CN111793366A - White carbon black-free solid silicon rubber for high-hardness rubber roller and preparation method thereof - Google Patents
White carbon black-free solid silicon rubber for high-hardness rubber roller and preparation method thereof Download PDFInfo
- Publication number
- CN111793366A CN111793366A CN202010791652.7A CN202010791652A CN111793366A CN 111793366 A CN111793366 A CN 111793366A CN 202010791652 A CN202010791652 A CN 202010791652A CN 111793366 A CN111793366 A CN 111793366A
- Authority
- CN
- China
- Prior art keywords
- rubber
- polysilsesquioxane
- silicone rubber
- carbon black
- white carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Rolls And Other Rotary Bodies (AREA)
Abstract
The invention discloses a solid silicon rubber without white carbon black for a high-hardness rubber roller and a preparation method thereof, relating to the technical field of rubber roller silicon rubber, wherein the silicon rubber comprises methyl vinyl silicon rubber raw rubber, polysilsesquioxane, diatomite, a silane coupling agent and a non-white carbon black auxiliary agent; the preparation method comprises the following steps: mixing raw methyl vinyl silicone rubber, polysilsesquioxane and a silane coupling agent into a group; then carrying out heating vulcanization treatment; cooling to below 90 ℃, and adding diatomite and a non-white carbon black auxiliary agent to obtain the silicone rubber. The rubber roll silicone rubber produced by the invention has lower abrasion value, the hardness and resilience reach the standard, the surface viscosity of the rubber roll silicone rubber is lower, and the stripping performance of the rubber roll silicone rubber and a plastic film is better.
Description
Technical Field
The invention relates to the technical field of silicone rubber rollers, in particular to solid silicone rubber for a high-hardness rubber roller without white carbon black and a preparation method thereof.
Background
The silicone rubber roller has good high temperature resistance, high pressure resistance, good insulativity, high resilience and other properties, and can be better applied to the field of manufacturing various large materials. In the plastic film production industry, the peeling performance between the silicone rubber roller and the film has higher requirements, so that the plastic film and the rubber roller can be normally separated to ensure the normal production of the plastic film.
In the related technology, for example, the chinese patent application publication No. CN110218455A discloses a low compression set rubber roll silicone rubber and a preparation method thereof, wherein the rubber roll silicone rubber comprises the following components in parts by weight: 100 parts of silicon rubber, 20-70 parts of white carbon black, 15-50 parts of filler, 1-3 parts of structural control agent, 2-6 parts of heat-resistant agent, 0.1-1 part of coupling agent and 0.1-1 part of release agent. The rubber roller silicone rubber has stable quality, excellent aging resistance, mechanical property, physical property and chemical property, and good use effect. Meanwhile, the rubber roll silicone rubber has the characteristics of simple preparation method, convenient process, strong operability, stable quality and strong practicability, solves the problems of temperature difference resistance and high compression set of the existing rubber roll silicone rubber, performs multiple modification on the modes of silicone rubber collocation, powder selection, treatment and the like, and has small compression set and high aging retention rate under the conditions of high strength and tearing.
In order to overcome the technical defects, the white carbon black and the structural control agent are added in the formula of the rubber roll silicone rubber, so that the surface of the rubber roll silicone rubber after vulcanization molding has certain viscosity, the stripping property of a film and a rubber roll in the production process of a plastic film is influenced, and the normal production of the plastic film is influenced.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide the solid silicon rubber for the high-hardness rubber roller without white carbon black, which has the advantages of high resilience and high stripping property under the condition of meeting the basic physical and mechanical properties and can ensure the normal production of the plastic film.
The second purpose of the invention is to provide a preparation method of the solid silicon rubber for the high-hardness rubber roller without white carbon black, which has the advantages of simple steps and high production efficiency.
In order to achieve the first object, the invention provides the following technical scheme:
the solid silicon rubber for the high-hardness rubber roll without the white carbon black is prepared from the following raw materials in parts by weight:
raw methyl vinyl silicone rubber: 1000 parts of (A);
polysilsesquioxane: 300-800 parts;
diatomite: 200-400 parts;
silane coupling agent: 1-10 parts;
non-white carbon black auxiliary agent: 0 to 100 portions;
wherein the molar mass of the raw methyl vinyl silicone rubber is 30W-50W, the average particle size of the polysilsesquioxane is 0.1-100um grade, and the vinyl content of the raw methyl vinyl silicone rubber is 0.03% -1%.
By adopting the technical scheme, the polysilsesquioxane is used for replacing white carbon black as a semi-reinforcing filler, has lower surface energy and a special structure, can reduce the viscosity of the surface of the rubber roller, has the functions of reinforcing and hardening the rubber roller, and reduces the abrasion value of the surface of the silicon rubber; the silicon dioxide of the diatomite can change or recover the position along with the movement of the rubber polymer chain, so that the resistance of the silicone rubber to deformation and damage is increased, the rubber material is dry and easy to polish, and the stripping performance of the silicone rubber roller and the plastic film is improved; the silane coupling agent improves the binding capacity of the diatomite, the polysilsesquioxane and the raw methyl vinyl silicone rubber, and enhances the reinforcing effect of the diatomite, so that the tensile strength and the wear resistance of the silicone rubber are improved, and the silicone rubber roller has high resilience and high stripping property under the condition of meeting the basic physical and mechanical properties, and can ensure the normal production of the plastic film.
Further, the non-white carbon black auxiliary agent is polytetrafluoroethylene micro powder with the weight portion of 50-100 portions.
By adopting the technical scheme, the polytetrafluoroethylene micro powder can improve the surface property of rubber, the friction property, the wear resistance and the demolding property of a polymer and the stripping property of a silicone rubber roller and a plastic film.
