Silica gel composite material and preparation method thereof

Abstract

The invention relates to a silica gel composite material and a preparation method thereof, and belongs to the technical field of high polymer materials. The silica gel composite material comprises the following components in parts by weight: 80-120 parts of methyl vinyl silicone rubber, 10-25 parts of vinyl silicone oil, 15-25 parts of titanium dioxide, 2-8 parts of a modifier, 2-6 parts of a foaming agent and 2-6 parts of a cross-linking agent, the quaternary ammonium salt in the modifier can eliminate static electricity of a material, N-vinylcarbazole is combined with anions on the surfaces of cell membranes of bacteria and molds, a synthetic system of protein and the cell membranes is destroyed, the N-vinylcarbazole and the quaternary ammonium salt cooperate to improve the antibacterial effect, thiourea of an intermediate has good ozone aging resistance and thermal oxidation resistance, free radicals can be captured, a chain reaction can be terminated, and the service life of the material is prolonged. The phosphorus-nitrogen flame retardant and the carbamate bond are synergistically flame-retardant, so that the service life of the composite material is prolonged; the silica gel composite material prepared by the invention not only has good antibacterial and anti-aging effects, but also has an excellent flame-retardant effect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer materials, and particularly relates to a silica gel composite material and a preparation method thereof. BACKGROUND

[0002] The silica gel material is a porous and viscoelastic new type of high polymer material, has the characteristics of high temperature resistance, high softness, light weight, sound and heat insulation, and shock absorption, and is widely applied to the fields of electric wires and cables, electronic appliances, aerospace, automobile manufacturing, new energy, national defense and military industry, and daily life.

[0003] However, the silica gel material is placed in air and is in contact with oxygen, so that an oxidation reaction is generated, the silica gel molecular chain is broken, and the material is hardened, which accelerates the aging of the material, and limits the use range of the silica gel material; in addition, the silica gel material is a hydrophobic substance, bacteria are easily attached to the surface of the silica gel material and breed on the surface, and when the silica gel material is used in human contact products, the health of people is threatened; the traditional antibacterial agent has poor compatibility with the silica gel matrix, is easily precipitated under high temperature and high humidity conditions, and influences the antibacterial durability, the mechanical properties and the antibacterial properties of the silica gel material, and influences the use effect; in addition, the silica gel material has a certain flame retardant effect, but with the improvement of the actual application demand, the flame retardant effect of the silica gel material can no longer meet the demand, therefore, it has important practical significance and application value to research and develop a silica gel composite material with good performance. SUMMARY

[0004] In order to solve the above technical problems, the application provides a silica gel composite material and a preparation method thereof.

[0005] The object of the application can be achieved by the following technical scheme.

[0006] A silica gel composite material and a preparation method thereof, comprising the following raw materials in parts by weight: 80-120 parts of methyl vinyl silicone rubber, 10-25 parts of vinyl silicone oil, 15-25 parts of titanium white, 2-8 parts of a modifier, 2-6 parts of a foaming agent, and 2-6 parts of a crosslinking agent.

[0007] The foaming agent is azodicarbonamide.

[0008] The crosslinking agent is 2,5-dimethyl-2,5-bis(tert-butyl peroxy) hexane.

[0009] The modifier is prepared by the following method.

[0010] Step A1: 3-dimethylamino-1-propanol and toluene diisocyanate are uniformly mixed, dibutyltin dilaurate is added under a nitrogen environment, reaction is carried out at 150 DEG C for 1h, and then the compound is prepared by continuing to react in a torque rheometer for 3h.

[0011] Furthermore, the ratio of 3-dimethylamino-1-propanol, toluene diisocyanate, and dibutyltin dilaurate is 0.02-0.06 mol: 0.01-0.03 mol: 0.08-0.12 g;

[0012] The compound was prepared by reacting the isocyanate bond of toluene diisocyanate with the hydroxyl group of 3-dimethylamino-1-propanol.

