CN115537120A - Heat-resistant grafted silicone resin coating and preparation method thereof - Google Patents
Heat-resistant grafted silicone resin coating and preparation method thereof Download PDFInfo
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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
- 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
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Abstract
The invention discloses a heat-resistant grafted silicone resin coating and a preparation method thereof 1 SiO 1.5 ) And repeating units of (R) and 2 R 3 SiO) with a polysiloxane of type D, followed by MPEG- (OH) 2 As chain extenders, R 4 3 SiOMe is an end-capping agent, and the MPEG grafted silicone resin is prepared by condensation between alkoxy and hydroxyl; and finally, compounding the MPEG grafted silicone resin serving as matrix resin with high-temperature-resistant pigment and filler, and preparing the heat-resistant grafted silicone resin coating by using a catalyst, an inhibitor, a functional assistant and different dispersion media. According to the difference of dispersion media, the coating can be prepared into a solvent type coating with high solid content (more than or equal to 90 percent) and can also be prepared into a water-based coating with high solid content (more than or equal to 70 percent) by self-emulsification, and the coating has the advantages of universality, environmental protection, low water absorption and high heat resistance (more than 800 ℃).
Description
Technical Field
The invention relates to a heat-resistant grafted silicone resin coating and a preparation method thereof, belonging to the technical field of organic silicon polymers.
Background
The silicone resin has excellent high temperature resistance, electrical insulation, weather resistance and chemical resistance, plays an important role in the industries of special coatings such as high temperature resistance and marine antifouling, and is particularly applied to parts and occasions where high temperature is generated, such as the heat insulation protection of missile spacecrafts, the exhaust pipe engine shell of airplanes and automobiles, heating ovens, chemical reactors, steam valves, motors, transformers and the like. With the rapid improvement of the performance of these equipments, higher requirements are put on the heat resistance of the silicone coating. The main factors influencing the heat resistance of the silicone resin coating are the heat resistance of the silicone resin matrix, the selection of heat-resistant pigment and filler and the pigment ratio. The substituent group of the silicone resin and the hydroxyl group at the chain end can influence the heat resistance of the silicone resin matrix, and the more phenyl substituent groups in the silicone resin, the higher the heat resistance is; elimination of the terminal hydroxyl groups reduces degradation reactions due to "back-biting" of the terminal hydroxyl groups. When the silicone resin coating is used at medium and low temperature (200-400 ℃), the silicone resin coating can be used together with the traditional pigment and filler, and for higher use temperature (above 400 ℃), the heat-stable inorganic pigment and the heat-resistant filler are used. The mass ratio of the pigment filler to the matrix resin in the coating formula becomes the pigment ratio, the higher the pigment ratio is, the higher the heat resistance of the coating is, but the viscosity is high, a large amount of solvent needs to be added for dilution, the film forming property of the resin and the coating performance are poor, and the coating is not environment-friendly.
At present, matrix resins of heat-resistant silicone resin coatings are mostly condensed type silicone resins containing terminal hydroxyl groups, and in order to obtain better film-forming properties, the molecular weight and viscosity of the resins are large, and the use forms are that the resins are diluted by organic solvents to have 50% of solid content, such as 'development of silicone high-temperature resistant coatings' (silicone materials, 2008, 369), and reports of CN102585696, CN1235996 and the like 805, and matrix silicone resin products (DC, 806 and the like) for commercial heat-resistant coatings are provided. When these condensed silicone resins are used to formulate coatings, additional solvent addition is often required due to the increased viscosity caused by the addition of the pigment and filler. The condensed silicone resin has a terminal hydroxyl group, and therefore, the heat resistance is insufficient. In order to solve the environmental problem, an aqueous heat-resistant silicone coating has been developed. CN114525078 prepares a high temperature (500 ℃) resistant anticorrosive coating by using Wake SILRES MPF E and 50E silicone resin emulsion as matrixes; the SILIKOPHEN P40W silicone resin emulsion matrix can also be used for preparing high temperature (350-650 ℃) resistant water-based heat-resistant coatings, but the silicone resin emulsions are obtained by an external emulsifier method, on one hand, the system still contains partial solvent for obtaining stable emulsion, and on the other hand, the emulsifier is often unfavorable for heat resistance.
