CN113337122A - Dealcoholized room temperature curing silicone rubber with ultra-long storage life and preparation method thereof - Google Patents
Dealcoholized room temperature curing silicone rubber with ultra-long storage life and preparation method thereof Download PDFInfo
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Abstract
The invention discloses dealcoholized room temperature curing silicone rubber with an ultra-long storage life, which comprises the following components in parts by weight: 80-120 parts of alpha, omega-hydroxyl-terminated polydimethylsiloxane, 5-20 parts of adhesive, 20-30 parts of synthetic rubber, 20-40 parts of reinforcing filler, 10-20 parts of extending filler, 0.5-1.5 parts of coloring carbon black, 4-8 parts of silane cross-linking agent mixture, 0.2-1 part of catalyst and 0.5-2 parts of coupling agent; the invention also provides a preparation method of the silicon rubber, and the dealcoholization type room temperature curing silicon rubber which has long storage period and good curing performance after long-time storage is obtained by anhydrous and oxygen-free kneading and mixing.
Description
Technical Field
The invention relates to the field of room temperature curing silicone rubber, and particularly relates to dealcoholization type room temperature curing silicone rubber with an ultra-long storage period and a preparation method thereof.
Background
The traditional dealcoholized room temperature vulcanized silicone rubber is prepared by taking alpha, omega-hydroxyl-terminated polydimethylsiloxane as matrix resin, taking polyfunctional silane as a cross-linking agent, taking tetraisopropyl titanate or titanium chelate as a catalyst, taking white carbon black, calcium carbonate and the like as fillers, and then taking other auxiliary agents (such as a plasticizer and the like) as auxiliary materials. The traditional dealcoholized room temperature vulcanized silicone rubber not only has the beneficial effects of room temperature curing, wide temperature resistance range, good weather resistance, excellent insulating property and the like, but also has the advantages that the removed micromolecules are methanol or ethanol, the base material is not corroded, and the harm to human bodies is small; therefore, the dealcoholized room temperature vulcanized silicone rubber is widely applied to the industries of electronics, buildings, automobiles, electronics and the like.
However, compared with the traditional dealcoholization type room temperature vulcanized silicone rubber, the traditional dealcoholization type room temperature vulcanized silicone rubber has the advantages of lower curing speed and short storage period compared with the types of removing ketoxime, deacidification and the like. And because of containing a certain amount of hydroxyl, macromolecular chain degradation can occur after the storage for a certain time, the molecular weight becomes small, the service performance is lost, or the curing is not performed. The application value of the product is greatly influenced, so that the problems of short storage period, poor curing performance after long-time storage and even no fixed rate of the dealcoholized room temperature curing silicone rubber are urgently needed to be solved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to solve the technical problem of providing dealcoholization type room temperature curing silicone rubber which has long storage life and can keep good curing performance after long-time storage and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the dealcoholization type room temperature curing silicone rubber with the ultra-long storage life comprises the following components in parts by weight: 80-120 parts of alpha, omega-hydroxyl-terminated polydimethylsiloxane, 5-20 parts of adhesive, 20-30 parts of synthetic rubber, 20-40 parts of reinforcing filler, 10-20 parts of extending filler, 0.5-1.5 parts of coloring carbon black, 4-8 parts of silane cross-linking agent mixture, 0.2-1 part of catalyst and 0.5-2 parts of coupling agent.
Further, the alpha, omega-hydroxyl-terminated polydimethylsiloxane is composed of alpha, omega-hydroxyl-terminated polydimethylsiloxane A and alpha, omega-hydroxyl-terminated polydimethylsiloxane B, the number average molecular weight of the alpha, omega-hydroxyl-terminated polydimethylsiloxane is 10000-600000, and the dynamic viscosity of the alpha, omega-hydroxyl-terminated polydimethylsiloxane is 1000-500000 cp at 25 ℃.
Further, the number average molecular weight of the α, ω -hydroxyl terminated polydimethylsiloxane a was 80000, and the number average molecular weight of the α, ω -hydroxyl terminated polydimethylsiloxane B was 600000; the mass ratio of the alpha, omega-hydroxyl-terminated polydimethylsiloxane A to the alpha, omega-hydroxyl-terminated polydimethylsiloxane B is 1-3: 1.
further, the adhesive is composed of at least one of silane modified polyisobutylene and silane modified polyacrylate.