[0013] Step A2: The compound, 6-chloro-1-hexene and methanol were mixed and reacted under nitrogen protection for 12 h. After cooling to room temperature, the mixture was washed and dried under vacuum at 60 °C for 24 h to obtain preproduct 1.

[0014] Furthermore, the ratio of the compound, 6-chloro-1-hexene, and methanol is 0.01-0.03 mol: 0.02-0.06 mol: 2 mL;

[0015] The compound was then subjected to a quaternization reaction with the chlorine atom of 6-chloro-1-hexene to prepare preproduct 1;

[0016] Step A3: Mix p-aminophenol and dimethyl sulfoxide evenly, slowly add allyl isothiocyanate under stirring, heat to 45-55℃, continue stirring for 3-4 hours, after the reaction is complete, filter, wash, dry, and obtain the intermediate.

[0017] Furthermore, the ratio of p-aminophenol, dimethyl sulfoxide, and allyl isothiocyanate is 0.01-0.03 mol: 10-15 mL: 0.01-0.03 mol;

[0018] Secondly, the intermediate was prepared by reacting the amino group of p-aminophenol with the isothiocyanate group of allyl isothiocyanate.

[0019] Step A4: Mix vinyltriethoxysilane and ethanol-water solution, then add intermediate and azobisisobutyronitrile and mix well. React at 80°C for 24 h. Then add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and N,N-dimethylformamide and mix. Stir at 150°C for 9 h. Filter at room temperature, wash, and vacuum dry at 60°C for 24 h to obtain preproduct 2.

[0020] Furthermore, the molar ratio of vinyltriethoxysilane, ethanol-water mixed solution, intermediate, azobisisobutyronitrile, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and N,N-dimethylformamide is 0.01-0.03 mol: 10-15 mL: 0.03-0.09 mol: 0.2 g: 0.01-0.03 mol: 10-50 mL, and the volume ratio of ethanol to deionized water in the ethanol-water mixed solution is 1:1;

[0021] Then, the silicon hydroxyl generated by hydrolysis of vinyl triethoxysilane and the hydroxyl of the intermediate react, the carbon-carbon double bond of the intermediate and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide react, to obtain a pre-product 2;

[0022] Step A5: Pre-product 1 and benzoyl peroxide are uniformly dispersed in xylene, and then pre-product 2, N-vinylcarbazole and methanol are added and uniformly mixed under nitrogen protection, and then the mixture is reacted at 90 DEG C for 4h, distilled under reduced pressure, washed, filtered and vacuum dried to obtain a modifier;

[0023] Further, the amount ratio of pre-product 1, benzoyl peroxide, xylene, pre-product 2, N-vinylcarbazole and methanol is 0.01-0.03mol:0.16g:50mL:0.01-0.03mol:10-12g:20-60mL;

[0024] Finally, the carbon-carbon double bond of pre-product 1, pre-product 2 and N-vinylcarbazole is copolymerized to obtain a modifier.

[0025] A preparation method of a silica gel composite material, specifically comprising the following steps:

[0026] S1, methyl vinyl silicone rubber, vinyl silicone oil, titanium white, modifier, foaming agent and crosslinking agent are put into a non-invasive material homogenizer, mixed for 120s, filtered, vacuumized after standing, and a mixture is obtained;

[0027] S2, the mixture is first mixed at 50-55 DEG C for 6-10min, then opened and mixed at 35-40 DEG C for 5-10min, and finally vulcanized in a vulcanizing machine at 155-165 DEG C for 6-15min to obtain a silica gel composite material.

[0028] The beneficial effects of the present application are:

[0029] The silica gel composite material has good antibacterial and aging resistance effects, and also has excellent flame retardation effect, further prolonging the service life.

