CN108192455B - Interpenetrating network structure polymer of silicon rubber-fluorocarbon coating and preparation method thereof - Google Patents
Interpenetrating network structure polymer of silicon rubber-fluorocarbon coating and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 74
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 39
- 239000010703 silicon Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- -1 methacryloxypropyl Chemical group 0.000 claims abstract description 85
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- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 13
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- 239000002994 raw material Substances 0.000 claims description 4
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- 230000009471 action Effects 0.000 claims description 3
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- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 22
- 239000011737 fluorine Substances 0.000 abstract description 22
- 229910052731 fluorine Inorganic materials 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 9
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- 239000003973 paint Substances 0.000 abstract description 2
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- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- 239000004579 marble Substances 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/28—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for wrinkle, crackle, orange-peel, or similar decorative effects
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention discloses an interpenetrating network structure polymer of silicon rubber-fluorocarbon coating, which is an interpenetrating network structure formed by an addition product of methacryloxypropyl polyhedral oligomeric silsesquioxane, silicon rubber and a fluorine-containing polymer. The addition product of the methacryloxypropyl POSS has the advantages that a part of double bonds are reserved and are copolymerized with a fluorine-containing monomer to form a fluorine-containing polymer chain while being crosslinked; and part of groups of methacryloxypropyl POSS are connected with trimethoxy silicon base to have the capability of crosslinking terminal hydroxyl polydimethylsiloxane, so that the silicon rubber and the fluorine-containing polymer are organically combined together by taking an addition product of the methacryloxypropyl POSS as a bridge to form an interpenetrating network structure. The preparation method is simple, the heat resistance and the strength of the interpenetrating network structure of the obtained polymer are improved, and the obtained polymer system has the characteristics of high mechanical strength, good heat resistance, good weather resistance, high adhesive force, good elasticity and the like, and can be used as materials such as paint, adhesive, elastomer and the like.
Description
Technical Field
The invention relates to an interpenetrating network structure polymer of silicon rubber-fluorocarbon coating, belonging to the technical field of high-molecular fine chemical industry.
Background
The silicone material and the fluorine-containing polymer are two hydrophobic materials which are most commonly used and have better effects, wherein the silicone rubber material has good hydrophobicity, good weather resistance and other properties and is widely applied in various fields; the fluorine-containing polymer has excellent hydrophobic and oleophobic properties and good chemical stability, and can be widely applied as high-temperature resistant materials, insulating materials, hydrophobic materials and the like. However, the mechanical property of the silicone rubber without the filler is poor, and the processability, chemical stability and the like of the silicone rubber with the filler are obviously reduced; the fluorine-containing polymer has high crystallinity and relatively poor processability due to the large electronegativity of fluorine atoms.
The combination of silicone rubber and fluoropolymer is not feasible using conventional polymer blending methods. Blends thereof are difficult to form because both silicone rubber and fluoropolymers tend to aggregate on themselves and are difficult to disperse uniformly. Even if the blend is temporarily formed, the stability of the blend is very poor as the fluoropolymer tends to migrate to aggregate itself and its stability is not at all satisfactory for the application. Polymer interpenetrating network structures are a viable approach to solving such problems. The respective polymer chains of the silicone rubber and the fluoropolymer are entangled with each other, so that the purpose of forced compatibility can be achieved, and the respective segment migration of the silicone rubber and the fluoropolymer is strictly restricted and cannot proceed, so that the long-term stability can be maintained. However, since silicone rubber is a crosslinked polymer, the solubility of the fluoropolymer is poor, and it is difficult to perform the conventional preparation method using an interpenetrating network structure.
Disclosure of Invention
The invention aims to solve the technical problem of providing the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating aiming at the defects in the prior art, the silicon rubber and the fluorine-containing polymer are organically combined together to form the interpenetrating network structure by adopting the addition product of the methacryloxypropyl cage polysilsesquioxane as a bridge, and the heat resistance and the mechanical strength of the interpenetrating network structure polymer are improved.
The technical scheme adopted by the invention for solving the problems is as follows:
an interpenetrating network structure polymer of silicon rubber-fluorocarbon paint is prepared from the addition product of methacryloxypropyl polyhedral oligomeric silsesquioxane (i.e. methacryloxypropyl POSS), silicon rubber and fluoropolymer through preparing interpenetrating network structure. Wherein, the structure of the addition product of methacryloxypropyl POSS) is shown as formula 1, and the structural schematic formula can be shown as formula 2.
