Silane modified high-performance structural sealing material based on diphenyl sulfone derivative regulation and control and preparation method of silane modified high-performance structural sealing material

Abstract

The invention relates to the technical field of sealing materials, in particular to a silane modified high-performance structural sealing material based on diphenyl sulfone derivative regulation and control and a preparation method of the silane modified high-performance structural sealing material. The silane modified high-performance structural sealing material based on diphenyl sulfone derivative regulation and control is prepared from the following raw materials in parts by weight: 80 to 100 parts of silane modified polyurethane, 10 to 15 parts of diphenyl sulfone derivative modified polyurethane, 20 to 40 parts of plasticizer, 100 to 150 parts of filler, 0.5 to 2 parts of organic solvent, 1 to 2 parts of thixotropic agent, 0.05 to 2 parts of catalyst, 0.5 to 2 parts of coupling agent and 0.03 to 1 part of light stabilizer. The silane modified high-performance structural sealing material based on diphenyl sulfone derivative regulation and control has excellent mechanical properties and adhesive properties, and still can maintain relatively excellent mechanical properties after water resistance and heat resistance tests.

Description

Technical Field

[0001] The present invention relates to the technical field of sealing materials, and particularly relates to a high-performance structural sealing material modified by silane regulated by diphenyl sulfone derivatives and a preparation method thereof. Background Art

[0002] Sealant is a functional material filled in the gaps between connecting parts and can play the roles of bonding and sealing after curing and drying. It also has various application effects such as waterproofing, dustproofing, shock absorption and pressure bearing. Compared with traditional sealing forms such as gaskets, spiral seals, and oil seals, sealants have the advantages of convenient construction, strong adaptability, good sealing effect and long service life, so they have gradually replaced many traditional sealing forms and have broad development and application prospects.

[0003] Polyurethane sealants were developed as early as the 1970s. With the development of society, the application market of polyurethane products has been continuously growing and expanding.

[0004] Patent technical literature CN105219337B discloses a two-component silane-modified polyether sealing material and a preparation method thereof. The two-component silane-modified polyether sealing material includes silane-modified polyether, plasticizer, extender filler A, reinforcing filler, color powder, thixotropic agent, light stabilizer. The sealant of this invention has good construction stability, greatly improves production efficiency, and can be widely applied in fields such as construction, automobiles, locomotives, electronic appliances, etc. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a high-performance structural sealing material modified by silane regulated by diphenyl sulfone derivatives and a preparation method thereof, so as to provide a sealing material with good water resistance and heat resistance.

[0006] Based on the above purpose, the present invention provides a high-performance structural sealing material modified by silane regulated by diphenyl sulfone derivatives, which comprises the following raw materials in parts by weight: 80-100 parts of silane-modified polyurethane, 10-15 parts of diphenyl sulfone derivative-modified polyurethane, 20-40 parts of plasticizer, 100-150 parts of filler, 0.5-2 parts of organic solvent, 1-2 parts of thixotropic agent, 0.05-2 parts of catalyst, 0.5-2 parts of coupling agent, 0.03-1 part of light stabilizer; The preparation steps of the diphenyl sulfone derivative-modified polyurethane are as follows: S1: Add 4,4'-diaminodiphenyl sulfone and terephthaloyl chloride to NMP containing 5% LiCl, and react at 0-5°C to obtain a diphenyl sulfone derivative with a molecular weight of 600-800; S2: Dissolve 4,4'-diphenylmethane diisocyanate and 10 - 12 g of polytetramethylene glycol in 40 - 50 ml of dimethylacetamide, react at 65 - 70 °C for 40 - 50 min, then add 6 - 7 g of diphenylsulfone derivative, react at 80 - 85 °C for 2 - 3 h, and then cool and stir for 90 min to obtain diphenylsulfone derivative-modified polyurethane; In step S1, the dosage ratio of 4,4'-diaminodiphenylsulfone, terephthaloyl chloride, and NMP is 24 - 25 g: 20 - 21 g: 200 - 220 ml; In step S2, the dosage ratio of 4,4'-diphenylmethane diisocyanate, polytetramethylene glycol, dimethylacetamide, and diphenylsulfone derivative is 5 - 6 g: 10 - 12 g: 40 - 50 ml: 6 - 7 g.

[0007] Preferably, the preparation steps of the silane-modified polyurethane are as follows: Under a nitrogen atmosphere, mix polyether diol, 3-isocyanatopropyltrimethoxysilane, and stannous octoate, react at 100 - 110 °C for 5 - 6 h, add porous silica, maintain at 90 °C for 5 h, perform vacuum degassing, and filter to obtain silane-modified polyurethane.

