CN113861426B - Addition type liquid silicone rubber and preparation method thereof - Google Patents
Addition type liquid silicone rubber and preparation method thereof Download PDFInfo
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- CN113861426B CN113861426B CN202111306224.1A CN202111306224A CN113861426B CN 113861426 B CN113861426 B CN 113861426B CN 202111306224 A CN202111306224 A CN 202111306224A CN 113861426 B CN113861426 B CN 113861426B
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Abstract
The invention provides addition type liquid silicone rubber and a preparation method thereof, belonging to the technical field of silicone rubber. The method comprises the steps of mixing MQ silicon resin, polysiloxane with sulfydryl on a side chain, phenyl polysilsesquioxane containing carbon-carbon double bonds and a photoinitiator, and carrying out ultraviolet illumination on the obtained mixed solution to obtain the addition type liquid silicone rubber. According to the invention, the silicon rubber is prepared by utilizing the click reaction of sulfydryl and a carbon-carbon double bond, the reaction can be carried out under the ultraviolet illumination condition under the excitation of a photoinitiator, the use of a metal catalyst is avoided, and meanwhile, the phenyl polysilsesquioxane containing the carbon-carbon double bond is dispersed in a silicon rubber matrix, so that the mechanical property of the silicon rubber can be improved. In addition, the invention utilizes the principle of sulfydryl double bond click reaction, the reaction condition is ultraviolet irradiation, high temperature condition is not needed, the reaction is rapid, the time is short, high temperature vulcanization can be avoided, and the vulcanization time is shortened.
Description
Technical Field
The invention relates to the technical field of silicone rubber, in particular to addition type liquid silicone rubber and a preparation method thereof.
Background
The silicon rubber is very important in the field of high polymer materials, and has excellent high and low temperature resistance, inertia, transparency, insulativity and hydrophobicity. The silicone rubber is easy to color, wide in hardness range, resistant to chemicals and widely applied to the fields of buildings, medical treatment, automobiles, electric power and the like. In recent years, addition type liquid silicone rubber is a variety of organosilicon materials which develops rapidly, and has attracted attention based on the excellent performance and wide application of addition type liquid silicone rubber, and has become a research hotspot in the field of organosilicon materials.
Compared with free radical crosslinking liquid silicone rubber or polycondensation type liquid silicone rubber, the addition type liquid silicone rubber has the characteristics of simple process, easy automatic production and the like, does not shrink and is non-toxic in the vulcanization process, has excellent hydrolytic stability and good low compression deformation performance, so that some traditional mixed silicone rubber products are replaced by the liquid silicone rubber.
At present, addition type liquid silicone rubber is generally obtained by carrying out hydrosilylation reaction on vinyl-containing siloxane and siloxane containing Si-H bonds under the action of a metal compound catalyst, but the method needs to use a metal catalyst.
Disclosure of Invention
The invention aims to provide addition type liquid silicone rubber and a preparation method thereof, and the addition type liquid silicone rubber can be obtained without using a metal catalyst.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of addition type liquid silicone rubber, which comprises the following steps:
mixing MQ silicon resin, polysiloxane with a sulfydryl-containing side chain, phenyl polysilsesquioxane and a photoinitiator, and carrying out ultraviolet illumination on the obtained mixed solution to obtain addition type liquid silicon rubber; both the MQ silicone resin and the phenyl polysilsesquioxane contain carbon-carbon double bonds.
Preferably, the wavelength of the ultraviolet light is 320-400 nm, and the irradiation distance is 5-20 mm.
Preferably, the time of ultraviolet irradiation is 10-30 min; the environment temperature during the ultraviolet irradiation is 0-40 ℃.
Preferably, the content of carbon-carbon double bonds in the MQ silicon resin is 1.2-1.8 wt%, and the viscosity is 6000-10000 mPa & s.
Preferably, the MQ silicone resin has a structure shown in formula 1:
preferably, the side chain mercapto-containing polysiloxane has a mercapto content of 19.8-22.8 wt% and a molecular weight of 832-2172 g/mol.
