Comb-shaped silane-terminated polyurethane polymer resins, methods of making and using the same

Abstract

The application provides a comb-type silane-terminated polyurethane polymer resin and a preparation method and application thereof. The comb-type silane-terminated polyurethane polymer resin is prepared from diisocyanate without an aromatic ring structure, polycaprolactone-type triol, polyether polyol prepared by a DMC process, a catalyst, an organic functional silane, a water-removing agent and a small-molecule saturated fatty alcohol, does not contain free NCO groups and organic mercury, lead and tin, can achieve a viscosity less than 25000 mpa*s, a storage stability greater than 12 months and strong yellowing resistance. By adding appropriate amounts of a plasticizer, a composite light stabilizer, a filler, a water-removing agent, a thixotropic agent, a coupling agent and a catalyst, a moisture-curable polymer adhesive with excellent comprehensive performance can be prepared, and the adhesive can be widely used in the elastic bonding and sealing between aluminum materials, stainless steel, galvanized plates, PVC, PC, ABS, ceramic tiles and wood floors and the like without primer coating, the body strength can be greater than 3 MPa, the elongation at break is greater than 450%, the failure mode is cohesive failure, and good bonding strength is achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of silane-modified polyurethane materials, in particular to an organic functional comb-type silane-terminated polyurethane polymer resin, a preparation method and application thereof. BACKGROUND

[0002] Polyurethane materials can obtain different structures and properties by adjusting the types and proportions of hard segments and soft segments due to their unique molecular structure of embedded hard segments and soft segments. The adhesives prepared from polyurethane materials are widely used in bonding and sealing in various fields. However, due to the influence of its own structure, the -NCO group contained in the polyurethane adhesive is prone to react with moisture in the air, generating carbon dioxide and producing bubbles during the curing process. When the product is exposed to moisture or humid weather, it will seriously affect the workability and bonding reliability of the product. On the other hand, the adhesion of polyurethane adhesive to different substrates is poor in universality. Different substrates often require different adhesive formulations. For some low-surface-energy metal or plastic materials, a solvent-containing primer or expensive and complex plasma equipment is usually required to treat the material surface to obtain good adhesion, which brings many inconveniences to actual production and causes certain pollution to the environment.

[0003] Silicone adhesives have good weather resistance and substrate adaptability, and are roughly divided into deacid type glue, dealcohol type glue and deoxime type glue. Traditional silicone sealant will precipitate silicone oil, which will attach to pollutants, especially for porous materials, which will cause difficult-to-remove pollution to the surrounding environment, and the surface cannot be painted. Different color requirements of glue require a lot of base glue color matching work. During the curing process, small molecules such as acetic acid or ethanol are released, which has a strong odor and can corrode some substrates.

[0004] Silane-modified polyurethane materials can combine the dual advantages of polyurethane and silicone glue, but the adhesives prepared from the current silane-modified polyurethane base resin have small strength, and often need to balance and adjust multiple different molecular chains and structures of the base resin to have corresponding performance indicators such as strength and elongation. The bonding strength is generally less than 2 MPa, and the elongation at break is less than 450%. The viscosity of the base resin is generally greater than 35,000 mPa*s, which limits the production and market application of downstream adhesives. SUMMARY

[0005] In view of the technical problems existing in the prior art, the present application aims to provide a comb-type silane-terminated polyurethane polymer resin, which can achieve a viscosity of less than 25000 mpa*s, a storage stability of more than 12 months, strong yellowing resistance, and can simultaneously endow the adhesive with good comprehensive performance such as moisture resistance, bonding strength, and elongation at break, so as to facilitate the bonding of the adhesive with different substrates without treatment, and the small viscosity facilitates the production process of downstream adhesive manufacturers.

[0006] The present application achieves the above technical purpose by the following technical solutions:

[0007] The present application provides a comb-type silane-terminated polyurethane polymer resin, which is prepared from the following raw materials in parts by weight: diisocyanate 1-3 parts, polymer polyol 1-3 parts, high molecular weight polyether polyol 90-98 parts, catalyst A 0.001-0.02 parts, organic functional silane 1-4 parts, small molecule saturated fatty alcohol 0.1-1 parts, and water removal agent A 0.1-1 parts; wherein the high molecular weight polyether polyol is a polyether polyol prepared by DMC process, with a functionality of 2 and a molecular weight of 8000-18000 g / mol; the catalyst A is an organic bismuth catalyst; the diisocyanate is a diisocyanate without aromatic ring structure; the polymer polyol is a polycaprolactone-type triol, with a functionality of 3 and a molecular weight of 300-1000 g / mol, and further, its structural formula is as follows,

[0008]

[0009] wherein 1.4≦x+y+z≦7.

