CN114874443B - Silicon rubber with low curing shrinkage and preparation method thereof - Google Patents
Silicon rubber with low curing shrinkage and preparation method thereof Download PDFInfo
- Publication number
- CN114874443B CN114874443B CN202210686888.3A CN202210686888A CN114874443B CN 114874443 B CN114874443 B CN 114874443B CN 202210686888 A CN202210686888 A CN 202210686888A CN 114874443 B CN114874443 B CN 114874443B
- Authority
- CN
- China
- Prior art keywords
- silicone rubber
- poss
- parts
- component
- organosilicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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. Solves the technical problems of high curing yield of the silicone rubber, obvious increase of viscosity of a curing system, increase of storage modulus and higher elastic modulus caused by adding a large amount of fillers for modification in the prior art. The structural formula of the T7-POSS organosilicon polymer is shown as 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 crosslinking network, is not limited, greatly reduces the shrinkage rate of the cured silicone rubber, and can also improve the ablation resistance of the cured silicone rubber, so that the spherical nano particles play the roles of reducing the curing shrinkage rate of the silicone rubber and improving the ablation resistance of the silicone rubber to the greatest 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 with a three-dimensional network structure formed after the cross-linking reaction of the linear polysiloxane, and has a unique organic-inorganic hybrid molecular chain structure. Silicone rubber can be classified into three categories according to the vulcanization mechanism: room temperature vulcanizing type, heating vulcanizing type and addition reaction type. The addition reaction type silicon rubber can be used for a long time within the temperature range of-65 ℃ to 200 ℃, can keep the soft and elastic performance, has excellent electrical performance and chemical stability, has the characteristics of weather resistance, water resistance and ozone resistance, has the remarkable characteristics of no toxicity, no smell, no corrosiveness, physiological inertia, low linear shrinkage rate, easy operation and the like, and is widely applied to the fields of military, construction, medical treatment, automobiles, aerospace, daily chemical, articles for daily use and the like.
However, the silicone rubber has weak strength after curing, and the silicone rubber is easy to generate the problem of volume shrinkage after curing due to factors such as structural change of the base rubber during the crosslinking process of cured molecules, which brings barriers to the application of the silicone rubber, and particularly, the silicone rubber has serious problems in the application of composite materials. Research shows that the addition of a certain proportion of filler is helpful for improving the mechanical property of the cured material and reducing the curing shrinkage and the thermal expansion coefficient, and the principle is as follows: the addition of the filler on the one hand causes the reduction of the functional group density of the curing system, and on the other hand, the volume occupied by the filler does not change with the progress of the reaction in the curing process, thereby slowing down the volume shrinkage of the reaction system. It is reported that the shape and particle size of the filler have a certain effect on the shrinkage of the cured system, and the addition of nanoparticles having a spherical structure can promote lower shrinkage of the material during curing than irregularly shaped nanoparticles. In addition, the change of the addition amount of the filler can also cause different curing shrinkage degrees, and in the proper addition amount range, the improvement of the addition amount of the filler is beneficial to obtaining lower curing shrinkage; however, as the addition amount of the filler is continuously increased, the viscosity of the curing system is obviously increased, the operation and the use of the material are seriously affected, and the storage modulus is also increased, so that the release of shrinkage stress is not facilitated. In addition, the large amount of filler introduced also tends to cause a higher modulus of elasticity, thereby increasing the possibility of stress generation. Therefore, the nanoparticle filler for reducing the curing shrinkage of the silicone rubber in the prior art is solid, and the filler addition amount 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 organosilicon polymer and a preparation method thereof, which are used for solving the technical problems of high curing yield of the silicone rubber, obvious increase of viscosity of a curing system, increase of storage modulus and higher elastic modulus caused by adding a large amount of fillers for modification in the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows.
The invention provides a T7-POSS organosilicon polymer, which has the following structural formula:
wherein R is isobutyl or cyclohexyl;
the average molecular weight of the T7-POSS organosilicon polymer is 1100-120000.
