CN114574097A - Bi-component normal-temperature curing epoxy modified MQ silicon resin coating - Google Patents
Bi-component normal-temperature curing epoxy modified MQ silicon resin coating Download PDFInfo
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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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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- 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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Abstract
The invention relates to the field of organic silicon resin coatings, and discloses a two-component normal-temperature curing epoxy modified MQ silicon resin coating. The epoxy modified MQ silicon resin is prepared by carrying out hydrosilylation reaction on hydrogen-containing MQ silicon resin and an organic matter containing epoxy groups and vinyl at the same time, and the epoxy value is 0.1-0.6. The hydrogen-containing MQ silicon resin is subjected to epoxy modification by a one-step method, the operation is simple and convenient, the grafting rate of the epoxy group in the MQ silicon resin is high, and the product quality is simple and convenient to control; the epoxy group reacts with the amino group in the organic amine curing agent, so that more crosslinking is generated in the MQ silicon resin coating, the binding property of the coating and a matrix can be enhanced, the corrosion resistance of the coating is improved, and the prepared coating has better stability.
Description
Technical Field
The invention relates to the field of organic silicon resin coatings, in particular to a two-component normal-temperature curing epoxy modified MQ silicon resin coating.
Background
The epoxy modified organic silicon resin combines the advantages of epoxy resin and organic silicon resin, and the coating has excellent properties of good adhesion, high and low temperature resistance, aging resistance, solvent resistance and the like, and is widely applied to the fields of heat resistance, ultraviolet resistance, corrosion resistance and the like. The conventional epoxy modified silicone resin is prepared by reacting and hybridizing hydroxyl or alkoxy in silicone resin with hydroxyl, epoxy and the like in epoxy resin under the action of a catalyst by using silicone oligomer and common epoxy resin such as E51, E44, E20 and the like, and has the defects of toxic catalyst, low reaction efficiency, difficult control of molecular structure, unstable product quality and the like.
MQ silicon resin is organosilicon tetrafunctional chain link (SiO)4/2Q units) are polymerized, via monofunctional chain links (R)3SiO1/2M units) end-capping a silicone resin. The MQ silicon resin is colorless and transparent, is in a viscous liquid or solid powder state according to different M/Q values and different molecular weights, has excellent heat resistance, film forming property, adhesiveness, water repellency, ultraviolet resistance and other properties, and is widely applied to the fields of organic silicon pressure-sensitive adhesives, silicon rubber, daily chemical products, mold release agents, defoaming agents and the like. The MQ silicone resin may be classified into methyl MQ silicone resin, phenyl MQ silicone resin, vinyl MQ silicone resin, hydrogen-containing MQ silicone resin, and the like, depending on the M unit. The hydrogen-containing MQ silicon resin contains active silicon hydrogen bonds, and can generate addition reaction with vinyl-containing organic matters to generate functional modified MQ silicon resin, such as epoxy modified MQ silicon resin, acrylic acid modified MQ silicon resin or polyester modified MQ silicon resin, and the like, thereby providing an effective way for structural design and functional development of novel MQ silicon resin. Chinese patent publication No. CN111057377A discloses a cationic photo-curing organosilicon compositionThe preparation method takes vinyl-terminated silicone oil as raw material to prepare aliphatic epoxy modified polydimethylsiloxane and alicyclic epoxy modified vinyl MQ silicone resin, and the aliphatic epoxy modified polydimethylsiloxane and the alicyclic epoxy modified vinyl MQ silicone resin are applied to the preparation of the cationic photocuring silicone composition.
However, at present, epoxy modification methods for MQ silicon resin are very complex, the molecular structure is unstable, and the product quality is difficult to stably control. And the research on the functional application aspects of heat resistance, ultraviolet resistance, corrosion resistance and the like of the two-component normal-temperature curing coating developed by the epoxy modified MQ silicon resin is few.
Disclosure of Invention
Aiming at the problems of complex synthesis process, poor quality of epoxy modified MQ silicon resin products, few application researches and the like in the prior art, the invention provides the bi-component normal-temperature cured epoxy modified MQ silicon resin coating, which has the advantages of simple preparation method and easily obtained raw materials, and the prepared epoxy modified MQ silicon resin has stable molecular structure and stable quality and can ensure the stable performance of the coating.
