CN113337122B - Dealcoholized room-temperature cured silicone rubber with ultra-long storage period and preparation method thereof - Google Patents
Dealcoholized room-temperature cured silicone rubber with ultra-long storage period and preparation method thereof Download PDFInfo
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Abstract
The invention discloses dealcoholized room-temperature cured silicone rubber with an ultra-long storage period, 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 incremental 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 dealcoholized room-temperature cured silicon rubber which has long storage period and good curing performance after long-time storage is obtained through anhydrous anaerobic kneading and mixing.
Description
Technical Field
The invention relates to the field of room-temperature cured silicone rubber, in particular to dealcoholized room-temperature cured 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, polyfunctional silane as a crosslinking agent, tetraisopropyl titanate or titanium chelate as a catalyst, white carbon black, calcium carbonate and the like as fillers, and other auxiliary agents (such as plasticizers and the like) as auxiliary agents. The traditional dealcoholized room temperature vulcanized silicone rubber has the beneficial effects of room temperature curing, wide temperature resistant range, good weather resistance, excellent insulating property and the like, and the removed micromolecules are methanol or ethanol, so that the dealcoholized room temperature vulcanized silicone rubber has no corrosion to a base material and is less harmful to human bodies; therefore, the dealcoholized room temperature vulcanized silicone rubber is widely applied to the industries of electronics, construction, automobiles, electronics and the like.
However, compared with the traditional dealcoholized room temperature vulcanized silicone rubber with the types of ketoxime removal, deacidification and the like, the traditional dealcoholized room temperature vulcanized silicone rubber has the advantages of slower curing speed and short storage period. And the polymer chain degradation occurs after a certain period of storage due to the fact that the polymer chain contains a certain amount of hydroxyl, the molecular weight is reduced, the usability is lost, or the polymer chain is not solidified. 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 unfixed phone of the dealcoholized room-temperature curing silicone rubber are urgently solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the dealcoholized room temperature cured silicone rubber which has long storage life and good curing performance after long-time storage and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
an ultra-long shelf life dealcoholized room temperature cured silicone rubber, 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 incremental 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 consists of alpha, omega-hydroxyl-terminated polydimethylsiloxane A and alpha, omega-hydroxyl-terminated polydimethylsiloxane B with the number average molecular weight of 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 alpha, omega-hydroxyl-terminated polydimethylsiloxane a was 80000, and the number average molecular weight of the alpha, omega-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 polyisobutene and silane modified polyacrylate.
Further, the adhesive is preferably a 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.
Further, the reinforcing filler is hydrophobic fumed silica subjected to one or more modification treatments of silazane, siloxane, chlorosilane and silicone solution, and the BET specific surface area is 100-400 m < 2 >/g.
Further, the incremental 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 phenylmethyltriethoxysilane.
Further, the silane cross-linking agent mixture is preferably a mixture of methyltriethoxysilane and vinyltrimethoxysilane in any ratio.
Further, the catalyst is composed of at least one of an organotin catalyst, titanate and chelate of titanium.
Further, the coupling agent is composed of at least one of gamma-aminopropyl triethoxysilane, gamma-mercaptopropyl trimethoxysilane and gamma-propyl trimethoxysilane.
Based on the agreed conception, the invention also provides a preparation method of the dealcoholized room temperature curing silicone rubber with the ultra-long storage period, which comprises the following steps:
s1: material pretreatment, namely respectively baking reinforcing filler, incremental filler, alpha, omega-hydroxyl-terminated polydimethylsiloxane, synthetic rubber, adhesive and colored carbon black at 100-120 ℃ for pre-drying treatment;
s2, pre-mixing the coloring carbon black and the incremental filler uniformly to obtain mixed powder;
s3, kneading and mixing the rubber material, firstly putting the synthetic rubber into a vacuum kneader, stirring and kneading, and then adding the adhesive for continuous stirring; adding the mixed powder obtained in the step S2, alpha, omega-hydroxyl-terminated polydimethylsiloxane and reinforcing filler in batches, starting a vacuum pump, maintaining the temperature at 110-130 ℃, removing residual moisture, and continuously and uniformly kneading to obtain pasty sizing material;
s4, cooling the pasty sizing material obtained in the step S3 to below 50 ℃, adding a silane cross-linking agent mixture, a catalyst and a coupling agent, continuously kneading under the normal pressure state of filling nitrogen, and uniformly stirring to obtain the dealcoholized room-temperature cured silicone rubber.
