WO2023070910A1 - 一种快干高耐候丙烯酸机械通用涂料及其制备方法和应用 - Google Patents

一种快干高耐候丙烯酸机械通用涂料及其制备方法和应用 Download PDF

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WO2023070910A1
WO2023070910A1 PCT/CN2021/139902 CN2021139902W WO2023070910A1 WO 2023070910 A1 WO2023070910 A1 WO 2023070910A1 CN 2021139902 W CN2021139902 W CN 2021139902W WO 2023070910 A1 WO2023070910 A1 WO 2023070910A1
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parts
coating
water
acrylic
stirring
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PCT/CN2021/139902
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English (en)
French (fr)
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谢海
唐帆
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江苏冠军科技集团股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates

Definitions

  • the invention relates to the technical field of coatings, in particular to a quick-drying and highly weather-resistant acrylic general-purpose coating for machinery, a preparation method and application thereof.
  • the purpose of the present invention is to overcome the defects in the prior art and provide a quick-drying high-weather resistance acrylic mechanical general coating and its preparation method and application.
  • the invention provides a quick-drying and highly weather-resistant acrylic general-purpose coating for machinery, which is prepared from the following raw materials in parts by mass:
  • Modified acrylic silicone resin 95-135 parts, water-based isocyanate curing agent 35-45 parts, precipitated barium sulfate 10-20 parts, ferric chloride 20-30 parts, dispersant 5-10 parts, leveling agent 3-8 parts.
  • the modified acrylic silicone resin is prepared from raw materials comprising the following mass ratios:
  • Acrylic monomer ⁇ -methacryloxypropyltrimethoxysilane: potassium persulfate: emulsifier: water 20-30: 5-10: 0.5-1: 2-3: 70-90;
  • the acrylic acid monomer comprises the following components by mass:
  • the emulsifier is one or more of OP-10, APG and AES.
  • the preparation method of the modified acrylic silicone resin comprises the following steps:
  • the quality of the first part of water in the step (1) is 40% to 50% of the water quality
  • the speed of dispersion in the step (1) is 400-500rpm, the time of dispersion is 20-30min, and the temperature of dispersion is 70-80°C;
  • the mixing method in the step (2) is stirring, the stirring speed is 400-500 rpm, the stirring time is 10-20 min, and the stirring temperature is 70-80°C.
  • the monomer system is mixed with water, and then ⁇ -methacryloxypropyltrimethoxysilane is added dropwise; the rate of the dropwise addition is 400-500mL/h;
  • the temperature of the polymerization reaction in the step (3) is 70-80° C.
  • the time of the polymerization reaction is 3-4 hours
  • the polymerization reaction is carried out under the condition of stirring, and the rotation speed of the stirring is 200-300 rpm.
  • the particle size of the precipitated barium sulfate is 200-300 ⁇ m
  • the particle size of the ferric chloride is 200-300 ⁇ m.
  • the present invention also provides a preparation method of the acrylic mechanical general coating, comprising the following steps:
  • the rotational speed of dispersion in the step (a) is 300-400 rpm, and the dispersion time is 15-25 minutes.
  • the mixing method in the step (b) is stirring, the stirring speed is 600-800 rpm, and the stirring time is 2-4 minutes.
  • the invention also provides the application of the acrylic mechanical universal coating on steel structure coating.
  • the invention provides a quick-drying and highly weather-resistant acrylic general coating for machinery, which comprises a modified acrylic silicone resin, a water-based isocyanate curing agent, precipitated barium sulfate, ferric chloride, a dispersant and a leveling agent.
  • This application polymerizes ⁇ -methacryloxypropyltrimethoxysilane and acrylic acid monomers to obtain a modified acrylic silicone resin, which improves the weather resistance and water resistance of acrylic coatings; the modified acrylic silicone resin and water-based isocyanate Combination of curing agent, the hydroxyl group in the coating and the isocyanate group in the curing agent are cross-linked and cured after coating, reducing the surface drying time so that the coating exhibits quick-drying performance after coating; the trivalent in ferric chloride Iron ions chelate with unreacted hydroxyl and carboxyl groups in the coating to form a bottom-up structure of substrate, resin, and ferric chloride, which enhances the adhesion of the coating film; precipitated barium sulfate is used as a filler to improve the water resistance of the coating
  • the dispersant can prevent the active ingredients in the paint from settling and ensure the uniformity of the paint system.
  • the paint provided by the application has low cost and simple process, and can effectively slow down metal corrosion
  • the invention provides a quick-drying and highly weather-resistant acrylic general-purpose coating for machinery, which is prepared from the following raw materials in parts by mass:
  • Modified acrylic silicone resin 95-135 parts, water-based isocyanate curing agent 35-45 parts, precipitated barium sulfate 10-20 parts, ferric chloride 20-30 parts, dispersant 5-10 parts, leveling agent 3-8 parts.
  • the modified acrylic silicone resin is 95-135 parts, preferably 100-130 parts, more preferably 110-120 parts.
  • the water-based isocyanate curing agent is 35-45 parts, preferably 36-44 parts, more preferably 38-42 parts.
  • the amount of the precipitated barium sulfate is 10-20 parts, preferably 12-18 parts, more preferably 14-16 parts.
