CN114874443A - Silicon rubber with low curing shrinkage rate and preparation method thereof - Google Patents
Silicon rubber with low curing shrinkage rate and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of silicone rubber, and particularly relates to silicone rubber with low curing shrinkage and a preparation method thereof. The method solves the technical problems that in the prior art, the curing yield of the silicon rubber is high, the viscosity of a curing system is obviously increased, the storage modulus is increased and the elastic modulus is higher due to the fact that a large amount of filler is added for modification. The structural formula of the T7-POSS organic silicon polymer is shown as a formula I. The T7-POSS organic silicon polymer is in a liquid state at room temperature, can be uniformly mixed with raw silicone rubber, can participate in a silicone rubber cross-linking network, is not limited, greatly reduces the shrinkage rate of the cured silicone rubber, can improve the ablation resistance of the cured silicone rubber, and plays a role of spherical nano particles in reducing the curing shrinkage rate of the silicone rubber and improving the ablation resistance of the silicone rubber to the maximum extent.
Description
Technical Field
The invention belongs to the technical field of silicone rubber, and particularly relates to silicone rubber with low curing shrinkage and a preparation method thereof.
Background
The silicone rubber is an elastomer material which is formed by linear polysiloxane after cross-linking reaction and has a three-dimensional network structure, and has a unique organic-inorganic hybrid molecular chain structure. According to different vulcanization mechanisms, silicone rubber can be divided into three types: room temperature vulcanization type, heat vulcanization type, and addition reaction type. The addition reaction type silicon rubber can be used for a long time in the temperature range of-65-200 ℃, can keep the soft elastic performance, has excellent electrical performance and chemical stability, simultaneously has weather resistance, water resistance and ozone resistance, has the remarkable characteristics of no toxicity, no odor, no corrosion, physiological inertia, low linear shrinkage rate, easy operation and the like, and is widely applied to the fields of military affairs, buildings, medical treatment, automobiles, aerospace, daily chemicals, articles for daily use and the like.
However, the strength of the silicon rubber is weak after curing, and in addition, the volume shrinkage is easy to occur due to factors such as structural change of the base rubber in the curing molecular crosslinking process of the silicon rubber, which brings obstacles to the application of the silicon rubber, and particularly causes serious problems in the application of the silicon rubber in composite materials. Research shows that the addition of a certain proportion of filler is helpful for improving the mechanical property of the material after curing and simultaneously reducing the curing shrinkage and the thermal expansion coefficient, and the principle is as follows: the addition of the filler causes the reduction of the density of functional groups of the curing system on one hand, and on the other hand, the volume occupied by the filler is not changed along with the progress of the reaction in the curing process, so that the volume shrinkage of the reaction system is slowed down. It is reported that the shape and particle size of the filler have some effect on the degree of shrinkage of the cured system, and the addition of nanoparticles having a spherical structure can promote a lower shrinkage of the material during curing compared to irregularly shaped nanoparticles. In addition, the change of the addition amount of the filler can cause different curing shrinkage degrees, and in a proper addition amount range, the addition amount of the filler is increased, so that lower curing shrinkage is obtained; however, as the addition amount of the filler continues to increase, the viscosity of the curing system obviously increases, the operation and use of the material are seriously influenced, the storage modulus also increases, and the release of shrinkage stress is not facilitated. In addition, the introduction of a large amount of filler also tends to result in a higher modulus of elasticity, thereby increasing the possibility of stress generation. Therefore, in the prior art, the nano particle filler for reducing the curing shrinkage of the silicone rubber is solid, and the addition amount of the filler is limited, so that the curing shrinkage rate required by some products is difficult to meet.
Disclosure of Invention
The invention provides a silicone rubber with low curing shrinkage, a T7-POSS organic silicon polymer and a preparation method thereof, aiming at solving the technical problems that in the prior art, the curing yield of silicone rubber is high, and modification by adding a large amount of filler is easy to cause the obvious increase of the viscosity of a curing system, the increase of the storage modulus and the higher elastic modulus.
