A modified auxiliary agent and its preparation method, as well as a polyurethane adhesive and its preparation method

Abstract

The present invention provides a modified additive, a preparation method thereof, a polyurethane adhesive and a preparation method thereof. The raw materials for preparing the modified additive provided by the present invention include: (1) trifunctional isocyanate; (2) S-glycidol; (3) amino silane coupling agent; (4) catalyst; (5) solvent; wherein, the dosage relationship among the trifunctional isocyanate, S-glycidol and amino silane coupling agent is as follows: Let the molar amount of trifunctional isocyanate be denoted as n1, the molar amount of S-glycidol be denoted as n2, and the molar amount of amino silane coupling agent be denoted as n3, then the proportional relationship among the three simultaneously satisfies Formula A and Formula B: n1∶n2∶n3 = 10∶(20 - 25)∶(5 - 10) Formula A; n1×3×(0.98 - 1.02) = n2 + n3 Formula B. The modified additive provided by the present invention can improve the compatibility and heat aging resistance of the polyurethane adhesive.

Description

Technical Field

[0001] The present invention relates to the field of adhesives, and particularly to a modified additive and its preparation method, as well as a polyurethane adhesive and its preparation method. Background Art

[0002] Due to excellent abrasion resistance, oil resistance and other advantages, polyurethane sealants are widely used as caulking and sealing materials for buildings, squares, and roads, as well as for sealing in automobile manufacturing, glass installation, electronic filling, submarines, rockets, etc.

[0003] Glass microspheres have the characteristics of low density and high strength, and are widely used in adhesives, coatings, plastic modification, etc. to reduce density and improve heat preservation and other properties. However, when glass microspheres are actually applied in polyurethane sealants, due to the lack of functional groups on their surface that can react with polyurethane sealants, their compatibility with polyurethane is poor. Usually, silane coupling agents need to be added to improve their compatibility, and then improve their room temperature strength. However, general silane coupling agents only play a role in improving compatibility and are difficult to have heat aging resistance performance, and cannot effectively solve the problem of poor heat aging resistance of polyurethane itself. Summary of the Invention

[0004] In view of this, the present invention provides a modified additive and its preparation method, as well as a polyurethane adhesive and its preparation method. The modified additive provided by the present invention can improve the compatibility and heat aging resistance of polyurethane adhesives.

[0005] The present invention provides a modified additive, and its preparation raw materials include:

[0006] (1) trifunctional isocyanate;

[0007] (2) S-glycidol;

[0008] (3) amino silane coupling agent;

[0009] (4) catalyst;

[0010] (5) solvent;

[0011] Wherein,

[0012] The dosage relationship of the trifunctional isocyanate, S-glycidol and amino silane coupling agent is as follows:

[0013] Denote the molar amount of trifunctional isocyanate as n1, the molar amount of S-glycidol as n2, and the molar amount of amino silane coupling agent as n3. Then the proportional relationship among the three simultaneously satisfies formula A and formula B:

[0014] n1∶n2∶n3 = 10∶(20 - 25)∶(5 - 10) formula A;

[0015] n1×3×(0.98 to 1.02) = n2 + n3, Formula B.

[0016] Preferably, the trifunctional isocyanate is at least one of HDI biuret, HDI trimer, TDI trimer, and IPDI trimer.

[0017] Preferably, the aminosilane coupling agent is at least one of bis(3-trimethoxysilylpropyl)amine, bis[3-(triethoxysilyl)propyl]amine, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-phenylaminomethyltriethoxysilane.

[0018] Preferably, the catalyst is dibutyltin dilaurate and / or dichlorodibutyltin; the solvent is at least one of ethyl acetate, toluene, and xylene.

[0019] Preferably, the mass ratio of the catalyst to the base material is (1 to 5):10000;

[0020] The mass ratio of the solvent to the base material is (45 to 100):100;

[0021] The base material is the trifunctional isocyanate, S-glycidol, and the aminosilane coupling agent.

[0022] The present invention also provides a preparation method of the modification aid described in the above technical solution, including the following steps:

[0023] a) Mix and react the trifunctional isocyanate, the solvent, and the aminosilane coupling agent to obtain Reactant 1;

[0024] b) Mix and react Reactant 1 with S-glycidol and the catalyst to obtain the modification aid.

[0025] Preferably, it specifically includes the following steps:

[0026] a) Mix the trifunctional isocyanate and the solvent to obtain a mixed solution;

[0027] Dropwise add the aminosilane coupling agent to the mixed solution under a protective atmosphere. After the addition is complete, first react at room temperature for 0.5 to 1 h, then heat to 50 to 70 °C and react for 1 to 2 h to obtain Reactant 1;

[0028] b) Mix Reactant 1 with S-glycidol, react at 55 to 65 °C for 3 to 5 h under a protective atmosphere, and then add the catalyst and react for 2 to 3 h to obtain the modification aid.

