CN112210215B - Low-tensile permanent deformation conductive silicone rubber and preparation method thereof - Google Patents
Low-tensile permanent deformation conductive silicone rubber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a conductive silicone rubber with low tensile permanent deformation and a preparation method thereof, and the conductive silicone rubber comprises the components of methyl vinyl silicone rubber crude rubber, methyl silicone rubber crude rubber, white carbon black, acetylene black, a silane coupling agent, hydroxyl silicone oil, methyl silicone oil, hydrogen-containing silicone oil, a vulcanizing agent and zinc stearate; the preparation method comprises the following steps: putting the raw materials into a kneading machine to prepare mixing base rubber; cooling the mixed base rubber, adding acetylene black, methyl silicone oil and methyl silicone rubber raw rubber, heating, stirring and discharging the rubber material; after the sizing material is kept stand and cooled, a vulcanizing agent is added on a double roller; and (3) carrying out compression molding on the conductive silicone rubber containing the vulcanizing agent and carrying out secondary vulcanization to obtain the product. The conductive silicone rubber has good processing performance and conductivity, is not adhered to a mold, and can still keep lower tensile permanent deformation under the condition of excellent electrical performance that the resistivity is less than or equal to 30 omega cm; meanwhile, the preparation process is simple, the mold opening is good, and the industrial production is easy to realize.
Description
Technical Field
The invention relates to the technical field of conductive silicone rubber, in particular to a low-tensile permanent-deformation high-temperature vulcanized conductive silicone rubber material and a preparation method thereof.
Background
The silicon rubber is (— Si-O-)nThe high molecular polymer which is a main chain and has side groups of organic groups has excellent heat resistance, low temperature resistance, weather resistance, ultraviolet resistance and biological characteristics. The silicon rubber has large molecular chain flexibility and weak interaction force among molecular chains, so that the vulcanized silicon rubber is soft and elastic, does not cause environmental pollution because of no softener, plasticizer, anti-aging agent and the like, and is very suitable for being used as an electronic component material.
At present, conductive silicone rubber is basically prepared by filling a silicone rubber-based rubber with a conductive auxiliary agent (metal powder, acetylene black and the like), a structure control agent, a vulcanizing agent and the like to meet the requirements of electrical property and mechanical property. But the preparation method has obvious defects, and the metal powder is used as the conductive additive, so that the cost is high, the processing difficulty is high, and the mechanical property of the product is poor; acetylene black is used as a conductive aid, so that the vulcanization speed of the product is low, the product is easy to stick to a mold, and the product shape is large. For example, patent application publication No. CN 103160128A discloses a conductive silicone rubber material with extremely low compression set and low hardness, which is prepared by adding conductive fillers with different shape coefficients into a silicone rubber body and forming network paths under the condition of low usage of the conductive fillers, and a preparation method thereof. The composition comprises: 100 parts of silicone rubber, 1-15 parts of vulcanizing agent, 0 or 1-8 parts of co-vulcanizing agent, 5-15 parts of carbon black and 0.5-5 parts of carbon nano tube. The patent mainly reduces the parts of conductive materials in a system by adding the carbon nano tube to achieve the low-voltage deformation performance, but does not relate to the permanent deformation of the tensile.
In order to solve the problem that the commonly produced conductive silicone rubber is not suitable for cold-shrink cable accessories due to the deviation of physical properties, the patent application with the publication number of CN 105778517A discloses a conductive silicone rubber composition in the cold-shrink cable accessories and a manufacturing method thereof, wherein the conductive silicone rubber composition comprises the following components in parts by weight: 95-105 parts of methyl vinyl organic silicon crude rubber, 0-20 parts of white carbon black, 5-40 parts of conductive carbon black, 0-20 parts of silicone oil, 0.05-1 part of zinc stearate, 0.5-3 parts of peroxide vulcanizing agent and 0-0.8 part of coupling agent; the invention is prepared by modifying raw materials in advance and carrying out multiple processes of banburying, scouring, filtering, vulcanizing and the like. The method for pretreating carbon black is adopted, the process is complex, and the prepared conductive silicon rubber material has high resistance, volume resistivity of 0.55 omega.m and poor conductivity, and cannot meet the use requirements of domestic and foreign high-end cable T-shaped head accessories.
Therefore, it is necessary to develop a low-tension permanent deformation conductive silicone rubber with excellent conductive performance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, so that the conductive silicone rubber which has low tensile permanent deformation, good processing performance and conductivity and is not adhered to a mold is provided.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the conductive silicone rubber with low tensile permanent deformation comprises the following components in parts by weight:
95-97 parts of methyl vinyl silicone rubber crude rubber, 3-5 parts of methyl silicone rubber crude rubber, 10-30 parts of white carbon black, 30-50 parts of acetylene black, 1-3 parts of silane coupling agent, 3-10 parts of hydroxyl silicone oil, 1-3 parts of methyl silicone oil, 1-5 parts of hydrogen-containing silicone oil, 1-2 parts of vulcanizing agent and 0.5-1 part of zinc stearate.
The raw methyl vinyl silicone rubber is formed by mixing raw methyl vinyl silicone rubber A, raw methyl vinyl silicone rubber B and raw methyl vinyl silicone rubber C, wherein the raw methyl vinyl silicone rubber A accounts for 10-60 parts, the raw methyl vinyl silicone rubber B accounts for 35-86.5 parts, and the raw methyl vinyl silicone rubber C accounts for 0.5-3 parts.