The invention also provides a preparation method of the T7-POSS organosilicon polymer, which comprises the following steps:
1) Preparation method of vinyl methyl organosilicon
Dissolving methyl phenyl dimethoxy silane, methyl vinyl silicone oil and dimethyl dimethoxy silane in an organic solvent, uniformly stirring, adding potassium hydroxide, heating and refluxing to react, 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 in vacuum to obtain vinyl methyl organosilicon;
2) Process for the preparation of incompletely condensed cyclohexyl trisilanols
Dropwise adding reactants into a device provided with lithium hydroxide monohydrate, deionized water and an organic solvent under the protection of inert atmosphere, heating and refluxing for reaction after the dropwise adding is completed, cooling to room temperature, adding concentrated hydrochloric acid for acidification, carrying out suction filtration, washing a product with water to be neutral, washing with acetonitrile to obtain a white solid, and carrying out vacuum drying to obtain incompletely condensed cyclohexyl trisilanol;
3) Preparation method of T7-POSS organosilicon polymer
And (3) dissolving the incompletely condensed cyclohexyl trisilicon alcohol 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, distilling under reduced pressure to remove the organic solvent, and drying in vacuum to obtain the T7-POSS organosilicon polymer.
It is more preferable that the method further comprises the steps of,
in the step 1), the mass ratio of the methyl phenyl dimethoxy silane to the methyl vinyl silicone oil to the dimethyl dimethoxy silane to the potassium hydroxide is 2:1:2:0.4;
in the step 2), the reactant is isobutyl trimethoxysilane or cyclohexyl trimethoxysilane, 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 method further comprises the steps of,
in the step 1), the heating reflux reaction is carried out for 10 hours at 85 ℃;
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 reflux reaction is heated to 90 ℃ and reflux is carried out for 6 hours.
The invention also provides the silicone rubber with low curing shrinkage, which comprises a component A and a component B in a mass ratio of 100:100;
the component A is formed by uniformly mixing 30-80 parts of T7-POSS organosilicon polymer and 20-30 parts of methyl vinyl silicone oil by weight, and the component B is formed by uniformly mixing 20-80 parts of palladium catalyst and 5-20 parts of hydrogen-containing organosilicon oil by weight.
Preferably, the catalyst comprises 50-80 parts by weight of T7-POSS organosilicon polymer and 20 parts by weight of methyl vinyl silicone oil, and the component B comprises 20-70 parts by weight of palladium catalyst and 5-10 parts by weight of hydrogen-containing organosilicon oil.
The invention also provides a preparation method of the silicon 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 die, and pressurizing, heating and vulcanizing to obtain the silicone rubber with low curing shrinkage.
Preferably, a three-roll mill is used to mix the A and B components 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 provided by the invention is in a liquid state at room temperature, can be uniformly mixed with raw silicone rubber, can participate in a silicone rubber crosslinking network, is not limited, greatly reduces the shrinkage rate of the cured silicone rubber, and can also improve the ablation resistance of the cured silicone rubber, so that the effect of the T7-POSS organic silicon polymer in reducing the curing shrinkage rate of the silicone rubber and improving the ablation resistance of the silicone rubber is exerted to the greatest extent.
The invention takes the liquid T7-POSS organosilicon polymer as the filler, can ensure that the T7-POSS organosilicon polymer is uniformly dispersed when being mixed with the raw silicone rubber, can effectively reduce the shrinkage rate of the silicone rubber after being heated and cured, and simultaneously improves the ablation resistance of the silicone rubber. Through test detection, the low-cure shrinkage silicone rubber disclosed by the invention has the following tensile strength at room temperature: 6.0-6.5 Mpa; non-volatile content (%): more than or equal to 99; pot life: not less than 6 hours; shore a hardness after 14 days: more than or equal to 40; cure shrinkage: 0.5 to 1.0 percent.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below, but it is to be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
The T7-POSS organosilicon polymer has the following structural formula:
wherein R is isobutyl or cyclohexyl;
the average molecular weight of the T7-POSS organosilicon polymer is 1100-120000.
