, stir under the vacuum condition of-0.092MPa at the stirring speed of 15rpm for 30min to remove bubbles, 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 by the embodiment are as follows:

[0154]

[0155] wherein the silane-modified polyether-polybutadiene has the following structure:

[0156]

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

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

[0159] (1) According to the molar ratio of the terminal hydroxyl epoxidized polybutadiene and isocyanate propyl triethoxysilane is 1:2, slowly drop the isocyanate propyl triethoxysilane in the terminal hydroxyl epoxidized polybutadiene (Kewei Polybd 600E, a = 0.68, b = 0.2, c = 0.12, hydroxyl value is 0.186 mol / 100g, epoxy value is 0.22 mol / 100g), and add the catalyst dibutyltin dilaurate, stir under nitrogen protection for about 4h (until there is no isocyanate group in the system measured by di-n-butylamine back titration method, stop the reaction), to obtain the silane-modified polybutadiene intermediate product.

[0160] wherein the addition amount of dibutyltin dilaurate is 0.05% of the total mass of the terminal hydroxyl epoxidized polybutadiene and isocyanate propyl triethoxysilane.

[0161] (2) According to the molar number of amino groups in the polyetheramine and the molar number of epoxy groups in the intermediate product is 2:1, add the polyetheramine D400 to the intermediate product of step (1), slowly warm up to 50°C, and react for 4h to obtain the silane-modified polyether-polybutadiene.

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

[0163] Mix the silane-modified polyether resin, the silane-modified polyether-polybutadiene, the fumed white carbon black, the stabilizer, and part of the plasticizer at 25 rpm for 40 min until they are stirred uniformly, add a water removal agent, stir at a low speed of 20 rpm for 20 min, finally add the remaining plasticizer and the coupling agent, and stir to degas under a vacuum condition of -0.092 MPa at a stirring speed of 15 rpm for 25 min to obtain the transparent hydrolysis-resistant silane-modified polyether adhesive.

[0164] Comparative Example 1:

[0165] The transparent hydrolysis-resistant silane-modified polyether sealant provided by the comparative example is different from the preparation method of Example 1 in that the silane-modified polyether-polybutadiene is not added, the weight fraction of the silane-modified polyether resin (STP-E10) is 50 parts, and the rest is the same as Example 1.

[0166] Comparative Example 2:

[0167] The transparent hydrolysis-resistant silane-modified polyether sealant provided by the present comparative example is prepared in the same way as in Example 1, except that the silane-modified polyether-polybutadiene is replaced by a hydroxyl-terminated epoxidized polybutadiene (Kraton Poly bd 600E, a = 0.68, b = 0.2, c = 0.12, hydroxyl value = 0.186 mol / 100 g, epoxy value = 0.22 mol / 100 g).

[0168] Comparative Example 3

[0169] The transparent hydrolysis-resistant silane-modified polyether sealant provided by the present comparative example is prepared in the same way as in Example 1, except that the silane-modified polyether-polybutadiene is replaced by the silane-modified polybutadiene intermediate prepared in step (1) of Example 1. The details are as follows:

[0170] The raw materials for preparing the transparent hydrolysis-resistant silane-modified polyether sealant provided by the present comparative example are as follows:

[0171]

[0172] The silane-modified polybutadiene intermediate is prepared by the following method:

[0173] The isocyanate propyl trimethoxysilane is slowly added to the hydroxyl-terminated epoxidized polybutadiene (Kraton Poly bd 600E, a = 0.68, b = 0.2, c = 0.12, hydroxyl value = 0.186 mol / 100 g, epoxy value = 0.22 mol / 100 g) at a molar ratio of 1:1.5, and a catalyst, dibutyltin dilaurate, is added, and the reaction is stirred for about 5 h under nitrogen protection (until there is no isocyanate group in the system as measured by the di-n-butylamine back titration method, the reaction is stopped), to obtain the silane-modified polybutadiene intermediate.

[0174] The amount of dibutyltin dilaurate added is 0.05% of the total mass of the hydroxyl-terminated epoxidized polybutadiene and the isocyanate propyl trimethoxysilane.