Further, in S1, the drying treatment time is 10-14 hours;
further, in S3, the vacuum degree of vacuum kneading is-0.08 to-0.1 Mpa, and the time of vacuum kneading is 2-4 h;
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 step S4 is 1 to 3 hours.
The invention adds alpha, omega-dihydroxyl polysiloxane with different molecular weights to mix, which can obviously improve the storage performance of the silicon rubber and shorten the surface drying time of the silicon rubber. Because the alpha, omega-dihydroxyl polysiloxane with low molecular weight and the alpha, omega-dihydroxyl polysiloxane with high molecular weight are simultaneously added into the system, the molecular chains of the alpha, omega-dihydroxyl polysiloxane with high molecular weight are relatively longer, the molecular chains of the alpha, omega-dihydroxyl polysiloxane with low molecular weight are relatively shorter, and the two can be mutually inserted, and after the crosslinking reaction with the crosslinking agent, the molecular arrangement tightness is favorably improved, the crosslinking density is increased, and the surface drying time of the silicone rubber is shortened; the amount of moisture penetrating into the material can be reduced under high temperature and high humidity, so that the storage performance is improved.
And secondly, the hydroxyl-terminated alpha, omega-dihydroxy polydimethylsiloxane can be completely modified into RO-terminated polysiloxane by virtue of the high hydrolytic activity of the oxysilane of the silane cross-linking agent mixture adopted by the invention, so that the intermolecular acting force is weakened, and the terminal alkoxy can be quickly and completely hydrolyzed to generate hydroxyl when the silicon rubber is vulcanized in moisture, so that condensation reaction is carried out with the cross-linking agent more fully, and the shorter surface drying time is realized.
Compared with the prior art, the invention has the following beneficial effects: 1. the dealcoholized room-temperature cured silicone rubber has longer storage time; 2. the curing performance after long-time preservation still keeps good curing performance; 3. the material has stable appearance and shape, long storage period and great plasticity. Specifically, the surface drying time of the dealcoholized room temperature cured silicone rubber is 30-60 min at the room temperature and the normal humidity (25 ℃,50% RH), 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 period is more than 400d.
Detailed Description
The present invention is illustrated below with reference to specific examples, which are mainly used to explain the principles, features and advantages of the invention, and are not limited to the following examples, which may be further modified without departing from the basic principles of experimentation.
Example 1:
s1: the preparation method comprises the following steps of material pretreatment, respectively placing 100 parts of alpha, omega-hydroxyl-terminated polydimethylsiloxane (comprising alpha, omega-hydroxyl-terminated polydimethylsiloxane A with the number average mass of 8 ten thousand and alpha, omega-hydroxyl-terminated polydimethylsiloxane with the number average mass of 60 ten thousand, wherein the mass ratio of the alpha, omega-hydroxyl-terminated polydimethylsiloxane A to the alpha, omega-hydroxyl-terminated polydimethylsiloxane is A: B=3:1), 10 parts of silane modified polyisobutene 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 coloring carbon black into a baking oven at 120 ℃ for drying for 8 hours for later use.
