CN113667310B - Liquid silicone rubber and preparation method and application thereof - Google Patents
Liquid silicone rubber and preparation method and application thereof Download PDFInfo
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- CN113667310B CN113667310B CN202110949118.9A CN202110949118A CN113667310B CN 113667310 B CN113667310 B CN 113667310B CN 202110949118 A CN202110949118 A CN 202110949118A CN 113667310 B CN113667310 B CN 113667310B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/398—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing boron or metal atoms
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2203/00—Macromolecular materials of the coating layers
- D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06N2203/066—Silicon polymers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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Abstract
The application belongs to the technical field of rubber, and particularly relates to liquid silicone rubber and a preparation method and application thereof. The application provides a liquid silicone rubber, including: a first mixture and a second mixture; the preparation method of the first mixture comprises the following steps: step 1, mixing raw materials and carrying out heat treatment to obtain base rubber; wherein the raw materials comprise vinyl silicone oil, white carbon black, a treating agent and water; step 2, mixing the base rubber, the vinyl silicone oil and the platinum catalyst to obtain a first mixture; the preparation method of the second mixture comprises the following steps: and mixing the vinyl silicone oil, the boron-containing group hydrogen-containing silicone oil and the inhibitor to obtain a second mixture. The application provides liquid silicone rubber and a preparation method and application thereof, and can effectively solve the technical problems that the existing liquid silicone rubber is poor in cohesiveness, and two adjacent layers of liquid silicone rubber layers are easy to separate and fall off when liquid silicone rubber is coated for multiple times.
Description
Technical Field
The application belongs to the technical field of rubber, and particularly relates to liquid silicone rubber and a preparation method and application thereof.
Background
With the improvement of living standard of people, the quality requirement on life is higher and higher. In consideration of the problems of safety, environmental protection and the like, the traditional products such as automobile chairs, household leather products, hotel decorative leather and the like are made of PVC, PU and the like, the traditional artificial leather material is high in quality and low in price, but the production process of the materials has great pollution to the environment, and the products have the defects of no aging resistance, easy abrasion and no air permeability; after the material is used, toxic gas generated after the material is used as garbage to be incinerated can cause secondary pollution to the environment. From the viewpoint of environmental protection, the liquid silicone rubber imitation leather product has the same hand feeling as the original product, is aging resistant and is gradually accepted by the people.
At present, the preparation process of the liquid silicon rubber imitation leather product has a plurality of processes, but due to the characteristics of the product, no matter which process is adopted, the liquid silicon rubber material needs to be coated at least twice, and the hand feeling and the strength of the imitation leather of people can be achieved. However, if two successive coats of liquid silicone rubber are used, the two adjacent layers of liquid silicone rubber are easily delaminated due to poor adhesion of the liquid silicone rubber.
Disclosure of Invention
In view of the above, the application provides a liquid silicone rubber, and a preparation method and an application thereof, which can effectively solve the technical problems that the existing liquid silicone rubber has poor cohesiveness, and two adjacent liquid silicone rubber layers are easy to separate and fall off when liquid silicone rubber is coated for multiple times.
The present application provides in a first aspect a liquid silicone rubber comprising: a first mixture and a second mixture;
the preparation method of the first mixture comprises the following steps:
step 1, mixing raw materials and carrying out heat treatment to obtain base rubber; wherein the raw materials comprise vinyl silicone oil, white carbon black, a treating agent and water;
step 2, mixing the base rubber, the vinyl silicone oil and the platinum catalyst to obtain a first mixture;
the preparation method of the second mixture comprises the following steps:
and mixing the vinyl silicone oil, the boron-containing group hydrogen-containing silicone oil and the inhibitor to obtain a second mixture.
Specifically, the white carbon black is fumed white carbon black; the specific surface area of the fumed silica is 200m 2 /g。
In another embodiment, the vinyl silicone oil has a viscosity in the range of 5000 to 100000mpa.s; the ethylene mass percentage content of the vinyl silicone oil is 0.05-0.5%.
In another embodiment, the vinyl silicone oil has a viscosity in the range of 10000 to 50000mpa.s.
Specifically, the viscosity of the vinyl silicone oil is 20000mpa.s.