In the previous researches, low-viscosity high-strength toughened silicone resin (CN 112280044) is prepared, the bulk viscosity under the condition of no solvent is lower than 1000mPa & s, the mechanical and heat-resistant properties after curing are excellent, the 5 percent thermal decomposition temperature is higher than 480 ℃, the 800 ℃ residual weight is more than 80 percent, and the low-viscosity high-strength toughened silicone resin is obviously superior to the existing condensed silicone resin. The silicone resin is used as a matrix, and is matched with heat-resistant pigment, filler and functional auxiliary agents, the total solvent consumption can be reduced to 20%, the long-term temperature resistance of the prepared heat-resistant coating can reach 700 ℃, and the heat-resistant coating can bear repeated cold and hot impact due to good toughness. However, when the temperature resistance is further improved and the face-to-face ratio is increased, the thixotropy of the system is obviously increased, and the problem of solvent supplement cannot be solved. Meanwhile, when the silicone resin matrix is used for preparing the water-based heat-resistant coating, an emulsifier still needs to be added.
Disclosure of Invention
Aiming at the problems of the existing solvent type and water-based silicone resin heat-resistant coatings, the invention provides a heat-resistant grafted silicone resin coating and a preparation method thereof. The invention firstly prepares an alkoxy-terminated prepolymer comprising a repeating unit of (R) 1 SiO 1.5 ) And repeating units of (R) and 2 R 3 SiO) polysiloxane type D; then, polyethylene glycol (MPEG- (OH) having a dihydroxyl group at one end was prepared 2 ) (ii) a Then MPEG- (OH) 2 As chain extenders, R 4 3 SiOMe is an end-capping agent, and the MPEG grafted silicone resin is prepared by condensation between alkoxy and hydroxyl; and finally, compounding the MPEG grafted silicone resin serving as matrix resin with high-temperature-resistant pigment and filler, and preparing the heat-resistant grafted silicone resin coating by using a catalyst, an inhibitor, a functional assistant and different dispersion media. According to different dispersion media, the coating can be prepared into a solvent type with high solid content, can also be conveniently prepared into a water-based coating through self-emulsification, has environmental protection and high heat resistance (above 800 ℃), and can meet the application requirements under various environments.
The invention is realized by the following technical scheme: a heat-resistant grafted silicone resin coating comprises the following components:
(A) MPEG grafted silicone resin having the structure shown below
Wherein R is 1 Is aryl, R 2 Is one or more than two of methyl, aryl or saturated alkyl with 2-10 carbon atoms, R 3 A vinyl group, a hydrogen group, an aryl group, a saturated hydrocarbon group having 1 to 10 carbon atoms, and at least one of a vinyl group, a hydrogen group, and an aryl group (the molar ratio of the three groups is preferably 1.3 to 0.8 4 Is saturated alkyl or aryl with 1 to 10 carbon atoms; a + b + c + d =1,a having a value of 0 < a < 0.5, b having a value of 0.005 < b < 0.02, c having a value of 0.5 < c < 1,d having a value of 0.05 < d < 0.5; m is an integer greater than zero and less than 30;
(B) The hydrosilylation catalyst can realize the storage stability of the silicone resin at room temperature and the rapid curing at high temperature, and preferably selects a silicone resin coated platinum complex;
(C) Inhibitors, preferably alkynyl and/or polyvinyl containing compounds;
(D) Pigments comprising heat-resistant inorganic pigments, preferably leafy aluminum paste, metal oxides such as STAPAR aluminum paste, HEUCODURR Black 9-100, 940, 953, 955, blue550-552, yellow252-255, and anticorrosive pigments, preferably organically modified zinc phosphate-based pigments such as HEUCOPHOSR ZPO, HEUCOPHOSR CTF;
(E) The filler is preferably one or more than two of kaolin, white carbon black, mica powder and wollastonite;
(F) The functional assistant for improving the coating construction and application performance comprises a dispersing agent, a flatting agent and a defoaming agent; the dispersant is preferably a polymer, such as TEGOR Dispers 670, TEGOR Dispers 750W; the leveling agent is preferably organic bentonite, such as Bentonir 38; defoamers are preferably silicones and aqueous mineral oils, such as TEGOR Airex 900, TEGOR Foamex K3;
(G) Organic solvent or water is used as dispersion medium; the organic solvent is preferably one of toluene, xylene, ethyl acetate, butyl acetate, dibasic acid ester and propylene glycol methyl ether acetate.