S2: mixing the colored carbon black and the activated calcium carbonate, and fully mixing the mixture by a planetary stirrer to obtain mixed powder;
s3: kneading and mixing the sizing material, putting the dried butyl rubber into a material cavity of a vacuum kneader, regulating the rotating speed of blades of the kneader, heating to 120 ℃, stirring and kneading for 20min, and then adding silane modified polyisobutene and continuously stirring for 0.5h. Adding 1/4 of the mixed powder obtained in the step S2 into a kneader and stirring for 0.5h, after uniformly mixing, adding alpha, omega-hydroxyl-terminated polydimethylsiloxane with different molecular weights, the mixed powder obtained in the step S2 and the gas-phase white carbon black 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 uniformly to form paste sizing material;
and S4, cooling the pasty sizing material obtained in the step S3 to 50 ℃, slowly sucking 4 parts of silane and silane cross-linking agent mixture (comprising methyltriethoxysilane and vinyltrimethoxysilane in a mass ratio of methyltriethoxysilane to vinyltrimethoxysilane=4:1) into the pasty sizing material by utilizing vacuum negative pressure, and vacuum packaging after kneading for 3 hours under normal pressure by using nitrogen gas and 1.2 parts of organotin catalyst (namely dibutyltin dilaurate).
In the embodiment 1, alpha, omega-dihydroxypolysiloxane with different molecular weights is added for mixing, the alpha, omega-dihydroxypolysiloxane with high molecular weight has relatively long molecular chain, the alpha, omega-dihydroxypolysiloxane with low molecular weight has relatively short molecular chain, and the alpha, omega-dihydroxypolysiloxane with low molecular weight can be mutually inserted, and after the alpha, omega-dihydroxypolysiloxane with low molecular weight and the alpha, omega-dihydroxypolysiloxane with low molecular weight react with a cross-linking agent, the compactness of molecular arrangement is improved, so that the cross-linking density is increased, and the surface drying time of the silicone rubber is shortened; the amount of moisture penetrating into the material can be reduced under high temperature and high humidity, so that the storage performance is improved. Secondly, the invention uses the mixture of vinyl trimethoxy silane and methyl triethoxy silane as a silane cross-linking agent as a vulcanizing agent, the hydrolytic activity of the oxy silane of the methyl triethoxy silane and the vinyl trimethoxy silane is higher, the hydroxyl-terminated alpha, omega-dihydroxy polydimethylsiloxane is completely modified into RO-terminated polysiloxane, the intermolecular acting force is weakened, and the terminal alkoxy can be quickly and completely hydrolyzed to generate hydroxyl when the silicon rubber is vulcanized in moisture, so that the condensation reaction is carried out with the cross-linking agent more fully, and the shorter surface drying time is realized.
The silane modified polyisobutene can also obtain good high-temperature and high-humidity aging resistance by introducing the silane modified polyisobutene, and the silane modified polyisobutene molecular chain contains a large number of symmetrical methyl groups and has good hydrophobicity. However, the common silane modified polyisobutene has poor compatibility with silicone rubber, and is easy to phase separate by simple physical mixing. After butyl rubber is added, the mixed sizing material contains a reactive group capable of being cured by moisture, can participate in curing and crosslinking reaction, forms an inter-transmission network structure with the molecular weight of organic silicon, is uniformly distributed in a silicone rubber curing and crosslinking network, and can greatly improve chemical stability and thermal stability by introducing the butyl rubber, so that the dealcoholized room temperature silicone rubber can greatly improve storage stability.
Example 2:
s1: raw material pretreatment, 100 parts of alpha, omega-hydroxyl-terminated polydimethylsiloxane (comprising alpha, omega-hydroxyl-terminated polydimethylsiloxane A with the number average mass of 8 ten thousand and alpha, omega-hydroxyl-terminated polydimethylsiloxane with the number average mass of 60 ten thousand, and the mass ratio of the alpha, omega-hydroxyl-terminated polydimethylsiloxane A to the alpha, omega-hydroxyl-terminated polydimethylsiloxane is A: B=3:1), 10 parts of silane modified polyisobutene 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 coloring carbon black are respectively placed in a baking oven at 120 ℃ for drying for 8 hours for later use.