[0175] The preparation method of the transparent hydrolysis-resistant silane-modified polyether sealant provided by the present comparative example is as follows:

[0176] The silane modified polyether resin, the silane modified polybutadiene intermediate product, the fumed white carbon black, the stabilizer and part of the plasticizer are mixed at 30 rpm for 50 min to be stirred uniformly, the water removing agent is added, low speed stirring is carried out at 20 rpm for 20 min, finally the remaining plasticizer and the coupling agent are added, and the defoaming is carried out under the condition of-0.092 vacuum at the stirring speed of 10 rpm for 30 min, so that the transparent hydrolysis resistant silane modified polyether glue is obtained.

[0177] Comparative Example 4

[0178] The transparent hydrolysis resistant silane modified polyether sealant provided by the comparative example is prepared by replacing the silane modified polyether-polybutadiene in the preparation method of Example 1 with polyether-polybutadiene, and the rest is the same as Example 1. Specifically as follows:

[0179] The raw materials for preparing the transparent hydrolysis resistant silane modified polyether glue provided by the comparative example are as follows:

[0180]

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

[0182] According to the molar number of amino groups in the polyether amine and the molar number of epoxy groups in the hydroxyl-terminated epoxidized polybutadiene, the polyether amine D400 is added to the hydroxyl-terminated epoxidized polybutadiene (Kewei Polybd 600E, a=0.68, b=0.2, c=0.12, hydroxyl value is 0.186 mol / 100g, epoxy value is 0.22 mol / 100g), and the temperature is raised to 50°C, and the reaction is carried out for 4h to obtain the polyether-polybutadiene.

[0183] The preparation method of the transparent hydrolysis resistant silane modified polyether glue provided by the example is as follows:

[0184] The silane modified polyether resin, the polyether-polybutadiene, the fumed white carbon black, the stabilizer and part of the plasticizer are mixed at 30 rpm for 50 min to be stirred uniformly, the water removing agent is added, low speed stirring is carried out at 20 rpm for 20 min, finally the remaining plasticizer and the coupling agent are added, and the defoaming is carried out under the condition of-0.092 vacuum at the stirring speed of 10 rpm for 30 min, so that the transparent hydrolysis resistant silane modified polyether glue is obtained.

[0185] Comparative Example 5:

[0186] The transparent hydrolysis resistant silane modified polyether sealant provided by the comparative example is prepared by replacing the silane modified polybutadiene in the preparation method of Example 2 with the same mass fraction of silane modified polyether resin (STP-E30), and the rest is the same as Example 2.

[0187] Comparative Example 6:

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

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

[0190] Tack-free 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 transmission: tested according to GB / T 1037-2021 standard.

[0193] Light transmittance: tested according to GB / T 2410-2008 standard. A 2mm thick sealant film was prepared, and a SM-2 type light transmittance tester was used to test the light transmittance thereof.

[0194] Waterproof sealing: tested according to GB / T 4208-2017 standard. A color-changing silicone was placed inside a square aluminum cavity with a skirt, a waterproof sealing model was prepared, and the sealant to be tested was used to bond between the glass and the skirt. After curing, the water absorption of the internal color-changing silicone was observed by bonding the glass plate and the aluminum model, and the sealing performance of the square cavity was detected. The result of waterproof sealing was mainly observed by whether the color-changing silicone in the waterproof sealing model appeared color change. If the silicone turned red, it meant that the waterproof sealing performance was failed, and if the silicone remained blue, it meant that the waterproof sealing performance was good.

