High performance sealant and method of making same

Abstract

This invention discloses a high-performance sealant and its preparation method, belonging to the field of sealant technology. The method includes adding 10-20 parts of diisononyl phthalate to 100 parts of hydroxyl-terminated polybutadiene and stirring; adding 60-90 parts of filler and stirring; adding 18-43 parts of composite functional additives and stirring to obtain a premixed base material; adding 15-25 parts of polymethylene polyphenyl polyisocyanate and 4-8 parts of silane coupling agent; adding 0.1-0.3 parts of composite catalyst; and then adding an ultraviolet absorber and an antioxidant, stirring to obtain a catalytically modified mixture; vacuum degassing and curing to obtain a high-performance sealant. The high-performance sealant prepared by this invention improves flexibility and displacement resistance, significantly increases elongation at break, and achieves a displacement capacity level of 20. It can flexibly adapt to slight deformations in building structures caused by temperature fluctuations and foundation settlement, avoiding cracking and detachment, and maintaining good fireproof sealing performance over a long period.

Description

Technical Field

[0001] This invention relates to the field of sealant technology, specifically to a high-performance sealant and its preparation method. Background Technology

[0002] In the field of fireproofing and sealing in buildings, fire-retardant sealants are key materials for ensuring building fire safety. After years of development, a relatively mature application system has been established. Their core function is to effectively seal under fire conditions through specific formulations, preventing the spread of fire and heat. However, existing fire-retardant sealants generally suffer from poor elongation, resulting in a hard texture after curing and a lack of sufficient flexibility. This defect directly leads to weak resistance to displacement. When the building structure undergoes slight deformation due to factors such as temperature changes and settlement, the sealant is prone to cracking and peeling, failing to maintain a good sealing effect and affecting the reliability of fireproof sealing.

[0003] Based on this, the present invention designs a high-performance sealant and its preparation method to solve the above problems. Summary of the Invention

[0004] To address the aforementioned shortcomings of existing technologies, this invention provides a method for preparing a high-performance sealant, thereby solving problems such as cracking and peeling of current fire-retardant sealants caused by structural deformation, and improving the fire-resistant sealing effect of the sealant. The method specifically includes the following steps: S1: Add dispersant to brucite powder and stir, add anhydrous ethanol and heat, add glycerol-L-proline ethanol solution, stir to react and obtain a mixture; S2: Add vanillin to the mixture of S1 and heat it to react and obtain a modified mixture. Dry and sieve to obtain modified brucite powder. S3: Weigh 60-90 parts by weight of modified brucite powder and 20-40 parts by weight of nano-titanium carbide and mix to obtain a filler; weigh 10-20 parts by weight of attapulgite powder and 5-15 parts by weight of polyimide microspheres and mix to obtain a composite functional additive; weigh 60-90 parts by weight of filler and 18-43 parts by weight of composite functional additive. S4: Add 100 parts by weight of hydroxyl-terminated polybutadiene to a high-speed stirring tank and heat it up. Add 10-20 parts by weight of diisononyl phthalate and stir. Add filler and stir. Add composite functional additives and stir to obtain a premixed base material. S5: Add 15-25 parts by weight of polymethylene polyphenyl polyisocyanate and 4-8 parts by weight of silane coupling agent to the premixed base material, heat and stir, cool down and add 0.1-0.3 parts by weight of composite catalyst, then add 0.5-1.5 parts by weight of ultraviolet absorber and 0.3-0.8 parts by weight of antioxidant, stir to obtain catalytically modified mixture; S6: The catalytically modified mixture is vacuum degassed and cured to obtain a high-performance sealant.

[0005] Furthermore, S1 specifically involves: adding 0.3-0.8 wt% of dispersant to brucite powder, stirring at 1500-2000 r / min for 20-30 min, adding anhydrous ethanol at a solid-liquid mass ratio of 1:8-12, raising the temperature to 45-60℃ at 2-4℃ / min, adding 1.5-3.0% by mass of anhydrous ethanol and a 10-15 wt% glycerol-L-proline ethanol solution in 3-5 portions, reducing the stirring speed to 800-1200 r / min, and reacting for 1.5-2.5 h to obtain a mixture.

