CN114891223A - Low-shrinkage condensed type organic silicon rubber and preparation method thereof - Google Patents
Low-shrinkage condensed type organic silicon rubber and preparation method thereof Download PDFInfo
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 44
- 239000004945 silicone rubber Substances 0.000 claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 229920001558 organosilicon polymer Polymers 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 229920002545 silicone oil Polymers 0.000 claims abstract description 22
- 239000003921 oil Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- -1 methoxy trisilanol Chemical compound 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000020477 pH reduction Effects 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- ITAHRPSKCCPKOK-UHFFFAOYSA-N ethyl trimethyl silicate Chemical compound CCO[Si](OC)(OC)OC ITAHRPSKCCPKOK-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 5
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- FXHMPXXENORCTG-UHFFFAOYSA-N CCO[SiH](O)[SiH2][SiH3] Chemical compound CCO[SiH](O)[SiH2][SiH3] FXHMPXXENORCTG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000306 component Substances 0.000 abstract description 52
- 238000004132 cross linking Methods 0.000 abstract description 5
- 229920001971 elastomer Polymers 0.000 abstract description 4
- 239000008358 core component Substances 0.000 abstract description 3
- 238000001723 curing Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 12
- 239000000945 filler Substances 0.000 description 11
- 238000000227 grinding Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 6
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000010561 standard procedure Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to low-shrinkage condensed type organic silicon rubber and a preparation method thereof, and relates to the technical field of rubber. The structural formula of the organic silicon matrix resin is shown as a formula 1. The organic silicon rubber comprises a component A and a component B; the component A is formed by mixing 30-80 parts of the T7-POSS organic silicon polymer and 10-30 parts of commercially available organic silicon oil; the component B is prepared by 5-10 parts of Pd catalyst and 5-20 parts of organic silicone oil according to a proportion; the weight ratio of the component A to the component B is 100 parts: 5-10 parts. The invention also provides a preparation method of the organic silicon matrix resin and the organic silicon rubber. The invention provides a low-shrinkage silicone rubber taking reactive T7-POSS (polyhedral oligomeric silsesquioxane) organic silicon matrix resin as a core component, which is prepared fromThe T7-POSS organic silicon matrix resin is in a liquid state at room temperature, can be uniformly mixed with other silicon rubber and can participate in a silicon rubber cross-linking network, so that the shrinkage rate of the silicon rubber during curing is greatly reduced, and the curing shrinkage rate can be as low as 0.5-1%.
Description
Technical Field
The invention relates to the technical field of rubber, in particular to low-shrinkage condensed type organic silicon rubber and a preparation method thereof.
Background
The silicone rubber is an elastomer material which is formed by linear polysiloxane after a crosslinking reaction and has a three-dimensional network structure. Because of having a unique organic-inorganic hybrid molecular chain structure, the silicon rubber can be divided into three types according to a vulcanization mechanism: room temperature vulcanization type, heat vulcanization type, and addition reaction type. The addition reaction type silicon rubber can be used for a long time at the temperature of-65-200 ℃, can keep the soft and elastic performance, has excellent electrical property and chemical stability, and simultaneously has weather resistance, water resistance and ozone resistance; the nano-silver-containing nano-silver powder has the obvious characteristics of no toxicity, no smell, no corrosion, physiological inertia, low linear shrinkage rate and easiness in operation, 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, silicone rubber is liable to undergo volume shrinkage after curing due to factors such as structural change of the base rubber itself during crosslinking of cured molecules, which causes obstacles to its application, and particularly, serious problems in the application to 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 reducing the curing shrinkage and the thermal expansion coefficient. The addition of the filler on the one hand causes a reduction in the density of the functional groups of the curing system; on the other hand, the volume occupied by the filler is not changed along with the reaction in the curing process, so that the volume shrinkage of the reaction system is slowed down, the shape and the particle size of the filler have certain influence on the shrinkage degree of the photocuring system, and the addition of the nanoparticles with spherical structures can promote the material to obtain lower shrinkage rate in the curing process compared with the irregular-shaped nanoparticles. In addition, the change of the addition amount of the filler can cause different degrees of light curing shrinkage, and within a proper addition amount range, the increase of the addition amount of the filler is beneficial to obtaining lower curing shrinkage. 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. The introduction of large amounts of conventional fillers also tends to result in higher elastic moduli, thereby increasing the likelihood of stress generation.