[0030] The quaternary ammonium salt of the pre-product 1 in the prepared modifier has electrostatic elimination characteristics and strong adsorption force, can effectively eliminate the static electricity of the material, and can penetrate the bacterial cell wall and react with the protein on the bacterial cell membrane, causing the membrane to rupture, causing the protein in the bacteria to leak, accelerating the death of the bacteria, thereby improving the antibacterial effect. Also, by virtue of the positive electric nature, the negative bacteria are adsorbed by electrostatic action, the surface charge distribution of the bacteria is disturbed, the normal activity of the cell membrane is affected, and the synthesis of the protein of the bacteria is hindered; in addition, the N-vinylcarbazole is combined with the anions on the surface of the cell membrane of the bacteria and the mold, destroys the synthesis system of the protein and the cell membrane, thereby inhibiting the reproduction of the bacteria and the mold, plays a role in sterilization, preservation and mold prevention, and cooperates with the quaternary ammonium salt to improve the antibacterial effect; the intermediate thiourea has good anti-ozone aging and anti-thermal oxidation performance, can capture free radicals, terminate chain reactions, delay the aging of the composite material, thereby effectively prolonging the service life and reducing the use cost; secondly, the phosphorus-nitrogen flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, as a high-thermal-stability phosphaphenanthrene compound, promotes the formation of a dense and continuous carbon layer during combustion, effectively isolates oxygen, blocks the exchange of heat and flammable gas, and inhibits combustion. Also, the use life is prolonged by cooperating with the urethane bond to synergistically flame retard. In addition, the modifier prepared by the present application is halogen-free, which helps to reduce pollution to the environment and damage to the ecosystem, is harmless to human health, and realizes sustainable development. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0032] Embodiment 1: A preparation method of a silica gel composite material, specifically comprising the following steps:

[0033] S1, the raw materials are weighed according to the weight parts, methyl vinyl silicone rubber 80 parts, vinyl silicone oil 10 parts, titanium dioxide 15 parts, modifier 2 parts (prepared by the present embodiment), foaming agent 2 parts, crosslinking agent 2 parts; the methyl vinyl silicone rubber, vinyl silicone oil, titanium dioxide, modifier, azobisformamide and 2,5-dimethyl-2,5-bis(tert-butyl peroxide) hexane are put into a non-invasive material homogenizer, mixed for 120 s, filtered and then vacuumized, to prepare a mixture;

[0034] S2, the mixture is first mixed at 50℃ for 6min, then opened at 35℃ for 5min, and finally vulcanized in a vulcanizing machine at 155℃ for 6min, to prepare a silica gel composite material;

[0035] The modifier is prepared by the following method:

[0036] Step A1: 0.02 mol 3-dimethylamino-1-propanol and 0.01 mol toluene diisocyanate were mixed uniformly, 0.08 g dibutyl tin dilaurate was added under nitrogen atmosphere, and the mixture was reacted at 150°C for 1 h and then was placed in a torque rheometer for continuous reaction for 3 h to prepare the compound;

[0037] Step A2: 0.01 mol of the compound, 0.02 mol of 6-chloro-1-hexene and 2 mL of methanol were mixed, and the mixture was reacted under nitrogen protection for 12 h. After cooling to room temperature, the mixture was washed and vacuum dried at 60°C for 24 h to prepare the pre-product 1;

[0038] Step A3: 0.01 mol of p-aminophenol and 10 mL of dimethyl sulfoxide were mixed uniformly, and 0.01 mol of allyl isothiocyanate was slowly added under stirring. The mixture was heated to 45°C and continuously stirred for 3 h. After the reaction was completed, the mixture was filtered, washed and dried to prepare the intermediate;

[0039] Step A4: 0.01 mol of vinyl triethoxysilane and 10 mL of a mixed solution of ethanol-water were mixed and stirred, and then 0.03 mol of the intermediate and 0.2 g of azobis isobutyronitrile were added and mixed uniformly. The mixture was reacted at 80°C for 24 h, and then 0.01 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10 mL of N,N-dimethylformamide were added and mixed. The mixture was stirred at 150°C for 9 h, filtered at room temperature, washed and vacuum dried at 60°C for 24 h to prepare the pre-product 2. The volume ratio of ethanol to deionized water in the mixed solution of ethanol-water was 1:1;

[0040] Step A5: 0.01 mol of the pre-product 1 and 0.16 g of benzoyl peroxide were uniformly dispersed in 50 mL of dimethylbenzene, and then 0.01 mol of the pre-product 2, 10 g of N-vinylcarbazole and 20 mL of methanol were added and mixed uniformly under nitrogen protection. The mixture was reacted at 90°C for 4 h, distilled under reduced pressure, washed, filtered and vacuum dried to prepare the modifier.