The T7-POSS organic silicon polymer provided by the invention is in a liquid state at room temperature, can be uniformly mixed with raw silicone rubber, can participate in a silicone rubber crosslinking network, is not limited, greatly reduces the shrinkage rate of the cured silicone rubber, and can also improve the ablation resistance of the cured silicone rubber, so that the effect of the T7-POSS organic silicon polymer in reducing the curing shrinkage rate of the silicone rubber and improving the ablation resistance of the silicone rubber is exerted to the greatest extent.
The invention provides a preparation method of a T7-POSS organosilicon polymer, which is not limited to the method, and comprises the following steps:
1) Preparation method of vinyl methyl organosilicon
100g of methyl phenyl dimethoxy silane, 50g of methyl vinyl silicone oil and 100g of dimethyl dimethoxy silane are dissolved in toluene and stirred for 15min, after 20g of potassium hydroxide is added, the system is heated to 85 ℃, stirred and refluxed for 10h, cooled to room temperature, filtered to remove unreacted potassium hydroxide, distilled under reduced pressure to remove toluene, and dried in vacuum at 40 ℃ for 24h, thus obtaining transparent semi-solid substance, namely vinyl methyl organosilicon, with the yield of about 85%.
2) Process for the preparation of incompletely condensed cyclohexyl trisilanols
3.3g of lithium hydroxide monohydrate and 1.27g of deionized water (total water content is 2.67 g) are weighed and placed in a 500mL three-neck flask, 165mL of a mixed solvent of acetone and methanol (88 vol% +12 vol%) is added, under the protection of nitrogen, 20g of cyclohexyl trimethoxy silane or isobutyl trimethoxy silane is slowly added, the temperature is raised to 65 ℃, stirring reaction is carried out for 14 hours, heating is stopped, cooling is carried out to room temperature, 150mL of concentrated hydrochloric acid (1 mol/L) is added for acidification, stirring reaction is carried out for 2 hours, reaction is stopped after acidification treatment, suction filtration is carried out, the product is washed with water to be neutral, acetonitrile is used for three times, white solid is obtained, vacuum drying is carried out at 35 ℃ for 48 hours, and the incompletely condensed cyclohexyl trisilyl (T7-POSS) is obtained, and the yield is about 60%.
3) Preparation method of T7-POSS organosilicon polymer
50g of the incompletely condensed cyclohexyl trisilicon alcohol (T7-POSS) prepared in the step 2) and 150g of the 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 6 hours, after cooling to room temperature, toluene is removed by reduced pressure distillation, and the mixture is dried for 4 hours at 40 ℃ in vacuum, so that the T7-POSS organosilicon polymer is obtained, and the yield is about 91%.
The synthetic route of the T7-POSS organosilicon polymer provided by the invention is as follows:
the invention also provides the silicone rubber with low curing shrinkage, which comprises a component A and a component B in a mass ratio of 100:100;
the component A is formed by uniformly mixing 30-80 parts of T7-POSS organosilicon polymer and 20-30 parts of methyl vinyl silicone oil, and the component B is formed by uniformly mixing 20-70 parts of palladium catalyst and 5-10 parts of hydrogen-containing organosilicon oil.
In the invention, based on parts by weight, the component A is preferably formed by uniformly mixing 50-80 parts of T7-POSS organosilicon polymer and 20-30 parts of methyl vinyl silicone oil, and the component B is formed by uniformly mixing 20-80 parts of palladium catalyst and 5-20 parts of hydrogen-containing organosilicon oil. More preferably, the component A is formed by uniformly mixing 50 parts of T7-POSS organosilicon 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 organosilicon oil; or, the component A is formed by uniformly mixing 60 parts of T7-POSS organosilicon 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 organosilicon oil, or, the component A is formed by uniformly mixing 80 parts of T7-POSS organosilicon polymer and 20 parts of methyl vinyl silicone oil, the component B is formed by uniformly mixing 50 parts of palladium catalyst and 10 parts of hydrogen-containing organosilicon oil, or, the component A is formed by uniformly mixing 80 parts of T7-POSS organosilicon polymer and 20 parts of methyl vinyl silicone oil, and the component B is formed by uniformly mixing 70 parts of palladium catalyst and 10 parts of hydrogen-containing organosilicon oil.