Further, the adhesive is preferably silane-modified polyisobutylene having a number average molecular weight of 2.5 ten thousand
Further, the synthetic rubber is composed of at least one of butadiene rubber, nitrile rubber and butyl rubber.
Furthermore, the reinforcing filler is hydrophobic fumed silica subjected to modification treatment by one or more of silazane, siloxane, chlorosilane and silicone solution, and the BET specific surface area is 100-400 m 2/g.
Further, the bulking filler is composed of at least one of hollow glass beads, diatomite and activated calcium carbonate.
Further, the silane cross-linking agent mixture is composed of at least one of methyltrimethoxysilane, methyltriethoxysilane, ethyl orthosilicate, vinyltrimethoxysilane and aniline methyltriethoxysilane.
Further, the silane crosslinking agent mixture is preferably a mixture of methyltriethoxysilane and vinyltrimethoxysilane in any proportion.
Further, the catalyst is composed of at least one of an organic tin catalyst, titanate and titanium chelate.
Further, the coupling agent is composed of at least one of gamma-aminopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane and gamma-propyltrimethoxysilane.
Based on the agreement inventive concept, the invention also provides a preparation method of the dealcoholization type room temperature curing silicone rubber with the ultra-long storage life, which comprises the following steps:
s1: pre-treating materials, namely baking a reinforcing filler, an incremental filler, alpha, omega-hydroxyl-terminated polydimethylsiloxane, synthetic rubber, an adhesive and colored carbon black at 100-120 ℃ respectively for pre-drying treatment;
s2, uniformly mixing the coloring carbon black and the incremental filler in advance to obtain mixed powder;
s3, kneading and mixing the rubber material, namely putting the synthetic rubber into a vacuum kneader, stirring and kneading the synthetic rubber, adding the adhesive and continuously stirring the synthetic rubber; adding the mixed powder obtained in the step S2, alpha, omega-hydroxyl-terminated polydimethylsiloxane and reinforcing filler in batches, then starting a vacuum pump, maintaining the temperature at 110-130 ℃, removing residual water, and continuously kneading uniformly to obtain a paste rubber material;
and S4, cooling the pasty rubber material obtained in the step S3 to below 50 ℃, adding a silane cross-linking agent mixture, a catalyst and a coupling agent, continuously kneading the mixture under the condition of introducing nitrogen and normal pressure, and uniformly stirring to obtain the dealcoholized room-temperature curing silicone rubber.
Further, in S1, the drying time is 10-14 h;
further, in S3, the vacuum degree of vacuum kneading is-0.08 to-0.1 Mpa, and the vacuum kneading time is 2 to 4 hours;
further, in S4, the adding mode of each component is vacuum negative pressure suction, and the vacuum negative pressure is-0.02 to-0.04 Mpa; and the kneading time of the step S4 is 1-3 h.
The invention adds alpha, omega-dihydroxy polysiloxane with different molecular weights for mixing, can obviously improve the storage performance of the silicon rubber, and simultaneously shortens the surface drying time of the silicon rubber. When the low-molecular-weight alpha, omega-dihydroxy polysiloxane and the high-molecular-weight alpha, omega-dihydroxy polysiloxane are added into the system at the same time, the molecular chain of the high-molecular-weight alpha, omega-dihydroxy polysiloxane is relatively longer, the molecular chain of the low-molecular-weight alpha, omega-dihydroxy polysiloxane is relatively shorter, the low-molecular-weight alpha, omega-dihydroxy polysiloxane and the high-molecular-weight omega-dihydroxy polysiloxane can be mutually interpenetrated, and after the low-molecular-weight alpha, omega-dihydroxy polysiloxane and the cross-linking agent are subjected to cross-linking reaction, the compactness of molecular arrangement is favorably improved, the cross-linking density is increased, and the surface drying time of the silicone rubber is shortened; under high temperature and high humidity, the amount of moisture permeating into the material can be reduced, so that the storage property can be improved.