Further, the vinyl content of the raw methyl vinyl silicone rubber is 0.03-1%.
By adopting the technical scheme, the vinyl content in the raw methyl vinyl silicone rubber is too low, the rebound resilience of the cured silicone rubber is poor, the vinyl content is too high, the cured silicone rubber is easy to embrittle, the wear resistance is poor, and the silicone rubber has high rebound resilience and good comprehensive performance by controlling the vinyl content in the raw methyl vinyl silicone rubber within a certain range.
Further, the silane coupling agent is one or a mixture of KH792, KH560 or A-172.
By adopting the technical scheme, the A-172 can build a molecular bridge between the diatomite inorganic filler and the organic matter methyl vinyl silicone rubber crude rubber, so that the reinforcing effect of the diatomite is enhanced, and the tensile strength and the wear resistance of the silicone rubber are improved.
Further, the polysilsesquioxane is modified polysilsesquioxane, and the preparation method of the modified polysilsesquioxane is as follows:
s01, adding water, polysilsesquioxane and vinylidene cyanide into a stirrer, wherein the mass ratio of the water to the polysilsesquioxane to the vinylidene cyanide is (3-4) to (1-3): (2:3), stirring at 200r/min-400r/min for 5min-10min to obtain a prefabricated mixture;
s02, placing the prefabricated mixture into a heating furnace, gradually raising the temperature to 65-75 ℃ within 10-15 min, and then dropwise adding a mixture of tert-butyl hydroperoxide and sodium metabisulfite, wherein the mass of the mixture of tert-butyl hydroperoxide and sodium metabisulfite is 1.4-2.1% of that of polysilsesquioxane.
By adopting the technical scheme, the polysilsesquioxane is modified by using the vinylidene cyanide, and the vinyl group is introduced, so that the activity of the polysilsesquioxane is improved, and the reinforcing effect of the polysilsesquioxane is enhanced, thereby reducing the abrasion value of the silicone rubber, improving the tensile strength and further improving the stripping property of the silicone rubber roller and the plastic film.
Further, the mass ratio of the tert-butyl hydroperoxide to the sodium metabisulfite is 2:3, obtaining the modified polysilsesquioxane.
By adopting the technical scheme, the polysilsesquioxane and the metadinitrile siloxane can be promoted to react by compounding the tert-butyl hydroperoxide and the sodium metabisulfite according to a certain proportion, so that an ethylene group is introduced, and the reinforcing effect of the polysilsesquioxane on the silicon rubber is improved.
Further, in step S02, the mixture of both t-butyl hydroperoxide and sodium metabisulfite is added dropwise to the heating furnace in two portions.
By adopting the technical scheme, the mixture of the tert-butyl hydroperoxide and the sodium metabisulfite is added into the heating furnace in times, so that the mixing uniformity can be improved, the reaction can be carried out at a constant speed, and the violent reaction is avoided.
Further, the silicon rubber is prepared from the following raw materials in parts by weight:
raw methyl vinyl silicone rubber: 1000 parts of (A);
modified polysilsesquioxane: 800 parts;
diatomite: 200 parts of (A);
a-172: 5 parts of a mixture;
polytetrafluoroethylene micro powder: 100 parts of (A);
the molar mass of the raw methyl vinyl silicone rubber is 40W, the vinyl content of the raw methyl vinyl silicone rubber is 0.03-1%, the average particle size of the modified polysilsesquioxane is 0.1-100um grade, and the preparation method of the modified polysilsesquioxane comprises the following steps:
s01, adding water, polysilsesquioxane and vinylidene cyanide into a stirrer, wherein the mass ratio of the water to the polysilsesquioxane to the vinylidene cyanide is 3: 1: 2, stirring for 5min at 200r/min to obtain a prefabricated mixture;
s02, placing the prefabricated mixture into a heating furnace, gradually heating to 65 ℃ within 10min, and then dropwise adding a mixture of tert-butyl hydroperoxide and sodium metabisulfite, wherein the mass ratio of the mixture of tert-butyl hydroperoxide and sodium metabisulfite to polysilsesquioxane is 1.4%, and the mass ratio of tert-butyl hydroperoxide to sodium metabisulfite is 2:3, so as to obtain the modified polysilsesquioxane.
By adopting the technical scheme, the rubber roll silicone rubber obtained by the scheme has higher strength and can reduce the abrasion value, thereby improving the stripping property of the rubber roll silicone rubber and a plastic film.
In order to achieve the second object, the invention provides the following technical scheme:
a preparation method of solid silicon rubber for high-hardness rubber rollers without white carbon black comprises the following steps:
s1, mixing raw methyl vinyl silicone rubber, polysilsesquioxane and a silane coupling agent in a kneading machine to form a cluster, and controlling the temperature system to be 80-100 ℃;
s2, heating to 150-160 ℃ in a kneader, and carrying out heat treatment for 2-3 h;
s3, cooling the product obtained in the step S2 to be below 90 ℃, adding diatomite and a non-white carbon black auxiliary agent, uniformly mixing, and cooling to obtain the silicon rubber.
By adopting the technical scheme, the silicon rubber raw material components are added into the kneader to be mixed, stirred, vulcanized and polymerized, the operation steps are simple, and the production efficiency is improved.