In another embodiment, the preparation method of the boron-containing group hydrogen-containing silicone oil comprises the following steps: reacting the boron-containing compound, the silane organic matter and the hydrogen-containing silicone oil at the temperature of 100-150 ℃ to obtain the boron-containing group hydrogen-containing silicone oil.
Specifically, the silane organic matter is selected from vinyltrimethoxysilane or/and vinyltriethoxysilane.
In another embodiment, the hydrogen content of the boron-containing group hydrogen-containing silicone oil is 0.2-1.2%. The application finds that the introduction of boron-containing groups on the main chain of the hydrogen-containing silicone oil can increase the cohesiveness of the liquid silicone rubber.
Specifically, the boron-containing compound is boric acid.
Specifically, the hydrogen-containing silicone oil is selected from the existing conventional hydrogen-containing silicone oil with the hydrogen content of 0.6-0.85%.
Specifically, the preparation method of the boron-containing group hydrogen-containing silicone oil comprises the following steps: boric acid, vinyl trimethoxy silane and hydrogen-containing silicone oil react at the temperature of 100-150 ℃ to obtain the boron-containing group hydrogen-containing silicone oil.
Specifically, in the preparation method of the boron-containing group hydrogen-containing silicone oil, the using amount of the boric acid is 1.5-2 g; the usage amount of the vinyl trimethoxy silane is 9.5 to 15g; the usage amount of the hydrogen-containing silicone oil is 83-89 g.
Specifically, in the preparation method of the boron-containing group hydrogen-containing silicone oil, the reaction time is 4 hours.
In another embodiment, the treating agent is selected from the group consisting of silazane treating agents and siloxane treating agents.
In another embodiment, the silazane treating agent is hexamethyldisilazane or/and vinyl silazane.
In particular, the vinyl silazane is selected from tetramethyldivinylsilazane.
In another embodiment, the siloxane treatment is selected from dimethyldimethoxysilane or/and dimethyldiethoxysilane.
In another embodiment, in step 2, the platinum catalyst is a complex of chloroplatinic acid and divinyltetramethyldisiloxane, and the platinum content of the platinum catalyst is 500 to 10000ppm.
Specifically, the platinum content of the complex is 2000ppm
In another embodiment, the inhibitor is selected from ethynyl-1-cyclohexanol or/and 2-methyl-3-butyn-2-ol.
In another embodiment, the raw materials comprise, in parts by weight:
the first mixture comprises:
65-100 parts of base rubber;
8-15 parts of vinyl silicone oil;
0.1 to 0.5 percent of platinum catalyst;
the second mixture includes:
60-70 parts of vinyl silicone oil;
30-40 parts of boron-containing group hydrogen-containing silicone oil;
0.36 to 0.5 percent of inhibitor.
In another embodiment, the raw materials comprise, in parts by weight:
the first mixture includes:
65-100 parts of base adhesive;
8-15 parts of vinyl silicone oil;
0.1-0.5 of platinum catalyst;
the second mixture includes:
60-70 parts of vinyl silicone oil;
30-40 parts of boron-containing group hydrogen-containing silicone oil;
0.36 to 0.5 percent of inhibitor.
In another embodiment, the raw material also comprises vinyl-terminated side chain high vinyl silicone oil, and the viscosity of the vinyl-terminated side chain high vinyl silicone oil ranges from 1000 to 80000mpa.
In another embodiment, the viscosity of the vinyl-terminated pendant high vinyl silicone oil is 1000mpa.s.
Specifically, the preparation method of the 1000mpa.s terminal vinyl side chain high vinyl silicone oil comprises the following steps: 100g of octamethylcyclotetrasiloxane D4, 1g of divinyl tetramethylsiloxane and 3g of tetravinyl tetramethylsiloxane are mixed, and the mixture reacts for 4 hours at the temperature of 100 ℃ under the action of a basic catalyst tetramethylammonium hydroxide (made into alkali glue), and then low molecules are removed, so that 1000mpa.s vinyl-terminated side chain high vinyl silicone oil is prepared.
In another embodiment, the vinyl content of the vinyl-terminated side chain high vinyl silicone oil is 0.5-5%.