  • the ferric chloride is 20-30 parts, preferably 22-28 parts, more preferably 24-26 parts.
  • the dispersant is 5-10 parts, preferably 6-9 parts, more preferably 7-8 parts.
  • the dispersant is RS610 dispersant, AMP-95 dispersant or BYK-199 dispersant.
  • the amount of the leveling agent is 3-8 parts, preferably 4-7 parts, more preferably 5-6 parts.
  • the leveling agent is Perenol F40 leveling agent, BYK-VP-354 leveling agent, BYK-VP-3609 leveling agent or Tego300 leveling agent.
  • both the dispersant and the leveling agent are commercially available.
  • the modified acrylic silicone resin is preferably prepared from raw materials comprising the following mass ratios:
  • Acrylic monomer ⁇ -methacryloxypropyltrimethoxysilane: potassium persulfate: emulsifier: water: 20-30: 5-10: 0.5-1: 2-3: 70-90.
  • the mass ratio of the acrylic monomer: ⁇ -methacryloxypropyltrimethoxysilane: potassium persulfate: emulsifier: water is preferably 20-30:5-10:0.5-1 : 2 ⁇ 3: 70 ⁇ 90, more preferably 22 ⁇ 28: 6 ⁇ 9: 0.6 ⁇ 0.9: 2.2 ⁇ 2.8: 75 ⁇ 85, more preferably 24 ⁇ 26: 7 ⁇ 8: 0.7 ⁇ 0.8: 2.4 ⁇ 2.6 : 78-82.
  • the acrylic acid monomer preferably comprises the following components in parts by mass:
  • the methyl methacrylate is preferably 20-25 parts, more preferably 21-24 parts, more preferably 22-23 parts.
  • the butyl methacrylate is preferably 20-25 parts, more preferably 21-24 parts, more preferably 22-23 parts.
  • the acrylic acid is preferably 1-2 parts, more preferably 1.2-1.8 parts, more preferably 1.4-1.6 parts.
  • methyl methacrylate is selected as the rigid monomer, which determines the impact resistance of the coating;
  • Butyl methacrylate is a flexible monomer, which can improve the water resistance of the coating;
  • acrylic acid affects the degree of reaction, and the more acrylic acid, The worse the water resistance, the less acrylic acid can effectively disperse the system and affect the performance of the coating.
  • the emulsifier is preferably one or more of OP-10, APG and AES.
  • the preparation method of the modified acrylic silicone resin preferably comprises the following steps:
  • the mass of the first part of water in the step (1) is preferably 40-50% of the water mass, more preferably 42-48%, more preferably 44-46%.
  • the rotational speed of dispersion in the step (1) is preferably 400-500 rpm, more preferably 420-480 rpm, more preferably 440-460 rpm; the dispersion time is preferably 20-30 min, more preferably 22 min ⁇ 28 min, more preferably 24 ⁇ 26 min; the temperature of the dispersion is preferably 70 ⁇ 80°C, more preferably 72 ⁇ 78°C, more preferably 74 ⁇ 76°C.
  • the mixing method in the step (2) is preferably stirring, and the stirring speed is preferably 400-500rpm, more preferably 420-480rpm, more preferably 440-460rpm; the stirring time is preferably 10-20 min, more preferably 12-18 min, more preferably 14-16 min; the stirring temperature is preferably 70-80°C, more preferably 72-78°C, more preferably 74-76°C.
  • the mixing in step (3) is preferably to add ⁇ -methacryloxypropyl trimethoxysilane dropwise after mixing the monomer system and water; the rate of dropping is preferably 400-500mL /h, more preferably 420 to 480 mL/h, more preferably 440 to 460 mL/h.
  • the particle size of the modified acrylic silicone resin is controlled by controlling the rate of dropping, thereby changing the brushing performance of the paint; if the dropping rate is too fast, the silane monomer and the acrylic monomer cannot fully react, and a uniform system cannot be obtained. Modified acrylic silicone resin; the dropping rate is too slow, which increases the reaction cost and wastes acrylic acid monomer.
  • the temperature of the polymerization reaction in the step (3) is preferably 70-80°C, more preferably 72-78°C, more preferably 74-76°C; the time of the polymerization reaction is preferably 3-4h , more preferably 3.2-3.8h, more preferably 3.4-3.6h; the polymerization reaction is preferably carried out under stirring conditions, the stirring speed is preferably 200-300rpm, more preferably 220-280rpm, more preferably 240 ⁇ 260rpm.
  • the polymerization reaction is carried out at a specific temperature, and the temperature is an important factor affecting the polymerization reaction, which determines the conversion rate of the monomer and can obtain a system with a high solid content; thereby changing the overall performance of the coating.
  • the rotational speed of the polymerization reaction can control the particle size of the modified acrylic silicone resin while affecting the stability of the system, thereby affecting the performance of the paint.
  • the acrylic acid monomer and ⁇ -methacryloxypropyltrimethoxysilane are polymerized, and silicon-oxygen bonds and carbon-silicon bonds are introduced.
  • the bonds of the two are high in energy and difficult to break, and have stable chemical properties and excellent weather resistance.
  • the particle size of the precipitated barium sulfate is preferably 200-300 ⁇ m, more preferably 220-280 ⁇ m, more preferably 240-260 ⁇ m; the particle size of the ferric chloride is preferably 200-300 ⁇ m, more preferably 220 to 280 ⁇ m, more preferably 240 to 260 ⁇ m.
