WO2020082703A1 - 一种高耐候水性防腐涂料制备方法 - Google Patents

一种高耐候水性防腐涂料制备方法 Download PDF

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WO2020082703A1
WO2020082703A1 PCT/CN2019/083548 CN2019083548W WO2020082703A1 WO 2020082703 A1 WO2020082703 A1 WO 2020082703A1 CN 2019083548 W CN2019083548 W CN 2019083548W WO 2020082703 A1 WO2020082703 A1 WO 2020082703A1
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杨辉
吴春春
罗仲宽
李跃
薛明
汪海风
徐强
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Zhejiang University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds

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  • the invention relates to the preparation technology of anti-corrosion coatings, in particular to a preparation method for a high weather-resistant anti-corrosion coating.
  • the marine environment is harsher than the general atmospheric environment, not only has high humidity, corrosive medium ion concentration, and high ultraviolet radiation. Therefore, anticorrosive coatings for marine environments have placed high requirements on the corrosion resistance and weather resistance of the coating, and are currently widely used.
  • the anti-corrosion coatings are mainly organic coatings, including acrylate, polyurethane, epoxy resin and other types of coatings. Among them, high-solid epoxy resin coatings are widely used on ships and offshore structures, but these organic coatings have low organic bond energy. It is prone to breakage caused by ultraviolet radiation, so it requires a large construction thickness (several hundreds of micrometers) and short service life.
  • the pure inorganic system coating has excellent resistance to ultraviolet aging, but the pure inorganic system coating is easy to crack, resulting in its corrosion resistance is much lower than the organic corrosion protection coating.
  • the addition of organic groups can improve the corrosion resistance of the coating to a certain extent, but the description of organic components and inorganic nanocomponents has always been problematic, and it cannot form a strong chemical bond to affect the overall performance of the coating.
  • the present invention uses silica sol and Al (OH) 3 sol as the inorganic phase, multi-component silane polymer as a film-forming modification substance to increase the density of the coating, and the organic group by chemical mechanical method It is firmly combined with the surface of inorganic components to prepare a water-based anticorrosive coating with excellent weather resistance and high corrosion resistance.
  • the technical problem to be solved by the present invention is to overcome the deficiencies in the prior art and provide a method for preparing a high-weather-resistant anticorrosive paint.
  • the solution of the present invention is:
  • a method for preparing a high-weather-resistant water-based anticorrosive paint which includes the following steps:
  • step (3) Under stirring conditions, add 20 parts by mass of the composite silica sol of step (1) to 10 parts by mass of the mixture obtained in step (2); after mixing for 10 minutes, add a nano-sand mill (such as LSM-1.4L type) Grinding for 20 to 30 minutes in the middle to obtain organosilane polymer composite silica sol;
  • a nano-sand mill such as LSM-1.4L type
  • the stirring conditions are all controlled at a stirring speed of 300 r / min.
  • the mass percentage concentration of the hydrochloric acid solution is 5%.
  • the SiO 2 sol is a water-based sol, the mass concentration is 40-50%, and the average particle diameter is 10-50 nm.
  • the Al (OH) 3 sol is a water-based sol with a mass concentration of 25-30% and an average particle size of 30-50 nm.
  • the rotation speed of the nano-sand mill is 1400 r / min
  • the grinding medium is zirconia beads
  • the diameter is 1 mm.
  • the present invention has the following beneficial effects:
  • Silica nanoparticles have a high resistance to ultraviolet aging.
  • the present invention uses KH570 and ethyl orthosilicate prepolymer to organic-inorganic composite of inorganic nano-oxide sol to improve the phase of organic groups and inorganic nano-phase Capacitance and reactivity, at the same time, the nano-sand milling method gives more mechanical energy between the inorganic nano-sol ions and the reactive groups of the prepolymer, which improves the degree of reaction and more fully combines, thereby improving the The compactness and weather resistance of the coating.
  • the corrosion resistance of the water-based paint is improved without changing the weather resistance of the water-based paint.
  • the invention provides a method for preparing a high-weather-resistant anticorrosive paint, which includes the following steps:
  • step (3) Under stirring conditions, add 20 parts by mass of the composite silica sol of step (1) to 10 parts by mass of the mixture obtained in step (2); after mixing for 10 minutes, add LSM-1.4L nano sand mill to grind 20 ⁇ 30min, get organosilane polymer composite silica sol;
  • the coating uses the following standards to test various aspects of performance:
  • the coating neutral salt spray test uses the copper acetate chloride salt spray accelerated test (CASS test standard).
  • the coatings prepared by mechanically grinding the sample coatings have high corrosion resistance and weather resistance, which are more than 30 days and 12 months, respectively, without modification by grinding Comparative example 1 with stirring, although the aging resistance is also higher than the organic coating, but compared with the sample 1, the corrosion resistance and aging resistance decreased.
  • the sample with excessive grinding time Comparative Example 2 compared with Sample 3 had a sharp drop in corrosion resistance of 2 days. It can be seen that organic-inorganic nanocompositing by mechanical grinding improves the corrosion resistance and aging resistance of the coating.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