S2, mixing the colored carbon black and the activated calcium carbonate, and pre-mixing the mixture by a planetary mixer to obtain mixed powder;
s3: kneading and mixing the sizing material, putting the dried butyl rubber into a material cavity of a vacuum kneader, regulating the rotating speed of blades of the kneader, heating to 120 ℃, stirring and kneading for 20min, and then adding silane modified polyisobutene and continuously stirring for 0.5h. Adding 1/4 of the mixed powder obtained in the step S2 into a kneader and stirring for 0.5h, after uniformly mixing, adding alpha, omega-hydroxyl-terminated polydimethylsiloxane with different molecular weights, the mixed powder obtained in the step S2 and the gas-phase white carbon black 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 uniformly to form paste sizing material;
s4: and (3) cooling the pasty sizing material obtained in the step (S3) to 50 ℃, slowly sucking 4 parts of a silane cross-linking agent mixture (containing methyltriethoxysilane and vinyltrimethoxysilane in a mass ratio of methyltriethoxysilane to vinyltrimethoxysilane=3:2) by utilizing vacuum negative pressure, 1.2 parts of an organotin catalyst (namely dibutyltin dilaurate) and 1.5 parts of gamma-aminopropyl triethoxysilane, flushing nitrogen, kneading for 3 hours at normal pressure, and vacuum packaging.
Example 3:
s1: raw material pretreatment, 100 parts of alpha, omega-hydroxyl-terminated polydimethylsiloxane (comprising alpha, omega-hydroxyl-terminated polydimethylsiloxane A with the number average mass of 8 ten thousand and alpha, omega-hydroxyl-terminated polydimethylsiloxane with the number average mass of 60 ten thousand, and the mass ratio of the alpha, omega-hydroxyl-terminated polydimethylsiloxane A to the alpha, omega-hydroxyl-terminated polydimethylsiloxane is A: B=1:1), 10 parts of silane modified polyisobutene 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 coloring carbon black are respectively placed in a baking oven at 120 ℃ for drying for 8 hours for later use.
S2: mixing the colored carbon black and the activated calcium carbonate, and pre-mixing the mixture by a planetary mixer to obtain mixed powder;
s3: kneading and mixing the sizing material, putting the dried butyl rubber into a material cavity of a vacuum kneader, regulating the rotating speed of blades of the kneader, heating to 120 ℃, stirring and kneading for 20min, and then adding silane modified polyisobutene and continuously stirring for 0.5h. Adding 1/4 of the mixed powder obtained in the step S2 into a kneader and stirring for 0.5h, after uniformly mixing, adding alpha, omega-hydroxyl-terminated polydimethylsiloxane with different molecular weights, the mixed powder obtained in the step S2 and the gas-phase white carbon black 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 uniformly to form paste sizing material;
s4: and (3) cooling the pasty sizing material obtained in the step (S3) to 50 ℃, slowly sucking 4 parts of silane-silane cross-linking agent mixture (comprising methyltriethoxysilane and vinyltrimethoxysilane with the mass ratio of methyltriethoxysilane to vinyltrimethoxysilane=4:1) by using vacuum negative pressure, 1.2 parts of organotin catalyst (namely dibutyltin dilaurate) and 1.5 parts of gamma-aminopropyl triethoxysilane, flushing nitrogen, kneading for 3 hours at normal pressure, and vacuum packaging.
Comparative example 1:
raw material pretreatment, 100 parts of alpha, omega-hydroxyl-terminated polydimethylsiloxane (comprising alpha, omega-hydroxyl-terminated polydimethylsiloxane A with the number average mass of 8 ten thousand and alpha, omega-hydroxyl-terminated polydimethylsiloxane with the number average mass of 60 ten thousand, and the mass ratio of the alpha, omega-hydroxyl-terminated polydimethylsiloxane A to the alpha, omega-hydroxyl-terminated polydimethylsiloxane is A: B=3:1), 10 parts of 2.5 ten thousand molecular weight silane modified polyisobutene, 30 parts of butyl rubber, 25 parts of hydrophobic fumed silica TS-720, 5 parts of activated calcium carbonate and 1 part of coloring carbon black are respectively placed in a baking oven at 120 ℃ for drying for 8 hours for standby.