In conclusion, the invention has the following beneficial effects:
firstly, polysilsesquioxane is used for replacing white carbon black as a semi-reinforcing filler, the polysilsesquioxane has lower surface energy and a special structure, the viscosity of the surface of the rubber roller can be reduced, the reinforcing and hardening effects on the rubber roller are achieved, and the abrasion value of the surface of the silicon rubber is reduced; the silicon dioxide of the diatomite can change or recover the position along with the movement of the rubber polymer chain, so that the resistance of the silicone rubber to deformation and damage is increased, the rubber material is dry and easy to polish, and the stripping performance of the silicone rubber roller and the plastic film is improved; the silane coupling agent improves the binding capacity of the diatomite, the polysilsesquioxane and the raw methyl vinyl silicone rubber, and enhances the reinforcing effect of the diatomite, so that the tensile strength and the wear resistance of the silicone rubber are improved, and the silicone rubber roller has high resilience and high stripping property under the condition of meeting the basic physical and mechanical properties, and can ensure the normal production of the plastic film.
Secondly, the polytetrafluoroethylene micro powder can improve the surface performance of rubber, the friction performance, the wear performance and the demolding performance of the polymer and the stripping performance of the silicone rubber roller and the plastic film.
And thirdly, the polysilsesquioxane is modified by using the vinylidene cyanide, and a vinyl group is introduced, so that the activity of the polysilsesquioxane is improved, the reinforcing effect of the polysilsesquioxane is enhanced, the abrasion value of the silicon rubber is reduced, the tensile strength is improved, and the stripping property of the silicon rubber roller and a plastic film is further improved.
Detailed Description
The present invention will be described in further detail with reference to examples.
The source of the raw materials used in the following examples and comparative examples are shown in table 1 below:
TABLE 1 sources of raw materials
Examples
Example 1
The solid silicon rubber for the high-hardness rubber roll without the white carbon black is prepared from the following raw materials in parts by weight:
raw methyl vinyl silicone rubber: 1000 kg;
polysilsesquioxane: 300 kg;
diatomite: 400 kg;
silane coupling agent: 1 kg;
wherein the molar mass of the raw methyl vinyl silicone rubber is 40W, the vinyl content of the raw methyl vinyl silicone rubber is 0.03-1%, the average particle size of the polysilsesquioxane is 0.1-100um grade, and the silane coupling agent is KH 792.
The preparation method of the solid silicon rubber for the high-hardness rubber roll without white carbon black comprises the following steps:
s1, mixing raw methyl vinyl silicone rubber, polysilsesquioxane and a silane coupling agent in a kneading machine to form a cluster, and controlling the temperature system to be 100 ℃;
s2, heating to 160 ℃ in a kneader, and carrying out heat treatment for 2 h;
s3, cooling the product obtained in the step S2 to be below 90 ℃, adding diatomite, uniformly mixing, and cooling to obtain the silicon rubber.
Example 2
The solid silicon rubber for the high-hardness rubber roll without the white carbon black is prepared from the following raw materials in parts by weight:
raw methyl vinyl silicone rubber: 1000 kg;
polysilsesquioxane: 500 kg;
diatomite: 200 kg;
silane coupling agent: 5 kg;
wherein the molar mass of the raw methyl vinyl silicone rubber is 50W, the vinyl content of the raw methyl vinyl silicone rubber is 0.03-1%, the average particle size of the polysilsesquioxane is 0.1-100um grade, and the silane coupling agent is KH 560.
The preparation method of the solid silicon rubber for the high-hardness rubber roll without white carbon black comprises the following steps:
s1, mixing raw methyl vinyl silicone rubber, polysilsesquioxane and a silane coupling agent in a kneading machine to form a cluster, and controlling the temperature system to be 90 ℃;
s2, heating to 155 ℃ in a kneader, and carrying out heat treatment for 3 h;
s3, cooling the product obtained in the step S2 to be below 90 ℃, adding diatomite, uniformly mixing, and cooling to obtain the silicon rubber.
Example 3
The solid silicon rubber for the high-hardness rubber roll without the white carbon black is prepared from the following raw materials in parts by weight:
raw methyl vinyl silicone rubber: 1000 kg;
polysilsesquioxane: 600 kg;
diatomite: 200 kg;
silane coupling agent: 10 kg;
wherein the molar mass of the raw methyl vinyl silicone rubber is 30W, the vinyl content of the raw methyl vinyl silicone rubber is 0.03-1%, the average particle size of the polysilsesquioxane is 0.1-100um grade, and the silane coupling agent is A-172.
The preparation method of the solid silicon rubber for the high-hardness rubber roll without white carbon black comprises the following steps:
s1, mixing raw methyl vinyl silicone rubber, polysilsesquioxane and A-172 in a kneader to form a mass, and controlling the temperature system to be 100 ℃;
s2, heating to 160 ℃ in a kneader, and carrying out heat treatment for 2 h;
s3, cooling the product obtained in the step S2 to be below 90 ℃, adding diatomite, uniformly mixing, and cooling to obtain the silicon rubber.
Example 4
The solid silicon rubber for the high-hardness rubber roll without the white carbon black is prepared from the following raw materials in parts by weight:
raw methyl vinyl silicone rubber: 1000 kg;
polysilsesquioxane: 800 kg;
diatomite: 200 kg;
silane coupling agent: 5 kg;
wherein the molar mass of the raw methyl vinyl silicone rubber is 40W, the vinyl content of the raw methyl vinyl silicone rubber is 0.03-1%, the average particle size of the polysilsesquioxane is 0.1-100um grade, and the silane coupling agent is A-172.
The preparation method of the solid silicon rubber for the high-hardness rubber roll without white carbon black comprises the following steps:
s1, mixing raw methyl vinyl silicone rubber, polysilsesquioxane and A-172 in a kneader to form a mass, and controlling the temperature system to be 90 ℃;
s2, heating to 150 ℃ in a kneader, and carrying out heat treatment for 3 h;
s3, cooling the product obtained in the step S2 to be below 90 ℃, adding diatomite, uniformly mixing, and cooling to obtain the silicon rubber.