一种高耐候水性防腐涂料制备方法，包括：在搅拌条件下，向粒子型纳米SiO 2溶胶中加入Al(OH) 3溶胶，陈化制得Al(OH) 3溶胶包覆的复合二氧化硅溶胶；将无水乙醇与去离子水混合，用盐酸溶液调节pH值，加入KH570和正硅酸乙酯，继续搅拌后加入复合二氧化硅溶胶；混合、研磨后，与醋酸、甲基三甲氧基硅烷混合并搅拌，得到高耐候水性防腐涂料。

Description

一种高耐候水性防腐涂料制备方法 技术领域
本发明涉及防腐涂层制备技术，特别涉及用于一种高耐候防腐涂料制备方法。
背景技术
海洋环境较一般大气环境苛刻，不仅湿度大、腐蚀介质离子浓度大、而且高紫外辐射，因而海洋环境用防腐涂料对涂层的耐腐蚀性能和耐候性能都提出了很高的要求，目前普遍使用的防腐涂料主要为有机涂料，包括丙烯酸酯、聚氨酯、环氧树脂等类型涂料，其中高固含环氧树脂涂料在船舶、海工结构表面应用广泛，但这几种有机涂料因有机键能低易出现紫外线照射引起的断裂，故均需较大的施工厚度(几百微米)、且使用寿命短等问题。
另一方面，纯无机体系涂层具有优异的耐紫外老化性能，但纯无机体系涂层很容易开裂，导致其防腐性能远低于有机防腐涂层。通过有机基团的加入在一定程度上可提高涂层的耐腐蚀性能，但有机组分与无机纳米组分的形容性一直存在问题，不能形成牢固的化学键合从而影响涂层的整体性能。
针对上述问题，本发明以二氧化硅溶胶和Al(OH) 3溶胶为无机相，通过多组分硅烷聚合物为成膜改性物质增加涂层的致密性，通过化学机械法将有机基团牢固结合在无机组分表面，制备出耐候性能优良且防腐性高的水性防腐涂料。
发明内容
本发明要解决的技术问题是，克服现有技术中的不足，提供一种高耐候防腐涂料制备方法。
为解决技术问题，本发明的解决方案是：
提供一种高耐候水性防腐涂料制备方法，包括如下步骤：
(1)在搅拌条件下，向粒子型纳米SiO 2溶胶中加入Al(OH) 3溶胶，保持Si∶Al摩尔比为5～1∶1，在50℃陈化24h后，制得Al(OH) 3溶胶包覆的复合二氧化硅溶胶；
(2)在搅拌条件下，将10质量份无水乙醇与0.2～0.5质量份去离子水混合；用质量百分比浓度5％的盐酸溶液调至pH值4～5，加入2～3质量份KH570；搅拌30min后，加入4～7质量份正硅酸乙酯，搅拌7h；
(3)在搅拌条件下，将20质量份步骤(1)的复合二氧化硅溶胶加入10质量份步骤(2)所得混合物；混合10min后，加入纳米砂磨机(如LSM-1.4L型)中研磨20～30min，得到有机硅烷聚合物复合二氧化硅溶胶；
(4)取有机硅烷聚合物复合二氧化硅溶胶20质量份、醋酸0.1份、甲基三甲氧基硅烷6～10质量份，混合并搅拌6h，得到高耐候水性防腐涂料。
本发明中，所述搅拌条件均控制搅拌速度为300r/min。
本发明中，所述盐酸溶液的质量百分比浓度为5％。
本发明中，所述步骤(1)中，SiO 2溶胶为水基溶胶，质量浓度为40～50％，平均粒径10～50nm。
本发明中，所述步骤(1)中，Al(OH) 3溶胶为水基溶胶，质量浓度在25～30％，平均粒径30～50nm。
本发明中，所述步骤(3)中，纳米砂磨机转速为1400r/min，研磨介质为氧化锆珠，直径1mm。
与现有制备技术相比，本发明具有以下有益效果：
二氧化硅纳米粒子具有很高的耐紫外老化性能，本发明采用KH570与正硅酸乙酯的预聚物对无机纳米氧化物溶胶进行有机无机复合，提高了有机基团与无机纳米相的相容性和反应性，同时通过纳米砂磨机研磨的方式赋予了无机纳米溶胶离子与预聚物反应基团之间更多的机械能，使其反应程度提高，更充分地相结合，从而提高了涂料的致密性和耐候性。通过本发明的制备工艺，水性涂料的耐候性不变的情况下，提高了水性涂料的耐腐蚀性能。
具体实施方式
以下通过实例进一步对本发明进行描述。
本发明提供了一种高耐候防腐涂料制备方法，包括如下步骤：
(1)在搅拌条件下，向粒子型纳米SiO 2溶胶中加入Al(OH)3溶胶，保持Si∶Al摩尔比为5～1∶1；在50℃陈化24h后，制得Al(OH)3溶胶包覆的复合二氧化硅溶胶；
(2)在搅拌条件下，将10质量份无水乙醇与0.2～0.5质量份去离子水混合；用质量百分比浓度5％的盐酸溶液调至pH值4～5，加入2～3质量份KH570；搅拌30min后，加入4～7质量份正硅酸乙酯，搅拌7h；
(3)在搅拌条件下，将20质量份步骤(1)的复合二氧化硅溶胶加入10质量份步骤(2)所得混合物；混合10min后，加入LSM-1.4L型纳米砂磨机中研磨20～30min，得到有机硅烷聚合物复合二氧化硅溶胶；
(4)取有机硅烷聚合物复合二氧化硅溶胶20质量份、醋酸0.1份、甲基三甲氧基硅烷6～10质量份，混合并搅拌6h，得到高耐候水性防腐涂料。
本发明所得涂料的使用方法示例：
将涂料喷涂在Q235钢表面，室温下表干30min后，经0.5h，170℃下固化后形成20～30微米厚的防腐涂层。
各实施例中的试验数据见表1，其中对比例1是将研磨改为搅拌20min。
涂层采用以下标准测试各方面性能：
1)涂层耐候性试验采用国家标准GB-T1865-1997测试。
2)涂层中性盐雾试验采用醋酸氯化铜盐雾加速试验(CASS测试标准)测试。
表1
Figure PCTCN2019083548-appb-000001
从表1中可以看出，通过机械研磨复合的样品涂料(序号1到4)制备的涂层耐腐蚀性能和耐候性均很高，分别在30天以上和12个月，而未经研磨改为搅拌的对比例1，耐老化性能虽然也较有机涂层的高，但与样品1比较，耐腐蚀及耐老化性能均下降。另一方面，研磨时间过量的样品(对比例2)与样品3比较，耐腐蚀性能急剧下降为2天。可见，机械研磨方式进行有机无机纳米复合提高了涂层的耐腐蚀性能和耐老化性能。
最后，还需要注意的是，以上列举的仅是本发明的具体实施例子。显然，本发明不限于以上实施例子，还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形，均应认为是本发明的保护范围。