The technical scheme adopted by the invention for solving the technical problems is as follows.
The invention provides a T7-POSS organic silicon polymer, which has the following structural formula:
wherein R is isobutyl or cyclohexyl;
the average molecular weight of the T7-POSS organic silicon polymer is 1100-120000.
The invention also provides a preparation method of the T7-POSS organic silicon polymer, which comprises the following steps:
1) preparation method of vinyl methyl organosilicon
Dissolving methyl phenyl dimethoxysilane, methyl vinyl silicone oil and dimethyl dimethoxysilane in an organic solvent, stirring uniformly, adding potassium hydroxide, heating for reflux reaction, cooling to room temperature after the reaction is finished, filtering to remove unreacted potassium hydroxide, distilling under reduced pressure to remove the organic solvent, and drying under vacuum to obtain vinyl methyl organosilicon;
2) process for preparing incompletely condensed cyclohexyltrisilanols
Under the protection of inert atmosphere, dropwise adding reactants into a device containing lithium hydroxide monohydrate, deionized water and an organic solvent, heating and refluxing for reaction after dropwise adding is completed, cooling to room temperature, adding concentrated hydrochloric acid for acidification, performing suction filtration, washing a product to be neutral by water, washing the product by acetonitrile to obtain a white solid, and performing vacuum drying to obtain incompletely condensed cyclohexyltrisilanol;
3) preparation method of T7-POSS organic silicon polymer
Dissolving the incompletely condensed cyclohexyl trisilanol prepared in the step 2) and the vinyl methyl organosilicon prepared in the step 1) in an organic solvent, heating and refluxing for reaction, cooling to room temperature after the reaction is finished, removing the organic solvent by reduced pressure distillation, and drying in vacuum to obtain the T7-POSS organosilicon polymer.
It is more preferable that the content of the organic compound,
in the step 1), the mass ratio of the methyl phenyl dimethoxysilane to the methyl vinyl silicone oil to the dimethyl dimethoxysilane to the potassium hydroxide is 2:1:2: 0.4;
in the step 2), the reactant is isobutyl trimethoxy silane or cyclohexyl trimethoxy silane, and the mass ratio of the lithium hydroxide monohydrate to the reactant is 3.3: 20;
in the step 3), the mass ratio of the incompletely condensed cyclohexyl trisilanol to the vinyl methyl organosilicon polymer is 1: 3.
It is more preferable that the content of the organic compound,
in the step 1), the heating reflux reaction is carried out at 85 ℃ for 10 hours;
in the step 2), the heating reflux reaction is carried out at 65 ℃ for 14h, and the acidification time is 2 h;
in the step 3), the heating reflux reaction is performed for 6h at 90 ℃.
The invention also provides a silicon rubber with low curing shrinkage, which comprises the component A and the component B in a mass ratio of 100: 100;
the component A is formed by uniformly mixing 30-80 parts by weight of T7-POSS organic silicon polymer and 20-30 parts by weight of methyl vinyl silicone oil, and the component B is formed by uniformly mixing 20-80 parts by weight of palladium catalyst and 5-20 parts by weight of hydrogen-containing organic silicone oil.
Preferably, the catalyst comprises, by weight, 50-80 parts of T7-POSS organic silicon polymer and 20 parts of methyl vinyl silicone oil which are uniformly mixed, and the component B comprises 20-70 parts of palladium catalyst and 5-10 parts of hydrogen-containing organic silicone oil which are uniformly mixed.
The invention also provides a preparation method of the silicone rubber with low curing shrinkage, which comprises the following steps:
and weighing the component A and the component B according to the proportion, uniformly mixing, placing in a mold, pressurizing, heating and vulcanizing to obtain the silicone rubber with low curing shrinkage.
Preferably, a three-roll mill is used to mix the component A and the component B uniformly.
Preferably, the vulcanization temperature is 160 +/-10 ℃, the vulcanization pressure is 5-10 MPa, and the vulcanization time is 20-30 min.
