A cyclic carbonate prepolymer, a silane-modified non-isocyanate polyurethane resin, and preparation methods and applications thereof

Abstract

The present invention relates to a cyclic carbonate prepolymer, a silane-modified non-isocyanate polyurethane resin, and a preparation method and application thereof. The cyclic carbonate prepolymer is prepared by the following steps: S1: reacting a polymer polyol with a dibasic acid anhydride to obtain a polymer polyacid; S2: adding glycerol carbonate and reacting to obtain the cyclic carbonate prepolymer; wherein the molecular weight M of the polymer polyol is w The cyclic carbonate prepolymer is chain extended with a small amount of diamine chain extender and aminosilane coupling agent to obtain a silane-modified non-isocyanate polyurethane resin. The silane-terminated modified non-isocyanate polyurethane resin is liquid at room temperature, has low viscosity, and has good interface wettability. The sealing adhesive prepared by using the silane-terminated modified non-isocyanate polyurethane resin as a base resin has excellent bonding force and good mechanical properties after curing.

Description

Technical Field

[0001] The invention belongs to the technical field of functional polymer materials, and specifically relates to a cyclic carbonate prepolymer, a silane-modified non-isocyanate polyurethane resin, and a preparation method and application thereof. Background Art

[0002] Silane-modified polyurethane resin is a silane-modified polyurethane material that combines the dual advantages of silicone resin and polyurethane resin, has good weather resistance and strength, and is widely used in sealants. The emergence of silane-modified polyurethane polyurethane sealants has solved the problems caused by the use of silicone glue in many industries, including the pungent odor produced by curing, the surface cannot be painted, and oil seepage. At the same time, compared with polyurethane glue, silane-modified polyurethane sealants have better weather resistance, and the sealants do not contain free isocyanates, organic solvents, etc. This silane-modified polyurethane resin combines the advantages of silicone glue and polyurethane glue to the maximum extent, while avoiding the disadvantages of silicone glue and polyurethane glue. Its application involves all walks of life, especially suitable for the bonding and sealing of structural parts such as home decoration, construction, and industrial assembly.

[0003] The traditional method of preparing silane-modified polyurethane resin requires a large amount of isocyanate, and the raw material for preparing isocyanate is highly toxic phosgene, which seriously harms human health and poses a great threat to the environment. At the same time, when isocyanate reacts with polyol, it will react with the moisture in the surrounding environment to generate carbon dioxide, which will cause bubbles inside the material and reduce the mechanical properties of the polyurethane material.

[0004] Silane-modified non-isocyanate polyurethane is a new type of environmentally friendly material. Its preparation does not require the use of raw materials containing -NCO, which meets the standards of "green chemistry", thus solving the problem that the preparation process of traditional silane-modified polyurethane materials is complicated and reduces the mechanical properties of polyurethane materials; at the same time, silane-modified non-isocyanate polyurethane has stronger intramolecular hydrogen bonds than traditional silane-modified polyurethanes, and the molecular forces are enhanced, giving it excellent chemical and heat resistance. Therefore, silane-modified non-isocyanate polyurethane has become a hot topic of research in countries around the world, and the development of silane-modified non-isocyanate polyurethane resins has important theoretical and economic value.

[0005] The Chinese patent for the invention titled "A high-strength dual-repair non-isocyanate polyurethane and its preparation method" prepares non-isocyanate polyurethane by reacting homemade pyrazole monomers and bicyclic carbonates, and then introduces disulfide bonds and coordination bonds into the polyurethane system to achieve a dual self-repairing system. The addition of diamino-terminated poly(dimethylsiloxane) introduces silicon elements, making the polyurethane material hydrophobic and improving the thermal stability of the material. Although this material has a tensile strength of up to 19.39MPa and is hydrophobic, it has poor wettability to the substrate, weak adhesion, and its preparation process is relatively complicated, making it difficult to promote on a large scale.

[0006] Therefore, it is particularly important to develop a silane-modified non-isocyanate polyurethane with good mechanical properties and strong adhesion. Summary of the invention

[0007] The purpose of the present invention is to overcome the problems of poor wetting performance and weak adhesive force of silane-modified non-isocyanate polyurethane in the prior art, and to provide a cyclic carbonate prepolymer. The cyclic carbonate prepolymer introduces a chain segment of a high molecular weight polymer polyol, and when the cyclic carbonate prepolymer is used as a component of a silane-modified non-isocyanate polyurethane resin, the silane-modified non-isocyanate polyurethane resin can be endowed with good mechanical properties, excellent adhesive force and good aging resistance in combination with other components.

