Finishing paint phenolic aldehyde modified organic silicon resin for windshield on lighter and preparation method of finishing paint phenolic aldehyde modified organic silicon resin

Abstract

The invention discloses finishing paint phenolic aldehyde modified organic silicon resin for a windshield on a lighter and a preparation method of the finishing paint phenolic aldehyde modified organic silicon resin. The water-based paint is prepared from the following raw materials: methyl trichlorosilane, dimethyl dichlorosilane, phenyl trichlorosilane, diphenyl dichlorosilane, methylbenzene, dimethylbenzene, acetone, propylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, n-butyl alcohol, ionized water, tap water, phenol, cardanol, 37% formaldehyde, methanol, benzyl alcohol, citric acid, oxalic acid, triethylamine and the like. According to the preparation method disclosed by the invention, the optimal methyl proportion and solvent system are screened out through a large number of contrast experiments, and the phenolic aldehyde modified organic silicon resin is prepared by adopting a hydrolysis method and a condensation method. The coating has the comprehensive properties of no smoking in high-temperature decomposition, flame retardancy, high bonding strength, lasting antifouling property, corrosion resistance, high temperature resistance, high chemical resistance, high adhesive force and good impact property.

Description

Technical Field

[0001] The present invention relates to a phenolic modified organic silicone resin for a windshield cover on a lighter, which is a polymer resin with wide application and excellent performance. It is a composite polymer compound formed by cross-linking polymerization of multiple phenolic modified organic silane monomers. The phenolic modified organic silicone resin has the advantages of excellent temperature resistance, chemical corrosion resistance, mechanical strength and the like. Background Art

[0002] The introduction of Si-O bonds in phenolic modified silicone resin gives it obvious advantages in mechanical properties, thermal elasticity, adhesion, glossiness, and compatibility with organic and inorganic fillers. It can be used as high-temperature resistant insulating varnish, high-temperature resistant adhesive, high-temperature resistant molding packaging material, high-temperature resistant coating, ablative material, silicone resin micropowder and other products. It is the largest and most widely used variety of silicone resin at present.

[0003] With the advent of a better life in the new century, people have put forward higher requirements for the living environment and material quality, especially for the performance of metal materials used in life. They not only need to operate at higher temperatures and more harsh high-pollution corrosive environments, but also have various properties such as impact resistance, high-strength mechanical properties and wear resistance. Ordinary organic coatings can hardly play the role of protecting metal materials. The development of high-temperature resistant organic coatings with better performance is becoming more and more urgent, among which the development of high-temperature resistant silicone coatings is more prominent. As a film-forming material of coatings, silicone resin is a key factor in the performance of coatings. Its unique thermal stability and oxidation stability make silicone resin widely used in coatings. There are many methods for synthesizing silicone resins. Among them, the method of synthesizing phenolic modified silicone resin by hydrolysis condensation method using organochlorosilane as raw material has attracted attention. The raw materials of this method are produced by direct method, the raw materials are easy to obtain, the output is large, and the cost is low. However, a large amount of hydrogen chloride gas is generated during the reaction of this method. When hydrogen chloride gas dissolves in water, it releases heat. The generated hydrochloric acid and heat accelerate the spontaneous condensation reaction of silanol intermediates in the hydrolysis reaction, making the reaction system easy to gel. Phenol and formaldehyde are highly toxic, but after being synthesized into polymers, their toxicity is greatly reduced and they can be used normally in life.

[0004] The invention develops a phenolic modified organic silicone resin for a windshield on a lighter through a large number of experimental screenings, optimization of different raw materials and selection of synthesis conditions. The raw materials are simple, cheap and the finished product has low hazard. The methyl bond of chlorosilane has the characteristics of high activity and more conducive to electrophilic substitution reaction. The phenyl bond of chlorosilane has the advantages of low volatility, good film-forming property and weather resistance. The phenolic resin has the advantages of flame retardancy and temperature resistance up to 200 DEG C, adhesiveness and low price. The phenolic modified organic silicone resin for a windshield on a lighter has the advantages of no smoke when decomposed at high temperature, flame retardancy, high bonding strength, long-lasting antifouling, high temperature resistance, high chemical resistance, high adhesion, high gloss and good impact performance. Summary of the invention

[0005] Purpose of the invention: The invention is to preferably obtain a phenolic modified silicone resin for a windshield on a lighter which has high application performance, does not emit smoke when decomposed at high temperature, is flame retardant, has a long-lasting anti-fouling effect, is resistant to high temperatures, has high chemical resistance, has high adhesion, high gloss, and good impact performance. Another purpose of the invention is to provide a method for preparing the resin.