Example 5
The solid silicone rubber for the high-hardness rubber roll without the white carbon black is different from the solid silicone rubber in example 4 in that the silicone rubber raw material components further comprise a non-white carbon black auxiliary agent, the weight of the non-white carbon black auxiliary agent is 50kg, the non-white carbon black auxiliary agent is polytetrafluoroethylene micro powder, and the non-white carbon black auxiliary agent and the diatomite are added into a kneader at the same time in step S3.
Example 6
The solid silicone rubber for the high-hardness rubber roll without the white carbon black is different from the solid silicone rubber in example 4 in that the silicone rubber raw material components further comprise a non-white carbon black auxiliary agent, the weight of the non-white carbon black auxiliary agent is 100kg, the non-white carbon black auxiliary agent is polytetrafluoroethylene micro powder, and the non-white carbon black auxiliary agent and the diatomite are added into a kneader at the same time in step S3.
Example 7
The solid silicon rubber for the high-hardness rubber roller without the white carbon black is different from the solid silicon rubber in the embodiment 4 in that the polysilsesquioxane is modified polysilsesquioxane, and the preparation method comprises the following steps:
s01, adding water, polysilsesquioxane and vinylidene cyanide into a stirrer, wherein the mass ratio of the water to the polysilsesquioxane to the vinylidene cyanide is 3: 1: 2, stirring for 5min at 200r/min to obtain a prefabricated mixture;
s02, placing the prefabricated mixture into a heating furnace, gradually heating to 65 ℃ within 10min, and then dropwise adding a mixture of tert-butyl hydroperoxide and sodium metabisulfite twice, wherein the mass ratio of the mixture of tert-butyl hydroperoxide and sodium metabisulfite to polysilsesquioxane is 1.4%, and the mass ratio of tert-butyl hydroperoxide to sodium metabisulfite is 2:3, so as to obtain the modified polysilsesquioxane.
Example 8
The solid silicon rubber for the high-hardness rubber roller without the white carbon black is different from the solid silicon rubber in the embodiment 4 in that polysilsesquioxane is modified polysilsesquioxane, and the preparation method of the modified polysilsesquioxane comprises the following steps:
s01, adding water, polysilsesquioxane and vinylidene cyanide into a stirrer, wherein the mass ratio of the water to the polysilsesquioxane to the vinylidene cyanide is 4: 3: 3, stirring for 10min at 400r/min to obtain a prefabricated mixture;
s02, placing the prefabricated mixture into a heating furnace, gradually heating to 75 ℃ within 15min, and then dropwise adding a mixture of tert-butyl hydroperoxide and sodium metabisulfite twice, wherein the mass ratio of the mixture of tert-butyl hydroperoxide and sodium metabisulfite is 2.1% of that of polysilsesquioxane, and the mass ratio of tert-butyl hydroperoxide and sodium metabisulfite is 2:3, so as to obtain the modified polysilsesquioxane.
Example 9
The solid silicon rubber for the high-hardness rubber roll without the white carbon black is prepared from the following raw materials in parts by weight:
raw methyl vinyl silicone rubber: 1000 kg;
modified polysilsesquioxane: 800 kg;
diatomite: 200 kg;
A-172：5kg；
polytetrafluoroethylene micro powder: 100 kg;
wherein, the molar mass of the raw methyl vinyl silicone rubber is 40W, the vinyl content of the raw methyl vinyl silicone rubber is 0.03-1%, the average particle size of the modified polysilsesquioxane is 0.1-100um grade, and the preparation method of the modified polysilsesquioxane comprises the following steps:
s01, adding water, polysilsesquioxane and vinylidene cyanide into a stirrer, wherein the mass ratio of the water to the polysilsesquioxane to the vinylidene cyanide is 3: 1: 2, stirring for 5min at 200r/min to obtain a prefabricated mixture;
s02, placing the prefabricated mixture into a heating furnace, gradually heating to 65 ℃ within 10min, and then dropwise adding a mixture of tert-butyl hydroperoxide and sodium metabisulfite, wherein the mass ratio of the mixture of tert-butyl hydroperoxide and sodium metabisulfite to polysilsesquioxane is 1.4%, and the mass ratio of tert-butyl hydroperoxide to sodium metabisulfite is 2:3, so as to obtain the modified polysilsesquioxane.
The preparation method of the solid silicon rubber for the high-hardness rubber roll without white carbon black comprises the following steps:
s1, mixing raw methyl vinyl silicone rubber, modified polysilsesquioxane and A-172 in a kneader to form a cluster, and controlling the temperature system to be 90 ℃;
s2, heating to 150 ℃ in a kneader, and carrying out heat treatment for 3 h;
s3, cooling the product obtained in the step S2 to be below 90 ℃, adding diatomite and polytetrafluoroethylene micro powder, mixing uniformly, and cooling to obtain the silicon rubber.
Comparative example
Comparative example 1
The solid silicon rubber for the high-hardness rubber roller without the white carbon black is different from the solid silicon rubber in the embodiment 4 in that the solid silicon rubber is prepared from the following raw materials in parts by weight:
raw methyl vinyl silicone rubber: 1000 kg;
diatomite: 200 kg;
silane coupling agent: 3 kg;
white carbon black: 500 kg;
hydroxyl-terminated polydimethylsiloxane: 50 kg;
wherein the silane coupling agent is A-172.