Disclosure of Invention
The invention provides a low-shrinkage condensed type organic silicon rubber and a preparation method thereof, aiming at solving the technical problem that the curing shrinkage rate required by some products is difficult to meet because the existing nano particle filler for preventing the curing shrinkage of the silicon rubber is solid and the addition amount is limited. The invention designs a reactive T7-POSS organic silicon matrix resin and low-shrinkage condensed silicon rubber taking the same as a core component, wherein the T7-POSS organic silicon matrix resin is in a liquid state at room temperature, can be uniformly mixed with other silicon rubber, can participate in a silicon rubber cross-linking network, and greatly reduces the shrinkage rate of the silicon rubber during curing.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides an organic silicon matrix resin which is a T7-POSS organic silicon polymer, and the structural formula is shown as formula 1:
wherein R is-CH 3 or-C 2 H 5 ，R 1 is-OCH 3 or-OC 2 H 5 ；
The average molecular weight of the silicone base resin represented by formula 1 is 5000-30000.
The invention also provides a preparation method of the organic silicon matrix resin, which comprises the following steps:
step 1, weighing catalysts of potassium hydroxide and deionized water, placing the catalysts in a three-neck flask, adding a mixed solvent of acetone and methanol, adding tetramethoxysilane or trimethoxyethoxysilane under the protection of nitrogen for reaction, stirring for reaction for 16 hours, stopping heating, cooling to room temperature, adding dilute hydrochloric acid for acidification, and continuing stirring for reaction; after acidification treatment, stopping reaction to obtain incompletely condensed methoxy trisilanol or ethoxy trisilanol (T7-POSS);
step 2, dissolving methoxyl trisilol or ethoxyl trisilol and commercially available dimethyl dimethoxy silane or dimethyl diethoxy silane in toluene, uniformly stirring, removing the toluene after the reaction is finished, and drying to obtain a brown yellow liquid T7-POSS organic silicon polymer shown in a formula 1;
the reaction formula is as follows:
preferably, the reaction temperature after adding the tetramethoxysilane or the trimethoxyethoxysilane in the step 1 is 85 ℃.
Preferably, the stirring reaction is continued in step 1 for 4 hours.
Preferably, the reaction temperature in step 2 is 65 ℃ and the reaction time is 10 h.
The invention also provides a low-shrinkage condensed type organic silicon rubber which is a condensed type silicon rubber and comprises a component A and a component B;
the component A is prepared by mixing 30-80 parts of the T7-POSS organic silicon polymer and 10-30 parts of commercially available organic silicon oil;
the component B is prepared by 5-10 parts of Pd catalyst and 5-20 parts of organic silicone oil according to a proportion;
the weight ratio of the component A to the component B is 100 parts: 5-10 parts.
It is preferable that: the condensed type organic silicon rubber:
the component A is prepared by mixing 60-80 parts of the T7-POSS organic silicon polymer and 20-30 parts of commercially available organic silicon oil;
the component B is prepared by 7-10 parts of Pd catalyst and 15-20 parts of organic silicone oil according to a proportion.
It is preferable that: the condensed type organic silicon rubber:
the component A is prepared by mixing 70-80 parts of the T7-POSS organic silicon polymer and 25-30 parts of commercially available organic silicon oil;
the component B is prepared by 8-10 parts of Pd catalyst and 15-20 parts of organic silicone oil according to a proportion.