[0006] The present invention adopts a hydrolysis method through a large number of experimental screenings, uses a mixture of a certain proportion of methylphenyl monomer dissolved in a solvent, stirs the mixture evenly and then transfers it to a constant pressure dropping funnel; then prepares a certain proportion of hydrolysis mixed liquid, and drips the mixture into the mixed liquid of a four-necked flask at a uniform speed, and maintains the reaction temperature by a process procedure. After the dropwise addition is completed, the temperature is raised for hydrolysis and condensation reaction, and after the reaction is completed, the mixture is allowed to stand for stratification, and the lower layer of acid water is discharged for further treatment (first acid and alkali neutralization and then to a sewage treatment plant for treatment); the upper layer of water silicon solution is washed with water until the pH is neutral. The neutral silicon solution is desolvated under negative pressure to obtain silanol. A certain proportion of phenols, formaldehyde and catalyst are added to a four-necked flask, the temperature is raised to a certain temperature, dehydrated under negative pressure, and then a catalyst is added at a certain temperature, and finally the solvent is cooled and added after the central control is qualified to obtain a phenolic prepolymer. The obtained silanol, phenolic prepolymer and catalyst are added to a four-necked flask, the temperature is raised to a certain temperature, and the temperature is raised for desolvation and polycondensation to obtain a phenolic modified silicone resin.

[0007] Technical solution, in order to achieve the above purpose, the technical solution adopted by the present invention is:

[0008] A phenolic modified silicone resin topcoat for a windshield on a lighter, which is made from the following raw materials:

[0009] Component A: one of monomethyltrichlorosilane, dimethyldichlorosilane, monophenyltrichlorosilane, diphenyldichlorosilane or a combination thereof;

[0010] Component B: one of phenol, cardanol, 37% formaldehyde (volume concentration) or a combination thereof;

[0011] Component C: one of citric acid, oxalic acid, triethylamine or a combination thereof;

[0012] Component D: one of zinc octoate, zinc isooctanoate, isopropyl titanate or a combination thereof;

[0013] Component E: one or a combination of toluene, xylene, methanol, benzyl alcohol, acetone, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, n-butanol, ionized water, and tap water.

[0014] As a preferred embodiment, the phenolic modified silicone resin topcoat for the windshield of the lighter described above is made of the following raw materials in percentage by weight:

[0015] Component A 12-20%, component B 15-35%, component C 1-5%, component D 0-1%, component E 45-60%.

[0016] As a preferred embodiment, the phenolic modified silicone resin topcoat for the windshield of the lighter described above is made of the following raw materials in percentage by weight:

[0017] Component A 14.4%; Component B 31.5%; Component C 3.5%, Component D 0.6%, Component E 50%.

[0018] As a preferred embodiment, the phenolic modified silicone resin topcoat for the windshield on the lighter described above is made of the following raw materials by weight: 32.3g of monomethyltrichlorosilane, 58.9g of dimethyldichlorosilane, 100.3g of monophenyltrichlorosilane, 19g of diphenyldichlorosilane, 410g of xylene, 670g of deionized water, 200g of phenol, 65g of cardanol, 243g of 37% formaldehyde, 20g of triethylamine, 15g of citric acid, 100g of methanol, and 0.8g of zinc isooctanoate.

[0019] As a preferred embodiment, the phenolic modified silicone resin topcoat for the windshield on the lighter described above is made of the following raw materials by weight: 32.3g of monomethyltrichlorosilane, 58.9g of dimethyldichlorosilane, 100.3g of monophenyltrichlorosilane, 19g of diphenyldichlorosilane, 410g of xylene, 670g of deionized water, 210g of phenol, 446g of 37% formaldehyde, 18g of oxalic acid, 100g of methanol, and 0.8g of zinc isooctanoate.