Claims (6)

  1. 一种高耐候水性防腐涂料制备方法，其特征在于，包括如下步骤：
    (1)在搅拌条件下，向粒子型纳米SiO 2溶胶中加入Al(OH) 3溶胶，保持Si∶Al摩尔比为5～1∶1；在50℃陈化24h后，制得Al(OH) 3溶胶包覆的复合二氧化硅溶胶；
    (2)在搅拌条件下，将10质量份无水乙醇与0.2～0.5质量份去离子水混合；用质量百分比浓度5％的盐酸溶液调至pH值4～5，加入2～3质量份KH570；搅拌30min后，加入4～7质量份正硅酸乙酯，搅拌7h；
    (3)在搅拌条件下，将20质量份步骤(1)的复合二氧化硅溶胶加入10质量份步骤(2)所得混合物；混合10min后，加入纳米砂磨机中研磨20～30min，得到有机硅烷聚合物复合二氧化硅溶胶；
    (4)取有机硅烷聚合物复合二氧化硅溶胶20质量份、醋酸0.1份、甲基三甲氧基硅烷6～10质量份，混合并搅拌6h，得到高耐候水性防腐涂料。
  2. 根据权利要求1所述的方法，其特征在于，所述搅拌条件均控制搅拌速度为300r/min。
  3. 根据权利要求1所述的方法，其特征在于，所述盐酸溶液的质量百分比浓度为5％。
  4. 根据权利要求1所述的方法，其特征在于，所述步骤(1)中，SiO 2溶胶为水基溶胶，质量浓度为40～50％，平均粒径10～50nm。
  5. 根据权利要求1所述的方法，其特征在于，所述步骤(1)中，Al(OH) 3溶胶为水基溶胶，质量浓度在25～30％，平均粒径30～50nm。
  6. 根据权利要求1所述的方法，其特征在于，所述步骤(3)中，纳米砂磨机转速为1400r/min，研磨介质为氧化锆珠，直径1mm。
PCT/CN2019/083548 2018-10-22 2019-04-19 一种高耐候水性防腐涂料制备方法 Ceased WO2020082703A1 (zh)

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丁新更 (DING, XINGENG): "KH570改性SiO2复合耐腐蚀涂层结构及性能 (Hydrolyze-polymerization Process and Anti-corrosion Property of KH570-SiO2 Composite Sol)", 材料工程 (JOURNAL OF MATERIALS ENGINEERING), no. 12, 31 December 2010 (2010-12-31), ISSN: 1001--438 *

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