CN112844994A - Temperature-resistant silica gel leather and preparation method thereof - Google Patents
Temperature-resistant silica gel leather and preparation method thereof Download PDFInfo
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- CN112844994A CN112844994A CN202011641070.7A CN202011641070A CN112844994A CN 112844994 A CN112844994 A CN 112844994A CN 202011641070 A CN202011641070 A CN 202011641070A CN 112844994 A CN112844994 A CN 112844994A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/12—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to leather
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2203/00—Other substrates
- B05D2203/24—Leather
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2601/00—Inorganic fillers
- B05D2601/20—Inorganic fillers used for non-pigmentation effect
- B05D2601/22—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2701/00—Coatings being able to withstand changes in the shape of the substrate or to withstand welding
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Abstract
The invention relates to the technical field of leather, in particular to temperature-resistant silica gel leather and a preparation method thereof, wherein the temperature-resistant silica gel leather comprises textile base cloth and a coating layer coated on the textile base cloth, the coating layer is prepared from a silica gel material, and the silica gel material comprises the following raw materials in parts by weight: 0-35 parts of vinyl MQ silicon resin, 0.1-0.5 part of platinum complex catalyst, 2-6 parts of modified aluminum hydroxide, 0-5 parts of methyl polysilicate, 2-6 parts of silylation reagent, 0.2-0.6 part of butyl titanate, 8-16 parts of filler, 100 parts of base adhesive, 1-3 parts of distilled water, 0-10 parts of cross-linking agent, 0.1-0.5 part of stabilizer and 0.5-1.5 parts of coupling agent. The silica gel leather provided by the invention has the advantages that the leather product has good flame retardant property and fire resistance, and has good properties such as tearing strength, tensile strength and elongation at break without using a flame retardant, and the large-scale industrial production can be realized.
Description
Technical Field
The invention relates to the technical field of leather, in particular to temperature-resistant silica gel leather and a preparation method thereof.
Background
The leather industry has been rapidly developed in recent decades, and people have increasingly increased demand for leather, and further have higher and higher requirements for safety performance of leather. The leather as a natural high polymer contains C, H, O, N elements, and can release CO and CO when being burnt2Nitrogen oxide and the like, especially in the scenes of air crash, fire and the like, the smoke generated by the combustion of the leather greatly threatens the life safety of people, so that the flame retardant property of the leather is enhanced, and precious time can be won for emergency escape, fire scene evacuation and fire rescue of people.
For furniture, home decoration and artware, leather is required to be environment-friendly, and higher wear-resistant and flame-retardant requirements are further provided for the leather. For traditional polyurethane leather, flame retardance is mainly realized by non-halogen and halogen flame retardants. Halogen flame retardants have great harm and are gradually eliminated, and non-halogen flame retardants, such as magnesium hydroxide, have good flame retardancy, but require a large amount of flame retardants to fully exert their effects, and the mechanical properties, texture, and the like of the material deteriorate as the amount of flame retardants increases. Meanwhile, the magnesium hydroxide has weak acting force in leather, is easy to run off in the scrubbing process, and has rapidly deteriorated flame retardant property after being scrubbed for a long time.
At present, two flame retardant research directions are roughly carried out on environment-friendly leather prepared by organic silica gel, wherein one research and development direction is to research and develop a novel flame retardant to be added into a leather surface finishing agent, and the other research and development direction is to improve and apply some existing flame retardants to some film forming agents which are more environment-friendly and more accord with performance requirements. The reason for this phenomenon is mainly that people generally believe that the leather coating needs to use resin with good film-forming property as the leather finishing agent, and the technical prejudice hinders people's research on flame-retardant leather.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the temperature-resistant silica gel leather which adopts a silica gel material as a coating layer, can enable a leather product to have good flame retardant property and fire resistance, better properties such as tearing strength, tensile strength and elongation at break and the like without using a flame retardant, has stable performance and low permanent deformation rate at break, and improves the tensile strength, tearing resistance and wear resistance of the leather by adding a filler; meanwhile, the filler has large specific surface area and low density, and can be easily gathered on a melting surface in the combustion process, so that a compact carbon layer is formed together with the platinum complex catalyst, the transfer of heat and substances between the melting surface and the outside is blocked, a synergistic flame retardant effect is achieved, the addition of the modified aluminum hydroxide not only improves the internal leakage property of the silica gel material, but also has lasting electric arc resistance, and the comprehensive performance of the prepared temperature-resistant silica gel leather is further improved.
The invention also aims to provide a preparation method of the temperature-resistant silica gel leather, which is simple, convenient to operate and control, stable in quality, high in production efficiency, low in production cost and capable of realizing large-scale industrial production.