[0020] The preparation method of the phenolic modified silicone resin topcoat for the windshield on the lighter of the present invention comprises the following steps:

[0021] (1) First, add a certain amount of component A and component E into a reaction container, stir evenly to obtain a mixture A, and transfer the mixture A into a constant pressure dropping funnel for standby use;

[0022] (2) Add component E to the reaction vessel, start stirring, heat the mixture to 20-30° C. in a water bath, and slowly add the mixture A in step (1) dropwise; continue the addition for 4-6 hours;

[0023] (3) When the addition is completed, the temperature is maintained at 25-30° C. for a period of time. When the maintenance is completed, the mixture is allowed to stand, and then the lower layer of acid water is separated. The upper layer of solvent silicon is washed with tap water. The pH test paper is neutral and the acid value is 0-1 mgKOH / g. The solvent silicon in step (3) is vacuum desolventized to obtain silanol B.

[0024] (4) adding a certain amount of component B and component C into a reaction container, raising the temperature to 80-90° C. for a period of time, performing negative pressure dehydration, adding a catalyst, and maintaining the temperature at 80-90° C. for a period of time, and finally cooling and adding a solvent after the intermediate control is qualified to obtain a phenolic prepolymer C;

[0025] (5) Add a certain amount of silanol B, phenolic prepolymer C and D components into a reaction vessel, raise the temperature, and perform a reflux condensation reaction. When the viscosity of the resin increases significantly and becomes viscous, cool it and add a certain amount of E component to obtain a phenolic modified silicone resin.

[0026] The preparation method of the phenolic modified silicone resin topcoat for the windshield on the lighter of the present invention comprises the following steps:

[0027] (1) First, add a certain amount of component A and component E into a four-necked flask and stir to obtain a mixture A. Transfer the mixture A into a constant pressure dropping funnel and set aside.

[0028] (2) Add component E to a four-necked flask, start stirring, heat the mixture to 20° C. in a water bath, and slowly drip the mixture A in step (1) at a drip rate of 1 drop / 1 second for 4 hours; during the dripping process, the temperature in the four-necked flask is maintained between 20-30° C. When the temperature exceeds 25° C., stop heating the mixture in the water bath and maintain the temperature. If the temperature rises rapidly, add ice cubes to cool the mixture and maintain the process temperature at 23-30° C.;

[0029] (3) When the step (2) is finished, the temperature is maintained at 25-30° C. for half an hour. After the temperature is maintained for half an hour, the lower layer of acid water is separated and the upper layer of solvent silicon is washed with tap water for 5-6 times. The pH test paper is neutral and the acid value is 0-1 mgKOH / g. After vacuum desolvation of the solvent silicon, silanol B is obtained and is ready for use.

[0030] (4) Add a certain amount of component B and component C to a 1000 ml four-necked flask, raise the temperature, maintain at 80-90° C. for 2 hours, maintain negative pressure vacuum desolventizing, and maintain the vacuum degree at -0.09 MPa for 45-60 minutes. After the desolventizing is completed, check the free phenol and aldehyde content by central control. After reaching the index, add component C and continue to react at 80-90° C. for 2 hours. After the maintenance is completed, control various indicators in the central control. After passing the test, cool down and add component E to obtain phenolic prepolymer C;

[0031] (5) Put silanol B, phenolic prepolymer C and D components into a four-necked flask and heat them to reflux for condensation reaction. When the temperature is maintained at 145°C and the viscosity of the resin increases significantly and becomes viscous, cool it and add a certain amount of component E to obtain a phenolic modified silicone resin.

[0032] As a preferred embodiment, in the above-mentioned preparation method of the phenolic modified silicone resin for the windshield of the lighter, after the materials in step (1) are stirred evenly, they are transferred to a constant pressure funnel and then nitrogen is passed throughout the process to prevent premature reaction with water vapor in the air and monomer leakage to pollute the environment;

[0033] When the temperature in the four-necked flask of step (2) reaches 20°C, start to slowly dropwise add mixture A, and observe whether there is any leakage to prevent the material from running, bubbling, or leaking; when the temperature in the four-necked flask is maintained at 25-30°C for 4 hours, control the process temperature well. In the middle and late stages of the dropwise addition, the reaction is more intense and the temperature rises rapidly. It is necessary to add ice in advance to control it at 4°C below the maximum process temperature;

[0034] After the reaction in step (3) is completed, the lower layer of acid water must be completely removed each time the water is washed, and the pH test paper finally shows neutrality, and the acid value measured by acid-base titration method reaches 0-1 mgKOH / g;