The invention also provides a preparation method of the low-shrinkage condensed type organic silicon rubber, which comprises the following steps:
the A, B components are uniformly mixed and then placed into a mold, pressurized at 5-10 MPa in an environment with the temperature of 25 +/-5 ℃ and the relative humidity of 55% +/-5, placed for 48 hours, and then placed for 72 hours in a standard environment after being taken out, so that the organic silicon rubber film is obtained.
It is preferable that: the thickness of the organic silicon rubber sheet is 3 mm.
The invention has the beneficial effects that:
the organic silicon matrix resin of the invention introduces the POSS structure into the molecular structure, and then spherical nano-particles of POSS can be introduced into the cross-linked grid of the silicon rubber without limit and uniformly, which can not be realized by inorganic solid particle fillers.
The invention provides a low-shrinkage silicone rubber taking reactive T7-POSS (polyhedral oligomeric silsesquioxane) organic silicon matrix resin as a core component, wherein the T7-POSS organic silicon matrix resin is in a liquid state at room temperature, can be uniformly mixed with other silicone rubber, can participate in a silicone rubber cross-linking network, greatly reduces the shrinkage rate of the silicone rubber during curing, and can be as low as 0.5-1%.
Detailed Description
The invention provides an organic silicon matrix resin which is a T7-POSS organic silicon polymer, and the structural formula is shown as formula 1:
wherein R is-CH 3 or-C 2 H 5 ，R 1 is-OCH 3 or-OC 2 H 5 ；
The average molecular weight of the silicone base resin represented by formula 1 is 5000-30000.
The invention also provides a preparation method of the organic silicon matrix resin, which comprises the following steps:
step 1, weighing catalysts of potassium hydroxide and deionized water, placing the catalysts in a three-neck flask, adding a mixed solvent of acetone and methanol, adding tetramethoxysilane or trimethoxyethoxysilane under the protection of nitrogen for reaction, stirring for reaction for 16 hours, stopping heating, cooling to room temperature, adding dilute hydrochloric acid for acidification, and continuing stirring for reaction; after acidification treatment, stopping reaction to obtain incompletely condensed methoxy trisilanol or ethoxy trisilanol (T7-POSS);
step 2, dissolving methoxyl trisilol or ethoxyl trisilol and commercially available dimethyl dimethoxy silane or dimethyl diethoxy silane in toluene, uniformly stirring, removing the toluene after the reaction is finished, and drying to obtain a brown yellow liquid T7-POSS organic silicon polymer shown in a formula 1;
the reaction formula is as follows:
in the preparation method of the organosilicon matrix resin, the temperature of the reaction after adding the tetramethoxysilane or the trimethoxyethoxysilane in the step 1 is 85 ℃.
In the preparation method of the silicone matrix resin of the present invention, the time for continuing the stirring reaction in step 1 is 4 hours.
In the preparation method of the silicone matrix resin of the present invention, the temperature of the reaction in step 2 is 65 ℃ and the reaction time is 10 hours.
One specific embodiment of the preparation method of the silicone matrix resin of the present invention is:
step 1, weighing 3.3g of catalyst potassium hydroxide and 1.27g of deionized water, placing the weighed materials into a 500mL three-neck flask, adding 165mL of acetone + methanol (88+12) mixed solvent, and protecting with nitrogen. Slowly adding 46g of tetramethoxysilane or trimethoxyethoxysilane, heating to 85 ℃, stirring for reacting for 16h, stopping heating, cooling to room temperature, adding 350mL of dilute hydrochloric acid (3 mass concentration) for acidification, and stirring for reacting for 4 h; after acidification treatment, the reaction is stopped, suction filtration is carried out, the product is washed to neutrality by water and is washed three times by acetone, and yellow solid is obtained. Then dried in vacuum at 35 ℃ for 48h to obtain incompletely condensed methoxy (ethoxy) trisilanol (T7-POSS) with a yield of about 58%.