[0010] As a preferred embodiment, the comb-type silane-terminated polyurethane polymer resin is prepared from the following raw materials in parts by weight: diisocyanate 1.3-2.28 parts, polymer polyol 1.7-2.48 parts, catalyst A 0.002-0.015 parts, high molecular weight polyether polyol 93-95 parts, organic functional silane 1.4-2.3 parts, small molecule saturated fatty alcohol 0.3-0.5 parts, and water removal agent A 0.3-0.5 parts.

[0011] In some embodiments, the polycaprolactone triol is selected from at least one of Capa 3031, Capa 3041, Capa 3050, Capa 3091 produced by Perstorp Company, France, PCL-3057, PCL-3087 produced by Hunan Poly Ren Company. C280、 C2120、 C2180.

[0012] As a preferred embodiment, the diisocyanate is selected from at least one of isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), hydrogenated xylene diisocyanate, cyclohexane dimethyldiisocyanate, 2,5(2,6)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane), 1,6-hexane diisocyanate.

[0013] As a preferred embodiment, the organofunctional silane is an NCO-terminated alkoxysilane coupling agent with the structure as follows:

[0014]

[0015] wherein R1 is selected from -CH3, -CH2CH3, -OCH3, -OCH2CH3,

[0016] R2 is selected from -CH3, -CH2CH3, -OCH3, -OCH2CH3, R3 is selected from one of -OCH3, -OCH2CH3, and R4 is selected from one of -CH2- or -(CH2)3-; further, the organofunctional silane is selected from at least one of 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 3-isocyanatopropyl dimethoxysilane, 3-isocyanatopropyl diethoxysilane, a-isocyanatomethyl trimethoxysilane, a-isocyanatomethyl triethoxysilane, a-isocyanatomethyl dimethoxysilane, a-isocyanatomethyl diethoxysilane.

[0017] As a preferred embodiment, the small molecule saturated fatty alcohol is at least one of a small molecule monohydric alcohol or a small molecule dihydric alcohol. Further, the small molecule saturated fatty alcohol is selected from at least one of a saturated fatty primary alcohol, a saturated fatty secondary alcohol, a saturated fatty tertiary alcohol, such as at least one of methanol, ethylene glycol, diethylene glycol, t-butyl alcohol.

[0018] As a preferred embodiment, the water scavenger A is at least one of vinyl silane, such as vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri(methoxyethoxy)silane.

[0019] As a preferred embodiment, the molar ratio of -NCO in diisocyanate to -OH in polycaprolactone triol is (2-2.2):1, and more preferably, the R value (molar ratio of -NCO / -OH) of diisocyanate to polycaprolactone triol is 2:1.

[0020] As a preferred embodiment, the typical molecular structure of the comb-shaped silane-terminated polyurethane polymer is as follows:

[0021]

[0022] wherein R5 is the non-NCO intermediate chain of the diisocyanate, and R6 is the non-OH intermediate chain of the high molecular weight polyether polyol.

[0023] The application also provides a preparation method of the above-mentioned comb-shaped silane-terminated polyurethane polymer resin, comprising the following steps: adding the polycaprolactone triol after dehydration treatment and a catalyst into a reaction container, adding diisocyanate after being warmed to 40-60℃, reacting for 1.5-2h under warming to 70-90℃, adding high molecular weight polyether dihydric alcohol, then reacting for 1.5-2h under 70-90℃, and then adding organic functional silane, and continuing to react for 2-3h under 70-90℃.

[0024] The prepolymer is cooled to 25-40℃, the water scavenger is added thereto, and after stirring for 15min, the small molecule saturated aliphatic alcohol is added to remove the unreacted NCO groups in the prepolymer, and then uniform stirring is continued to obtain the product.

[0025] The application also aims to protect the application of the above-mentioned comb-shaped silane-terminated polyurethane polymer resin in preparing the moisture-curable silane-modified polyurethane adhesive.