  • the addition of barium sulfate can improve the water resistance of the coating, the surface hardness of the coating, and prevent the coating from being damaged;
  • the ferric ion in the ferric chloride and the unreacted hydroxyl and carboxyl in the coating are chelated to form the following:
  • the structure of the base material, resin and ferric chloride enhances the adhesion of the coating film.
  • the present invention also provides a preparation method of the acrylic mechanical general coating, comprising the following steps:
  • the rotational speed of dispersion in the step (a) is preferably 300-400 rpm, more preferably 320-380 rpm, more preferably 340-360 rpm; the dispersion time is preferably 15-25 min, more preferably 16 min ⁇ 24 min, more preferably 18 ⁇ 22 min.
  • the mixing method in the step (b) is preferably stirring, and the stirring speed is preferably 600-800rpm, more preferably 650-750rpm, more preferably 680-720rpm; the stirring time is preferably 2 to 4 minutes, more preferably 2.5 to 3.5 minutes, more preferably 2.8 to 3.2 minutes.
  • the use of the coating needs to be ready-to-use, because the isocyanate group in the water-based isocyanate curing agent and the hydroxyl group in the modified acrylic silicone resin will undergo cross-linking and curing, which will affect the use of the coating; Response, after the coating is applied, the dry time is greatly reduced, reducing the waiting time.
  • the invention also provides the application of the acrylic mechanical universal coating on steel structure coating.
  • Table 1 The properties of the modified acrylic silicone resin obtained in this example are shown in Table 1.
  • modified acrylic silicone resin Take 115 parts of modified acrylic silicone resin, 40 parts of water-based isocyanate curing agent, 15 parts of precipitated barium sulfate with a particle size of 250 ⁇ m, 25 parts of ferric chloride with a particle size of 250 ⁇ m, 8 parts of RS610 dispersant, and 5 parts of Perenol F40 leveling agent.
  • Disperse modified acrylic silicone resin, precipitated barium sulfate, ferric chloride, dispersant and leveling agent at 350 rpm for 20 minutes to obtain a mixed slurry; stir the mixed slurry and water-based isocyanate curing agent at 700 rpm for 3 minutes to obtain acrylic acid General purpose coating for machinery.
  • GB/T1720-1989 measure the adhesion, measure the impact resistance according to GB/T1732-2993, measure the hardness according to GB/T6739-1996, measure according to GB/T1733-93 Water resistance is measured, weather resistance is measured according to GB/T1865-80, surface dry time is measured according to GB/T1728-79(88), and abrasion resistance is measured according to GB/T1768-1989. The measurement results are recorded in Table 6.
  • modified acrylic silicone resin Take 95 parts of modified acrylic silicone resin, 35 parts of water-based isocyanate curing agent, 10 parts of precipitated barium sulfate with a particle size of 200 ⁇ m, 20 parts of ferric chloride with a particle size of 200 ⁇ m, 5 parts of AMP-95 dispersant, and 3 parts of Tego300 fluid leveling agent.
  • Disperse modified acrylic silicone resin, precipitated barium sulfate, ferric chloride, dispersant and leveling agent at 300 rpm for 15 minutes to obtain a mixed slurry; stir the mixed slurry and water-based isocyanate curing agent at 600 rpm for 2 minutes to obtain acrylic acid General purpose coating for machinery.
  • modified acrylic silicone resin Take 135 parts of modified acrylic silicone resin, 45 parts of water-based isocyanate curing agent, 20 parts of precipitated barium sulfate with a particle size of 300 ⁇ m, 30 parts of ferric chloride with a particle size of 230 ⁇ m, 10 parts of BYK-199 dispersant, 8 parts of BYK- VP-354 leveling agent.
  • Disperse modified acrylic silicone resin, precipitated barium sulfate, ferric chloride, dispersant and leveling agent at 400 rpm for 25 minutes to obtain a mixed slurry; stir the mixed slurry and water-based isocyanate curing agent at 800 rpm for 4 minutes to obtain acrylic acid General purpose coating for machinery.
  • Example 1 The difference between this comparative example and Example 1 is that the amount of gamma-methacryloxypropyl trimethoxysilane is adjusted to 100g, and the rest of the conditions remain unchanged.
  • the properties of the modified acrylic silicone resin prepared by testing are as follows: Table 4 shows.
  • the modified coating prepared in this comparative example was tested according to the method in Example 1. The measurement results are recorded in Table 6.
  • Example 2 The difference between this comparative example and Example 1 is that the dropping rate of ⁇ -methacryloxypropyltrimethoxysilane is adjusted to 1.5L/h, and the rest of the conditions remain unchanged.
  • the prepared modified acrylic silicon The properties of the resin are shown in Table 5.
  • the modified coating prepared in this comparative example was tested according to the method in Example 1. The measurement results are recorded in Table 6.
  • Example 6 The difference between this comparative example and Example 1 is that the amount of water-based isocyanate curing agent added is 70 parts, and other conditions remain unchanged; the modified coating prepared in this comparative example is tested according to the method in Example 1. The measurement results are recorded in Table 6.
  • the present invention provides a quick-drying and highly weather-resistant acrylic general-purpose coating for machinery.