Step 2, dissolving 100 g of methoxy (ethoxy) trisilicol (T7-POSS) and 600 g of commercially available dimethyldimethoxysilane or 600 g of dimethyldiethoxysilane in 1000 ml of toluene at room temperature, uniformly stirring, heating the reaction system to 65 ℃, reacting for 10 hours, carrying out reduced pressure distillation to remove the toluene, and carrying out vacuum drying for 48 hours to obtain a brown yellow liquid T7-POSS organic silicon polymer, wherein the yield is about 62%. (if the batch preparation is less than 30 kg, the reactants and the solvent can be added according to the proportion).
The invention also provides a low-shrinkage condensed type organic silicon rubber which is a condensed type silicon rubber and comprises a component A and a component B; the component A is prepared by mixing 30-80 parts of the T7-POSS organic silicon polymer and 10-30 parts of commercially available organic silicon oil; the component B is prepared by 5-10 parts of Pd catalyst and 5-20 parts of organic silicone oil according to a proportion;
the weight ratio of the component A to the component B is 100 parts: 5-10 parts.
It is preferable that: the condensed type organic silicon rubber:
the component A is prepared by mixing 60-80 parts of the T7-POSS organic silicon polymer and 20-30 parts of commercially available organic silicon oil;
the component B is prepared by 7-10 parts of Pd catalyst and 15-20 parts of organic silicone oil according to a proportion.
It is preferable that: the condensed type organic silicon rubber:
the component A is prepared by mixing 70-80 parts of the T7-POSS organic silicon polymer and 25-30 parts of commercially available organic silicon oil;
the component B is prepared by 8-10 parts of Pd catalyst and 15-20 parts of organic silicone oil according to a proportion.
The invention also provides a preparation method of the low-shrinkage condensed type organic silicon rubber, which comprises the following steps:
the A, B components are uniformly mixed and then put into a mould, the pressure is 5-10 MPa in the environment with the temperature of 25 +/-5 ℃ and the relative humidity of 55% +/-5, the mixture is placed for 48 hours, and the film is taken out and then placed in a standard environment for 72 hours to obtain the organic silicon rubber film with the thickness of 3 mm.
The organic silicon matrix resin of the invention introduces the POSS structure into the molecular structure, and then spherical nano-particles of POSS can be introduced into the cross-linked grid of the silicon rubber without limit and uniformly, which can not be realized by inorganic solid particle fillers.
Preparation example of T7-POSS Silicone base resin
Step 1, weighing 3.3g of catalyst lithium hydroxide and 1.27g of deionized water, placing the weighed materials into a 500mL three-neck flask, adding 165mL of acetone + methanol (volume ratio of 88: 12) mixed solvent, and protecting with nitrogen. Slowly adding 46g of tetramethoxysilane or 46g of trimethoxyethoxysilane, heating to 85 ℃, stirring for reacting for 16 hours, stopping heating, cooling to room temperature, adding 350mL of dilute hydrochloric acid (with the mass concentration of 3 percent) for acidifying, and stirring for reacting for 4 hours; after acidification treatment, the reaction is stopped, suction filtration is carried out, the product is washed to neutrality by water and is washed three times by acetone, and yellow solid is obtained. Then vacuum drying at 35 ℃ for 48h to obtain incompletely condensed methoxy-or ethoxy-trisilicol (T7-POSS) with a yield of about 58%.
Step 2, dissolving 100 g of methoxy trisilanol or 100 g of ethoxy trisilanol and 600 g of commercially available dimethyl dimethoxy silane or 600 g of dimethyl diethoxy silane in 1000 ml of toluene at room temperature, uniformly stirring, heating the reaction system to 65 ℃, reacting for 10 hours, distilling under reduced pressure to remove the toluene, and vacuum drying for 48 hours to obtain a brown yellow liquid T7-POSS organic silicon polymer with the yield of about 62%.