The invention also provides a preparation method of the silicon 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 die, and pressurizing, heating and vulcanizing to obtain the silicone rubber with low curing shrinkage.
In the technical scheme, a three-roller grinder is preferably adopted to uniformly mix 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 is a rubber sheet, and the thickness is preferably 3.2mm.
The low-cure shrinkage silicone rubber of the invention has room temperature tensile strength: 6.0-6.5 Mpa; non-volatile content (%): more than or equal to 99; pot life: not less than 6 hours; shore a hardness after 14 days: more than or equal to 40; cure shrinkage: 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 indicated. In order to enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be described in further detail with reference to examples.
In the following examples, various processes and methods, which are not described in detail, are conventional methods well known in the art. Materials, reagents, devices, instruments, equipment and the like used in the examples described below are commercially available unless otherwise specified.
The invention is further illustrated below with reference to examples.
Example 1
1) Preparation of T7-POSS organosilicon polymers
1a) Preparation method of vinyl methyl organosilicon
100g of methyl phenyl dimethoxy silane, 50g of methyl vinyl silicone oil and 100g of dimethyl dimethoxy silane are dissolved in toluene and stirred for 15min, after 20g of potassium hydroxide is added, the system is heated to 85 ℃, stirred and refluxed for 10h, cooled to room temperature, filtered to remove unreacted potassium hydroxide, distilled under reduced pressure to remove toluene, and dried in vacuum at 40 ℃ for 24h, thus obtaining transparent semi-solid substance, namely vinyl methyl organosilicon, with the yield of about 85%.
1b) Process for the preparation of incompletely condensed cyclohexyl trisilanols
3.3g of lithium hydroxide monohydrate and 1.27g of deionized water (total water content is 2.67 g) are weighed and placed in a 500mL three-neck flask, 165mL of a mixed solvent of acetone and methanol (88 vol% +12 vol%) is added, 20g of cyclohexyl trimethoxysilane is slowly added under the protection of nitrogen, the temperature is raised to 65 ℃, stirring reaction is carried out for 14 hours, heating is stopped, the temperature is reduced to room temperature, 150mL of concentrated hydrochloric acid (1 mol/L) is added for acidification, stirring reaction is carried out for 2 hours, reaction is stopped after acidification treatment, suction filtration is carried out, the product is washed with water to be neutral, acetonitrile is used for three times, white solid is obtained, vacuum drying is carried out at 35 ℃ for 48 hours, and the incompletely condensed cyclohexyl trisilanol (T7-POSS) is obtained, and the yield is about 60%.
1c) Preparation method of T7-POSS organosilicon polymer
50g of the incompletely condensed cyclohexyl trisilicon alcohol (T7-POSS) prepared in the step 2) and 150g of the 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 6 hours, after cooling to room temperature, toluene is removed by reduced pressure distillation, and the mixture is dried for 4 hours at 40 ℃ in vacuum, so that the T7-POSS organosilicon polymer is obtained, and 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 components A and B into a three-roller grinder, uniformly mixing, putting the mixture into a die, pressurizing the mixture at 160+/-10 ℃ for 5-10 MPa, and vulcanizing the mixture for 20-30 min to obtain the silicone rubber (3.2 mm thick sheet) with low curing shrinkage rate;
based on weight: the component A is formed by uniformly mixing 50 parts of T7-POSS organosilicon 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 polymers
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 components A and B into a three-roller grinder, uniformly mixing, putting the mixture into a die, pressurizing the mixture at 160+/-10 ℃ for 5-10 MPa, and vulcanizing the mixture for 20-30 min to obtain the silicone rubber (3.2 mm thick sheet) with low curing shrinkage rate;
based on weight: the component A is formed by uniformly mixing 60 parts of T7-POSS organosilicon 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 silicone oil.