[0026] The application also provides a moisture-curable silane-modified polyurethane adhesive, which is prepared mainly by compounding the above-mentioned comb-shaped silane-terminated polyurethane polymer resin, water scavenger B, environment-friendly plasticizer, filler, coupling agent, and catalyst B. The specific preparation comprises the following steps:

[0027] The silane-terminated polyurethane polymer resin, plasticizer, composite light stabilizer, filler, water scavenger B, and thixotropic agent are added into a dynamic mixer, vacuum stirring is carried out for 15-30min, then the coupling agent is added, vacuum stirring is continued for 10-20min, finally the catalyst B is added, and vacuum stirring is carried out for 10-20min to obtain the product.

[0028] As a preferred embodiment, the moisture-curable silane-modified polyurethane adhesive is composed of 18-45% of silane-terminated polyurethane polymer resin, 10-30% of plasticizer, 0.2-1% of composite light stabilizer, 40-50% of filler, 0.5-1% of water-removing agent B, 0.5-1.5% of coupling agent, 0.05-1% of catalyst B and 0-2% of thixotropic agent.

[0029] Further, the plasticizer is a commonly commercially available environment-friendly plasticizer, including but not limited to one or more of phosphate plasticizer, epoxy compound plasticizer, alkyl sulfonate plasticizer or polyoxypropylene polyol, polyoxypropylene-ethylene oxide copolymer polyether polyol, the composite light-heat stabilizer is one or more of commonly commercially available benzotriazole, salicylate, benzophenone, hindered amine, phosphite light-heat stabilizer, the filler is one or more of calcium carbonate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, kaolin, silicon powder, halloysite, montmorillonite, bentonite, silica aluminate, titanium white, carbon black, the water-removing agent B is one or more of vinyl silane, p-methyl benzene sulfonic isocyanate, zeolite, oxazolidine compound, the coupling agent is amino silane coupling agent, the catalyst B is organic tin catalyst, and the thixotropic agent is one or more of fumed hydrophobic silica, organically modified bentonite, polyamide wax and polyurea compound.

[0030] Compared with the prior art, the present application has the following advantages:

[0031] The comb-shaped silane-terminated polyurethane polymer resin provided by the application is prepared from specific proportions of isocyanate, polymer triol, high molecular weight polyether polyol, organic functional silane, catalyst, water removing agent and small molecule saturated fatty alcohol. The comb-shaped backbone structure is formed by using polycaprolactone triol, which has higher strength support and hydrolysis resistance compared with ordinary polyols. The high molecular weight polyether polyol prepared by DMC process has narrow molecular weight distribution, reduces side reactions, and the overall viscosity is less than 25000 mpa*s. The comb-shaped molecular structure is prepared by effective bridging between polycaprolactone triol and high molecular weight polyether polyol prepared by DMC process, which can increase the crosslinking density during curing, improve the strength after curing, and the long molecular chain of high molecular weight polyether polyol can also ensure that the system has high elongation at break. The resin system does not contain free NCO groups and organic mercury, lead and tin, has a storage stability of more than 12 months, uses a diisocyanate system without benzene ring structure, avoids yellowing after oxidation of the benzene ring, and has strong yellowing resistance. The comb-shaped silane-terminated polyurethane polymer resin can be prepared into a moisture-curable polymer adhesive with excellent comprehensive performance by adding appropriate plasticizers, composite light stabilizers, fillers, water removing agents, thixotropic agents, coupling agents and catalysts. The adhesive can be widely used in elastic bonding and sealing between various materials such as aluminum, stainless steel, galvanized sheet, PVC, PC / ABS, ceramic tile and wood floor without primer or other special treatment. The body strength is greater than 3 MPa, the elongation at break is greater than 450%, the adhesive failure mode is cohesive failure, and the adhesive has good bonding strength and elongation at break. DETAILED DESCRIPTION

[0032] The application will be further described in conjunction with specific examples, so that those skilled in the art can more clearly understand the application.

[0033] The following examples are used to illustrate the application, but not to limit the scope of the application. Based on the specific examples in the application, all other examples obtained by those skilled in the art without creative labor are within the scope of the application.

[0034] In the examples of the application, all raw material components are commercially available products well known to those skilled in the art, unless otherwise specified. In the examples of the application, the technical means used are conventional means well known to those skilled in the art, unless otherwise specified.

[0035] Key material sources:

[0036] Poly caprolactone triols: functionality 3, molecular weight 300-1000 g / moL, selected from Capa 3031, Capa 3041, Capa 3050, Capa 3091 produced by Perstorp Company of France, PCL-3057, PCL-3087 produced by Hunan Juren Company, Poly-T303, Poly-T305, Poly-T309 produced by Arch Company of the United States.