[0006] Furthermore, S2 specifically involves adding 0.8-1.5% vanillin by mass of the mixture to the mixture of S1, heating to 60-75℃ at 1-2℃ / min, reducing the stirring rate to 600-800 r / min, reacting for 1-2 h to obtain a modified mixture, and then vacuum drying the modified mixture at 70-90℃ and -0.07 to -0.09 MPa for 3-5 h, sieving to obtain modified brucite powder.

[0007] Furthermore, S4 specifically involves: adding 100 parts by weight of hydroxyl-terminated polybutadiene to a high-speed stirred tank, heating it to 40-55℃ at a rate of 2-4℃ / min, adding 10-20 parts by weight of diisononyl phthalate, stirring for 30-60 min, adding filler at a rate of 1.67-3.33 parts by weight / min, and after all the filler in S3 has been added, adjusting the speed to 800-1200 r / min and stirring for 1.5-3 h, adding composite functional additives at a rate of 2.33-5.56 parts by weight / min, and after all the composite functional additives in S3 have been added, reducing the speed to 600-800 r / min and stirring for 1-2 h to obtain the premixed base material.

[0008] Furthermore, S5 specifically involves adding 15-25 parts by weight of polymethylene polyphenyl polyisocyanate and 4-8 parts by weight of KH-550 to the premixed base material, heating to 55-65℃ at 5-8℃ / min, stirring for 40-80min, cooling to 30-40℃ at 3-4℃ / min, adding 0.1-0.3 parts by weight of composite catalyst, then adding 0.5-1.5 parts by weight of ultraviolet absorber and 0.3-0.8 parts by weight of antioxidant, and stirring at 150-260r / min for 30-50min to obtain the catalytically modified mixture.

[0009] Furthermore, the composite catalyst is composed of stannous octoate and tetrabutyl titanate in a mass ratio of 4-7:5-9.

[0010] Furthermore, S6 specifically involves: placing the catalytically modified mixture under a vacuum of -0.08 to -0.095 MPa and at 30-40°C for 20-40 minutes to degas, then injecting the degassed material into a sealed container and maturing it at 25-35°C and 40-60% relative humidity for 12-24 hours to obtain a high-performance sealant.

[0011] A high-performance sealant is prepared according to the preparation method described above.

[0012] Compared with the prior art, the beneficial effects of this invention are as follows: 1. The high-performance sealant prepared by this invention can improve flexibility and displacement resistance, significantly improve elongation at break, and achieve a displacement capacity level of 20. It can flexibly adapt to slight deformations of building structures caused by temperature fluctuations and foundation settlement, avoid cracking and falling off, and maintain good fireproof sealing performance for a long time.

[0013] 2. This invention significantly enhances low-temperature crack resistance and environmental tolerance. It is less prone to cracking in low-temperature environments, and after multiple cold-pull-hot-press cycle tests, the bond failure depth is small. It can still maintain structural integrity and bond stability under complex working conditions such as alternating high and low temperatures and humidity changes, and is suitable for building needs under different climatic conditions. Detailed Implementation