Compared with the prior art, the invention has the beneficial effects that:
the T7-POSS organic silicon polymer is in a liquid state at room temperature, can be uniformly mixed with raw silicon rubber, can participate in a silicon rubber cross-linking network, is not limited, greatly reduces the shrinkage rate of the silicon rubber during curing, can improve the ablation resistance of the cured silicon rubber, and plays a role of the T7-POSS organic silicon polymer in reducing the curing shrinkage rate of the silicon rubber and improving the ablation resistance of the silicon rubber to the maximum extent.
The liquid T7-POSS organic silicon polymer is used as the filler, so that the T7-POSS organic silicon polymer can be uniformly dispersed when the liquid T7-POSS organic silicon polymer is mixed with raw silicone rubber, the shrinkage rate of the silicone rubber after heating and curing can be effectively reduced, and the ablation resistance of the silicone rubber can be improved. Through test detection, the low-curing shrinkage silicone rubber has the following tensile strength at room temperature: 6.0-6.5 Mpa; non-volatile content (%): not less than 99; the working life is as follows: the time is more than or equal to 6 hours; shore a hardness after 14 days: not less than 40; curing shrinkage rate: 0.5 to 1.0 percent.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention, but it is to be understood that the description is intended to illustrate further features and advantages of the invention, and not to limit the scope of the claims.
The T7-POSS organic silicon polymer has the following structural formula:
wherein R is isobutyl or cyclohexyl;
the average molecular weight of the T7-POSS organic silicon polymer is 1100-120000.
The T7-POSS organic silicon polymer is in a liquid state at room temperature, can be uniformly mixed with raw silicon rubber, can participate in a silicon rubber cross-linking network, is not limited, greatly reduces the shrinkage rate of the silicon rubber during curing, can improve the ablation resistance of the cured silicon rubber, and plays a role of the T7-POSS organic silicon polymer in reducing the curing shrinkage rate of the silicon rubber and improving the ablation resistance of the silicon rubber to the maximum extent.
The invention provides a preparation method of a T7-POSS organic silicon polymer, which is not limited in the preparation method and comprises the following steps:
1) preparation method of vinyl methyl organosilicon
Dissolving 100g of methyl phenyl dimethoxysilane, 50g of methyl vinyl silicone oil and 100g of dimethyl dimethoxysilane in toluene, stirring for 15min, adding 20g of potassium hydroxide, heating the system to 85 ℃, stirring and refluxing for 10h, cooling to room temperature, filtering to remove unreacted potassium hydroxide, distilling under reduced pressure to remove toluene, and drying in vacuum at 40 ℃ for 24h to obtain a transparent semisolid substance, namely vinyl methyl silicone, wherein the yield is about 85%.
2) Process for preparing incompletely condensed cyclohexyltrisilanols
Weighing 3.3g of lithium hydroxide monohydrate catalyst and 1.27g of deionized water (total water amount is 2.67g), placing the mixture in a 500mL three-neck flask, adding 165mL of acetone + methanol (88 vol.% +12 vol.%) mixed solvent, slowly adding 20g of cyclohexyltrimethoxysilane or isobutyltrimethoxysilane under the protection of nitrogen, heating to 65 ℃, stirring for reacting for 14h, stopping heating, cooling to room temperature, adding 150mL of concentrated hydrochloric acid (1mol/L), acidifying, stirring for reacting for 2h, stopping reaction, performing suction filtration, washing a product with water to be neutral, washing the product with acetonitrile for three times to obtain a white solid, and performing vacuum drying at 35 ℃ for 48h to obtain incompletely condensed cyclohexyltrisilanol (T7-POSS), wherein the yield is about 60%.