Further, the molecular weight of the raw methyl vinyl silicone rubber A is 60-70 ten thousand, wherein the molar content of vinyl is 0.03-0.05%; the molecular weight of the raw methyl vinyl silicone rubber B is 80-90 ten thousand, wherein the molar content of vinyl is 0.20-0.25%; the molecular weight of the raw methyl vinyl silicone rubber C is 80-90 ten thousand, wherein the molar content of vinyl is 3% -5%;
in the invention, the molecular weight of the methyl silicone rubber raw rubber is 75-85 ten thousand.
In the invention, the specific surface area of the white carbon black is 200-400 m2/g。
In the invention, the specific surface area of the acetylene black is more than or equal to 400m2The oil absorption value is 100-200 mL/100 g.
In the invention, the silane coupling agent is at least one of methyl triethoxysilane, vinyl triethoxysilane and vinyl trimethoxysilane.
In the invention, the viscosity of the hydroxyl silicone oil is 50-1000 cs.
In the invention, the molecular weight of the methyl silicone oil is 50-70 ten thousand.
In the invention, the viscosity of the hydrogen-containing silicone oil is 10-100 cs, and the hydrogen molar content is 0.2-1.5%.
In the present invention, the vulcanizing agent is selected from the group consisting of 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane peroxide.
A preparation method of conductive silicone rubber with low tensile permanent deformation comprises the following steps:
A. putting raw methyl vinyl silicone rubber, hydroxyl silicone oil, hydrogen-containing silicone oil and zinc stearate into a kneading machine;
B. adding the white carbon black and the silane coupling agent into the kneading machine in the step A in 2-3 batches, mixing into a mass, taking the mass out of the pot, cooling and standing for 8-14 hours;
C. b, putting the rubber material cooled to be less than or equal to 50 ℃ in the step B into the kneader again, heating to 160-175 ℃, stirring for 1-2 hours, and vacuumizing for 1 hour, wherein the vacuum degree is more than or equal to 0.08MPa, so as to obtain a mixed base rubber;
D. taking the mixed base rubber obtained in the step C out of the pot, cooling and standing for 8-14 hours, and then putting the mixed base rubber cooled to be less than or equal to 50 ℃ into the kneader again;
E. adding acetylene black into the kneading machine in the step D in 4-6 batches, mixing into a dough, adding methyl silicone oil and methyl silicone rubber raw rubber, heating to 130-175 ℃, stirring for 1-2 hours, and discharging the rubber material;
F. after the sizing material is cooled and stands for 8-14 hours, adding a vulcanizing agent on the double rollers to obtain conductive silicone rubber containing the vulcanizing agent;
H. and F, carrying out die pressing on the conductive silicone rubber containing the vulcanizing agent in the step F for 10-15 minutes at the temperature of 160-180 ℃ for forming to obtain primary vulcanized conductive silicone rubber, and carrying out secondary vulcanization on the primary vulcanized conductive silicone rubber at the temperature of 180-200 ℃ for 2-4 hours to obtain the low-tensile permanent deformation conductive silicone rubber.
Further, in the step B, adding the white carbon black and the silane coupling agent in batches, wherein the time interval between each addition is 25-45 minutes.
Further, in the step E, acetylene black is added in portions, and the interval time of each addition is 25-45 minutes.
Further, in the step E, the rotating speed of the kneading machine is controlled to be 10 r/min-25 r/min, and the rotating speed ratio of the stirring paddles is 1: 1-1: 1.5.
Compared with the prior art, the invention has the outstanding advantages and beneficial technical effects that:
1. according to the invention, through the matching of three raw methyl vinyl silicone rubbers with different molecular weights and different vinyl molar contents, the cross-linking structure of the conductive silicone rubber is improved, the distribution condition of concentrated cross-linking points is adjusted, the concentrated cross-linking points are increased, and the cross-linking density is increased, so that the conductive silicone rubber can still keep 50-70 Shore A hardness, 10% or less of tensile permanent deformation (100 ℃ multiplied by 24 h), 5% or less of tensile permanent deformation and lower tensile permanent deformation with TC 90 less than 100s under the condition that the conductive silicone rubber is filled with acetylene black to achieve excellent electrical property with volume resistivity of 30 omega cm or less.
2. In order to solve the problems that the vulcanization speed of the conductive silicone rubber is slowed down, the conductive silicone rubber is stuck to a mold, the rubber material is embrittled by increasing the consumption of the vulcanizing agent and the strength is reduced due to the addition of the acetylene black, the vulcanization speed of the conductive silicone rubber can be increased, the vulcanization degree of the rubber material is increased and the electrical property of the conductive silicone rubber is improved under the condition that the consumption of the vulcanizing agent is not increased through the addition of the hydrogen-containing silicone oil; and the use of the methyl silicone rubber is matched, so that the toughness of the rubber material can be improved, and the mucosa characteristic of the conductive silicone rubber can be improved.
3. According to the invention, hydroxyl silicone oil, hydrogen-containing silicone oil and a specific silane coupling agent are added in the step A and the step B to treat the hydroxyl on the surface of the white carbon black, so that the vulcanization condition of the conductive silicone rubber is effectively improved, and the conductive silicone rubber has good processing performance and is not adhered to a mold.