[0014] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0015] Example 1: This example discloses a method for preparing a high-performance sealant, including the following steps: S1: Add 0.3wt% of dispersant (polyethylene glycol 400) to brucite powder (Lingshou County Zhanxing Mineral Products Co., Ltd., product number 06, the same below), stir at 1500 r / min for 20 min, add anhydrous ethanol at a solid-liquid mass ratio of 1:8, heat to 45℃ at 2℃ / min, add 1.5% by mass of anhydrous ethanol in a glycerol-L-proline ethanol solution (mass fraction of 10wt%) in 3 portions, reduce the stirring speed to 800 r / min, react for 1.5 h to obtain a mixture; S2: Add 0.8% vanillin by mass of the mixture to the mixture of S1, heat to 60℃ at 1℃ / min, reduce the stirring rate to 600r / min, react for 1h to obtain a modified mixture, vacuum dry the modified mixture at 70℃ and -0.07MPa for 3h, and sieve (filter mesh size 1μm) to obtain modified brucite powder. S3: Weigh 60 parts of modified magnesia powder and 20 parts of nano titanium carbide (Sichuan Xinjinchun Metal Materials Co., Ltd., product mesh size 60-200 mesh, the same below) by weight and mix them to obtain the filler. Weigh 10 parts of attapulgite powder and 5 parts of polyimide microspheres by weight and mix them to obtain the composite functional additive. Weigh out 60 parts of filler and 18 parts of composite functional additives by weight; The polyimide microspheres were prepared by the method described in Example 1 of Chinese Patent Publication No. CN105801857B, "A Method for Preparing Polyimide Microspheres and the Same," specifically as follows: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (1.0 mol, 310.21 g), methanol (10 mol, 320.40 g), and tetrahydrofuran (16 mol, 1154 g) were added to a three-necked flask and heated under reflux at 70 °C for 4 h to obtain a mixture. The mixture was cooled to room temperature, and aromatic diamine (0.5 mol, 128.6 g), 4,4'-diaminodiphenylmethane (0.5 mol, 99.14 g), and polysiloxane (8.0 g) were added. The mixture was stirred at 25 °C for 8 h to obtain a polymer mixture. The mixture was rotary evaporated and then dried under reduced pressure to obtain a precursor powder with a particle size of 140 mesh. The precursor powder was transferred to a mold and foamed at 150 °C for 1 h, and then heated to 300 °C for 1 h for imidization to obtain polyimide microspheres.

[0016] S4: Add 100 parts by weight of hydroxyl-terminated polybutadiene (Wuhan Smike Biotechnology Co., Ltd., CAS No. 69102-90-5, the same below) to a high-speed stirred tank, heat to 40℃ at 2℃ / min, add 10 parts by weight of diisononyl phthalate, stir for 30 min, add filler at a rate of 1.67 parts by weight / min, after all the filler in S3 has been added, adjust the speed to 800 r / min, stir for 1.5 h, add composite functional additives at a rate of 2.33 parts by weight / min, after all the composite functional additives in S3 have been added, reduce the speed to 600 r / min, stir for 1 h, and obtain the premixed base material; S5: Add 15 parts by weight of polymethylene polyphenyl polyisocyanate (Zhongshan Dixin Chemical Co., Ltd., EINECS No. 922-627-7, the same below) and 4 parts by weight of KH-550 to the premixed base material, heat to 55℃ at 5℃ / min, stir for 40min, cool to 30℃ at 3℃ / min, add 0.1 parts by weight of composite catalyst (composed of stannous octoate and tetrabutyl titanate in a mass ratio of 4:5), then add 0.5 parts by weight of ultraviolet absorber (UV-350) and 0.3 parts by weight of antioxidant (BASF antioxidant 1098), stir at 150r / min for 30min to obtain catalytically modified mixture; S6: The catalytically modified mixture is placed under a vacuum of -0.08MPa and 30℃ for 20 minutes to degas. The degassed material is then injected into a sealed container and cured at 25℃ and 40% relative humidity for 12 hours to obtain a high-performance sealant.