A second aspect of the present application provides a method for preparing a liquid silicone rubber,
the preparation method of the first mixture comprises the following steps:
step 1, mixing raw materials and carrying out heat treatment to obtain base rubber; wherein the raw materials comprise vinyl silicone oil, white carbon black, a treating agent and water;
step 2, mixing the base rubber, the vinyl silicone oil and the platinum catalyst to obtain a first mixture;
the preparation method of the second mixture comprises the following steps:
and mixing the vinyl silicone oil, the boron-containing group hydrogen-containing silicone oil and the inhibitor to obtain a second mixture.
In another embodiment, in step 1, the temperature of the heat treatment is 150 ℃.
The third aspect of the application discloses application of the liquid silicone rubber or the liquid silicone rubber prepared by the preparation method in synthetic leather products.
In another embodiment, the first mixture and the second mixture are mixed to provide a third mixture;
coating the third mixture on the surface of a product, and curing and forming to obtain a synthetic leather product;
the mass ratio of the first mixture to the second mixture is (1-10): 1; the temperature of the curing molding is 80-150 ℃, and the time of the curing molding is 1-20 min.
In another embodiment, the mass ratio of the first mixture to the second mixture is (1 to 100): (1-2); the temperature of the curing molding is 60-80 ℃, and the time of the curing molding is 2-10 min.
In another embodiment, the mass ratio of the first mixture to the second mixture is 10:1; the mass ratio of the first mixture to the second mixture is 1:1; the mass ratio of the first mixture to the second mixture is 50.
In another embodiment, the number of applications is 2, 3, 4, 5, 6, 7, 8, 9 or 10. Specifically, after each coating, the coating is dried for 5 to 10 minutes and then coated again.
The purpose of the application is to overcome the defects that in the prior art, liquid silicone rubber is poor in cohesiveness, and two adjacent layers of liquid silicone rubber layers are easy to separate and fall off when liquid silicone rubber is coated for multiple times. The boron-containing group hydrogen-containing silicone oil is creatively added into the addition type liquid silicone rubber system, the boron-containing group hydrogen-containing silicone oil is added, the cohesiveness of the adjacent liquid silicone rubber layer can be obviously improved, the addition type liquid silicone rubber is prepared, the addition type liquid silicone rubber can be coated on the surface of a synthetic leather product for multiple times, the adjacent liquid silicone rubber layer achieves cohesive failure, and the delaminating phenomenon cannot be generated.
Detailed Description
The application provides liquid silicone rubber and a preparation method and application thereof, and aims to solve the technical defects that in the prior art, liquid silicone rubber is poor in cohesiveness, and two adjacent layers of liquid silicone rubber layers are easy to separate and fall off when liquid silicone rubber is coated for multiple times.
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The raw materials and reagents used in the following examples are commercially available or self-made.
The vinyl silicone oils used in the following examples have substantially identical molecular structures, differing primarily in molecular weight (i.e., viscosity). Base materials of different viscosities have a significant influence on the product properties, in particular the viscosity before curing.
Preparation of 1000mpa.s terminal vinyl side chain high vinyl silicone oil used in the following examples: 100g of D4 (octamethylcyclotetrasiloxane), 1g of divinyl tetramethylsiloxane and 3g of tetravinyl tetramethylsiloxane react for 4 hours at the temperature of 100 ℃ under the action of a basic catalyst tetramethylammonium hydroxide (made into alkali glue), and then low molecules are removed to prepare 1000mpa.s vinyl-terminated side chain high vinyl silicone oil.
The hydrogen content of the hydrogen-containing silicone oil of the following examples was in the range of 0.2 to 1.2%. The introduction of boron-containing groups on the main chain of the hydrogen-containing silicone oil can effectively increase the cohesiveness of the liquid silicone rubber.
The hydrogen-containing silicone oil used in the following comparative examples is conventional hydrogen-containing silicone oil, and may be linear hydrogen-containing silicone oil or cyclic hydrogen-containing silicone oil.