[0029] The present invention also provides a polyurethane adhesive. Calculated by mass parts, its preparation raw materials include:

[0030]

[0031]

[0032] Among them,

[0033] the modification aid is the modification aid described in the above technical solution or the modification aid prepared by the preparation method described in the above technical solution.

[0034] Preferably, the NCO content of the polyurethane prepolymer is 2% - 5%, and the viscosity is 20,000 - 60,000 mPa·s;

[0035] the plasticizer is at least one of DOP, DIDP, DINP, DBP and DIBP;

[0036] the catalyst is dibutyltin dilaurate and / or dichlorodibutyltin.

[0037] The present invention also provides a preparation method of the polyurethane adhesive described in the above technical solution, comprising the following steps:

[0038] Mix the polyurethane prepolymer, plasticizer, calcium carbonate, glass microspheres, modification aid and catalyst to obtain the polyurethane adhesive.

[0039] The modification aid provided by the present invention uses trifunctional isocyanate, amino silane coupling agent, S-glycidol, catalyst and solvent as raw materials, and a certain proportional relationship is controlled among the trifunctional isocyanate, amino silane coupling agent and S-glycidol, so as to obtain a modification aid containing a certain amount of epoxy groups and silicon-oxygen-carbon bonds, which can improve the compatibility and anti-aging property of the polyurethane adhesive at the same time.

[0040] The test results show that the modification aid of the present invention can make the thermal aging strength (70°C × 15 days) of the polyurethane adhesive reach more than 2 MPa, and the strength after thermal aging increases slightly compared with that before thermal aging, showing excellent heat aging strength. Detailed implementation mode

[0041] The present invention provides a modification aid, and its preparation raw materials include:

[0042] (1) Trifunctional isocyanate;

[0043] (2) S-glycidol;

[0044] (3) Amino silane coupling agent;

[0045] (4) Catalyst;

[0046] (5) Solvent;

[0047] Among them,

[0048] The dosage relationship among the trifunctional isocyanate, S-glycidol and the aminosilane coupling agent is as follows:

[0049] Denote the molar amount of the trifunctional isocyanate as n1, the molar amount of S-glycidol as n2, and the molar amount of the aminosilane coupling agent as n3. Then the proportional relationship among the three simultaneously satisfies Equation A and Equation B:

[0050] n1∶n2∶n3 = 10∶(20 - 25)∶(5 - 10) Equation A;

[0051] n1×3×(0.98 - 1.02) = n2 + n3 Equation B.

[0052] The modified additive provided by the present invention uses a trifunctional isocyanate, an aminosilane coupling agent, S-glycidol, a catalyst and a solvent as raw materials, and controls a certain proportional relationship among the trifunctional isocyanate, the aminosilane coupling agent and S-glycidol, so as to obtain a modified additive containing a certain amount of epoxy groups and silicon-oxygen-carbon bonds, which can improve the compatibility and anti-aging property of the polyurethane adhesive at the same time.

[0053] In the present invention, the trifunctional isocyanate is preferably at least one of HDI biuret (i.e., hexamethylene diisocyanate biuret), HDI trimer (i.e., hexamethylene diisocyanate trimer), TDI trimer (i.e., toluene diisocyanate trimer) and IPDI trimer (i.e., isophorone diisocyanate trimer). The present invention has no special limitation on the source of the trifunctional isocyanate, and it can be a commercially available product or prepared according to the conventional preparation methods in the art.

[0054] In the present invention, the S-glycidol is also written as (S)-glycidol, and its source has no special limitation, and it can be a commercially available product.

[0055] In the present invention, the aminosilane coupling agent is preferably at least one of bis(3-trimethoxysilylpropyl)amine, bis[3-(triethoxysilyl)propyl]amine, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and N-phenylaminomethyltriethoxysilane. The present invention has no special limitation on the source of the aminosilane coupling agent, and it can be a commercially available product.

[0056] In the present invention, the dosage relationship among the trifunctional isocyanate, S-glycidol and the aminosilane coupling agent is as follows: Denote the molar amount of the trifunctional isocyanate as n1, the molar amount of S-glycidol as n2, and the molar amount of the aminosilane coupling agent as n3. Then the proportional relationship among the three simultaneously satisfies Equation A and Equation B:

[0057] n1∶n2∶n3 = 10∶(20 - 25)∶(5 - 10) formula A;

[0058] n1×3×(0.98 - 1.02) = n2 + n3 formula B.