4. According to the invention, the methyl silicone rubber raw rubber is added in the hot mixing step E, so that the permanent deformation of the rubber material at break can be effectively improved, the toughness of the rubber material is improved, and the mold opening performance of the rubber material is improved.
5. According to the invention, the rotating speed of the kneader is controlled in the step E, so that the phenomenon that the electrical property of the conductive silicone rubber is reduced because the chain bead-shaped structure of the acetylene black is broken by the over-high rotating speed is avoided. Meanwhile, the rotating speed of the kneading machine is controlled, so that acetylene black can be fully dispersed without pretreatment, and the mechanical property and the electrical property of the conductive silicone rubber are improved.
6. According to the invention, the white carbon black base rubber is firstly cold-mixed in the step B, and then the acetylene black is added in the step E, so that the treating agent and the hydroxyl silicone oil can be fully contacted with the white carbon black and the carbon black through cold mixing, and the white carbon black and the carbon black cannot be volatilized by heating. And C, standing for 8-14 hours after the cold mixing in the step B, so that the treatment degree of the white carbon black can be improved, and the tensile permanent deformation performance of the conductive silicone rubber can be improved.
Detailed Description
The present invention will be described in further detail with reference to examples, but it should be understood that the present invention is not limited to the following examples.
Example 1
The embodiment provides a low-tensile permanent deformation conductive silicone rubber which comprises the following components in parts by weight:
methyl vinyl silicone rubber crude rubber 95 parts
5 parts of raw methyl silicone rubber
15 portions of white carbon black
Acetylene black 35 parts
Silane coupling agent 2 parts
5 parts of hydroxyl silicone oil
2 parts of methyl silicone oil
Hydrogen-containing silicone oil 4 parts
Vulcanizing agent 1 part
1 part of zinc stearate
In the composition of the embodiment, the raw methyl vinyl silicone rubber is prepared by mixing 50 parts of raw methyl vinyl silicone rubber A, 43 parts of raw methyl vinyl silicone rubber B and 2 parts of raw methyl vinyl silicone rubber C;
further, the molecular weight of the raw methyl vinyl silicone rubber A is 60 ten thousand, wherein the molar content of vinyl is 0.05 percent; the molecular weight of the raw methyl vinyl silicone rubber B is 90 ten thousand, wherein the molar content of vinyl is 0.20 percent; the molecular weight of the raw methyl vinyl silicone rubber C is 90 ten thousand, wherein the molar content of vinyl is 5 percent.
The preparation method of the low-tensile permanent deformation conductive silicone rubber comprises the following steps:
A. putting raw methyl vinyl silicone rubber, hydroxyl silicone oil, hydrogen-containing silicone oil and zinc stearate into a kneading machine;
B. b, adding the white carbon black and the silane coupling agent into the kneading machine in the step A in 2 batches at intervals of 40 minutes every time, mixing and agglomerating, taking the rubber material out of the pot, cooling and standing for 12 hours;
C. putting the rubber material cooled to be less than or equal to 50 ℃ in the step B into the kneader again, heating to 175 ℃, stirring for 1 hour, vacuumizing for 1 hour, and obtaining the mixing base rubber, wherein the vacuum degree is more than or equal to 0.08 MPa;
D. taking the mixed base rubber obtained in the step C out of the pot, cooling and standing for 12 hours, and then putting the mixed base rubber cooled to be less than or equal to 50 ℃ into the kneader again;
E. adding acetylene black into the kneading machine in the step D in 4 batches, mixing into a dough, adding methyl silicone oil and methyl silicone rubber raw rubber, heating to 175 ℃, and stirring for 1 hour to obtain a rubber material; the rotating speed of the fast paddle of the kneader is 15r/min, the rotating speed of the slow paddle is 10r/min, and the feeding interval is 45 min;
F. after the sizing material is cooled and stands for 12 hours, adding a vulcanizing agent on the double rollers to obtain conductive silicone rubber containing the vulcanizing agent;
H. and F, carrying out die pressing on the conductive silicone rubber containing the vulcanizing agent in the step F at the temperature of 165 ℃ for 12 minutes for forming to obtain primary vulcanized conductive silicone rubber, and carrying out secondary vulcanization on the primary vulcanized conductive silicone rubber at the temperature of 200 ℃ for 2 hours to obtain the low-tensile permanent-deformation conductive silicone rubber.
Example 2
The embodiment provides a low-tensile permanent deformation conductive silicone rubber which comprises the following components in parts by weight:
methyl vinyl silicone rubber crude rubber 95 parts
5 parts of raw methyl silicone rubber
13 portions of white carbon black
Acetylene black 40 parts
Silane coupling agent 2 parts
6 parts of hydroxyl silicone oil
Methyl silicone oil 1 part
1.5 parts of hydrogen-containing silicone oil
Vulcanizing agent 1 part
1 part of zinc stearate
In the composition of the embodiment, the raw methyl vinyl silicone rubber is prepared by mixing 40 parts of raw methyl vinyl silicone rubber A, 54 parts of raw methyl vinyl silicone rubber B and 1 part of raw methyl vinyl silicone rubber C;
further, the molecular weight of the raw methyl vinyl silicone rubber A is 70 ten thousand, wherein the molar content of vinyl is 0.03 percent; the molecular weight of the raw methyl vinyl silicone rubber B is 80 ten thousand, wherein the molar content of vinyl is 0.25 percent; the molecular weight of the raw methyl vinyl silicone rubber C is 80 ten thousand, wherein the molar content of vinyl is 3 percent.