The dosage of the component (B) is 1-50ppm; the dosage of the component (C) is 50-500ppm; the amount of component (D) is 20 to 50 parts by mass per 100 parts by mass of the grafted silicone resin of component (a); the amount of the component (E) is 40-70 parts by mass; the amount of the component (F) is 1 to 5 parts by mass; when the component (G) is an organic solvent, the using amount is 10-40 parts by mass; when the component (G) is water, the amount is 60 to 100 parts by mass.
The mass ratio of the dispersing agent, the flatting agent and the defoaming agent in the component (F) is 3-1:0-1:1, the proportion of the heat-resistant inorganic pigment and the anticorrosive pigment in the component (D) is 1.5-1:1.
the preparation method of the MPEG grafted silicone resin comprises the following steps:
(1) Preparation of the repeating unit of (R) 1 SiO 1.5 ) The preparation method of the T-type polysiloxane is the same as CN112280044B, and trialkoxysilane R 1 Si(OR) 3 Hydrolyzing and polycondensing under the catalysis of organic acid;
(2) Preparation of polysiloxane MeO (R) in form D 2 R 3 SiO) n Me, the preparation method is as follows: uniformly mixing dialkoxysilane mixture containing phenyl, hydrogen and vinyl, acetic acid and catalytic amount of trifluoromethanesulfonic acid, heating to 50-55 deg.C, reacting for 2-4h, cooling, adding neutralizer, stirring for reaction, filtering, and distilling the filtrate under reduced pressure to remove low-boiling-point substances to obtain alkoxy-terminated D-type polysiloxane MeO (R) 2 R 3 SiO) n Me；
(3) Preparation of MPEG- (OH) 2
A reference method (J.Am.chem.Soc.2001, 123, P18-25) uses polyethylene glycol monomethyl ether (MPEG) and 2,2-dimethylolpropionic acid as raw materials to prepare polyethylene glycol (MPEG- (OH) with one end being methoxy-terminated and one end being dihydroxyl through three steps of cross ketone protection, esterification and cross ketone removal protection 2 )；
(4) The T-type polysiloxane obtained in (1), the D-type polysiloxane obtained in (2), and the MPEG- (OH) obtained in (3) 2 And R 4 3 And (2) uniformly mixing SiOMe, adding a solvent and a catalytic amount of a catalyst, heating the reaction solution under stirring, separating out a mixture of alcohol and the solvent, cooling the reaction when no obvious alcohol is distilled off, and then carrying out reduced pressure distillation to remove low-boiling-point substances to obtain the MPEG grafted silicon resin.
The neutralizing agent in the step (2) is calcium carbonate or magnesium carbonate; in the step (2), the molar ratio of the phenyl group to the hydrogen group to the vinyl dialkoxysilane is 1:0.3-0.8:0.3 to 0.7, the molar ratio of alkoxy groups contained in the dialkoxysilane mixture to acetic acid and trifluoromethanesulfonic acid being 1:0.125-5:0.0001-0.001.
The solvent in the step (4) is one or a combination of more than two of benzene, toluene and xylene, preferably toluene and xylene; in the step (4), the catalyst is titanate compound, preferably tetrabutyl titanate and tetraisopropyl titanate. The T-type polysiloxane (R) in the step (4) 1 SiO 1.5 ) Polysiloxane of type D (R) 2 R 3 SiO)、MPEG-(OH) 2 An end-capping agent (R) 4 3 SiO 0.5 ) The molar ratio of the titanate catalyst is 1:1.7-2.5:0.03-0.06:0.5-1:0.001-0.005.