[0017] Example 2: This example discloses a method for preparing a high-performance sealant, including the following steps: S1: Add 0.8wt% dispersant (polyethylene glycol 400) to brucite powder, stir at 2000 r / min for 30 min, add anhydrous ethanol at a solid-liquid mass ratio of 1:12, heat to 60℃ at 4℃ / min, add 3.0% by mass of anhydrous ethanol in 5 portions of glycerol-L-proline ethanol solution (mass fraction of 15wt%), reduce the stirring speed to 1200 r / min, react for 2.5 h to obtain a mixture; S2: Add 1.5% vanillin by mass of the mixture to the mixture of S1, heat to 75℃ at 2℃ / min, reduce the stirring rate to 800r / min, react for 2h to obtain a modified mixture, dry the modified mixture under vacuum at 90℃ and -0.09MPa for 5h, and sieve (filter mesh size 1μm) to obtain modified brucite powder. S3: Weigh 90 parts of modified magnesia powder and 40 parts of nano-titanium carbide by weight and mix them to obtain a filler. Weigh 20 parts of attapulgite powder and 15 parts of polyimide microspheres by weight and mix them to obtain a composite functional additive. Weigh out 90 parts of filler and 43 parts of composite functional additives by weight; S4: Add 100 parts by weight of hydroxyl-terminated polybutadiene to a high-speed stirred tank, heat to 55°C at 4°C / min, add 20 parts by weight of diisononyl phthalate, stir for 60 min, add filler at a rate of 3.33 parts by weight / min, after all the filler in S3 has been added, adjust the speed to 1200 r / min, stir for 3 h, add composite functional additives at a rate of 5.56 parts by weight / min, after all the composite functional additives in S3 have been added, reduce the speed to 800 r / min, stir for 2 h, and obtain the premixed base material; S5: Add 25 parts by weight of polymethylene polyphenyl polyisocyanate and 8 parts by weight of KH-550 to the premixed base material, heat to 65°C at 8°C / min, stir for 80 min, cool to 40°C at 4°C / min, add 0.3 parts by weight of composite catalyst (composed of stannous octoate and tetrabutyl titanate in a mass ratio of 7:9), then add 1.5 parts by weight of ultraviolet absorber (UV-350) and 0.8 parts by weight of antioxidant (BASF antioxidant 1098), stir at 260 r / min for 50 min to obtain the catalytically modified mixture; S6: The catalytically modified mixture was placed under a vacuum of -0.095 MPa and 40°C for 40 min to degas. The degassed material was then injected into a sealed container and cured at 35°C and 60% relative humidity for 24 h to obtain a high-performance sealant.

[0018] Example 3: This example discloses a method for preparing a high-performance sealant, including the following steps: S1: Add 0.6 wt% dispersant (polyethylene glycol 400) to brucite powder, stir at 1800 r / min for 26 min, add anhydrous ethanol at a solid-liquid mass ratio of 1:9, heat to 52℃ at 3℃ / min, add 2.4% by mass of anhydrous ethanol in glycerol-L-proline ethanol solution (mass fraction of 12 wt%) in 4 portions, reduce the stirring speed to 1050 r / min, react for 2 h to obtain a mixture; S2: Add 1.2% vanillin by mass of the mixture to the mixture of S1, heat to 68℃ at 2℃ / min, reduce the stirring rate to 680r / min, react for 2h to obtain a modified mixture, vacuum dry the modified mixture at 82℃ and -0.08MPa for 4h, and sieve (filter mesh size 1μm) to obtain modified brucite powder; S3: Weigh 82 parts of modified magnesia powder and 36 parts of nano-titanium carbide by weight and mix them to obtain a filler. Weigh 17 parts of attapulgite powder and 11 parts of polyimide microspheres by weight and mix them to obtain a composite functional additive. Weigh out 72 parts of filler and 33 parts of composite functional additives by weight; S4: Add 100 parts by weight of hydroxyl-terminated polybutadiene to a high-speed stirred tank, heat to 48°C at 3°C / min, add 17 parts by weight of diisononyl phthalate, stir for 52 min, add filler at a rate of 2.46 parts by weight / min. After all the filler in S3 has been added, adjust the speed to 1100 r / min and stir for 2 h. Add composite functional additives at a rate of 4.58 parts by weight / min. After all the composite functional additives in S3 have been added, reduce the speed to 740 r / min and stir for 2 h to obtain the premixed base material. S5: Add 21 parts by weight of polymethylene polyphenyl polyisocyanate and 6 parts by weight of KH-550 to the premixed base material, heat to 61°C at 7°C / min, stir for 64 min, cool to 33°C at 4°C / min, add 0.24 parts by weight of composite catalyst (composed of stannous octoate and tetrabutyl titanate in a mass ratio of 5:7), then add 1.2 parts by weight of ultraviolet absorber (UV-350) and 0.5 parts by weight of antioxidant (BASF antioxidant 1098), stir at 210 r / min for 44 min to obtain catalytically modified mixture; S6: The catalytically modified mixture was placed under a vacuum of -0.095 MPa and 37°C for 35 min to degas. The degassed material was then injected into a sealed container and cured at 31°C and 52% relative humidity for 18 h to obtain a high-performance sealant.