According to the scheme, the structure of the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating is schematically shown in figure 1.
The preparation method of the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating comprises the following steps: the addition product of methacryloxypropyl polyhedral oligomeric silsesquioxane (namely methacryloxypropyl POSS) reacts with fluorocarbon coating monomer and hydroxyl-terminated polydimethylsiloxane in a solvent under the action of an initiator to generate a silicone rubber-fluorocarbon coating interpenetrating network structure polymer solution through crosslinking.
Further preferably, the solvent can be removed from the solution of the interpenetrating network structure polymer of the silicone rubber-fluorocarbon coating, so as to obtain the interpenetrating network structure polymer of the silicone rubber-fluorocarbon coating.
According to the scheme, the reaction temperature in the preparation method is 60-90 ℃, and the reaction time is 2-6 h.
According to the scheme, the dosage of each raw material in the preparation method is as follows according to the mass portion: 2-5 parts of methacryloxypropyl POSS addition product, 5-40 parts of fluorocarbon coating monomer and 15-50 parts of hydroxyl-terminated polydimethoxysilane. And (3) appropriate amount of solvent and initiator.
Further preferably, the preparation method comprises the following raw materials in parts by mass: 2-5 parts of methacryloxypropyl POSS addition product, 5-40 parts of fluorocarbon coating monomer, 15-50 parts of hydroxyl-terminated polydimethoxysilane, 40 parts of solvent and 0.1-1 part of initiator.
According to the scheme, the solvent in the preparation method is one or a mixture of more than one of organic solvents such as tetrahydrofuran, n-heptane, cyclohexane, toluene and the like.
According to the scheme, the fluorocarbon coating monomer in the preparation method is one or a mixture of more than one of hexafluorobutyl methacrylate, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate, dodecafluoroheptyl acrylate and the like.
According to the scheme, the hydroxyl-terminated polydimethylsiloxane in the preparation method is commercially available hydroxyl-terminated polydimethylsiloxane (HPDMS), and the molecular weight is 5000-100000.
According to the scheme, the initiator in the preparation method is one or a mixture of more than one of benzoyl peroxide, azobisisobutyronitrile and the like.
According to the scheme, the addition product of the methacryloxypropyl polyhedral oligomeric silsesquioxane (namely the methacryloxypropyl POSS) is obtained by the addition reaction of the methacryloxypropyl POSS and trimethoxy silane. Wherein the addition reaction is a traditional hydrosilylation method, a platinum complex catalyst is used, and the reaction equation is shown in figure 2.
The basic principle of the invention is as follows: carrying out hydrosilylation on partial double bonds of methacryloxypropyl POSS to obtain an addition product of the methacryloxypropyl POSS, wherein partial double bonds are reserved, and the addition product is copolymerized with a fluorine-containing monomer to form a fluorine-containing polymer chain while crosslinking; and part of groups of methacryloxypropyl POSS are connected with trimethoxy silicon base to have the capability of crosslinking terminal hydroxyl polydimethylsiloxane, so that the silicon rubber and the fluorine-containing polymer are organically combined together by taking an addition product of the methacryloxypropyl POSS as a bridge to form an interpenetrating network structure. Since the cross-linking of the silicone rubber and the formation of the fluoropolymer are performed simultaneously, they form a stable interpenetrating network structure in solution, and the reaction is shown in fig. 3.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention prepares the incompatible silicone rubber and fluorocarbon coating into a stable polymer system through the bridging action of POSS, successfully prepares the interpenetrating network structure polymer of the silicone rubber-fluorocarbon coating, combines the advantages of the two, and has better elasticity and mechanical property, good heat resistance, good weather resistance, good processing performance and wide application range.
2. The interpenetrating network structure of the silicone rubber-fluorocarbon coating obtained by the invention can exist in the form of solution, so that the interpenetrating network structure has strong permeability, strong coatability and convenient construction.
3. The preparation method is simple, the heat resistance and the strength of the interpenetrating network structure of the obtained polymer are improved to a certain extent by adding POSS, and the obtained polymer system has the characteristics of high mechanical strength, good heat resistance, good weather resistance, high adhesion, good elasticity and the like, and can be used as materials such as coatings, adhesives, elastomers and the like.