[0008] Preferably, the weight ratio of polyether diol, 3-isocyanatopropyltrimethoxysilane, stannous octoate, and porous silica is 600 - 620 g: 20 - 21 g: 0.5 - 0.6 g: 10 - 12 g.

[0009] Preferably, the molecular weight of the polyether diol is 12000.

[0010] Preferably, the plasticizer is one of DINP and DIDP.

[0011] Preferably, the filler is one of heavy calcium carbonate, nano-active calcium carbonate, silica powder, and kaolin.

[0012] Preferably, the organic solvent is one of toluene, xylene, ethyl acetate, and acetone.

[0013] Preferably, the thixotropic agent is one of polyamide wax and fumed silica.

[0014] Preferably, the catalyst is one of stannous octoate and dibutyltin dilaurate.

[0015] Preferably, the coupling agent is one of γ-aminopropyltriethoxysilane and N-aminoethyl-γ-aminopropyltrimethoxysilane.

[0016] Preferably, the light stabilizer is one of UV-9, 326, and 327 of BASF.

[0017] Preferably, the molecular weight of the polytetramethylene glycol described in step S2 is 1000.

[0018] Furthermore, the present invention also provides a preparation method of a silane-modified high-performance structural sealant regulated by a diphenyl sulfone derivative. The preparation steps are as follows: Add the filler and the plasticizer into a planetary stirring kettle, heat and raise the temperature while stirring to perform high-temperature dehydration. Subsequently, add the silane-modified polyurethane, the diphenyl sulfone derivative-modified polyurethane, the organic solvent, the thixotropic agent, the penetrant, the catalyst, the coupling agent, and the light stabilizer into the planetary stirring kettle, stir to make them evenly mixed, discharge and seal in a can to obtain the silane-modified high-performance structural sealant regulated by the diphenyl sulfone derivative.

[0019] Advantages of the present invention: In the present invention, by grafting the diphenyl sulfone derivative into the polyurethane crosslinking network, due to the rigid structure of the diphenyl sulfone derivative and the ability to increase the crosslinking density of the polyurethane network, the mechanical properties, water resistance, and heat resistance of the sealant are all improved.

[0020] In the present invention, by further regulating the molecular weight of the diphenyl sulfone derivative, the lower molecular weight diphenyl sulfone derivative (600 - 800) is more likely to diffuse in the system and react with the polyurethane chain segments, forming a more uniform crosslinking network, further improving the mechanical properties, water resistance, and heat resistance of the sealant. Specific embodiments

[0021] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to specific embodiments.

[0022] Example 1: A silane-modified high-performance structural sealant regulated by a diphenyl sulfone derivative, and the specific preparation steps are as follows: (1) Under a nitrogen atmosphere, mix 600 g of polyether diol, 20 g of 3-isocyanatopropyltrimethoxysilane, and 0.5 g of stannous octoate, react at 100 °C for 5 h, add 10 g of porous silica, keep at 90 °C for 5 h, perform vacuum degassing, and filter to obtain the silane-modified polyurethane. (2) Add 24 g of 4,4'-diaminodiphenyl sulfone and 20 g of terephthaloyl chloride into 200 ml of NMP containing 5% LiCl, react at 0 °C to obtain a diphenyl sulfone derivative with a molecular weight of 600. (3) Dissolve 5 g of 4,4'-diphenylmethane diisocyanate and 10 g of polytetramethylene glycol in 40 ml of dimethylacetamide, react at 65 °C for 40 min, then add 6 g of the diphenyl sulfone derivative, react at 80 °C for 2 h, and then cool and stir for 90 min to obtain the diphenyl sulfone derivative-modified polyurethane. (4) Add 100 g of silica powder and 20 g of DINP into a planetary stirring kettle, heat up while stirring to conduct high-temperature dehydration. Subsequently, add 80 g of silane-modified polyurethane, 10 g of diphenyl sulfone derivative-modified polyurethane, 0.5 g of toluene, 1 g of polyamide wax, 0.05 g of stannous octoate, 0.5 g of γ-aminopropyltriethoxysilane, and 0.03 g of UV-9 into the planetary stirring kettle, stir to make them evenly mixed, discharge the material into a can and seal it to obtain a high-performance structural sealant based on diphenyl sulfone derivative-regulated silane modification.