[0008] Another object of the present invention is to provide a silane-terminated modified non-isocyanate polyurethane resin.

[0009] Another object of the present invention is to provide a method for preparing the above-mentioned silane-terminated modified non-isocyanate polyurethane resin.

[0010] Another object of the present invention is to provide the use of the above-mentioned silane-modified non-isocyanate polyurethane in the preparation of sealing adhesives.

[0011] In order to achieve the above invention object, the present invention adopts the following technical scheme:

[0012] A cyclic carbonate prepolymer is prepared by the following steps:

[0013] S1: reacting a polymer polyol with a dibasic acid anhydride to obtain a polymer polyacid;

[0014] S2: adding glycerol carbonate to react to obtain the cyclic carbonate prepolymer;

[0015] Wherein, the molecular weight M of the polymer polyol is w It ranges from 2000 to 20000.

[0016] High molecular weight polymer polyol (molecular weight M w≥2000) in the esterification reaction and transesterification reaction process, the hydroxyl group has poor reactivity, long reaction time and low conversion rate. In order to solve this problem, the present invention adopts dibasic acid anhydride with high reactivity to react with polymer polyol to generate polymer polyacid, and the reaction speed of the reaction is fast, the reaction time is short, and the conversion efficiency of the reaction is high. The polymer polyacid is then reacted with glycerol carbonate to obtain a cyclic carbonate prepolymer, and the chain segment of high molecular weight polymer polyol is introduced into the cyclic carbonate prepolymer, which can be used as the reaction raw material of silane-terminated modified non-isocyanate polyurethane resin, and with the cooperation of other components, the silane-modified non-isocyanate polyurethane resin can be given good mechanical properties, excellent bonding strength and good aging resistance.

[0017] Preferably, the polymer polyol is one or more of polyether diol, polycarbonate diol, polyester diol, polyether triol, polycarbonate triol or polyester triol.

[0018] Preferably, the dibasic acid anhydride is one or more of succinic anhydride, phthalic anhydride or maleic anhydride.

[0019] Preferably, the molar ratio of the carboxyl group in the polymer polyacid to the hydroxyl group in the glycerol carbonate is 1:(1.8-3.3).

[0020] Preferably, the reaction temperature of the reaction in step S1 is 80 to 130° C., and the reaction time is 6 to 24 hours.

[0021] Preferably, the reaction temperature of the reaction in step S2 is 80-130° C., and the reaction time is 6-8 hours.

[0022] Preferably, the reaction in step S2 is carried out under an inert atmosphere.

[0023] More preferably, the inert atmosphere in step S2 is one of nitrogen atmosphere, argon or helium.

[0024] Preferably, a catalyst is also added to the reaction in step S2.

[0025] More preferably, the catalyst in step S2 is one or more of dibutyltin dilaurate, pyridine, methanesulfonic acid, and pyridine sulfonate.

[0026] Specifically, polymer polyol and dibasic acid anhydride are added to a three-necked flask connected to a water separator and a condenser, and the mixture is heated to 80-130° C. and reacted for 6-24 hours. Then, glycerol carbonate and a catalyst are added, and the mixture is reacted for 6-8 hours at 80-130° C. in a nitrogen atmosphere. The reaction rate is monitored by detecting the acid value of the system during the reaction to complete the preparation of the cyclic carbonate prepolymer.

[0027] A silane-terminated modified non-isocyanate polyurethane resin comprises the following components in parts by weight:

[0028] 50-95 parts of the above cyclic carbonate prepolymer;

[0029] 0.5 to 10 parts of aminosilane coupling agent;

[0030] 0.01 to 10 parts of diamine chain extender.

[0031] The silane-terminated modified non-isocyanate polyurethane resin of the present invention is obtained by firstly subjecting a cyclic carbonate prepolymer and a diamine chain extender to a chain extension reaction, and then subjecting an aminosilane coupling agent to a terminal reaction.