  • the amount of ⁇ -methacryloxypropyl trimethoxysilane increases or the rate of dripping increases. After increasing, it will seriously affect the performance of the coating. This is because there is unreacted ⁇ -methacryloxypropyltrimethoxysilane in the coating, which cannot be used as an active ingredient to improve the performance of the coating; the addition of water-based isocyanate curing agent increases When it is too large, there will be excess isocyanate groups in the coating system reacting with water, generating carbon dioxide to escape from the coating, forming pinholes and reducing the weather resistance of the coating.
  • the coating obtained within the dosage range of the present invention has excellent comprehensive performance, short drying time after coating, excellent water resistance and weather resistance, and avoids corrosion of mechanical products caused by rainwater and other reasons in the open environment.

Abstract

本发明属于涂料技术领域。本发明提供了一种快干高耐候丙烯酸机械通用涂料，包含改性丙烯酸硅树脂95～135份、水性异氰酸酯固化剂35～45份、沉淀硫酸钡10～20份、氯化铁20～30份、分散剂5～10份、流平剂3～8份。本申请将γ-甲基丙烯酰氧基丙基三甲氧基硅烷和丙烯酸单体进行聚合，得到了改性丙烯酸硅树脂，提高了丙烯酸涂料的耐候防水性；将改性丙烯酸硅树脂和水性异氰酸酯固化剂结合，在涂覆后涂料中的羟基基团和固化剂中的异氰酸酯基团交联固化，降低表干时间使得涂料在涂覆后呈现出速干的性能。本申请提供的涂料成本低，工艺简单，在机械表面涂覆后可有效的减缓金属的腐蚀，降低成本。

Description

一种快干高耐候丙烯酸机械通用涂料及其制备方法和应用 技术领域
本发明涉及涂料技术领域，尤其涉及一种快干高耐候丙烯酸机械通用涂料及其制备方法和应用。
背景技术
机械工程以增加生产、提高劳动生产率、提高生产的经济性为目标来研制和发展新的机械产品，这些机械产品不仅降低了人的劳动还创造了巨大的收益。但是在这些产品的使用过程中，会因为使用环境的变化，酸碱度的改变，水气的侵蚀等出现不同程度的损耗，损耗出现后会加速机械的使用寿命提高成本，在统计中机械表面的金属损耗占据了生产成本的大部分。基于此人们开发出不同的方法来降低损耗，其中有金属表面涂油法，覆盖氧化层法，制造防腐蚀合金等。但是上述方法不仅工艺复杂而且成本高，偏离了金属防腐的初衷。所以现在亟需一种新的方法来提高金属表面的防腐性。
发明内容
本发明的目的在于克服现有技术中的缺陷，提供一种快干高耐候丙烯酸机械通用涂料及其制备方法和应用。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种快干高耐候丙烯酸机械通用涂料，由包含下列质量份的原料制备得到：
改性丙烯酸硅树脂95～135份、水性异氰酸酯固化剂35～45份、沉淀硫酸钡10～20份、氯化铁20～30份、分散剂5～10份、流平剂3～8份。
作为优选，所述改性丙烯酸硅树脂由包含下列质量比的原料制备得到：
丙烯酸单体：γ-甲基丙烯酰氧基丙基三甲氧基硅烷：过硫酸钾：乳化剂：水为20～30：5～10：0.5～1：2～3：70～90；
所述丙烯酸单体包含下列质量份的组分：
甲基丙烯酸甲酯20～25份、甲基丙烯酸丁酯20～25份、丙烯酸1～2份；
所述乳化剂为OP-10、APG和AES中的一种或几种。
作为优选，所述改性丙烯酸硅树脂的制备方法，包含下列步骤：
(1)将过硫酸钾、乳化剂和第一部分水分散，得到基底体系；
(2)将丙烯酸单体和基底体系混合，得到单体体系；
(3)将单体体系、γ-甲基丙烯酰氧基丙基三甲氧基硅烷和剩余的水混合后发生聚合反应，即获得丙烯酸机械通用涂料。