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

[0196] Table 1

[0197]

[0198]

[0199] From the experimental results of Table 1, it can be seen that the transparent hydrolysis-resistant silane-modified polyether sealant prepared by the present application, after adding the silane-modified polyether-polybutadiene, has a lower water vapor transmission rate while maintaining good transparency, and after the sealant is prepared into a waterproof sealing model and immersed in water for 12 months, the internal discolored silicone remains blue, indicating that it has good waterproof sealing effect. The silane-modified polyether sealant prepared without adding silane-modified polyether-polybutadiene (Comparative Example 1 and Comparative Example 5) and the silane-modified polyether sealant prepared by directly adding hydroxyl-terminated epoxidized polybutadiene (Comparative Example 2) have a higher water vapor transmission rate, and after they are respectively prepared into a waterproof sealing model and immersed in water for 3 months, discoloration of the silicone inside the model occurs, indicating that they have poor long-term water-resistant bonding effect. This result also indicates that the unmodified hydroxyl-terminated epoxidized polybutadiene can only act as a partial plasticizer in the sealant, and with the passage of time, the sealant will precipitate the hydroxyl-terminated epoxidized polybutadiene, thus failing to achieve good water resistance, resulting in the interface layer peeling off due to water absorption and swelling during long-term immersion in water. The addition of the silane-modified polyether-polybutadiene prepared by the present application can ensure its stability during long-term use without causing precipitation failure, thus effectively reducing the water permeability of the sealant and improving its hydrolysis resistance.

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

[0201] The waterproof sealing model prepared from the commercially available transparent silane-modified polyether sealant of Comparative Example 6 also exhibits discoloration of the silicone after being immersed in water for 3 months, indicating that the waterproof sealing performance is ineffective.

[0202] Comparative Example 3 and Comparative Example 4 each use only isocyanate propyl trimethoxysilane or polyether amine to graft-modify the hydroxyl-terminated epoxidized polybutadiene, and the waterproof performance of the obtained silane-modified polyether sealant is improved compared to Comparative Example 1 without adding polybutadiene, but its waterproof performance, mechanical properties, and light transmittance are all poorer than Example 1. This indicates that the graft modification of polybutadiene with isocyanate propyl trimethoxysilane and polyether amine simultaneously has a synergistic effect, which can more effectively improve the waterproof and water-resistant performance of the obtained polyether sealant, while maintaining good light transmittance and mechanical properties.

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

[0204] The above-mentioned embodiments only express several embodiments of the application, which are described in detail and specifically, but cannot be understood as a limitation to the scope of the patent right of the application. It should be pointed out that, for those skilled in the art, several modifications and improvements can be made without departing from the concept of the application, which all belong to the protection scope of the application. Therefore, the protection scope of the patent right of the application should be subject to the appended claims.

Claims

1. A silane-modified polyether-polybutadiene, characterized in that, Its structural formula is as follows: Where n and m are positive integers, and the ratio of n to m is (2~5):1, and R is methyl or ethyl; a=0.6~0.7, b=0.18~0.22, c=0.1~0.

15.

2. The silane-modified polyether-polybutadiene according to claim 1, characterized in that, a=0.68, b=0.2, c=0.

12.

3. A silane-modified polyether-polybutadiene, characterized in that, It is obtained by reacting silane-modified polybutadiene with polyetheramine, wherein the silane-modified polybutadiene is obtained by reacting hydroxyl-terminated epoxidized polybutadiene with isocyanate silane; The structural formula of the hydroxyl-terminated epoxidized polybutadiene is: Where a = 0.6–0.7, b = 0.18–0.22, and c = 0.1–0.15; The structural formula of the polyetheramine is: Where n and m are positive integers, and the ratio of n to m is (2~5):

1.

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

5. The silane-modified polyether-polybutadiene according to claim 4, characterized in that, The molar ratio of the terminal hydroxyl epoxidized polybutadiene to isocyanate silane is 1:1.5 to 2.

6. The silane-modified polyether-polybutadiene according to claim 4, characterized in that, The molar ratio of epoxy groups in the silane-modified polybutadiene to amino groups in the polyetheramine is 1:1.8-2.

7. The silane-modified polyether-polybutadiene according to any one of claims 3-6, characterized in that, The hydroxyl-terminated epoxidized polybutadiene has a hydroxyl value of 0.17–0.2 mol / 100 g; and / or, The hydroxyl-terminated epoxidized polybutadiene has an epoxy value of 0.20–0.30 mol / 100g; and / or, The polyetheramine has a molecular weight of 400–3000; and / or, The isocyanate silane is 3-isocyanatepropylalkoxysilane.