Preferably, the side-chain mercapto-containing polysiloxane comprises poly (mercaptopropyl methyl) siloxane; the poly (mercaptopropyl methyl) siloxane has a structure represented by formula 2:
preferably, the phenyl polysilsesquioxane comprises a material represented by formula 3:
Preferably, the molar ratio of the total molar amount of carbon-carbon double bonds in the MQ silicon resin and the phenyl polysilsesquioxane to the molar amount of the mercapto groups in the side chain mercapto group-containing polysiloxane is 1: 1.
The invention provides addition type liquid silicone rubber prepared by the preparation method in the scheme.
The invention provides a preparation method of addition type liquid silicone rubber, which comprises the following steps: mixing MQ silicon resin, polysiloxane with a sulfydryl-containing side chain, phenyl polysilsesquioxane and a photoinitiator, and carrying out ultraviolet illumination on the obtained mixed solution to obtain addition type liquid silicon rubber; both the MQ silicone resin and the phenyl polysilsesquioxane contain carbon-carbon double bonds.
The invention utilizes the click reaction of sulfydryl and carbon-carbon double bonds to prepare the silicon rubber, and the reaction can be carried out under the ultraviolet illumination condition under the excitation of a photoinitiator, thereby avoiding the use of a metal catalyst.
Furthermore, the phenyl polysilsesquioxane containing carbon-carbon double bonds is dispersed in the silicon rubber matrix, so that the mechanical property of the silicon rubber can be improved.
In addition, the existing addition type liquid silicone rubber is obtained by carrying out hydrosilylation reaction on siloxane containing vinyl and siloxane containing Si-H bonds under the action of a metal compound catalyst, and the silicon rubber is usually required to be vulcanized for more than 0.5H at the temperature of 150-200 ℃; the invention utilizes the principle of sulfydryl double bond click reaction, the reaction condition is ultraviolet irradiation, high temperature condition is not needed, the reaction is rapid, the time is short (only 10-30 min of irradiation), high temperature vulcanization can be avoided, and the vulcanization time is shortened.
Drawings
FIG. 1 is a flow chart of the process for preparing addition type liquid silicone rubber according to the present invention;
FIG. 2 is a graph of the dielectric constant of a portion of silicone rubber in the present invention.
Detailed Description
The invention provides a preparation method of addition type liquid silicone rubber, which comprises the following steps:
mixing MQ silicon resin, polysiloxane with a sulfydryl-containing side chain, phenyl polysilsesquioxane and a photoinitiator, and carrying out ultraviolet illumination on the obtained mixed solution to obtain addition type liquid silicon rubber; both the MQ silicone resin and the phenyl polysilsesquioxane contain carbon-carbon double bonds.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
The preparation method comprises the step of mixing MQ silicon resin, polysiloxane with sulfydryl on a side chain, phenyl polysilsesquioxane and a photoinitiator to obtain a mixed solution.
In the present invention, the MQ silicone resin contains carbon-carbon double bonds; the content of carbon-carbon double bonds in the MQ silicon resin is preferably 1.2-1.8 wt%, and more preferably 1.4-1.6 wt%; the viscosity is preferably 6000 to 10000 mPas, more preferably 7000 to 8000 mPas. In the invention, the content of the carbon-carbon double bonds refers to the mass of the "C ═ C" in the content of the MQ silicone resin. In the present invention, the structure of the MQ silicone resin is preferably as shown in formula 1:
in the invention, the double bond content of the MQ silicon resin with the structure shown in the formula 1 is 1.6 wt%, and the viscosity is 8000 mPa.
In the present invention, the mercapto group content of the side chain mercapto group-containing polysiloxane is preferably 19.8 to 22.8 wt%, more preferably 20.5 to 22.3 wt%, and most preferably 21.97 wt%; the molecular weight is preferably 832 to 2172g/mol, more preferably 1000 to 1700g/mol, and most preferably 1502 g/mol. In the present invention, the content of the mercapto group means that the mass of "-SH" accounts for the mass of the polysiloxane.
In the present invention, the side-chain mercapto group-containing polysiloxane includes poly (mercaptopropyl methyl) siloxane; the poly (mercaptopropyl methyl) siloxane has a structure represented by formula 2:
in the present invention, the poly (mercaptopropyl methyl) siloxane had a mercapto content of 21.97 wt% and a molecular weight of 1502 g/mol.