[0035] When the pressure is slowly increased during the negative pressure desolventizing step (4), pay attention to temperature control to prevent material from being washed away; the desolventized liquid is recycled and treated in a wastewater plant; the free formaldehyde content can be repeatedly measured in the later stage to maintain the stability of the product;

[0036] When step (5) starts, pay attention to temperature increase to prevent material rushing; in the late stage of the reaction, the material reacts violently, so always observe the situation to prevent the material from rising too fast and spraying. After the condensation reaction is completed, add component E when it is cooled to 120°C, and control the solid content, viscosity, acid value, etc. After the control is qualified, cool it to below 80°C and discharge the material.

[0037] Beneficial effects: The present invention has the following advantages:

[0038] The present invention adopts a hydrolysis method and a condensation method through a large number of experimental screenings, and preferably adjusts the optimal methyl ratio and selects a phenolic modified silicone resin of the system of the suitable solvent. The combined application of triethylamine and citric acid can ensure the normal reaction of phenolic aldehyde on the one hand, and can make the content of free phenolic aldehyde decrease steadily and slowly on the other hand; the use of cardanol can increase the flexibility of the product, and the brittleness of phenol is relatively large, but the reaction of cardanol and formaldehyde is incomplete, and the yield is less than that of the same phenol; the combined use of cardanol and phenol can improve the yield and flexibility, reduce brittleness without reducing hardness; diphenyldichlorosilane has a higher temperature and cost than monophenyltrichlorosilane in chain opening, but can increase the gloss and stability of the product, so adding a small amount of diphenyldichlorosilane can improve the product quality but does not greatly affect the increase in cost; the increase in the amount of monomethyltrichlorosilane compared with dimethyldichlorosilane can improve the dryness of the product, reduce the toughness, and control the ratio of monomethyl and dimethyl. The phenolic modified silicone resin topcoat for the windshield on the lighter of the present invention has comprehensive properties such as no smoke when decomposed at high temperature, flame retardancy, high bonding strength, long-lasting antifouling, high temperature resistance, high adhesion, good impact resistance, and relatively low viscosity, relatively reasonable cost, and strong practicality. DETAILED DESCRIPTION

[0039] Example 1

[0040] 1. A method for preparing a phenolic modified silicone resin topcoat for a windshield on a lighter, comprising the following steps:

[0041] (1) First, 32.3 g of monomethyltrichlorosilane, 58.9 g of dimethyldichlorosilane, 100.3 g of monophenyltrichlorosilane, 19 g of diphenyldichlorosilane, and 280 g of xylene were added to a four-necked flask, and nitrogen was passed through the flask for protection. The mixture was stirred to obtain a mixture A, and the mixture A was transferred to a constant pressure dropping funnel for standby use;

[0042] (2) Add 130 g of xylene and 670 g of ionized water into a four-necked flask, start stirring, heat the mixture to 20° C. in a water bath, and slowly add the mixture A of step (1) dropwise at a rate of 1 drop / 1 second; the temperature in the four-necked flask is maintained between 20-30° C. When the temperature exceeds 25° C., stop heating in the water bath, add ice cubes to cool the mixture to maintain the process temperature at 20-30° C., and continue adding dropwise for 4 hours;

[0043] (3) When the addition is completed, the temperature is maintained at 25-30° C. for half an hour. After the maintenance is completed, the mixture is allowed to stand for half an hour, and then the lower layer of acid water is separated. The upper layer of solvent silicon is washed with tap water for 6 times. The pH test paper is neutral, and the acid value is 0-1 mgKOH / g. After vacuum desolvation of the solvent silicon, the solid content is 60%, and the yield of silanol is 70%, and 248 g of silanol B is obtained;

[0044] (4) Add 200 g of phenol, 65 g of cardanol, 243 g of 37% formaldehyde, and 20 g of triethylamine to a four-necked flask, stir, raise the temperature, and maintain it at about 82° C. for 2 hours. After the maintenance, remove about 70% of the solvent by vacuum under negative pressure. The vacuum degree is maintained at -0.09 MPa for 45 minutes. After the desolventizing is completed, the central control checks that the free phenol content is <2% and the free aldehyde content is <1%. After reaching the target, add 15 g of citric acid and continue to maintain the reaction at 88° C. for 2 hours. After the maintenance is completed, the central control controls various indicators. After passing the test, cool down and add 100 g of methanol. The solid content is 80% and the yield is 86%, thereby obtaining 419 g of phenolic prepolymer C;