In the components of the embodiment, the molecular weight of raw methyl silicone rubber is 75 ten thousand; the specific surface area of the white carbon black is 400m2(ii)/g; the silane coupling agent is methyl triethoxysilane; the vulcanizing agent is selected from peroxide 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
The preparation method of the low-tensile permanent deformation conductive silicone rubber comprises the following steps:
A. putting raw methyl vinyl silicone rubber, hydroxyl silicone oil, hydrogen-containing silicone oil and zinc stearate into a kneading machine;
B. adding the white carbon black and the silane coupling agent into the kneader in the step A in 3 batches, wherein the interval time of each addition is 30 minutes, and after the mixture is kneaded into a mass, taking the mass out of the pot, cooling and standing for 14 hours;
C. b, putting the rubber material cooled to be less than or equal to 50 ℃ in the step B into the kneader again, heating to 160 ℃, stirring for 2 hours, vacuumizing for 1 hour, and obtaining the mixing base rubber, wherein the vacuum degree is more than or equal to 0.08 MPa;
D. taking the mixed base rubber obtained in the step C out of the pot, cooling and standing for 12 hours, and then putting the mixed base rubber cooled to be less than or equal to 50 ℃ into the kneader again;
E. adding acetylene black into the kneading machine in the step D in 5 batches, mixing into a mass, adding methyl silicone oil and methyl silicone rubber crude rubber, heating to 150 ℃, stirring for 2 hours, and discharging the rubber, wherein the fast paddle rotating speed of the kneading machine is 25r/min, the slow paddle rotating speed is 25r/min, and the feeding interval is 25 min;
F. after the sizing material is cooled and stands for 14 hours, adding a vulcanizing agent on the double rollers to obtain conductive silicone rubber containing the vulcanizing agent;
H. and F, carrying out die pressing on the conductive silicone rubber containing the vulcanizing agent in the step F for 15 minutes at the temperature of 165 ℃ for forming to obtain primary vulcanized conductive silicone rubber, and carrying out secondary vulcanization on the primary vulcanized conductive silicone rubber at the temperature of 180 ℃ for 4 hours to obtain the low-tensile permanent-deformation conductive silicone rubber.
Example 3
The embodiment provides a low-tensile permanent deformation conductive silicone rubber which comprises the following components in parts by weight:
methyl vinyl silicone rubber crude rubber 95 parts
5 parts of raw methyl silicone rubber
20 portions of white carbon black
Acetylene black 40 parts
3 parts of silane coupling agent
8 parts of hydroxyl silicone oil
2 parts of methyl silicone oil
Hydrogen-containing silicone oil 3 parts
Vulcanizing agent 1 part
0.5 part of zinc stearate
In the composition of the embodiment, the raw methyl vinyl silicone rubber is prepared by mixing 10 parts of raw methyl vinyl silicone rubber A, 84.5 parts of raw methyl vinyl silicone rubber B and 0.5 part of raw methyl vinyl silicone rubber C;
further, the molecular weight of the raw methyl vinyl silicone rubber A is 65 ten thousand, wherein the molar content of vinyl is 0.04 percent; the molecular weight of the raw methyl vinyl silicone rubber B is 90 ten thousand, wherein the molar content of vinyl is 0.20 percent; the molecular weight of the raw methyl vinyl silicone rubber C is 85 ten thousand, wherein the molar content of vinyl is 4 percent.
In the components of the embodiment, the molecular weight of raw methyl silicone rubber is 80 ten thousand; the specific surface area of the white carbon black is 200m2(ii)/g; the specific surface area of the acetylene black is more than or equal to 400m2The oil absorption value is 100mL/100 g; the silane coupling agent is vinyl triethoxysilane; the viscosity of the hydroxyl silicone oil is 100 cs; the molecular weight of the methyl silicone oil is 50 ten thousand; the viscosity of the hydrogen-containing silicone oil is 10cs, and the hydrogen content is 1%; the vulcanizing agent is selected from peroxide 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
The preparation method of the low-tensile permanent deformation conductive silicone rubber comprises the following steps:
A. putting raw methyl vinyl silicone rubber, hydroxyl silicone oil, hydrogen-containing silicone oil and zinc stearate into a kneading machine;
B. adding the white carbon black and the silane coupling agent into the kneading machine in the step A in 3 batches, mixing and agglomerating, taking the rubber material out of the pot, cooling and standing for 8 hours, wherein the interval time of each addition is 45 minutes;
C. b, putting the rubber material cooled to be less than or equal to 50 ℃ in the step B into the kneader again, heating to 170 ℃, stirring for 1.5 hours, vacuumizing for 1 hour, and obtaining the mixing base rubber, wherein the vacuum degree is more than or equal to 0.08 MPa;
D. taking the mixed base rubber obtained in the step C out of the pot, cooling and standing for 10 hours, and then putting the mixed base rubber cooled to be less than or equal to 50 ℃ into the kneader again;
E. adding acetylene black into the kneading machine in the step D in 4 batches, wherein the interval time of each addition is 25 minutes, mixing into a mass, adding methyl silicone oil and methyl silicone rubber crude rubber, heating to 130 ℃, stirring for 1.5 hours, discharging the rubber, wherein the fast paddle rotating speed of the kneading machine is 24r/min, the slow paddle rotating speed is 17r/min, and the feeding interval is 30 min;
F. after the sizing material is cooled and kept stand for 8 hours, adding a vulcanizing agent on the double rollers to obtain conductive silicone rubber containing the vulcanizing agent;
H. and F, carrying out die pressing on the conductive silicone rubber containing the vulcanizing agent in the step F at the temperature of 165 ℃ for 12 minutes for forming to obtain primary vulcanized conductive silicone rubber, and carrying out secondary vulcanization on the primary vulcanized conductive silicone rubber at the temperature of 200 ℃ for 2 hours to obtain the low-tensile permanent-deformation conductive silicone rubber.