[0037] High molecular weight polyether polyols: functionality 2, molecular weight 8000-18000 g / moL, selected from DL-8000D, DL-12000D produced by Shandong Lanshengdong Company, BD2-8000A, BD2-12000A, BD2-18000A produced by Huai'an Bad Polyurethane Company, and C280, C2120, C2180.

[0038] Catalyst A: BiCAT 8118, BiCAT 8108 produced by Leading Company, MB19, MB20 produced by Wincat Company, BCAT-T100R, BCAT-E25A, BCAT-E28A, BCAT-E16, BCAT-E20 produced by Guangzhou Yourun Company.

[0039] Example 1

[0040] This example provides a comb-type silane-terminated polyurethane polymer resin, and the reaction raw materials are shown in the following table:

[0041] Raw materials Specific material name or model number Amount (parts) Polycaprolactone triol PCL-3057 1.44 Catalyst A BCAT-T100R 0.002 Diisocyanate Isophorone diisocyanate 1.75 High molecular weight polyether polyol DL-12000D 94.28 Organofunctional silane 3-isocyanatopropyl trimethoxysilane 1.73 Water scavenger A Vinyl trimethoxysilane 0.3 Small molecule saturated aliphatic alcohol Methanol 0.5

[0042] The preparation method comprises the following steps:

[0043] Add dehydrated poly caprolactone triols and catalyst A to the reaction container, heat to 50℃, then add diisocyanate, then react at 80℃ for 1.5h, then add high molecular weight polyether polyols, then continue to react at 80℃ for 2h, then add organic functional silane, and continue to react at 80℃ for 2.5h.

[0044] Cool the polymer to 25-40℃, add water removing agent A to it, stir for 15min, then add small molecule saturated aliphatic alcohol to remove unreacted NCO groups in the prepolymer, and continue to stir until uniform, and then obtain.

[0045] Example 2

[0046] This example provides a comb-type silane-terminated polyurethane polymer resin, and the reaction raw materials are shown in the following table:

[0047] Raw materials Specific material name or model number Amount (parts) Polycaprolactone triol PCL-3087 2.15 Catalyst A BiCAT 8108 0.015 Isocyanate 4,4'-Methylenebis(cyclohexyl isocyanate) 2.04 High molecular weight polyether polyol BD2-12000A 93.44 Organofunctional silane 3-isocyanatopropyl dimethoxysilane 1.56 Water scavenger A Vinyl trimethoxysilane 0.3 Small molecule saturated aliphatic alcohol Diethylene glycol 0.5

[0048] The preparation method is the same as that of Example 1.

[0049] Example 3

[0050] This example provides a comb-type silane-terminated polyurethane polymer resin, and the reaction raw materials are shown in the following table:

[0051]

[0052]

[0053] The preparation method is the same as that of Example 1.

[0054] Example 4

[0055] This example provides a comb-type silane-terminated polyurethane polymer resin, and the reaction raw materials are shown in the following table:

[0056]

[0057] The preparation method is the same as that of Example 1.

[0058] Example 5

[0059] This example provides a comb-type silane-terminated polyurethane polymer resin, and the reaction raw materials are shown in the following table:

[0060]

[0061]

[0062] The preparation method is the same as that of Example 1.

[0063] Comparative Example 1

[0064] This comparative example provides a silane-terminated polyurethane polymer resin, and the preparation method is the same as that of Example 1, except that the polycaprolactone triol is replaced by polyoxypropylene triol N-330, and the catalyst A is replaced by dibutyltin dilaurate.

[0065] Comparative Example 2

[0066] This comparative example provides a silane-terminated polyurethane polymer resin, and the preparation method is basically the same as that of Test Example 1, except that the high molecular weight polyether polyol is replaced by polyether glycol PPG-4000 produced by KOH process.

[0067] Comparative Example 3

[0068] This comparative example provides a silane-terminated polyurethane polymer resin, which is prepared in the same manner as in Test Example 1, except that the reaction raw material is as follows: the diisocyanate is replaced by diphenylmethane diisocyanate, and the catalyst A is replaced by dibutyl tin dilaurate.