The purpose of the invention is realized by the following technical scheme: the temperature-resistant silica gel leather comprises a textile base cloth and a coating layer coated on the textile base cloth, wherein the coating layer is made of a silica gel material, and the silica gel material comprises the following raw materials in parts by weight:
the platinum complex catalyst is a platinum-tetravinyl tetramethyl-cyclotetrasiloxane complex with the Pt mass fraction of 2.0%; the base adhesive is a mixture consisting of alpha, omega-divinyl polydimethylsiloxane and polymethylvinylsiloxane according to the weight ratio of 0.9-1.1: 0-0.4; the viscosity of the alpha, omega-divinyl polydimethylsiloxane (25 ℃) is 600000 mPas, and the viscosity of the polymethylvinylsiloxane (25 ℃) is 1000 mPas; the viscosity (25 ℃) of the vinyl MQ silicon resin is 300 mPas, and the vinyl content is 5.4-5.8%.
Further, the silica gel material comprises the following raw materials in parts by weight:
the silica gel leather adopts the silica gel material as the coating layer, can obtain better flame retardant property under the condition of not using a flame retardant, and improves the tensile property, the tear resistance and the wear resistance of the leather by adding the filler. Meanwhile, the filler has large specific surface area and low density, and is easy to gather on a melting surface in the combustion process, so that a compact carbon layer is formed together with the platinum complex catalyst, the transfer of heat and substances between the melting surface and the outside is blocked, a synergistic flame retardant effect is achieved, the addition of the modified aluminum hydroxide not only improves the internal leakage property of the silica gel material, but also has lasting electric arc resistance and subjectivity, and the comprehensive performance of the prepared temperature-resistant silica gel leather is further improved. The adopted vinyl MQ silicon resin can improve the crosslinking density and the thermal aging performance of the silicon base gel, and the mechanical property of the prepared silica gel material is improved along with the increase of the crosslinking density; the modified aluminum hydroxide content has obvious influence on the electric leakage, mark generation and ablation performance of the silicon rubber material, when the addition of the modified aluminum hydroxide is not more than 100 percent, the internal leakage of the silicon rubber material can be obviously improved, the lasting arc resistance and the subjectivity are achieved, the unmodified aluminum hydroxide is an inorganic material with strong polarity, so that the particles are easy to agglomerate and have poor compatibility with the basic glue, when used alone, the filling amount is required to reach more than 60 percent to have better flame retardant effect, but the processing property and the mechanical property of the polymer are seriously influenced, therefore, the modified aluminum hydroxide with more excellent performance, smaller particle size, higher surface activation degree, good thermal stability and high decomposition temperature is obtained by modifying the aluminum hydroxide, so that the thermal stability of the aluminum hydroxide flame retardant is improved, and the compatibility between the modified aluminum hydroxide and a basic adhesive material is improved; the addition of the methyl polysilicate is matched with the modified aluminum hydroxide, so that the mechanical strength of the silica gel material can be improved; the addition of the butyl titanate can improve the performance and the high-temperature resistance of the silica gel material, and the butyl titanate can improve the adhesion of the silica gel material during the crosslinking reaction, so that the adhesive force of the coating layer is improved.
Preferably, each part of the modified aluminum hydroxide is prepared by the following steps:
s1, weighing 30-40 parts of aluminum hydroxide micro powder and 1-3 parts of ethyl acetate by weight, adding into a reaction device, heating to 80-100 ℃, stirring at the speed of 200-400r/min for 20-40min, and cooling to obtain a mixture A for later use;
s2, weighing 1-3 parts by weight of ammonium dihydrogen phosphate, 1-3 parts by weight of tetramethylammonium hydroxide and 1-3 parts by weight of zinc stearate, uniformly mixing, adding the mixture A obtained in the step S1, heating to 90-130 ℃, continuously stirring for 60-120min, heating the mixed system to 110-140 ℃, preserving heat for 1-4h, and cooling to obtain the modified aluminum hydroxide.
The modified aluminum hydroxide prepared by the method has a good promotion effect on improving the anti-creeping, mark-forming and ablation performances of the silicone rubber material, and the unmodified aluminum hydroxide is a strong-polarity inorganic material, is easy to agglomerate among particles and poor in compatibility with the base rubber, has a good flame retardant effect when the filling amount is more than 60% when the modified aluminum hydroxide is used alone, but seriously influences the processing performance and the mechanical performance of the polymer.
Preferably, each part of the silylating agent is at least one of hexamethyldisilazane, trimethylchlorosilane, hexamethyldisiloxane, dimethyldichlorosilane, methyltrichlorosilane, trimethylchlorosilane, phenyltriethoxysilane, hexamethyldisilazane, methyltriethoxysilane, t-butyldimethylchlorosilane, hexadecyltrimethoxysilane, octyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; more preferably, each portion of the silylating agent is hexamethyldisilazane.
Hexamethyldisilazane is preferably adopted in the silylation reagent, and the silica gel material with good mechanical property can be obtained by an extrusion process by utilizing the polymerization of hexamethyldisilazane and base gel with a large number of unsaturated bonds and higher bond energy of groups.
Preferably, each part of the filler is a mixture of fumed silica and acetylene black according to the weight ratio of 0.8-1.6: 0-0.3. Each part of the cross-linking agent is a mixture of titanium dioxide and methyl hydrogen polysiloxane according to the weight ratio of 0.1-0.3: 0.4-0.8.