3) Preparation method of T7-POSS organic silicon polymer
50g of incompletely condensed cyclohexyl trisilanol (T7-POSS) prepared in the step 2) and 150g of vinyl methyl organosilicon polymer prepared in the step 1) are dissolved in 500mL of toluene, the temperature is raised to 90 ℃, the mixture is stirred and refluxed for 6h, after the mixture is cooled to room temperature, the toluene is removed through reduced pressure distillation, and vacuum drying is carried out for 4h at the temperature of 40 ℃, so that the T7-POSS organosilicon polymer is obtained, wherein the yield is about 91%.
The synthetic route of the T7-POSS organic silicon polymer is as follows:
the invention also provides a silicon rubber with low curing shrinkage, which comprises the component A and the component B in a mass ratio of 100: 100;
the component A is formed by uniformly mixing 30-80 parts by weight of T7-POSS organic silicon polymer and 20-30 parts by weight of methyl vinyl silicone oil, and the component B is formed by uniformly mixing 20-70 parts by weight of palladium catalyst and 5-10 parts by weight of hydrogen-containing organic silicone oil.
According to the invention, preferably, the component A is prepared by uniformly mixing 50-80 parts by weight of T7-POSS organic silicon polymer and 20-30 parts by weight of methyl vinyl silicone oil, and the component B is prepared by uniformly mixing 20-80 parts by weight of palladium catalyst and 5-20 parts by weight of hydrogen-containing organic silicone oil. More preferably, the component A is formed by uniformly mixing 50 parts of T7-POSS organic silicon polymer and 20 parts of methyl vinyl silicone oil, and the component B is formed by uniformly mixing 20 parts of palladium catalyst and 5 parts of hydrogen-containing organic silicone oil; or the component A is prepared by uniformly mixing 60 parts of T7-POSS organic silicon polymer and 20 parts of methyl vinyl silicone oil, and the component B is prepared by uniformly mixing 20 parts of palladium catalyst and 5 parts of hydrogen-containing organic silicone oil, or the component A is prepared by uniformly mixing 80 parts of T7-POSS organic silicon polymer and 20 parts of methyl vinyl silicone oil, and the component B is prepared by uniformly mixing 50 parts of palladium catalyst and 10 parts of hydrogen-containing organic silicone oil, or the component A is prepared by uniformly mixing 80 parts of T7-POSS organic silicon polymer and 20 parts of methyl vinyl silicone oil, and the component B is prepared by uniformly mixing 70 parts of palladium catalyst and 10 parts of organic silicone hydrogen-containing oil.
The invention also provides a preparation method of the silicone rubber with low curing shrinkage, which comprises the following steps:
and weighing the component A and the component B according to the proportion, uniformly mixing, placing in a mold, pressurizing, heating and vulcanizing to obtain the silicone rubber with low curing shrinkage.
In the above technical scheme, a three-roll grinder is preferably used for uniformly mixing the component A and the component B.
In the technical scheme, the vulcanization temperature is preferably 160 +/-10 ℃, the vulcanization pressure is preferably 5-10 MPa, and the vulcanization time is preferably 20-30 min.
In the technical scheme, the silicon rubber with low curing shrinkage rate is a rubber sheet, and the preferred thickness is 3.2 mm.
The low-curing shrinkage silicone rubber of the invention has the following room-temperature tensile strength: 6.0-6.5 Mpa; non-volatile content (%): not less than 99; the working life is as follows: the time is more than or equal to 6 hours; shore a hardness after 14 days: not less than 40; curing shrinkage rate: 0.5 to 1.0 percent.
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified. In order to make those skilled in the art better understand the technical solution of the present invention, the present invention will be further described in detail with reference to the following embodiments.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art. Materials, reagents, devices, instruments, apparatuses and the like used in the following examples are commercially available unless otherwise specified.
The present invention is further illustrated by the following examples.