[0032] The silane-terminated modified non-isocyanate polyurethane resin introduces the main chain structure of a high molecular weight polymer polyol, is liquid at room temperature, has low viscosity, has good interfacial wetting ability on the substrate, and has strong bonding strength. More importantly, the main chain structure of the high molecular weight polymer polyol, in combination with hydroxyl and diamine chain extension units, can effectively regulate the molecular weight and hard segment structure of the silane-terminated modified non-isocyanate polyurethane resin, making the three-dimensional network structure of the resin controllable after curing, on the one hand, improving the tensile strength and shear strength of the resin, and having excellent bonding strength; on the other hand, it also improves the modulus, elongation at break and Shore hardness of the resin, and has good mechanical properties. At the same time, due to the introduction of siloxane groups, the silane-terminated modified non-isocyanate polyurethane resin has good aging resistance, thereby maintaining excellent bonding strength and good mechanical properties.

[0033] In addition, the silane-modified non-isocyanate polyurethane contains a hydroxyl group on the β-carbon atom of the structural unit carbamate, which can form an intramolecular hydrogen bond with the carbonyl group in the carbamate bond, compensating for the weak bond structure in traditional polyurethane from the molecular structure, further improving the aging resistance and mechanical properties of the resin, as well as improving the chemical resistance and hydrolysis resistance of the resin.

[0034] Preferably, the aminosilane coupling agent is one or more of 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane.

[0035] Preferably, the diamine chain extender is p-phenylenediamine, ethylenediamine or a diamine having a molecular weight of w One or more polyetheramines with a molecular weight of 200 to 500.

[0036] Preferably, the molar ratio of the cyclic carbonate prepolymer to the aminosilane coupling agent is 1:(1.5-3.3).

[0037] Preferably, the molar ratio of the diamine chain extender to the aminosilane coupling agent is (0.1-5):1.

[0038] More preferably, the molar ratio of the diamine chain extender to the aminosilane coupling agent is (0.2-2):1.

[0039] The preparation method of the silane-terminated modified non-isocyanate polyurethane resin comprises the following steps: mixing a cyclic carbonate prepolymer, an aminosilane coupling agent and a diamine chain extender, heating and reacting the mixture to obtain the silane-terminated modified non-isocyanate polyurethane resin.

[0040] The silane-terminated modified non-isocyanate polyurethane resin is prepared by a carbonate aminolysis method, and does not use highly toxic and moisture-sensitive isocyanate as a raw material. This is not only environmentally friendly, but also does not generate bubbles inside the material during the preparation process, thereby ensuring that the silane-terminated modified non-isocyanate polyurethane resin has good mechanical properties.

[0041] Preferably, the heating temperature is 50-150°C.

[0042] More preferably, the heating temperature is 70-120°C.

[0043] More preferably, the heating temperature is 80-100°C.

[0044] Preferably, the reaction time of the reaction is 6 to 24 hours.

[0045] Preferably, a solvent may be added to the reaction system of the reaction.

[0046] More preferably, the solvent is one or more of petroleum ether, ethyl acetate, cyclohexane, toluene and xylene.

[0047] Specifically, a cyclic carbonate prepolymer, an aminosilane coupling agent and a diamine chain extender are added into a three-necked flask, and reacted at 80 to 100° C. for 6 to 24 hours to obtain a silane-terminated modified non-isocyanate polyurethane resin.

[0048] The use of the above-mentioned silane-terminated modified non-isocyanate polyurethane resin in the preparation of sealing adhesives is also within the protection scope of the present invention.

[0049] The sealing adhesive prepared by using the silane-terminated modified non-isocyanate polyurethane resin as the base resin has strong adhesion to glass and cement substrates, high tensile strength and shear strength; has good mechanical properties, high modulus, elongation at break and Shore hardness; also has good aging resistance, chemical resistance and hydrolysis resistance, and is particularly suitable for the fields of construction, home improvement, automobiles, etc.

[0050] Compared with the prior art, the present invention has the following beneficial effects:

[0051] (1) The cyclic carbonate prepolymer of the present invention introduces a chain segment of a high molecular weight polymer polyol. When it is used as a component of a silane-modified non-isocyanate polyurethane resin, in combination with other components, the silane-modified non-isocyanate polyurethane resin can be endowed with good mechanical properties, excellent adhesion and good aging resistance.

[0052] (2) The silane-terminated modified non-isocyanate polyurethane resin of the present invention is liquid at room temperature, has low viscosity, has good interfacial wetting ability to the substrate, and has strong bonding strength. After curing, it has excellent bonding strength, high tensile strength and high shear strength; it has good mechanical properties, and the resin has high modulus, elongation at break and Shore hardness.