Secondly, the silane cross-linking agent mixture adopted by the invention has higher oxysilane hydrolytic activity, so that the hydroxyl-terminated alpha, omega-dihydroxy polydimethylsiloxane can be completely modified into RO-terminated polysiloxane, the intermolecular acting force is weakened, and when the silicon rubber is vulcanized in moisture, the terminal alkoxy can be quickly and completely hydrolyzed to generate hydroxyl, so that the silicon rubber can be more fully subjected to condensation reaction with the cross-linking agent, and the short surface drying time is realized.
Compared with the prior art, the invention has the beneficial effects that: firstly, the dealcoholized room temperature curing silicone rubber has longer storage time; secondly, the curing performance can still keep good after long-time storage; and thirdly, the material has stable appearance and shape, long storage period and larger plasticity. Specifically, the surface drying time of the prepared dealcoholization type room temperature curing silicone rubber under normal temperature and normal humidity (25 ℃, 50% RH) is 30-60 min, the tensile strength after curing is more than or equal to 2Mpa, the elongation at break is more than or equal to 350%, the hardness is more than or equal to 30Shore A, and the storage life is more than 400 d.
Detailed Description
The present invention is illustrated below by way of specific examples, which are provided primarily for the purpose of illustrating the principles, features and advantages of the invention, and are not to be construed as limited to the examples described below, which may be further modified without departing from the principles of the experiment.
Example 1:
s1: the material is pretreated, 100 parts of alpha, omega-hydroxyl-terminated polydimethylsiloxane (comprising 8 ten thousand of alpha, omega-hydroxyl-terminated polydimethylsiloxane A and 60 ten thousand of alpha, omega-hydroxyl-terminated polydimethylsiloxane A in a mass ratio of A: B to 3:1), 10 parts of silane modified polyisobutylene with the average molecular weight of 2.5 ten thousand, 30 parts of butyl rubber, 25 parts of hydrophobic fumed silica TS-720, 5 parts of activated calcium carbonate and 1 part of colored carbon black are respectively placed in an oven at 120 ℃ for drying for 8 hours for later use.
S2: mixing the coloring carbon black and the activated calcium carbonate and fully mixing the coloring carbon black and the activated calcium carbonate by a planetary stirrer to obtain mixed powder;
s3: and (3) kneading and mixing the rubber material, putting the dried butyl rubber into a material cavity of a vacuum kneader, adjusting the rotating speed of blades of the kneader, heating to 120 ℃, stirring and kneading for 20min, adding silane modified polyisobutylene, and continuously stirring for 0.5 h. 1/4, adding the mixed powder obtained by S2 into a kneader, stirring for 0.5h, after uniform mixing, adding alpha, omega-hydroxyl-terminated polydimethylsiloxane with different molecular weights, the rest of the mixed powder obtained by S2 and fumed silica in batches, starting a vacuum pump after the powder is added, keeping the vacuum degree at-0.1 Mpa, continuously kneading and mixing for 2h, and keeping the temperature at 120 ℃ to remove residual moisture. Continuously kneading the mixture evenly to obtain a pasty sizing material;
s4, cooling the paste rubber material obtained in the step S3 to 50 ℃, slowly sucking 4 parts of silane cross-linking agent mixture (containing methyl triethoxysilane and vinyl trimethoxy silane in a mass ratio of methyl triethoxysilane to vinyl trimethoxy silane being 4: 1), 1.2 parts of organic tin catalyst (namely dibutyltin dilaurate) and 1.5 parts of gamma-aminopropyl triethoxysilane by utilizing vacuum negative pressure, and kneading the mixture for 3 hours under normal pressure by injecting nitrogen and then carrying out vacuum packaging.
In the embodiment 1, alpha, omega-dihydroxy polysiloxane with different molecular weights is added and mixed, the molecular chain of the high molecular weight alpha, omega-dihydroxy polysiloxane is relatively longer, the molecular chain of the low molecular weight alpha, omega-dihydroxy polysiloxane is relatively shorter, the high molecular weight alpha, omega-dihydroxy polysiloxane and the low molecular weight alpha, omega-dihydroxy polysiloxane can be mutually interpenetrated, and after the alpha, omega-dihydroxy polysiloxane and a cross-linking agent are subjected to cross-linking reaction, the compactness of molecular arrangement is favorably improved, the cross-linking density is increased, and the surface drying time of the silicone rubber is shortened; under high temperature and high humidity, the amount of moisture permeating into the material can be reduced, so that the storage property can be improved. Secondly, the invention uses the mixture of vinyltrimethoxysilane and methyltriethoxysilane compounded into a silane cross-linking agent as a vulcanizing agent, the hydrolysis activity of the oxysilane of the methyltriethoxysilane and the vinyltrimethoxysilane is higher, so that the hydroxyl-terminated alpha, omega-dihydroxy polydimethylsiloxane is completely modified into RO-terminated polysiloxane, the intermolecular force is weakened, and when the silicon rubber is vulcanized in moisture, the terminal alkoxy can be hydrolyzed more quickly and completely to generate hydroxyl, the silicon rubber and the cross-linking agent are subjected to condensation reaction more fully, and the surface drying time is shorter.