[0019] Comparative Example 1: The difference between this comparative example and Example 3 is that, in S1, no glycerol-L-proline ethanol solution was added.

[0020] Comparative Example 2: The difference between this comparative example and Example 3 is that in S2, vanillin is replaced with vanillin ethyl ketone, while other reaction conditions remain unchanged.

[0021] Comparative Example 3: The difference between this comparative example and Example 3 is that in S2, only vanillin was replaced with vanillin ethyl ketone, and the reaction time was extended to 4 hours.

[0022] Comparative Example 4: The difference between this comparative example and Example 3 is that in S3, only the polyimide microspheres were replaced with polyimide (Kaiming Plastics (Dongguan) Co., Ltd., brand name SP-1).

[0023] Experimental Example 1: The elongation at break (%) of the high-performance sealant prepared by the present invention was tested according to GB / T 13477.8-2017.

[0024] Experimental Example 2: The temperature (°C) at which cracks appeared in the high-performance sealant prepared in this invention when bent (bending diameter 6mm) according to GB / T 13477.7-2002. The specimen was treated for three cycles at the following temperature: a) Treat at 70±2℃ for 16 hours; b) Treat at (-10±3)℃, (-20±3)℃, (-30±3)℃... for 8 hours.

[0025] Experimental Example 3: The displacement capability level of the high-performance sealant prepared by this invention was tested according to GB / T 22083-2008, and the levels were 25, 20, 12.5 and 7.5 respectively; Grades 25 and 20 are suitable for Class G (sealing for glazed joints) and Class F (sealing for building joints other than glazed joints), while grades 12.5 and 7.5 are suitable for Class F sealants.

[0026] Experimental Example 4: The elastic recovery rate (%) of the high-performance sealant prepared by this invention was tested according to GB / T 13477.17-2017.

[0027] Experimental Example 5: The bonding failure depth (mm) of the high-performance sealant prepared in this invention after cold stretching-hot pressing cycle (-20℃ for 3h + 70℃ for 3h, cycled for 7 days) was tested according to GB / T 13477.13-2019.

[0028] The results are shown in the table below: Table 1. Performance test results of the examples and comparative examples

[0029] As shown in the table above, the addition of glycerol-L-proline has a significant impact on the displacement capability and bond failure depth of the sealant. Its absence leads to a decrease in displacement grade and a deterioration in bond stability. Replacing vanillin with vanillin ethyl ketone results in a decline in elongation at break, low-temperature crack resistance, and elastic recovery rate. However, extending the reaction time can partially compensate for the performance defects. Replacing polyimide microspheres with ordinary polyimide significantly reduces low-temperature crack resistance and bond stability.