Kneading and mixing the sizing material, putting the pretreated alpha, omega-hydroxyl-terminated polydimethylsiloxane, silane modified polyisobutene and butyl rubber into a vacuum kneader at one time, regulating 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 uniformly mixing, starting a vacuum pump after the powder is added, keeping the vacuum degree at-0.1 Mpa, continuously kneading and mixing for 2 hours, and keeping the temperature at 110-130 ℃ to remove residual moisture. Continuously kneading the mixture uniformly to form paste sizing material;
then the sizing material is cooled to 50 ℃, 4 parts of a silane cross-linking agent mixture (comprising methyltriethoxysilane and vinyltrimethoxysilane with the mass ratio of methyltriethoxysilane to vinyltrimethoxysilane=4:1) and 1.2 parts of an organotin catalyst (namely dibutyltin dilaurate) are slowly sucked into the sizing material by utilizing vacuum negative pressure, and the sizing material are vacuum-packaged after being kneaded for 3 hours under normal pressure by flushing nitrogen.
Comparative example 2:
raw material pretreatment, 100 parts of alpha, omega-hydroxyl-terminated polydimethylsiloxane (comprising alpha, omega-hydroxyl-terminated polydimethylsiloxane A with the number average mass of 8 ten thousand and alpha, omega-hydroxyl-terminated polydimethylsiloxane with the number average mass of 60 ten thousand, and the mass ratio of the alpha, omega-hydroxyl-terminated polydimethylsiloxane A to the alpha, omega-hydroxyl-terminated polydimethylsiloxane is A: B=3:1), 10 parts of 2.5 ten thousand molecular weight silane modified polyisobutene, 30 parts of butyl rubber, 25 parts of hydrophobic fumed silica TS-720, 5 parts of activated calcium carbonate and 1 part of coloring carbon black are respectively placed in a baking oven at 120 ℃ for drying for 8 hours for standby.
Kneading and mixing the sizing material, putting the dried butyl rubber into a material cavity of a vacuum kneader, regulating the rotating speed of blades of the kneader, heating to 120 ℃, stirring and kneading for 20min, and then adding silane modified polyisobutene and continuously stirring for 0.5h. Mixing the colored carbon black and the activated calcium carbonate in advance, fully mixing the mixed powder by a planetary mixer, adding 1/4 of the mixed powder into a kneader, stirring for 0.5h, adding alpha, omega-hydroxyl-terminated polydimethylsiloxane with different molecular weights, the rest mixed powder and the gas-phase white carbon black in batches after the mixed powder is uniformly mixed, 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 ℃ to remove residual moisture. Continuously kneading the mixture uniformly to form paste 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-aminopropyl triethoxysilane are slowly sucked by utilizing vacuum negative pressure, nitrogen is flushed, and the mixture is kneaded for 3 hours at normal pressure and then vacuum-packaged.
The performance of the examples and comparative examples are compared as follows:
table 1 qualitative test after 7d standing 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 |
Table 2 qualitative test after 7d standing at 70 c
| Performance of | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Surface drying time/min | 45 | 38 | 32 | No surface dryness | No surface dryness |
| Tensile Strength/MPa | 2.9 | 2.3 | 1.9 | / | / |
| Elongation at break/% | 472 | 420 | 285 | / | / |
| hardness/Shore A | 32 | 32 | 24 | / | / |
Table 3 qualitative test after 10d at 70 c
| Performance of | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Surface drying time/min | 45 | 38 | 32 | No surface dryness | No surface dryness |
| Tensile Strength/MPa | 2.9 | 2.3 | 1.9 | / | / |
| Elongation at break/% | 513 | 483 | 365 | / | / |
| hardness/Shore A | 30 | 28 | 22 | / | / |
TABLE 4 pot 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 | Not less than 12 months | Not less than 10 months | Not less than 6 months | Not less than 3 months |
| Placing at 70 DEG C | ≥12d | ≥10d | ≥10d | ≥3d | ≥2d |
Wherein, the manual accelerated aging study 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, it can be considered that aging of 7d rubber in an oven at 70℃is equivalent to one year under normal conditions. Thus, the storage stability of the rubber was verified herein on accelerated aging using a laboratory oven.
As can be seen from tables 1 to 4, the examples of the present invention have a shorter tack-free time, have a longer storage property, have a smaller change in the overall properties after long-term storage, and can better ensure the storage properties of the dealcoholized room-temperature-curable silicone rubber.