8. The silane-modified polyether-polybutadiene according to claim 7, characterized in that, The molecular weight of the polyetheramine is 400 to 2000.

9. The silane-modified polyether-polybutadiene according to claim 7, characterized in that, The isocyanate silane is at least one selected from 3-isocyanate propyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, and 3-isocyanate propylmethyldimethoxysilane.

10. A method for preparing silane-modified polyether-polybutadiene according to any one of claims 3-9, characterized in that, Includes the following steps: Under inert gas protection, the terminal hydroxyl epoxidized polybutadiene and isocyanate silane react in the presence of a catalyst to obtain silane-modified polybutadiene, which is then reacted with the polyether amine to obtain the silane-modified polyether-polybutadiene.

11. The method for preparing silane-modified polyether-polybutadiene according to claim 10, characterized in that, The catalyst is dibutyltin dilaurate; and / or The catalyst is added in an amount of 0.02–0.5% of the total mass of the terminal hydroxyl-terminated epoxidized polybutadiene and isocyanate silane; and / or, The reaction time for hydroxyl-terminated epoxidized polybutadiene and isocyanate silane is 2 h to 6 h; and / or, The reaction temperature of silane-modified polybutadiene with the polyetheramine is 50℃~60℃, and the reaction time is 2h~6h.

12. A silane-modified polyether sealant, characterized in that, The raw materials used in its preparation include the silane-modified polyether-polybutadiene as described in any one of claims 1-9.

13. The silane-modified polyether sealant according to claim 12, characterized in that, It is prepared from raw materials comprising the following components, in parts by weight:

14. The silane-modified polyether sealant according to claim 13, characterized in that, The silane-modified polyether sealant is prepared from raw materials comprising the following components, by weight:

15. The silane-modified polyether sealant according to claim 13 or 14, 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; and / or, The plasticizer is a polyether polyol or phthalate plasticizer; and / or... The fumed silica is a hydrophobic fumed silica; and / or... The stabilizer is selected from at least one of Tinuvin 326, Tinuvin 770, Tinuvin 328, and Tinuvin 540; and / or, The dehydrating agent is a vinylsilane-based dehydrating agent; and / or, The coupling agent is an aminosilane coupling agent.

16. The silane-modified polyether sealant according to claim 15, characterized in that, The silane-modified polyether resin is selected from... STP-E10 STP-E30 and At least one of STP-XB502.

17. The silane-modified polyether sealant according to claim 15, characterized in that, The plasticizer is selected from at least one of PPG2000, PPG3000, PPG5000, diisononyl phthalate, and diisodecyl phthalate.

18. The silane-modified polyether sealant according to claim 15, characterized in that, The fumed silica is selected from Evonik Degussa R974 and Evonik Degussa R972. H18 At least one of H20, Cabot TS620 and Cabot TS610.

19. The silane-modified polyether sealant according to claim 15, characterized in that, The dehydrating agent is selected from at least one of vinyltriethoxysilane, vinyltrimethoxysilane, and vinylmethyldimethoxysilane.

20. The silane-modified polyether sealant according to claim 15, characterized in that, The coupling agent is selected from at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane.

21. A method for preparing the silane-modified polyether sealant according to any one of claims 13-20, characterized in that, Includes the following steps: The silane-modified polyether resin, silane-modified polyether-polybutadiene, a portion of the plasticizer, fumed silica and stabilizer are mixed evenly, and then the dehydrating agent, the remaining plasticizer and coupling agent are added in sequence. The mixture is stirred and degassed under vacuum to obtain the final product.

22. The method for preparing the silane-modified polyether sealant according to claim 21, characterized in that, The mixing speed is 20 rpm to 50 rpm, and the mixing time is 30 min to 60 min.

23. The method for preparing the silane-modified polyether sealant according to claim 21, characterized in that, The stirring and degassing speed is 10 rpm to 30 rpm, and the time is 20 min to 40 min.

24. The method for preparing the silane-modified polyether sealant according to claim 22, characterized in that, The vacuum level of the vacuum condition is -0.09MPa to -0.1MPa.

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