[0059] That is, among n1, n2, and n3, the proportional relationship of formula A is first satisfied, and on this basis, the requirements of formula B are further satisfied. In formula A, n1∶n2∶n3 can specifically be 10∶20∶5, 10∶20∶6, 10∶20∶7, 10∶20∶8, 10∶20∶9, 10∶20∶10, 10∶21∶5, 10∶21∶6, 10∶21∶7, 10∶21∶8, 10∶21∶9, 10∶21∶10, 10∶22∶5, 10∶22∶6, 10∶22∶7, 10∶22∶8, 10∶22∶9, 10∶22∶10, 10∶23∶5, 10∶23∶6, 10∶23∶7, 10∶23∶8, 10∶23∶9, 10∶23∶10, 10∶24∶5, 10∶24∶6, 10∶24∶7, 10∶24∶8, 10∶24∶9, 10∶24∶10, 10∶25∶5, 10∶25∶6, 10∶25∶7, 10∶25∶8, 10∶25∶9, 10∶25∶10. Formula B is (2.94 - 3.06)n1 = n2 + n3, and can specifically be 2.94n1 = n2 + n3, 2.95n1 = n2 + n3, 2.96n1 = n2 + n3, 2.97n1 = n2 + n3, 2.98n1 = n2 + n3, 2.99n1 = n2 + n3, 3.00n1 = n2 + n3, 3.01n1 = n2 + n3, 3.02n1 = n2 + n3, 3.03n1 = n2 + n3, 3.04n1 = n2 + n3, 3.05n1 = n2 + n3, 3.06n1 = n2 + n3. Under the control of the specific dosage relationship of the present invention, a reaction product containing a certain amount of epoxy groups and silicon-oxygen-carbon bonds is formed among the trifunctional isocyanate, S-glycidol, and amino silane coupling agent, which helps to improve the compatibility and anti-aging properties of the polyurethane adhesive simultaneously.

[0060] In the present invention, the catalyst is preferably dibutyltin dilaurate and / or dichlorodibutyltin. There is no special limitation on the source of the catalyst in the present invention, and it can be a commercially available product. In the present invention, the mass ratio of the catalyst∶base material is preferably (1 - 5)∶10000, and can specifically be 1∶10000, 2∶10000, 3∶10000, 4∶10000, 5∶10000; among them, the mass of the base material refers to the total mass of the above-mentioned trifunctional isocyanate, S-glycidol, and amino silane coupling agent.

[0061] In the present invention, the solvent is preferably at least one of ethyl acetate, toluene, and xylene. The present invention has no special limitation on the source of the solvent, and commercial products can be used. In the present invention, the mass ratio of the solvent to the base material is preferably (45-100):100, specifically, it can be 45:100, 50:100, 55:100, 56:100, 57:100, 60:100, 65:100, 70:100, 75:100, 78:100, 80:100, 85:100, 90:100, 95:100, 100:100; wherein, the mass of the base material refers to the total mass of the above trifunctional isocyanate, S-glycidol, and amino silane coupling agent.

[0062] The present invention also provides a preparation method of the modifying agent described in the above technical solution, including the following steps:

[0063] a) Mix and react trifunctional isocyanate, solvent, and amino silane coupling agent to obtain reactant 1;

[0064] b) Mix and react reactant 1 with S-glycidol and a catalyst to obtain the modifying agent.

[0065] Among them, the types and dosages of trifunctional isocyanate, solvent, amino silane coupling agent, S-glycidol, and catalyst are the same as those described in the previous technical solution, and will not be elaborated here one by one.

[0066] Regarding step a):

[0067] In the present invention, in step a), it is preferred to first mix trifunctional isocyanate and solvent to obtain a mixed solution. Among them, there is no special limitation on the mixing method, and the materials can be mixed evenly according to the conventional mixing method in the art, and a mixed solution is obtained after mixing evenly.

[0068] In the present invention, after obtaining the mixed solution, an amino silane coupling agent is added dropwise to the mixed solution under a protective atmosphere. Among them, the type of gas providing the protective atmosphere is not particularly limited and can be a conventional protective gas in the art, such as nitrogen or argon. In the present invention, the above-mentioned dropwise addition is preferably carried out under stirring conditions, that is, the amino silane is added dropwise while stirring. After the dropwise addition is completed, the reaction is first carried out at room temperature; the specific room temperature can be 10 to 30 °C, specifically 10 °C, 15 °C, 20 °C, 25 °C, 30 °C; the reaction time is preferably 0.5 to 1 h, specifically 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h, 1.0 h. After the reaction at room temperature, heating is continued for the reaction; the heating is preferably to 50 to 70 °C, specifically 50 °C, 51 °C, 52 °C, 53 °C, 54 °C, 55 °C, 56 °C, 57 °C, 58 °C, 59 °C, 60 °C, 61 °C, 62 °C, 63 °C, 64 °C, 65 °C, 66 °C, 67 °C, 68 °C, 69 °C, 70 °C; the reaction time after heating to the above temperature is preferably 1 to 2 h, specifically 1 h, 1.5 h, 2 h. After the above reaction, Reactant 1 is obtained.