The silane modified polyisobutylene also can obtain good aging resistance under high temperature and high humidity by introducing the silane modified polyisobutylene, and the molecular chain of the silane modified polyisobutylene contains a large amount of symmetrical methyl groups, so that the silane modified polyisobutylene has good hydrophobicity. However, the compatibility of the common silane modified polyisobutylene and the silicone rubber is poor, and the simple physical mixing is easy to separate. After the butyl rubber is added, the mixed rubber contains moisture-curable reactive groups, can participate in curing crosslinking reaction, forms an inter-transmission network structure with the molecular weight of the organic silicon, is uniformly distributed in a silicone rubber curing crosslinking network, and can greatly improve the chemical stability and the thermal stability by introducing the butyl rubber, so that the dealcoholization type room-temperature silicone rubber disclosed by the invention can greatly improve the storage stability.
Example 2:
s1: the raw materials are pretreated, 100 parts of alpha, omega-hydroxyl-terminated polydimethylsiloxane (comprising 8 ten thousand of alpha, omega-hydroxyl-terminated polydimethylsiloxane A and 60 ten thousand of alpha, omega-hydroxyl-terminated polydimethylsiloxane A in average mass, wherein the mass ratio of the alpha, omega-hydroxyl-terminated polydimethylsiloxane A to the omega-hydroxyl-terminated polydimethylsiloxane A is that A: B is 3:1), 10 parts of silane modified polyisobutylene with the average molecular weight of 2.5 ten thousand, 30 parts of butyl rubber, 25 parts of hydrophobic fumed silica TS-720, 5 parts of activated calcium carbonate and 1 part of colored carbon black are respectively placed in an oven at 120 ℃ and dried for 8 hours for later use.
S2, mixing the colored carbon black and the activated calcium carbonate and premixing the mixture by a planetary stirrer to obtain mixed powder;
s3: and (3) kneading and mixing the rubber material, putting the dried butyl rubber into a material cavity of a vacuum kneader, adjusting the rotating speed of blades of the kneader, heating to 120 ℃, stirring and kneading for 20min, adding silane modified polyisobutylene, and continuously stirring for 0.5 h. 1/4, adding the mixed powder obtained by S2 into a kneader, stirring for 0.5h, after uniform mixing, adding alpha, omega-hydroxyl-terminated polydimethylsiloxane with different molecular weights, the rest of the mixed powder obtained by S2 and fumed silica in batches, starting a vacuum pump after the powder is added, keeping the vacuum degree at-0.1 Mpa, continuously kneading and mixing for 2h, and keeping the temperature at 120 ℃ to remove residual moisture. Continuously kneading the mixture evenly to obtain a pasty sizing material;
s4: and cooling the pasty sizing material obtained in the step S3 to 50 ℃, slowly sucking 4 parts of a silane cross-linking agent mixture (containing methyl triethoxysilane and vinyl trimethoxysilane, wherein the mass ratio of the methyl triethoxysilane to the vinyl trimethoxysilane is 3: 2), 1.2 parts of an organic tin catalyst (namely dibutyltin dilaurate) and 1.5 parts of gamma-aminopropyl triethoxysilane into the pasty sizing material by utilizing vacuum negative pressure, kneading the mixture for 3 hours under normal pressure by injecting nitrogen, and then carrying out vacuum packaging.