Example 4
The embodiment provides a low-tensile permanent deformation conductive silicone rubber which comprises the following components in parts by weight:
96 parts of raw methyl vinyl silicone rubber
Raw methyl silicone rubber 3 parts
30 portions of white carbon black
Acetylene black 30 parts
1 part of silane coupling agent
6 parts of hydroxyl silicone oil
Methyl silicone oil 3 parts
1 part of hydrogen-containing silicone oil
Vulcanizing agent 2 parts
0.8 portion of zinc stearate
In the composition of the embodiment, the raw methyl vinyl silicone rubber is prepared by mixing 58 parts of raw methyl vinyl silicone rubber A, 35 parts of raw methyl vinyl silicone rubber B and 3 parts of raw methyl vinyl silicone rubber C;
further, the molecular weight of the raw methyl vinyl silicone rubber A is 67 ten thousand, wherein the molar content of vinyl is 0.03 percent; the molecular weight of the raw methyl vinyl silicone rubber B is 90 ten thousand, wherein the molar content of vinyl is 0.25 percent; the molecular weight of the raw methyl vinyl silicone rubber C is 86 ten thousand, wherein the molar content of vinyl is 3.5 percent.
In the components of the embodiment, the molecular weight of raw methyl silicone rubber is 85 ten thousand; the specific surface area of the white carbon black is 300m2(ii)/g; the specific surface area of the acetylene black is more than or equal to 400m2The oil absorption value is 200mL/100 g; the silane coupling agent is vinyl trimethoxy silane; the viscosity of the hydroxyl silicone oil is 200 cs; molecular weight of methyl silicone oil70 ten thousand; the viscosity of the hydrogen-containing silicone oil is 100cs, and the hydrogen content is 0.2%; the vulcanizing agent is selected from peroxide 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
The preparation method of the low-tensile permanent deformation conductive silicone rubber comprises the following steps:
A. putting raw methyl vinyl silicone rubber, hydroxyl silicone oil, hydrogen-containing silicone oil and zinc stearate into a kneading machine;
B. adding the white carbon black and the silane coupling agent into the kneading machine in the step A in 3 batches, mixing and agglomerating, taking the rubber material out of the pot, cooling and standing for 10 hours; the time interval between each addition was 40 minutes;
C. b, putting the rubber material cooled to be less than or equal to 50 ℃ in the step B into the kneader again, heating to 165 ℃, stirring for 2 hours, vacuumizing for 1 hour, and obtaining the mixing base rubber, wherein the vacuum degree is more than or equal to 0.08 MPa;
D. taking the mixed base rubber obtained in the step C out of the pot, cooling and standing for 8 hours, and then putting the mixed base rubber cooled to be less than or equal to 50 ℃ into the kneader again;
E. adding acetylene black into the kneading machine in the step D in 6 batches, wherein the interval time of each addition is 45 minutes, mixing and agglomerating, adding methyl silicone oil and methyl silicone rubber crude rubber, heating to 165 ℃, stirring for 1 hour, and discharging rubber material; the rotating speed of the fast paddle of the kneader is 22r/min, the rotating speed of the slow paddle is 15r/min, and the feeding interval is 35 min;
F. after the sizing material is cooled and stands for 10 hours, adding a vulcanizing agent on the double rollers to obtain conductive silicone rubber containing the vulcanizing agent;
H. and F, carrying out die pressing on the conductive silicone rubber containing the vulcanizing agent in the step F for 13 minutes at the temperature of 165 ℃ to form primary vulcanized conductive silicone rubber, and carrying out secondary vulcanization on the primary vulcanized conductive silicone rubber at the temperature of 185 ℃ for 3.5 hours to obtain the low-tensile permanent-deformation conductive silicone rubber.