Compared with the prior art, the invention adopts an environment-friendly preparation process, and adopts the synthesis process design of alkoxy polysiloxane prepolymer and single-ended dihydroxyl polyethylene glycol MPEG- (OH) 2 The construction of (2) realizes that MPEG is taken as a side chain to be introduced into a silicone resin structure to obtain a long side chain branched polysiloxane resin structure. The beneficial effects brought by the method are as follows:
(1) Because the MPEG is arranged on the side chain, the silicone resin not only keeps the characteristics of low viscosity (less than or equal to 1000 mPa.s), high strength (tensile strength more than or equal to 15 MPa) and high heat resistance (5 percent of thermal decomposition temperature more than or equal to 450 ℃ and 800 ℃ residual weight more than or equal to 80 percent), but also has obvious viscosity reduction effect. Therefore, when the solvent type coating is prepared, the pigment ratio can be obviously improved, the solvent dosage is reduced, the heat resistance of the coating is improved, and the long-term temperature resistance of more than 800 ℃ and the cold-hot circulation of more than 100 times can be met.
(2) The MPEG grafted silicone resin has low viscosity, and PEG has good water solubility, so that the resin can be conveniently self-emulsified to prepare a water-based heat-resistant silicone resin coating without adding an emulsifier and an organic solvent, and the heat resistance of the resin can reach the level equivalent to that of a solvent-based coating. The PEG is positioned at the side chain, so that the emulsion has smaller particle size, high solid content and better stability, and simultaneously, the low water absorption rate (less than or equal to 2%) is kept after the film is formed.
(3) The MPEG grafted silicon resin is used as the matrix resin, can be prepared into a solvent type with high solid content (more than or equal to 90 percent) according to the use requirement, can also be prepared into a water-based coating with high solid content (more than or equal to 70 percent) by self-emulsification, has wide use range, and has universality, environmental protection and high heat resistance.
The performance effectively solves the high heat-resistant and anti-corrosion protection requirements in the fields of aerospace, high-end equipment, chemical equipment, new energy, motor and electric appliances and the like, and meets the requirements of environmental protection.
Drawings
FIG. 1 is a diagram of the preparation of the MPEG grafted silicone resin of example 2 1 H NMR spectrum.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1: MPEG- (OH) 2 Synthesis of (2)
100g of 2,2 '-dimethylolpropionic acid, 140mL of 2,2' -dimethoxypropane and 7.1g of p-toluenesulfonic acid are sequentially added into 500mL of acetone, and the mixture is stirred and reacted for 2 hours at room temperature; then, 50mL of NaOH (1.6 g) in methanol was added for neutralization, the solvent was removed under reduced pressure, the obtained white solid was dissolved in 500mL of dichloromethane, and insoluble matter was filtered off to obtain a dichloromethane solution. To the dichloromethane solution, 1000g of MPEG-OH (molecular weight 800, m = 16), 170g of N, N' -Dicyclohexyl (DCC) and 18.6g of 4-Dimethylaminopyridine (DMAP) were added, and the mixture was reacted at room temperature for 36 hours, followed by filtration, and the filtrate was concentrated and dried to obtain a white solid. The white solid was dissolved in 500mL of methanol, and 100mL of 1M HCl solution was added and reacted at 50 ℃ for 6 hours. After the reaction, the solvent was removed by concentration under reduced pressure, the product was dissolved in chloroform, and the organic phase was extracted with anhydrous MgSO 4 After drying, filtration and removal of the solvent, 940g of white was obtainedColor solid MPEG- (OH) 2 。
Example 2
135g of deionized water, 400g of toluene and 10g of acetic acid are added into a four-neck flask provided with a thermometer, a stirring paddle and a reflux condenser, the mixture is uniformly stirred, and 991g of phenyltrimethoxysilane is added dropwise. After the addition, the mixture was heated to reflux, reacted for 2 hours, and then cooled to room temperature. Distilling off low-boiling-point substances under the pressure of less than 10KPa and the temperature of 80 ℃ to obtain 640g of liquid trifunctional silicone resin prepolymer.
911.5g of methylphenyldimethoxysilane, 3242 g of methylvinyldimethoxysilane, 264.4g of methyldimethoxysilane and 255g of methyldimethoxysilane were put into a four-necked flask equipped with a thermometer, a stirring paddle and a reflux condenser, mixed well, then 211.7g of acetic acid and 1.3g of trifluoromethanesulfonic acid were added, and the mixture was raised to 50-55 ℃ to react for 4 hours. After the reaction is finished, cooling, adding 6.5g of calcium carbonate for neutralization reaction for 1 hour, filtering, and distilling the filtrate under reduced pressure to remove low-boiling-point substances to obtain 1130g of alkoxy-terminated D-type polysiloxane.