[0069] Comparative Example 4

[0070] This comparative example provides a silane-terminated polyurethane polymer resin, which is prepared in the following manner:

[0071] Into a reaction vessel, 96 parts of high molecular weight polyether polyol BD2-12000A after dehydration treatment and 0.01 parts of dibutyl tin dilaurate catalyst were added, and after being warmed to 50°C, 0.8 parts of diphenylmethane diisocyanate was added, and then reacted at 80°C for 2h. Subsequently, 2.4 parts of 3-isocyanate propyl trimethoxysilane was added, and the reaction was continued at 80°C for 2-3h.

[0072] The polymer was cooled to 25-40°C, and 0.3 parts of vinyl trimethoxysilane as a water removing agent was added thereto, and after stirring for 15 min, 0.5 parts of a small molecule saturated aliphatic alcohol methanol was added to remove the unreacted NCO groups in the prepolymer, and the stirring was continued until uniform, and then the product was obtained.

[0073] Physical and chemical properties and application performance testing:

[0074] (1) The silane-terminated polyurethane polymer resins of Examples 1-5 and Comparative Examples 1-4 were respectively tested for appearance, viscosity, yellowing resistance and storage stability.

[0075] Appearance: The test was carried out in accordance with the provisions of GB / T9761, and the appearance color uniformity of the silane-terminated polyurethane polymer resin was observed under natural daylight lighting conditions.

[0076] Viscosity test: The viscosity test method was in accordance with GB / T2794.

[0077] Aging yellowing resistance test: The silane-terminated polyurethane polymer resin was placed in a transparent clean sealed glass bottle, and was aged and heated in an oven at 60°C for 90 days, and whether the resin was yellowed was observed.

[0078] Storage stability test: The silane-terminated polyurethane polymer resin was stored under standard environment (temperature 23±2°C, humidity 50±5%), and whether there was turbidity or skinning was observed every 30 days.

[0079] The test results are shown in the following table:

[0080]

[0081]

[0082] As can be seen from the above table, compared with Comparative Examples 1, 3 and 4, the silane-terminated polyurethane polymer resins prepared in Examples 1-5 are clear and transparent in appearance, have viscosity of 15000-25000 mPa*s, good yellowing resistance and good storage stability. Compared with Comparative Example 2, the high molecular weight chain polyether polyol produced by DMC process has narrower molecular weight distribution and does not contain potassium ions which affect polymerization catalysis, and the resin prepared therefrom has relatively higher storage stability compared with the ordinary polyether polyol prepared by KOH process. Compared with Comparative Examples 3 and 4, the resin prepared therefrom is not easily oxidized and has excellent yellowing resistance.

[0083] (2) A one-component moisture-curable adhesive was prepared using the silane-terminated polyurethane polymer resins prepared in Examples 1-5 and Comparative Examples 1-4, respectively, and the raw material composition thereof is shown in the following table:

[0084]

[0085]

[0086] The preparation of the one-component moisture-curable adhesive comprises the following steps:

[0087] The silane-terminated polyurethane polymer resin, plasticizer, composite light stabilizer, filler, water-removing agent B and thixotropic agent were added to a dynamic mixer and stirred under vacuum for 15-30 min, then the coupling agent was added and stirred under vacuum for another 10-20 min, and finally the catalyst B was added and stirred under vacuum for another 10-20 min to obtain the one-component moisture-curable adhesive.

[0088] (3) The one-component moisture-curable adhesive prepared in (2) was tested for performance, and the test indexes and methods are as follows:

[0089] Appearance: The appearance color uniformity of the prepared moisture-curable adhesive was observed under natural daylight illumination according to GB / T 9761.

[0090] Tack-free time: The prepared adhesive was adjusted for at least 12 hours under constant temperature and humidity conditions (temperature 23±2°C, humidity 50±5%), and the adhesive was evenly scraped to a thickness of about 2 mm, and the time when the finger did not leave marks on the surface of the adhesive was tested.

[0091] Tensile strength and elongation at break were tested according to GB / T 528.

[0092] Shear strength was tested according to GB / T 7124 tensile shear strength test method. All substrates were not treated in advance.

[0093] Moisture and heat aging resistance: the cured adhesive was put into a humidity chamber with temperature 85±2℃ and humidity 85±5% for 15 days, then the tensile and shear properties of the adhesive were tested.

[0094] Extrusion force test: the adhesive was filled into a soft package with diameter of 50mm and sealed. After 12 hours of conditioning in a constant temperature and humidity chamber, the adhesive was pressed down to a 3mm diameter hole at a rate of 60mm / min, and the force value at displacement of 60mm was tested.