In the present invention, the poly (mercaptopropyl methyl) siloxane is preferably prepared by the following process:
adding 30-60 mL of deionized water into a three-neck flask, dropwise adding 36 wt% of concentrated hydrochloric acid into the deionized water, and controlling the pH value of the deionized water to be 3-4; placing a three-neck flask in an ice-water bath, slowly dropwise adding 10g of mercaptopropyl methyl dimethoxysilane into the three-neck flask, and stirring for 10-60 min to enable mercaptopropyl methyl dimethoxysilane to generate a hydrolysis reaction; then, raising the reaction temperature to 60-80 ℃, reacting for 0.5-4 h, then performing vacuum filtration on the product at 40-80 ℃, removing methanol and most of water in the system, and polymerizing the hydrolysate to generate a prepolymer; reacting 80g of the prepolymer, 2g of hexamethyldisiloxane and 1.7g of acid clay catalyst in an oil bath at 100 ℃ for 2-4 h; filtering the obtained product to remove acid clay; and (3) carrying out suspended evaporation on the residual product in an oil bath environment at the temperature of 120 ℃ to remove small molecular substances to obtain the poly (mercaptopropyl methyl) siloxane.
In the present invention, the phenyl polysilsesquioxane preferably comprises a material represented by formula 3:
In the present invention, the phenyl polysilsesquioxane having the structure represented by formula 3 is preferably prepared by itself, and the preparation method is preferably: the preparation method comprises the steps of charging 300mL of acetone into a three-neck flask provided with a magnetic stirring device, a constant pressure dropping funnel and a reflux condenser, heating the mixture at 70 ℃ in an oil bath, then respectively adding 0.1mol of phenyltrimethoxysilane and 0.1mol of methacryloxy-trimethoxysilane into the flask, after the reaction system reflows, dropping 8mL of a 10mg/mL sodium hydroxide aqueous solution into the reaction system by using the constant pressure dropping funnel, then keeping the mixture at 70 ℃ for 18 hours, cooling the obtained mixture to room temperature, neutralizing the mixture to be neutral by using diluted hydrochloric acid, finally washing the mixture for 2-3 times by using deionized water, and removing acetone by rotary evaporation at 60 ℃ to obtain 10.5g of a product, namely the phenyl polysilsesquioxane containing carbon double bonds and having the structure shown in formula 3.
In the present invention, the initiator preferably includes one or more, more preferably more, of benzoin, benzoin ethyl ether, benzoin butyl ether, benzoin dimethyl ether, 2-hydroxy-2-adduct-1-phenyl ketone, and 1-hydroxy-cyclohexyl-phenyl ketone. When the initiator comprises a plurality of the above substances, the specific proportion of each initiator is not particularly required, and any proportion can be adopted. In the invention, the dosage of the initiator is preferably 0.8-1.2% of the mass of the MQ silicon resin, and more preferably 1%.
In the present invention, the molar ratio of the total molar amount of carbon-carbon double bonds in the MQ silicon resin and phenyl polysilsesquioxane to the molar amount of mercapto groups in the side chain mercapto group-containing polysiloxane is preferably 1: 1; the ratio of the mass of the phenyl polysilsesquioxane to the mass of the MQ silicon resin is preferably 0.1-0.3, and in the embodiment of the invention, the ratio is specifically 0.1, 0.15, 0.2, 0.25 or 0.3. The invention improves the mechanical property of the silicon rubber by controlling the dosage of the MQ silicon resin, the polysiloxane with the mercapto group on the side chain and the phenyl polysilsesquioxane.
In the present invention, mixing of the MQ silicon resin, the side chain mercapto group-containing polysiloxane, the phenyl polysilsesquioxane containing a carbon-carbon double bond, and the photoinitiator is preferably performed at room temperature under stirring conditions. In the present invention, the stirring time is preferably 30 to 40 minutes. The present invention has no particular requirement on the rate of agitation, and may employ agitation rates well known in the art.
In the present invention, the mixed solution is milky white.
After obtaining the mixed solution, the present invention preferably pours the mixed solution into a glass plate mold, stands at room temperature, and then performs ultraviolet irradiation.
In the invention, the standing time is preferably 0.5-3 h, and more preferably 1-2 h. According to the invention, the static standing is adopted to remove air bubbles in the mixed solution, so that the mechanical property of the cured silicone rubber is more excellent.