[0069] Regarding step b):

[0070] In the present invention, in step b), it is preferred to first mix Reactant 1 with S-glycidol. Specifically, after obtaining Reactant 1 in step a), S-glycidol is added to Reactant 1 and stirred and mixed evenly. Then, the reaction is carried out under a protective atmosphere. Among them, the type of gas providing the protective atmosphere is not particularly limited and can be a conventional protective gas in the art, such as nitrogen or argon. The reaction temperature is preferably 55 to 65 °C, specifically 55 °C, 56 °C, 57 °C, 58 °C, 59 °C, 60 °C, 61 °C, 62 °C, 63 °C, 64 °C, 65 °C. The reaction time is preferably 3 to 5 h, specifically 3 h, 3.5 h, 4 h, 4.5 h, 5 h. After the above reaction, a catalyst is added to continue the reaction. The temperature for the continued reaction is also preferably 55 to 65 °C, specifically 55 °C, 56 °C, 57 °C, 58 °C, 59 °C, 60 °C, 61 °C, 62 °C, 63 °C, 64 °C, 65 °C. The reaction time for the continued reaction is preferably 2 to 3 h, specifically 2 h, 2.5 h, 3 h. After the above reaction, a modified auxiliary agent is obtained.

[0071] In the above preparation method provided by the present invention, the trifunctional isocyanate is first diluted with a solvent, and the coupling agent is added under inert conditions. The amino group in the coupling agent reacts rapidly with the isocyanate group, and then the temperature is raised to continue the reaction until it is complete; then S-glycidol is added. Under the condition of 55-65 °C, the hydroxyl group in S-glycidol reacts with the remaining isocyanate group in the first step, and then a catalyst is added to make the reaction complete, and finally an auxiliary agent product containing at least two epoxy groups and 1.5 siloxane-carbon bonds in the molecular chain is synthesized.

[0072] The modified additive provided by the present invention uses trifunctional isocyanate, amino silane coupling agent, S-glycidol, catalyst and solvent as raw materials, and a certain proportional relationship is controlled among the trifunctional isocyanate, amino silane coupling agent and S-glycidol, so as to obtain a modified additive containing a certain amount of epoxy groups and silicon-oxygen-carbon bonds, which can improve the compatibility and anti-aging property of the polyurethane adhesive at the same time.

[0073] The present invention also provides a polyurethane adhesive, and its preparation raw materials include, by mass:

[0074]

[0075] Among them,

[0076] The modified additive is the modified additive described in the above technical solution or the modified additive prepared by the preparation method described in the above technical solution.

[0077] In the present invention, the polyurethane prepolymer is preferably a polyurethane prepolymer with an NCO content of 2% to 5% and a viscosity of 20000 to 60000 mPa·s. Among them, the NCO content can specifically be 2%, 3%, 4%, 5%. The viscosity can specifically be 20000 mPa·s, 25000 mPa·s, 28000 mPa·s, 30000 mPa·s, 35000 mPa·s, 38000 mPa·s, 40000 mPa·s, 45000 mPa·s, 50000 mPa·s, 55000 mPa·s, 60000 mPa·s. The present invention has no special limitation on the source of the polyurethane prepolymer, which can be a commercially available product or prepared according to the conventional preparation method in the art.

[0078] In the present invention, the plasticizer is preferably at least one of DOP (i.e., dioctyl phthalate), DIDP (i.e., diisodecyl phthalate), DINP (i.e., diisononyl phthalate), DBP (i.e., dibutyl phthalate) and DIBP (i.e., diisobutyl phthalate). The present invention has no special limitation on the source of the plasticizer, and it can be a commercially available product. In the present invention, based on 100 parts of the polyurethane prepolymer, the dosage of the plasticizer is 10 to 30 parts, and can specifically be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts.

[0079] In the present invention, the calcium carbonate is preferably nano calcium carbonate. The particle size of the nano calcium carbonate is preferably 40-100 nm, and in some embodiments of the present invention, it is 40-80 nm. The present invention has no special limitation on the source of the calcium carbonate, and it can be a commercially available product. In the present invention, based on 100 parts of the polyurethane prepolymer, the dosage of the calcium carbonate is 20-40 parts, specifically 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts.

[0080] In the present invention, the specifications of the glass microspheres are preferably: particle size D90 is 15-110 μm, true density is 0.2-0.7 g / cm 3 . Among them, the particle size D90 can specifically be 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 105 μm, 110 μm. The true density can specifically be 0.20 g / cm 3 , 0.25 g / cm 3 , 0.30 g / cm 3 , 0.35 g / cm 3 , 0.40 g / cm 3 , 0.42 g / cm 3 , 0.45 g / cm 3 , 0.50 g / cm 3 , 0.55 g / cm 3 , 0.60 g / cm 3 , 0.65 g / cm 3 , 0.70 g / cm 3 . In some embodiments of the present invention, the specifications of the glass microspheres are: particle size D90 is 40 μm, true density is 0.42 g / cm 3 . The present invention has no special limitation on the source of the glass microspheres, and it can be a commercially available product. In the present invention, based on 100 parts of the polyurethane prepolymer, the dosage of the glass microspheres is 10-30 parts, specifically 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts.