The fumed silica adopted in the filler has small particle size, the specific surface area is 200 plus one square meter per gram (300 square meters per gram), the mechanical strength and the tracking resistance of the silicone rubber can be improved when the fumed silica is dispersed in the silicone rubber, the compatibility of the fumed silica and the silicone rubber is better, and the prepared silicone rubber has excellent heat-conducting property, so that the heat generated by electric arc can be dissipated timely, and the tracking resistance of the silicone rubber material is improved.
Preferably, each of the stabilizers is ethynylcyclohexanol. Each part of the coupling agent is at least one of gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, aminopropyltriethoxysilane and aminopropyltriethoxysilane.
The silane coupling agent adopted by the invention plays a role in connecting inorganic matters and organic matters, can greatly improve the physical and mechanical properties of the reinforced sizing material, and improves the wettability and the dispersibility of the fumed silica in the base rubber.
The invention also provides a preparation method of the temperature-resistant silica gel leather, which comprises the following steps:
1) adding the base rubber, the methyl polysilicate and the vinyl MQ silicon resin into a vacuum kneader according to the parts by weight, kneading and stirring for 4-8min, adding one third of the total amount of the filler and one third of the total amount of the modified aluminum hydroxide into the kneader, stirring uniformly, adding the silanization reagent and the distilled water, continuously stirring for 25-35min, adding the rest fumed silica and the modified aluminum hydroxide twice, heating to 145-155 ℃ for rubber mixing after agglomeration, refining for 50-70min under the vacuum condition of- (0.08-0.10) MPa during rubber mixing, and discharging to obtain a base material for later use;
2) adding the cross-linking agent, the stabilizing agent, the coupling agent, the butyl titanate, the platinum complex catalyst and the base material obtained in the step 1) into a stirrer according to the parts by weight, and uniformly mixing to obtain a finished product rubber material.
3) Coating the finished product rubber obtained in the step 2) on a textile base fabric, vulcanizing for 4-8min at the temperature of 190 ℃ with 170-; a vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide is added during vulcanization, the weight ratio of the finished rubber material to the vulcanizing agent is 100:1-1.5, the vulcanization temperature is 160-200 ℃, and the vulcanization time is 6-12 min.
The temperature-resistant silica gel leather is prepared by adopting the steps, the preparation method is simple, the operation and the control are convenient, the quality is stable, the production efficiency is high, and the production cost is low. Meanwhile, the filler has large specific surface area and low density, and is easy to gather on a melting surface in a combustion process, so that a compact carbon layer is formed together with the platinum complex catalyst, the transfer of heat and substances between the melting surface and the outside is blocked, a synergistic flame retardant effect is achieved, the addition of the modified aluminum hydroxide not only improves the internal leakage property of the silica gel material, but also has lasting electric arc resistance and subjectivity, the comprehensive performance of the prepared temperature-resistant silica gel leather is further improved, and large-scale industrial production can be achieved. Wherein, the temperature in the rubber mixing process in the step 1) needs to be strictly controlled to be 145-155 ℃, if the temperature is too high, the filling effect of the fumed silica is not good, the reinforcing effect of the fumed silica on the base rubber is not favorable, and if the stirring speed is too low, the mutual reinforcing effect between the fumed silica and the base rubber is also not favorable; in addition, the temperature during vulcanization in the step 3) needs to be strictly controlled to be 70-190 ℃, if the temperature is too high, part of rubber materials can be coked, and the quality of finally prepared leather is influenced; the 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide is adopted, so that the vulcanization efficiency is high, the vulcanization time is shortened, the strength performance of rubber materials is prevented from being reduced in a long-time vulcanization process, the vulcanization temperature and time are strictly controlled, the prepared leather product has good flame retardant property and fire resistance, and has good performances such as tearing strength, tensile strength and elongation at break, the performance is stable, the elongation set at break is low, and the application range is wide.
The invention has the beneficial effects that: the temperature-resistant silica gel leather disclosed by the invention adopts the silica gel material as the coating layer, so that the leather product has good flame retardant property and fire resistance, better properties such as tearing strength, tensile strength and elongation at break and the like without using a flame retardant, stable performance, low permanent deformation at break and wide application range, and the tensile strength, the tearing resistance and the wear resistance of the leather are improved by adding the filler; meanwhile, the filler has large specific surface area and low density, and is easy to gather on a melting surface in the combustion process, so that a compact carbon layer is formed together with the platinum complex catalyst, the transfer of heat and substances between the melting surface and the outside is blocked, a synergistic flame retardant effect is achieved, the addition of the modified aluminum hydroxide not only improves the internal leakage property of the silica gel material, but also has lasting electric arc resistance and subjectivity, and the comprehensive performance of the prepared temperature-resistant silica gel leather is further improved.