[0053] (3) The sealing adhesive prepared by using the silane-terminated modified non-isocyanate polyurethane resin as the base resin has strong adhesion to glass and cement substrates, high tensile strength and shear strength; has good mechanical properties, high modulus, elongation at break and Shore hardness; and has good aging resistance, chemical resistance and hydrolysis resistance, and is particularly suitable for the fields of construction, home decoration, and automobiles. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 The figure is a schematic diagram of the reaction process of the silane-modified non-isocyanate polyurethane resin of the present invention. DETAILED DESCRIPTION

[0055] The present invention is further described below in conjunction with examples and comparative examples. These examples are only typical descriptions of the present invention, but the present invention is not limited thereto. The test methods used in the following examples and comparative examples are conventional methods unless otherwise specified, and the raw materials, reagents, etc. used are raw materials and reagents that can be obtained from conventional commercial sources such as commercial purchases, etc. unless otherwise specified.

[0056] 1. Resin testing method:

[0057] 1. Viscosity test: The viscosity was measured at 25°C using a Brookfield (RV type) rotational viscometer.

[0058] 2. The hydroxyl value content is tested according to GB / T 12008.3-2009 by titration method.

[0059] 3. The primary amine content is tested according to ASTM D2074-2007 by titration method.

[0060] 4. Molecular weight distribution determination: Gel permeation chromatography (GPC) was used for testing, THF was used as the mobile phase, and the instrument model was WATERS GPC.

[0061] 2. Source of raw materials:

[0062] 1. 3-Aminopropyltrimethoxysilane, purchased from Momentive, product brand: A-1110.

[0063] 2. 3-Aminopropyltriethoxysilane, purchased from Momentive, product brand: A-1100.

[0064] 3. 3-Isocyanatepropyltrimethoxysilane, purchased from Momentive, product brand: A-Link35.

[0065] 4. MDI-100, purchased from Wanhua Chemical, product brand: MDI-100.

[0066] 5. Polypropylene oxide ether triol, molecular weight M w The molecular weight is 4000, the functionality is 2, purchased from Wuhan Aoke, brand PPG4000.

[0067] 6. Polypropylene oxide ether diol, molecular weight M w The VORANOL is 8000 and the functionality is 2. It is purchased from Dow Chemical with the brand name: VORANOL 8000LM.

[0068] 7. Polypropylene oxide ether triol, molecular weight M w The molecular weight is 2000, the functionality is 2, purchased from Bluestar Dongda, brand: DL-2000D.

[0069] 8. Polypropylene oxide ether triol, molecular weight M w The molecular weight is 5000, the functionality is 3, and it is purchased from Wanhua Chemical with the brand name: F3135.

[0070] 9. Polypropylene oxide ether diol, molecular weight M w The molecular weight is 12000, the functionality is 2, purchased from Wuhan Aoke, the brand is PPG12000.

[0071] 10. Polypropylene oxide ether diol, molecular weight M w The molecular weight is 20000, the functionality is 2, purchased from Wuhan Aoke, brand PPG20000.

[0072] 11. Molecular weight of polyetheramine M w The molecular weight is 230, the functionality is 2, and it is purchased from Akel, and the brand name is polyetheramine D230.

[0073] 12. Polyetheramine molecular weight M w The molecular weight of the polyetheramine is 430 and the functionality is 2. It is purchased from Huntsman and is branded as polyetheramine D430.

[0074] 13. IPDI, ethylenediamine, hexamethylenediamine, butanediamine, p-phenylenediamine and maleic anhydride were purchased from Aladdin, brand: None.

[0075] Example 1

[0076] This embodiment provides a silane-modified non-isocyanate polyurethane resin, and the preparation method thereof is as follows: 1200 g of a molecular weight M w The polyoxypropylene ether diol with a molecular weight of 12000 and 22g of succinic anhydride were heated to 120°C. After reacting for 12 hours, 23.6g of glycerol carbonate and 6g of pyridine were added. The reaction was carried out for 8 hours at 120°C in a nitrogen atmosphere. The reaction speed was detected by detecting the acid value of the system during the reaction to complete the preparation of the bicyclic carbonate prepolymer. The bicyclic carbonate prepolymer obtained by the above reaction and 6g of molecular weight M w 60 g of ethylenediamine and 20 g of 3-aminopropyltrimethoxysilane are added into a three-necked flask, and stirred to react at 100° C. until the primary amine value content of the system is less than 0.1%, thereby obtaining a silane-modified non-isocyanate polyurethane resin with a viscosity of 31500 cP.