Example 1
The embodiment of the application provides a liquid silicone rubber, and the specific preparation method comprises the following steps:
1. 100 parts by weight of vinyl silicone oil with viscosity of 20000mpa.s are added into a kneader and stirred uniformly, and then 40 parts by weight of vinyl silicone oil with specific surface area of 200m 2 And stirring the fumed silica/g, 8 parts by weight of hexamethyldisilazane, 1 part by weight of tetramethyldivinylsilazane and 2.5 parts by weight of water in a kneader for 3 hours, heating to 150 ℃, performing vacuum heat treatment for 4 hours, discharging, and passing through a three-roll grinder to obtain the base adhesive.
Adding 15 parts by weight of vinyl silicone oil with the viscosity of 10000mpa.s into 100 parts by weight of the base adhesive, and adding 0.5 part by weight of platinum catalyst to be uniformly stirred in a planetary stirrer to prepare an agent A; wherein the platinum catalyst is a complex of chloroplatinic acid and divinyltetramethyldisiloxane (the platinum content of the platinum complex is 2000 ppm).
2. Uniformly stirring 70 parts by weight of vinyl silicone oil with the viscosity of 5000mpa.s, 30 parts by weight of hydrogen-containing silicone oil (with the hydrogen content of 0.75%) and 0.36 part by weight of 1-ethynylcyclohexanol in a high-speed dispersion machine to obtain an agent B; the preparation method of the hydrogen-containing silicone oil (with hydrogen content of 0.75%) comprises the following steps: 1.5g of boric acid, 9.5g of vinyltrimethoxysilane and 89g of hydrogen-containing silicone oil with the hydrogen content of 0.85 percent are reacted for 4 hours at the temperature of 120 ℃ to obtain the boron-containing group hydrogen-containing silicone oil with the hydrogen content of 0.75 percent.
3. Mixing the agent A and the agent B according to the ratio of A: b =10:1 part by weight of the silicone rubber composition was mixed and molded to obtain a liquid silicone rubber.
The liquid silicone rubber is used for manufacturing a standard sample, and the performance of the standard sample is tested, wherein the hardness is 56 Shore A (GB/T531.1-2008), the tensile strength is 7.3mpa, the elongation is 336%, the tear strength is 15KN/m, and the resilience is 63%.
The method comprises the steps of directly coating the liquid silicone rubber on the surface of release paper, baking for 5 minutes at 110 ℃ to obtain a first coating, coating the liquid silicone rubber on the surface of the first coating to form a second coating, finally pasting a base material, namely sequentially coating two layers of liquid silicone rubber and one layer of base material on the release paper, baking for 5 minutes at 110 ℃, tearing off the base material by hands after the liquid silicone rubber is completely cured, and if the two layers of silicone rubber are not delaminated, tearing off the base material after the silicone rubber is broken, which indicates that the coating is in cohesive failure, which is an acceptable condition, the silicone rubber meets the actual requirements, but if the two layers of silicone rubber are directly delaminated, the silicone rubber does not meet the actual requirements. The delamination of the first and second coating layers was observed and it was found that the present example was acceptable in that the first and second coating layers failed cohesively and did not delaminate from each other, and that the silicone rubber was in accordance with practical requirements.
Example 2
The embodiment of the application provides a liquid silicone rubber, and the specific preparation method comprises the following steps:
1. 100 parts by weight of vinyl silicone oil with viscosity of 20000mpa.s and 5 parts by weight of high vinyl silicone oil with end vinyl side chain with viscosity of 1000mpa.s are added into a kneader and stirred uniformly, and then 40 parts by weight of high vinyl silicone oil with specific surface area of 200m 2 Per g fumed silica, 10% by weightHexamethyldisilazane, 1 part by weight of tetramethyldivinylsilazane, 1 part by weight of dimethyldimethoxysilane and 3.5 parts by weight of water were stirred in a kneader for 3 hours, then heated to 150 ℃ for vacuum heat treatment for 4 hours, discharged, and passed through a three-roll mill to obtain a base rubber.
100 parts by weight of the base rubber is added with 8 parts by weight of vinyl silicone oil with viscosity of 10000mpa.s and 0.5 part by weight of platinum catalyst to be evenly stirred in a planetary mixer to prepare the agent A. Wherein the platinum catalyst is a complex of chloroplatinic acid and divinyltetramethyldisiloxane (platinum content of the platinum complex is 2000 ppm).