The preparation method of the temperature-resistant silica gel leather is simple, convenient to operate and control, stable in quality, high in production efficiency, low in production cost and capable of realizing large-scale industrial production.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
The temperature-resistant silica gel leather comprises a textile base cloth and a coating layer coated on the textile base cloth, wherein the coating layer is made of a silica gel material, and the silica gel material comprises the following raw materials in parts by weight:
the platinum complex catalyst is a platinum-tetravinyl tetramethyl-cyclotetrasiloxane complex with the Pt mass fraction of 2.0%; the base adhesive is a mixture of alpha, omega-divinyl polydimethylsiloxane and polymethylvinylsiloxane in a weight ratio of 1: 0.3; the viscosity of the alpha, omega-divinyl polydimethylsiloxane (25 ℃) is 600000 mPas, and the viscosity of the polymethylvinylsiloxane (25 ℃) is 1000 mPas; the vinyl MQ silicone resin has a viscosity (25 ℃) of 300 mPas and a vinyl content of 5.4%.
Each part of the modified aluminum hydroxide is prepared by the following steps:
s1, weighing 30 parts of aluminum hydroxide micro powder and 1 part of ethyl acetate by weight, adding into a reaction device, heating to 80 ℃, stirring at the speed of 200r/min for 20min, and cooling to obtain a mixture A for later use;
s2, weighing 1 part by weight of ammonium dihydrogen phosphate, 1 part by weight of tetramethylammonium hydroxide and 1 part by weight of zinc stearate, uniformly mixing, adding the mixture A obtained in the step S1, heating to 90 ℃, continuously stirring for 60-120min, heating the mixed system to 110 ℃, preserving heat for 1h, and cooling to obtain the modified aluminum hydroxide.
Each of the silylating agents is hexamethyldisilazane.
Each part of the filler is fumed silica.
Each part of the cross-linking agent is a mixture of titanium dioxide and methyl hydrogen polysiloxane according to the weight ratio of 0.1: 0.4.
Each part of the stabilizer is ethynyl cyclohexanol; each part of the coupling agent is gamma-glycidoxypropyltrimethoxysilane.
The preparation method of the temperature-resistant silica gel leather comprises the following steps:
1) adding the base rubber into a vacuum kneader according to the parts by weight, kneading and stirring for 4min, adding one third of the total amount of the filler and one third of the total amount of the modified aluminum hydroxide into the kneader, stirring uniformly, adding the silanization reagent and the distilled water, continuously stirring for 25min, adding the rest fumed silica and the modified aluminum hydroxide twice, heating to 145 ℃ after agglomeration for rubber mixing, refining for 50min under the vacuum condition of-0.08 MPa during rubber mixing, and discharging to obtain a base material for later use;
2) adding the stabilizer, the coupling agent, the butyl titanate, the platinum complex catalyst and the base material obtained in the step 1) into a stirrer according to the parts by weight, and uniformly mixing to obtain a finished product rubber material.
3) Coating the finished product rubber obtained in the step 2) on a textile base fabric, vulcanizing for 4min at 170 ℃, baking, curing and forming, attaching release paper, and rolling to obtain the temperature-resistant silica gel leather; and a vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide is added during vulcanization, the weight ratio of the finished product rubber material to the vulcanizing agent is 100:1, the vulcanization temperature is 160 ℃, and the vulcanization time is 6 min.
Example 2
The temperature-resistant silica gel leather comprises a textile base cloth and a coating layer coated on the textile base cloth, wherein the coating layer is made of a silica gel material, and the silica gel material comprises the following raw materials in parts by weight:
the platinum complex catalyst is a platinum-tetravinyl tetramethyl-cyclotetrasiloxane complex with the Pt mass fraction of 2.0%; the base glue is alpha, omega-divinyl polydimethylsiloxane; the viscosity (25 ℃) of the alpha, omega-divinylpolydimethylsiloxane is 600000 mPas; the vinyl MQ silicone resin has a viscosity (25 ℃) of 300 mPas and a vinyl content of 5.5 percent.
Each part of the modified aluminum hydroxide is prepared by the following steps:
s1, weighing 33 parts of aluminum hydroxide micro powder and 1.5 parts of ethyl acetate by weight, adding into a reaction device, heating to 85 ℃, stirring at the speed of 250r/min for 25min, and cooling to obtain a mixture A for later use;
s2, weighing 1.5 parts by weight of ammonium dihydrogen phosphate, 1.5 parts by weight of tetramethylammonium hydroxide and 1.5 parts by weight of zinc stearate, uniformly mixing, adding the mixture A obtained in the step S1, heating to 100 ℃, continuously stirring for 75min, heating the mixed system to 117 ℃, preserving heat for 2h, and cooling to obtain the modified aluminum hydroxide.
Each of the silylating agents is hexamethyldisilazane.
Each part of the filler is fumed silica.
Each part of the cross-linking agent is a mixture of titanium dioxide and methyl hydrogen polysiloxane according to the weight ratio of 0.2: 0.6.
Each part of the stabilizer is ethynyl cyclohexanol; each part of the coupling agent is gamma-glycidoxypropyltrimethoxysilane.