Example 3
1) Preparation of T7-POSS organosilicon polymers
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 components A and B into a three-roller grinder, uniformly mixing, putting the mixture into a die, pressurizing the mixture at 160+/-10 ℃ for 5-10 MPa, and vulcanizing the mixture for 20-30 min to obtain the silicone rubber (3.2 mm thick sheet) with low curing shrinkage rate;
based on weight: the component A is formed by uniformly mixing 60 parts of T7-POSS organosilicon 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 silicone oil.
Example 4
1) Preparation of T7-POSS organosilicon polymers
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 components A and B into a three-roller grinder, uniformly mixing, putting the mixture into a die, pressurizing the mixture at 160+/-10 ℃ for 5-10 MPa, and vulcanizing the mixture for 20-30 min to obtain the silicone rubber (3.2 mm thick sheet) with low curing shrinkage rate;
based on weight: the component A is formed by uniformly mixing 80 parts of T7-POSS organosilicon polymer and 20 parts of methyl vinyl silicone oil; the component B is formed by uniformly mixing 50 parts of palladium catalyst and 10 parts of hydrogen-containing organic silicone oil.
Example 5
1) Preparation of T7-POSS organosilicon polymers
The procedure of example 1 was repeated except that the cyclohexanetrimethoxysilane was replaced with isobutyltrimethoxysilane.
2) Preparation of Silicone rubber
Taking the component A and the component B according to the mass ratio of 100:100, putting the components A and B into a three-roller grinder, uniformly mixing, putting the mixture into a die, pressurizing the mixture at 160+/-10 ℃ for 5-10 MPa, and vulcanizing the mixture for 20-30 min to obtain the silicone rubber (3.2 mm thick sheet) with low curing shrinkage rate;
based on weight: the component A is formed by uniformly mixing 80 parts of T7-POSS organosilicon polymer and 20 parts of methyl vinyl silicone oil; the component B is formed by uniformly mixing 50 parts of palladium catalyst and 10 parts of hydrogen-containing organic silicone oil.
Example 6
1) Preparation of T7-POSS organosilicon polymers
The procedure of example 1 was repeated except that the cyclohexanetrimethoxysilane was replaced with isobutyltrimethoxysilane.
2) Preparation of Silicone rubber
Taking the component A and the component B according to the mass ratio of 100:100, putting the components A and B into a three-roller grinder, uniformly mixing, putting the mixture into a die, pressurizing the mixture at 160+/-10 ℃ for 5-10 MPa, and vulcanizing the mixture for 20-30 min to obtain the silicone rubber (3.2 mm thick sheet) with low curing shrinkage rate;
based on weight: the component A is formed by uniformly mixing 80 parts of T7-POSS organosilicon polymer and 20 parts of methyl vinyl silicone oil; the component B is formed by uniformly mixing 70 parts of palladium catalyst and 10 parts of hydrogen-containing organic silicone oil.
The properties of the silicone rubbers (films) of examples 1 to 6 having low cure shrinkage were examined. The test results are shown in Table 1.
TABLE 1 Properties of Low cure shrinkage Silicone rubber (film) from examples 1 to 6
As can be seen from Table 1, the invention uses the liquid T7-POSS organosilicon polymer as the filler, can ensure that the T7-POSS organosilicon polymer is uniformly dispersed when being mixed with the raw silicone rubber, can effectively reduce the shrinkage rate of the silicone rubber after being heated and cured, and has excellent ablation resistance. Through test detection, the low-cure shrinkage silicone rubber disclosed by the invention has the following tensile strength at room temperature: 6.0-6.5 Mpa; non-volatile content (%): more than or equal to 99; pot life: not less than 6 hours; shore a hardness after 14 days: more than or equal to 40; cure shrinkage: 0.5 to 1.0 percent.