[0030] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a high-performance sealant, characterized in that, Includes the following steps: S1: Add dispersant to brucite powder and stir, add anhydrous ethanol and heat, add glycerol-L-proline ethanol solution, stir to react and obtain a mixture; S2: Add vanillin to the mixture of S1 and heat it to react and obtain a modified mixture. Dry and sieve to obtain modified brucite powder. S3: Weigh 60-90 parts by weight of modified brucite powder and 20-40 parts by weight of nano-titanium carbide and mix to obtain a filler; weigh 10-20 parts by weight of attapulgite powder and 5-15 parts by weight of polyimide microspheres and mix to obtain a composite functional additive; weigh 60-90 parts by weight of filler and 18-43 parts by weight of composite functional additive. S4: Add 100 parts by weight of hydroxyl-terminated polybutadiene to a high-speed stirred tank and heat it. Add 10-20 parts by weight of diisononyl phthalate and stir. Add filler and stir. Then add composite functional additives and stir to obtain a premixed base material. S5: Add 15-25 parts by weight of polymethylene polyphenyl polyisocyanate and 4-8 parts by weight of silane coupling agent to the premixed base material, heat and stir, cool down and add 0.1-0.3 parts by weight of composite catalyst, then add 0.5-1.5 parts by weight of ultraviolet absorber and 0.3-0.8 parts by weight of antioxidant, stir to obtain catalytically modified mixture; S6: The catalytically modified mixture is vacuum degassed and cured to obtain a high-performance sealant.

2. The method for preparing the high-performance sealant according to claim 1, characterized in that, S1 is specifically as follows: Add 0.3-0.8 wt% of dispersant to brucite powder, stir at 1500-2000 r / min for 20-30 min, add anhydrous ethanol at a solid-liquid mass ratio of 1:8-12, raise the temperature to 45-60℃ at 2-4℃ / min, add 1.5-3.0% by mass of anhydrous ethanol and a 10-15 wt% glycerol-L-proline ethanol solution in 3-5 portions, reduce the stirring rate to 800-1200 r / min, and react for 1.5-2.5 h to obtain a mixture.

3. The method for preparing the high-performance sealant according to claim 1, characterized in that, S2 is specifically as follows: add 0.8-1.5% vanillin by mass of the mixture to the mixture of S1, heat to 60-75℃ at 1-2℃ / min, reduce the stirring rate to 600-800r / min, react for 1-2h to obtain a modified mixture, vacuum dry the modified mixture at 70-90℃ and -0.07 to -0.09MPa for 3-5h, sieve to obtain modified brucite powder.

4. The method for preparing the high-performance sealant according to claim 1, characterized in that, S4 specifically involves adding 100 parts by weight of hydroxyl-terminated polybutadiene to a high-speed stirred tank, heating it to 40-55℃ at a rate of 2-4℃ / min, adding 10-20 parts by weight of diisononyl phthalate, stirring for 30-60 min, adding filler at a rate of 1.67-3.33 parts by weight / min, and after all the filler in S3 has been added, adjusting the speed to 800-1200 r / min and stirring for 1.5-3 h, adding composite functional additives at a rate of 2.33-5.56 parts by weight / min, and after all the composite functional additives in S3 have been added, reducing the speed to 600-800 r / min and stirring for 1-2 h to obtain the premixed base material.

5. The method for preparing the high-performance sealant according to claim 1, characterized in that, S5 specifically involves adding 15-25 parts by weight of polymethylene polyphenyl polyisocyanate and 4-8 parts by weight of KH-550 to the premixed base material, heating to 55-65℃ at 5-8℃ / min, stirring for 40-80min, cooling to 30-40℃ at 3-4℃ / min, adding 0.1-0.3 parts by weight of composite catalyst, then adding 0.5-1.5 parts by weight of ultraviolet absorber and 0.3-0.8 parts by weight of antioxidant, and stirring at 150-260r / min for 30-50min to obtain the catalytically modified mixture.

6. The method for preparing the high-performance sealant according to claim 1, characterized in that, The composite catalyst is composed of stannous octoate and tetrabutyl titanate in a mass ratio of 4-7:5-9.

7. The method for preparing the high-performance sealant according to claim 1, characterized in that, S6 specifically involves: placing the catalytically modified mixture under a vacuum of -0.08 to -0.095 MPa and at 30-40°C for 20-40 minutes to degas, then injecting the degassed material into a sealed container and maturing it at 25-35°C and 40-60% relative humidity for 12-24 hours to obtain a high-performance sealant.

8. A high-performance sealant prepared by the preparation method according to any one of claims 1-7.

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