[0077] The reaction process diagram of the silane-modified non-isocyanate polyurethane resin is shown in Figure 1 shown.

[0078] Example 2

[0079] This embodiment provides a silane-modified non-isocyanate polyurethane resin, and the preparation method thereof is as follows: 500 g of a molecular weight M w The polyoxypropylene ether triol with a molecular weight of 5000 and 20g of succinic anhydride were heated to 120°C. After reacting for 12 hours, 23.6g of glycerol carbonate and 6g of methanesulfonic acid were added. The reaction was carried out for 8 hours at 120°C in a nitrogen atmosphere. The reaction speed was detected by detecting the acid value of the system during the reaction to complete the preparation of the bicyclic carbonate prepolymer. The bicyclic carbonate prepolymer obtained by the above reaction and 10g molecular weight M w 230 g of polyetheramine and 42 g of 3-aminopropyltriethoxysilane are added into a three-necked flask, and the mixture is stirred and reacted at 100° C. until the primary amine content of the system is less than 0.1%, thereby obtaining a silane-modified non-isocyanate polyurethane resin with a viscosity of 16800 cP.

[0080] Example 3

[0081] This embodiment provides a silane-modified non-isocyanate polyurethane resin, and the preparation method thereof is as follows: 800 g of a molecular weight M wThe polyoxypropylene ether diol with a molecular weight of 8000 and 29.6 g of phthalic anhydride were heated to 120°C. After reacting for 12 hours, 23.6 g of glycerol carbonate and 6 g of pyridine were added. The reaction was carried out for 8 hours at 120°C in a nitrogen atmosphere. The reaction speed was detected by detecting the acid value of the system during the reaction to complete the preparation of the bicyclic carbonate prepolymer. The bicyclic carbonate prepolymer obtained by the above reaction and 10 g molecular weight M w 430 g of polyetheramine and 42 g of 3-aminopropyltriethoxysilane were added into a three-necked flask, and the mixture was stirred and reacted at 100° C. until the primary amine content of the system was less than 0.1%, thereby obtaining a silane-modified non-isocyanate polyurethane resin with a viscosity of 27860 cP.

[0082] Example 4

[0083] This embodiment provides a silane-modified non-isocyanate polyurethane resin, and the preparation method thereof is as follows: 500 g of a molecular weight M w The polyoxypropylene ether triol with a molecular weight of 5000 and 30g of maleic anhydride are heated to 120°C, and after reacting for 12 hours, 35.4g of glycerol carbonate and 9g of pyridine are added, and the reaction is carried out for 8 hours at 120°C in a nitrogen atmosphere. The reaction speed is detected by detecting the acid value of the system during the reaction to complete the preparation of the tricyclic carbonate prepolymer. The tricyclic carbonate prepolymer obtained by the above reaction, 5g of polyetheramine with a molecular weight of 230 and 63g of 3-aminopropyltriethoxysilane are added to a three-necked flask, and stirred at 100°C to react until the primary amine value content of the system is less than 0.1%, and a silane-modified non-isocyanate polyurethane resin with a viscosity of 17200cP is obtained.

[0084] Example 5

[0085] This embodiment provides a silane-modified non-isocyanate polyurethane resin, and the preparation method thereof is as follows: 200 g of a molecular weight M w The polyoxypropylene ether triol with a molecular weight of 2000 and 20g of succinic anhydride were heated to 120°C. After reacting for 12 hours, 23.6g of glycerol carbonate and 6g of pyridine were added. The reaction was carried out at 120°C in a nitrogen atmosphere for 8 hours. The reaction speed was detected by monitoring the acid value of the system during the reaction to complete the preparation of the bicyclic carbonate prepolymer. The bicyclic carbonate prepolymer obtained by the above reaction and 10g molecular weight M w 230 g of polyetheramine and 42 g of 3-aminopropyltriethoxysilane are added into a three-necked flask, and the mixture is stirred and reacted at 100° C. until the primary amine content of the system is less than 0.1%, thereby obtaining a silane-modified non-isocyanate polyurethane resin with a viscosity of 13600 cP.