In the invention, the wavelength of the ultraviolet light is preferably 320-400 nm, more preferably 330-380 nm, and further preferably 340-360 nm; the irradiation distance is preferably 5 to 20mm, more preferably 8 to 16mm, and further preferably 10 to 14 mm. In the invention, the power of the ultraviolet lamp used for the ultraviolet illumination is preferably 1 kW; the time of the ultraviolet irradiation is preferably 10-30 min, and more preferably 15-25 min. The present invention preferably provides for uv illumination of the front and back sides of the glass sheet mold to promote adequate curing. In the invention, the time of ultraviolet irradiation refers to the total time of front and back side irradiation. In the present invention, the time of the front and back side ultraviolet irradiation is preferably the same.
In the invention, the environment temperature during the ultraviolet irradiation is preferably 0-40 ℃, and more preferably room temperature.
In the ultraviolet irradiation process, the photoinitiator is excited and cracked into free radicals under the irradiation of ultraviolet light, mercapto double bonds are initiated to generate a click chemical reaction, and the reaction product is cured into an crosslinked network, so that the addition type liquid silicone rubber is obtained.
FIG. 1 is a process flow diagram for preparing addition type liquid silicone rubber according to the present invention. As shown in figure 1, MQ silicon resin, polysiloxane containing sulfydryl on a side chain, phenyl polysilsesquioxane containing carbon-carbon double bonds and a photoinitiator are mixed, the obtained mixed solution is stood for defoaming and then is subjected to ultraviolet irradiation, and the addition type liquid silicone rubber is obtained.
The invention provides addition type liquid silicone rubber prepared by the preparation method in the scheme.
The addition type liquid silicone rubber and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
The MQ silicone resin used in the following examples has a structure shown in formula 1, the polysiloxane containing mercapto groups in the side chains has a structure shown in formula 2, and phenyl polysilsesquioxane (hereinafter referred to as phenyl POSS containing carbon-carbon double bonds) has a structure shown in formula 3.
Example 1
20g of MQ silicon resin, 3.39g of polysiloxane containing sulfydryl on a side chain, 2g of phenyl POSS containing carbon-carbon double bonds and 0.2g of photoinitiator (benzoin dimethyl ether) are placed into a beaker at room temperature, mechanical stirring is carried out for 35 minutes to obtain milky white solution, the milky white solution is poured into two glass plates, the beaker is placed for 1 hour at room temperature, after bubbles in the solution are removed, the beaker is placed into an ultraviolet lamp with the power of 1KW, the wavelength of 380nm and the irradiation distance of 10mm to be cured for 10 minutes respectively on the front side and the back side, and the silicon rubber is obtained. The molar ratio of the total molar weight of carbon-carbon double bonds in the raw materials to sulfydryl is 1: 1; the mass ratio of the phenyl POSS containing carbon-carbon double bonds to the MQ silicon resin is 0.1.
Example 2
This example is different from example 1 in that phenyl POSS having a carbon-carbon double bond was used in an amount of 3g, and a mercapto polysiloxane having a mercapto group in a side chain was used in an amount of 4.24g, and the rest was the same as in example 1. The molar ratio of the total molar weight of carbon-carbon double bonds in the raw materials to the mercapto groups is 1: 1; the mass ratio of the phenyl POSS containing carbon-carbon double bonds to the MQ silicon resin is 0.15.
Example 3
This example is different from example 1 in that phenyl POSS having a carbon-carbon double bond was used in an amount of 4g, and a mercapto polysiloxane having a mercapto group in a side chain was used in an amount of 5.12g, and the rest was the same as in example 1. The molar ratio of the total molar weight of carbon-carbon double bonds in the raw materials to sulfydryl is 1: 1; the mass ratio of the phenyl POSS containing carbon-carbon double bonds to the MQ silicon resin is 0.2.
Example 4
This example is different from example 1 in that phenyl POSS having a carbon-carbon double bond was used in an amount of 5g, and a mercapto polysiloxane having a mercapto group in a side chain was used in an amount of 5.97g, and the rest was the same as in example 1. The molar ratio of the total molar weight of carbon-carbon double bonds in the raw materials to sulfydryl is 1: 1; the mass ratio of the phenyl POSS containing carbon-carbon double bonds to the MQ silicon resin is 0.25.