Drawings
FIG. 1 is a schematic structural diagram of an interpenetrating network structure polymer of a silicone rubber-fluorocarbon coating.
FIG. 2 is a schematic representation of the addition of methacryloxypropyl POSS with trimethoxysilane to produce an adduct of methacryloxypropyl POSS.
FIG. 3 is a schematic representation of the reaction of an adduct of methacryloxypropyl POSS) with a fluoromonomer, a hydroxyl terminated polydimethylsiloxane to form an interpenetrating network polymer.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the present invention is not limited to the following examples.
In the following examples, the structure of the addition product of methacryloxypropyl POSS) is shown as formula 1, the schematic structure of the addition product can be shown as formula 2, and the preparation method comprises the following steps: methacryloxypropyl POSS was subjected to addition reaction with trimethoxysilane according to a conventional hydrosilylation method using a platinum complex catalyst to obtain an adduct of methacryloxypropyl POSS (tested by NMR, H.R. 0.56,16H, 1.04,8H, 1.17,12H, 1.53,16H, 2.01, 12H, 2.38,4H, 3.55,36H, 4.06,8H, 4.20,8H, 6.40,4H, 6.48, 4H). The reaction equation is shown in FIG. 2.
Example 1
An interpenetrating network structure polymer of silicon rubber-fluorocarbon coating is an interpenetrating network structure formed by an addition product of methacryloxypropyl polyhedral oligomeric silsesquioxane (namely methacryloxypropyl POSS), silicon rubber and a fluorine-containing polymer, and the structural expression formula of the interpenetrating network structure polymer is shown as a formula 1.
The preparation method of the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating comprises the following steps: 2g of methacryloxypropyl POSS addition product is added into 40g of tetrahydrofuran solvent, 40g of hexafluorobutyl acrylate, 17g of hydroxyl-terminated polydimethylsiloxane with the molecular weight of 5000 and 1g of benzoyl peroxide initiator are sequentially added, after uniform stirring, the mixture is refluxed for 5 hours at 80 ℃ to obtain a polymer interpenetrating network structure solution, most of the solvent is evaporated, and the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating is obtained after natural drying.
Example 2
An interpenetrating network structure polymer of silicon rubber-fluorocarbon coating is an interpenetrating network structure formed by an addition product of methacryloxypropyl polyhedral oligomeric silsesquioxane (namely methacryloxypropyl POSS), silicon rubber and a fluorine-containing polymer, and the structural expression formula of the interpenetrating network structure polymer is shown as a formula 1.
The preparation method of the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating comprises the following steps: adding 5g of methacryloxypropyl POSS addition product into 40g of solvent n-heptane, sequentially adding 5g of hexafluorobutyl methacrylate, 49.9g of hydroxyl-terminated polydimethylsiloxane with the molecular weight of 100000 and 0.1g of initiator azobisisobutyronitrile, uniformly stirring, refluxing for 2 hours at 90 ℃ to obtain a polymer interpenetrating network structure solution, evaporating most of the solvent, and naturally drying to obtain the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating.
Example 3
An interpenetrating network structure polymer of silicon rubber-fluorocarbon coating is an interpenetrating network structure formed by an addition product of methacryloxypropyl polyhedral oligomeric silsesquioxane (namely methacryloxypropyl POSS), silicon rubber and a fluorine-containing polymer, and the structural expression formula of the interpenetrating network structure polymer is shown as a formula 1.
The preparation method of the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating comprises the following steps: 2g of methacryloxypropyl POSS adduct is added into 40g of solvent toluene, 20g of dodecafluoroheptyl methacrylate, 37.5g of terminal hydroxyl polydimethylsiloxane with the molecular weight of 50000 and 0.5g of initiator azobisisobutyronitrile are sequentially added, after uniform stirring, the mixture is refluxed for 6 hours at 70 ℃ to obtain a polymer interpenetrating network structure solution, most of the solvent is evaporated, and the polymer interpenetrating network structure of the silicon rubber-fluorocarbon coating is obtained after natural drying.
Example 4
An interpenetrating network structure polymer of silicon rubber-fluorocarbon coating is an interpenetrating network structure formed by an addition product of methacryloxypropyl polyhedral oligomeric silsesquioxane (namely methacryloxypropyl POSS), silicon rubber and a fluorine-containing polymer, and the structural expression formula of the interpenetrating network structure polymer is shown as a formula 1.