2. Uniformly stirring 60 parts by weight of vinyl silicone oil with the viscosity of 3000mpa.s, 40 parts by weight of hydrogen-containing silicone oil (with the hydrogen content of 0.5%) and 0.5 part by weight of 1-ethynylcyclohexanol in a high-speed dispersion machine to obtain an agent B; the preparation method of the hydrogen-containing silicone oil (with hydrogen content of 0.5%) comprises the following steps: 2g of boric acid, 15g of vinyl trimethoxy silane and 83g of hydrogen-containing silicone oil with the hydrogen content of 0.6 percent are reacted for 4 hours at the temperature of 120 ℃ to obtain the boron-containing group hydrogen-containing silicone oil with the hydrogen content of 0.5 percent.
3. Mixing the agent A and the agent B according to the ratio of A: b =10:1 part by weight of the silicone rubber composition was mixed and molded to obtain a liquid silicone rubber.
The liquid silicone rubber is made into a standard sample, and the performance of the standard sample is tested, wherein the hardness is 57 Shore A (GB/T531.1-2008), the tensile strength is 7.6mpa, the elongation is 410%, the tear strength is 13KN/m, and the resilience is 65%.
The method comprises the steps of directly coating the liquid silicone rubber on the surface of release paper, baking for 5 minutes at 120 ℃ to obtain a first coating, coating the liquid silicone rubber on the surface of the first coating to form a second coating, finally pasting a base material, namely sequentially coating two layers of liquid silicone rubber and one layer of base material on the release paper, baking for 5 minutes at 110 ℃, tearing off the base material by hands after the liquid silicone rubber is completely cured, and if the two layers of silicone rubber are not delaminated, tearing off the base material after the silicone rubber is broken, which indicates that the coating is in cohesive failure, which is an acceptable condition, the silicone rubber meets the actual requirements, but if the two layers of silicone rubber are directly delaminated, the silicone rubber does not meet the actual requirements. The delamination of the first and second coating layers was observed, and it was found that the first and second coating layers were cohesive failure, and the two coating layers were not delaminated from each other, which is acceptable, and the silicone rubber was satisfactory.
Comparative example 1
The comparative example of the application provides a control sample, and the specific preparation method comprises the following steps:
1. 100 parts by weight of vinyl silicone oil with the viscosity of 50000mpa.s and 10 parts by weight of high vinyl silicone oil with a terminal vinyl side chain with the viscosity of 1000mpa.s are added into a kneader and stirred uniformly, and then 40 parts by weight of high vinyl silicone oil with the specific surface area of 200m 2 And stirring the fumed silica/g, 8 parts by weight of hexamethyldisilazane, 1 part by weight of tetramethyldivinylsilazane and 2 parts by weight of water in a kneader for 3 hours, heating to 150 ℃ for heat treatment for 3 hours, vacuumizing for 2 hours, discharging, and passing through a three-roll grinder to obtain the base adhesive.
Adding 15 parts by weight of vinyl silicone oil with the viscosity of 10000mpa.s into 100 parts by weight of the base adhesive, and adding 0.5 part by weight of platinum catalyst to be uniformly stirred in a planetary stirrer to prepare an agent A; wherein the platinum catalyst is a complex of chloroplatinic acid and divinyltetramethyldisiloxane (platinum content of the platinum complex is 2000 ppm).
2. Uniformly stirring 70 parts by weight of vinyl silicone oil with the viscosity of 5000mpa.s, 30 parts by weight of hydrogen-containing silicone oil and 0.36 part by weight of 1-ethynylcyclohexanol in a high-speed dispersion machine to obtain an agent B; the preparation method of the hydrogen-containing silicone oil comprises the following steps: 50g of octamethylcyclotetrasiloxane D4 and 50g of hydrogen-containing silicone oil with hydrogen content of 1.6% are reacted at 80 ℃ for 8 hours under the action of 10g of catalyst cation exchange resin, and low molecules are removed to obtain the hydrogen-containing silicone oil, wherein the hydrogen content of the hydrogen-containing silicone oil is 0.75%.
3. Mixing the agent A and the agent B according to the proportion of A: b =10:1 weight part of the composition was mixed and molded to obtain a control sample.