Liquid trifunctional silicon resin prepolymer, alkoxy-terminated D-type polysiloxane, 200g of MPEG- (OH) 2 And 336gMe 3 SiOMe was mixed homogeneously, and 1000g of toluene and 5g of tetraisopropyl titanate were added. Heating the reaction solution to 80 ℃ under stirring, separating out the mixture of alcohol and solvent, cooling the reaction when no significant alcohol is distilled off, and then distilling under reduced pressure to remove low-boiling-point substances to obtain the average unit formula (PhSiO) 1.5 ) 0.28 (MPEG) 0.014 (MePhSiO) 0.28 (MeViSiO) 0.112 (MeHSiO) 0.134 (Me 3 SiO 0.5 ) 0.18 The MPEG grafted silicone resin (in MPEG, m =16 according to the structural formula) of (a), the viscosity was 910mPa · s.
1 HNMR: the peak at δ =7 to 8ppm is Si-C 6 H 5 The characteristic peak of (1), the peak of delta =5.5 to 6.25ppm is assigned as Si-CH = CH 2 δ =4.5 to 5ppm represents a characteristic peak of Si — H, and δ =3.5 to 3.7ppm represents CH 2 CH 2 A characteristic peak of O, δ =0 to 0.5ppm, is Si-CH 3 Characteristic peak of (1).
Example 3
The preparation was carried out as in example 2, the siloxane segments were adjusted andMPEG-(OH) 2 to give an average unit formula of (PhSiO) 1.5 ) 0.29 (MPEG) 0.01 (MePhSiO) 0.26 (MeViSiO) 0.11 (MeHSiO) 0.14 (Me 3 SiO 0.5 ) 0.19 The MPEG graft silicone resin of (1), having a viscosity of 850 mPas.
Example 4
The preparation according to example 2 was carried out, adjusting the siloxane segments and MPEG- (OH) 2 To give an average unit formula of (PhSiO) 1.5 ) 0.30 (MPEG) 0.018 (MePhSiO) 0.282 (MeViSiO) 0.11 (MeHSiO) 0.14 (Me 3 SiO 0.5 ) 0.15 The MPEG graft silicone resin of (1), having a viscosity of 980 mPas.
Comparative example 1
Referring to CN112280044 example 3, an average unit formula of (PhSiO) 1.5 ) 0.25 (MePhSiO) 0.31 (MeViSiO) 0.14 (MeHSiO) 0.17 (Me 3 SiO 0.5 ) 0.13 The viscosity of the T-D-M block silicone resin (2) is 790 mPas. The resin was free of MPEG grafting.
The silicone resins prepared in examples 2, 3, 4 and comparative example 1 were mixed with a silicone resin-coated catalyst ([ (COD) Pt (C.ident.CPh) in an amount of 10ppm in terms of Pt 2 ]) And an inhibitor (ethynylcyclohexanol, 300 ppm) were mixed well and cured at 200 ℃ for 4h. The cured samples were tested for mechanical properties and heat resistance and the results are shown in table 1.
TABLE 1 Silicone matrix Performance parameters
| Example 2 | Example 3 | Example 4 | Comparative example 1 | |
| viscosity/mPas | 910 | 850 | 980 | 790 |
| hardness/Shore D | 65 | 67 | 70 | 65 |
| Tensile strength/MPa | 16 | 18 | 18 | 20 |
| T d5％ (N 2 )/℃ | 465 | 471 | 460 | 482 |
| Residual weight/% at 800 ℃ | 80.8 | 81.5 | 80.5 | 82.7 |
As can be seen from table 1: MPEG graft modified Silicone (examples)2. 3, 4) was slightly lower than that of a pure silicone resin of similar structure (comparative example 1), but still exhibited excellent heat resistance (T) d5％ More than or equal to 460 ℃ and more than or equal to 80 percent of residual weight at 800 ℃, is obviously superior to the conventional silicon resin (T) d5％ The residual weight is between 350 and 420 ℃ and between 20 and 60 percent at 800 ℃.