[0045] (5) Add 248 g of silanol B, 419 g of phenolic prepolymer C, and 0.8 g of zinc isooctanoate into a 1000 ml four-necked flask, and heat the mixture. Reverse condensation reaction is carried out, and the solvent is released and the temperature is raised. When the temperature is maintained at 145° C. and the viscosity of the resin increases significantly and becomes viscous, the mixture is cooled and 100 g of xylene is added to obtain a phenolic modified silicone resin.

[0046] 2. The resin prepared in Example 1 and various fillers in Table 1 below were put into a preparation tank in proportion, stirred in a sand mill (2000 rpm), filtered, and made into a resin varnish slurry, and then diluted with 28% co-solvent, sprayed on a plate, and the varnish thickness reached 23 μm; after the varnish plate was made, it was baked in an oven at 300°C for 10 minutes, and the performance was measured. The performance test is shown in Table 2.

[0047] Table 1 Phenolic modified silicone resin industrial coating formulation composition

[0048] Raw material name Weight(g) Phenolic modified silicone resin prepared in Example 1 60 Defoamer BYK022 0.2 Leveling agent BYK307 0.3 Dispersant BYK190 0.5 Epoxy Curing Agent 2041 11 Benzyl alcohol 8 Xylene 12 n-Butanol 8

[0049] Table 2 Paint film performance test results

[0050] Appearance Smooth and particle-free Visual inspection Self-drying 40 minutes GB / T1728 luster 125° GB / T1743-1989 Hardness (pencil scratch) 5H GB / T6739-2006 Impact resistance(kg) 50 GB / T1732-2020 Flexibility 1mm GB / T1731-2020 Adhesion (circle method) Level 1 GB / T1720-2020 Temperature resistance (oven baking) 500℃ / 72h GB / T1735-2009 .

[0051] Example 2

[0052] A method for preparing a phenolic modified silicone resin topcoat for a windshield on a lighter comprises the following steps:

[0053] (1) First, 32.3 g of monomethyltrichlorosilane, 58.9 g of dimethyldichlorosilane, 100.3 g of monophenyltrichlorosilane, 19 g of diphenyldichlorosilane, and 280 g of xylene were added to a 500 ml four-necked flask, and nitrogen was passed through the flask for protection. The mixture A was uniformly stirred and transferred into a constant pressure dropping funnel for standby use;

[0054] (2) Add 130 g of xylene and 670 g of ionized water into a 2000 ml four-necked flask, start stirring, heat the mixture to 20° C. in a water bath, and slowly add the mixture A of step (1) dropwise at a rate of 1 drop / 1 second; the temperature in the four-necked flask is maintained between 20-30° C. When the temperature exceeds 25° C., stop heating in the water bath, add ice cubes to cool the process temperature to 20-30° C., and continue adding dropwise for 4 hours;

[0055] (3) When the addition is completed, the temperature is maintained at 25-30° C. for half an hour. After the maintenance is completed, the mixture is allowed to stand for half an hour, and then the lower layer of acid water is separated. The upper layer of solvent silicon is washed with tap water for 6 times. The pH test paper is neutral, and the acid value is 0-1 mgKOH / g. After vacuum desolvation of the solvent silicon, the solid content is 60%, and the yield of silanol is 70%, and 248 g of silanol B is obtained;

[0056] (4) Add 210 g of phenol, 446 g of 37% formaldehyde, and 18 g of oxalic acid to a 1000 ml four-necked flask, stir, raise the temperature, and maintain it at about 80° C. for 2 hours. After the maintenance, remove about 70% of the solvent by vacuum under negative pressure. The vacuum degree is maintained at -0.09 MPa for 45 minutes. After the desolventizing is completed, the central control checks that the free phenol content is <2% and the free aldehyde content is <1%. After reaching the target, continue to maintain the reaction at 82° C. for 2 hours. After the maintenance is completed, the central control controls various indicators. After passing the test, cool down and add 100 g of methanol. The solid content is 80% and the yield is 88%, thereby obtaining 432 g of phenolic prepolymer C;

[0057] (5) Add 248 g of silanol B, 432 g of phenolic prepolymer C, and 0.8 g of zinc isooctanoate into a 1000 ml four-necked flask, and heat it up. Reflux for condensation reaction. Add the solvent and heat it up. When the temperature is maintained at 145° C. and the viscosity of the resin increases significantly and becomes viscous, cool it, and add 113 g of xylene to obtain a phenolic modified silicone resin.