[0041] Example 2: A preparation method of a silica gel composite material, specifically comprising the following steps:

[0042] S1, the raw materials were weighed according to the weight parts, methyl vinyl silicone rubber 100 parts, vinyl silicone oil 17 parts, titanium white 20 parts, modifier 6 parts (prepared by the present example), foaming agent 4 parts, crosslinking agent 4 parts; the methyl vinyl silicone rubber, vinyl silicone oil, titanium white, modifier, azobisformamide and 2,5-dimethyl-2,5-bis(tert-butyl peroxide) hexane were put into a non-invasive material homogenizer, mixed for 120 s, filtered, vacuumized and prepared into a mixture;

[0043] S2, the mixture is first mixed at 52℃ for 8min, then opened at 37℃ for 7min, and finally vulcanized in a vulcanizing machine at 160℃ for 10min to obtain a silica gel composite material;

[0044] The modifier is prepared by the following method:

[0045] Step A1: 0.04 mol 3-dimethylamino-1-propanol and 0.02 mol toluene diisocyanate are mixed uniformly, 0.10 g of dibutyltin dilaurate is added under nitrogen atmosphere, and the reaction is carried out at 150℃ for 1h, and then the reaction is continued in a torque rheometer for 3h to obtain the compound;

[0046] Step A2: 0.02 mol of the compound, 0.04 mol of 6-chloro-1-hexene and 2 mL of methanol are mixed, and the reaction is carried out under nitrogen protection for 12h, and after cooling to room temperature, washing, vacuum drying at 60℃ for 24h to obtain the pre-product 1;

[0047] Step A3: 0.02 mol of p-aminophenol and 12 mL of dimethyl sulfoxide are mixed uniformly, 0.02 mol of allyl isothiocyanate is slowly added under stirring, and the temperature is raised to 50℃, and the stirring is continued for 3.5h, and after the reaction is completed, the intermediate is obtained by filtration, washing and drying;

[0048] Step A4: 0.02 mol of vinyltriethoxysilane and 13 mL of ethanol-water mixed solution are mixed and stirred, and then 0.06 mol of the intermediate and 0.2 g of azobisisobutyronitrile are added and mixed uniformly, and the reaction is carried out at 80℃ for 24h, and then 0.02 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 40 mL of N,N-dimethylformamide are added and mixed, and the stirring is carried out at 150℃ for 9h, and then the pre-product 2 is obtained by filtration, washing and vacuum drying at 60℃ for 24h, and the volume ratio of ethanol to deionized water in the ethanol-water mixed solution is 1:1;

[0049] Step A5: 0.02 mol of the pre-product 1 and 0.16 g of benzoyl peroxide are uniformly dispersed in 50 mL of xylene, and then 0.02 mol of the pre-product 2, 11 g of N-vinylcarbazole and 40 mL of methanol are added and mixed uniformly under nitrogen protection, and the reaction is carried out at 90℃ for 4h, and then the modifier is obtained by distillation under reduced pressure, washing, filtration and vacuum drying.

[0050] Example 3: A method for preparing a silica gel composite material, specifically comprising the following steps:

[0051] S1, the raw materials were weighed by parts by weight, methyl vinyl silicone rubber 120 parts, vinyl silicone oil 25 parts, titanium dioxide 25 parts, modifier 8 parts (prepared by this example), foaming agent 6 parts, crosslinking agent 6 parts; the methyl vinyl silicone rubber, vinyl silicone oil, titanium dioxide, modifier, azodicarbonamide and 2,5-dimethyl-2,5-bis(tert-butyl peroxide) hexane were put into a non-invasive material homogenizer, mixed for 120 s, filtered and vacuumed after standing, to obtain a mixture;