[0086] Example 6

[0087] This embodiment provides a silane-modified non-isocyanate polyurethane resin, and the preparation method thereof is as follows: 400 g of a molecular weight M w The polyoxypropylene ether triol with a molecular weight of 4000 and 20g of maleic anhydride are heated to 120°C, and after reacting for 12 hours, 23.6g of glycerol carbonate and 6g of pyridine are added, and the reaction is carried out for 8 hours at 120°C in a nitrogen atmosphere. The reaction speed is detected by detecting the acid value of the system during the reaction to complete the preparation of the bicyclic carbonate prepolymer. The bicyclic carbonate prepolymer obtained by the above reaction, 10g of p-phenylenediamine and 42g of 3-aminopropyltriethoxysilane are added to a three-necked flask, and stirred at 100°C to react until the primary amine value content of the system is less than 0.1%, and a silane-modified non-isocyanate polyurethane resin with a viscosity of 19500cP is obtained.

[0088] Example 7

[0089] This embodiment provides a silane-modified non-isocyanate polyurethane resin, and the preparation method thereof is as follows: 2000 g of a molecular weight M w The polyoxypropylene ether diol of 20000 and 20g of maleic anhydride are heated to 120°C, and after reacting for 12 hours, 23.6g of glycerol carbonate and 6g of pyridine are added, and the reaction is carried out for 8 hours at 120°C in a nitrogen atmosphere. The reaction speed is detected by detecting the acid value of the system during the reaction to complete the preparation of the bicyclic carbonate prepolymer. The bicyclic carbonate prepolymer obtained by the above reaction, 10g of hexamethylenediamine and 36g of 3-aminopropyltriethoxysilane are added to a three-necked flask, and stirred at 100°C to react until the primary amine value content of the system is less than 0.1%, and a silane-modified non-isocyanate polyurethane resin with a viscosity of 62700cP is obtained.

[0090] Example 8

[0091] This embodiment provides a silane-modified non-isocyanate polyurethane resin, and the preparation method thereof is as follows: 2000 g of a molecular weight M w The polyoxypropylene ether diol of 20000 and 20g of maleic anhydride are heated to 120°C, and after reacting for 12 hours, 23.6g of glycerol carbonate and 6g of pyridine are added, and the reaction is carried out for 8 hours at 120°C in a nitrogen atmosphere. The reaction speed is detected by detecting the acid value of the system during the reaction to complete the preparation of the bicyclic carbonate prepolymer. The bicyclic carbonate prepolymer obtained by the above reaction, 2g of butanediamine and 36g of 3-aminopropyltriethoxysilane are added to a three-necked flask, and stirred at 100°C to react until the primary amine value content of the system is less than 0.1%, and a silane-modified non-isocyanate polyurethane resin with a viscosity of 58600cP is obtained.

[0092] Comparative Example 1

[0093] This comparative example provides a silane-terminated modified polyether polyurethane adhesive resin, the preparation method of which is as follows: 600g molecular weight M w 5000 g of polypropylene oxide ether triol, 75 g of MDI-100 and 78.3 g of 3-aminopropyltrimethoxysilane were added into a 2L three-necked flask and heated to 70°C with stirring. After adding 0.2 g of organotin catalyst, the mixture was reacted at 70°C until the NCO content of the system was less than 0.1%, thereby obtaining a silane-terminated modified polyether polyurethane adhesive resin SPUR1 with a viscosity of 27300 cP.

[0094] Comparative Example 2

[0095] This comparative example provides a silane-terminated modified polyether polyurethane adhesive resin, the preparation method of which is as follows: 750g molecular weight M w 12000 g of polypropylene oxide ether diol, 33.34 g of MDI-100 and 39.2 g of 3-aminopropyltrimethoxysilane were added into a 2L three-necked flask and heated to 80°C with stirring. After adding 0.2 g of organotin catalyst, the mixture was reacted at 80°C until the NCO content of the system was less than 0.1%, thereby obtaining a silane-terminated modified polyether polyurethane adhesive resin SPUR2 with a viscosity of 23800 cP.

[0096] Comparative Example 3

[0097] This comparative example provides a silane-terminated modified polyether polyurethane adhesive resin, the preparation method of which is as follows: 300g molecular weight M w 2000g of polypropylene oxide ether triol, 33.34g of MDI-100 and 39.2g of 3-aminopropyltrimethoxysilane were added into a 2L three-necked flask and heated to 80°C with stirring. After adding 0.2g of organotin catalyst, the mixture was reacted at 80°C until the NCO content of the system was less than 0.1%, thereby obtaining a silane-terminated modified polyether polyurethane adhesive resin SPUR3 with a viscosity of 16200cP.