[0058] 2. The resin prepared in Example 2 and various fillers in Table 3 below were put into a preparation tank in proportion, stirred in a sand mill (2000 rpm), filtered, and made into a resin varnish slurry, and then diluted with 28% co-solvent, sprayed on a plate, and the varnish thickness reached 23 μm; after the varnish plate was made, it was baked in an oven at 300°C for 10 minutes, and the performance was measured. The performance test is shown in Table 4.

[0059] Table 3 Phenolic modified silicone resin industrial coating formula composition

[0060]

[0061]

[0062] Table 4 Paint film performance test results

[0063] Appearance Smooth and particle-free Visual inspection Self-drying 35 minutes GB / T1728 luster 110° GB / T1743-1989 Hardness (pencil scratch) 3H GB / T6739-2006 Impact resistance(kg) 40 GB / T1732-2020 Flexibility 2mm GB / T1731-2020 Adhesion (circle method) Level 3 GB / T1720-2020 Temperature resistance (oven baking) 500℃ / 60h GB / T1735-2009 .

[0064] Example 3

[0065] A method for preparing a phenolic modified silicone resin topcoat for a windshield on a lighter comprises the following steps:

[0066] (1) First, 44.5 g of monomethyltrichlorosilane, 50.6 g of dimethyldichlorosilane, 116.4 g of monophenyltrichlorosilane, and 280 g of xylene were added to a 500 ml four-necked flask, and nitrogen was passed through the flask for protection. The mixture A was uniformly stirred and transferred into a constant pressure dropping funnel for standby use;

[0067] (2) Add 130 g of xylene and 670 g of ionized water into a 2000 ml four-necked flask, start stirring, heat the mixture to 20° C. in a water bath, and slowly add the mixture A of step (1) dropwise at a rate of 1 drop / 1 second; the temperature in the four-necked flask is maintained between 20-30° C. When the temperature exceeds 25° C., stop heating in the water bath, add ice cubes to cool the process temperature to 20-30° C., and continue adding dropwise for 4 hours;

[0068] (3) When the addition is completed, the temperature is maintained at 25-30° C. for half an hour. After the maintenance is completed, the mixture is allowed to stand for half an hour, and then the lower layer of acid water is separated. The upper layer of solvent silicon is washed with tap water for 6 times. The pH test paper is neutral, and the acid value is 0-1 mgKOH / g. After vacuum desolvation of the solvent silicon, the solid content is 60%, and the yield of silanol is 68%, and 239 g of silanol B is obtained;

[0069] (4) Add 250 g of cardanol, 297 g of 37% formaldehyde, and 36 g of triethylamine to a 1000 ml four-necked flask, stir, raise the temperature, maintain at about 90° C. for 2 hours, and remove about 70% of the solvent by vacuum at the end of the maintenance. The vacuum degree is maintained at -0.09 MPa for 45 minutes. After the desolventizing is completed, the central control checks that the free phenol content is <2% and the free aldehyde content is <1%. After reaching the target, continue to maintain the reaction at 90° C. for 2 hours. After the maintenance is completed, the central control controls various indicators. After passing the test, cool down and add 100 g of methanol. The solid content is 80% and the yield is 84%, thereby obtaining 415 g of phenolic prepolymer C;

[0070] (5) Add 239 g of silanol B, 415 g of phenolic prepolymer C, and 0.8 g of zinc isooctanoate into a 1000 ml four-necked flask, and heat it up. Reflux for condensation reaction. Add the solvent and heat it up. When the temperature is maintained at 150° C. and the viscosity of the resin increases significantly and becomes viscous, cool it, and add 96 g of xylene to obtain a phenolic modified silicone resin.

[0071] 2. The resin prepared in Example 3 and various fillers in Table 5 below were put into a preparation tank in proportion, stirred in a sand mill (2000 rpm), filtered, and made into a resin varnish slurry, which was then diluted with 28% of a co-solvent and sprayed onto a plate to make the varnish thickness reach 23 μm; after the varnish plate was made, it was baked in an oven at 300°C for 10 minutes and the performance was measured. The performance test is shown in Table 6.