The preparation method of the temperature-resistant silica gel leather comprises the following steps:
1) adding the base gum and the vinyl MQ silicon resin into a vacuum kneader according to the parts by weight, kneading and stirring for 5min, adding one third of the total amount of the filler and one third of the total amount of the aluminum hydroxide into the kneader, stirring uniformly, adding a silanization reagent and distilled water, continuously stirring for 28min, adding the rest fumed silica and the aluminum hydroxide twice, heating to 148 ℃ after agglomeration for rubber mixing, refining for 55min under the vacuum condition of-0.085 MPa during rubber mixing, and discharging to obtain a base material for later use;
2) adding the cross-linking agent, the stabilizing agent, the coupling agent, the butyl titanate, the platinum complex catalyst and the base material obtained in the step 1) into a stirrer according to the parts by weight, and uniformly mixing to obtain a finished product rubber material.
3) Coating the finished product rubber obtained in the step 2) on a textile base fabric, vulcanizing for 5min at 175 ℃, baking, curing and forming, attaching release paper, and rolling to obtain the temperature-resistant silica gel leather; and a vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide is added during vulcanization, the weight ratio of the finished product rubber material to the vulcanizing agent is 100:1.2, the vulcanization temperature is 170 ℃, and the vulcanization time is 7 min.
Example 3
The temperature-resistant silica gel leather comprises a textile base cloth and a coating layer coated on the textile base cloth, wherein the coating layer is made of a silica gel material, and the silica gel material comprises the following raw materials in parts by weight:
the platinum complex catalyst is a platinum-tetravinyl tetramethyl-cyclotetrasiloxane complex with the Pt mass fraction of 2.0%; the base glue is alpha, omega-divinyl polydimethylsiloxane; the viscosity (25 ℃) of the alpha, omega-divinylpolydimethylsiloxane is 600000 mPas; the vinyl MQ silicone resin has a viscosity (25 ℃) of 300 mPas and a vinyl content of 5.6 percent.
Each part of the modified aluminum hydroxide is prepared by the following steps:
s1, weighing 35 parts of aluminum hydroxide micro powder and 2 parts of ethyl acetate by weight, adding into a reaction device, heating to 90 ℃, stirring at the speed of 300r/min for 30min, and cooling to obtain a mixture A for later use;
s2, weighing 2 parts by weight of ammonium dihydrogen phosphate, 2 parts by weight of tetramethylammonium hydroxide and 2 parts by weight of zinc stearate, uniformly mixing, adding the mixture A obtained in the step S1, heating to 110 ℃, continuously stirring for 90min, heating the mixed system to 125 ℃, keeping the temperature for 3h, and cooling to obtain the modified aluminum hydroxide.
Each of the silylating agents is hexamethyldisilazane.
Each part of the filler is a mixture of fumed silica and acetylene black according to the weight ratio of 1.2: 0.2.
Each part of the cross-linking agent is a mixture of titanium dioxide and methyl hydrogen polysiloxane according to the weight ratio of 0.2: 0.6.
Each part of the stabilizer is ethynyl cyclohexanol; each part of the coupling agent is gamma-glycidoxypropyltrimethoxysilane.
The preparation method of the temperature-resistant silica gel leather comprises the following steps:
1) adding the base gum and the vinyl MQ silicon resin into a vacuum kneader according to the parts by weight, kneading and stirring for 6min, adding one third of the total amount of the filler and one third of the total amount of the aluminum hydroxide into the kneader, stirring uniformly, adding a silanization reagent and distilled water, continuously stirring for 30min, adding the rest fumed silica and the aluminum hydroxide twice, heating to 150 ℃ after agglomeration, carrying out rubber mixing, refining for 60min under the vacuum condition of-0.09 MPa during rubber mixing, and discharging to obtain a base material for later use;
2) adding the cross-linking agent, the stabilizing agent, the coupling agent, the butyl titanate, the platinum complex catalyst and the base material obtained in the step 1) into a stirrer according to the parts by weight, and uniformly mixing to obtain a finished product rubber material.
3) Coating the finished product rubber obtained in the step 2) on a textile base fabric, vulcanizing for 6min at 180 ℃, baking, curing and forming, attaching release paper, and rolling to obtain the temperature-resistant silica gel leather; and a vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide is added during vulcanization, the weight ratio of the finished product rubber material to the vulcanizing agent is 100:1.3, the vulcanization temperature is 180 ℃, and the vulcanization time is 9 min.
Example 4
The temperature-resistant silica gel leather comprises a textile base cloth and a coating layer coated on the textile base cloth, wherein the coating layer is made of a silica gel material, and the silica gel material comprises the following raw materials in parts by weight:
the platinum complex catalyst is a platinum-tetravinyl tetramethyl-cyclotetrasiloxane complex with the Pt mass fraction of 2.0%; the base glue is alpha, omega-divinyl polydimethylsiloxane; the viscosity (25 ℃) of the alpha, omega-divinylpolydimethylsiloxane is 600000 mPas; the vinyl MQ silicone resin has a viscosity (25 ℃) of 300 mPas and a vinyl content of 5.7 percent.