Example 1
1) Preparation of T7-POSS organosilicon polymer
1a) Preparation method of vinyl methyl organosilicon
Dissolving 100g of methyl phenyl dimethoxysilane, 50g of methyl vinyl silicone oil and 100g of dimethyl dimethoxysilane in toluene, stirring for 15min, adding 20g of potassium hydroxide, heating the system to 85 ℃, stirring and refluxing for 10h, cooling to room temperature, filtering to remove unreacted potassium hydroxide, distilling under reduced pressure to remove toluene, and drying in vacuum at 40 ℃ for 24h to obtain a transparent semisolid substance, namely vinyl methyl silicone, wherein the yield is about 85%.
1b) Process for preparing incompletely condensed cyclohexyltrisilanols
Weighing 3.3g of lithium hydroxide monohydrate catalyst and 1.27g of deionized water (total water amount is 2.67g), placing the mixture in a 500mL three-neck flask, adding 165mL of acetone + methanol (88 vol.% +12 vol.%) mixed solvent, slowly adding 20g of cyclohexyl trimethoxy silane under the protection of nitrogen, heating to 65 ℃, stirring for reaction for 14h, stopping heating, cooling to room temperature, adding 150mL of concentrated hydrochloric acid (1mol/L), acidifying, stirring for reaction for 2h, stopping reaction after acidification, performing suction filtration, washing a product with water to be neutral, washing the product with acetonitrile for three times to obtain a white solid, and performing vacuum drying at 35 ℃ for 48h to obtain incompletely condensed cyclohexyl trisilanol (T7-POSS), wherein the yield is about 60%.
1c) Preparation method of T7-POSS organic silicon polymer
50g of incompletely condensed cyclohexyl trisilanol (T7-POSS) prepared in the step 2) and 150g of vinyl methyl organosilicon polymer prepared in the step 1) are dissolved in 500mL of toluene, the temperature is raised to 90 ℃, the mixture is stirred and refluxed for 6h, after the mixture is cooled to room temperature, the toluene is removed through reduced pressure distillation, and vacuum drying is carried out for 4h at the temperature of 40 ℃, so that the T7-POSS organosilicon polymer is obtained, wherein the yield is about 91%.
2) Preparation of Silicone rubber
Taking the component A and the component B according to the mass ratio of 100:100, putting the component A and the component B into a three-roll grinder, uniformly mixing, putting the mixture into a mould, pressurizing at 160 +/-10 ℃ for 5-10 MPa, and vulcanizing for 20-30 min to obtain the silicone rubber (3.2mm thick film) with low curing shrinkage;
by weight: the component A is formed by uniformly mixing 50 parts of T7-POSS organic silicon polymer and 20 parts of methyl vinyl silicone oil; the component B is formed by uniformly mixing 20 parts of palladium catalyst and 5 parts of hydrogen-containing organic silicone oil (202).
Example 2
1) Preparation of T7-POSS organosilicon polymer
The same as in example 1.
2) Preparation of Silicone rubber
Taking the component A and the component B according to the mass ratio of 100:100, putting the component A and the component B into a three-roll grinder, uniformly mixing, putting the mixture into a mould, pressurizing at 160 +/-10 ℃ for 5-10 MPa, and vulcanizing for 20-30 min to obtain the silicone rubber (3.2mm thick film) with low curing shrinkage;
by weight: the component A is formed by uniformly mixing 60 parts of T7-POSS organic silicon polymer and 20 parts of methyl vinyl silicone oil; the component B is formed by uniformly mixing 20 parts of palladium catalyst and 10 parts of hydrogen-containing organic silicon oil.
Example 3
1) Preparation of T7-POSS organosilicon polymer
The same as in example 1.
2) Preparation of Silicone rubber
Taking the component A and the component B according to the mass ratio of 100:100, putting the component A and the component B into a three-roll grinder, uniformly mixing, putting the mixture into a mould, pressurizing at 160 +/-10 ℃ for 5-10 MPa, and vulcanizing for 20-30 min to obtain the silicon rubber (3.2mm thick rubber sheet) with low curing shrinkage;
by weight: the component A is formed by uniformly mixing 60 parts of T7-POSS organic silicon polymer and 20 parts of methyl vinyl silicone oil; the component B is formed by uniformly mixing 20 parts of palladium catalyst and 10 parts of hydrogen-containing organic silicon oil.