It is apparent that the above embodiments are merely examples for clarity of illustration and are not limiting examples. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (9)
- T7-POSS silicone polymer, characterized by the following structural formula:wherein R is isobutyl or cyclohexyl;the average molecular weight of the T7-POSS organosilicon polymer is 1100-120000.
- 2. The method for preparing the T7-POSS organosilicon polymer according to claim 1, comprising the following steps:1) Preparation method of vinyl methyl organosiliconDissolving methyl phenyl dimethoxy silane, methyl vinyl silicone oil and dimethyl dimethoxy silane in an organic solvent, uniformly stirring, adding potassium hydroxide, heating and refluxing to react, 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 in vacuum to obtain vinyl methyl organosilicon;2) Process for the preparation of incompletely condensed cyclohexyl trisilanols or isobutyl trisilanolsDropwise adding reactants into a device provided with lithium hydroxide monohydrate, deionized water and an organic solvent under the protection of inert atmosphere, heating and refluxing for reaction after the dropwise adding is completed, cooling to room temperature, adding concentrated hydrochloric acid for acidification, carrying out suction filtration, washing a product with water to be neutral, washing with acetonitrile to obtain white solid, and carrying out vacuum drying to obtain incompletely condensed cyclohexyl trisilanol or isobutyl trisilanol;3) Preparation method of T7-POSS organosilicon polymerAnd 2) dissolving the incompletely condensed cyclohexyl trisilanol or isobutyl 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.
- 3. The method for producing a T7-POSS silicone polymer according to claim 2, characterized in that,in the step 1), the mass ratio of the methyl phenyl dimethoxy silane to the methyl vinyl silicone oil to the dimethyl dimethoxy silane to the potassium hydroxide is 2:1:2:0.4;in the step 2), the reactant is isobutyl trimethoxysilane or cyclohexyl trimethoxysilane, 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 or isobutyl trisilanol to the vinyl methyl organosilicon is 1:3.
- 4. The method for producing a T7-POSS silicone polymer according to claim 2, characterized in that,in the step 1), the heating reflux reaction is carried out for 10 hours at 85 ℃;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 reflux reaction is heated to 90 ℃ and reflux is carried out for 6 hours.
- 5. The silicone 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 formed by uniformly mixing 30-80 parts of the T7-POSS organosilicon polymer according to claim 1 with 20-30 parts of methyl vinyl silicone oil, and the component B is formed by uniformly mixing 20-80 parts of palladium catalyst with 5-20 parts of hydrogen-containing organosilicon oil.
- 6. The low cure shrinkage silicone rubber according to claim 5, wherein the composition comprises, by weight, 50 to 80 parts of the T7-POSS silicone polymer and 10 to 20 parts of the methyl vinyl silicone oil, and the composition B comprises 20 to 70 parts of the palladium catalyst and 5 to 10 parts of the hydrogen-containing silicone oil.
- 7. The method for producing a low cure shrinkage silicone rubber according to claim 5 or 6, comprising the steps of:and weighing the component A and the component B according to the proportion, uniformly mixing, placing in a die, and pressurizing, heating and vulcanizing to obtain the silicone rubber with low curing shrinkage.
- 8. The method for preparing a low cure shrinkage silicone rubber according to claim 7, wherein the a-component and the B-component are uniformly mixed by a three-roll mill.