Each part of the modified aluminum hydroxide is prepared by the following steps:
s1, weighing 38 parts of aluminum hydroxide micro powder and 2.5 parts of ethyl acetate by weight, adding into a reaction device, heating to 95 ℃, stirring at the speed of 350r/min for 35min, and cooling to obtain a mixture A for later use;
s2, weighing 2.5 parts by weight of ammonium dihydrogen phosphate, 2.5 parts by weight of tetramethylammonium hydroxide and 2.5 parts by weight of zinc stearate, uniformly mixing, adding the mixture A obtained in the step S1, heating to 120 ℃, continuously stirring for 105min, heating the mixed system to 132 ℃, preserving heat for 4h, and cooling to obtain the modified aluminum hydroxide.
Each of the silylating agents is hexamethyldisilazane.
Each part of the filler is a mixture of fumed silica and acetylene black according to the weight ratio of 1.2: 0.2.
Each part of the cross-linking agent is a mixture of titanium dioxide and methyl hydrogen polysiloxane according to the weight ratio of 0.2: 0.6.
Each part of the stabilizer is ethynyl cyclohexanol; each part of the coupling agent is gamma-glycidoxypropyltrimethoxysilane.
The preparation method of the temperature-resistant silica gel leather comprises the following steps:
1) adding the base rubber, the methyl polysilicate and the vinyl MQ silicon resin into a vacuum kneader according to the parts by weight, kneading and stirring for 7min, adding one third of the total amount of the filler and one third of the total amount of the aluminum hydroxide into the kneader, stirring uniformly, adding the silanization reagent and the distilled water, continuously stirring for 33min, adding the rest fumed silica and the rest aluminum hydroxide twice, heating to 153 ℃ after agglomeration, refining for 65min under the vacuum condition of-0.095 MPa during rubber refining, and discharging to obtain a base material for later use;
2) adding the cross-linking agent, the stabilizing agent, the coupling agent, the butyl titanate, the platinum complex catalyst and the base material obtained in the step 1) into a stirrer according to the parts by weight, and uniformly mixing to obtain a finished product rubber material.
3) Coating the finished product rubber obtained in the step 2) on a textile base fabric, vulcanizing for 7min at 185 ℃, baking, curing and forming, attaching release paper, and rolling to obtain the temperature-resistant silica gel leather; and a vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide is added during vulcanization, the weight ratio of the finished product rubber material to the vulcanizing agent is 100:1.4, the vulcanization temperature is 190 ℃, and the vulcanization time is 10 min.
Example 5
The temperature-resistant silica gel leather comprises a textile base cloth and a coating layer coated on the textile base cloth, wherein the coating layer is made of a silica gel material, and the silica gel material comprises the following raw materials in parts by weight:
the platinum complex catalyst is a platinum-tetravinyl tetramethyl-cyclotetrasiloxane complex with the Pt mass fraction of 2.0%; the base adhesive is a mixture of alpha, omega-divinyl polydimethylsiloxane and polymethylvinylsiloxane in a weight ratio of 1.1: 0.4; the viscosity of the alpha, omega-divinyl polydimethylsiloxane (25 ℃) is 600000 mPas, and the viscosity of the polymethylvinylsiloxane (25 ℃) is 1000 mPas; the vinyl MQ silicone resin has a viscosity (25 ℃) of 300 mPas and a vinyl content of 5.8 percent.
Each part of the modified aluminum hydroxide is prepared by the following steps:
s1, weighing 40 parts of aluminum hydroxide micro powder and 3 parts of ethyl acetate by weight, adding into a reaction device, heating to 100 ℃, stirring at the speed of 400r/min for 40min, and cooling to obtain a mixture A for later use;
s2, weighing 3 parts by weight of ammonium dihydrogen phosphate, 3 parts by weight of tetramethylammonium hydroxide and 3 parts by weight of zinc stearate, uniformly mixing, adding the mixture A obtained in the step S1, heating to 130 ℃, continuously stirring for 120min, heating the mixed system to 140 ℃, keeping the temperature for 4h, and cooling to obtain the modified aluminum hydroxide.
Each of the silylating agents is hexamethyldisilazane.
Each part of the filler is a mixture of fumed silica and acetylene black according to the weight ratio of 1.6: 0.3.
Each part of the cross-linking agent is a mixture of titanium dioxide and methyl hydrogen polysiloxane according to the weight ratio of 0.3: 0.8.
Each part of the stabilizer is ethynyl cyclohexanol; each part of the coupling agent is gamma-glycidoxypropyltrimethoxysilane.
The preparation method of the temperature-resistant silica gel leather comprises the following steps:
1) adding the base rubber, the methyl polysilicate and the vinyl MQ silicon resin into a vacuum kneader according to the parts by weight, kneading and stirring for 8min, adding one third of the total amount of the filler and one third of the total amount of the aluminum hydroxide into the kneader, stirring uniformly, adding the silanization reagent and the distilled water, continuously stirring for 35min, adding the rest fumed silica and the rest aluminum hydroxide twice, heating to 155 ℃ after agglomeration, refining for 70min under the vacuum condition of-0.10 MPa during rubber refining, and discharging to obtain a base material for later use;
2) adding the cross-linking agent, the stabilizing agent, the coupling agent, the butyl titanate, the platinum complex catalyst and the base material obtained in the step 1) into a stirrer according to the parts by weight, and uniformly mixing to obtain a finished product rubber material.