The preparation method of the solid silicon rubber for the high-hardness rubber roll without white carbon black comprises the following steps:
s1, mixing raw methyl vinyl silicone rubber, hydroxyl-terminated polydimethylsiloxane, white carbon black and A-172 in a kneader to form a cluster, and controlling the temperature system to be 90 ℃;
s2, heating to 150 ℃ in a kneader, and carrying out heat treatment for 3 h;
s3, cooling the product obtained in the step S2 to be below 90 ℃, adding diatomite, uniformly mixing, and cooling to obtain the silicon rubber.
Comparative example 2
The solid silicon rubber for the high-hardness rubber roller without the white carbon black is different from the solid silicon rubber in the embodiment 4 in that the solid silicon rubber is prepared from the following raw materials in parts by weight:
raw methyl vinyl silicone rubber: 1000 kg;
polysilsesquioxane: 500 kg;
diatomite: 200 kg;
silane coupling agent: 3 kg;
white carbon black: 300 kg;
hydroxyl-terminated polydimethylsiloxane: 35 kg;
wherein the silane coupling agent is A-172.
The preparation method of the solid silicon rubber for the high-hardness rubber roll without white carbon black comprises the following steps:
s1, mixing raw methyl vinyl silicone rubber, polysilsesquioxane, hydroxyl-terminated polydimethylsiloxane, white carbon black and A-172 in a kneader to form a mass, and controlling the temperature system to be 90 ℃;
s2, heating to 150 ℃ in a kneader, and carrying out heat treatment for 3 h;
s3, cooling the product obtained in the step S2 to be below 90 ℃, adding diatomite, uniformly mixing, and cooling to obtain the silicon rubber.
Comparative example 3
The solid silicon rubber for the high-hardness rubber roller without the white carbon black is different from the solid silicon rubber in the embodiment 4 in that polysilsesquioxane is not added in the raw material components of the silicon rubber.
Comparative example 4
The solid silicon rubber for the high-hardness rubber roll without the white carbon black is different from the solid silicon rubber in the embodiment 4 in that diatomite is not added in the raw material components of the silicon rubber.
Comparative example 5
The solid silicon rubber for the high-hardness rubber roll without the white carbon black is different from the solid silicon rubber for the embodiment 4 in that the kieselguhr is replaced by quartz powder.
Comparative example 6
The solid silicon rubber for the high-hardness rubber roll without the white carbon black is different from the solid silicon rubber for the embodiment 4 in that the kieselguhr is replaced by calcium carbonate.
Comparative example 7
The solid silicon rubber for the high-hardness rubber roll without the white carbon black is different from the solid silicon rubber in the embodiment 4 in that A-172 is not added in the raw material components of the silicon rubber.
Performance test
The hardness of the silicone rubbers of examples 1 to 9 and comparative examples 1 to 7 was measured using a Shore A durometer, and hardness particles (Shore A) having a size of 30X 7mm and a flat surface were prepared before the measurement, and when the hardness was 55Shore A-75Shore A, the silicone rubbers were used as the preferred hardness of the silicone rubbers;
the tensile strength (MPa) of 3.3 in GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber is adopted to detect the tensile strength of the silicone rubber of examples 1-9 and comparative examples 1-7, and when the tensile strength is more than 1.5MPa, the tensile strength can be used as the preferable tensile strength of the silicone rubber;
the elongation (%) of the silicone rubber of examples 1-9 and comparative examples 1-7 is detected by using the elongation (%) of 3.2 in GB/T528-2009 determination of tensile stress strain properties of vulcanized rubber or thermoplastic rubber, and when the elongation is more than 180%, the elongation can be used as the preferable elongation of the silicone rubber;
the rebound resilience (%) of the silicone rubber in examples 1-9 and comparative examples 1-7 is detected by GB/T1681-2009 determination of rebound resilience of vulcanized rubber, and when the rebound resilience is more than 55%, the silicone rubber can be used as the preferable rebound resilience of the silicone rubber;
the silicone rubber abrasion values (CM) of examples 1 to 9 and comparative examples 1 to 7 were measured using GB/T25262-2010 guide for abrasion test on vulcanized rubber or thermoplastic rubber3) Abrasion value less than 0.025CM3The abrasion value is preferably the abrasion value of the silicone rubber.
TABLE 2 summary of test data for examples 1-9 and comparative examples 1-4
According to comparison of detection data of example 4 and comparative examples 1 to 3 in table 2, it can be seen that by adding polysilsesquioxane instead of white carbon black and hydroxyl-terminated polydimethylsiloxane to the silicone rubber raw material, the abrasion value of the silicone rubber can be significantly reduced, and the rebound resilience can be improved. The white carbon black and the hydroxyl-terminated polydimethylsiloxane are added into the silicone rubber to increase the surface viscosity of the rubber roller and reduce the stripping property of the plastic film and the rubber roller. Polysilsesquioxane is used for replacing white carbon black as a semi-reinforcing filler, has lower surface energy and a special structure, can reduce the viscosity of the surface of the rubber roller, has hardening performance on the rubber roller, and reduces the abrasion value of the surface of silicon rubber.
As can be seen from comparison of the test data of example 4 and comparative examples 4 to 6 in table 2, by adding diatomaceous earth to the silicone rubber raw material, the hardness of the silicone rubber can be improved while the abrasion value is reduced. Compared with quartz powder and calcium carbonate, the diatomite has better hardening performance, the silicon dioxide in the diatomite and the methyl vinyl silicone rubber raw rubber have stronger interaction, and the silicon dioxide in the diatomite can change or recover the position along with the movement of a rubber polymer chain, so that the resistance of the silicone rubber to deformation and damage is increased, the rubber material is drier and easy to polish, and the stripping performance of the silicone rubber roller and a plastic film is improved.