Claims (6)
1. The dealcoholized room-temperature cured silicone rubber with the ultra-long storage period 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 incremental 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 alpha, omega-hydroxyl-terminated polydimethylsiloxane consists of alpha, omega-hydroxyl-terminated polydimethylsiloxane A and alpha, omega-hydroxyl-terminated polydimethylsiloxane B with the number average molecular weight of 10000-600000, and the dynamic viscosity of the alpha, omega-hydroxyl-terminated polydimethylsiloxane B at 25 ℃ is 1000-500000 cp;
the number average molecular weight of the alpha, omega-hydroxyl-terminated polydimethylsiloxane A is 80000, and the number average molecular weight of the alpha, omega-hydroxyl-terminated polydimethylsiloxane B is 600000; the mass ratio of the alpha, omega-hydroxyl-terminated polydimethylsiloxane A to the alpha, omega-hydroxyl-terminated polydimethylsiloxane B is 1-3:1, a step of;
the silane cross-linking agent mixture comprises the following components in percentage by mass: 1 and vinyltrimethoxysilane;
the preparation method of the dealcoholized room-temperature cured silicone rubber with the ultra-long storage period is characterized by comprising the following steps of:
s1: material pretreatment, namely respectively baking reinforcing filler, incremental filler, alpha, omega-hydroxyl-terminated polydimethylsiloxane, synthetic rubber, adhesive and colored carbon black at 100-120 ℃ for pre-drying treatment;
s2, pre-mixing the coloring carbon black and the incremental filler uniformly to obtain mixed powder;
s3, kneading and mixing the rubber material, firstly putting the synthetic rubber into a vacuum kneader, stirring and kneading, and then adding the adhesive for continuous stirring; adding the mixed powder obtained in the step S2, alpha, omega-hydroxyl-terminated polydimethylsiloxane and reinforcing filler in batches, starting a vacuum pump, maintaining the temperature at 110-130 ℃, removing residual moisture, and continuously and uniformly kneading to obtain pasty sizing material;
s4, cooling the pasty sizing material obtained in the step S3 to below 50 ℃, adding a silane cross-linking agent mixture, a catalyst and a coupling agent, continuously kneading under the normal pressure state of filling nitrogen, and uniformly stirring to obtain the dealcoholized room-temperature cured silicone rubber.
2. The silicone rubber of claim 1, wherein the adhesive is comprised of at least one of a silane-modified polyisobutylene, a silane-modified polyacrylate.
3. The silicone rubber according to claim 1, wherein the synthetic rubber is composed of at least one of butadiene rubber, nitrile rubber, butyl rubber.
4. The silicone rubber according to claim 1, wherein,
the reinforcing filler is hydrophobic fumed silica subjected to one or more modification treatments in silazane, siloxane, chlorosilane and silicone solution, and the BET specific surface area is 100-400 m < 2 >/g;
the incremental filler consists of at least one of hollow glass beads, diatomite and active calcium carbonate;
the catalyst is composed of at least one of an organotin catalyst, titanate and titanium chelate.
5. The silicone rubber according to claim 1, wherein the coupling agent consists of at least one of γ -aminopropyl triethoxysilane, γ -mercaptopropyl trimethoxysilane, γ -propyl trimethoxysilane.
6. The silicone rubber according to claim 1, wherein in the preparation method,
s1, drying treatment is carried out for 10-14 hours;
s3, vacuum kneading is carried out for 2-4 hours under the vacuum degree of-0.08 to-0.1 Mpa;
s4, the adding mode of each component is vacuum negative pressure suction, wherein the vacuum negative pressure is-0.02 to-0.04 Mpa; and the kneading time of step S4 is 1 to 3 hours.
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| CN114716969A (en) * | 2022-04-26 | 2022-07-08 | 江苏金贸科技发展有限公司 | High-displacement modified silicone adhesive |
| CN115785892A (en) * | 2022-11-09 | 2023-03-14 | 湖南航天三丰科工有限公司 | Silicone rubber sealant and preparation method thereof |
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