[0081] In the present invention, the modification assistant is the one described above, and will not be elaborated here. In the present invention, based on 100 parts of the polyurethane prepolymer, the amount of the modification assistant is 0.5 to 1 part, specifically, it can be 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, or 1.0 part.

[0082] In the present invention, the catalyst is preferably dibutyltin dilaurate and / or dichlorodibutyltin. There is no special limitation on the source of the catalyst in the present invention, and it can be a commercially available product. In the present invention, based on 100 parts of the polyurethane prepolymer, the amount of the catalyst is 0.02 to 0.1 part, specifically, it can be 0.02 part, 0.03 part, 0.04 part, 0.05 part, 0.06 part, 0.07 part, 0.08 part, 0.09 part, or 0.10 part.

[0083] The present invention also provides a method for preparing the polyurethane adhesive described in the above technical solution, which includes the following steps: mixing the polyurethane prepolymer, plasticizer, calcium carbonate, glass microspheres, modification assistant, and catalyst to obtain the polyurethane adhesive.

[0084] Among them, the types and amounts of the polyurethane prepolymer, plasticizer, calcium carbonate, glass microspheres, modification assistant, and catalyst are the same as those described in the previous technical solution, and will not be elaborated one by one here.

[0085] In the present invention, the above preparation method preferably specifically includes: first, stirring and mixing the polyurethane prepolymer and the plasticizer, then adding calcium carbonate and stirring and mixing, and finally adding glass microspheres, a modifying agent and a catalyst and stirring and mixing. The temperature of each of the above mixing steps is preferably independently selected from 20 to 40 °C, and specifically can be 20 °C, 25 °C, 30 °C, 35 °C, 40 °C. Each of the above mixing steps is preferably carried out under vacuum conditions, and the vacuum pressure of each mixing step is preferably independently selected from -0.095 MPa to -0.098 MPa, and specifically can be -0.095 MPa, -0.096 MPa, -0.097 MPa, -0.098 MPa. The stirring rate of each of the above mixing steps is preferably independently selected from 30 to 60 rpm, and specifically can be 30 rpm, 35 rpm, 40 rpm, 45 rpm, 50 rpm, 55 rpm, 60 rpm. In each of the above mixing steps, the time of the first mixing (i.e., stirring and mixing the polyurethane prepolymer and the plasticizer) is preferably 10 to 15 min, and specifically can be 10 min, 11 min, 12 min, 13 min, 14 min, 15 min. The time of the second mixing (i.e., adding calcium carbonate and stirring and mixing) is preferably 15 to 30 min, and specifically can be 15 min, 20 min, 25 min, 30 min. The time of the last mixing (i.e., adding glass microspheres, a modifying agent and a catalyst and stirring and mixing) is preferably 10 to 15 min, and specifically can be 10 min, 11 min, 12 min, 13 min, 14 min, 15 min. After the above treatment, a polyurethane adhesive is obtained.

[0086] In the present invention, a polyurethane prepolymer, a plasticizer, calcium carbonate, glass microspheres, a modifying agent and a catalyst are mixed in a certain proportion to obtain a polyurethane adhesive. During the use of this polyurethane adhesive, the silicon-oxygen-carbon bond in the modifying agent reacts with the glass microspheres and fillers to enhance the binding force between the glass microspheres, fillers and the matrix. Moreover, in the later use, the epoxy functional group in the modifying agent slowly reacts with the urethane after the colloid is cured, and reacts with the polyurethane main body to form new crosslinking points to increase the strength, so as to resist the strength loss caused by matrix cracking. Through the cooperation of various effects, the heat aging resistance of the polyurethane adhesive can be effectively improved.

[0087] The test results show that the modifying agent of the present invention can make the heat aging strength (70 °C × 15 days) of the polyurethane adhesive reach more than 2 MPa, and the strength after heat aging is slightly increased compared with that before heat aging, showing excellent heat aging strength.

[0088] In order to further understand the present invention, the preferred embodiments of the present invention will be described below in conjunction with examples. However, it should be understood that these descriptions are only for further explaining the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0089] In the following examples, unless otherwise specified, the raw materials are commercially available products. Among them, the calcium carbonate is nano calcium carbonate with a particle size of 40 - 80 nm, provided by Shanxi Lanhua Huaming Nano Materials. The D90 particle size of the glass microspheres is 40 μm and the true density is 0.42 g / cm 3 , provided by Zhengzhou Shenglaite Hollow Microsphere New Materials Co., Ltd.