Example 5
The embodiment provides a low-tensile permanent deformation conductive silicone rubber which comprises the following components in parts by weight:
raw methyl vinyl silicone rubber 97 parts
Raw methyl silicone rubber 4 parts
White carbon black 10 parts
Acetylene black 50 parts
Silane coupling agent 2.5 parts
8 parts of hydroxyl silicone oil
Methyl silicone oil 1.5 parts
Hydrogen-containing silicone oil 2 parts
Vulcanizing agent 1.5 parts
0.5 part of zinc stearate
In the composition of the embodiment, the raw methyl vinyl silicone rubber is prepared by mixing 60 parts of raw methyl vinyl silicone rubber A, 36 parts of raw methyl vinyl silicone rubber B and 1 part of raw methyl vinyl silicone rubber C;
further, the molecular weight of the raw methyl vinyl silicone rubber A is 63 ten thousand, wherein the molar content of vinyl is 0.04%; the molecular weight of the raw methyl vinyl silicone rubber B is 86 ten thousand, wherein the molar content of vinyl is 0.20 percent; the molecular weight of the raw methyl vinyl silicone rubber C is 85 ten thousand, wherein the molar content of vinyl is 4.5 percent.
In the components of the embodiment, the molecular weight of raw methyl silicone rubber is 78 ten thousand; the specific surface area of the white carbon black is 350m2(ii)/g; the specific surface area of the acetylene black is more than or equal to 400m2The oil absorption value is 150mL/100 g; the silane coupling agent consists of 1.5 parts of methyltriethoxysilane and 1 part of vinyl trimethoxy silane; the viscosity of the hydroxyl silicone oil is 1000 cs; the molecular weight of the methyl silicone oil is 60 ten thousand; the viscosity of the hydrogen-containing silicone oil is 80cs, and the hydrogen content is 1.5%; the vulcanizing agent is selected from peroxide 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
The preparation method of the low-tensile permanent deformation conductive silicone rubber of the embodiment is the same as that of the embodiment 1.
Example 6
The embodiment provides a low-tensile permanent deformation conductive silicone rubber which comprises the following components in parts by weight:
raw methyl vinyl silicone rubber 97 parts
Raw methyl silicone rubber 3 parts
White carbon black 25 parts
Acetylene black 30 parts
Silane coupling agent 1.5 parts
Hydroxyl silicone oil 7 parts
2.5 parts of methyl silicone oil
5 parts of hydrogen-containing silicone oil
Vulcanizing agent 1 part
1 part of zinc stearate
In the composition of the embodiment, the raw methyl vinyl silicone rubber is prepared by mixing 10 parts of raw methyl vinyl silicone rubber A, 86.5 parts of raw methyl vinyl silicone rubber B and 0.5 part of raw methyl vinyl silicone rubber C; the silane coupling agent consists of 1 part of methyl triethoxysilane and 0.5 part of vinyl triethoxysilane; the viscosity of the hydroxyl silicone oil is 50 cs; the molecular weight of the methyl silicone oil is 65 ten thousand; the hydrogen-containing silicone oil had a viscosity of 50cs and a hydrogen content of 1.0%, and the other ingredients were the same as in example 4.
The preparation method of the low-tensile permanent deformation conductive silicone rubber of the embodiment is the same as that of the embodiment 1.
Example 7
The embodiment provides a low-tensile permanent deformation conductive silicone rubber which comprises the following components in parts by weight:
96 parts of raw methyl vinyl silicone rubber
Raw methyl silicone rubber 4 parts
28 parts of white carbon black
Acetylene black 45 parts
3 parts of silane coupling agent
10 parts of hydroxyl silicone oil
2 parts of methyl silicone oil
Hydrogen-containing silicone oil 3 parts
Vulcanizing agent 2 parts
1 part of zinc stearate
In the composition of the embodiment, the raw methyl vinyl silicone rubber is prepared by mixing 19 parts of raw methyl vinyl silicone rubber A, 75 parts of raw methyl vinyl silicone rubber B and 2 parts of raw methyl vinyl silicone rubber C; the silane coupling agent consists of 1 part of methyl triethoxysilane, 1 part of vinyl triethoxysilane and 1 part of vinyl trimethoxysilane; the viscosity of the hydroxyl silicone oil is 500 cs; the other ingredients were the same as in example 5.
The preparation method of the low-tensile permanent deformation conductive silicone rubber of the embodiment is the same as that of the embodiment 1.
Comparative example 1
The comparative example provides a low-tensile permanent deformation conductive silicone rubber which comprises the following components in parts by mass:
methyl vinyl silicone rubber crude rubber 95 parts
5 parts of raw methyl silicone rubber
15 portions of white carbon black
Acetylene black 35 parts
Silane coupling agent 2 parts
5 parts of hydroxyl silicone oil
2 parts of methyl silicone oil
Hydrogen-containing silicone oil 4 parts
Vulcanizing agent 1 part
1 part of zinc stearate
In the components of the comparative example, the raw methyl vinyl silicone rubber is formed by mixing 94 parts of raw methyl vinyl silicone rubber A and 1 part of raw methyl vinyl silicone rubber C;
further, the molecular weight of the raw methyl vinyl silicone rubber A is 65 ten thousand, wherein the molar content of vinyl is 0.05 percent; the molecular weight of the raw methyl vinyl silicone rubber B is 85 ten thousand, wherein the molar content of vinyl is 0.20 percent; the molecular weight of the raw methyl vinyl silicone rubber C is 80 ten thousand, wherein the molar content of vinyl is 5 percent.
The specific components were the same as in example 1 except that the raw methyl vinyl silicone rubber B was not contained, and the preparation was carried out in the same manner as in example 1.