3) Coating the finished product rubber obtained in the step 2) on a textile base fabric, vulcanizing for 8min at 190 ℃, baking, curing and forming, attaching release paper, and rolling to obtain the temperature-resistant silica gel leather; and a vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide is added during vulcanization, the weight ratio of the finished product rubber material to the vulcanizing agent is 100:1.5, the vulcanization temperature is 200 ℃, and the vulcanization time is 12 min.
Example 6
The temperature-resistant silica gel leather comprises a textile base cloth and a coating layer coated on the textile base cloth, wherein the coating layer is made of a silica gel material, and the silica gel material comprises the following raw materials in parts by weight:
the platinum complex catalyst is a platinum-tetravinyl tetramethyl-cyclotetrasiloxane complex with the Pt mass fraction of 2.0%; the base adhesive is a mixture of alpha, omega-divinyl polydimethylsiloxane and polymethylvinylsiloxane in a weight ratio of 1.1: 0.4; the viscosity of the alpha, omega-divinyl polydimethylsiloxane (25 ℃) is 600000 mPas, and the viscosity of the polymethylvinylsiloxane (25 ℃) is 1000 mPas; the vinyl MQ silicone resin has a viscosity (25 ℃) of 300 mPas and a vinyl content of 5.8 percent.
Each part of the modified aluminum hydroxide is prepared by the following steps:
s1, weighing 40 parts of aluminum hydroxide micro powder and 3 parts of ethyl acetate by weight, adding into a reaction device, heating to 100 ℃, stirring at the speed of 400r/min for 40min, and cooling to obtain a mixture A for later use;
s2, weighing 3 parts by weight of ammonium dihydrogen phosphate, 3 parts by weight of tetramethylammonium hydroxide and 3 parts by weight of zinc stearate, uniformly mixing, adding the mixture A obtained in the step S1, heating to 130 ℃, continuously stirring for 120min, heating the mixed system to 140 ℃, keeping the temperature for 4h, and cooling to obtain the modified aluminum hydroxide.
Each of the silylating agents is hexamethyldisilazane.
Each part of the filler is a mixture of fumed silica and acetylene black according to the weight ratio of 1.6: 0.3.
Each part of the cross-linking agent is a mixture of titanium dioxide and methyl hydrogen polysiloxane according to the weight ratio of 0.3: 0.8.
Each part of the stabilizer is ethynyl cyclohexanol; each part of the coupling agent is gamma-glycidoxypropyltrimethoxysilane.
The preparation method of the temperature-resistant silica gel leather comprises the following steps:
1) adding the base rubber, the methyl polysilicate and the vinyl MQ silicon resin into a vacuum kneader according to the parts by weight, kneading and stirring for 8min, adding one third of the total amount of the filler and one third of the total amount of the aluminum hydroxide into the kneader, stirring uniformly, adding the silanization reagent and the distilled water, continuously stirring for 35min, adding the rest fumed silica and the rest aluminum hydroxide twice, heating to 155 ℃ after agglomeration, refining for 70min under the vacuum condition of-0.10 MPa during rubber refining, and discharging to obtain a base material for later use;
2) adding the cross-linking agent, the stabilizing agent, the coupling agent, the butyl titanate, the platinum complex catalyst and the base material obtained in the step 1) into a stirrer according to the parts by weight, and uniformly mixing to obtain a finished product rubber material.
3) Coating the finished product rubber obtained in the step 2) on a textile base fabric, vulcanizing for 8min at 190 ℃, baking, curing and forming, attaching release paper, and rolling to obtain the temperature-resistant silica gel leather; and a vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide is added during vulcanization, the weight ratio of the finished product rubber material to the vulcanizing agent is 100:1.5, the vulcanization temperature is 200 ℃, and the vulcanization time is 12 min.
Comparative example 1
This comparative example differs from example 5 above in that: the comparative example is not added with modified aluminum hydroxide, and the rest of the comparative example is the same as example 1, and is not repeated.
Comparative example 2
This comparative example differs from example 3 above in that: in this comparative example, zinc stearate was not added in the preparation of modified aluminum hydroxide, and the rest of the comparative example was the same as example 3 and will not be described again.
The silica materials for the coating layers of the temperature-resistant silica gel leathers prepared in the specific examples 1, 3 and 5 and the comparative examples 1 to 2 were respectively subjected to a correlation performance test, and the test results are shown in table 1:
the test standards of each performance parameter are rebound (GB/T30709-.
TABLE 1
As can be seen from Table 1, the silica materials for the coating layer of the temperature-resistant silica gel leather prepared in the embodiments 1 and 3 have excellent mechanical properties, good flame retardance, peeling strength and hardness, good tearing strength, tensile strength, rebound resilience and elongation, and excellent comprehensive properties.