[0090] Example 1

[0091] 1. Synthesis of the modification aid:

[0092] 1.1 Preparation of raw materials:

[0093] (1) Trifunctional isocyanate - HDI biuret, 1.0 mol;

[0094] (2) S - glycidol, 2.50 mol;

[0095] (3) Amino - silane coupling agent - bis[3 - (triethoxysilyl)propyl]amine, 0.50 mol;

[0096] (4) Catalyst - dibutyltin dilaurate, mass ratio of catalyst to base material = 2∶10000;

[0097] (5) Solvent - ethyl acetate, mass ratio of solvent to base material = 57∶100.

[0098] In the above raw materials, the proportional relationship of the three substances in the base material satisfies formula A: n1∶n2∶n3 = 1.0∶2.5∶0.50 = 10∶25∶5; at the same time, it also satisfies formula B: (2.94 - 3.06)n1 = n2 + n3 = 3.00.

[0099] 1.2 Preparation process:

[0100] a) Mix the trifunctional isocyanate and the solvent evenly to obtain a mixed solution. Under a nitrogen atmosphere and stirring conditions, dropwise add the amino - silane coupling agent to the mixed solution, react at room temperature of 25 °C for 0.5 h first, and then heat to 60 °C and react for 1.5 h to obtain reactant 1.

[0101] b) Add S - glycidol to reactant 1, react at 60 °C for 4 h under a nitrogen atmosphere, and then add the catalyst and continue to react for 2.5 h to obtain the modification aid.

[0102] 2. Preparation of the polyurethane adhesive:

[0103] 2.1 Preparation of raw materials:

[0104]

[0105] 2.2 Preparation process:

[0106] Under the conditions of 30 °C and -0.096 MPa, first stir the polyurethane prepolymer and the plasticizer at 50 rpm for 15 min, then add calcium carbonate and stir for 20 min, and finally add glass microspheres, the modified additive and the catalyst and stir for 15 min. Then take out of the kettle to obtain the polyurethane adhesive.

[0107] Example 2

[0108] 1. Synthesis of the modified additive:

[0109] 1.1 Preparation of raw materials:

[0110] (1) Trifunctional isocyanate - HDI trimer, 1.0 mol;

[0111] (2) S-glycidol, 2.0 mol;

[0112] (3) Amino silane coupling agent - bis(3-trimethoxysilylpropyl)amine, 1.0 mol;

[0113] (4) Catalyst - dibutyltin dilaurate, mass ratio of catalyst to base material = 1.0:10000;

[0114] (5) Solvent - ethyl acetate, mass ratio of solvent to base material = 45:100.

[0115] In the above raw materials, the proportional relationship of the three substances in the base material satisfies formula A: n1:n2:n3 = 1.0:2.0:1.0 = 10:20:10; at the same time, it also satisfies formula B: (2.94 - 3.06)n1 = n2 + n3 = 3.00.

[0116] 1.2 Preparation process:

[0117] a) Mix the trifunctional isocyanate and the solvent evenly to obtain a mixed solution. Under a nitrogen atmosphere and stirring conditions, dropwise add the amino silane coupling agent to the mixed solution. First react at room temperature of 25 °C for 1 h, and then heat to 50 °C and react for 2 h to obtain reactant 1.

[0118] b) Add S-glycidol to reactant 1, react at 55 °C for 5 h under a nitrogen atmosphere, and then add the catalyst and continue to react for 3 h to obtain the modified additive.

[0119] 2. Preparation of the polyurethane adhesive:

[0120] 2.1 Preparation of raw materials:

[0121]

[0122] 2.2 Preparation process:

[0123] Under the conditions of 20 °C and -0.095 MPa, first stir the polyurethane prepolymer and the plasticizer at 40 rpm for 15 min, then add calcium carbonate and stir for 30 min, and finally add glass beads, the modified additive and the catalyst and stir for 15 min. Then take out of the kettle to obtain the polyurethane adhesive.

[0124] Example 3

[0125] 1. Synthesis of the modified additive:

[0126] 1.1 Preparation of raw materials:

[0127] (1) Trifunctional isocyanate - TDI trimer, 1 mol;

[0128] (2) S-glycidol, 2.0 mol;

[0129] (3) Amino silane coupling agent - γ-aminopropyltriethoxysilane, 1.0 mol;

[0130] (4) Catalyst - dibutyltin dilaurate, mass ratio of catalyst to base material = 1:10000;

[0131] (5) Solvent - ethyl acetate, mass ratio of solvent to base material = 56:100.

[0132] In the above raw materials, the proportional relationship of the three substances in the base material satisfies formula A: n1:n2:n3 = 1.0:2.0:1.0 = 10:20:10; at the same time, it also satisfies formula B: (2.94 - 3.06)n1 = n2 + n3 = 3.00.