In order to achieve the purpose, the invention adopts the following technical scheme:
a double-component normal temperature curing epoxy modified MQ silicon resin coating comprises epoxy modified MQ silicon resin and an organic amine curing agent; the epoxy modified MQ silicon resin is generated by reacting hydrogen-containing MQ silicon resin with an organic matter containing epoxy groups and vinyl groups at the same time, and the epoxy value is 0.1-0.6.
Epoxy modification is carried out on the MQ silicone resin by adopting a simple process, and an epoxy group is introduced into the MQ silicone resin. The epoxy group in the epoxy modified MQ silicon resin is reacted with the amino group in the organic amine curing agent, so that more crosslinking is generated in the MQ silicon resin coating, the binding property of the coating and a matrix can be enhanced, the corrosion resistance of the coating is improved, and the prepared coating has stronger stability.
Preferably, the preparation method of the epoxy modified MQ silicon resin comprises the following steps: adding an organic matter containing epoxy groups and vinyl groups simultaneously into the hydrogen-containing MQ silicon resin solution, wherein the molar ratio of silicon hydrogen bonds to vinyl groups is 0.8-1.2: 1, introducing nitrogen for 10-30 min after mixing, heating to 50-100 ℃, dropwise adding a catalyst, reacting for 3-10 h, and removing the solvent to obtain the epoxy modified MQ silicon resin.
A certain number of silicon-hydrogen bonds exist in the hydrogen-containing MQ silicon resin, and the silicon-hydrogen bonds and the compound containing unsaturated bonds can perform addition reaction under certain conditions. By utilizing hydrosilylation reaction, organic matter containing epoxy group and vinyl simultaneously reacts with hydrogen-containing MQ silicon resin, epoxy group is introduced into the Q structure of the hydrogen-containing MQ silicon resin, and the hydrogen-containing MQ silicon resin is subjected to epoxy modification. Compared with the traditional MQ silicon resin epoxy modification method, the method only needs one-step reaction, is simple and convenient to operate, has high grafting rate of the epoxy group in the MQ silicon resin, can control the modification degree by controlling the molar ratio of the silicon-hydrogen bond to the vinyl, and is convenient to control the product quality.
Preferably, the M/Q value of the hydrogen-containing MQ silicon resin is 0.5-1.5, and the mass ratio of hydrogen is 0.2-1.0%. The quantity of the silicon-hydrogen bonds in the hydrogen-containing MQ silicon resin and the proportion thereof in the Q structure both have obvious influence on the synthesis efficiency and the final quality of the product. If the number of the silicon-hydrogen bonds is insufficient, effective synthesis and modification are difficult to perform; if the number of the silicon-hydrogen bonds is too large, the stability of the epoxy modified MQ silicon resin obtained after the reaction is reduced.
Preferably, the organic compound containing both epoxy group and vinyl group is one of allyl glycidyl ether and 4-vinylbenzyl glycidyl ether.
Preferably, the organic amine curing agent is one or two of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, 3-divinyltriaminopropyltrimethoxysilane and 3-divinyltriaminopropylmethyldimethoxysilane.
More preferably, the organic amine curing agent is one or two of 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane and 3-diethylenetriaminopropyltrimethoxysilane.
Preferably, the hydrogen-containing MQ silicon resin solution is toluene or xylene solution of hydrogen-containing MQ silicon resin, and the solid content is 30-80%.
Preferably, the catalyst is chloroplatinic acid, and the dosage of the chloroplatinic acid accounts for 20-50 ppm of the total weight of the reactants. Compared with an acid/alkali catalysis system, the catalyst with metal platinum is used for catalyzing hydrosilylation, the possibility of self ring-opening reaction of epoxy groups is reduced, the reliability of the quantity of the epoxy groups introduced into the hydrogen-containing MQ silicon resin is ensured, and the structural complication of the modified MQ silicon resin caused by the generation of other by-products is reduced.
Preferably, the mass ratio of the epoxy modified MQ silicon resin to the organic amine curing agent is 3-10: 1.
Therefore, the invention has the following beneficial effects: (1) by utilizing hydrosilylation reaction, reacting organic matter containing epoxy group and vinyl with hydrogen-containing MQ silicon resin, introducing the epoxy group into a Q structure of the hydrogen-containing MQ silicon resin through one-step reaction, carrying out epoxy modification on the hydrogen-containing MQ silicon resin, and having simple and convenient operation, high grafting ratio of the epoxy group in the MQ silicon resin and simple and convenient product quality control; (2) the MQ silicon resin is subjected to epoxy modification by a simple process, and the epoxy group reacts with the amino group in the organic amine curing agent, so that more crosslinking is generated in the MQ silicon resin coating, the associativity of the coating and a matrix can be enhanced, the corrosion resistance of the coating is improved, and the prepared coating has stronger stability.