Specific example 1:
the silicone rubber matrix A comprises the following components: 40 parts of T7-POSS organosilicon polymer (R is-CH) 3 ，R 1 is-OCH 3 ) Mixing with 10 parts of commercially available methyl vinyl silicone oil;
the silicone rubber matrix B comprises the following components: 5 parts of Pd catalyst and 10 parts of 202 hydrogen-containing silicone oil;
adding 100 parts of the silicone rubber matrix A component and 5 parts of the silicone rubber matrix B component into a three-roll grinding machine, grinding and mixing for 10-15 minutes, then putting into a mold, pressurizing for 5-10 MPa in a standard environment (25 ℃ plus or minus 5 ℃, relative humidity 55 percent plus or minus 5), standing for 48 hours, taking out the film, and then standing for 72 hours in the standard environment to obtain the silicone rubber film with the thickness of 3 mm. The other performance parameters except the shrinkage rate are all tested by referring to the national standard method. The shrinkage test is calculated according to the volume reduction of the obtained film before and after curing. The performance parameters after testing were as follows:
tensile strength: 3.5 Mpa;
non-volatile content (%): not less than 98;
the working life is as follows: not less than 4 hours;
shore a hardness after 14 days: 30, of a nitrogen-containing gas;
volume shrinkage: 1.0 percent.
Specific example 2:
the silicone rubber matrix A comprises the following components: 50 parts of T7-POSS organosilicon polymer (R is-C) 2 H 5 ，R 1 is-OC 2 H 5 ) Mixing with 10 parts of commercially available methyl vinyl silicone oil;
the silicone rubber matrix B comprises the following components: 6 parts of Pd catalyst and 10 parts of 202 hydrogen-containing silicone oil;
adding 100 parts of the silicone rubber matrix A component and 5 parts of the silicone rubber matrix B component into a three-roll grinding machine, grinding and mixing for 10-15 minutes, then putting into a mold, pressurizing for 5-10 MPa in a standard environment (25 ℃ plus or minus 5 ℃, relative humidity 55 percent plus or minus 5), standing for 48 hours, taking out the film, and then standing for 72 hours in the standard environment to obtain the silicone rubber film with the thickness of 3 mm. The other performance parameters except the shrinkage rate are all tested by referring to the national standard method. The shrinkage test is calculated according to the volume reduction of the obtained film before and after curing. The performance parameters after testing were as follows:
tensile strength: 3.9 Mpa;
non-volatile content (%): not less than 98;
the working life is as follows: not less than 4 hours;
shore a hardness after 14 days: 32, a first step of removing the first layer;
volume shrinkage: 0.9 percent.
Specific example 3:
the silicone rubber matrix A comprises the following components: 60 parts of T7-POSS organosilicon polymer (R is-C) 2 H 5 ，R 1 is-OCH 3 ) Mixing with 20 parts of commercially available methyl vinyl silicone oil;
the silicone rubber matrix B comprises the following components: 7 parts of Pd catalyst and 15 parts of 202 hydrogen-containing silicone oil;
adding 100 parts of the silicone rubber matrix A component and 7 parts of the silicone rubber matrix B component into a three-roll grinding machine, grinding and mixing for 10-15 minutes, then putting into a mold, pressurizing for 5-10 MPa in a standard environment (25 ℃ plus or minus 5 ℃, relative humidity 55 percent plus or minus 5), standing for 48 hours, taking out the film, and then standing for 72 hours in the standard environment to obtain the silicone rubber film with the thickness of 3 mm. The other performance parameters except the shrinkage rate are all tested by referring to the national standard method. The shrinkage test is calculated according to the volume reduction of the obtained film before and after curing. The performance parameters after testing were as follows:
tensile strength: 4.2 Mpa;
non-volatile content (%): not less than 98;
the working life is as follows: not less than 4 hours;
shore a hardness after 14 days: 325;
volume shrinkage: 0.7 percent.