Example 5
This example is different from example 1 in that phenyl POSS having a carbon-carbon double bond was used in an amount of 6g, and a mercapto polysiloxane having a mercapto group in a side chain was used in an amount of 6.83g, and the rest was the same as in example 1. The molar ratio of the total molar weight of carbon-carbon double bonds in the raw materials to the mercapto groups is 1: 1; the mass ratio of the phenyl POSS containing carbon-carbon double bonds to the MQ silicon resin is 0.3.
Comparative example 1
This comparative example is different from example 1 in that the amount of the side chain mercapto group-containing polysiloxane was 1.62g, and the phenyl POSS having carbon-carbon double bonds was not added, and the rest was the same as example 1. The molar ratio of the total molar weight of carbon-carbon double bonds in the raw materials to the mercapto groups is 1.1: 1.
Comparative example 2
This comparative example is different from example 1 in that the amount of the side chain mercapto group-containing polysiloxane was 1.98g, and the phenyl POSS having carbon-carbon double bonds was not added, and the rest was the same as example 1. The molar ratio of the total molar weight of carbon-carbon double bonds in the raw materials to the mercapto groups is 0.9: 1.
Comparative example 3
This comparative example is different from example 1 in that the amount of the side chain mercapto group-containing polysiloxane was 1.78g, and the phenyl POSS having carbon-carbon double bonds was not added, and the rest was the same as example 1. The molar ratio of the total molar weight of carbon-carbon double bonds in the raw materials to the mercapto groups is 1: 1.
Comparative example 4
This comparative example is different from example 1 in that the amount of the side chain mercapto polysiloxane was 2.53g, the amount of the carbon-carbon double bond-containing phenyl POSS was 1g, and the rest was the same as example 1. The molar ratio of the total molar amount of carbon-carbon double bonds in the raw materials to the mercapto groups is 1: 1; the mass ratio of the phenyl POSS containing carbon-carbon double bonds to the MQ silicon resin is 0.05.
1. The results of the thermal weight loss curve tests on the silicone rubbers of examples 2 and 4 show that the 5% initial decomposition temperatures of the silicone rubbers of examples 2 and 4 are 352 ℃ and 343 ℃, respectively, and are kept at a higher level, which indicates that the prepared silicone rubber containing the phenyl POSS with carbon-carbon double bonds has good thermal stability, higher high temperature resistance and wide application prospect.
2. FIG. 2 is a graph of the dielectric constant of silicone rubber with 3g and 5g of the carbon-carbon double bond containing phenyl POSS added in examples 2 and 4, respectively. As can be seen from fig. 2, the dielectric constants of the silicone rubbers in examples 2 and 4 are 2.54 and 2.16, respectively. When 3g and 5g of phenyl POSS containing carbon-carbon double bonds are added, the dielectric constant of the silicon rubber is reduced to be less than 3, which shows that the prepared silicon rubber containing phenyl POSS containing carbon-carbon double bonds has excellent electrical insulation performance, does not change greatly in a wide frequency range, and has wide prospect of being applied to electrical insulation materials.
3. The silicone rubbers prepared in the examples and comparative examples were tested using a model Shanghai Dejie DXLL-5000 electronic tensile tester. The bars were cut into dumbbells, measured according to GB/T528-1998, at a tensile speed of 20 mm/min. Five groups of each sample were tested and averaged. The test results are shown in Table 1.