As can be seen from the comparison among examples 1, 3 and 5 and comparative examples 1-2, the addition of the modified aluminum hydroxide can make the silica material for the coating layer of the temperature-resistant silica leather have good flame retardancy, peeling strength, hardness, rebound resilience and elongation, while the modification of the aluminum hydroxide can further improve the flame retardancy, peeling strength, rebound resilience and elongation of the silica material for the coating layer of the temperature-resistant silica leather, and simultaneously make the silica material also have good tearing strength, tensile strength, hardness and adhesion strength, and the comprehensive performance is excellent, thereby having wide market prospect and application value.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. A temperature-resistant silica gel leather is characterized in that: the coating comprises a textile base fabric and a coating layer coated on the textile base fabric, wherein the coating layer is made of a silica gel material, and the silica gel material comprises the following raw materials in parts by weight:
2. the temperature-resistant silica gel leather according to claim 1, characterized in that: the base adhesive is a mixture consisting of alpha, omega-divinyl polydimethylsiloxane and polymethylvinylsiloxane according to the weight ratio of 0.9-1.1: 0-0.4; the viscosity of the alpha, omega-divinylpolydimethylsiloxane (25 ℃) is 600000 mPas, and the viscosity of the polymethylvinylsiloxane (25 ℃) is 1000 mPas.
3. The temperature-resistant silica gel leather according to claim 1, characterized in that: the viscosity (25 ℃) of the vinyl MQ silicon resin is 300 mPas, and the vinyl content is 5.4-5.8%.
4. The temperature-resistant silica gel leather according to claim 1, characterized in that: each part of the modified aluminum hydroxide is prepared by the following steps:
s1, weighing 30-40 parts of aluminum hydroxide micro powder and 1-3 parts of ethyl acetate by weight, adding into a reaction device, heating to 80-100 ℃, stirring at the speed of 200-400r/min for 20-40min, and cooling to obtain a mixture A for later use;
s2, weighing 1-3 parts by weight of ammonium dihydrogen phosphate, 1-3 parts by weight of tetramethylammonium hydroxide and 1-3 parts by weight of zinc stearate, uniformly mixing, adding the mixture A obtained in the step S1, heating to 90-130 ℃, continuously stirring for 60-120min, heating the mixed system to 110-140 ℃, preserving heat for 1-4h, and cooling to obtain the modified aluminum hydroxide.
5. The temperature-resistant silica gel leather according to claim 1, characterized in that: each part of the silanization reagent is at least one of hexamethyldisilazane, trimethylchlorosilane, hexamethyldisiloxane, dimethyldichlorosilane, methyltrichlorosilane, trimethylchlorosilane, phenyltriethoxysilane, hexamethyldisilazane, methyltriethoxysilane, tert-butyldimethylchlorosilane, hexadecyltrimethoxysilane, octyltriethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane.
6. The temperature-resistant silica gel leather according to claim 1, characterized in that: each part of the filler is a mixture of fumed silica and acetylene black according to the weight ratio of 0.8-1.6: 0-0.3.
7. The temperature-resistant silica gel leather according to claim 1, characterized in that: each part of the cross-linking agent is a mixture of titanium dioxide and methyl hydrogen polysiloxane according to the weight ratio of 0.1-0.3: 0.4-0.8.
8. The temperature-resistant silica gel leather according to claim 1, characterized in that: each part of the stabilizer is ethynyl cyclohexanol.
9. The temperature-resistant silica gel leather according to claim 1, characterized in that: each part of the coupling agent is at least one of gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, aminopropyltriethoxysilane and aminopropyltriethoxysilane.
10. The preparation method of the temperature-resistant silica gel leather according to any one of claims 1 to 9, which is characterized by comprising the following steps: is prepared by the following steps:
1) adding the base rubber, the methyl polysilicate and the vinyl MQ silicon resin into a vacuum kneader according to the parts by weight, kneading and stirring for 4-8min, adding one third of the total amount of the filler and one third of the total amount of the aluminum hydroxide into the kneader, stirring uniformly, adding the silanization reagent and the distilled water, continuously stirring for 25-35min, adding the rest fumed silica and the aluminum hydroxide twice, heating to 145-155 ℃ for rubber mixing after agglomeration, refining for 50-70min under the vacuum condition of- (0.08-0.10) MPa during rubber mixing, and discharging to obtain a base material for later use;
2) adding the cross-linking agent, the stabilizing agent, the coupling agent, the butyl titanate, the platinum complex catalyst and the base material obtained in the step 1) into a stirrer according to the parts by weight, and uniformly mixing to obtain a finished product rubber material.
3) Coating the finished product rubber obtained in the step 2) on a textile base fabric, vulcanizing for 4-8min at the temperature of 170-190 ℃, baking, curing and molding, attaching release paper, and rolling to obtain the temperature-resistant silica gel leather.
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| CN115895268A (en) * | 2022-07-14 | 2023-04-04 | 江门市澳卓实业有限公司 | Tear-resistant silica gel leather and preparation process and application thereof |
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