[0052] S2, the mixture was first mixed at 55℃ for 10 min, then opened at 40℃ for 10 min, and finally vulcanized in a vulcanizing machine at 165℃ for 15 min to obtain a silicone composite material;

[0053] The modifier was prepared by the following method:

[0054] Step A1: 0.06 mol 3-dimethylamino-1-propanol and 0.03 mol toluene diisocyanate were mixed uniformly, 0.12 g of dibutyltin dilaurate was added under nitrogen atmosphere, and the reaction was carried out at 150℃ for 1 h, and then the reaction was continued in a torque rheometer for 3 h to obtain a compound;

[0055] Step A2: 0.03 mol of the compound, 0.06 mol of 6-chloro-1-hexene and 2 mL of methanol were mixed, and the reaction was carried out under nitrogen protection for 12 h, and after cooling to room temperature, washing and vacuum drying at 60℃ for 24 h, a pre-product 1 was obtained;

[0056] Step A3: 0.03 mol of p-aminophenol and 15 mL of dimethyl sulfoxide were mixed uniformly, 0.03 mol of allyl isothiocyanate was slowly added under stirring, and the temperature was raised to 55℃, and the stirring was continued for 4 h, after the reaction was completed, the mixture was filtered, washed and dried to obtain an intermediate;

[0057] Step A4: 0.03 mol of vinyl triethoxysilane and 15 mL of ethanol-water mixed solution were mixed and stirred, then 0.09 mol of the intermediate and 0.2 g of azobisisobutyronitrile were added and mixed uniformly, and the reaction was carried out at 80℃ for 24 h, then 0.03 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 50 mL of N,N-dimethylformamide were added and mixed, and the stirring was carried out at 150℃ for 9 h, then the mixture was filtered, washed and vacuum dried at 60℃ for 24 h to obtain a pre-product 2, the volume ratio of ethanol to deionized water in the ethanol-water mixed solution was 1:1;

[0058] Step A5: 0.03 mol of the pre-product 1 and 0.16 g of benzoyl peroxide were uniformly dispersed in 50 mL of dimethylbenzene, and then 0.03 mol of the pre-product 2, 12 g of N-vinylcarbazole and 60 mL of methanol were added and mixed uniformly under nitrogen protection, and the reaction was carried out at 90℃ for 4 h, then the mixture was distilled under reduced pressure, washed, filtered and vacuum dried to obtain the modifier.

[0059] Comparative Example 1: This comparative example is a silica gel composite material, which is different from Example 3 in that an equal amount of silver salt antibacterial agent is used instead of the modifier prepared in Example 3, and the rest is the same.

[0060] Comparative Example 2: This comparative example is a silica gel composite material, which is different from Example 3 in that an equal amount of magnesium hydroxide is used instead of the modifier prepared in Example 3, and the rest is the same.

[0061] Performance test: The silica gel composite materials prepared in Examples 1-3 and Comparative Examples 1-2 are cut into standard test sizes, and the antibacterial test is carried out according to the standard GB / T 31402-2015; the appearance after aging for 100h is observed according to the standard GB / T 14522-2008 "Artificial Climate Aging Test Method for Plastic, Coating and Rubber Materials in Mechanical Industry Products Fluorescent Ultraviolet Lamp"; the oxygen index is tested according to IS04589-2; and the test results are shown in Table 1:

[0062] Table 1

[0063]

[0064] From the data tested in Table 1, it can be seen that the silica gel composite material prepared by the present application has good antibacterial and aging resistance. From Table 1, it can also be seen that the silica gel composite material prepared by the present application has good flame retardant effect and prolongs the service life.

[0065] The above content is only an example and description of the concept of the present application. Those skilled in the art can make various modifications or supplements to the described specific examples or use similar ways to replace them, as long as they do not deviate from the concept of the present application or exceed the scope defined by the present claims, and they should belong to the protection scope of the present application.