[0023] Example 2: A high-performance structural sealant based on diphenyl sulfone derivative-regulated silane modification, and the specific preparation steps are as follows: (1) Under a nitrogen atmosphere, mix 610 g of polyether diol, 21 g of 3-isocyanatopropyltrimethoxysilane, and 0.5 g of stannous octoate, react at 105 °C for 6 h, add 11 g of porous silica, keep it at 90 °C for 5 h, conduct decompression degassing, and filter press to obtain silane-modified polyurethane; (2) Add 25 g of 4,4'-diaminodiphenyl sulfone and 20 g of terephthaloyl chloride into 205 ml of NMP containing 5% LiCl, react at 3 °C to obtain a diphenyl sulfone derivative with a molecular weight of 700; (3) Dissolve 5.5 g of 4,4'-diphenylmethane diisocyanate and 11 g of polytetramethylene glycol in 45 ml of dimethylacetamide, react at 68 °C for 45 min, then add 6.5 g of diphenyl sulfone derivative, react at 83 °C for 3 h, and then cool and stir for 90 min to obtain diphenyl sulfone derivative-modified polyurethane; (4) Add 130 g of silica powder and 30 g of DINP into a planetary stirring kettle, heat up while stirring to conduct high-temperature dehydration. Subsequently, add 90 g of silane-modified polyurethane, 13 g of diphenyl sulfone derivative-modified polyurethane, 1 g of toluene, 1.5 g of polyamide wax, 1 g of stannous octoate, 1 g of γ-aminopropyltriethoxysilane, and 0.05 g of UV-9 into the planetary stirring kettle, stir to make them evenly mixed, discharge the material into a can and seal it to obtain a high-performance structural sealant based on diphenyl sulfone derivative-regulated silane modification.

[0024] Example 3: A high-performance structural sealant based on diphenyl sulfone derivative-regulated silane modification, and the specific preparation steps are as follows: (1) Under a nitrogen atmosphere, mix 620 g of polyether diol, 21 g of 3-isocyanatopropyltrimethoxysilane, and 0.6 g of stannous octoate, react at 110 °C for 6 h, add 12 g of porous silica, keep it at 90 °C for 5 h, conduct decompression degassing, and filter press to obtain silane-modified polyurethane; (2) Add 25 g of 4,4'-diaminodiphenyl sulfone and 21 g of terephthaloyl chloride to 220 ml of NMP containing 5% LiCl, and react at 5 °C to obtain a diphenyl sulfone derivative with a molecular weight of 800; (3) Dissolve 6 g of 4,4'-diphenylmethane diisocyanate and 12 g of polytetramethylene glycol in 50 ml of dimethylacetamide, react at 70 °C for 50 min, then add 7 g of the diphenyl sulfone derivative, react at 85 °C for 3 h, and then cool and stir for 90 min to obtain a diphenyl sulfone derivative-modified polyurethane; (4) Add 150 g of silica powder and 40 g of DINP to a planetary stirring kettle, heat up while stirring to perform high-temperature dehydration, and then add 100 g of silane-modified polyurethane, 15 g of diphenyl sulfone derivative-modified polyurethane, 2 g of toluene, 2 g of polyamide wax, 2 g of stannous octoate, 2 g of γ-aminopropyltriethoxysilane, and 1 g of UV-9 to the planetary stirring kettle, stir to mix evenly, discharge and seal in a can to obtain a silane-modified high-performance structural sealant regulated by a diphenyl sulfone derivative.

[0025] Comparative Example 1: A silane-modified high-performance structural sealant regulated by a diphenyl sulfone derivative, and the specific preparation steps are as follows: (1) Under a nitrogen atmosphere, mix 610 g of polyether diol, 21 g of 3-isocyanatopropyltrimethoxysilane, and 0.5 g of stannous octoate, react at 105 °C for 6 h, add 11 g of porous silica, hold at 90 °C for 5 h, carry out vacuum degassing, and filter to obtain a silane-modified polyurethane; (2) Add 130 g of silica powder and 30 g of DINP to a planetary stirring kettle, heat up while stirring to perform high-temperature dehydration, and then add 103 g of silane-modified polyurethane, 13 g of diphenyl sulfone derivative-modified polyurethane, 1 g of toluene, 1.5 g of polyamide wax, 1 g of stannous octoate, 1 g of γ-aminopropyltriethoxysilane, and 0.05 g of UV-9 to the planetary stirring kettle, stir to mix evenly, discharge and seal in a can to obtain a silane-modified high-performance structural sealant regulated by a diphenyl sulfone derivative.