[0098] Comparative Example 4

[0099] This comparative example provides a silane-terminated modified polyether polyurethane adhesive resin, the preparation method of which is as follows: 300g molecular weight M w 2000 g of polypropylene oxide ether triol, 33.34 g of IPDI and 39.2 g of 3-aminopropyltrimethoxysilane were added into a 2L three-necked flask and heated to 80°C with stirring. After adding 0.2 g of organotin catalyst, the mixture was reacted at 80°C until the NCO content of the system was less than 0.1%, thereby obtaining a silane-terminated modified polyether polyurethane adhesive resin SPUR4 with a viscosity of 15300 cP.

[0100] The resins of Examples 1 to 8 and Comparative Examples 1 to 4 were used to prepare sealing adhesives according to the components in Table 1 and compared.

[0101] Table 1

[0102] Components weight / % Resin (self-made, refer to Examples and Comparative Examples) 35 Diisononyl phthalate 30 Carbon Black 18 Nano Calcium Carbonate 15 Crosslinking agent 1 Organic tin 1

[0103] The surface drying time, tensile strength, shear strength, 100% modulus, elongation at break, and Shore A hardness of the obtained sealing adhesive were tested according to national standards. The test results are shown in Table 2:

[0104] Table 2

[0105]

[0106] As shown in Table 2, the sealing adhesive prepared by the silane-terminated modified non-isocyanate polyurethane resin of Examples 1 to 8 has excellent adhesion to substrates such as glass and building materials, that is, high tensile strength and shear strength; good mechanical properties, that is, high 100% modulus, elongation at break and Shore hardness; good aging resistance, that is, high retention rates of tensile strength, 100% modulus and elongation at break before and after aging, and all properties can meet the application requirements of sealants. The silane-terminated modified polyether polyurethane resin of Comparative Examples 1 to 4 is not only easy to gel during the reaction, but also has an uncontrollable cross-linking network, which leads to poor adhesion of the sealing adhesive prepared therefrom, that is, low tensile strength and shear strength; general mechanical properties, that is, low 100% modulus, elongation at break and Shore hardness, which cannot meet the industry demand for high-strength sealants. Therefore, the silane-terminated modified non-isocyanate polyurethane resin prepared by the present invention not only meets the national green environmental protection requirements and reduces the raw material cost of the product, but also the sealing adhesive prepared therefrom has obvious advantages in performance compared with traditional silane-modified polyurethane resins.

[0107] The above describes the specific embodiments of the present invention. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art may make various modifications or variations within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A silane-terminated modified non-isocyanate polyurethane resin for preparing a sealing adhesive, characterized in that: The composition comprises the following components in parts by weight: 50-95 parts of cyclic carbonate prepolymer; 0.5 to 10 parts of aminosilane coupling agent; 0.01 to 10 parts of diamine chain extender; The cyclic carbonate prepolymer is prepared by the following steps: S1: reacting a polymer polyol with a dibasic acid anhydride to obtain a polymer polyacid; S2: adding glycerol carbonate and reacting to obtain the cyclic carbonate prepolymer; Wherein, the molecular weight M of the polymer polyol is w 4000~5000; The polymer polyol is a polyether triol; The diamine chain extender is p-phenylenediamine or a molecular weight M w One or more polyetheramines with a molecular weight of 200 to 500.

2. The silane-terminated modified non-isocyanate polyurethane resin according to claim 1, characterized in that: The dibasic acid anhydride is one or more of succinic anhydride, phthalic anhydride or maleic anhydride.

3. The silane-terminated modified non-isocyanate polyurethane resin according to claim 1, characterized in that: The molar ratio of the carboxyl group in the polymer polyacid to the hydroxyl group in the carbonated glycerol is 1:(1.8-3.3).

4. The silane-terminated modified non-isocyanate polyurethane resin according to claim 1, characterized in that: The aminosilane coupling agent is one or more of 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane.

5. The method for preparing the silane-terminated modified non-isocyanate polyurethane resin according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: mixing a cyclic carbonate prepolymer, an aminosilane coupling agent and a diamine chain extender, heating and reacting the mixture to obtain the silane-terminated modified non-isocyanate polyurethane resin.

6. The preparation method according to claim 5, characterized in that: The heating temperature is 50 to 150° C.; the reaction time is 6 to 24 hours.

7. Use of the silane-terminated modified non-isocyanate polyurethane resin according to any one of claims 1 to 4 in the preparation of sealing adhesives.

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