The preparation method of the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating comprises the following steps: adding 3g of methacryloxypropyl POSS addition product into 40g of solvent cyclohexane, sequentially adding 15g of dodecafluoroheptyl methacrylate, 15g of dodecafluoroheptyl acrylate, 26.5g of hydroxyl-terminated polydimethylsiloxane with the molecular weight of 10000 and 0.5g of initiator benzoyl peroxide, uniformly stirring, refluxing at 80 ℃ for 5 hours to obtain a polymer interpenetrating network structure solution, evaporating most of the solvent, and naturally drying to obtain the silicon rubber-fluorocarbon coating interpenetrating network structure polymer.
Example 5
An interpenetrating network structure polymer of silicon rubber-fluorocarbon coating is an interpenetrating network structure formed by an addition product of methacryloxypropyl polyhedral oligomeric silsesquioxane (namely methacryloxypropyl POSS), silicon rubber and a fluorine-containing polymer, and the structural expression formula of the interpenetrating network structure polymer is shown as a formula 1.
The preparation method of the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating comprises the following steps: adding 5g of methacryloxypropyl POSS addition product into 20g of solvent cyclohexane and 20g of toluene, sequentially adding 39.5g of dodecafluoroheptyl methacrylate, 15g of hydroxyl-terminated polydimethylsiloxane with the molecular weight of 20000, 0.5g of initiator benzoyl peroxide and 0.5g of initiator azobisisobutyronitrile, uniformly stirring, refluxing at 80 ℃ for 5 hours to obtain a polymer interpenetrating network structure solution, evaporating most of the solvent, and naturally drying to obtain the interpenetrating network structure polymer of the silicone rubber-fluorocarbon coating.
Example 6
An interpenetrating network structure polymer of silicon rubber-fluorocarbon coating is an interpenetrating network structure formed by an addition product of methacryloxypropyl polyhedral oligomeric silsesquioxane (namely methacryloxypropyl POSS), silicon rubber and a fluorine-containing polymer, and the structural expression formula of the interpenetrating network structure polymer is shown as a formula 1.
The preparation method of the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating comprises the following steps: 2g of methacryloxypropyl POSS addition product is added into 20g of tetrahydrofuran solvent and 20g of n-heptane, 10g of dodecafluoroheptyl methacrylate, 15g of hexafluorobutyl acrylate, 32g of terminal hydroxyl polydimethylsiloxane with the molecular weight of 50000 and 1g of benzoyl peroxide initiator are sequentially added, after uniform stirring, the mixture is refluxed for 5 hours at 80 ℃ to obtain a polymer interpenetrating network structure solution, and most of the solvent is evaporated and naturally dried to obtain the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating.
Example 7
An interpenetrating network structure polymer of silicon rubber-fluorocarbon coating is an interpenetrating network structure formed by an addition product of methacryloxypropyl polyhedral oligomeric silsesquioxane (namely methacryloxypropyl POSS), silicon rubber and a fluorine-containing polymer, and the structural expression formula of the interpenetrating network structure polymer is shown as a formula 1.
The preparation method of the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating comprises the following steps: adding 3g of methacryloxypropyl POSS addition product into 20g of tetrahydrofuran solvent and 20g of cyclohexane solvent, sequentially adding 12g of dodecafluoroheptyl methacrylate, 12g of dodecafluoroheptyl acrylate, 32.5g of hydroxyl-terminated polydimethylsiloxane with the molecular weight of 50000, 0.25g of benzoyl peroxide initiator and 0.25g of azodiisobutyronitrile initiator, uniformly stirring, refluxing at 80 ℃ for 5 hours to obtain a polymer interpenetrating network structure solution, evaporating most of the solvent, and naturally drying to obtain the interpenetrating network structure polymer of the silicone rubber-fluorocarbon coating.
Example 8
An interpenetrating network structure polymer of silicon rubber-fluorocarbon coating is an interpenetrating network structure formed by an addition product of methacryloxypropyl polyhedral oligomeric silsesquioxane (namely methacryloxypropyl POSS), silicon rubber and a fluorine-containing polymer, and the structural expression formula of the interpenetrating network structure polymer is shown as a formula 1.