Examples 5 to 7 and comparative example 2
Preparation of solvent-based heat-resistant paint: the resins of examples 2 to 4 and comparative example 1 were mixed with the catalyst, inhibitor, pigment and filler, and functional aid, respectively, in a mill, and a small amount of solvent was added according to the viscosity change. The specific formula is shown in table 2, and the balance is parts by mass except for the silicon resin coated catalyst and the ethynyl cyclohexanol inhibitor. The coating is brushed and coated on the surface of a steel plate, and the steel plate is used for performance test after being cured for 4h and 72h at the temperature of 200 ℃. The solid content, heat resistance, cold-hot cycle, water absorption and water resistance tests refer to GB/T1725-2007, GB/T1735-2009, HG/T0004-2012, HG2-1612-85 and GB/T1733-93 respectively.
TABLE 2 formulation (parts by mass) and Properties of solvent-based heat-resistant coating
As can be seen from table 2: under similar pigment ratios, the MPEG graft modified silicone resin was used as a substrate to prepare a coating with a higher solid content (examples 5, 6, 7), and at the same time, the coating had better process operability (spreadability and fluidity), and was uniform and complete after film formation, so that the coating had excellent temperature resistance at a high temperature of 800 ℃. And when the pure silicone resin adopts similar pigment ratio (comparative example 2), the fluidity is poor, even if a solvent is added, the improvement is not large, and the film has more defects after being formed, cannot bear the high temperature of 800 ℃ and is easy to crack.
Examples 8 to 10 and comparative example 3
Preparing the water-based heat-resistant coating: the resins of examples 2-4 and comparative example 1 are dispersed with a proper amount of deionized water at a high speed (2000 rmp/min) to form an emulsion, and then the catalyst, the inhibitor, the pigment and filler and the functional auxiliary agent are added and mixed evenly in a grinding machine. The specific formula is shown in table 3, and the balance is parts by mass except for the silicon resin coated catalyst and the ethynyl cyclohexanol inhibitor. The coating is brushed on the surface of the steel plate, cured for 4h at 200 ℃ and used for performance test after 72h. The stability test is described in GB/T6753.3-1986, and the other tests are shown in Table 2.
TABLE 3 aqueous heat-resistant coating formulations and Properties
As can be seen from table 3: the MPEG grafted and modified silicone resin is used as a substrate, so that the high-solid-content water-based paint (examples 8, 9 and 10) can be obtained through self-emulsification, is milky homogeneous liquid, and has excellent stability and high temperature resistance. When pure silicone resin was used as a matrix, a stable and uniform aqueous coating material could not be obtained (comparative example 3), and floating and delamination were likely to occur.
The above description is for the purpose of describing preferred embodiments of the present invention, and is not intended to limit the scope of the present invention, and various modifications and variations may be made by those skilled in the art without inventive faculty based on the technical solution of the present invention.
Claims (10)
1. The heat-resistant grafted silicone resin coating is characterized by comprising the following components:
(A) Grafting silicone resin;
(B) A hydrosilylation catalyst;
(C) An inhibitor;
(D) A pigment;
(E) A filler;
(F) A functional auxiliary agent;
(G) Organic solvent or water is used as a dispersion medium;
the structural formula of the grafted silicone resin is shown as (I):
wherein R is 1 Is aryl, R 2 Is methyl, aryl orOne or more kinds of C2-C10 saturated alkyl, R 3 Is vinyl, hydrogen radical, aryl, saturated hydrocarbon radical with 1-10 carbon atoms, and at least contains vinyl, hydrogen radical and aryl simultaneously, R 4 Is a saturated alkyl or aryl with 1 to 10 carbon atoms; a + b + c + d =1,a having a value of 0 < a < 0.5, b having a value of 0.005 < b < 0.02, c having a value of 0.5 < c < 1,d having a value of 0.05 < d < 0.5; m is an integer greater than zero and less than 30.
2. The heat-resistant grafted silicone coating according to claim 1, wherein R is 3 The mol ratio of the medium vinyl group, the hydrogen group and the aryl group is 1:0.3-0.8:0.3-0.7.