TABLE 1 mechanical Properties of the Silicone rubbers
The data in the table 1 show that the addition type liquid silicone rubber prepared by the invention has good mechanical properties, and the results of the examples 1-5 compared with the phenyl POSS not added in the comparative example 3 show that the mechanical strength of the silicone rubber is improved by using the phenyl POSS with carbon-carbon double bonds, and the defect of low mechanical strength of the room-temperature vulcanized liquid silicone rubber is overcome. Compared with the comparative example 4, the differences of the examples 1 to 5 are that the POSS content is different, and the results show that the phenyl POSS content of the carbon-carbon double bond has obvious influence on the mechanical strength of the silicone rubber. Compared with the results of comparative examples 1 to 3, the results show that when phenyl POSS containing carbon-carbon double bonds is not added, the mechanical properties of the obtained silicone rubber are not good even if the molar ratio of the carbon-carbon double bonds to the sulfydryl in the raw materials is adjusted.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (9)
1. The preparation method of the addition type liquid silicone rubber is characterized by comprising the following steps:
mixing MQ silicon resin, polysiloxane with a sulfydryl-containing side chain, phenyl polysilsesquioxane and a photoinitiator, and carrying out ultraviolet illumination on the obtained mixed solution to obtain addition type liquid silicon rubber; both the MQ silicon resin and the phenyl polysilsesquioxane contain carbon-carbon double bonds;
the molar ratio of the total molar weight of carbon-carbon double bonds in the MQ silicon resin and the phenyl polysilsesquioxane to the molar weight of sulfydryl in the polysiloxane containing sulfydryl on the side chain is 1: 1; the ratio of the mass of the phenyl polysilsesquioxane to the mass of the MQ silicon resin is 0.1-0.3.
2. The method according to claim 1, wherein the ultraviolet light has a wavelength of 320 to 400nm and an irradiation distance of 5 to 20 mm.
3. The preparation method according to claim 1, wherein the time of the ultraviolet irradiation is 10-30 min; the environment temperature during the ultraviolet irradiation is 0-40 ℃.
4. The preparation method according to claim 1, wherein the MQ silicone resin has a carbon-carbon double bond content of 1.2 to 1.8 wt% and a viscosity of 6000 to 10000 mPa-s.
5. The preparation method of claim 4, wherein the MQ silicone resin has a structure shown in formula 1:
6. the method according to claim 1, wherein the side-chain mercapto-containing polysiloxane has a mercapto group content of 19.8 to 22.8 wt% and a molecular weight of 832 to 2172 g/mol.
7. The production method according to claim 6, wherein the side-chain mercapto-containing polysiloxane comprises poly (mercaptopropyl methyl) siloxane; the poly (mercaptopropyl methyl) siloxane has a structure represented by formula 2:
8. the method of claim 1, wherein the phenyl polysilsesquioxane comprises a material represented by formula 3:
9. The addition type liquid silicone rubber prepared by the preparation method of any one of claims 1 to 8.
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| US4810731A (en) * | 1986-01-09 | 1989-03-07 | Shin-Etsu Chemical Co., Ltd. | Ultraviolet-curable organopolysiloxane composition |
| CN104448838A (en) * | 2014-12-25 | 2015-03-25 | 中科院广州化学有限公司 | High-fluidity click light-cured heat conduction heteropolysilicon rubber and preparation method thereof |
| CN106317898A (en) * | 2016-08-17 | 2017-01-11 | 广东工业大学 | Photocured organosilicone elastomer and preparation method and application thereof |
| CN106519237A (en) * | 2016-10-21 | 2017-03-22 | 沈阳化工大学 | Diphenyl siloxy polyhedral oligomeric silsesquioxane silicone rubber cross-linking agent and preparation method thereof |
| CN107722281A (en) * | 2017-09-18 | 2018-02-23 | 青岛科技大学 | A kind of silicon rubber based on POSS reinforcement and crosslinking and preparation method thereof |
| CN109384929A (en) * | 2018-05-29 | 2019-02-26 | 山东省科学院新材料研究所 | A kind of organosilicon cross-linking agent and preparation method thereof containing polyhedral oligomeric silsesquioxane structure |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4810731A (en) * | 1986-01-09 | 1989-03-07 | Shin-Etsu Chemical Co., Ltd. | Ultraviolet-curable organopolysiloxane composition |
| CN104448838A (en) * | 2014-12-25 | 2015-03-25 | 中科院广州化学有限公司 | High-fluidity click light-cured heat conduction heteropolysilicon rubber and preparation method thereof |
| CN106317898A (en) * | 2016-08-17 | 2017-01-11 | 广东工业大学 | Photocured organosilicone elastomer and preparation method and application thereof |
| CN106519237A (en) * | 2016-10-21 | 2017-03-22 | 沈阳化工大学 | Diphenyl siloxy polyhedral oligomeric silsesquioxane silicone rubber cross-linking agent and preparation method thereof |
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