Example 4
1) Preparation of T7-POSS organosilicon polymer
The same as in example 1.
2) Preparation of Silicone rubber
Taking the component A and the component B according to the mass ratio of 100:100, putting the component A and the component B into a three-roll grinder, uniformly mixing, putting the mixture into a mould, pressurizing at 160 +/-10 ℃ for 5-10 MPa, and vulcanizing for 20-30 min to obtain the silicone rubber (3.2mm thick film) with low curing shrinkage;
by weight: the component A is formed by uniformly mixing 80 parts of T7-POSS organic silicon polymer and 20 parts of methyl vinyl silicone oil; the component B is prepared by uniformly mixing 50 parts of palladium catalyst and 10 parts of hydrogen-containing organic silicon oil.
Example 5
1) Preparation of T7-POSS organosilicon polymer
The cyclohexyltrimethoxysilane was replaced with isobutyltrimethoxysilane, as in example 1.
2) Preparation of Silicone rubber
Taking the component A and the component B according to the mass ratio of 100:100, putting the component A and the component B into a three-roll grinder, uniformly mixing, putting the mixture into a mould, pressurizing at 160 +/-10 ℃ for 5-10 MPa, and vulcanizing for 20-30 min to obtain the silicone rubber (3.2mm thick film) with low curing shrinkage;
by weight: the component A is formed by uniformly mixing 80 parts of T7-POSS organic silicon polymer and 20 parts of methyl vinyl silicone oil; the component B is prepared by uniformly mixing 50 parts of palladium catalyst and 10 parts of hydrogen-containing organic silicon oil.
Example 6
1) Preparation of T7-POSS organosilicon polymer
The cyclohexyltrimethoxysilane was replaced with isobutyltrimethoxysilane, as in example 1.
2) Preparation of Silicone rubber
Taking the component A and the component B according to the mass ratio of 100:100, putting the component A and the component B into a three-roll grinder, uniformly mixing, putting the mixture into a mould, pressurizing at 160 +/-10 ℃ for 5-10 MPa, and vulcanizing for 20-30 min to obtain the silicone rubber (3.2mm thick film) with low curing shrinkage;
by weight: the component A is formed by uniformly mixing 80 parts of T7-POSS organic silicon polymer and 20 parts of methyl vinyl silicone oil; the component B is prepared by uniformly mixing 70 parts of palladium catalyst and 10 parts of hydrogen-containing organic silicon oil.
The properties of the low curing shrinkage silicone rubbers (films) of examples 1 to 6 were examined. The test results are shown in table 1.
Table 1 properties of low cure shrinkage silicone rubbers (films) of examples 1 to 6
As can be seen from Table 1, the liquid T7-POSS organic silicon polymer is used as a filler, so that the T7-POSS organic silicon polymer can be uniformly dispersed when being mixed with raw silicone rubber, the shrinkage rate of the silicone rubber after being heated and cured can be effectively reduced, and the silicone rubber has excellent ablation resistance. Through test detection, the low-curing shrinkage silicone rubber has the following tensile strength at room temperature: 6.0-6.5 Mpa; non-volatile content (%): not less than 99; the working life is as follows: the time is more than or equal to 6 hours; shore a hardness after 14 days: not less than 40; curing shrinkage rate: 0.5 to 1.0 percent.