Example 3:
s1: the raw materials are pretreated, 100 parts of alpha, omega-hydroxyl-terminated polydimethylsiloxane (comprising 8 ten thousand of alpha, omega-hydroxyl-terminated polydimethylsiloxane A and 60 ten thousand of alpha, omega-hydroxyl-terminated polydimethylsiloxane A in average mass, wherein the mass ratio of the alpha, omega-hydroxyl-terminated polydimethylsiloxane A to the omega-hydroxyl-terminated polydimethylsiloxane A is 1:1), 10 parts of silane modified polyisobutylene with the average molecular weight of 2.5 ten thousand, 30 parts of butyl rubber, 25 parts of hydrophobic fumed silica TS-720, 5 parts of activated calcium carbonate and 1 part of colored carbon black are respectively placed in an oven at 120 ℃ and dried for 8 hours for later use.
S2: mixing the coloring carbon black and the activated calcium carbonate and premixing the mixture by a planetary stirrer to obtain mixed powder;
s3: and (3) kneading and mixing the rubber material, putting the dried butyl rubber into a material cavity of a vacuum kneader, adjusting the rotating speed of blades of the kneader, heating to 120 ℃, stirring and kneading for 20min, adding silane modified polyisobutylene, and continuously stirring for 0.5 h. 1/4, adding the mixed powder obtained by S2 into a kneader, stirring for 0.5h, after uniform mixing, adding alpha, omega-hydroxyl-terminated polydimethylsiloxane with different molecular weights, the rest of the mixed powder obtained by S2 and fumed silica in batches, starting a vacuum pump after the powder is added, keeping the vacuum degree at-0.1 Mpa, continuously kneading and mixing for 2h, and keeping the temperature at 120 ℃ to remove residual moisture. Continuously kneading the mixture evenly to obtain a pasty sizing material;
s4: and cooling the pasty sizing material obtained in the step S3 to 50 ℃, slowly sucking 4 parts of silane cross-linking agent mixture (containing methyl triethoxysilane and vinyl trimethoxy silane in a mass ratio of methyl triethoxysilane to vinyl trimethoxy silane being 4: 1), 1.2 parts of organic tin catalyst (namely dibutyltin dilaurate) and 1.5 parts of gamma-aminopropyl triethoxysilane by utilizing vacuum negative pressure, and kneading the mixture for 3 hours under normal pressure by flushing nitrogen, and then carrying out vacuum packaging.
Comparative example 1:
the raw materials are pretreated, 100 parts of alpha, omega-hydroxyl-terminated polydimethylsiloxane (comprising 8 ten thousand of alpha, omega-hydroxyl-terminated polydimethylsiloxane A and 60 ten thousand of alpha, omega-hydroxyl-terminated polydimethylsiloxane A in average mass, wherein the mass ratio of the alpha, omega-hydroxyl-terminated polydimethylsiloxane A to the omega-hydroxyl-terminated polydimethylsiloxane A is that A: B is 3:1), 10 parts of 2.5 ten thousand molecular weight silane modified polyisobutylene, 30 parts of butyl rubber, 25 parts of hydrophobic fumed silica TS-720, 5 parts of activated calcium carbonate and 1 part of colored carbon black are respectively placed in an oven at 120 ℃ to be dried for 8 hours for later use.
Kneading and mixing the sizing material, putting the pretreated alpha, omega-hydroxyl-terminated polydimethylsiloxane, silane modified polyisobutylene and butyl rubber into a vacuum kneader at one time, adjusting the rotating speed of a blade of the kneader, heating to 120 ℃, adding the fumed silica, the activated calcium carbonate and the colored carbon black in batches after uniform mixing, starting a vacuum pump after the powder is added, keeping the vacuum degree at-0.1 Mpa, continuously kneading and mixing for 2h, keeping the temperature at 110-130 ℃, and removing residual moisture. Continuously kneading the mixture evenly to obtain a pasty sizing material;
then, the sizing material is cooled to 50 ℃, 4 parts of a silane cross-linking agent mixture (containing methyl triethoxysilane and vinyl trimethoxysilane in a mass ratio of 4: 1), 1.2 parts of an organic tin catalyst (namely dibutyltin dilaurate) and 1.5 parts of gamma-aminopropyl triethoxysilane are slowly sucked in by using vacuum negative pressure, nitrogen is filled in the sizing material, and the sizing material is vacuum-packaged after being kneaded for 3 hours under normal pressure.