3. The heat-resistant grafted silicone resin coating according to claim 1,
the hydrosilylation catalyst of the component (B) is a silicone resin coated platinum complex;
the component (C) inhibitor is a compound containing alkynyl and/or polyvinyl;
the component (D) pigment comprises a heat-resistant inorganic pigment and an anticorrosive pigment;
the filler of the component (E) is one or more than two of kaolin, white carbon black, mica powder and wollastonite;
the component (F) is a functional assistant and comprises a dispersant, a flatting agent and a defoaming agent;
the organic solvent of the component (G) is any one of toluene, xylene, ethyl acetate, butyl acetate, dibasic acid ester and propylene glycol methyl ether acetate.
4. The heat-resistant grafted silicone resin coating according to claim 3, wherein the heat-resistant inorganic pigment is a leafy aluminum paste or a metal oxide; the anticorrosive pigment is an organic modified zinc phosphate pigment.
5. The heat-resistant grafted silicone resin coating according to claim 3, wherein the dispersant is a polymer-based dispersant; the leveling agent is an organic bentonite leveling agent; the defoaming agent is an organic silicon defoaming agent or a water-based mineral oil defoaming agent.
6. The heat-resistant grafted silicone resin coating according to any one of claims 1 to 5,
the dosage of the component (B) is 1-50ppm; the dosage of the component (C) is 50-500ppm;
the component (D) is used in an amount of 20 to 50 parts by mass per 100 parts by mass of the grafted silicone resin of the component (a); the amount of the component (E) is 40-70 parts by mass; the amount of the component (F) is 1 to 5 parts by mass; when the component (G) is an organic solvent, the using amount is 10-40 parts by mass; when the component (G) is water, the amount is 60 to 100 parts by mass.
7. The method for preparing a heat-resistant grafted silicone resin coating according to claim 1 or 2, wherein the grafted silicone resin (A) is prepared by the following method:
(1) Preparation of the repeating unit R 1 SiO 1.5 The T-type polysiloxane of (1);
(2) Preparation of polysiloxane MeO (R) in form D 2 R 3 SiO) n Me；
(3) Preparation of MPEG- (OH) 2 ；
(4) The T-type polysiloxane obtained in (1), the D-type polysiloxane obtained in (2), and the MPEG- (OH) obtained in (3) 2 And a blocking agent R 4 3 And (2) uniformly mixing SiOMe, adding a solvent and a catalytic amount of a catalyst, heating the reaction solution under stirring, separating out a mixture of alcohol and the solvent, cooling the reaction when no obvious alcohol is distilled off, and then carrying out reduced pressure distillation to remove low-boiling-point substances to obtain the MPEG grafted silicon resin.
8. The method for preparing a heat-resistant grafted silicone resin coating according to claim 7, wherein the solvent in step (4) is one or a combination of two or more of benzene, toluene and xylene; in the step (4), the catalyst is a titanate compound; in step (4), T-type polysiloxane, D-type polysiloxane, MPEG- (OH) 2 、R 4 3 The mol ratio of SiOMe to titanate catalyst is 1:1.7-2.5:0.03-0.06:0.5-1:0.001-0.005.
9. The method of claim 7, wherein step (2) is performed to prepare polysiloxane MeO (R) in form D 2 R 3 SiO) n Me is specifically: uniformly mixing dialkoxysilane mixture containing phenyl, hydrogen and vinyl, acetic acid and trifluoromethanesulfonic acid, heating to 50-55 deg.C for reaction, cooling after the reaction is finished, adding neutralizer, stirring for reaction, filtering, and distilling the filtrate under reduced pressure to remove low-boiling-point substances to obtain alkoxy-terminated D-type polysiloxane MeO (R) 2 R 3 SiO) n Me。
10. The method for preparing a heat-resistant grafted silicone resin coating according to claim 9, wherein the neutralizing agent of step (2) is calcium carbonate or magnesium carbonate; the molar ratio of alkoxy groups contained in the dialkoxysilane mixture to acetic acid and trifluoromethanesulfonic acid was 1:0.125-5:0.0001-0.001.
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