[0133] 1.2 Preparation process:

[0134] a) Mix the trifunctional isocyanate and the solvent evenly to obtain a mixed solution. Under a nitrogen atmosphere and stirring conditions, dropwise add the amino silane coupling agent to the mixed solution, react at room temperature of 25 °C for 1 h first, and then heat to 70 °C and react for 1 h to obtain reactant 1.

[0135] b) Add S-glycidol to reactant 1, react at 65 °C for 3 h under a nitrogen atmosphere, and then add the catalyst and continue to react for 2 h to obtain the modified additive.

[0136] 2. Preparation of the polyurethane adhesive:

[0137] 2.1 Preparation of raw materials:

[0138]

[0139] 2.2 Preparation process:

[0140] Under the conditions of 40 °C and -0.098 MPa, first stir the polyurethane prepolymer and the plasticizer at 60 rpm for 10 min, then add calcium carbonate and stir for 10 min, and finally add glass microspheres, the modified additive and the catalyst and stir for 15 min. Then take out of the kettle to obtain the polyurethane adhesive.

[0141] Comparative Example 1

[0142] Preparation of the polyurethane adhesive:

[0143] Carry out according to Example 1, except that the modified additive is replaced with silane coupling agent KH560 having the same weight as the solid content of the modified additive (total weight of trifunctional isocyanate, S-glycidol and amino silane coupling agent).

[0144] Comparative Example 2

[0145] 1. Synthesis of the modified additive:

[0146] Carry out according to Example 1, except that the amount of S-glycidol is increased to 5 mol and the amount of amino silane coupling agent is reduced to 0.2 mol. That is, the proportional relationship of the three substances in the base material is n1∶n2∶n3 = 1.0∶5∶0.2 = 10∶50∶2; (2.94 - 3.06)n1 = 2.94 - 3.06, n2 + n3 = 5.2. The dosage relationship of the three substances in the base material does not satisfy the relational expression A: n1∶n2∶n3 = 10∶(20 - 25)∶(5 - 10), nor does it satisfy the relational expression B: (2.94 - 3.06)n1 = n2 + n3.

[0147] 2. Preparation of the polyurethane adhesive:

[0148] Carry out according to Example 1, except that the solid content of the modified additive (total weight of trifunctional isocyanate, S-glycidol and amino silane coupling agent) is replaced with the modified additive obtained in Comparative Example 2 having the same solid content (total weight of trifunctional isocyanate, S-glycidol and amino silane coupling agent).

[0149] Comparative Example 3

[0150] 1. Synthesis of the modified additive:

[0151] Implemented according to Example 1, except that the amount of S-glycidol is reduced to 1 mol and the amount of amino-silane coupling agent is increased to 3 mol. That is, the proportional relationship of the three substances in the base material is n1∶n2∶n3 = 1.0∶1∶3 = 10∶10∶30, (2.94~3.06)n1 = 2.94~3.06, and n2 + n3 = 4. The dosage relationship of the three substances in the base material does not satisfy the relationship A: n1∶n2∶n3 = 10∶(20~25)∶(5~10), nor does it satisfy the relationship B: (2.94~3.06)n1 = n2 + n3.

[0152] 2. Preparation of polyurethane adhesive:

[0153] Implemented according to Example 1, except that the solid content of the modification aid (total weight of trifunctional isocyanate, S-glycidol and amino-silane coupling agent) is replaced with the modification aid obtained in Comparative Example 3 with the same solid content (total weight of trifunctional isocyanate, S-glycidol and amino-silane coupling agent).

[0154] Example 4: Product testing

[0155] Each polyurethane adhesive sample was scraped into a thin sheet of 40 cm × 15 cm × 2 mm, cured for 7 days under standard conditions (temperature 23°C, relative humidity 50%), and then cut into several dumbbell-shaped pieces (at this time it is the standard sample). Take a part of the dumbbell-shaped pieces to test the tensile strength and elongation at break (at this time it is the standard performance); then take another part of the dumbbell-shaped pieces to conduct a thermal aging test at 70°C and test the tensile strength and elongation at break of the sample. The adhesive samples obtained in Examples 1-3 and Comparative Examples 1-3 were all tested by the above tests, and the results are shown in Table 1.