[0072] Table 5 Phenolic modified silicone resin industrial coating formula composition

[0073] Raw material name Weight(g) Example 3 Phenolic modified silicone resin prepared 60 Defoamer BYK022 0.2 Leveling agent BYK307 0.3 Dispersant BYK190 0.5 Epoxy Curing Agent 2041 11 Benzyl alcohol 8 Xylene 12 n-Butanol 8

[0074] Table 6 Paint film performance test results:

[0075]

[0076]

[0077] By comparing Example 3 with Example 1, when diphenyldichlorosilane is missing in Example 3, the gloss drops from 125° to 98°; the amounts of monomethyltrichlorosilane and dimethyldichlorosilane are increased, and the self-drying property is improved; when phenol is added in Example 1, the hardness is increased from 3H to 5H.

[0078] By comparing Example 2 with Example 1, the silanols in Example 2 and Example 1 are the same, and the difference is that the formula of the phenolic prepolymer is different. Example 2 does not have cardanol, the phenolic ratio is different, and the formaldehyde ratio is large, resulting in varying degrees of decline in gloss, hardness, impact resistance, flexibility, and adhesion, which also reflects the importance of the phenolic prepolymer in the system.

[0079] Finally, the self-drying performance of the resin in Example 1 is moderate, the high temperature resistance meets the requirements, and other indicators are also acceptable, which shows that the scientific ratio of each component has achieved a very good and unexpected technical effect.

[0080] Furthermore, the comparison results of the above embodiments show that due to the different raw materials of each component and the different amounts of the raw materials, the performance thereof varies greatly, and the comprehensive performance of embodiment 1 of the present invention is significantly better than that of the other embodiments.

[0081] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A phenolic modified silicone resin topcoat for a windshield on a lighter, characterized in that: It is made from the following raw materials: Component A: one of monomethyltrichlorosilane, dimethyldichlorosilane, monophenyltrichlorosilane, diphenyldichlorosilane or a combination thereof; Component B: one of phenol, cardanol, 37% formaldehyde or a combination thereof; Component C: one of citric acid, oxalic acid, triethylamine or a combination thereof; Component D: one of zinc octoate, zinc isooctanoate, isopropyl titanate or a combination thereof; Component E: one or a combination of toluene, xylene, methanol, benzyl alcohol, acetone, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, n-butanol, ionized water, and tap water.

2. The phenolic modified silicone resin topcoat for the windshield of the lighter according to claim 1, characterized in that: It is made of the following raw materials in weight percentage: Component A 12-20%, component B 15-35%, component C 1-5%, component D 0-1%, component E 45-60%.

3. The phenolic modified silicone resin topcoat for the windshield of the lighter according to claim 1, characterized in that: It is made of the following raw materials in weight percentage: Component A 14.4%; Component B 31.5%; Component C 3.5%, Component D 0.6%, Component E 50%.

4. The phenolic modified silicone resin topcoat for the windshield of a lighter according to claim 1, characterized in that: It is prepared from the following raw materials by weight: 32.3g of monomethyltrichlorosilane, 58.9g of dimethyldichlorosilane, 100.3g of monophenyltrichlorosilane, 19g of diphenyldichlorosilane, 410g of xylene, 670g of ionized water, 200g of phenol, 65g of cardanol, 243g of 37% formaldehyde, 20g of triethylamine, 15g of citric acid, 100g of methanol and 0.8g of zinc isooctanoate.

5. The phenolic modified silicone resin topcoat for the windshield of the lighter according to claim 1, characterized in that: The invention is prepared from the following raw materials by weight: 32.3 g of monomethyltrichlorosilane, 58.9 g of dimethyldichlorosilane, 100.3 g of monophenyltrichlorosilane, 19 g of diphenyldichlorosilane, 410 g of xylene, 670 g of ionized water, 210 g of phenol, 446 g of 37% formaldehyde, 18 g of oxalic acid, 100 g of methanol and 0.8 g of zinc isooctanoate.