The preparation method of the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating comprises the following steps: 4g of methacryloxypropyl POSS addition product is added into 20g of n-heptane solvent, 10g of toluene and 10g of tetrahydrofuran, 10g of dodecafluoroheptyl methacrylate, 10g of dodecafluoroheptyl acrylate, 35.8g of hydroxyl-terminated polydimethylsiloxane with the molecular weight of 30000, 0.1g of benzoyl peroxide initiator and 0.1g of azodiisobutyronitrile initiator are sequentially added, after uniform stirring, the mixture is refluxed for 5 hours at 80 ℃ to obtain a polymer interpenetrating network structure solution, most of the solvent is evaporated, and the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating is obtained after natural drying.
Example 9
An interpenetrating network structure polymer of silicon rubber-fluorocarbon coating is an interpenetrating network structure formed by an addition product of methacryloxypropyl polyhedral oligomeric silsesquioxane (namely methacryloxypropyl POSS), silicon rubber and a fluorine-containing polymer, and the structural expression formula of the interpenetrating network structure polymer is shown as a formula 1.
The preparation method of the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating comprises the following steps: adding 5g of methacryloxypropyl POSS addition product into 20g of tetrahydrofuran solvent, 10g of toluene and 10g of cyclohexane, sequentially adding 5g of dodecafluoroheptyl methacrylate, 5g of hexafluorobutyl acrylate, 5g of dodecafluoroheptyl methacrylate, 39g of hydroxyl-terminated polydimethylsiloxane with the molecular weight of 80000, 0.5g of azodiisobutyronitrile as an initiator and 0.5g of benzoyl peroxide, uniformly stirring, refluxing at 80 ℃ for 5 hours to obtain a polymer interpenetrating network structure solution, evaporating most of the solvent, and naturally drying to obtain the interpenetrating network structure polymer of the silicone rubber-fluorocarbon coating.
Example 10
An interpenetrating network structure polymer of silicon rubber-fluorocarbon coating is an interpenetrating network structure formed by an addition product of methacryloxypropyl polyhedral oligomeric silsesquioxane (namely methacryloxypropyl POSS), silicon rubber and a fluorine-containing polymer, and the structural expression formula of the interpenetrating network structure polymer is shown as a formula 1.
The preparation method of the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating comprises the following steps: adding 3g of methacryloxypropyl POSS addition product into 10g of tetrahydrofuran solvent, 10g of toluene, 10g of cyclohexane and 10g of n-heptane, sequentially adding 8g of dodecafluoroheptyl methacrylate, 5g of hexafluorobutyl acrylate, 5g of dodecafluoroheptyl acrylate, 38g of hydroxyl-terminated polydimethylsiloxane with the molecular weight of 50000, 0.5g of benzoyl peroxide as an initiator and 0.5g of azodiisobutyronitrile as an initiator, uniformly stirring, refluxing at 80 ℃ for 5 hours to obtain a polymer interpenetrating network structure solution, evaporating most of the solvent, and naturally drying to obtain the interpenetrating network structure polymer of the silicone rubber-fluorocarbon coating.
Example 11
An interpenetrating network structure polymer of silicon rubber-fluorocarbon coating is an interpenetrating network structure formed by an addition product of methacryloxypropyl polyhedral oligomeric silsesquioxane (namely methacryloxypropyl POSS), silicon rubber and a fluorine-containing polymer, and the structural expression formula of the interpenetrating network structure polymer is shown as a formula 1.
The preparation method of the interpenetrating network structure polymer of the silicon rubber-fluorocarbon coating comprises the following steps: adding 5g of methacryloxypropyl POSS addition product into 10g of tetrahydrofuran solvent, 10g of toluene, 10g of cyclohexane and 10g of n-heptane, sequentially adding 10g of dodecafluoroheptyl methacrylate, 10g of hexafluorobutyl acrylate, 5g of dodecafluoroheptyl methacrylate, 5g of dodecafluoroheptyl acrylate, 24g of hydroxyl-terminated polydimethylsiloxane with the molecular weight of 100000, 0.5g of benzoyl peroxide as an initiator and 0.5g of azodiisobutyronitrile as an initiator, uniformly stirring, refluxing at 80 ℃ for 5 hours to obtain a polymer interpenetrating network structure solution, evaporating most of the solvent, and naturally drying to obtain the interpenetrating network structure polymer of the silicone rubber-fluorocarbon coating.