作为优选，所述步骤(1)中第一部分水的质量为水质量的40～50％；
所述步骤(1)中分散的转速为400～500rpm，所述分散的时间为20～30min，所述分散的温度为70～80℃；
所述步骤(2)中混合的方式为搅拌，所述搅拌的转速为400～500rpm，所述搅拌的时间为10～20min，所述搅拌的温度为70～80℃。
作为优选，所述步骤(3)中混合为单体体系和水混合后滴加γ-甲基丙烯酰氧基丙基三甲氧基硅烷；所述滴加的速率为400～500mL/h；
所述步骤(3)中聚合反应的温度为70～80℃，所述聚合反应的时间为3～4h，所述聚合反应在搅拌条件下进行，所述搅拌的转速为200～300rpm。
作为优选，所述沉淀硫酸钡的粒径为200～300μm，所述氯化铁的粒径为200～300μm。
本发明还提供了所述丙烯酸机械通用涂料的制备方法，包含下列步骤：
(a)将改性丙烯酸硅树脂、沉淀硫酸钡、氯化铁、分散剂和流平剂分散得到混合浆料；
(b)将混合浆料和水性异氰酸酯固化剂混合后即得丙烯酸机械通用涂料。
作为优选，所述步骤(a)中分散的转速为300～400rpm，所述分散的时间为15～25min。
作为优选，所述步骤(b)中混合的方式为搅拌，所述搅拌的转速为600～800rpm，所述搅拌的时间为2～4min。
本发明还提供了所述丙烯酸机械通用涂料在钢结构涂覆上的应用。
本发明提供了一种快干高耐候丙烯酸机械通用涂料，包含改性丙烯酸硅树脂、水性异氰酸酯固化剂、沉淀硫酸钡、氯化铁、分散剂和流平剂。本申请将γ-甲基丙烯酰氧基丙基三甲氧基硅烷和丙烯酸单体进行聚合，得到了改性丙烯酸硅树脂，提高了丙烯酸涂料的耐候防水性；将改性丙烯酸硅树脂和 水性异氰酸酯固化剂结合，在涂覆后涂料中的羟基基团和固化剂中的异氰酸酯基团交联固化，降低表干时间使得涂料在涂覆后呈现出速干的性能；氯化铁中的三价铁离子和涂料中未反应的羟基、羧基螯合，形成由下到上的底材、树脂、氯化铁的结构，增强了涂膜的附着力；沉淀硫酸钡作为体质填料，提高涂料的耐水性，分散剂可以防止涂料中的有效成分沉降，保证涂料体系的均匀。本申请提供的涂料成本低，工艺简单，在机械表面涂覆后可有效的减缓金属的腐蚀，降低成本。
具体实施方式
本发明提供了一种快干高耐候丙烯酸机械通用涂料，由包含下列质量份的原料制备得到：
改性丙烯酸硅树脂95～135份、水性异氰酸酯固化剂35～45份、沉淀硫酸钡10～20份、氯化铁20～30份、分散剂5～10份、流平剂3～8份。
在本发明中，所述改性丙烯酸硅树脂为95～135份，优选为100～130份，更优选为110～120份。
在本发明中，所述水性异氰酸酯固化剂为35～45份，优选为36～44份，更优选为38～42份。
在本发明中，所述沉淀硫酸钡为10～20份，优选为12～18份，更优选为14～16份。
在本发明中，所述氯化铁为20～30份，优选为22～28份，更优选为24～26份。
在本发明中，所述分散剂为5～10份，优选为6～9份，更优选为7～8份。
在本发明中，所述分散剂为RS610分散剂、AMP-95分散剂或BYK-199分散剂。
在本发明中，所述流平剂为3～8份，优选为4～7份，更优选为5～6份。
在本发明中，所述流平剂为Perenol F40流平剂、BYK-VP-354流平剂、BYK-VP-3609流平剂或Tego300流平剂。
在本发明中，分散剂和流平剂均为市售所得。
在本发明中，所述改性丙烯酸硅树脂优选由包含下列质量比的原料制备得到：
丙烯酸单体：γ-甲基丙烯酰氧基丙基三甲氧基硅烷：过硫酸钾：乳化剂：水为20～30：5～10：0.5～1：2～3：70～90。
在本发明中，所述丙烯酸单体：γ-甲基丙烯酰氧基丙基三甲氧基硅烷：过硫酸钾：乳化剂：水的质量比优选为20～30：5～10：0.5～1：2～3：70～90，进一步优选为22～28：6～9：0.6～0.9：2.2～2.8：75～85，更优选为24～26：7～8：0.7～0.8：2.4～2.6：78～82。
在本发明中，所述丙烯酸单体优选包含下列质量份的组分：
甲基丙烯酸甲酯20～25份、甲基丙烯酸丁酯20～25份、丙烯酸1～2份。
在本发明中，所述甲基丙烯酸甲酯优选为20～25份，进一步优选为21～24份，更优选为22～23份。
在本发明中，所述甲基丙烯酸丁酯优选为20～25份，进一步优选为21～24份，更优选为22～23份。
在本发明中，所述丙烯酸优选为1～2份，进一步优选为1.2～1.8份，更优选为1.4～1.6份。
在本发明中，选用甲基丙烯酸甲酯作为刚性单体，决定了涂料的抗冲击性能；甲基丙烯酸丁酯为柔性单体，可以改善涂料的耐水性；丙烯酸影响反应程度，丙烯酸越多，耐水性越差，丙烯酸越少不能将体系进行有效的分散，影响涂料的性能。
在本发明中，所述乳化剂优选为OP-10、APG和AES中的一种或几种。
在本发明中，所述改性丙烯酸硅树脂的制备方法，优选包含下列步骤：