[0026] Comparative Example 2: A silane-modified high-performance structural sealant regulated by a diphenyl sulfone derivative, and the specific preparation steps are as follows: (1) Under a nitrogen atmosphere, mix 610 g of polyether diol, 21 g of 3-isocyanatopropyltrimethoxysilane, and 0.5 g of stannous octoate, react at 105 °C for 6 h, add 11 g of porous silica, hold at 90 °C for 5 h, carry out vacuum degassing, and filter to obtain a silane-modified polyurethane; (2) 25 g of 4,4'-diaminodiphenyl sulfone and 20 g of terephthaloyl chloride were added to 205 ml of NMP containing 5% LiCl, and the reaction was carried out at 3 °C to obtain a diphenyl sulfone derivative with a molecular weight of 700; (3) 130 g of silica powder and 30 g of DINP were added to a planetary stirring kettle, heated and stirred while raising the temperature for high-temperature dehydration. Subsequently, 103 g of silane-modified polyurethane, 6.5 g of diphenyl sulfone derivative, 1 g of toluene, 1.5 g of polyamide wax, 1 g of stannous octoate, 1 g of γ-aminopropyltriethoxysilane, and 0.05 g of UV-9 were added to the planetary stirring kettle, stirred to mix evenly, discharged and sealed in cans to obtain a high-performance structural sealant based on diphenyl sulfone derivative-regulated silane modification.

[0027] Comparative Example 3: A high-performance structural sealant based on diphenyl sulfone derivative-regulated silane modification, and the specific preparation steps are as follows: The difference from Example 2 is that the molecular weight of the diphenyl sulfone derivative is 3000, and the remaining steps are the same as those in Example 2.

[0028] Performance Test Tensile strength: Tested according to GB / T 13477.8-2017, and the test results are shown in Table 1; Adhesion performance: Tested according to GB / T 7124-2008, and the test results are shown in Table 1; Water resistance: Tested according to GB / T 13477.8-2017, and its tensile properties were tested after soaking in water for 30 d, and the test results are shown in Table 1; Heat resistance: Tested according to GB / T 13477.8-2017, and its tensile properties were tested after maintaining at 80 °C for 14 d, and the test results are shown in Table 1.

[0029]

[0030] Data analysis: The high-performance structural sealant based on diphenyl sulfone derivative-regulated silane modification of the present invention has excellent mechanical properties and adhesion performance, and still maintains relatively excellent mechanical properties after water resistance and heat resistance tests.

[0031] From the data of Example 2 and Comparative Example 1 in Table 1, it can be seen that by adding diphenyl sulfone derivatives to the raw materials in the present invention, the mechanical properties, water resistance and heat resistance of the sealing material are all improved. This is mainly because: on the one hand, diphenyl sulfone derivatives have a rigid structure, which can restrict the movement of polymer segments, increase the tensile strength of the material, and at the same time can enhance the intermolecular crosslinking density to form stronger physical crosslinking points, thereby improving the overall mechanical strength of the material; on the other hand, diphenyl sulfone derivatives are usually insoluble in water, and the aromatic rings in their molecular structures increase the hydrophobicity, which helps to reduce water penetration; at the same time, the benzene ring provides good heat resistance, making diphenyl sulfone derivatives themselves have high thermal stability, and thus the water resistance and heat resistance of the sealing material are both improved.

[0032] From the data of Example 2 and Comparative Example 2 in Table 1, it can be seen that by grafting diphenyl sulfone derivatives into the polyurethane crosslinking network in the present invention, the mechanical properties, water resistance and heat resistance of the sealing material are all improved. This may be because when diphenyl sulfone derivatives are directly added, there may be compatibility problems between diphenyl sulfone derivatives and silane-modified polyurethane, which will lead to poor interfacial bonding, and thus affect the overall mechanical properties and environmental resistance of the material. At the same time, direct mixing may result in incomplete crosslinking reaction and the inability to form the expected three-dimensional network structure, which will reduce the modulus and strength of the material and reduce the resistance to moisture and heat.

[0033] From the data of Example 2 and Comparative Example 3 in Table 1, it can be seen that by further regulating the molecular weight of diphenyl sulfone derivatives in the present invention, the mechanical properties, water resistance and heat resistance of the sealing material are further improved. This is mainly because compared with high molecular weight, lower molecular weight diphenyl sulfone derivatives (600 - 800) are more likely to diffuse in the system and react with polyurethane segments to form a more uniform crosslinking network, making their mechanical properties and heat resistance better. At the same time, small molecular weight diphenyl sulfone derivatives can more closely fill the voids between polymer chains to form a denser structure, thereby effectively blocking the water penetration path and enhancing the water resistance.

[0034] Those of ordinary skill in the art should understand that: the discussion of any above embodiment is only exemplary and is not intended to imply that the scope of the present invention is limited to these examples; under the concept of the present invention, the technical features in the above embodiments or different embodiments can also be combined, and the steps can be implemented in any order, and there are many other variations in different aspects of the present invention as described above, which are not provided in detail for the sake of brevity.