Comparative example 2:
the raw materials are pretreated, 100 parts of alpha, omega-hydroxyl-terminated polydimethylsiloxane (comprising 8 ten thousand of alpha, omega-hydroxyl-terminated polydimethylsiloxane A and 60 ten thousand of alpha, omega-hydroxyl-terminated polydimethylsiloxane A in average mass, wherein the mass ratio of the alpha, omega-hydroxyl-terminated polydimethylsiloxane A to the omega-hydroxyl-terminated polydimethylsiloxane A is that A: B is 3:1), 10 parts of 2.5 ten thousand molecular weight silane modified polyisobutylene, 30 parts of butyl rubber, 25 parts of hydrophobic fumed silica TS-720, 5 parts of activated calcium carbonate and 1 part of colored carbon black are respectively placed in an oven at 120 ℃ to be dried for 8 hours for later use.
And (3) kneading and mixing the rubber material, putting the dried butyl rubber into a material cavity of a vacuum kneader, adjusting the rotating speed of blades of the kneader, heating to 120 ℃, stirring and kneading for 20min, adding silane modified polyisobutylene, and continuously stirring for 0.5 h. Mixing the colored carbon black and the activated calcium carbonate in advance, adding 1/4 mixed powder into a kneader, stirring for 0.5h, after uniform mixing, adding alpha, omega-hydroxyl-terminated polydimethylsiloxane with different molecular weights, the rest mixed powder and fumed silica in batches, starting a vacuum pump after the powder is added, keeping the vacuum degree at-0.1 Mpa, continuously kneading and mixing for 2h, and keeping the temperature at 110-130 ℃, and removing residual moisture. Continuously kneading the mixture evenly to obtain a pasty sizing material; then the sizing material is cooled to 50 ℃, 4 parts of methyltriethoxysilane, 1.2 parts of organotin catalyst (namely dibutyltin dilaurate) and 1.5 parts of gamma-aminopropyltriethoxysilane are slowly sucked in by utilizing vacuum negative pressure, nitrogen is filled in, and the mixture is kneaded for 3 hours under normal pressure and then is packaged in vacuum.
The examples and comparative examples were compared in terms of performance as follows:
TABLE 1 qualitative test after 7 days at room temperature
| Performance of | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Surface drying time/min | 45 | 38 | 32 | 45 | 60 |
| Tensile strength/MPa | 3.2 | 2.8 | 2.5 | 2.1 | 3 |
| Elongation at break/% | 420 | 385 | 330 | 300 | 315 |
| hardness/Shore A | 35 | 38 | 30 | 32 | 28 |
Qualitative test after standing at 270 ℃ for 7 days in Table
| Performance of | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Surface drying time/min | 45 | 38 | 32 | Without surface drying | Without surface drying |
| Tensile strength/MPa | 2.9 | 2.3 | 1.9 | / | / |
| Elongation at break/% | 472 | 420 | 285 | / | / |
| hardness/Shore A | 32 | 32 | 24 | / | / |
Qualitative test after standing at 370 ℃ for 10 days
| Performance of | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Surface drying time/min | 45 | 38 | 32 | Without surface drying | Without surface drying |
| Tensile strength/MPa | 2.9 | 2.3 | 1.9 | / | / |
| Elongation at break/% | 513 | 483 | 365 | / | / |
| hardness/Shore A | 30 | 28 | 22 | / | / |
TABLE 4 shelf life at different temperatures
| Performance of | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Standing at room temperature | Not less than 14 months | More than or equal to 12 months | More than or equal to 10 months | More than or equal to 6 months | More than or equal to 3 months |
| Standing at 70 deg.C | ≥12d | ≥10d | ≥10d | ≥3d | ≥2d |
Wherein artificial accelerated aging research is mainly adopted. To a certain extent, the mechanism of the accelerated aging of the artificial oven is basically consistent with that of the natural aging of rubber. In general, the aging of the rubber in an oven placed at 70 ℃ for 7d can be considered equivalent to one year under normal conditions. Thus, the storage stability of the rubber is demonstrated herein using a laboratory oven accelerated aging.
As can be seen from tables 1 to 4, the examples of the present invention have a short tack-free time, a long storage property, and a small change in the overall properties after a long-term storage, and can better ensure the storage properties of the dealcoholized room temperature-curable silicone rubber.