Detailed Description
The invention is further described with reference to specific embodiments. It is to be understood that these examples are suitable for illustrating the basic features and advantages of the invention, and the invention is not to be limited in scope by the following examples; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions used in routine experiments.
Not specifically illustrated in the following examples, all starting materials are commercially available or prepared by methods conventional in the art. The epoxy value of the epoxy modified MQ silicon resin is tested according to a hydrochloric acid-acetone method in the standard GB/T1677 & 2008 determination of the epoxy value of the plasticizer.
Example 1
A two-component normal temperature curing epoxy modified MQ silicon resin coating comprises epoxy modified MQ silicon resin and an organic amine curing agent, wherein the organic amine curing agent is 3-aminopropyl triethoxysilane.
The preparation method of the epoxy modified MQ silicon resin comprises the following steps: dissolving hydrogen-containing MQ silicon resin (the M/Q value is 1.0, the hydrogen mass ratio is 0.6%) by dimethylbenzene to prepare a solution with the solid content of 60%, adding allyl glycidyl ether into the solution according to the molar ratio of a silicon-hydrogen bond to vinyl being 1.1:1, introducing nitrogen for 10min after mechanical mixing and dissolving, heating to 75 ℃, dropwise adding a chloroplatinic acid catalyst, wherein the dosage of the chloroplatinic acid is 30ppm of the sum of the weight of reactants, continuing to react for 5h after dropwise adding is finished, cooling, and stopping reaction to obtain the epoxy modified MQ silicon resin solution. The epoxy value of the prepared epoxy modified MQ silicon resin is 0.35.
When the epoxy modified MQ silicon resin is used, 3-aminopropyltriethoxysilane is added into the prepared epoxy modified MQ silicon resin solution, the mass ratio of the epoxy modified MQ silicon resin to the 3-aminopropyltriethoxysilane is 3:1, after the epoxy modified MQ silicon resin solution and the 3-aminopropyltriethoxysilane are uniformly mixed, a film is formed by spraying, and the epoxy modified MQ silicon resin solution is cured at normal temperature.
Example 2
A two-component normal temperature curing epoxy modified MQ silicon resin coating comprises epoxy modified MQ silicon resin and an organic amine curing agent, wherein the organic amine curing agent is 3-aminopropyltrimethoxysilane.
The preparation method of the epoxy modified MQ silicon resin comprises the following steps: dissolving hydrogen-containing MQ silicon resin (the M/Q value is 0.8, the hydrogen mass ratio is 0.5%) by using dimethylbenzene to prepare a solution with the solid content of 50%, adding allyl glycidyl ether into the solution according to the molar ratio of a silicon-hydrogen bond to vinyl of 1:1, introducing nitrogen for 30min after mechanical mixing and dissolving, heating to 50 ℃, dropwise adding a chloroplatinic acid catalyst, wherein the dosage of the chloroplatinic acid is 20ppm of the sum of the weight of reactants, continuing to react for 10h after dropwise adding, cooling, stopping reaction and obtaining the epoxy modified MQ silicon resin solution. The epoxy value of the prepared epoxy modified MQ silicon resin is 0.32.
When the epoxy modified MQ silicon resin is used, 3-aminopropyltrimethoxysilane is added into the prepared epoxy modified MQ silicon resin solution, the mass ratio of the epoxy modified MQ silicon resin to the 3-aminopropyltrimethoxysilane is 6:1, the epoxy modified MQ silicon resin and the 3-aminopropyltrimethoxysilane are uniformly mixed, and then the mixture is blade-coated to form a film and is cured at normal temperature.
Example 3
A two-component normal temperature curing epoxy modified MQ silicon resin coating comprises epoxy modified MQ silicon resin and an organic amine curing agent, wherein the organic amine curing agent is 3-diethylenetriaminopropyltrimethoxysilane.