[0095] Stability test: the adhesive filled into the soft package was sealed and put into an oven at 70℃ for 7 days of aging. After 12 hours of conditioning in a constant temperature and humidity chamber, the extrusion force test was performed.

[0096] The test results are shown in the following table:

[0097]

[0098] Among them, the failure modes are (1) cohesive failure of CF adhesive, (2) adhesive failure of AF, and (3) mixed failure of adhesion and cohesion in ACFP peeling mode.

[0099] From the above results, it can be seen that the moisture-curable adhesives prepared from the comb-type silane-modified polyurethane resins prepared in Examples 1-5 have uniform appearance without impurities and other agglomerations. Different active NCO-terminated silane coupling agents can be used to obtain different tack-free times, and the tack-free times of the Examples are in the range of 10-40 min, which can be easily adjusted. The adhesives have relatively small extrusion forces of 150-250 N, which facilitates the construction of the adhesives.

[0100] Compared with Comparative Examples 1, 3 and 4, the use of organic bismuth catalyst to synthesize the base resin can effectively catalyze the synthesis of the hydroxyl-terminated prepolymer and the NCO-terminated special silane, and can also reduce the catalysis of the reaction between the siloxane and the moisture in the prepared adhesive. After aging, the extrusion force does not increase significantly, the bulk strength is greater than 3 MPa, the elongation at break is greater than 450%, the adhesion strength with different substrates is greater than 2.5 MPa, the failure mode is cohesive failure, and the adhesives have good resistance to double 85 moisture and heat.

[0101] Compared with Example 1, the base resin of Comparative Example 1 does not use polycaprolactone triol as the comb structure skeleton, and has smaller bulk strength and poor moisture and heat resistance. The adhesion strength with the substrate is less than 1.5 MPa. The base resin uses an organic tin catalyst, which not only catalyzes the synthesis of the base resin, but also catalyzes the moisture curing of the prepared adhesive, resulting in a decrease in the storage stability of the prepared adhesive and a significant increase in the extrusion force after aging.

[0102] Compared with Example 1, the high molecular weight polyether polyol in Comparative Example 2 is not prepared by the DMC process, but a polyether polyol with a molecular weight of 4000 g / mol and a relatively short molecular chain is prepared by the KOH process. The moisture-curable adhesive prepared has a low elongation at break, a relatively small crosslinking and entanglement between molecular chains, and a certain decrease in bulk strength and shear strength. Since the polyether polyol prepared by the KOH process contains potassium ions, it can weakly catalyze the moisture curing of the prepared adhesive, resulting in a decrease in the storage stability of the adhesive and a large extrusion force after aging.

[0103] Compared with Example 1, the high molecular weight polyether polyol in Comparative Example 3 is copolymerized with the polycaprolactone triol as the structural backbone, but diphenyl methane diisocyanate containing a benzene ring structure and being solid at room temperature is used. The resin viscosity is large, the prepared adhesive has a large extrusion force, and the use of organotin catalyst in the synthetic resin leads to a decrease in the storage stability of the adhesive.

[0104] In Comparative Example 4, the polycaprolactone triol is not used as the comb-shaped structural backbone, and the bulk strength is significantly reduced without the polycaprolactone polyol providing strength support.

[0105] The inventors further found through experiments that when the mass ratio of the raw materials in the moisture-curable silane-modified polyurethane adhesive is as follows: 18% to 45% of the silane-terminated polyurethane polymer resin, 10% to 30% of the plasticizer, 0.2 to 1% of the composite light stabilizer, 40% to 50% of the filler, 0.5 to 1% of the water-removing agent, 0.5 to 1.5% of the coupling agent, 0.05 to 1% of the catalyst, and 0 to 2% of the thixotropic agent, and the plasticizer is one or more of the commonly used environmentally friendly plasticizers on the market, such as phosphate plasticizers, epoxy compound plasticizers, alkyl sulfonate plasticizers, or polyoxypropylene polyols, polyoxypropylene-ethylene oxide copolymer polyether polyols, the composite light and heat stabilizer is one or more of the commonly used benzotriazole, salicylate, benzophenone, hindered amine, and phosphite light and heat stabilizers on the market, the filler is one or more of calcium carbonate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, kaolin, silica powder, halloysite, montmorillonite, palygorskite, silico-aluminate, titanium white, and carbon black, the water-removing agent B is one or more of vinyl silane, p-methylbenzenesulfonyl isocyanate, zeolite, and oxazolidine compound, the coupling agent is amino silane coupling agent, the catalyst B is organotin catalyst, and the thixotropic agent is one or more of fumed hydrophobic silica, organically modified bentonite, polyamide wax, and polyurea compound, the adhesive with an extrusion force of 150 N to 250 N, a bulk strength greater than 3 MPa, an elongation at break greater than 450%, and an adhesive strength to different substrates greater than 2.5 MPa can be prepared, the failure mode is cohesive failure, and the adhesive has good resistance to double 85 damp heat.