Claims

1. A high-performance structural sealant modified by silane regulated by diphenyl sulfone derivatives, characterized in that, It includes the following raw materials in parts by weight: 80 - 100 parts of silane - modified polyurethane, 10 - 15 parts of diphenyl sulfone derivative - modified polyurethane, 20 - 40 parts of plasticizer, 100 - 150 parts of filler, 0.5 - 2 parts of organic solvent, 1 - 2 parts of thixotropic agent, 0.05 - 2 parts of catalyst, 0.5 - 2 parts of coupling agent, 0.03 - 1 part of light stabilizer; The preparation steps of the diphenyl sulfone derivative - modified polyurethane are as follows: S1: Add 4,4'-diaminodiphenyl sulfone and terephthaloyl chloride into NMP containing 5% LiCl, and react at 0 - 5 °C to obtain a diphenyl sulfone derivative with a molecular weight of 600 - 800; S2: Dissolve 4,4'-diphenylmethane diisocyanate and 10 - 12 g of polytetramethylene glycol in 40 - 50 ml of dimethylacetamide, react at 65 - 70 °C for 40 - 50 min, then add 6 - 7 g of diphenyl sulfone derivative, react at 80 - 85 °C for 2 - 3 h, and then cool and stir for 90 min to obtain diphenyl sulfone derivative - modified polyurethane; In step S1, the dosage ratio of 4,4'-diaminodiphenyl sulfone, terephthaloyl chloride, and NMP is 24 - 25 g:20 - 21 g:200 - 220 ml; In step S2, the dosage ratio of 4,4'-diphenylmethane diisocyanate, polytetramethylene glycol, dimethylacetamide, and diphenyl sulfone derivative is 5 - 6 g:10 - 12 g:40 - 50 ml:6 - 7 g.

2. The high-performance structural sealant modified with silane regulated by diphenyl sulfone derivative according to claim 1, characterized in that, The preparation steps of the silane - modified polyurethane are as follows: Under a nitrogen atmosphere, mix polyether diol, 3 - isocyanatopropyltrimethoxysilane, and stannous octoate, react at 100 - 110 °C for 5 - 6 h, add porous silica, keep at 90 °C for 5 h, perform vacuum degassing, and filter to obtain silane - modified polyurethane.

3. The high-performance structural sealant modified with silane regulated by diphenyl sulfone derivative according to claim 2, wherein, The weight ratio of polyether diol, 3 - isocyanatopropyltrimethoxysilane, stannous octoate, and porous silica is 600 - 620 g:20 - 21 g:0.5 - 0.6 g:10 - 12 g.

4. The high-performance structural sealant modified with silane regulated by diphenyl sulfone derivative according to claim 2, characterized in that The molecular weight of the polyether diol is 12000.

5. The high-performance structural sealant modified with silane regulated by diphenyl sulfone derivative according to claim 1, characterized in that The plasticizer is one of DINP and DIDP; the filler is one of heavy calcium carbonate, nano - active calcium carbonate, silica powder, and kaolin.

6. The high-performance structural sealant modified with silane regulated by diphenyl sulfone derivative according to claim 1, characterized in that, The organic solvent is one of toluene, xylene, ethyl acetate, and acetone; the thixotropic agent is one of polyamide wax and fumed silica.

7. The high-performance structural sealant modified with silane regulated by diphenyl sulfone derivative according to claim 1, characterized in that, The catalyst is one of stannous octoate and dibutyltin dilaurate; the coupling agent is one of γ - aminopropyltriethoxysilane and N - (2 - aminoethyl) - γ - aminopropyltrimethoxysilane.

8. The high-performance structural sealant modified by silane regulated by diphenyl sulfone derivative according to claim 1, characterized in that, The light stabilizer is one of UV - 9, 326, and 327 from BASF.

9. The high-performance structural sealant modified with silane regulated by diphenyl sulfone derivative according to claim 1, characterized in that, In step S2, the molecular weight of the polytetramethylene glycol is 1000.

10. A preparation method of a high-performance structural sealant modified by silane regulated by a diphenyl sulfone derivative according to any one of claims 1-9, characterized in that, The preparation steps are as follows: Add the filler and the plasticizer into a planetary stirring kettle, heat up while stirring to perform high-temperature dehydration. Subsequently, add the silane-modified polyurethane, the diphenyl sulfone derivative-modified polyurethane, the organic solvent, the thixotropic agent, the penetrant, the catalyst, the coupling agent, and the light stabilizer into the planetary stirring kettle, stir to make them evenly mixed, discharge and seal in cans to obtain a high-performance structural sealant based on silane modification regulated by diphenyl sulfone derivatives.

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