(1)将过硫酸钾、乳化剂和第一部分水分散，得到基底体系；
(2)将丙烯酸单体和基底体系混合，得到单体体系；
(3)将单体体系、γ-甲基丙烯酰氧基丙基三甲氧基硅烷和剩余的水混合后发生聚合反应，即获得改性丙烯酸硅树脂。
在本发明中，所述步骤(1)中第一部分水的质量优选为水质量的40～50％，进一步优选为42～48％，更优选为44～46％。
在本发明中，所述步骤(1)中分散的转速优选为400～500rpm，进一步优选为420～480rpm，更优选为440～460rpm；所述分散的时间优选为20～30min，进一步优选为22～28min，更优选为24～26min；所述分散的温度 优选为70～80℃，进一步优选为72～78℃，更优选为74～76℃。
在本发明中，所述步骤(2)中混合的方式优选为搅拌，所述搅拌的转速优选为400～500rpm，进一步优选为420～480rpm，更优选为440～460rpm；所述搅拌的时间优选为10～20min，进一步优选为12～18min，更优选为14～16min；所述搅拌的温度优选为70～80℃，进一步优选为72～78℃，更优选为74～76℃。
在本发明中，所述步骤(3)中混合优选为单体体系和水混合后滴加γ-甲基丙烯酰氧基丙基三甲氧基硅烷；所述滴加的速率优选为400～500mL/h，进一步优选为420～480mL/h，更优选为440～460mL/h。
在本发明中，通过控制滴加的速率来控制改性丙烯酸硅树脂的颗粒大小，从而改变涂料的涂刷性能；滴加速率过快硅烷单体和丙烯酸单体无法充分反应，不能得到体系均匀的改性丙烯酸硅树脂；滴加速率过慢，增加反应成本，浪费丙烯酸单体。
在本发明中，所述步骤(3)中聚合反应的温度优选为70～80℃，进一步优选为72～78℃，更优选为74～76℃；所述聚合反应的时间优选为3～4h，进一步优选为3.2～3.8h，更优选为3.4～3.6h；所述聚合反应优选在搅拌条件下进行，所述搅拌的转速优选为200～300rpm，进一步优选为220～280rpm，更优选为240～260rpm。
在本发明中，聚合反应在特定的温度下进行，温度是影响聚合反应的重要因素，决定单体的转化率，可以得到固含量高的体系；从而改变涂料的综合性能。
在本发明中，聚合反应的转速在影响体系稳定性的同时还能控制改性丙烯酸硅树脂的颗粒大小，影响涂料的性能。
在本发明中，将丙烯酸单体和γ-甲基丙烯酰氧基丙基三甲氧基硅烷进行聚合，引入了硅氧键和碳硅键，两者键能高不易断裂，化学性质稳定具有优异的耐候性。
在本发明中，所述沉淀硫酸钡的粒径优选为200～300μm，进一步优选为220～280μm，更优选为240～260μm；所述氯化铁的粒径优选为200～300μm，进一步优选为220～280μm，更优选为240～260μm。
在本发明中，硫酸钡的加入可以提高涂料的耐水性、涂层表面硬度，防止涂层破损；氯化铁中的三价铁离子和涂料中未反应的羟基、羧基螯合，形成由下到上的底材、树脂、氯化铁的结构，增强了涂膜的附着力。
本发明还提供了所述丙烯酸机械通用涂料的制备方法，包含下列步骤：
(a)将改性丙烯酸硅树脂、沉淀硫酸钡、氯化铁、分散剂和流平剂分散得到混合浆料；
(b)将混合浆料和水性异氰酸酯固化剂混合后即得丙烯酸机械通用涂料。
在本发明中，所述步骤(a)中分散的转速优选为300～400rpm，进一步优选为320～380rpm，更优选为340～360rpm；所述分散的时间优选为15～25min，进一步优选为16～24min，更优选为18～22min。
在本发明中，所述步骤(b)中混合的方式优选为搅拌，所述搅拌的转速优选为600～800rpm，进一步优选为650～750rpm，更优选为680～720rpm；所述搅拌的时间优选为2～4min，进一步优选为2.5～3.5min，更优选为2.8～3.2min。
在本发明中，涂料的使用需要即用即配，因为水性异氰酸酯固化剂中的异氰酸酯基团和改性丙烯酸硅树脂中的羟基基团会发生交联固化，影响涂料的使用；同时因为交联反应，在涂料涂覆后表干时间大幅度降低，降低等待时间。
本发明还提供了所述丙烯酸机械通用涂料在钢结构涂覆上的应用。
下面结合实施例对本发明提供的技术方案进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。
实施例1
取100g丙烯酸单体、32gγ-甲基丙烯酰氧基丙基三甲氧基硅烷、2.8g过硫酸钾、10gOP-10和320g水；其中丙烯酸单体中甲基丙烯酸甲酯为23份、甲基丙烯酸丁酯为22份、丙烯酸为1.5份。
将过硫酸钾、OP-10和144g的水在450rpm转速、75℃下分散25min获得基底体系；将丙烯酸单体和基底体系在450rpm转速、75℃下搅拌15min获得单体体系；将单体体系和剩余的水混合，调整转速为250rpm，温度为 75℃，将γ-甲基丙烯酰氧基丙基三甲氧基硅烷以450mL/h的速率滴加，滴加结束后反应3.5h，获得改性丙烯酸硅树脂，经检测本实施例得到改性丙烯酸硅树脂的性质如表1所示。