[0106] It is necessary to point out here that the above embodiments are only for further illustrating and describing the technical solutions of the present application, and are not for further limiting the technical solutions of the present application. The method of the present application is only a preferred embodiment, and is not used for limiting the protection scope of the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A comb-type silane-terminated polyurethane polymer resin, characterized in that, It is prepared from the following raw materials in parts by weight: 1-3 parts of diisocyanate, 1-3 parts of polymeric polyol, 90-98 parts of high molecular weight polyether polyol, Catalyst A: 0.001~0.02 parts 1-4 parts of organic functional silane, 0.1 to 1 part of small molecule saturated fatty alcohols, and Dehydrating agent A: 0.1~1 parts; The high molecular weight polyether polyol is a polyether polyol prepared by the DMC process, with a functionality of 2 and a molecular weight of 8000~18000 g / mol; the polymer polyol is a polycaprolactone-type triol with a functionality of 3 and a molecular weight of 300~1000 g / mol; the catalyst A is an organic bismuth catalyst; the diisocyanate is a diisocyanate without an aromatic ring structure; and the small molecule saturated fatty alcohol is at least one of a small molecule monohydric alcohol or a dihydric alcohol.

2. The comb-type silane-terminated polyurethane polymer resin according to claim 1, characterized in that, It is prepared from the following raw materials in parts by weight: 1.3~2.28 parts of diisocyanate, 1.7~2.48 parts of polymer polyol, 0.002~0.015 parts of catalyst A, 93~95 parts of high molecular weight polyether polyol, 1.4~2.3 parts of organic functional silane, 0.3~0.5 parts of small molecule saturated fatty alcohol, and 0.3~0.5 parts of dehydrating agent A.

3. The comb-type silane-terminated polyurethane polymer resin according to claim 1, characterized in that, The diisocyanate is selected from at least one of isophorone diisocyanate, 4,4'-methylene di(cyclohexyl isocyanate), hydrogenated dimethyl diisocyanate, 2,5(2,6)-di(isocyanate methyl)bicyclo[2.2.1]heptane, and 1,6-hexyl diisocyanate.

4. The comb-type silane-terminated polyurethane polymer resin according to claim 1, characterized in that, The organic functional silane is an NCO-terminated alkoxysilane coupling agent.

5. The comb-type silane-terminated polyurethane polymer resin according to claim 1, characterized in that, The dehydrating agent A is vinylsilane.

6. The comb-type silane-terminated polyurethane polymer resin according to claim 1, characterized in that, The molar ratio of -NCO in diisocyanate to -OH in polycaprolactone triol is (2~2.2):

1.

7. The method for preparing the comb-type silane-terminated polyurethane polymer resin according to any one of claims 1 to 6, characterized in that, Includes the following steps: Dehydrated polycaprolactone triol and catalyst A are added to the reaction vessel. After heating to 40-60℃, diisocyanate is added. The temperature is raised to 70-90℃ and the reaction is carried out for 1.5-2 hours. High molecular weight polyether polyol is added and the reaction is carried out at 70-90℃ for 1.5-2 hours. Then, organofunctional silane is added and the reaction is carried out at 70-90℃ for 2-3 hours. Cool the prepolymer to 25℃~40℃, add dehydrating agent A, stir, add small molecule saturated fatty alcohol to remove unreacted NCO groups in the prepolymer, and continue stirring until homogeneous to obtain the final product.

8. The use of the comb-type silane-terminated polyurethane polymer resin according to any one of claims 1 to 6 in the preparation of moisture-curable silane-modified polyurethane adhesives.

9. A moisture-curable silane-modified polyurethane adhesive, characterized in that, It is prepared by combining the comb-type silane-terminated polyurethane polymer resin according to any one of claims 1 to 6 with dehydrating agent B, environmentally friendly plasticizer, filler, coupling agent and catalyst B.

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