And (3) preparing a standard sample from the control sample, and testing the performance of the standard sample, wherein the hardness of the standard sample is 55 Shore A (GB/T531.1-2008), the tensile strength is 7.5mpa, the elongation is 345%, the tear strength is 16KN/m, and the resilience is 62%.
Directly coating the control sample on the surface of release paper, baking for 5 minutes at 120 ℃ to obtain a first coating, coating the liquid silicone rubber on the surface of the first coating to form a second coating, finally pasting a substrate, namely, sequentially coating two layers of liquid silicone rubber and one layer of substrate on the release paper, baking for 5 minutes at 110 ℃, tearing off the substrate by hands after the liquid silicone rubber is completely cured, and if the two layers of silicone rubber are not delaminated, tearing off the substrate after the silicone rubber is broken, which indicates that the coating is in cohesive failure, which is an acceptable condition, the silicone rubber meets the actual requirements, but if the two layers of silicone rubber are directly delaminated, the silicone rubber does not meet the actual requirements. The delamination of the first and second coatings was observed, and the delamination between the two coatings of this comparative example was unacceptable, and the silicone rubber did not meet the practical requirements.
Comparative example 2
The comparative example of the application provides a control sample, and the specific preparation method comprises the following steps:
1. 100 parts by weight of vinyl silicone oil with a viscosity of 10000mpa.s and 5 parts by weight of terminal vinyl side chain high vinyl silicone oil with a viscosity of 10000mpa.s are added into a kneader and are stirred uniformly, and then 40 parts by weight of vinyl side chain high vinyl silicone oil with a specific surface area of 200m 2 And stirring the fumed silica/g, 8 parts by weight of hexamethyldisilazane, 2 parts by weight of dimethyldimethoxysilane and 2.5 parts by weight of water in a kneader for 3 hours, heating to 150 ℃ for heat treatment for 4 hours, vacuumizing for 2 hours, discharging, and passing through a three-roll grinder to obtain the base rubber.
100 parts by weight of the base rubber is added with 10 parts by weight of vinyl silicone oil with viscosity of 10000mpa.s and 0.5 part by weight of platinum catalyst to be uniformly stirred in a planetary stirrer to prepare the agent A. Wherein the platinum catalyst is a complex of chloroplatinic acid and divinyltetramethyldisiloxane (platinum content of the platinum complex is 2000 ppm).
2. Uniformly stirring 60 parts by weight of vinyl silicone oil with the viscosity of 5000mpa.s, 40 parts by weight of hydrogen-containing silicone oil and 0.36 part by weight of 1-ethynylcyclohexanol in a high-speed dispersion machine to obtain an agent B; the preparation method of the hydrogen-containing silicone oil comprises the following steps: 70g of octamethylcyclotetrasiloxane D4 and 30g of hydrogen-containing silicone oil with the hydrogen content of 1.6 percent are reacted for 8 hours at 80 ℃ under the action of 10g of catalyst cation exchange resin, and low molecules are removed to obtain the hydrogen-containing silicone oil, wherein the hydrogen content of the hydrogen-containing silicone oil is 0.5 percent.
3. Mixing the agent A and the agent B according to the proportion of A: b =10:1 weight part of the composition was mixed and molded to obtain a control sample.
And (3) preparing a standard sample from the control sample, and testing the performance of the standard sample, wherein the hardness of the standard sample is 50 Shore A (GB/T531.1-2008), the tensile strength is 7.0mpa, the elongation is 360%, the tear strength is 11KN/m, and the resilience is 57%.
Directly coating the control sample on the surface of release paper, baking for 5 minutes at 120 ℃ to obtain a first coating, coating the liquid silicone rubber on the surface of the first coating to form a second coating, finally pasting a substrate, namely, sequentially coating two layers of liquid silicone rubber and one layer of substrate on the release paper, baking for 5 minutes at 110 ℃, tearing off the substrate by hands after the liquid silicone rubber is completely cured, and if the two layers of silicone rubber are not delaminated, tearing off the substrate after the silicone rubber is broken, which indicates that the coating is in cohesive failure, which is an acceptable condition, the silicone rubber meets the actual requirements, but if the two layers of silicone rubber are directly delaminated, the silicone rubber does not meet the actual requirements. The delamination of the first and second coatings was observed, and the delamination between the two coatings of this comparative example was unacceptable, and the silicone rubber did not meet the practical requirements.