Comparative example 2
The embodiment provides a low-tensile permanent deformation conductive silicone rubber which comprises the following components in parts by weight:
methyl vinyl silicone rubber crude rubber 95 parts
5 parts of raw methyl silicone rubber
13 portions of white carbon black
Acetylene black 40 parts
Silane coupling agent 2 parts
6 parts of hydroxyl silicone oil
Methyl silicone oil 1 part
1.5 parts of hydrogen-containing silicone oil
Vulcanizing agent 1 part
1 part of zinc stearate
In the composition of the embodiment, the raw methyl vinyl silicone rubber is formed by mixing 94 parts of raw methyl vinyl silicone rubber B and 1 part of raw methyl vinyl silicone rubber C;
further, the molecular weight of the raw methyl vinyl silicone rubber B is 80 ten thousand, wherein the molar content of vinyl is 0.25 percent; the molecular weight of the raw methyl vinyl silicone rubber C is 80 ten thousand, wherein the molar content of vinyl is 3 percent.
In the components of the embodiment, the molecular weight of raw methyl silicone rubber is 75 ten thousand; the specific surface area of the white carbon black is 400m2(ii)/g; the silane coupling agent is methyl triethoxysilane; the vulcanizing agent is selected from peroxide 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
The specific components and preparation method are the same as those in example 2 except that raw rubber A does not contain methyl vinyl silicone rubber.
Comparative example 3
This example provides a low tensile set conductive silicone rubber, which is composed of the following components (same as in example 3) in parts by mass:
methyl vinyl silicone rubber crude rubber 95 parts
5 parts of raw methyl silicone rubber
20 portions of white carbon black
Acetylene black 40 parts
3 parts of silane coupling agent
8 parts of hydroxyl silicone oil
2 parts of methyl silicone oil
Hydrogen-containing silicone oil 3 parts
Vulcanizing agent 1 part
0.5 part of zinc stearate
The preparation method comprises the following steps:
a preparation method of conductive silicone rubber with low tensile permanent deformation comprises the following steps:
A. putting raw methyl vinyl silicone rubber, hydroxyl silicone oil, hydrogen-containing silicone oil and zinc stearate into a kneading machine, and starting to heat;
B. and B, adding the white carbon black and the silane coupling agent in 2-3 batches and the acetylene black in 4-6 batches into the kneading machine in the step A, mixing into a dough, adding methyl silicone oil and methyl silicone rubber raw rubber, controlling the temperature at 160-175 ℃, stirring for 1-2 hours, and discharging the rubber material at the rotating speed of 40 r/min.
C. After the sizing material is cooled and stands for 8-14 hours, adding a vulcanizing agent on the double rollers to obtain conductive silicone rubber containing the vulcanizing agent;
D. and C, carrying out die pressing on the conductive silicone rubber containing the vulcanizing agent in the step C at the temperature of 160-180 ℃ for 10-15 minutes for forming to obtain primary vulcanized conductive silicone rubber, and carrying out secondary vulcanization on the primary vulcanized conductive silicone rubber at the temperature of 180-200 ℃ for 2-4 hours to obtain the low-tensile permanent deformation conductive silicone rubber.
Further, in the step B, adding the white carbon black and the silane coupling agent in batches, wherein the time interval between each addition is 25-45 minutes.
Further, in the step B, acetylene black is added in portions, and the interval time of each addition is 25-45 minutes.
The conductive silicone rubber prepared in each of the above examples and comparative examples was prepared into test specimens for performance testing, and the test results are shown in table 1 below:
TABLE 1
From the above test results, it can be seen that, through the electrical property test, the volume resistivity of the conductive silicone rubber prepared from the raw material components of examples 1 to 7 of the present invention is 13 to 19 Ω · cm, the shore a hardness thereof is 55 to 72, the tensile permanent set is 5 to 9% (100 ℃x24 h), the tensile permanent set is 3 to 5%, and the TC 90 is 79 to 94 s. Comparative example 1 the conductive silicone rubber prepared from the raw material components has a tensile permanent set of 16% (100 ℃ C.. times.24 h) and a tensile permanent set of 10%; comparative example 2 the conductive silicone rubber prepared from the raw material composition had a permanent set at break of 11% and a TC 90 of 212 s; comparative example 3 the conductive silicone rubber prepared from the raw material composition had a volume resistivity of 83 Ω · cm; none of which meets the requirements of the present invention. The conductive silicone rubber has low resistivity, high hardness, low tensile permanent deformation and tensile permanent deformation, short vulcanization time, good conductivity and low tensile permanent deformation, and can better meet the use requirements of high-end cable accessory places at home and abroad.
The above-described embodiments are merely intended to better illustrate the present invention and should not be construed as limiting the scope of the present invention, and any modifications, equivalents, improvements, etc. based on the above-described embodiments of the present invention are intended to fall within the scope of the present invention.