Preparing an elastomer from the interpenetrating network structure polymer of the silicone rubber-fluorocarbon coating obtained in the embodiment on a polytetrafluoroethylene plate, and measuring the tensile strength and the elongation at break according to the method of GB/T528-one 2009; coating the interpenetrating network structure polymer solution of the obtained silicon rubber-fluorocarbon coating on the surfaces of different base materials (including iron, copper, aluminum, glass, concrete, wood and marble), and measuring the adhesive force of the interpenetrating network structure polymer solution on the different base materials according to the method of GB 9286-88; the contact angle of the surface of the interpenetrating network structure polymer sample of the obtained silicon rubber-fluorocarbon coating is measured according to the method of GB/T30447-2013. The test results of each example are shown in table 1.
TABLE 1 basic Properties of the interpenetrating network polymers obtained in examples 1 to 10
From table 1, it can be seen that: the interpenetrating network structure polymer of the silicone rubber-fluorocarbon coating has higher tensile strength which is generally more than 3MPa, meets the requirements of general application, has generally better elasticity, has elongation at break which is generally more than 400 percent, and meets the requirements of most application occasions on elasticity; moreover, the hydrophobic property is good, the contact angle is generally more than 140 degrees, and the water resistance is good; in addition, the adhesive force on the surface of the glass is relatively poor (generally on the national standard level 2 or 3), and the adhesive force on metals such as iron, copper and aluminum and building materials such as concrete, wood and marble is good, and generally on the national standard level 0 or 1.
The foregoing is a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and changes can be made without departing from the inventive concept of the present invention, and these are all within the scope of the present invention.
Claims (9)
1. An interpenetrating network structure polymer of silicon rubber-fluorocarbon coating, characterized by that it is by the addition product of methyl acryloyl oxypropyl cage polysilsesquioxane and silicone rubber and fluoropolymer form the interpenetrating network structure; the structure of the addition product of the methacryloxypropyl polyhedral oligomeric silsesquioxane is shown as a formula 1:
2. the method for preparing the interpenetrating network structure polymer of silicone rubber-fluorocarbon coating of claim 1, wherein the interpenetrating network structure polymer of silicone rubber-fluorocarbon coating is prepared by reacting an addition product of methacryloxypropyl cage polysilsesquioxane with fluorocarbon coating monomer and hydroxyl-terminated polydimethylsiloxane in a solvent under the action of an initiator and crosslinking.
3. The method for preparing the interpenetrating network structure polymer of silicone rubber-fluorocarbon coating according to claim 2, further comprising the step of removing the solvent from the solution of the interpenetrating network structure polymer of silicone rubber-fluorocarbon coating to obtain the interpenetrating network structure polymer of silicone rubber-fluorocarbon coating.
4. The method for preparing the interpenetrating network structure polymer of the silicone rubber-fluorocarbon coating according to claim 2, wherein the reaction temperature is 60-90 ℃ and the reaction time is 2-6 h.
5. The preparation method of the interpenetrating network structure polymer of silicone rubber-fluorocarbon coating according to claim 2, wherein the amount of each raw material is in parts by mass: 2-5 parts of methacryloxypropyl POSS addition product, 5-40 parts of fluorocarbon coating monomer and 15-50 parts of hydroxyl-terminated polydimethoxysilane.
6. The preparation method of the interpenetrating network structure polymer of silicone rubber-fluorocarbon coating according to claim 2, wherein the amount of each raw material is in parts by mass: 2-5 parts of methacryloxypropyl POSS addition product, 5-40 parts of fluorocarbon coating monomer, 15-50 parts of hydroxyl-terminated polydimethoxysilane, 40 parts of solvent and 0.1-1 part of initiator.
7. The method for preparing the interpenetrating network structure polymer of silicone rubber-fluorocarbon coating according to claim 2, wherein the fluorocarbon coating monomer is one or more selected from hexafluorobutyl methacrylate, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate and dodecafluoroheptyl acrylate.
8. The method for preparing the interpenetrating network structure polymer of the silicone rubber-fluorocarbon coating according to claim 2, wherein the hydroxyl terminated polydimethylsiloxane is hydroxyl terminated polydimethylsiloxane having a molecular weight of 5000-100000.
9. Coatings, adhesives, elastomers comprising the interpenetrating network polymer of the silicone rubber-fluorocarbon coating of claim 1.
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