As can be seen from comparison of the test data of example 4 and comparative example 7 in Table 2, by adding A-172 to the silicone rubber raw material, the tensile strength of the silicone rubber can be improved and the abrasion value can be reduced. A-172 can build a molecular bridge between the diatomite inorganic filler and the organic matter methyl vinyl silicone rubber crude rubber, so that the bonding capacity of the diatomite and the methyl vinyl silicone rubber crude rubber is improved, the reinforcing effect of the diatomite is enhanced, and the tensile strength and the wear resistance of the silicone rubber are improved.
According to the comparison of the detection data of the examples 4 and 5-6 in the table 2, the abrasion value can be reduced by adding the polytetrafluoroethylene micro powder into the silicone rubber, and the surface performance of the rubber can be improved by the polytetrafluoroethylene micro powder, so that the friction performance, the abrasion performance and the demolding performance of the silicone rubber polymer are improved, and the stripping performance of the silicone rubber roller and the plastic film is improved.
According to the comparison of the detection data of the examples 4 and 7-8 in the table 2, the polysilsesquioxane is modified by using the vinylidene cyanide, and the vinyl group is introduced, so that the activity of the polysilsesquioxane is improved, the reinforcing effect of the polysilsesquioxane is enhanced, the abrasion value of the silicone rubber is reduced, the tensile strength and resilience of the silicone rubber are improved, and the stripping property of the silicone rubber roller and a plastic film is further improved.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (9)
1. The solid silicon rubber for the high-hardness rubber roller without the white carbon black is characterized by being prepared from the following raw materials in parts by weight:
raw methyl vinyl silicone rubber: 1000 parts of (A);
polysilsesquioxane: 300-800 parts;
diatomite: 200-400 parts;
silane coupling agent: 1-10 parts;
non-white carbon black auxiliary agent: 0 to 100 portions;
wherein the molar mass of the raw methyl vinyl silicone rubber is 30W-50W, and the average particle size of the polysilsesquioxane is 0.1-100um grade.
2. The solid silicone rubber for the high-hardness rubber covered roller without the white carbon black of claim 1, wherein the non-white carbon black auxiliary agent is polytetrafluoroethylene micro powder with a weight portion of 50-100 parts.
3. The solid silicon rubber for the high-hardness rubber roller without the white carbon black is characterized in that the vinyl content of the raw methyl vinyl silicon rubber is 0.03-1%.
4. The solid silicone rubber for the high-hardness rubber covered roller without the white carbon black of claim 1, wherein the silane coupling agent is one or a mixture of KH792, KH560 and A-172.
5. The solid silicone rubber for the high-hardness rubber covered roller without the white carbon black of claim 1, wherein the polysilsesquioxane is modified polysilsesquioxane, and the preparation method of the modified polysilsesquioxane is as follows:
s01, adding water, polysilsesquioxane and vinylidene cyanide into a stirrer, wherein the mass ratio of the water to the polysilsesquioxane to the vinylidene cyanide is (3-4) to (1-3): (2:3), stirring at 200r/min-400r/min for 5min-10min to obtain a prefabricated mixture;
s02, placing the prefabricated mixture into a heating furnace, gradually raising the temperature to 65-75 ℃ within 10-15 min, and then dropwise adding a mixture of tert-butyl hydroperoxide and sodium metabisulfite, wherein the mass of the mixture of tert-butyl hydroperoxide and sodium metabisulfite is 1.4-2.1% of that of polysilsesquioxane.
6. The solid silicone rubber for the high-hardness rubber covered roller without the white carbon black of claim 5, wherein the mass ratio of the tert-butyl hydroperoxide to the sodium metabisulfite is 2:3, obtaining the modified polysilsesquioxane.
7. The silica-free solid silicone rubber for high-hardness rubber covered rollers according to claim 5, wherein in step S02, the mixture of t-butyl hydroperoxide and sodium metabisulfite is added dropwise into the heating furnace in two portions.
8. The solid silicone rubber for the high-hardness rubber roll without the white carbon black according to claim 1, wherein the silicone rubber is prepared from the following raw materials in parts by weight:
raw methyl vinyl silicone rubber: 1000 parts of (A);
modified polysilsesquioxane: 800 parts;
diatomite: 200 parts of (A);
a-172: 5 parts of a mixture;
polytetrafluoroethylene micro powder: 100 parts of (A);
the molar mass of the raw methyl vinyl silicone rubber is 40W, the vinyl content of the raw methyl vinyl silicone rubber is 0.03-1%, the average particle size of the modified polysilsesquioxane is 0.1-100um grade, and the preparation method of the modified polysilsesquioxane comprises the following steps:
s01, adding water, polysilsesquioxane and vinylidene cyanide into a stirrer, wherein the mass ratio of the water to the polysilsesquioxane to the vinylidene cyanide is 3: 1: 2, stirring for 5min at 200r/min to obtain a prefabricated mixture;
s02, placing the prefabricated mixture into a heating furnace, gradually heating to 65 ℃ within 10min, and then dropwise adding a mixture of tert-butyl hydroperoxide and sodium metabisulfite, wherein the mass ratio of the mixture of tert-butyl hydroperoxide and sodium metabisulfite to polysilsesquioxane is 1.4%, and the mass ratio of tert-butyl hydroperoxide to sodium metabisulfite is 2:3, so as to obtain the modified polysilsesquioxane.