[0156] Table 1: Product performance

[0157]

[0158] It can be seen from the test results in Table 1 that the thermal aging strength (70°C × 15 days) of the samples in Examples 1-3 of the present invention reaches more than 2 MPa, and the strength increases after thermal aging, showing excellent heat aging strength. Compared with the examples, the thermal aging strength of Comparative Example 1 is significantly reduced, which proves that compared with ordinary modifiers, the modification aid of the present invention can effectively improve the heat aging strength of polyurethane adhesives. Compared with the examples, the thermal aging strength of Comparative Examples 2-3 is significantly reduced, and the strength of Comparative Examples 2-3 before and after thermal aging shows a decreasing trend, which proves that if the dosage relationship of trifunctional isocyanate, S-glycidol and amino-silane coupling agent does not satisfy the relationship A and formula B at the same time, it is not conducive to improving the thermal aging resistance of polyurethane adhesives. Only by controlling the dosage relationship of the specific formula A and formula B of the present invention can the thermal aging resistance of polyurethane adhesives be effectively improved.

[0159] In this article, specific examples are used to elaborate on the principles and implementation manners of the present invention. The description of the above embodiments is only used to help understand the method and its core idea of the present invention, including the best mode, and also enables any person skilled in the art to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that for those of ordinary skill in the art in the technical field, without departing from the principles of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. The protection scope of the present invention patent is defined by the claims and may include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements similar to the literal description of the claims, or if they include equivalent structural elements that have no substantial difference from the literal description of the claims, then these other embodiments should also be included within the scope of the claims.

Claims

1. A modified auxiliary agent, characterized in that, Its preparation raw materials include: (1) trifunctional isocyanate; (2) S-glycidol; (3) amino-silane coupling agent; (4) catalyst; (5) solvent; Among them, the dosage relationship of the trifunctional isocyanate, S-glycidol and amino-silane coupling agent is as follows: Denote the molar amount of the trifunctional isocyanate as n1, the molar amount of S-glycidol as n2, and the molar amount of the amino-silane coupling agent as n3, then the proportional relationship among the three simultaneously satisfies Formula A and Formula B: n1∶n2∶n3 = 10∶(20~25)∶(5~10) Formula A; n1×3×(0.98~1.02) = n2 + n3 Formula B; the trifunctional isocyanate is at least one of HDI biuret, HDI trimer, TDI trimer and IPDI trimer; the amino-silane coupling agent is at least one of bis(3-trimethoxysilylpropyl)amine, bis[3-(triethoxysilyl)propyl]amine, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and N-phenylaminomethyltriethoxysilane; the catalyst is at least one of dibutyltin dilaurate and dichlorodibutyltin; The preparation method of the modification assistant includes the following steps: a) Mix and react the trifunctional isocyanate, solvent and amino-silane coupling agent to obtain Reactant 1; b) Mix and react Reactant 1 with S-glycidol and the catalyst to obtain the modification assistant.

2. The modifying aid according to claim 1, wherein The solvent is at least one of ethyl acetate, toluene and xylene.

3. The modifying aid according to claim 1, wherein The mass ratio of the catalyst to the base material is (1~5)∶10000; The mass ratio of the solvent to the base material is (45~100)∶100; The base material is the trifunctional isocyanate, S-glycidol and amino-silane coupling agent.

4. A preparation method of the modifying aid according to any one of claims 1 to 3, characterized in that, It includes the following steps: a) Mix and react the trifunctional isocyanate, solvent and amino-silane coupling agent to obtain Reactant 1; b) Mix and react Reactant 1 with S-glycidol and the catalyst to obtain the modification assistant.

5. The preparation method according to claim 4, characterized in that, Specifically includes the following steps: a) Mix the trifunctional isocyanate and the solvent to obtain a mixed solution; Dropwise add the amino-silane coupling agent to the mixed solution under a protective atmosphere. After the dropwise addition, first react at room temperature for 0.5~1 h, then heat to 50~70 °C and react for 1~2 h to obtain Reactant 1; b) Mix Reactant 1 with S-glycidol, react at 55~65 °C for 3~5 h under a protective atmosphere, and then add the catalyst and react for 2~3 h to obtain the modification assistant.

6. A polyurethane adhesive, characterized in that, By mass, its preparation raw materials include: 100 parts of polyurethane prepolymer; 10~30 parts of plasticizer; 20~40 parts of calcium carbonate; 10~30 parts of glass microspheres; 0.5~1 part of modification assistant; 0.02~0.1 part of catalyst; Among them, the modification assistant is the modification assistant described in any one of Claims 1~3 or the modification assistant prepared by the preparation method described in any one of Claims 4~5; 7. The polyurethane adhesive according to claim 6, characterized in that, The NCO content of the polyurethane prepolymer is 2%~5%, and the viscosity is 20000~60000 mPa·s; The plasticizer is at least one of DOP, DIDP, DINP, DBP, and DIBP; The catalyst is at least one of dibutyltin dilaurate and dichlorodibutyltin.

8. A method for preparing the polyurethane adhesive according to any one of claims 6 to 7, characterized in that, It includes the following steps: Mix a polyurethane prepolymer, a plasticizer, calcium carbonate, glass microspheres, a modification aid, and a catalyst to obtain a polyurethane adhesive.

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