表1
  改性丙烯酸硅树脂
羟值(mgKOH/g) 112
Tg(℃) 28
固含量(％) 46
黏度(mPa·s) 105
pH 7.1
从表1中可以看出，本实施例制备得到的改性丙烯酸硅树脂性能优良，羟值和Tg符合作为涂料基体的要求。
取115份改性丙烯酸硅树脂、40份水性异氰酸酯固化剂、15份粒径为250μm的沉淀硫酸钡、25份粒径为250μm的氯化铁、8份RS610分散剂、5份Perenol F40流平剂。
将改性丙烯酸硅树脂、沉淀硫酸钡、氯化铁、分散剂和流平剂在350rpm转速下分散20min得到混合浆料；将混合浆料和水性异氰酸酯固化剂在700rpm转速下搅拌3min，获得丙烯酸机械通用涂料。
将本实施例制备得到快干高耐候丙烯酸机械通用涂料按照GB/T1720-1989测定附着力，按照GB/T1732-2993测定耐冲击性，按照GB/T6739-1996测定硬度，按照GB/T1733-93测定耐水性，按照GB/T1865-80测定耐候性，按照GB/T1728-79(88)测定表干时间，按照GB/T1768-1989测定耐磨损性。测定结果记录在表6中。
实施例2
取40g丙烯酸单体、10gγ-甲基丙烯酰氧基丙基三甲氧基硅烷、1g过硫酸钾、4gAPG和140g水；其中丙烯酸单体中甲基丙烯酸甲酯为20份、甲基丙烯酸丁酯为20份、丙烯酸为1份。
将过硫酸钾、APG和56g的水在400rpm转速、70℃下分散20min获得基底体系；将丙烯酸单体和基底体系在400rpm转速、75℃下搅拌10min获 得单体体系；将单体体系和剩余的水混合，调整转速为200rpm，温度为70℃，将γ-甲基丙烯酰氧基丙基三甲氧基硅烷以400mL/h的速率滴加，滴加结束后反应3h，获得改性丙烯酸硅树脂，经检测本实施例得到改性丙烯酸硅树脂的性质如表2所示。
表2
  改性丙烯酸硅树脂
羟值(mgKOH/g) 105
Tg(℃) 29.3
固含量(％) 45
黏度(mPa·s) 100
pH 7.1
从表2中可以看出，本实施例制备得到的改性丙烯酸硅树脂性能优良，羟值和Tg符合作为涂料基体的要求。
取95份改性丙烯酸硅树脂、35份水性异氰酸酯固化剂、10份粒径为200μm的沉淀硫酸钡、20份粒径为200μm的氯化铁、5份AMP-95分散剂、3份Tego300流平剂。
将改性丙烯酸硅树脂、沉淀硫酸钡、氯化铁、分散剂和流平剂在300rpm转速下分散15min得到混合浆料；将混合浆料和水性异氰酸酯固化剂在600rpm转速下搅拌2min，获得丙烯酸机械通用涂料。
将本实施例制备得到快干高耐候丙烯酸机械通用涂料按照实施例1中的方法进行测试。测定结果记录在表6中。
实施例3
取180g丙烯酸单体、60gγ-甲基丙烯酰氧基丙基三甲氧基硅烷、6g过硫酸钾、18gAES和540g水；其中丙烯酸单体中甲基丙烯酸甲酯为25份、甲基丙烯酸丁酯为25份、丙烯酸为2份500rpm转速、80℃下分散30min获得基底体系；将丙烯酸单体和基底体系在500rpm转速、80℃下搅拌20min获得单体体系；将单体体系和剩余的水混合，调整转速为300rpm，温度为80℃，将γ-甲基丙烯酰氧基丙基三甲氧基硅烷以500mL/h的速率滴加，滴加结束后反应4h，获得改性丙烯酸硅树脂，经检测本实施例得到改性丙烯酸硅树脂的 性质如表3所示。
表3
  改性丙烯酸硅树脂
羟值(mgKOH/g) 114
Tg(℃) 28.6
固含量(％) 47
黏度(mPa·s) 102
pH 7
从表3中可以看出，本实施例制备得到的改性丙烯酸硅树脂性能优良，羟值和Tg符合作为涂料基体的要求。
取135份改性丙烯酸硅树脂、45份水性异氰酸酯固化剂、20份粒径为300μm的沉淀硫酸钡、30份粒径为230μm的氯化铁、10份BYK-199分散剂、8份BYK-VP-354流平剂。
将改性丙烯酸硅树脂、沉淀硫酸钡、氯化铁、分散剂和流平剂在400rpm转速下分散25min得到混合浆料；将混合浆料和水性异氰酸酯固化剂在800rpm转速下搅拌4min，获得丙烯酸机械通用涂料。
将本实施例制备得到快干高耐候丙烯酸机械通用涂料按照实施例1中的方法进行测试。测定结果记录在表6中。
对比例1
本对比例和实施例1的区别在于，将γ-甲基丙烯酰氧基丙基三甲氧基硅烷的用量调整为100g，其余的条件不变，测试制备得到的改性丙烯酸硅树脂的性质如表4所示。
表4
  改性丙烯酸硅树脂
羟值(mgKOH/g) 142
Tg(℃) 12
固含量(％) 43
黏度(mPa·s) 98
pH 7
从表4可以看出，因为γ-甲基丙烯酰氧基丙基三甲氧基硅烷的用量增大，羟值和Tg也随之改变，但是仍能用于涂料。
将本对比例制备得到改性涂料按照实施例1中的方法进行测试。测定结果记录在表6中。
对比例2
本对比例和实施例1的区别在于，γ-甲基丙烯酰氧基丙基三甲氧基硅烷的滴加速率调整为1.5L/h，其余的条件不变，测试制备得到的改性丙烯酸硅树脂的性质如表5所示。