Claims (9)
1. A preparation method of conductive silicone rubber with low tensile permanent deformation is characterized in that: the method comprises the following steps:
A. putting raw methyl vinyl silicone rubber, hydroxyl silicone oil, hydrogen-containing silicone oil and zinc stearate into a kneading machine;
B. adding the white carbon black and the silane coupling agent into the kneading machine in the step A in 2-3 batches, mixing into a mass, taking the mass out of the pot, cooling and standing for 8-14 hours;
C. b, putting the rubber material cooled to be less than or equal to 50 ℃ in the step B into the kneader again, heating to 160-175 ℃, stirring for 1-2 hours, and vacuumizing for 1 hour, wherein the vacuum degree is more than or equal to 0.08MPa, so as to obtain a mixed base rubber;
D. taking the mixed base rubber obtained in the step C out of the pot, cooling and standing for 8-14 hours, and then putting the mixed base rubber cooled to be less than or equal to 50 ℃ into the kneader again;
E. adding acetylene black into the kneading machine in the step D in 4-6 batches, mixing into a dough, adding methyl silicone oil and methyl silicone rubber raw rubber, heating to 130-175 ℃, stirring for 1-2 hours, and discharging the rubber material;
F. after the sizing material is cooled and stands for 8-14 hours, adding a vulcanizing agent on the double rollers to obtain conductive silicone rubber containing the vulcanizing agent;
H. molding the conductive silicone rubber containing the vulcanizing agent in the step F for 10-15 minutes at the temperature of 160-180 ℃ to obtain primary vulcanized conductive silicone rubber, and then carrying out secondary vulcanization on the primary vulcanized conductive silicone rubber at the temperature of 180-200 ℃ for 2-4 hours to obtain the low-tensile permanent deformation conductive silicone rubber;
the low-tensile permanent deformation conductive silicone rubber comprises the following components in parts by weight: 95-97 parts of methyl vinyl silicone rubber crude rubber, 3-5 parts of methyl silicone rubber crude rubber, 10-30 parts of white carbon black, 30-50 parts of acetylene black, 1-3 parts of silane coupling agent, 3-10 parts of hydroxyl silicone oil, 1-3 parts of methyl silicone oil, 1-5 parts of hydrogen-containing silicone oil, 1-2 parts of vulcanizing agent and 0.5-1 part of zinc stearate; the vulcanizing agent is peroxide 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane;
the raw methyl vinyl silicone rubber is formed by mixing raw methyl vinyl silicone rubber A, raw methyl vinyl silicone rubber B and raw methyl vinyl silicone rubber C;
the molecular weight of the raw methyl vinyl silicone rubber A is 60-70 ten thousand, wherein the molar content of vinyl is 0.03-0.05%; the molecular weight of the raw methyl vinyl silicone rubber B is 80-90 ten thousand, wherein the molar content of vinyl is 0.20-0.25%; the molecular weight of the raw methyl vinyl silicone rubber C is 80-90 ten thousand, wherein the molar content of vinyl is 3-5%.
2. The method for preparing a low-tension permanent deformation conductive silicone rubber according to claim 1, wherein: 10-60 parts of raw methyl vinyl silicone rubber A, 35-86.5 parts of raw methyl vinyl silicone rubber B and 0.5-3 parts of raw methyl vinyl silicone rubber C.
3. The method for preparing a low-tension permanent deformation conductive silicone rubber according to claim 1, wherein: the molecular weight of the raw methyl silicone rubber is 75-85 ten thousand.
4. The method for preparing a low-tension permanent deformation conductive silicone rubber according to claim 1, wherein: the specific surface area of the white carbon black is 200-400 m2/g。
5. The method for preparing a low-tension permanent deformation conductive silicone rubber according to claim 1, wherein: the specific surface area of the acetylene black is more than or equal to 400m2The oil absorption value is 100-200 mL/100 g.
6. The method for preparing a low-tension permanent deformation conductive silicone rubber according to claim 1, wherein: the silane coupling agent is at least one of methyl triethoxysilane, vinyl triethoxysilane and vinyl trimethoxysilane.
7. The method for preparing a low-tension permanent deformation conductive silicone rubber according to claim 1, wherein: the viscosity of the hydroxyl silicone oil is 50-1000 cs; the molecular weight of the methyl silicone oil is 50-70 ten thousand; the viscosity of the hydrogen-containing silicone oil is 10-100 cs, and the hydrogen content is 0.2-1.5%.
8. The method for preparing a low-tension permanent deformation conductive silicone rubber according to claim 1, wherein: and B, adding the white carbon black and the silane coupling agent in a plurality of times, wherein the time interval between each addition is 25-45 minutes.
9. The method for preparing a low-tension permanent deformation conductive silicone rubber according to claim 1, wherein: in the step E, acetylene black is added in several times, and the interval time of each addition is 25-45 minutes; the rotating speed of the kneader is controlled to be 10 r/min-25 r/min, and the rotating speed ratio of the stirring paddle is 1: 1-1: 1.5.
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| CN114058187A (en) * | 2021-12-03 | 2022-02-18 | 东莞市蔚美硅材料科技有限公司 | Silicone rubber with low permanent deformation at break and preparation method thereof |
| CN114196212A (en) * | 2021-12-30 | 2022-03-18 | 东莞市正安有机硅科技有限公司 | Low-compression permanent-deformation rubber compound and preparation method thereof |
| CN115029002A (en) * | 2022-07-06 | 2022-09-09 | 昆山堃烨电子科技有限公司 | Preparation method of conductive silicone rubber |
| CN116690931A (en) * | 2023-06-09 | 2023-09-05 | 东莞市裕天硅橡胶科技有限公司 | Preparation process and product of silica gel heating pipe for pneumoperitoneum machine |
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