9. The preparation method of the solid silicon rubber for the high-hardness rubber covered roller without the white carbon black in any one of claims 1 to 8, which is characterized by comprising the following steps:
s1, mixing raw methyl vinyl silicone rubber, polysilsesquioxane and a silane coupling agent in a kneading machine to form a cluster, and controlling the temperature system to be 80-100 ℃;
s2, heating to 150-160 ℃ in a kneader, and carrying out heat treatment for 2-3 h;
s3, cooling the product obtained in the step S2 to be below 90 ℃, adding diatomite and a non-white carbon black auxiliary agent, uniformly mixing, and cooling to obtain the silicon rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010791652.7A CN111793366A (en) | 2020-08-07 | 2020-08-07 | White carbon black-free solid silicon rubber for high-hardness rubber roller and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010791652.7A CN111793366A (en) | 2020-08-07 | 2020-08-07 | White carbon black-free solid silicon rubber for high-hardness rubber roller and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111793366A true CN111793366A (en) | 2020-10-20 |
Family
ID=72828230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010791652.7A Pending CN111793366A (en) | 2020-08-07 | 2020-08-07 | White carbon black-free solid silicon rubber for high-hardness rubber roller and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111793366A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337119A (en) * | 2021-05-27 | 2021-09-03 | 厦门汉升橡塑制品有限公司 | Weather-resistant silicone rubber and preparation method thereof |
| CN113773534A (en) * | 2021-08-31 | 2021-12-10 | 歌尔股份有限公司 | Vibrating diaphragm of sound generating device and sound generating device thereof |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5424352A (en) * | 1993-03-23 | 1995-06-13 | Toshiba Silicone Co., Ltd. | Heat-conductive silicone rubber composition |
| CN1738867A (en) * | 2002-12-04 | 2006-02-22 | 罗狄亚化学公司 | Single-component, adhesive, silicon elastomer composition which can be crosslinked by polyaddition |
| US20070244249A1 (en) * | 2006-04-06 | 2007-10-18 | General Electric Company | Two-part translucent silicone rubber-forming composition |
| CN102181159A (en) * | 2011-03-15 | 2011-09-14 | 杭州师范大学 | Polysilsesquioxane reinforced light emitting diode (LED) encapsulation organic silicon rubber and preparation method thereof |
| CN102399527A (en) * | 2011-09-30 | 2012-04-04 | 江苏江永新材料科技有限公司 | Room temperature curing lamp adhesive and manufacturing method thereof |
| CN102977613A (en) * | 2012-12-17 | 2013-03-20 | 肇庆皓明有机硅材料有限公司 | Method for preparing halogen-free and flame-retardant silicon rubber |
| CN104830063A (en) * | 2015-03-16 | 2015-08-12 | 芜湖荣基密封系统有限公司 | Anti-tearing and anti-aging silicone rubber slurry used for preparing ultrathin sealing rubber layer and preparation method thereof |
| CN104893310A (en) * | 2015-06-29 | 2015-09-09 | 山东东岳有机硅材料有限公司 | Polysilsesquioxane-contained liquid silicone rubber for LED packaging and preparation method of polysilsesquioxane-contained liquid silicone rubber |
| CN106243730A (en) * | 2016-08-23 | 2016-12-21 | 陈建琴 | A kind of rubber roller for industry high-hardness high-rebound silastic material |
| CN106810874A (en) * | 2016-12-30 | 2017-06-09 | 沈阳化工大学 | A kind of silicon rubber of use itrile group POSS auxiliary agents synthesis |
| CN108530902A (en) * | 2018-05-15 | 2018-09-14 | 许媛 | A kind of resistance oil silicone rubber and preparation method thereof being modified based on nitrile rubber |
| CN108659541A (en) * | 2018-05-30 | 2018-10-16 | 雷春生 | A kind of preparation method of silicone molding rubber |
| CN109280391A (en) * | 2018-09-03 | 2019-01-29 | 苏州歌诗夫新材料有限公司 | A kind of high-low temperature resistant, high-intensitive silica gel rubber compound and preparation method thereof |
| CN109943076A (en) * | 2019-03-29 | 2019-06-28 | 中国科学院长春应用化学研究所 | A kind of sulphurated siliastic and preparation method thereof |
| CN111269362A (en) * | 2020-03-19 | 2020-06-12 | 浙江龙圣华橡胶股份有限公司 | Rubber molding method and rubber |
-
2020
- 2020-08-07 CN CN202010791652.7A patent/CN111793366A/en active Pending
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5424352A (en) * | 1993-03-23 | 1995-06-13 | Toshiba Silicone Co., Ltd. | Heat-conductive silicone rubber composition |
| CN1738867A (en) * | 2002-12-04 | 2006-02-22 | 罗狄亚化学公司 | Single-component, adhesive, silicon elastomer composition which can be crosslinked by polyaddition |
| US20070244249A1 (en) * | 2006-04-06 | 2007-10-18 | General Electric Company | Two-part translucent silicone rubber-forming composition |
| CN102181159A (en) * | 2011-03-15 | 2011-09-14 | 杭州师范大学 | Polysilsesquioxane reinforced light emitting diode (LED) encapsulation organic silicon rubber and preparation method thereof |
| CN102399527A (en) * | 2011-09-30 | 2012-04-04 | 江苏江永新材料科技有限公司 | Room temperature curing lamp adhesive and manufacturing method thereof |
| CN102977613A (en) * | 2012-12-17 | 2013-03-20 | 肇庆皓明有机硅材料有限公司 | Method for preparing halogen-free and flame-retardant silicon rubber |
| CN104830063A (en) * | 2015-03-16 | 2015-08-12 | 芜湖荣基密封系统有限公司 | Anti-tearing and anti-aging silicone rubber slurry used for preparing ultrathin sealing rubber layer and preparation method thereof |