The preparation method of the epoxy modified MQ silicon resin comprises the following steps: dissolving hydrogen-containing MQ silicon resin (the M/Q value is 0.6, the hydrogen mass ratio is 0.4%) by using toluene to prepare a solution with the solid content of 40%, adding allyl glycidyl ether into the solution according to the molar ratio of a silicon-hydrogen bond to vinyl of 0.8:1, introducing nitrogen for 20min after mechanical mixing and dissolving, heating to 80 ℃, dropwise adding a chloroplatinic acid catalyst, wherein the dosage of the chloroplatinic acid is 40ppm of the sum of the weight of reactants, continuing to react for 4h after dropwise adding, cooling, stopping reaction and obtaining the epoxy modified MQ silicon resin solution. The epoxy value of the prepared epoxy modified MQ silicon resin is 0.20.
When the epoxy modified MQ silicone resin is used, 3-diethylenetriaminopropyltrimethoxysilane is added into the prepared epoxy modified MQ silicone resin solution, the mass ratio of the epoxy modified MQ silicone resin to the 3-diethylenetriaminopropyltrimethoxysilane is 10:1, the epoxy modified MQ silicone resin and the 3-diethylenetriaminopropyltrimethoxysilane are uniformly mixed, and then the mixture is brushed to form a film and is cured at normal temperature.
Example 4
A two-component normal temperature curing epoxy modified MQ silicon resin coating comprises epoxy modified MQ silicon resin and an organic amine curing agent, wherein the organic amine curing agent is N-2-aminoethyl-3-aminopropyltriethoxysilane.
The preparation method of the epoxy modified MQ silicon resin comprises the following steps: dissolving hydrogen-containing MQ silicon resin (the M/Q value is 1.5, the hydrogen mass ratio is 1.0%) by using toluene to prepare a solution with the solid content of 80%, adding 4-vinylbenzyl glycidyl ether into the solution according to the molar ratio of a silicon-hydrogen bond to vinyl of 0.9:1, mechanically mixing and dissolving, introducing nitrogen for 30min, heating to 100 ℃, dropwise adding a chloroplatinic acid catalyst, wherein the dosage of the chloroplatinic acid accounts for 35ppm of the total weight of reactants, continuing to react for 3h after the dropwise adding is finished, cooling, and stopping the reaction to obtain the epoxy modified MQ silicon resin solution. The epoxy value of the prepared epoxy modified MQ silicon resin is 0.60.
When the epoxy modified MQ silicon resin is used, N-2-aminoethyl-3-aminopropyltriethoxysilane is added into the prepared epoxy modified MQ silicon resin solution, the mass ratio of the epoxy modified MQ silicon resin to the N-2-aminoethyl-3-aminopropyltriethoxysilane is 4:1, after uniform mixing, the mixture is sprayed to form a film, and the film is cured at normal temperature.
Example 5
A two-component normal temperature curing epoxy modified MQ silicon resin coating comprises epoxy modified MQ silicon resin and an organic amine curing agent, wherein the organic amine curing agent is 3-aminopropyl methyl diethoxy silane.
The preparation method of the epoxy modified MQ silicon resin comprises the following steps: dissolving hydrogen-containing MQ silicon resin (the M/Q value is 1.2, the hydrogen mass ratio is 0.8%) by using dimethylbenzene to prepare a solution with the solid content of 60%, adding allyl glycidyl ether into the solution according to the molar ratio of a silicon-hydrogen bond to vinyl being 1.2:1, introducing nitrogen for 15min after mechanical mixing and dissolving, heating to 80 ℃, dropwise adding a chloroplatinic acid catalyst, wherein the dosage of the chloroplatinic acid is 30ppm of the sum of the weight of reactants, continuing to react for 5h after dropwise adding, cooling, stopping reaction and obtaining the epoxy modified MQ silicon resin solution. The epoxy value of the prepared epoxy modified MQ silicon resin is 0.40.
When the epoxy modified MQ silicon resin is used, 3-aminopropyl methyl diethoxysilane is added into the prepared epoxy modified MQ silicon resin solution, the mass ratio of the epoxy modified MQ silicon resin to the 3-aminopropyl methyl diethoxysilane is 7:1, after uniform mixing, the mixture is sprayed to form a film, and the film is cured at normal temperature.
Example 6
A two-component normal temperature curing epoxy modified MQ silicon resin coating comprises epoxy modified MQ silicon resin and an organic amine curing agent, wherein the organic amine curing agent is 3-diethylenetriaminopropyltrimethoxysilane.