Claims (10)
1. The dealcoholization type room temperature curing silicone rubber with the ultra-long storage life is characterized by comprising the following components in parts by weight: 80-120 parts of alpha, omega-hydroxyl-terminated polydimethylsiloxane, 5-20 parts of adhesive, 20-30 parts of synthetic rubber, 20-40 parts of reinforcing filler, 10-20 parts of extending filler, 0.5-1.5 parts of coloring carbon black, 4-8 parts of silane cross-linking agent mixture, 0.2-1 part of catalyst and 0.5-2 parts of coupling agent.
2. The silicone rubber according to claim 1, wherein the α, ω -hydroxyl terminated polydimethylsiloxane is composed of α, ω -hydroxyl terminated polydimethylsiloxane a and α, ω -hydroxyl terminated polydimethylsiloxane B having a number average molecular weight of 10000 to 600000, and the α, ω -hydroxyl terminated polydimethylsiloxane has a kinematic viscosity of 1000 to 500000cp at 25 ℃.
3. The silicone rubber according to claim 2, wherein the a, ω -hydroxyl terminated polydimethylsiloxane a has a number average molecular weight of 80000, and the a, ω -hydroxyl terminated polydimethylsiloxane B has a number average molecular weight of 600000; the mass ratio of the alpha, omega-hydroxyl-terminated polydimethylsiloxane A to the alpha, omega-hydroxyl-terminated polydimethylsiloxane B is 1-3: 1.
4. the silicone rubber according to claim 1, wherein the adhesive is composed of at least one of silane-modified polyisobutylene and silane-modified polyacrylate.
5. The silicone rubber according to claim 1, wherein the synthetic rubber is composed of at least one of butadiene rubber, nitrile rubber, and butyl rubber.
6. The silicone rubber according to claim 1,
the reinforcing filler is hydrophobic fumed silica subjected to modification treatment by one or more of silazane, siloxane, chlorosilane and silicone solution, and the BET specific surface area is 100-400 m 2/g;
the incremental filler is composed of at least one of hollow glass microspheres, diatomite and active calcium carbonate;
the catalyst is composed of at least one of organic tin catalyst, titanate and titanium chelate.
7. The silicone rubber according to claim 1, wherein the silane crosslinker mixture is comprised of at least one of methyltrimethoxysilane, methyltriethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, anilinomethyltriethoxysilane.
8. The silicone rubber according to claim 1, wherein the coupling agent is composed of at least one of gamma-aminopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, and gamma-propyltrimethoxysilane.
9. The method for preparing the dealcoholization type room temperature curing silicone rubber with the ultra-long storage life according to any one of claims 1 to 8, comprising the steps of:
s1: pre-treating materials, namely baking a reinforcing filler, an incremental filler, alpha, omega-hydroxyl-terminated polydimethylsiloxane, synthetic rubber, an adhesive and colored carbon black at 100-120 ℃ respectively for pre-drying treatment;
s2, uniformly mixing the coloring carbon black and the incremental filler in advance to obtain mixed powder;
s3, kneading and mixing the rubber material, namely putting the synthetic rubber into a vacuum kneader, stirring and kneading the synthetic rubber, adding the adhesive and continuously stirring the synthetic rubber; adding the mixed powder obtained in the step S2, alpha, omega-hydroxyl-terminated polydimethylsiloxane and reinforcing filler in batches, then starting a vacuum pump, maintaining the temperature at 110-130 ℃, removing residual water, and continuously kneading uniformly to obtain a paste rubber material;
and S4, cooling the pasty rubber material obtained in the step S3 to below 50 ℃, adding a silane cross-linking agent mixture, a catalyst and a coupling agent, continuously kneading the mixture under the condition of introducing nitrogen and normal pressure, and uniformly stirring to obtain the dealcoholized room-temperature curing silicone rubber.
10. The production method according to claim 9,
in S1, the drying time is 10-14 h;
in S3, the vacuum degree of vacuum kneading is-0.08 to-0.1 Mpa, and the vacuum kneading time is 2 to 4 hours;
in S4, the adding mode of each component is vacuum negative pressure suction, and the vacuum negative pressure is-0.02 to-0.04 Mpa; and the kneading time of the step S4 is 1-3 h.
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