表5
  改性丙烯酸硅树脂
羟值(mgKOH/g) 128
Tg(℃) 14
固含量(％) 43
黏度(mPa·s) 98
pH 7
从表5中可以看出，滴加速率过快后，部分γ-甲基丙烯酰氧基丙基三甲氧基硅烷来不及进行聚合反应，影响树脂性能。
将本对比例制备得到改性涂料按照实施例1中的方法进行测试。测定结果记录在表6中。
对比例3
本对比例和实施例1的区别在于，水性异氰酸酯固化剂加入量为70份，其余条件不变；将本对比例制备得到改性涂料按照实施例1中的方法进行测试。测定结果记录在表6中。
表6
  实施例1 实施例2 实施例3 对比例1 对比例2 对比例3
附着力(级) 1 1 1 6 6 5
耐冲击性(cm) 53 52 53 24 20 32
硬度(H) 5 5 4 3 2 2
耐水性(天) 9 9 8 2 2 3
耐候性(级) 1 1 1 4 4 出现针孔
表干(h) 1.8 2.0 1.9 4 3.5 4.2
实干(h) 10.5 11 10.8 24.6 21.7 23.5
耐磨损性(g) 0.018 0.021 0.020 0.103 0.086 0.112
由以上实施例可知，本发明提供了一种快干高耐候丙烯酸机械通用涂料，通过实施例可以看出，γ-甲基丙烯酰氧基丙基三甲氧基硅烷的用量增大或者滴加速率增大后，会严重影响涂料的性能，这是因为涂料中有未反应的γ-甲基丙烯酰氧基丙基三甲氧基硅烷，无法作为有效成分提高涂料性能；水性异氰酸酯固化剂加入量增大后，涂料体系中会有多余的异氰酸酯基团与水反应，生成二氧化碳从涂层中逸出，形成针孔降低涂层的耐候性。在本发明的用量范围内得到的涂料，具有优异的综合性能，涂覆后干燥时间短，耐水性和耐候性优异，避免了机械产品在露天环境中因为雨水等原因造成的腐蚀。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

  1. 一种快干高耐候丙烯酸机械通用涂料，其特征在于，由包含下列质量份的原料制备得到：
    改性丙烯酸硅树脂95～135份、水性异氰酸酯固化剂35～45份、沉淀硫酸钡10～20份、氯化铁20～30份、分散剂5～10份、流平剂3～8份。
  2. 如权利要求1所述的涂料，其特征在于，所述改性丙烯酸硅树脂由包含下列质量比的原料制备得到：
    丙烯酸单体：γ-甲基丙烯酰氧基丙基三甲氧基硅烷：过硫酸钾：乳化剂：水为20～30：5～10：0.5～1：2～3：70～90；
    所述丙烯酸单体包含下列质量份的组分：
    甲基丙烯酸甲酯20～25份、甲基丙烯酸丁酯20～25份、丙烯酸1～2份；
    所述乳化剂为OP-10、APG和AES中的一种或几种。
  3. 如权利要求2所述的涂料，其特征在于，所述改性丙烯酸硅树脂的制备方法，包含下列步骤：
    (1)将过硫酸钾、乳化剂和第一部分水分散，得到基底体系；
    (2)将丙烯酸单体和基底体系混合，得到单体体系；
    (3)将单体体系、γ-甲基丙烯酰氧基丙基三甲氧基硅烷和剩余的水混合后发生聚合反应，即获得改性丙烯酸硅树脂。
  4. 如权利要求3所述的涂料，其特征在于，所述步骤(1)中第一部分水的质量为水质量的40～50％；
    所述步骤(1)中分散的转速为400～500rpm，所述分散的时间为20～30min，所述分散的温度为70～80℃；
    所述步骤(2)中混合的方式为搅拌，所述搅拌的转速为400～500rpm，所述搅拌的时间为10～20min，所述搅拌的温度为70～80℃。
  5. 如权利要求3或4所述的涂料，其特征在于，所述步骤(3)中混合为单体体系和水混合后滴加γ-甲基丙烯酰氧基丙基三甲氧基硅烷；所述滴加的速率为400～500mL/h；
    所述步骤(3)中聚合反应的温度为70～80℃，所述聚合反应的时间为3～4h，所述聚合反应在搅拌条件下进行，所述搅拌的转速为200～300rpm。
  6. 如权利要求1、2、3或4所述的涂料，其特征在于，所述沉淀硫酸 钡的粒径为200～300μm，所述氯化铁的粒径为200～300μm。
  7. 权利要求1～6任意一项所述丙烯酸机械通用涂料的制备方法，其特征在于，包含下列步骤：
    (a)将改性丙烯酸硅树脂、沉淀硫酸钡、氯化铁、分散剂和流平剂分散得到混合浆料；
    (b)将混合浆料和水性异氰酸酯固化剂混合后即得丙烯酸机械通用涂料。
  8. 如权利要求7所述的制备方法，其特征在于，所述步骤(a)中分散的转速为300～400rpm，所述分散的时间为15～25min。
  9. 如权利要求7或8所述的制备方法，其特征在于，所述步骤(b)中混合的方式为搅拌，所述搅拌的转速为600～800rpm，所述搅拌的时间为2～4min。
  10. 权利要求1～6任意一项所述丙烯酸机械通用涂料在钢结构涂覆上的应用。
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