Specific example 4:
the silicone rubber matrix A comprises the following components: 70 parts of T7-POSS organosilicon polymer (R is-CH) 3 ，R 1 is-OC 2 H 5 ) Mixing with 20 parts of commercially available methyl vinyl silicone oil;
the silicone rubber matrix B comprises the following components: 8 parts of Pd catalyst and 15 parts of 202 hydrogen-containing silicone oil;
adding 100 parts of the silicone rubber matrix A component and 7 parts of the silicone rubber matrix B component into a three-roll grinding machine, grinding and mixing for 10-15 minutes, then putting into a mold, pressurizing for 5-10 MPa in a standard environment (25 ℃ plus or minus 5 ℃, relative humidity 55 percent plus or minus 5), standing for 48 hours, taking out the film, and then standing for 72 hours in the standard environment to obtain the silicone rubber film with the thickness of 3 mm. The other performance parameters except the shrinkage rate are all tested by referring to the national standard method. The shrinkage test is calculated according to the volume reduction of the obtained film before and after curing. The performance parameters after testing were as follows:
tensile strength: 4.6 Mpa;
non-volatile content (%): not less than 98;
the working life is as follows: not less than 4 hours;
shore a hardness after 14 days: 35;
volume shrinkage: 0.6 percent.
Specific example 5:
the silicone rubber matrix A comprises the following components: 80 parts of T7-POSS organosilicon polymer (R is-CH) 3 ，R 1 is-OCH 3 ) Mixing with 25 parts of commercially available methyl vinyl silicone oil;
the silicone rubber matrix B comprises the following components: 10 parts of Pd catalyst and 20 parts of 202 hydrogen-containing silicone oil;
adding 100 parts of the silicone rubber matrix A component and 10 parts of the silicone rubber matrix B component into a three-roll grinder, grinding and mixing for 10-15 minutes, putting into a mold, pressurizing for 5-10 MPa in a standard environment (25 +/-5 ℃ and 55 +/-5 percent of relative humidity), standing for 48 hours, taking out the film, and standing for 72 hours in the standard environment to obtain the silicone rubber film with the thickness of 3 mm. The other performance parameters except the shrinkage rate are all tested by referring to the national standard method. The shrinkage test is calculated according to the volume reduction of the obtained film before and after curing. The performance parameters after testing were as follows:
tensile strength: 5.0 Mpa;
non-volatile content (%): not less than 98;
the working life is as follows: not less than 4 hours;
shore a hardness after 14 days: 42;
volume shrinkage: 0.5 percent.
Specific example 6:
the silicone rubber matrix A comprises the following components: 80 parts of T7-POSS organosilicon polymer (R is-CH) 3 ，R 1 is-OCH 3 ) Mixing with 30 parts of commercially available methyl vinyl silicone oil;
the silicone rubber matrix B comprises the following components: 10 parts of Pd catalyst and 20 parts of 202 hydrogen-containing silicone oil;
adding 100 parts of the silicone rubber matrix A component and 10 parts of the silicone rubber matrix B component into a three-roll grinder, grinding and mixing for 10-15 minutes, putting into a mold, pressurizing for 5-10 MPa in a standard environment (25 +/-5 ℃ and 55 +/-5 percent of relative humidity), standing for 48 hours, taking out the film, and standing for 72 hours in the standard environment to obtain the silicone rubber film with the thickness of 3 mm. The other performance parameters except the shrinkage rate are all tested by referring to the national standard method. The shrinkage test is calculated according to the volume reduction of the obtained film before and after curing. The performance parameters after testing were as follows:
tensile strength: 5.1 Mpa;
non-volatile content (%): not less than 98;
the working life is as follows: not less than 4 hours;
shore a hardness after 14 days: 45, a first step of;
volume shrinkage: 0.5 percent.
It should be understood that the above examples are only for clarity of illustration 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 required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. An organic silicon matrix resin is characterized in that the organic silicon matrix resin is a T7-POSS organic silicon polymer, and the structural formula is shown as formula 1:
wherein R is-CH 3 or-C 2 H 5 ，R 1 is-OCH 3 or-OC 2 H 5 ；
The average molecular weight of the silicone base resin represented by formula 1 is 5000-30000.