- 9. The method for preparing a silicone rubber with low cure shrinkage 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210686888.3A CN114874443B (en) | 2022-06-17 | 2022-06-17 | Silicon rubber with low curing shrinkage and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210686888.3A CN114874443B (en) | 2022-06-17 | 2022-06-17 | Silicon rubber with low curing shrinkage and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114874443A CN114874443A (en) | 2022-08-09 |
| CN114874443B true CN114874443B (en) | 2023-10-13 |
Family
ID=82681867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210686888.3A Active CN114874443B (en) | 2022-06-17 | 2022-06-17 | Silicon rubber with low curing shrinkage and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114874443B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5484867A (en) * | 1993-08-12 | 1996-01-16 | The University Of Dayton | Process for preparation of polyhedral oligomeric silsesquioxanes and systhesis of polymers containing polyhedral oligomeric silsesqioxane group segments |
| JP2009263596A (en) * | 2008-04-30 | 2009-11-12 | Konishi Kagaku Ind Co Ltd | Incompletely condensed oligosilsesquioxane and its production method |
| CN103602070A (en) * | 2013-11-28 | 2014-02-26 | 中国科学院长春应用化学研究所 | Silicone rubber composite material and preparation method thereof |
| CN103613610A (en) * | 2013-07-04 | 2014-03-05 | 东莞上海大学纳米技术研究院 | Vinyl hepta-phenyl silsesquioxane material and preparation method |
| CN104327289A (en) * | 2014-09-15 | 2015-02-04 | 杭州师范大学 | Preparation method and application of organic functional group-terminated trapezoid polysilsesquioxane-containing block optical transparent organic silicone resin |
| CN104559195A (en) * | 2014-12-26 | 2015-04-29 | 东莞市长安东阳光铝业研发有限公司 | POSS modified liquid silicone rubber and preparation method thereof |
| CN104829826A (en) * | 2015-05-13 | 2015-08-12 | 中国科学院长春应用化学研究所 | Primary-hydroxyl-terminated polyepichlorohydrin and preparation method thereof |
| CN104892922A (en) * | 2015-04-14 | 2015-09-09 | 中国科学院长春应用化学研究所 | Hydroxyl terminated polyepichlorohydrin and preparation method thereof |
| CN106432728A (en) * | 2016-09-21 | 2017-02-22 | 沈阳化工大学 | Phenyl(dimethylsiloxy) cage type silsesquioxane silicone rubber crosslinking agent and preparation method thereof |
| CN112143169A (en) * | 2020-06-30 | 2020-12-29 | 西北工业大学 | High-silica fiber reinforced reactive silsesquioxane modified hybrid phenolic composite material and preparation method thereof |
| CN113105605A (en) * | 2021-04-06 | 2021-07-13 | 杭州师范大学 | UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material and preparation and application thereof |
-
2022
- 2022-06-17 CN CN202210686888.3A patent/CN114874443B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5484867A (en) * | 1993-08-12 | 1996-01-16 | The University Of Dayton | Process for preparation of polyhedral oligomeric silsesquioxanes and systhesis of polymers containing polyhedral oligomeric silsesqioxane group segments |
| JP2009263596A (en) * | 2008-04-30 | 2009-11-12 | Konishi Kagaku Ind Co Ltd | Incompletely condensed oligosilsesquioxane and its production method |
| CN103613610A (en) * | 2013-07-04 | 2014-03-05 | 东莞上海大学纳米技术研究院 | Vinyl hepta-phenyl silsesquioxane material and preparation method |
| CN103602070A (en) * | 2013-11-28 | 2014-02-26 | 中国科学院长春应用化学研究所 | Silicone rubber composite material and preparation method thereof |
| CN104327289A (en) * | 2014-09-15 | 2015-02-04 | 杭州师范大学 | Preparation method and application of organic functional group-terminated trapezoid polysilsesquioxane-containing block optical transparent organic silicone resin |
| CN104559195A (en) * | 2014-12-26 | 2015-04-29 | 东莞市长安东阳光铝业研发有限公司 | POSS modified liquid silicone rubber and preparation method thereof |
| CN104892922A (en) * | 2015-04-14 | 2015-09-09 | 中国科学院长春应用化学研究所 | Hydroxyl terminated polyepichlorohydrin and preparation method thereof |