Claims

1. A method for producing a silica gel composite material, characterized by, Specifically comprising the following steps: S1, the raw materials are weighed by weight parts, methyl vinyl silicone rubber 80-120 parts, vinyl silicone oil 10-25 parts, titanium white 15-25 parts, modifier 2-8 parts, foaming agent 2-6 parts, crosslinking agent 2-6 parts; the methyl vinyl silicone rubber, vinyl silicone oil, titanium white, modifier, foaming agent and crosslinking agent are put into a non-invasive material homogenizer, mixed for 120s, filtered, vacuumized and rested to prepare a mixture; S2, the mixture is first mixed at 50-55℃ for 6-10min, then opened at 35-40℃ for 5-10min, and finally vulcanized in a vulcanizing machine at 155-165℃ for 6-15min to prepare a silicone composite material; The modifier is prepared by the following method: Step A1: 3-dimethylamino-1-propanol and toluene diisocyanate are uniformly mixed, dibutyltin dilaurate is added under nitrogen environment, reacted at 150℃ for 1h, and then placed in a torque rheometer for continuous reaction for 3h to prepare a compound; Step A2: the compound, 6-chloro-1-hexene and methanol are mixed, reacted for 12h under nitrogen protection, washed after cooling to room temperature, and vacuum dried at 60℃ for 24h to prepare a pre-product 1; Step A3: p-aminophenol and dimethyl sulfoxide are uniformly mixed, allyl isothiocyanate is slowly added under stirring, heated to 45-55℃, and continuously stirred for 3-4h, then filtered, washed and dried after reaction to prepare an intermediate; Step A4: vinyltriethoxysilane and an ethanol-water mixed solution are mixed and stirred, then the intermediate and azobisisobutyronitrile are uniformly mixed, reacted at 80℃ for 24h, then 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and N,N-dimethylformamide are mixed and stirred at 150℃ for 9h, filtered at room temperature, washed, and vacuum dried at 60℃ for 24h to prepare a pre-product 2; Step A5: the pre-product 1 and benzoyl peroxide are uniformly dispersed in xylene, then the pre-product 2, N-vinylcarbazole and methanol are uniformly mixed under nitrogen protection, reacted at 90℃ for 4h, distilled under reduced pressure, washed, filtered and vacuum dried to prepare the modifier.

2. The method for preparing a silicone composite material according to claim 1, characterized in that, The amount ratio of 3-dimethylamino-1-propanol, toluene diisocyanate and dibutyltin dilaurate in step A1 is 0.02-0.06mol:0.01-0.03mol:0.08-0.12g.

3. The method for preparing a silicone composite material according to claim 1, characterized in that, The amount ratio of the compound, 6-chloro-1-hexene and methanol in step A2 is 0.01-0.03mol:0.02-0.06mol:2mL.

4. The method for preparing a silicone composite material according to claim 1, characterized in that, The amount ratio of p-aminophenol, dimethyl sulfoxide and allyl isothiocyanate in step A3 is 0.01-0.03mol:10-15mL:0.01-0.03mol.

5. The method for preparing a silicone composite material according to claim 1, characterized in that, The amount ratio of vinyltriethoxysilane, ethanol-water mixed solution, intermediate, azobisisobutyronitrile, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, N, N-dimethylformamide in step A4 is 0.01-0.03 mol: 10-15 mL: 0.03-0.09 mol: 0.2 g: 0.01-0.03 mol: 10-50 mL, and the volume ratio of ethanol and deionized water in the ethanol-water mixed solution is 1:

1.

6. The method for preparing a silicone composite material according to claim 1, characterized in that, The amount ratio of pre-product 1, benzoyl peroxide, dimethylbenzene, pre-product 2, N-vinylcarbazole, methanol in step A5 is 0.01-0.03 mol: 0.16 g: 50 mL: 0.01-0.03 mol: 10-12 g: 20-60 mL.

7. The method for preparing a silicone composite material according to claim 1, characterized in that, The foaming agent is azodicarbonamide, and the crosslinking agent is 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane.

8. A silica gel composite material, characterized by, Prepared according to the preparation method in any one of claims 1-7. Prepared according to the preparation method in any one of claims 1-7.

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