The preparation method of the epoxy modified MQ silicon resin comprises the following steps: dissolving hydrogen-containing MQ silicon resin (the M/Q value is 1.0, the hydrogen mass ratio is 0.5%) by using dimethylbenzene to prepare a solution with the solid content of 60%, adding 4-vinylbenzyl glycidyl ether into the solution according to the molar ratio of a silicon-hydrogen bond to vinyl being 1.05:1, mechanically mixing and dissolving, introducing nitrogen for 25min, heating to 70 ℃, dropwise adding a chloroplatinic acid catalyst, wherein the dosage of the chloroplatinic acid accounts for 50ppm of the sum of the weight of reactants, continuing to react for 8h after the dropwise adding is finished, cooling, and stopping the reaction to obtain the epoxy modified MQ silicon resin solution. The epoxy value of the prepared epoxy modified MQ silicon resin is 0.20.
When the epoxy modified MQ silicon resin is used, a mixture of 3-aminopropyltriethoxysilane and 3-diethylenetriaminopropyltrimethoxysilane in a mass ratio of 5:1 is added into the prepared epoxy modified MQ silicon resin solution, the mass ratio of the epoxy modified MQ silicon resin to the mixture is 3.5:1, and after the epoxy modified MQ silicon resin and the mixture are uniformly mixed manually, the mixture is sprayed to form a film and is cured at normal temperature.
Example 7
A two-component normal temperature curing epoxy modified MQ silicon resin coating comprises epoxy modified MQ silicon resin and an organic amine curing agent, wherein the organic amine curing agent is 3-diethylenetriaminopropyltrimethoxysilane.
The preparation method of the epoxy modified MQ silicon resin comprises the following steps: dissolving hydrogen-containing MQ silicon resin (the M/Q value is 0.9, the hydrogen mass ratio is 0.7%) by using dimethylbenzene to prepare a solution with the solid content of 60%, adding allyl glycidyl ether into the solution according to the molar ratio of a silicon-hydrogen bond to vinyl being 1.05:1, introducing nitrogen for 20min after mechanical mixing and dissolving, heating to 75 ℃, dropwise adding a chloroplatinic acid catalyst, wherein the dosage of the chloroplatinic acid is 35ppm of the sum of the weights of reactants, continuing to react for 5h after dropwise adding, cooling, stopping reaction and obtaining the epoxy modified MQ silicon resin solution. The epoxy value of the prepared epoxy modified MQ silicon resin is 0.32.
When the epoxy modified MQ silicone resin is used, a mixture of 3-diethylenetriaminopropyltrimethoxysilane and 3-diethylenetriaminopropyltrimethoxysilane is added into the prepared epoxy modified MQ silicone resin solution in a mass ratio of 2:1, the mass ratio of the epoxy modified MQ silicone resin to the mixture is 5:1, and after the epoxy modified MQ silicone resin and the mixture are uniformly mixed by hand, the mixture is blade-coated to form a film and is cured at normal temperature.
Example 8
A two-component normal temperature curing epoxy modified MQ silicon resin coating comprises epoxy modified MQ silicon resin and an organic amine curing agent, wherein the organic amine curing agent is 3-aminopropyl triethoxysilane.
The preparation method of the epoxy modified MQ silicon resin comprises the following steps: dissolving hydrogen-containing MQ silicon resin (the M/Q value is 0.5, the hydrogen mass ratio is 0.2%) by using dimethylbenzene to prepare a solution with the solid content of 30%, adding allyl glycidyl ether into the solution according to the molar ratio of a silicon-hydrogen bond to vinyl of 1.1:1, introducing nitrogen for 20min after mechanical mixing and dissolving, heating to 85 ℃, dropwise adding a chloroplatinic acid catalyst, wherein the dosage of the chloroplatinic acid is 45ppm of the sum of the weights of reactants, continuing to react for 6h after dropwise adding, cooling, stopping reaction and obtaining the epoxy modified MQ silicon resin solution. The epoxy value of the prepared epoxy modified MQ silicon resin is 0.10.
When the epoxy modified MQ silicon resin is used, 3-aminopropyltriethoxysilane is added into the prepared epoxy modified MQ silicon resin solution, the mass ratio of the epoxy modified MQ silicon resin to the 3-aminopropyltriethoxysilane is 8:1, after uniform mixing, the mixture is sprayed to form a film, and the film is cured at normal temperature.
Comparative example 1
The comparative example differs from example 1 only in that the hydrogen-containing MQ silicone resin used in the preparation method had an M/Q value of 1.6 and a hydrogen mass ratio of 0.6%.