2. The method for preparing the silicone base resin according to claim 1, comprising the steps of:
step 1, weighing catalysts of potassium hydroxide and deionized water, placing the catalysts in a three-neck flask, adding a mixed solvent of acetone and methanol, adding tetramethoxysilane or trimethoxyethoxysilane under the protection of nitrogen for reaction, stirring for reaction for 16 hours, stopping heating, cooling to room temperature, adding dilute hydrochloric acid for acidification, and continuing stirring for reaction; after acidification treatment, stopping reaction to obtain incompletely condensed methoxy trisilanol or ethoxy trisilanol (T7-POSS);
step 2, dissolving methoxyl trisilol or ethoxyl trisilol and commercially available dimethyl dimethoxy silane or dimethyl diethoxy silane in toluene, uniformly stirring, removing the toluene after the reaction is finished, and drying to obtain a brown yellow liquid T7-POSS organic silicon polymer shown in a formula 1;
the reaction formula is as follows:
3. the method according to claim 2, wherein the reaction temperature after the addition of the tetramethoxysilane or the trimethoxyethoxysilane in step 1 is 85 ℃.
4. The method according to claim 2, wherein the stirring reaction in step 1 is continued for 4 hours.
5. The method according to claim 2, wherein the reaction temperature in the step 2 is 65 ℃ and the reaction time is 10 hours.
6. The low-shrinkage condensed type organic silicon rubber is characterized by being condensed type silicon rubber and comprising a component A and a component B;
the component A is prepared by mixing 30-80 parts of T7-POSS organic silicon polymer shown in formula 1 of claim 1 with 10-30 parts of commercially available organic silicon oil;
the component B is prepared by 5-10 parts of Pd catalyst and 5-20 parts of organic silicone oil according to a proportion;
the weight ratio of the component A to the component B is 100 parts: 5-10 parts.
7. The silicone rubber according to claim 6,
the component A is prepared by mixing 60-80 parts of T7-POSS organic silicon polymer shown in formula 1 of claim 1 with 20-30 parts of commercially available organic silicon oil;
the component B is prepared by 7-10 parts of Pd catalyst and 15-20 parts of organic silicone oil according to a proportion.
8. The silicone rubber according to claim 6,
the component A is prepared by mixing 70-80 parts of T7-POSS organic silicon polymer shown in formula 1 of claim 1 with 25-30 parts of commercially available organic silicon oil;
the component B is prepared by 8-10 parts of Pd catalyst and 15-20 parts of organic silicone oil according to a proportion.
9. A method for preparing the low shrinkage condensed type silicone rubber according to claims 6 to 8, comprising the steps of:
the A, B components are uniformly mixed and then placed into a mold, pressurized at 5-10 MPa in an environment with the temperature of 25 +/-5 ℃ and the relative humidity of 55% +/-5, placed for 48 hours, and then placed for 72 hours in a standard environment after being taken out, so that the organic silicon rubber film is obtained.
10. The method of claim 9, wherein the silicone rubber sheet has a thickness of 3 mm.
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| JP2007063389A (en) * | 2005-08-31 | 2007-03-15 | Dow Corning Toray Co Ltd | Heat-curable and low-specific gravity liquid silicone rubber composition and low-specific gravity silicone rubber molded product |
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| CN111040166A (en) * | 2019-11-28 | 2020-04-21 | 湖北新四海化工股份有限公司 | Environment-friendly moisture-curing silicone resin and preparation method thereof |
| CN111072712A (en) * | 2019-12-23 | 2020-04-28 | 东莞市贝特利新材料有限公司 | Organic silicon tackifier, preparation method thereof and high-transparency self-adhesive addition type organic silicon rubber composition |
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| JP2007063389A (en) * | 2005-08-31 | 2007-03-15 | Dow Corning Toray Co Ltd | Heat-curable and low-specific gravity liquid silicone rubber composition and low-specific gravity silicone rubber molded product |
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| CN109735300A (en) * | 2018-12-29 | 2019-05-10 | 浙江炬泰新材料科技有限公司 | A kind of high-strength waterproof silicone rubber for sealing and preparation method thereof |
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