To sum up, the liquid silicone rubber that this application provided is an addition type liquid silicone rubber, and the hydrogen-containing silicone oil that this application creatively added contains the boron group is in order to improve the cohesiveness on adjacent liquid silicone rubber layer, can coat in the article outside many times, and adjacent liquid silicone rubber layer reaches cohesive failure, can not produce the delaminating phenomenon.
The foregoing is only a preferred embodiment of the present application and it should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.
Claims (8)
1. A liquid silicone rubber, comprising: a first mixture and a second mixture;
the preparation method of the first mixture comprises the following steps:
step 1, mixing raw materials and carrying out heat treatment to obtain base rubber; wherein the raw materials comprise vinyl silicone oil, white carbon black, a treating agent and water;
step 2, mixing the base adhesive, the vinyl silicone oil and a platinum catalyst to obtain a first mixture;
the preparation method of the second mixture comprises the following steps:
mixing vinyl silicone oil, boron-containing group hydrogen-containing silicone oil and an inhibitor to obtain a second mixture;
the preparation method of the boron-containing group hydrogen-containing silicone oil comprises the following steps: reacting boric acid, vinyl trimethoxy silane and hydrogen-containing silicone oil at the temperature of 100-150 ℃ to obtain boron-group-containing hydrogen-containing silicone oil;
in the preparation method of the boron-containing group hydrogen-containing silicone oil, the using amount of the boric acid is 1.5-2 g; the usage amount of the vinyl trimethoxy silane is 9.5 to 15g; the using amount of the hydrogen-containing silicone oil is 83-89 g;
the raw materials comprise the following components in parts by weight:
65 to 100 portions of vinyl silicone oil;
20-40 parts of white carbon black;
9-12 parts of treating agent;
2.5 to 3.5 percent of water;
the first mixture includes:
65 to 100 portions of base rubber;
8 to 15 percent of vinyl silicone oil;
0.1 to 0.5 percent of platinum catalyst;
the second mixture includes:
60 to 70 parts of vinyl silicone oil;
30 to 40 percent of boron-containing group hydrogen-containing silicone oil;
0.36 to 0.5 percent of inhibitor.
2. The liquid silicone rubber according to claim 1, wherein the vinyl silicone oil has a viscosity in the range of 5000-100000mpa.s; the vinyl silicone oil has a vinyl mass percent of 0.05 to 0.5 percent.
3. The liquid silicone rubber according to claim 1, wherein in step 1, the treating agent is selected from a silazane treating agent and a siloxane treating agent.
4. The liquid silicone rubber according to claim 1, wherein in step 2, the platinum catalyst is a complex of chloroplatinic acid and divinyltetramethyldisiloxane, and the platinum content of the platinum catalyst is 500 to 10000 ppm; the inhibitor is selected from ethynyl-1-cyclohexanol or/and 2-methyl-3-butyn-2-ol.
5. The liquid silicone rubber according to claim 1, wherein the raw material further comprises a vinyl-terminated side chain high vinyl silicone oil, and the viscosity of the vinyl-terminated side chain high vinyl silicone oil ranges from 1000 to 80000mpa.s.
6. A method of preparing the liquid silicone rubber of any of claims 1~5,
the preparation method of the first mixture comprises the following steps:
step 1, mixing raw materials and carrying out heat treatment to obtain base rubber; wherein the raw materials comprise vinyl silicone oil, white carbon black, a treating agent and water;
step 2, mixing the base rubber, the vinyl silicone oil and the platinum catalyst to obtain a first mixture;
the preparation method of the second mixture comprises the following steps:
and mixing the vinyl silicone oil, the boron-group-containing hydrogen-containing silicone oil and the inhibitor to obtain a second mixture.
7. Use of the liquid silicone rubber of any one of claims 1~5 in a synthetic leather product.
8. Use according to claim 7, wherein the first mixture and the second mixture are mixed to obtain a third mixture;
coating the third mixture on the surface of a product, and curing and forming to obtain a synthetic leather product;
the mass ratio of the first mixture to the second mixture is (1 to 10): 1; the temperature of the curing molding is 80-150 ℃, and the time of the curing molding is 1-20 min.
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