Comparative example 2
The comparative example differs from example 1 only in that the hydrogen-containing MQ silicone resin used in the preparation method had an M/Q value of 0.4 and a hydrogen mass ratio of 0.2%.
Comparative example 3
The comparative example differs from example 1 only in that the hydrogen-containing MQ silicone resin used in the preparation process had an M/Q value of 1.0 and a hydrogen mass ratio of 0.1%.
Comparative example 4
This comparative example differs from example 1 only in that the molar ratio of silicon hydrogen bonds to vinyl groups in the preparation process was 1.3: 1.
Comparative example 5
This comparative example differs from example 1 only in that the molar ratio of silicon hydrogen bonds to vinyl groups in the preparation process was 0.7: 1.
Comparative example 6
This comparative example differs from example 1 only in that chloroplatinic acid was used in an amount of 60ppm based on the sum of the weights of the reactants in the preparation process.
Comparative example 7
This comparative example differs from example 1 only in that chloroplatinic acid was used in an amount of 10ppm based on the sum of the weights of the reactants in the preparation process.
Comparative example 8
This comparative example differs from example 1 only in that the weight ratio of epoxy modified MQ silicone resin to curing agent in the preparation process was 2: 1.
Comparative example 9
This comparative example differs from example 1 only in that the weight ratio of epoxy modified MQ silicone resin to curing agent in the preparation process was 11: 1.
The tack free time of the coatings was tested according to the HG/T4755-2014 polysiloxane coatings Standard. The paint adhesion was tested according to the Standard GB9286-1998 test for marking test on paint films of paints and varnishes. The test results are shown in table 1 below.
TABLE 1 surface drying time and adhesion of the coating
| Group of | Open time (h) | Adhesion force |
| Example 1 | 1.5 | Level 0 |
| Example 2 | 1.0 | Level 1 |
| Example 3 | 4.0 | Level 1 |
| Example 4 | 6.0 | Grade 3 |
| Example 5 | 5.0 | Stage 2 |
| Example 6 | 2.5 | Level 1 |
| Example 7 | 2.0 | Level 0 |
| Example 8 | 3.0 | Grade 3 |
| Comparative example 1 | — | — |
| Comparative example 2 | 2.0 | >Grade 3 |
| Comparative example 3 | >6.0 | >Grade 3 |
| Comparative example 4 | 3.0 | Grade 3 |
| Comparative example 5 | 5.0 | Stage 2 |
| Comparative example 6 | 1.5 | Level 0 |
| Comparative example 7 | >6.0 | >Grade 3 |
| Comparative example 8 | 1.0 | >Grade 3 |
| Comparative example 9 | >6.0 | >Grade 3 |
As can be seen from the above-mentioned examples 1-8, according to the method of the present invention, the two-component room temperature curing epoxy modified MQ silicone resin coating with strong adhesion and high stability can be prepared, and the properties thereof can be controlled by controlling the process parameters. The preparation process is simple and convenient to operate, and the product has stable properties.
Comparative examples 1 to 9 the example 1 having the best overall performance among the above 8 examples was set as a basis. As can be seen from comparative examples 1 and 2, the M/Q value of the hydrogen-containing MQ silicone resin needs to be within a reasonable range, and if the M/Q value is too high, the molecular weight of the prepared epoxy modified MQ silicone resin is too small, the viscosity is too low, and the epoxy modified MQ silicone resin cannot be cured to form a film; if the content is too low, the proportion of inorganic components (namely-O-Si-O-structure) in the prepared epoxy modified MQ silicon resin is too high, the film forming property of the resin is not good, the film layer is brittle, and the adhesive force of the resin is greatly reduced. Comparative example 3 illustrates that if the hydrogen mass ratio in the hydrogen-containing MQ silicon resin is too low, the epoxy value of the prepared epoxy modified MQ silicon resin is too low, and the surface drying time and the adhesive force of the coating are seriously influenced. The comparative example 4 increases the dosage of the hydrogen-containing MQ silicon resin, when the dosage of the hydrogen-containing MQ silicon resin is excessive, more silicon hydrogen bonds are not reacted to generate epoxy groups, so that the subsequent groups participating in the curing reaction are reduced, the surface drying time of the coating is increased, and the adhesive force is reduced. Comparative example 5 shows that when the amount of the vinyl glycidyl ether used was too large, a certain amount of the vinyl glycidyl ether remained after the reaction and volatilized slowly during the curing film-forming process, resulting in an increase in the surface drying time of the coating and a decrease in the adhesion. Comparative example 6 illustrates the addition of an excess of chloroplatinic acid catalyst to produce a coating having properties similar to example 1, but the use of excess catalyst increases cost. Comparative example 7 shows that when the chloroplatinic acid catalyst is insufficient, the hydrosilylation reaction efficiency is reduced, which results in insufficient modification degree, on one hand, the epoxy value of the modified silicone resin is lower in the subsequent film-forming curing process, so that the groups participating in the reaction are reduced, and on the other hand, after the reaction is finished, the hydrogen-containing MQ silicone resin and the allyl glycidyl ether remain, which results in obviously increased surface drying time of the coating and poor adhesion. In comparative example 8, an excessive amount of the organic amine curing agent was used, and although the tack-free time could be shortened, the curing agent itself was hydrolyzed and polycondensed to form a coating material, thereby deteriorating the adhesion of the entire coating material. Comparative example 9 shows that when the organic amine curing agent is too low, the coating curing is significantly slowed, the adhesion is poor, and sometimes even the curing film cannot be formed.