| CN104893310A (en) * | 2015-06-29 | 2015-09-09 | 山东东岳有机硅材料有限公司 | Polysilsesquioxane-contained liquid silicone rubber for LED packaging and preparation method of polysilsesquioxane-contained liquid silicone rubber |
| CN106243730A (en) * | 2016-08-23 | 2016-12-21 | 陈建琴 | A kind of rubber roller for industry high-hardness high-rebound silastic material |
| CN106810874A (en) * | 2016-12-30 | 2017-06-09 | 沈阳化工大学 | A kind of silicon rubber of use itrile group POSS auxiliary agents synthesis |
| CN108530902A (en) * | 2018-05-15 | 2018-09-14 | 许媛 | A kind of resistance oil silicone rubber and preparation method thereof being modified based on nitrile rubber |
| CN108659541A (en) * | 2018-05-30 | 2018-10-16 | 雷春生 | A kind of preparation method of silicone molding rubber |
| CN109280391A (en) * | 2018-09-03 | 2019-01-29 | 苏州歌诗夫新材料有限公司 | A kind of high-low temperature resistant, high-intensitive silica gel rubber compound and preparation method thereof |
| CN109943076A (en) * | 2019-03-29 | 2019-06-28 | 中国科学院长春应用化学研究所 | A kind of sulphurated siliastic and preparation method thereof |
| CN111269362A (en) * | 2020-03-19 | 2020-06-12 | 浙江龙圣华橡胶股份有限公司 | Rubber molding method and rubber |
Non-Patent Citations (6)
| Title |
|---|
| （加）GEORGE WYPYCH编著，程斌等译: "《填料手册》", 31 October 2002, 中国石化出版社 * |
| LUO, SUI-LIAN等: "Effect of Rosin Ester on Water-resistant Adhesion Oximized RTV-1 Silicone Rubber Sealant", 《ADVANCED MATERIALS RESEARCH》 * |
| 刘玉峰等: "嵌段型聚倍半硅氧烷-硅橡胶的制备及性能", 《高分子材料科学与工程》 * |
| 孙履厚主编: "《精细化工新材料与技术》", 30 April 1998, 中国石化出版社 * |
| 王成彪等编: "《摩擦学材料及表面工程》", 29 February 2012, 国防工业出版社 * |
| 葛铁军等: "OPS/乙烯基硅橡胶复合材料的性能研究", 《橡胶工业》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337119A (en) * | 2021-05-27 | 2021-09-03 | 厦门汉升橡塑制品有限公司 | Weather-resistant silicone rubber and preparation method thereof |
| CN113773534A (en) * | 2021-08-31 | 2021-12-10 | 歌尔股份有限公司 | Vibrating diaphragm of sound generating device and sound generating device thereof |
| CN113773534B (en) * | 2021-08-31 | 2023-08-04 | 歌尔股份有限公司 | Vibrating diaphragm of sound production device and sound production device thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yu et al. | A comprehensive study on lignin as a green alternative of silica in natural rubber composites | |
| EP0062427B1 (en) | Method of improving silicone rubber composition | |
| KR101923160B1 (en) | Modified conjugated diene polymer, preparation method thereof and modifying agent | |
| CN111793366A (en) | White carbon black-free solid silicon rubber for high-hardness rubber roller and preparation method thereof | |
| KR101620882B1 (en) | Use of polyorganosiloxanes in the processing and vulcanization of rubber | |
| CN110240746A (en) | A kind of anti-skidding heat-proof aging EVA, NR composite foam material and preparation method thereof | |
| CN106496911B (en) | Artificial grass wear-resistant functional master batch, and preparation method and application thereof | |
| CN107189307A (en) | A kind of tire tread rubber and its preparation | |
| CN115368649B (en) | Anti-skid rubber sole and preparation method thereof | |
| TWI843861B (en) | Silane coupling agent composition containing silane compound and protein modifier, and rubber composition containing the same | |
| JP6407023B2 (en) | Epoxidized natural rubber-based mixture with reversible electrical behavior | |
| WO2021256296A1 (en) | Silane coupling agent composition, and rubber composition comprising same | |
| CN109824966B (en) | Wear-resistant oil-resistant engineering sole material and preparation method thereof | |
| US8053507B2 (en) | Highly filled elastomeric resin compositions with added microsilica for processability | |
| CN112175257A (en) | Foamed wear-resistant rubber | |
| JP5923451B2 (en) | Method of using polyorganosiloxane, method of vulcanizing rubber, vulcanized rubber, vulcanizing agent for rubber, masterbatch and mixture | |
| CN109776979A (en) | Carbon nano tube-doped Ionic Liquid Modified butyl rubber resilient body and preparation method | |
| CN110204803B (en) | Light-weight rubber product and preparation method thereof | |
| CN108727825A (en) | Firm silicone rubber and preparation method thereof | |
| CN110272571B (en) | High-wear-resistance rubber | |
| JP4302547B2 (en) | Modified natural rubber latex, modified natural rubber and method for producing them | |
| Katueangngan et al. | Interfacial interactions of silica and natural rubber enhanced by hydroxyl telechelic natural rubber as interfacial modifier | |
| CN109608706A (en) | A kind of preparation method of graphene rubber composite material | |
| CN114907590A (en) | Synthetic rubber wet masterbatch and preparation method and application thereof | |
| KR101918369B1 (en) | Method for preparing modified conjugated diene polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210419 Address after: No.18, Gongye South Road, overseas Chinese Economic Development Zone, Chengnan Town, Ninghua County, Sanming City, Fujian Province, 365400 Applicant after: Fujian gutai silicone material Co.,Ltd. Address before: Building C1, C2 and C3, No.1 Yinling street, tiantoujiao, Qiaotou town, Dongguan City, Guangdong Province 523000 Applicant before: Dongguan gutai silicone Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201020 |
|
| RJ01 | Rejection of invention patent application after publication |