It should be understood that the above-described embodiments are merely examples for clarity of description and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither necessary nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (9)
- A T7-POSS silicone polymer characterized by the structural formula:
wherein R is isobutyl or cyclohexyl;the average molecular weight of the T7-POSS organic silicon polymer is 1100-120000. - 2. The method of making a T7-POSS silicone polymer as set forth in claim 1 comprising the steps of:1) preparation method of vinyl methyl organic siliconDissolving methyl phenyl dimethoxysilane, methyl vinyl silicone oil and dimethyl dimethoxysilane in an organic solvent, stirring uniformly, adding potassium hydroxide, heating for reflux reaction, cooling to room temperature after the reaction is finished, filtering to remove unreacted potassium hydroxide, distilling under reduced pressure to remove the organic solvent, and drying under vacuum to obtain vinyl methyl organosilicon;2) process for preparing incompletely condensed cyclohexyltrisilanolsUnder the protection of inert atmosphere, dropwise adding reactants into a device containing lithium hydroxide monohydrate, deionized water and an organic solvent, heating and refluxing to react after dropwise adding is finished, cooling to room temperature, adding concentrated hydrochloric acid to acidify, performing suction filtration, washing a product to be neutral by water, washing the product by acetonitrile to obtain a white solid, and performing vacuum drying to obtain incompletely condensed cyclohexyl trisilanol;3) preparation method of T7-POSS organic silicon polymerDissolving incompletely condensed cyclohexyl trisilanol prepared in the step 2) and vinyl methyl organosilicon prepared in the step 1) in an organic solvent, heating for reflux reaction, cooling to room temperature after the reaction is finished, removing the organic solvent by reduced pressure distillation, and drying in vacuum to obtain the T7-POSS organosilicon polymer.
- 3. The method of making a T7-POSS silicone polymer of claim 2, wherein,in the step 1), the mass ratio of the methyl phenyl dimethoxysilane to the methyl vinyl silicone oil to the dimethyl dimethoxysilane to the potassium hydroxide is 2:1:2: 0.4;in the step 2), the reactant is isobutyl trimethoxy silane or cyclohexyl trimethoxy silane, and the mass ratio of the lithium hydroxide monohydrate to the reactant is 3.3: 20;in the step 3), the mass ratio of the incompletely condensed cyclohexyl trisilanol to the vinyl methyl organosilicon polymer is 1: 3.
- 4. The method of making a T7-POSS silicone polymer of claim 2, wherein,in the step 1), the heating reflux reaction is carried out at 85 ℃ for 10 hours;in the step 2), the heating reflux reaction is carried out for 14 hours at 65 ℃ and the acidification time is 2 hours;in the step 3), the heating reflux reaction is carried out for 6 hours at 90 ℃.
- 5. The silicon rubber with low curing shrinkage is characterized in that the raw materials comprise a component A and a component B in a mass ratio of 100: 100;the component A is prepared by uniformly mixing 30-80 parts by weight of the T7-POSS organic silicon polymer of claim 1 with 20-30 parts by weight of methyl vinyl silicone oil, and the component B is prepared by uniformly mixing 20-80 parts by weight of palladium catalyst with 5-20 parts by weight of hydrogen-containing organic silicone oil.
- 6. The low-curing-shrinkage silicone rubber according to claim 5, wherein the component B is prepared by uniformly mixing 50-80 parts by weight of T7-POSS silicone polymer and 10-20 parts by weight of methyl vinyl silicone oil, and the component B is prepared by uniformly mixing 20-70 parts by weight of palladium catalyst and 5-10 parts by weight of hydrogen-containing silicone oil.
- 7. The method for preparing a low curing shrinkage silicone rubber according to claim 5 or 6, characterized by the steps of:and weighing the component A and the component B according to the proportion, uniformly mixing, placing in a mold, pressurizing, heating and vulcanizing to obtain the silicone rubber with low curing shrinkage.
- 8. The method for preparing a low curing shrinkage silicone rubber according to claim 7, wherein the component A and the component B are uniformly mixed by a three-roll mill.
- 9. The preparation method of the low curing shrinkage silicone rubber according to claim 7, wherein the vulcanization temperature is 160 ± 10 ℃, the vulcanization pressure is 5-10 MPa, and the vulcanization time is 20-30 min.
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| CN115960464B (en) * | 2022-11-07 | 2023-10-24 | 杭州师范大学 | Liquid vinyl cage polysilsesquioxane modified addition type liquid silicone rubber and preparation method thereof |
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