In addition, in experiments, the epoxy value of the epoxy modified MQ silicon resin is adjusted to be lower than 0.1 or higher than 0.6 by changing parameters such as the M/Q value, the hydrogen mass ratio, the molar ratio with allyl glycidyl ether and the like of the hydrogen-containing MQ silicon resin, so that the curing time of the paint is prolonged, the adhesive force is poor, and the preparation of the two-component normal-temperature curing epoxy modified MQ silicon resin paint is not facilitated.
Claims (9)
1. A bi-component normal temperature curing epoxy modified MQ silicon resin coating is characterized in that the components comprise epoxy modified MQ silicon resin and organic amine curing agent; the epoxy modified MQ silicon resin is generated by reacting hydrogen-containing MQ silicon resin with an organic matter containing epoxy groups and vinyl groups at the same time, and the epoxy value is 0.1-0.6.
2. The two-component normal temperature curing epoxy modified MQ silicon resin coating as claimed in claim 1, wherein the preparation method of the epoxy modified MQ silicon resin comprises the following steps: adding an organic matter containing epoxy groups and vinyl groups simultaneously into the hydrogen-containing MQ silicon resin solution, wherein the molar ratio of silicon hydrogen bonds to vinyl groups is 0.8-1.2: 1, introducing nitrogen for 10-30 min after mixing, heating to 50-100 ℃, dropwise adding a catalyst, reacting for 3-10 h, and removing the solvent to obtain the epoxy modified MQ silicon resin.
3. The two-component normal-temperature curing epoxy modified MQ silicon resin coating as claimed in claim 2, wherein the hydrogen-containing MQ silicon resin has an M/Q value of 0.5-1.5 and a hydrogen mass ratio of 0.2-1.0%.
4. The two-component room temperature curing epoxy modified MQ silicone resin coating as claimed in claim 2, wherein the organic material containing both epoxy group and vinyl group is one of allyl glycidyl ether and 4-vinylbenzyl glycidyl ether.
5. The two-component normal temperature curing epoxy modified MQ silicon resin coating as claimed in claim 2, the organic amine curing agent is characterized by being one or two of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, 3-divinyltriaminopropyltrimethoxysilane and 3-divinyltriaminopropylmethyldimethoxysilane.
6. The two-component room-temperature-curing epoxy-modified MQ silicon resin coating as claimed in claim 5, wherein the organic amine curing agent is one or two of 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, and 3-diethylenetriaminopropyltrimethoxysilane.
7. The two-component room-temperature-curing epoxy-modified MQ silicon resin coating as claimed in claim 2, wherein the hydrogen-containing MQ silicon resin solution is toluene or xylene solution of hydrogen-containing MQ silicon resin, and the solid content is 30-80%.
8. The two-component normal-temperature curing epoxy modified MQ silicon resin coating as claimed in claim 2, wherein the catalyst is chloroplatinic acid, and the dosage of the chloroplatinic acid accounts for 20-50 ppm of the total weight of the reactants.
9. The two-component normal-temperature curing epoxy modified MQ silicon resin coating as claimed in claim 2, wherein the mass ratio of the epoxy modified MQ silicon resin to the organic amine curing agent is 3-10: 1.
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