6. The phenolic modified silicone resin topcoat for the windshield of a lighter according to claim 1, characterized in that: It is prepared from the following raw materials by weight: 44.5g of monomethyltrichlorosilane, 50.6g of dimethyldichlorosilane, 116.4g of monophenyltrichlorosilane, 410g of xylene, 670g of ionized water, 250g of cardanol, 297g of 37% formaldehyde, 36g of triethylamine, 100g of methanol and 0.8g of zinc isooctanoate.

7. The method for preparing the phenolic modified silicone resin topcoat for the windshield of lighters according to any one of claims 1 to 6, characterized in that: The following steps are involved: (1) First, add a certain amount of component A and component E into a reaction container, stir evenly to obtain a mixture A, and transfer the mixture A into a constant pressure dropping funnel for standby use; (2) Add a certain amount of component E into the reaction vessel, start stirring, heat the mixture to 20-30° C. in a water bath, and slowly add the mixture A in step (1) dropwise; continue the addition for 4-6 hours; (3) When the addition is completed, the temperature is maintained at 25-30° C. for a period of time. When the maintenance is completed, the mixture is allowed to stand, and then the lower layer of acid water is separated. The upper layer of solvent silicon is washed with tap water. The pH test paper is neutral and the acid value is 0-1 mgKOH / g. The solvent silicon in step (3) is vacuum desolventized to obtain silanol B. (4) adding a certain amount of component B and component C into a reaction container, raising the temperature to 80-90° C. for a period of time, performing negative pressure dehydration, adding a catalyst, and maintaining the temperature at 80-90° C. for a period of time, and finally cooling and adding a solvent after the intermediate control is qualified to obtain a phenolic prepolymer C; (5) Add a certain amount of silanol B, phenolic prepolymer C and D components into a reaction vessel, raise the temperature, and perform a reflux condensation reaction. When the viscosity of the resin increases significantly and becomes viscous, cool it and add a certain amount of E component to obtain a phenolic modified silicone resin.

8. The method for preparing the phenolic modified silicone resin topcoat for the windshield on the lighter according to claim 7, characterized in that: The following steps are involved: (1) First, add a certain amount of component A and component E into a four-necked flask and stir to obtain a mixture A. Transfer the mixture A into a constant pressure dropping funnel and set aside. (2) Add a certain amount of component E into a four-necked flask, start stirring, heat the mixture to 20° C. in a water bath, and slowly drip the mixture A in step (1) at a drip rate of 1 drop / 1 second for 4 hours; during the dripping process, the temperature in the four-necked flask is maintained between 20-30° C. When the temperature exceeds 25° C., stop heating the flask in the water bath and maintain the temperature. If the temperature rises rapidly, add ice cubes to cool it down and maintain the process temperature at 23-30° C.; (3) When the addition is completed, continue to maintain at 25-30°C for half an hour. After the maintenance is completed, let it stand for half an hour, then separate the lower layer of acid water, wash the upper layer of solvent silicon with tap water 5-6 times, the pH test paper is neutral, and the acid value is 0-1 mgKOH / g. After vacuum desolvation of the solvent silicon, silanol B is obtained and is ready for use; (4) Add a certain amount of component B and component C to a four-necked flask, raise the temperature, maintain it at 80-90° C. for 1-2 hours, maintain the negative pressure vacuum desolventizing, and maintain the vacuum degree at -0.09 MPa for 45-60 minutes. After the desolventizing is completed, check the free phenol and aldehyde content through the central control. After reaching the index, add component C and continue to react at 80-90° C. for 1-2 hours. After the maintenance is completed, control the various indicators in the central control. After passing the test, cool down and add component E to obtain phenolic prepolymer C; (5) A certain amount of silanol B, phenolic prepolymer C and D components are placed in a four-necked flask and heated to reflux for condensation reaction. When the temperature is maintained at 145°C and the viscosity of the resin increases significantly and becomes viscous, the flask is cooled and a certain amount of component E is added to obtain a phenolic modified silicone resin.

9. The method for preparing the phenolic modified silicone resin topcoat for the windshield on the lighter according to claim 8, characterized in that: After the condensation reaction is completed, add component E when the temperature is cooled to 120°C. After the solid content, viscosity and acid value are qualified, cool the mixture to below 80°C and discharge the mixture to obtain phenolic modified silicone resin.

10. Use of the phenolic modified silicone resin according to any one of claims 1 to 6 in preparing a topcoat for a windshield on a lighter.

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