| CN104829826A (en) * | 2015-05-13 | 2015-08-12 | 中国科学院长春应用化学研究所 | Primary-hydroxyl-terminated polyepichlorohydrin and preparation method thereof |
| CN106432728A (en) * | 2016-09-21 | 2017-02-22 | 沈阳化工大学 | Phenyl(dimethylsiloxy) cage type silsesquioxane silicone rubber crosslinking agent and preparation method thereof |
| CN112143169A (en) * | 2020-06-30 | 2020-12-29 | 西北工业大学 | High-silica fiber reinforced reactive silsesquioxane modified hybrid phenolic composite material and preparation method thereof |
| CN113105605A (en) * | 2021-04-06 | 2021-07-13 | 杭州师范大学 | UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material and preparation and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Improving the Damping Properties of Nanocomposites by Monodispersed Hybrid POSS Nanoparticles: Preparation and Mechanisms;wei wei等;《Polymers》;第11卷(第4期);第1-15页 * |
| 胡建坤等.半缩合低聚硅氧烷的合成及应用进展.《有机硅材料》.2014,(第5期),第382-387页. * |
| 范敬辉等.笼形倍半硅氧烷/硅橡胶复合材料的性能研究.《橡胶工业》.2013,第60卷(第60期),第202-205页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114874443A (en) | 2022-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Thermal behaviour and mechanical properties of novel RTV silicone rubbers using divinyl-hexa [(trimethoxysilyl) ethyl]-POSS as cross-linker | |
| CN107722281B (en) | Silicon rubber based on POSS reinforcement and crosslinking and preparation method thereof | |
| CN109776804B (en) | Cross-linkable POSS reinforced polyurethane nano hybrid material and preparation method thereof | |
| CN114874443B (en) | Silicon rubber with low curing shrinkage and preparation method thereof | |
| Zhang et al. | Synthesis and characterization of addition-type silicone rubbers (ASR) using a novel cross linking agent PH prepared by vinyl-POSS and PMHS | |
| Dong et al. | Amine-functionalized POSS as cross-linkers of polysiloxane containing γ-chloropropyl groups for preparing heat-curable silicone rubber | |
| EP1789254A2 (en) | High use temperature nanocompositie resins | |
| JP4998702B2 (en) | Articles coated or surface-treated with a coating agent composition | |
| CN109735203B (en) | Semi-closed cage-shaped trifunctional epoxy ether group POSS (polyhedral oligomeric silsesquioxane) composite material, paint and preparation method | |
| CN110437624B (en) | Transparent bifunctional epoxy resin-silicon rubber block network material | |
| CN110698613A (en) | Preparation method of high-crosslinking organic silicon rubber | |
| CN116535755B (en) | Modified hydrogenated nitrile rubber composition and application thereof in sealing oil injection ring | |
| CN115960464B (en) | Liquid vinyl cage polysilsesquioxane modified addition type liquid silicone rubber and preparation method thereof | |
| Dong et al. | Aminopropyl-modified silica as cross-linkers of polysiloxane containing γ-chloropropyl groups for preparing heat-curable silicone rubber | |
| Yuan et al. | A novel LDH nanofiller intercalated by silsesquioxane for preparing organic/inorganic hybrid composites | |
| CN109897227B (en) | Polyether amine modified graphene oxide and epoxy nanocomposite thereof | |
| KR20140012333A (en) | Graphene-polyamide based composite and manufacturing method thereof | |
| CN114874496B (en) | High-strength low-curing shrinkage silicone rubber and preparation method thereof | |
| Mominul Alam et al. | Preparation and characterization of rigid polyimide-clay-polydimethylsiloxane hybrid | |
| CN114958001B (en) | High-strength ablation-resistant silicone rubber and preparation method thereof | |
| CN108864406B (en) | High-mechanical-strength GO/TPU in-situ polymerization method | |
| CN114891223A (en) | Low-shrinkage condensed type organic silicon rubber and preparation method thereof | |
| Selvaganapathi et al. | Preparation of siloxane-modified tetraglycidyl epoxy-clay nanocomposites-its thermal and morphological properties | |
| CN111958891A (en) | Polysilane type tyre isolating agent | |
| CN115073744B (en) | High-cohesiveness silicon rubber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |