WO2018001100A1 - 一种水溶性有机硅树脂及其应用 - Google Patents

一种水溶性有机硅树脂及其应用 Download PDF

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Publication number
WO2018001100A1
WO2018001100A1 PCT/CN2017/088332 CN2017088332W WO2018001100A1 WO 2018001100 A1 WO2018001100 A1 WO 2018001100A1 CN 2017088332 W CN2017088332 W CN 2017088332W WO 2018001100 A1 WO2018001100 A1 WO 2018001100A1
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Prior art keywords
water
reaction
silicone resin
aqueous
resin
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PCT/CN2017/088332
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English (en)
French (fr)
Inventor
曾志玲
梁文波
王宇
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佛山市珀力玛高新材料有限公司
彩虹高新材料（莱阳）有限公司
香港金和化工（莱阳）有限公司
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Priority claimed from CN201610503793.8A external-priority patent/CN106047163B/zh
Priority claimed from CN201610508606.5A external-priority patent/CN106117559B/zh
Application filed by 佛山市珀力玛高新材料有限公司, 彩虹高新材料（莱阳）有限公司, 香港金和化工（莱阳）有限公司 filed Critical 佛山市珀力玛高新材料有限公司
Publication of WO2018001100A1 publication Critical patent/WO2018001100A1/zh

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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
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • 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
    • C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds

Definitions

  • the invention belongs to the field of water-based coatings, and in particular relates to a water-soluble silicone resin and a water-soluble silicone coating.
  • Silicone resin is a polyorganosiloxane with a highly cross-linked network structure. It has the dual characteristics of organic resin and inorganic materials. It has unique physical and chemical properties. Silicone resin is one of the four major silicone materials (silicone mainly Divided into four categories of silicone oil, silicone rubber, silicone resin and silane coupling agent), it has high temperature resistance, weather resistance and chemical resistance that are difficult to achieve with common organic resins. The research progress of silicone resin has progressed quite rapidly this year. It has been used in industry.
  • CN103897197A discloses a preparation method of a silicone-modified polyester epoxy resin, comprising the following steps: (a) providing a mixture of the following components: a polyester reactant having a hydroxyl group content of 8 to 17.1%; a polysiloxane; a hydroxyl group and an epoxy functional epoxy resin; an optional polymerization catalyst; wherein the weight ratio of the polysiloxane to the polyester reactant is (30 to 90): (10 to 70); The weight of the hydroxy and epoxy functional epoxy resin is from 5 to 15% by weight based on the total weight of the polysiloxane and polyester reactant; the polymerization catalyst comprises the polysiloxane and polyester reactant 0 to 0.5% of the total weight; (b) The mixture is reacted at a reaction temperature of 120 to 170 ° C for 3 to 4 hours to obtain a silicone-modified polyester epoxy resin according to the present invention.
  • the invention combines the advantages of polyester and epoxy resin, has excellent heat resistance and yellowing resistance, but the prepared coating has
  • CN103450465A discloses a preparation method of a silicone modified polyester, comprising the following steps: 1) adding 28.5-50 parts by weight of a polyol, 10-63 parts by weight of a polysiloxane, and 0.01-0.05 in a reaction vessel. a part by weight of the polymerization catalyst, which is reacted at a reaction temperature of 130 to 200 ° C for 2 to 4 hours; 2) 17 to 40 parts by weight of a polybasic acid is added to the reactant obtained in the step 1), and the temperature is further raised to 200. Constant temperature reaction after ⁇ 250 °C, when the acid value is 30 The reaction was completed at ⁇ 10 mgKOH/g to obtain the silicone-modified polyester of the present invention.
  • the water-soluble resin prepared by the invention has good heat resistance, but its dimensional stability is poor.
  • the common preparation method of water-based resin is Sealing with an aqueous group, but because of the complexity of the multi-resin reaction, the blocking agent may react with the ester group in the molecular chain to break the molecular chain, changing the distribution of the resin molecular chain, which will affect the physical properties of the resin. .
  • CN104559565A discloses a nano-silica coating comprising the following components, 45 parts of aqueous acrylic resin, 5 parts of pentaerythritol, 4 parts of bentonite, 5 parts of butyl acetate, 2 parts of mica powder, 1 part of aluminum tripolyphosphate, and nanometer two. 3 parts of silicon oxide, 4 parts of zinc phosphate, 8 parts of quartz powder, 1 part of titanium dioxide, 10 parts of organic fluorine epoxy resin, 40 parts of epoxy resin, 20 parts of silicone resin, 4 parts of polydifluoro resin, xylene 1 serving.
  • the water-based paint prepared by the invention has a good decorative effect, but the heat hardness and other physical properties are relatively poor.
  • the present invention provides a method for preparing a water-soluble silicone resin, comprising the following steps:
  • the weight ratio of the bisphenol A, epichlorohydrin, triol, diol, dibasic acid, antioxidant, catalyst, trimellitic anhydride and silicone intermediate is: 5-10:5-10:20- 30:20-30:30-40:0.2-0.6:0.1-0.8:5-10:60-80;
  • the water-soluble silicone resin has a viscosity of from 6000 to 10000 mps at 25 °C.
  • the aqueous blocking agent comprises trimellitic anhydride, trimesic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-tricarboxycyclohexane, 1,2,4-tricarboxycyclohexane And a combination of one or more of 1,2,3-tricarboxycyclohexane.
  • the triol is one or two of trimethylolpropane and trimethylolethane;
  • the diol is one or two of neopentyl glycol and diethylene glycol; the dibasic acid is one or two of terephthalic acid and oxalic acid.
  • the silicone intermediate comprises one of methyl methoxy silane, methyl ethoxy silane, methoxy silane, ethoxy silane, phenyl methyl silane and phenyl methoxy silane. Or more than one.
  • the lanthanide catalyst is one or more of Sb 2 O 3 , Sb(Ac) 3 (S-21), and ethylene glycol oxime (S-24).
  • the antioxidant is one of triphenyl phosphate and triphenyl phosphite.
  • the present invention also provides the use of the above water-soluble silicone resin for the preparation of a coating.
  • the invention also provides a dispersion liquid containing the above water-soluble silicone resin, wherein the dispersion liquid is prepared by taking a water-soluble silicone resin, dissolving in acetone, adding an appropriate amount of triethylamine, stirring with a high-speed mixer, and then going to the system. The appropriate amount of deionized water is added dropwise, and the original transparent solution gradually becomes milky white. After adding water to a certain amount, the silicone resin dispersion is obtained by continuing high-speed stirring, wherein the water-soluble silicone resin has a solid content of 50-60%.
  • the present invention adopts a combination of a trihydric alcohol and a glycol, and adjusts an appropriate ratio in combination with the remaining components of the technical solution, so that the prepared resin has high hardness and good impact resistance.
  • the present invention adopts a reasonable aqueous blocking agent and an amount to carry out aqueous sealing according to the technical scheme, and the obtained water-soluble silicone resin has good water solubility;
  • the invention selects bisphenol A and epichlorohydrin in combination with the technical scheme of the invention to reasonably adjust the remaining components and reaction parameters, so that the water-soluble resin prepared by the invention has epoxy resin, polyester resin and silicone resin
  • the combination of performance and performance of the obtained water-soluble silicone resin has good storage stability and thermal stability.
  • the invention also provides a water soluble silicone coating.
  • a water-soluble silicone coating comprising water-based silicone resin, nano-silica, titanium dioxide and auxiliary agent, wherein the weight ratio of water-based silicone resin, nano-silica, titanium dioxide and auxiliary agent is: 70-80 : 1-5: 0.5-1: 5-20, the remaining amount is water, the nano silica has an average particle diameter of 100-300 nm; the titanium white fineness is 6000 mesh or more; the aqueous silicone resin It is an aqueous silicone resin having an acid value of 25 ⁇ 10 mgKOH/g modified with polyester or epoxy resin.
  • the invention also provides a water-soluble silicone coating comprising an aqueous silicone resin, nano silica, titanium dioxide and an auxiliary agent, wherein the weight ratio of the aqueous silicone resin, the nano silica, the titanium dioxide and the auxiliary agent is : 70-80: 1-5: 0.5-1: 5-20, the nano-silica has an average particle diameter of 100-300 nm; the titanium white fineness is 6000 mesh or more; the aqueous silicone resin is An aqueous silicone resin having an acid value of 25 ⁇ 10 mg KOH/g modified with a polyester or an epoxy resin.
  • the invention also provides a preparation method of the water-soluble silicone coating: the aqueous silicone resin and the nano silica are blended at a high shear rate for 0.5-1 hour, and then dispersed by ultrasonic for 0.5-1 hour to obtain a blend.
  • Aqueous nano-silica resin after dissolving the above-mentioned blended aqueous nano-silica resin, adding a neutralizing agent, adding deionized water under high-speed stirring until the solution is a white translucent emulsion to obtain a dispersion; the titanium dioxide and An auxiliary agent is added to the above dispersion, and the mixture is adjusted to be alkaline, and its pH is 7.2 to 8.1 to obtain a water-soluble silicone coating.
  • the invention also provides a preparation method of the aqueous silicone resin, comprising the steps of: adding a triol, a glycol, a dibasic acid and an epoxy resin to the reactor, and heating the mixture to 165-180 ° C first, to dissolve the material After 1 hour, the antioxidant is added, the temperature is controlled at 180-220 ° C, and the reaction is carried out until the acid value is less than 8.0.
  • the reaction is carried out by adding a silicone resin intermediate and a catalyst, the reaction temperature is 160-200 ° C, and the reaction time is 3-4 hours.
  • trimellitic anhydride is added dropwise to carry out aqueous capping, the reaction temperature is maintained, and the reaction is carried out for 1-2 hours.
  • the acid value is 25 ⁇ 10 mgKOH/g, the reaction is completed, and an aqueous silicone resin is prepared.
  • the weight ratio of the epoxy resin, triol, glycol, dibasic acid, antioxidant, catalyst, trimellitic anhydride and silicone resin intermediate is: 10-20: 20-30: 20-30: 30-40: 0.2-0.6: 0.1-0.8: 5-10: 60-80.
  • the triol is one or two of trimethylolpropane and trimethylolethane
  • the glycol is one of neopentyl glycol and diethylene glycol or Two kinds
  • the dibasic acid is one or two of terephthalic acid and oxalic acid.
  • the catalyst is tetrabutyl titanate; the antioxidant is one of triphenyl phosphate and triphenyl phosphite.
  • the auxiliary agent comprises one or more of a thickener, a dispersant, a film former, an antifoaming agent, and a leveling agent.
  • the thickener can increase the viscosity of the latex, and can be selected according to specific needs, and the thickener can be one of hydroxymethyl cellulose, carboxymethyl cellulose, sodium polyacrylate, polyvinyl alcohol and hydroxyethyl cellulose.
  • the dispersing agent may be one or more of sodium tripolyphosphate, sodium tetrapolyphosphate and sodium hexametaphosphate
  • the film forming aid may be ethylene glycol ether, ethylene glycol butyl ether, ethylene glycol One or more of an alcohol and a propylene glycol.
  • the invention adopts nano-silica having a particle diameter of 100-300 mesh and titanium white powder of 6000 mesh or more, and is combined with a special process, and the water-soluble silicone coating prepared by a reasonable formula, ratio and method has good water solubility. Properties, impact resistance, water resistance and heat hardness.
  • the water-soluble silicone coating prepared by the invention adopts the water-based silicone resin modified by the combination of trihydric alcohol and glycol, which not only makes the coating have good water solubility, but also has the cooperation of triol and glycol.
  • the resin not only has good heat hardness, but also maintains impact resistance.
  • the water-soluble silicone coating prepared by the invention has the excellent performances of silicone, epoxy resin and polyester resin, adopts a reasonable proportion formula, and has good heat resistance with nano silica.
  • the nano-silica selected by the invention is thoroughly mixed with the modified water-based silicone resin under ultrasonic dispersion, the particle size is reasonable, the dosage ratio is reasonable, the agglomeration of the nano-silica in the resin is avoided, and the coating is provided with good hardness and wear resistance. The advantage of high sex.
  • the assay method of the present invention is based on the following criteria:
  • edges were sealed with a self-drying edge sealer, and then two-thirds of the sample was immersed in a 5% aqueous solution of hydrochloric acid and a 5% aqueous solution of Na OH for 24 hours. Thereafter, the sample was taken out and the residual acid or lye was washed away with distilled water, and the residual water was removed by a filter paper. Observe whether the film is detached, foamed, cracked, discolored, etc., if not, pass.
  • the bonding force of the coating film to the substrate is called adhesion and is measured according to the method of GB1720-70.
  • the adhesion tester is used to evaluate the integrity of the film in the range of the scratches of the round line, expressed in series.
  • the dried coating film sample plate is fixed on the measuring instrument, and after adjusting the needle, the rocking handle is shaken clockwise, and the standard drawing length of the round rolling line is 7-8 cm.
  • the sample was taken out, the paint on the scratches was removed with a paint brush, and the scratches were observed with a 4x magnifying glass and rated. Level 1 is the best, and grade 7 has the worst adhesion.
  • the acid value is defined as the number of milligrams of potassium hydroxide consumed by neutralizing 1 gram of resin, which can reflect the content of carboxyl groups in the resin. Determination method: adding about 0.5g of silicone resin into the tapered crucible, adding about 30ml of acetone solution to dissolve the polyester resin, adding 2-3 drops of phenolphthalein indicator, titrating with the calibration KOH solution, recording the volume of the used KOH solution, The average value was measured three times.
  • the aqueous dispersion After the aqueous dispersion is prepared, it is observed after standing for 1 day, if the dispersion is in a transparent state, the water solubility is good; If it is turbid, it is water-soluble; if it has a bottom or a solution, it is poor in water solubility.
  • Adopt Japanese Mitsubishi pencil the test method and standard are determined by national standard GB/T 6739-2006;
  • the sample is electrically heated by heating, the temperature of the sample is raised to the required temperature, then the voltage is controlled, the temperature is kept stable, and the test method is tested with reference to the pencil hardness;
  • Impact resistance can also be called impact strength, that is, the coating film applied to the substrate is subjected to the impact of high-rate gravity, and the ability to undergo rapid deformation without cracking or falling off from the substrate is in accordance with GB/T 1732.
  • impact strength that is, the coating film applied to the substrate is subjected to the impact of high-rate gravity, and the ability to undergo rapid deformation without cracking or falling off from the substrate is in accordance with GB/T 1732.
  • -93 "Paint film impact resistance test” standard requires the determination of the impact resistance of the coating film, the weight of the weight is 1t, characterized by the maximum height that can cause damage to the paint film, the unit is cm.
  • the measuring instrument adopts the REFO-60MINI type gloss meter, and the test method and standard are determined by the national standard GB/T9754-2007.
  • the paint film sample was prepared according to GB1727-92 "General Preparation Method of Paint Film". This standard specifies the materials for the preparation of general paint films, the surface treatment of the bottom plate, the method of making the board, the drying and condition adjustment of the paint film, the constant temperature and humidity conditions, and the thickness of the paint film.
  • step (1) 100 g of trimethylolpropane, 100 g of neopentyl glycol and 140 g of terephthalic acid are added to the reaction of the step (1), which is first heated to 165 ° C, and 1 g of triphenyl phosphate is added after the material is dissolved and kept for 1 hour. After controlling the temperature to 180 ° C and reacting to an acid value of less than 8.0 mg KOH / g, 100 g of methyl ethoxysilane, 150 g of phenylmethylsilane and 1 g of Sb 2 O 3 were added to carry out the reaction, and the temperature was controlled at 180 ° C. After 3 hours, the acid value was sampled.
  • step (1) 120 g of trimethylolethane, 130 g of diethylene glycol and 180 g of oxalic acid are added to the reaction of the step (1), which is first heated to 170 ° C, and after the material is dissolved and kept for 1 hour, 2 g of phosphorous acid is added.
  • Triphenyl ester the temperature is controlled at 180-220 ° C, after the reaction to an acid value of less than 8.0 mg KOH / g, 100 methyl ethoxy silane, 250 methoxy silane and 1 g Sb 2 O 3 are added for reaction, the temperature is controlled at 180 °C, the reaction time was sampled and tested for acid value at 4 hours.
  • step (1) 200 g of trimethylolpropane and 140 g of terephthalic acid are added to the reaction of the step (1), which is first heated to 165 ° C, and after the material is dissolved and kept for 1 hour, 1 g of triphenyl phosphate is added to control the temperature. After reacting at 180 ° C to an acid value of less than 8.0 mg KOH / g, 100 g of methyl ethoxysilane, 150 g of phenylmethylsilane and 1 g of Sb 2 O 3 were added to carry out the reaction, and the temperature was controlled at 180 ° C, and the reaction time was 3 hours.
  • silicone resin A1 Take 200g of silicone resin A1, dissolve it with acetone, add appropriate amount of triethylamine, stir with high speed mixer, then add appropriate amount of deionized water to the system, the original transparent solution slowly turns into milky white, add water to a certain amount, Continue high-speed stirring to obtain a silicone resin dispersion A1 with a solid content of 55%;
  • silicone resin A1 Take 200g of silicone resin A1, dissolve it with acetone, add appropriate amount of triethylamine, stir with high speed mixer, then add appropriate amount of deionized water to the system, the original transparent solution slowly turns into milky white, add water to a certain amount, Continue high-speed stirring to obtain a silicone resin dispersion A1 with a solid content of 55%;
  • step (1) 100 g of trimethylolpropane, 100 g of neopentyl glycol and 140 g of terephthalic acid are added to the reaction of the step (1), which is first heated to 165 ° C, and 1 g of triphenyl phosphate is added after the material is dissolved and kept for 1 hour. After controlling the temperature to 180 ° C and reacting to an acid value of less than 8.0 mg KOH / g, 100 g of methyl ethoxysilane, 150 g of phenylmethylsilane and 1 g of Sb 2 O 3 were added to carry out the reaction, and the temperature was controlled at 180 ° C. After 3 hours, the acid value was sampled.
  • the silicone resin A (Example 1) prepared above, the silicone resin B (Example 2), the silicone resin A1 (Comparative Example 1), the silicone resin A2 (Comparative Example 2), and the silicone resin A3 ( Comparative Example 3) Thermal hardness test, heat resistance and weather resistance test;
  • the silicone resin dispersion A (Example 1) prepared above, the silicone resin dispersion B (Example 2), the silicone resin dispersion A1 (Comparative Example 1), the silicone resin dispersion A2 (Comparative Example 2), and the silicone resin dispersion Liquid A3 (Comparative Example 3) was subjected to water solubility test and storage stability test, and specific test data of the above silicone resin and silicone resin dispersion are shown in Table 1.
  • Example 1 the silicone resin dispersion prepared in Example 1 and Example 2 has good water solubility and storage stability, and has good heat resistance and weather resistance; Comparative Example 1 after removing the triol Although the thermal hardness and heat resistance have no significant influence, the impact resistance is poor, storage stability and weather resistance are relatively poor; Comparative Example 2 is based on the prior art silicone modified polyester epoxy resin. Preparation of resin water by aqueous capping with trimellitic anhydride The solubility is poor, and the storage stability is not good. In Comparative Example 3, after changing the proportion formula of the present scheme, the properties of the prepared resin are poor in water solubility and the like.
  • the above description of the present invention combines polyester, epoxy resin and silicone by a reasonable ratio and method to make up for the deficiency of the three resins, and the prepared resin has more comprehensive and superior properties.
  • Triphenyl ester the temperature is controlled at 200 ° C, the reaction to an acid value of less than 8.0, 75g of methyl phenyl silicone intermediate, 0.5g of tetrabutyl titanate reaction, the reaction temperature is 180 ° C, the reaction time is 4
  • the reaction acid value is less than 8 mgKOH/g
  • 5 g of trimellitic anhydride is added dropwise to carry out aqueous capping
  • the reaction temperature is maintained, and the reaction is carried out for 2 hours.
  • the acid value is 25 ⁇ 10 mgKOH/g, the reaction is completed to prepare an aqueous silicone resin C.
  • Preparation of water-soluble silicone coating 70g of water-based silicone resin C, 4g of nano-silica (powder of 200nm particle size) was blended at high shear rate for 1 hour, and then dispersed by ultrasonic wave for 1 hour. a water-containing nano-silica resin; the above-mentioned blended aqueous nano-silica resin is dissolved in acetone, and then triethylamine is added, and deionized water is added dropwise under high-speed stirring until the solution is a white translucent emulsion to obtain a dispersion; 10 g of titanium dioxide (fineness of 7000 mesh) and 5 g of sodium tripolyphosphate and 5 g of ethylene glycol diethyl ether were added to the above dispersion, and the mixture was adjusted to be alkaline, and the pH was 7.2-8.1 to obtain a water-soluble silicone coating C. .
  • Triphenyl ester the temperature is controlled at 200 ° C, the reaction to an acid value of less than 8.0, 75g of methyl phenyl silicone intermediate, 0.5g of tetrabutyl titanate reaction, the reaction temperature is 180 ° C, the reaction time is 4
  • the reaction acid value is less than 8 mgKOH/g
  • 5 g of trimellitic anhydride is added dropwise to carry out aqueous capping
  • the reaction temperature is maintained, and the reaction is carried out for 2 hours.
  • the acid value is 25 ⁇ 10 mgKOH/g, the reaction is completed, and an aqueous silicone resin D is obtained.
  • Preparation of water-soluble silicone coating 75g of water-based silicone resin D, 1g of nano-silica (powder of 200nm particle size) was blended at high shear rate for 0.5 hours, and then dispersed by ultrasonic wave for 1 hour.
  • a water-containing nano-silica resin a water-containing nano-silica resin
  • the above-mentioned blended aqueous nano-silica resin is dissolved in acetone, and then triethylamine is added, and deionized water is added dropwise under high-speed stirring until the solution is a white translucent emulsion to obtain a dispersion; 15g titanium dioxide (fineness is 6500 mesh) And 10 g of sodium tripolyphosphate, 5 g of ethylene glycol ether, and 5 g of hydroxymethylcellulose were added to the above dispersion, and the mixture was adjusted to be alkaline to have a pH of 7.2 to 8.1 to obtain a water-soluble silicone coating material D.
  • Example 3 Compared with Example 3, the particle size of the nano-silica in Comparative Example 4 was 50 nm, and the remaining components and amounts were the same as in Example 3, and the rest of the process was the same as in Example 3 to obtain a water-soluble silicone coating C1.
  • Example 3 Compared with Example 3, the blended aqueous nano-silica resin in Comparative Example 5 was not subjected to ultrasonic treatment, and the remaining components and amounts were the same as in Example 3, and the other processes were the same as in Example 3 to obtain a water-soluble silicone coating C2.
  • Example 3 Compared with Example 3, the ratio of the aqueous silicone resin, the nano silica and the titanium white powder in Comparative Example 6 is not within the scope of the present scheme, the amount of the aqueous silicone resin is adjusted to 60 g, and the amount of the nano silica is adjusted to 8 g, the amount of titanium dioxide was adjusted to 30 g, the remaining components and amounts were the same as in Example 3, and the rest of the process was the same as in Example 3 to obtain a water-soluble silicone coating C3.
  • Example 3 Compared with Example 3, the process of preparing the aqueous silicone resin was removed in Comparative Example 7, using a conventional aqueous silicone resin (containing methoxy and phenyl silicone resin), and the remaining components and amounts were the same as in Example 3, and the remaining processes were the same. In the same manner as in Example 3, a water-soluble silicone coating material C4 was obtained.
  • coating C The above-mentioned water-based silicone coating C (referred to as coating C), water-based silicone coating D (referred to as coating D), aqueous silicone coating C1 (referred to as coating C1), aqueous silicone coating C2 (referred to as coating C2), aqueous silicone coating C3
  • coating C3 The properties of (referred to as coating C3) and aqueous silicone coating C4 (referred to as coating C4) are shown in Table 1.
  • the coatings C and D prepared by the solution of the invention have better performance, not only high hardness but also good flexibility and impact resistance, and good acid and alkali resistance and water resistance;
  • the particle size of the nano-silica is 50 nm. Due to the large particle size, the dispersion effect is not good, and the combination with the other components in the formulation is not ideal, and the relative acid and alkali resistance and storage stability are the same.
  • Comparative Example 5 the mixing method is directly mixed, which makes the nano silica easy to precipitate, the prepared dispersion is unstable, and the relative wear resistance, storage stability and heat hardness are poor; 6 changes in the ratio of water-based silicone resin, nano-silica and titanium dioxide, all aspects of performance are poor, the amount of nano-silica compared to silicone resin, if the amount is too small, for performance improvement Not obvious, if the addition amount is too much, affecting water solubility, other properties can not be guaranteed, if the ratio of water-based silicone resin, nano-silica and titanium dioxide is not within a reasonable range, it will cause poor compatibility and cannot reach Good performance, and even affect the original stability of the resin.
  • the solution of the invention has reasonable formula ratio and reasonable preparation method, and the prepared water-based silicone coating has various excellent properties.

Abstract

一种有机硅树脂的制备方法，采用双酚A和环氧氯丙烷制备环氧树脂，将该环氧树脂与三元醇、二元醇和二元酸反应，再加入有机硅中间体进行反应，采用水性封端剂进行水性封端，控制反应温度、时间、酸值等条件得到水性有机硅树脂。一种水溶性有机硅涂料，采用水性有机硅树脂、纳米二氧化硅、钛白粉和助剂的重量比为：70-80：1-5：0.5-1：5-20，所述纳米二氧化硅为平均粒径为100-300纳米的粉末；所述钛白粉细度为6000目以上；所述水性有机硅树脂为用聚酯、环氧树脂改性后的酸值为25±10mgKOH/g的水性有机硅树脂。

Description

一种水溶性有机硅树脂及其应用 技术领域
本发明属于水性涂料领域，具体涉及一种水溶性有机硅树脂和水溶性有机硅涂料。
背景技术
硅树脂是具有高度交联网状结构的聚有机硅氧烷，兼具有机树脂及无机材料的双重特性，具有独特的物理、化学性能，有机硅树脂是4大有机硅材料之一(有机硅主要分为硅油、硅橡胶、硅树脂和硅烷偶联剂四大类)，具有一般有机树脂难以达到的耐高温、耐候及耐化学品性，今年来有机硅树脂的研究工作进展相当快，以下成果已在工业上运用。
近年来，由于生态环境的恶化，环境保护愈来愈受到世界的关注。各个国家都制定了相关法规来严格限制涂料中的有机挥发物(VOC)的排放。我国政府也于1989年12月颁布了环境保护法以及“绿色”标志规定等，以限制VOC的排放。溶剂型涂料含有大量VOC成分，不仅污染环境浪费资源还危害人们的健康。低污染的水性涂料、光固化涂料、粉末涂料和高固体分涂料已成为涂料的发展方向。水性涂料相对其他低污染涂料而言，由于具有可实现技术途径多、应用面广、安全、施工相对简单等优点而成为首选品种，更为广大涂料科技人员关注和涂料用户的青睐，VOC主要来源于涂料的分散介质和成膜物，水性树脂生产技术的发展，使得水性涂料逐步代替溶剂型涂料成为可能。
CN103897197A公开了一种有机硅改性聚酯环氧树脂的制备方法，包括以下步骤：(a)提供如下组分的混合物：羟基含量8～17.1％的聚酯反应物；聚硅氧烷；含羟基及环氧官能基的环氧树脂；可选的聚合反应催化剂；其中，所述聚硅氧烷与聚酯反应物的重量比为(30～90)：(10～70)；所述含羟基及环氧官能基的环氧树脂的重量占所述聚硅氧烷与聚酯反应物的总重量的5～15％；所述聚合反应催化剂占所述聚硅氧烷与聚酯反应物的总重量的0～0.5％；(b)所述混合物在120～170℃的反应温度下反应3～4小时，得到本发明所述的有机硅改性聚酯环氧树脂。该发明结合聚酯和环氧树脂的优点，具有优异的耐热耐黄变性能，但其制备的涂料柔韧性差，并且不具备水溶性，不利于绿色环保涂料。
CN103450465A公开了一种有机硅改性聚酯的制备方法，包括如下步骤：1)在反应容器中加入28.5～50重量份的多元醇、10～63重量份的聚硅氧烷、以及0.01～0.05重量份的聚合反应催化剂，在130～200℃的反应温度下反应2～4小时；2)将17～40重量份的多元酸加入到所述步骤1)得到的反应物中，继续升温到200～250℃后恒温反应，当酸值为30 ±10mgKOH/g时反应完成，得到本发明所述的有机硅改性聚酯。该发明制备的水溶性树脂具有较好的耐热性能，但其尺寸稳定性差，
关于聚酯硅树脂改性的水溶性树脂研究较多，但制备改性后的树脂很难达到多性能优化，很难将多种树脂的优点集中到同一树脂上，水性树脂常见的制备方法为采用水性基团进行封端，但因为多树脂反应的复杂性，封端剂可能会跟分子链中的酯基发生反应，使分子链断裂，改变树脂分子链分布，会使树脂物理性能受到影响。
CN104559565A公开了一种纳米二氧化硅涂料，包含下列组成部分，水性丙烯酸树脂45份，季戊四醇5份，膨润土4份，乙酸丁酯5份，云母粉2份，三聚磷酸铝1份，纳米二氧化硅3份，磷酸锌4份，石英粉8份，钛白粉1份，有机氟环氧树脂10份，环氧树脂40份，有机硅树脂20份，偏聚二氟树脂4份，二甲苯1份。该发明制备的水性涂料具有较好的装饰效果，但热硬度和其他物理性能相对较差。
发明内容
为解决上述问题，本发明提供一种水溶性有机硅树脂的制备方法，包括如下步骤：
(1)将双酚A和环氧氯丙烷加入反应器，搅拌至充分混合，加入过量NaOH进行反应，反应温度为60-120℃，反应时间为3-10小时；
(2)将三元醇、二元醇和二元酸加入步骤(1)的反应中，将先加热至165-180℃，待物料溶解保温1小时后加入抗氧剂，将温度控制在180-220℃，反应至酸值小于8.0mgKOH/g后，加入硅树脂中间体、锑系催化剂进行反应，反应温度为160-200℃，反应时间为3-4小时，当反应酸值低于8mgKOH/g时滴加水性封端剂进行水性封端，保持反应温度，反应1-2小时，当酸值为25±10mgKOH/g时反应完成，制备得到水溶性有机硅树脂；
所述双酚A、环氧氯丙烷、三元醇、二元醇、二元酸、抗氧剂、催化剂、偏苯三酸酐和硅树脂中间体的重量比为：5-10：5-10：20-30：20-30：30-40：0.2-0.6：0.1-0.8：5-10：60-80；
所述水溶性有机硅树脂在25℃时的粘度为6000-10000mps。
优选的，所述水性封端剂包含偏苯三酸酐、均苯三甲酸、1,2,3-苯三甲酸、1,3,5-三羧基环己烷、1,2,4-三羧基环己烷以及1,2,3-三羧基环己烷中的一种或多种的组合。
优选的，所述三元醇为三羟甲基丙烷和三羟甲基乙烷中的一种或两种；
优选的，所述二元醇为新戊二醇和一缩二乙二醇中的一种或两种；所述二元酸为对苯二甲酸和乙二酸中的一种或两种。
优选的，所述硅树脂中间体包含甲基甲氧基硅烷、甲基乙氧基硅烷、甲氧基硅烷、乙氧基硅烷、苯基甲基硅烷和苯基甲氧基硅烷中的一种或一种以上。
优选的，所述锑系催化剂为Sb2O3、Sb(Ac)3(S-21)和乙二醇锑(S-24)中的一种或一种以上。
优选的，所述抗氧剂为磷酸三苯酯和亚磷酸三苯酯中的一种。
本发明还提供上述水溶性有机硅树脂用于制备涂料的用途。
本发明还提供一种含有上述的水溶性有机硅树脂的分散液，分散液的制备方法为：取水溶性有机硅树脂，用丙酮溶解后，加入适量三乙胺，用高速搅拌机搅拌，然后往体系里滴加适量去离子水，原本透明的溶液慢慢变成乳白色，加水到一定量后，继续高速搅拌即得到硅树脂分散液，其中水溶性有机硅树脂的固含量为50-60％。
本发明提供一种水溶性有机硅树脂的制备方法的有益效果：
(1)本发明采用三元醇、二元醇相互配合，结合本技术方案的其余组分调整适当比例，实现制备的树脂不仅硬度高而且耐冲击性能好
(2)本发明根据本技术方案选用合理的水性封端剂及用量进行水性封端，实现得到的水溶性有机硅树脂具备较好的水溶性；
(3)本发明选用双酚A和环氧氯丙烷结合本发明的技术方案合理调整其余组分及反应参数，使本发明制备的水溶性树脂具有环氧树脂、聚酯树脂和有机硅树脂三者性能的结合，实现得到的水溶性有机硅树脂具备较好贮存稳定性和热稳定性。
本发明还提供一种水溶性有机硅涂料。
一种水溶性有机硅涂料，包含水性有机硅树脂、纳米二氧化硅、钛白粉和助剂，其中，水性有机硅树脂、纳米二氧化硅、钛白粉和助剂的重量比为：70-80：1-5：0.5-1：5-20，其余量为水，所述纳米二氧化硅平均粒径为100-300纳米的粉末；钛白粉细度为6000目以上；所述水性有机硅树脂为用聚酯、环氧树脂改性后的酸值为25±10mgKOH/g的水性有机硅树脂。
本发明还提供一种水溶性有机硅涂料，包含水性有机硅树脂、纳米二氧化硅、钛白粉和助剂，其中，水性有机硅树脂、纳米二氧化硅、钛白粉和助剂的重量比为：70-80：1-5：0.5-1：5-20，所述纳米二氧化硅平均粒径为100-300纳米的粉末；钛白粉细度为6000目以上；所述水性有机硅树脂为用聚酯、环氧树脂改性后的酸值为25±10mgKOH/g的水性有机硅树脂。
本发明还提供所述水溶性有机硅涂料的制备方法：将水性有机硅树脂、纳米二氧化硅在高剪切速率下共混0.5-1小时，再用超声波分散0.5-1小时，得到共混水性纳米二氧化硅树脂；将上述共混水性纳米二氧化硅树脂溶解后加入中和剂，在高速搅拌作用下滴加去离子水，直至溶液呈白色半透明乳液得到分散液；将钛白粉和助剂加入上述分散液中，将混合物调节至碱性，其pH值为7.2-8.1，得到水溶性有机硅涂料。
本发明还提供水性有机硅树脂的制备方法，包括如下步骤：将三元醇、二元醇、二元酸和环氧树脂加入反应器中，将先加热至165-180℃，待物料溶解保温1小时后加入抗氧剂，将温度控制在180-220℃，反应至酸值小于8.0后，加入硅树脂中间体、催化剂进行反应，反应温度为160-200℃，反应时间为3-4小时，当反应酸值低于8mgKOH/g时滴加偏苯三酸酐进行水性封端，保持反应温度，反应1-2小时，当酸值为25±10mgKOH/g时反应完成，制备得到水性有机硅树脂。
优选的，所述环氧树脂、三元醇、二元醇、二元酸、抗氧剂、催化剂、偏苯三酸酐和硅树脂中间体的重量比为：10-20：20-30：20-30：30-40：0.2-0.6：0.1-0.8：5-10：60-80。
优选的，所述三元醇为三羟甲基丙烷和三羟甲基乙烷中的一种或两种；所述二元醇为新戊二醇和一缩二乙二醇中的一种或两种；所述二元酸为对苯二甲酸和乙二酸中的一种或两种。
优选的，所述催化剂为钛酸四丁酯；所述抗氧剂为磷酸三苯酯和亚磷酸三苯酯中的一种。
优选的，所述助剂包含增稠剂、分散剂、成膜剂、消泡剂和流平剂中的一种或一种以上。增稠剂能增加乳胶的粘度，可根据具体需求进行选择，所述增稠剂可为羟甲基纤维素、羧甲基纤维素、聚丙烯酸钠、聚乙烯醇和羟乙基纤维素中的一种或几种；分散剂可为三聚磷酸钠、四聚磷酸钠和六偏磷酸钠中的一种或几种；成膜助剂可为乙二醇乙醚、乙二醇丁醚、乙二醇、丙二醇中的一种或几种。
本发明的有益效果：
(1)本发明采用粒径为100-300目的纳米二氧化硅和6000目以上钛白粉，同时与特殊工艺结合，合理的配方、比例及方法制备得到的水溶性有机硅涂料具有较好的水溶性、抗冲击性能、耐水性和热硬度。
(2)本发明制备的水溶性有机硅涂料，采用三元醇、二元醇混合改性的水性有机硅树脂，不仅使涂料具有较好的水溶性，同时，三元醇和二元醇的配合，使树脂不仅具备较好的热硬度，还能保持耐冲击性能。
(3)本发明制备的水溶性有机硅涂料，具备有机硅、环氧树脂和聚酯树脂3者的优良性能，采用合理的比例配方，配合纳米二氧化硅具备较好的耐热性能，本发明选用的纳米二氧化硅在超声波分散下与改性后的水性有机硅树脂充分混合，粒径合理，用量配比合理，避免纳米二氧化硅在树脂中的团聚，赋予涂料硬度好、耐磨性高的优点。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进一步详细说明，但本发明要求的保护范围并不局限于实施例。
本发明的测定方法按照如下标准：
1.耐酸性和耐碱性
用自干性能好的封边漆进行封边，然后将试样的三分之二浸没在5％盐酸水溶液和5％Na OH水溶液中保持24小时。之后取出样品并用蒸馏水洗去残留的酸液或者碱液，并用滤纸吸去残留的水。观察膜是否有脱落、起泡，开裂，变色等显现，若无则通过。
2.附着力的测定
涂膜对底材的结合力称为附着力，按GB1720-70方法测定。使用附着力测定仪，按照圆滚线划痕范围内的涂膜完整度评定，以级数表示。将实干的涂膜样板固定在测定仪上，调整好针头之后按顺时针摇动摇柄，圆滚线划痕标准图长为7～8cm。取出样板，用漆刷除去划痕上的漆屑，用4倍放大镜观察划痕并评级。1级最好，7级附着力最差。
3.柔韧性测定
按照国家标准《涂膜柔韧性测试》(GB/T1731-1993)的方法，在恒温恒湿的条件下，用大拇指的力量在2～3s内，绕棒弯曲样板，取下后用四倍放大镜观察涂膜是否有裂纹或剥落等现象。以不引起漆膜破坏的直径最小的轴棒表示涂膜的柔韧性(共7个直径分别为1mm,2mm,3mm,4mm,5mm,10mm,15mm)。
4.酸值测定
酸值定义为中和1克树脂所消耗的氢氧化钾的毫克数，可以体现出树脂中羧基的含量。测定方法：在锥形甁中加入约0.5g有机硅树脂，加入30ml左右丙酮溶液溶解聚酯树脂，再加入2-3滴酚酞指示剂，用标定的KOH溶液滴定，记录所用KOH溶液的体积，测定三次取平均值。
5.水溶性测试
配制好水性分散体后，静置1天后观察，如果分散体呈现透明状态，则水溶性好；如 果有些浑浊，则水溶性一般；如果有沉底或溶物，则水溶性差。
6.储存稳定性测试
常温下静置3个月后，如果水分散体的状态与3个月前相同，则储存稳定性好；如果水分散体有沉底出现，但用玻璃棒易搅起，则稳定性一般；如果水分散体完全分层，则为稳定性差。
7.铅笔硬度测试
采用日本三菱铅笔，检验方法及标准采用国标GB/T 6739-2006测定；
8.热硬度测试
将样品通上电加热，待样品温度升至所要求的温度，然后控制电压，保持温度稳定，参照铅笔硬度的测试方法进行测试；
9.抗冲击性
耐冲击性也可以称为冲击强度，即指涂于基材上的涂膜受高速率重力的冲击作用，发生快速变形却不会出现开裂或者从基材上脱落的能力，按照GB/T 1732-93《漆膜耐冲击测定法》的标准要求测定涂膜的抗冲击性能，重锤重量为1t，以能够不引起破坏漆膜的最大高度来表征，单位为cm。
10.耐水性
基本参照GB1733-93漆膜耐水性测定法进行，不采用标准中所述室温浸泡方法，而用加温浸泡法，在40±1℃的条件下浸泡，观察漆膜有无发白起泡现象。
11.耐磨性能测试
将产品放置在杜邦专用的耐磨机上，施加4.9kg的压力，加入少量的洗洁精和水，采用3M-7447#百洁布，每250次更换一次百洁布。以10条基体露白终止测试，计算总次数。
12.光泽
测定仪器采用REFO-60MINI型光泽计，检验方法及标准采用国标GB/T9754-2007测定。
固化漆膜的制备：漆膜试样按照GB1727-92《漆膜一般制备法》进行制备。此标准规定了制备一般漆膜的材料，底板的表面处理、制板方法、漆膜的干燥和状态调节、恒温恒湿条件以及漆膜厚度等。
制备水溶性有机硅树脂的具体实施例
实施例1
水溶性有机硅树脂的制备：
(1)将20g双酚A和30g环氧氯丙烷加入反应器，搅拌至充分混合保持50℃，加入过量NaOH进行反应，保持80℃反应3小时；
(2)将100g三羟甲基丙烷、100g新戊二醇和140g对苯二甲酸加入步骤(1)的反应中，将先加热至165℃，待物料溶解保温1小时后加入1g磷酸三苯酯，将温度控制在180℃，反应至酸值小于8.0mgKOH/g后，加入100g甲基乙氧基硅烷、150g苯基甲基硅烷和1g Sb2O3进行反应，控制温度在180℃，反应时间为3小时后取样测试酸值，当反应酸值低于8mgKOH/g时滴加30g偏苯三酸酐进行水性封端，保持温度，反应1小时后取样测定酸值，当酸值为25±10mgKOH/g时反应完成，降温，然后加入正丁醇、二甲苯等溶剂搅拌30分钟，调整树脂粘度6000-10000mps，冷却至室温，制备得到水溶性有机硅树脂A；
水溶性有机硅树脂分散液的制备：
取200g水溶性有机硅树脂A，用丙酮溶解后，加入适量三乙胺，用高速搅拌机搅拌，然后往体系里滴加适量去离子水，原本透明的溶液慢慢变成乳白色，加水到一定量后，继续高速搅拌即得到固含量55％的硅树脂分散液A；
实施例2
水溶性有机硅树脂的制备：
(1)将25g双酚A和30g环氧氯丙烷加入反应器，搅拌至充分混合，加入过量NaOH进行反应，保持100℃反应4小时；
(2)将120g三羟甲基乙烷、130g一缩二乙二醇和180g乙二酸加入步骤(1)的反应中，将先加热至170℃，待物料溶解保温1小时后加入2g亚磷酸三苯酯，将温度控制在180-220℃，反应至酸值小于8.0mgKOH/g后，加入100甲基乙氧基硅烷、250甲氧基硅烷和1gSb2O3进行反应，控制温度在180℃，反应4小时候取样测试酸值，当反应酸值低于8mgKOH/g时滴加40g偏苯三酸酐进行水性封端，保持反应温度，反应2小时后取样测量酸值，当酸值为25±10mgKOH/g时反应完成，降温，然后加入正丁醇、二甲苯等溶剂搅拌30分钟，调整树脂粘度6000-10000mps，冷却至室温，制备得到水溶性有机硅树脂B；
水溶性有机硅树脂分散液的制备：
取200g水溶性有机硅树脂B，用丙酮溶解后，加入适量三乙胺，用高速搅拌机搅拌，然后往体系里滴加适量去离子水，原本透明的溶液慢慢变成乳白色，加水到一定量后，继续高速搅拌即得到固含量为54％的硅树脂分散液B；
对比例1
(1)将20g双酚A和30g环氧氯丙烷加入反应器，搅拌至充分混合保持50℃，加入过量NaOH进行反应，保持80℃反应3小时；
(2)将200g三羟甲基丙烷和140g对苯二甲酸加入步骤(1)的反应中，将先加热至165℃，待物料溶解保温1小时后加入1g磷酸三苯酯，将温度控制在180℃，反应至酸值小于8.0mgKOH/g后，加入100g甲基乙氧基硅烷、150g苯基甲基硅烷和1g Sb2O3进行反应，控制温度在180℃，反应时间为3小时后取样测试酸值，当反应酸值低于8mgKOH/g时滴加30g偏苯三酸酐进行水性封端，保持温度，反应1小时后取样测定酸值，冷却至室温，制备得到有机硅树脂A1；
有机硅树脂分散液的制备：
取200g有机硅树脂A1，用丙酮溶解后，加入适量三乙胺，用高速搅拌机搅拌，然后往体系里滴加适量去离子水，原本透明的溶液慢慢变成乳白色，加水到一定量后，继续高速搅拌即得到固含量55％的硅树脂分散液A1；
对比例2
在通有氮气的反应容器中加入268g三羟甲基丙烷、166g间苯二甲酸，加热升温至220℃后恒温反应，脱水，当酸值降到10mgKOH/g以下时，降温至140℃，加入适量丙二醇甲醚醋酸酯(PMA)，制得固含量为75％的聚酯反应物，羟基含量17.1％；取40g上述固含量为75％的聚酯反应物加入到反应容器中，加热升温至100℃后，加入70g纯苯基聚硅氧烷，8g双酚A型环氧树脂(环氧当量为806-909)，0.5g的钛酸四丁酯作催化剂及35g的PMA为溶剂，继续升温到约120℃，滴加40g偏苯三酸酐进行封端，反应1小时后冷却至室温，制备得到有机硅树脂A2；
有机硅树脂分散液的制备：
取200g有机硅树脂A1，用丙酮溶解后，加入适量三乙胺，用高速搅拌机搅拌，然后往体系里滴加适量去离子水，原本透明的溶液慢慢变成乳白色，加水到一定量后，继续高速搅拌即得到固含量55％的硅树脂分散液A1；
对比例3
(1)将20g双酚A和2g环氧氯丙烷加入反应器，搅拌至充分混合保持50℃，加入过量NaOH进行反应，保持80℃反应3小时；
(2)将100g三羟甲基丙烷、100g新戊二醇和140g对苯二甲酸加入步骤(1)的反应中，将先加热至165℃，待物料溶解保温1小时后加入1g磷酸三苯酯，将温度控制在180℃， 反应至酸值小于8.0mgKOH/g后，加入100g甲基乙氧基硅烷、150g苯基甲基硅烷和1g Sb2O3进行反应，控制温度在180℃，反应时间为3小时后取样测试酸值，当反应酸值低于8mgKOH/g时滴加2g偏苯三酸酐进行水性封端，保持温度，反应1小时后取样测定酸值，降温，然后加入正丁醇、二甲苯等溶剂搅拌30分钟，调整树脂粘度6000-10000mps，冷却至室温，制备得到有机硅树脂A；
效果实施例
将上述制备得到的有机硅树脂A(实施例1)、有机硅树脂B(实施例2)、有机硅树脂A1(对比例1)、有机硅树脂A2(对比例2)和有机硅树脂A3(对比例3)进行热硬度测试、耐热性和耐候性测试；
上述制备的硅树脂分散液A(实施例1)、硅树脂分散液B(实施例2)、硅树脂分散液A1(对比例1)、硅树脂分散液A2(对比例2)和硅树脂分散液A3(对比例3)进行水溶性测试、储存稳定性测试，上述有机硅树脂及硅树脂分散液的具体测试数据见表1。
表1有机硅树脂及硅树脂分散液性能
Figure PCTCN2017088332-appb-000001
从表1可以看出，实施例1和实施例2制备的硅树脂分散液具有较好的水溶性和贮存稳定性，并且耐热性能及耐候性能较好；对比例1在去掉三元醇后，虽然热硬度和耐热性能没有较大影响，但其耐冲击性能较差，储存稳定性和耐候性都相对较差；对比例2在现有技术有机硅改性聚酯环氧树脂的基础上用偏苯三酸酐进行水性封端，制备得到的树脂水 溶性较差，储存稳定性也不好；对比例3在改变了本方案比例配方后，制备的树脂水溶性等各项性能都较差。
上述说明本发明通过合理的比例和方法将聚酯、环氧树脂和有机硅进行结合，弥补3种树脂相互的不足，制备的树脂性能更全面，更优良。
水溶性有机硅涂料的具体实施例
实施例3
水性有机硅树脂的制备：将20g三元醇、30g二元醇、35g二元酸和15g环氧树脂加入反应器中，将先加热至170℃，待物料溶解保温1小时后加入0.4g磷酸三苯酯，将温度控制在200℃，反应至酸值小于8.0后，加入75g甲基苯基硅树脂中间体、0.5g钛酸四丁酯进行反应，反应温度为180℃，反应时间为4小时，当反应酸值低于8mgKOH/g时滴加5g偏苯三酸酐进行水性封端，保持反应温度，反应2小时，当酸值为25±10mgKOH/g时反应完成，制备得到水性有机硅树脂C。
水溶性有机硅涂料的制备：将70g水性有机硅树脂C、4g纳米二氧化硅(粒径为200纳米的粉末)在高剪切速率下共混1小时，再用超声波分散1小时，得到共混水性纳米二氧化硅树脂；将上述共混水性纳米二氧化硅树脂用丙酮溶解后加入三乙胺，在高速搅拌作用下滴加去离子水，直至溶液呈白色半透明乳液得到分散液；将10g钛白粉(细度为7000目)和5g三聚磷酸钠、5g乙二醇乙醚加入上述分散液中，将混合物调节至碱性，其pH值为7.2-8.1，得到水溶性有机硅涂料C。
实施例4
水性有机硅树脂的制备：将25g三元醇、25g二元醇、40g二元酸和10g环氧树脂加入反应器中，将先加热至170℃，待物料溶解保温1小时后加入0.3g磷酸三苯酯，将温度控制在200℃，反应至酸值小于8.0后，加入75g甲基苯基硅树脂中间体、0.5g钛酸四丁酯进行反应，反应温度为180℃，反应时间为4小时，当反应酸值低于8mgKOH/g时滴加5g偏苯三酸酐进行水性封端，保持反应温度，反应2小时，当酸值为25±10mgKOH/g时反应完成，制备得到水性有机硅树脂D。
水溶性有机硅涂料的制备：将75g水性有机硅树脂D、1g纳米二氧化硅(粒径为200纳米的粉末)在高剪切速率下共混0.5小时，再用超声波分散1小时，得到共混水性纳米二氧化硅树脂；将上述共混水性纳米二氧化硅树脂用丙酮溶解后加入三乙胺，在高速搅拌作用下滴加去离子水，直至溶液呈白色半透明乳液得到分散液；将15g钛白粉(细度为6500目) 和10g三聚磷酸钠、5g乙二醇乙醚、5g羟甲基纤维素加入上述分散液中，将混合物调节至碱性，其pH值为7.2-8.1，得到水溶性有机硅涂料D。
对比例4
与实施例3相比，对比例4中纳米二氧化硅的粒径为50纳米，其余组分和用量与实施例3相同，其余工艺与实施例3相同，得到水溶性有机硅涂料C1。
对比例5
与实施例3相比，对比例5中共混水性纳米二氧化硅树脂不采用超声波处理，其余组分和用量与实施例3相同，其余工艺与实施例3相同，得到水溶性有机硅涂料C2。
对比例6
与实施例3相比，对比例6中水性有机硅树脂、纳米二氧化硅和钛白粉的比例不在本方案范围内，将水性有机硅树脂的用量调整为60g，纳米二氧化硅的用量调整为8g，钛白粉的用量调整为30g，其余组分和用量与实施例3相同，其余工艺与实施例3相同，得到水溶性有机硅涂料C3。
对比例7
与实施例3相比，对比例7中去掉制备水性有机硅树脂过程，采用常规水性有机硅树脂(含甲氧基及苯基硅树脂)，其余组分和用量与实施例3相同，其余工艺与实施例3相同，得到水溶性有机硅涂料C4。
效果实施例
上述水性有机硅涂料C(简称涂料C)、水性有机硅涂料D(简称涂料D)、水性有机硅涂料C1(简称涂料C1)、水性有机硅涂料C2(简称涂料C2)、水性有机硅涂料C3(简称涂料C3)和水性有机硅涂料C4(简称涂料C4)的性能如表1。
表1
Figure PCTCN2017088332-appb-000002
Figure PCTCN2017088332-appb-000003
从表1可以看出本发明方案制备的涂料C和涂料D具备较好的性能，不仅热硬度高还具备较好的柔韧性和耐冲击性能，耐酸碱性及耐水性也较好；对比例4中纳米二氧化硅的粒径为50纳米，由于粒径较大，使其分散效果不好，与配方中其余组分的配合想不理想，相对的耐酸碱性和储存稳定性等较差；对比例5中将混合方法采用直接混合后，会使纳米二氧化硅容易析出，制备的分散液不稳定，相对的耐磨性、储存稳定性和热硬度等性能较差；对比例6中改变水性有机硅树脂、纳米二氧化硅和钛白粉的比例后，各方面性能都较差，纳米二氧化硅的用量相对于有机硅树脂来说，若加入量过少，对于性能的提升不明显，若加入量过多，影响水溶性，其他性能也不能保证，水性有机硅树脂、纳米二氧化硅和钛白粉的比例若不在合理范围内，会造成配合性不好并不能达到很好的性能，甚至会影响树脂原有的稳定性。
综上所述，本发明方案，配方比例合理，制备方法合理，制备的水性有机硅涂料具备多种优良性能。
根据上述说明书的揭示和教导，本发明所属领域的技术人员还可以对上述实施方式进行变更和修改。因此，本发明并不局限于上面揭示和描述的具体实施方式，对发明的一些修改和变更也应当落入本发明的权利要求的保护范围内。此外，尽管本说明书中使用了一些特定的术语，但这些术语只是为了方便说明，并不对本发明构成任何限制。

Claims (13)

  1. 一种水溶性有机硅树脂的制备方法，其特征在于，包括如下步骤：
    (1)将双酚A和环氧氯丙烷加入反应器，搅拌至充分混合，加入过量NaOH进行反应，反应温度为60-120℃，反应时间为3-10小时；
    (2)将三元醇、二元醇和二元酸加入步骤(1)的反应中，将先加热至165-180℃，待物料溶解保温1小时后加入抗氧剂，将温度控制在180-220℃，反应至酸值小于8.0mgKOH/g后，加入硅树脂中间体、锑系催化剂进行反应，反应温度为160-200℃，反应时间为3-4小时，当反应酸值低于8mgKOH/g时滴加水性封端剂进行水性封端，保持反应温度，反应1-2小时，当酸值为25±10mgKOH/g时反应完成，制备得到水溶性有机硅树脂；
    所述双酚A、环氧氯丙烷、三元醇、二元醇、二元酸、抗氧剂、催化剂、偏苯三酸酐和硅树脂中间体的重量比为：5-10：5-10：20-30：20-30：30-40：0.2-0.6：0.1-0.8：5-10：60-80；
    所述水溶性有机硅树脂在25℃时的粘度为6000-10000mps。
  2. 根据权利要求1所述的水溶性有机硅树脂的制备方法，其特征在于，所述水性封端剂包含偏苯三酸酐、均苯三甲酸、1,2,3-苯三甲酸、1,3,5-三羧基环己烷、1,2,4-三羧基环己烷以及1,2,3-三羧基环己烷中的一种或多种的组合。
  3. 根据权利要求1所述的一种水溶性有机硅树脂的制备方法，其特征在于，所述三元醇为三羟甲基丙烷和三羟甲基乙烷中的一种或两种；所述二元醇为新戊二醇和一缩二乙二醇中的一种或两种；所述二元酸为对苯二甲酸和乙二酸中的一种或两种。
  4. 根据权利要求1所述的一种水溶性有机硅树脂的制备方法，其特征在于，所述硅树脂中间体包含甲基甲氧基硅烷、甲基乙氧基硅烷、甲氧基硅烷、乙氧基硅烷、苯基甲基硅烷和苯基甲氧基硅烷中的一种或一种以上。
  5. 根据权利要求1所述的一种水溶性有机硅树脂的制备方法，其特征在于，所述锑系催化剂为Sb2O3、Sb(Ac)3(S-21)和乙二醇锑(S-24)中的一种或一种以上。
  6. 根据权利要求1所述的一种水溶性有机硅树脂的制备方法，其特征在于，所述抗氧剂为磷酸三苯酯和亚磷酸三苯酯中的一种。
  7. 权利要求1-6任一项所述的水溶性有机硅树脂用于制备涂料的用途。
  8. 一种水溶性有机硅涂料，其特征在于，包含水性有机硅树脂、纳米二氧化硅、钛白粉和助剂，其中，水性有机硅树脂、纳米二氧化硅、钛白粉和助剂的重量比为：70-80：1-5：0.5-1：5-20，所述纳米二氧化硅平均粒径为100-300纳米的粉末；所述钛白粉细度为6000 目以上；所述水性有机硅树脂为用聚酯、环氧树脂改性后的酸值为25±10mgKOH/g的水性有机硅树脂，
    所述水溶性有机硅涂料的制备方法为：将水性有机硅树脂、纳米二氧化硅在高剪切速率下共混0.5-1小时，再用超声波分散0.5-1小时，得到共混水性纳米二氧化硅树脂；将上述共混水性纳米二氧化硅树脂溶解后加入中和剂，在高速搅拌作用下滴加去离子水，直至溶液呈白色半透明乳液得到分散液；将钛白粉和助剂加入上述分散液中，将混合物调节至碱性，其pH值为7.2-8.1，得到水溶性有机硅涂料。
  9. 根据权利要求8所述的一种水溶性有机硅涂料，其特征在于，所述水性有机硅树脂的制备方法包括如下步骤：将三元醇、二元醇、二元酸和环氧树脂加入反应器中，将先加热至165-180℃，待物料溶解保温1小时后加入抗氧剂，将温度控制在180-220℃，反应至酸值小于8.0后，加入硅树脂中间体、催化剂进行反应，反应温度为160-200℃，反应时间为3-4小时，当反应酸值低于8mgKOH/g时滴加偏苯三酸酐进行水性封端，保持反应温度，反应1-2小时，当酸值为25±10mgKOH/g时反应完成，制备得到水性有机硅树脂。
  10. 根据权利要求9所述的一种水溶性有机硅涂料，其特征在于，所述环氧树脂、三元醇、二元醇、二元酸、抗氧剂、催化剂、偏苯三酸酐和硅树脂中间体的重量比为：10-20：20-30：20-30：30-40：0.2-0.6：0.1-0.8：5-10：60-80。
  11. 根据权利要求9所述的一种水溶性有机硅涂料，其特征在于，所述三元醇为三羟甲基丙烷和三羟甲基乙烷中的一种或两种；所述二元醇为新戊二醇和一缩二乙二醇中的一种或两种；所述二元酸为对苯二甲酸和乙二酸中的一种或两种。
  12. 根据权利要求9所述的一种水溶性有机硅涂料，其特征在于，所述催化剂为钛酸四丁酯；所述抗氧剂为磷酸三苯酯和亚磷酸三苯酯中的一种。
  13. 根据权利要求8所述的一种水溶性有机硅涂料，其特征在于，所述助剂包含增稠剂、分散剂、成膜剂、消泡剂和流平剂中的一种或一种以上。
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113025203A (zh) * 2021-04-30 2021-06-25 贵州航天风华精密设备有限公司 一种水性有机硅环保防热涂料及其制备方法
CN113292730A (zh) * 2021-04-16 2021-08-24 虎皇新材料科技集团有限公司 一种改性有机硅树脂及其制备方法和常温固化涂料
CN114184538A (zh) * 2021-12-02 2022-03-15 攀钢集团重庆钛业有限公司 一种加速钛白粉在pp样板中的耐候性测试方法及pp样板
CN114525078A (zh) * 2021-12-24 2022-05-24 南京长江涂料有限公司 一种水性改性有机硅耐高温防腐涂料及其制备方法
CN115537120A (zh) * 2022-11-03 2022-12-30 山东省科学院新材料研究所 一种耐热接枝硅树脂涂料及其制备方法
CN116082643A (zh) * 2023-02-17 2023-05-09 江苏乐离新材料科技有限公司 一种聚乙烯醇树脂有机硅改性水溶性设备保护膜溶液的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101307220A (zh) * 2008-07-10 2008-11-19 天津市凯华绝缘材料有限公司 有机硅改性聚酯电子封装材料
CN101503510A (zh) * 2009-03-09 2009-08-12 嘉兴市清河高力绝缘有限公司 一种用于硅钢片绝缘处理的水溶性聚酯树脂的制备方法
CN103897197A (zh) * 2012-12-28 2014-07-02 慧智科技（中国）有限公司 有机硅改性聚酯环氧树脂的制备方法
CN105482089A (zh) * 2015-12-26 2016-04-13 杭州吉华高分子材料股份有限公司 一种水溶性有机硅改性聚酯树脂及其制备方法与应用
CN106047163A (zh) * 2016-06-28 2016-10-26 佛山市珀力玛高新材料有限公司 一种水溶性有机硅涂料
CN106117559A (zh) * 2016-06-29 2016-11-16 佛山市珀力玛高新材料有限公司 一种水溶性有机硅树脂及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101307220A (zh) * 2008-07-10 2008-11-19 天津市凯华绝缘材料有限公司 有机硅改性聚酯电子封装材料
CN101503510A (zh) * 2009-03-09 2009-08-12 嘉兴市清河高力绝缘有限公司 一种用于硅钢片绝缘处理的水溶性聚酯树脂的制备方法
CN103897197A (zh) * 2012-12-28 2014-07-02 慧智科技（中国）有限公司 有机硅改性聚酯环氧树脂的制备方法
CN105482089A (zh) * 2015-12-26 2016-04-13 杭州吉华高分子材料股份有限公司 一种水溶性有机硅改性聚酯树脂及其制备方法与应用
CN106047163A (zh) * 2016-06-28 2016-10-26 佛山市珀力玛高新材料有限公司 一种水溶性有机硅涂料
CN106117559A (zh) * 2016-06-29 2016-11-16 佛山市珀力玛高新材料有限公司 一种水溶性有机硅树脂及其制备方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113292730A (zh) * 2021-04-16 2021-08-24 虎皇新材料科技集团有限公司 一种改性有机硅树脂及其制备方法和常温固化涂料
CN113025203A (zh) * 2021-04-30 2021-06-25 贵州航天风华精密设备有限公司 一种水性有机硅环保防热涂料及其制备方法
CN114184538A (zh) * 2021-12-02 2022-03-15 攀钢集团重庆钛业有限公司 一种加速钛白粉在pp样板中的耐候性测试方法及pp样板
CN114184538B (zh) * 2021-12-02 2024-03-01 攀钢集团重庆钛业有限公司 一种加速钛白粉在pp样板中的耐候性测试方法及pp样板
CN114525078A (zh) * 2021-12-24 2022-05-24 南京长江涂料有限公司 一种水性改性有机硅耐高温防腐涂料及其制备方法
CN115537120A (zh) * 2022-11-03 2022-12-30 山东省科学院新材料研究所 一种耐热接枝硅树脂涂料及其制备方法
CN115537120B (zh) * 2022-11-03 2023-07-21 山东省科学院新材料研究所 一种耐热接枝硅树脂涂料及其制备方法
CN116082643A (zh) * 2023-02-17 2023-05-09 江苏乐离新材料科技有限公司 一种聚乙烯醇树脂有机硅改性水溶性设备保护膜溶液的制备方法

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