[go: up one dir, main page]

WO2022198961A1 - 一种石墨烯改性的水性弹性涂料组合物及其制备方法 - Google Patents

一种石墨烯改性的水性弹性涂料组合物及其制备方法 Download PDF

Info

Publication number
WO2022198961A1
WO2022198961A1 PCT/CN2021/120928 CN2021120928W WO2022198961A1 WO 2022198961 A1 WO2022198961 A1 WO 2022198961A1 CN 2021120928 W CN2021120928 W CN 2021120928W WO 2022198961 A1 WO2022198961 A1 WO 2022198961A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
add
aqueous solution
parts
composition
Prior art date
Application number
PCT/CN2021/120928
Other languages
English (en)
French (fr)
Inventor
胡中源
陈燕
郑毅
唐智谋
张晓军
Original Assignee
龙牌涂料(北京)有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 龙牌涂料(北京)有限公司 filed Critical 龙牌涂料(北京)有限公司
Publication of WO2022198961A1 publication Critical patent/WO2022198961A1/zh

Links

Classifications

    • 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
    • C09D125/00—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 at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • 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
    • C09D127/00—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 at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—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 at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • 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
    • 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
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • 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
    • C09D5/18—Fireproof paints including high temperature resistant 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the present application relates to the technical field of coatings, in particular to a graphene-modified water-based elastic coating composition and a preparation method thereof.
  • Exterior wall coatings are exposed to the outdoors for a long time, and are affected by sunlight, rain, wind and sand, and changes in cold and heat. Especially in the northwest region, the climate is dry, the ultraviolet rays are strong, and the temperature difference between day and night is large, which causes the wall to crack. The appearance of cracks not only affects the aesthetics of building finishes, but also adversely affects or even harms the building itself.
  • the elastic coatings have gradually become the dominant material in exterior wall decoration because of their good elastic stretching and ability to effectively cover wall cracks.
  • the elastic brushed coating has a concave-convex texture and texture, which can repair the cracks in the wall, with outstanding finishing effect and strong three-dimensional effect, so it is loved by people.
  • the elastic brushed paint has a strong three-dimensional decoration and can form a strong visual effect, its performance is single, it does not have the functions of fire prevention and antibacterial, and it has poor stain resistance.
  • there are more dust and suspended substances in the atmosphere there are more dust and suspended substances in the atmosphere, and the uneven texture is more likely to be contaminated with pollutants and affect the decorative effect of the wall.
  • the purpose of this application is to provide a kind of graphene-modified water-based elastic coating composition and preparation method thereof, so as to solve the problem that the elastic brushing coating that exists in the above-mentioned prior art has single performance, does not have functions such as fire prevention and antibacterial, and is resistant to contamination at the same time. Poor performance issue.
  • the application provides a graphene-modified water-based elastic coating composition, which comprises the following components in parts by mass:
  • the concentration of graphene in the graphene aqueous solution is 1.2 mg/ml to 1.4 mg/ml.
  • the composition may further comprise 0.4 part to 0.6 part of a preservative.
  • the composition may consist of the following components in parts by mass:
  • the concentration of graphene in the graphene aqueous solution is 1.2 mg/ml to 1.4 mg/ml.
  • the elastic emulsion can be styrene-acrylic emulsion, pure acrylic emulsion, silicone-acrylic emulsion or fluorocarbon emulsion or a mixture thereof;
  • the titanium dioxide can be rutile titanium dioxide;
  • the filler can be talc or Heavy calcium or a mixture thereof.
  • the wetting agent may be a polyoxyalkylene alkyl ether type non-ionic wetting agent, such as commercially available SN996 or Clariant's LCN088 (which is zero VOC, no alkylphenol polyoxygen Vinyl ether compounds (APEO) environmental protection additives), can improve the floating color of the paint, and also has a certain antifreeze performance, remove the addition of antifreeze, greatly reduce the VOC content.
  • a polyoxyalkylene alkyl ether type non-ionic wetting agent such as commercially available SN996 or Clariant's LCN088 (which is zero VOC, no alkylphenol polyoxygen Vinyl ether compounds (APEO) environmental protection additives)
  • Clariant's LCN088 which is zero VOC, no alkylphenol polyoxygen Vinyl ether compounds (APEO) environmental protection additives
  • the dispersant may be sodium polycarboxylate, zero VOC, such as the commercially available Japanese Nopco SN-5027 or Dow Chemical's Quick Easy.
  • the neutralizing agent may be 2-amino-2-methyl-1-propanol, such as commercially available Angus AMP-95 or Clariant's KF100.
  • the defoaming agent may be mineral oil, silicone or polyether or a mixture thereof, such as commercially available products such as Nopco SN1360 and BASF A10.
  • the film-forming aid can be a diester type high-boiling organic compound, such as an organic compound with a boiling point greater than 260 degrees Celsius, such as commercially available Eastman OE300.
  • the preservative may be free of methylchloroisothiazolinone (CIT), adsorbable organic halogen (AOX) and organic volatiles (VOC), and the active ingredient of the preservative may be 1 , 2-benzisothiazolinone (BIT) and methylisothiazolinone (MIT), such as Thor's MBS or Dow Chemical's CJ-1.
  • CIT methylchloroisothiazolinone
  • AOX adsorbable organic halogen
  • VOC organic volatiles
  • the active ingredient of the preservative may be 1 , 2-benzisothiazolinone (BIT) and methylisothiazolinone (MIT), such as Thor's MBS or Dow Chemical's CJ-1.
  • the thickener can be an anionic hydrophobically modified acrylic alkali-swellable thickener, such as TZ-801, which has a very significant effect on improving low-shear viscosity, has high-efficiency thickening effect and more High pseudoplasticity, so that the coating can achieve a moderate three-dimensional pattern effect during construction.
  • TZ-801 an anionic hydrophobically modified acrylic alkali-swellable thickener
  • the graphene aqueous solution can be prepared from graphene nanosheets with a sheet diameter of 1-3 ⁇ m and a thickness of 1-5 nm.
  • the preparation method of the graphene aqueous solution may include the following steps: adding water as a dispersion medium in an ultrasonic device, then adding isopropanol, polyvinylpyrrolidone and graphene sheets, ultrasonically dispersing for 2-3 hours, Set for 24-48h, take the upper layer liquid and place it in a centrifuge, centrifuge at 5000-6000r/min for 30-40min, take the upper layer liquid, and obtain the graphene aqueous solution.
  • the water can be 65 wt%
  • the isopropanol can be 5 wt%
  • the polyvinylpyrrolidone can be 10 wt%
  • the graphene can be 20 wt%.
  • the application provides a method for preparing the above-mentioned graphene-modified water-based elastic coating composition, the method comprising the following steps:
  • the present application selects graphene nano-sheets with a sheet diameter of 1-3 ⁇ m and a thickness of 1-5 nm.
  • the hexagonal carbon ring formed by sp 2 hybridization has high specific surface area, rapid electrical conductivity, excellent chemical stability, outstanding mechanical properties, high thermal conductivity and other properties, which can impart flame retardant, anti-corrosion and anti-fouling effects to coatings.
  • graphene Since graphene is only a few nanometers thick and has high adsorption properties between nanomaterial particles, it is difficult to be completely dispersed, and due to the inherent hydrophobicity of pure carbon materials, graphene cannot be fully dispersed in other materials.
  • graphene nanosheets are dissolved and ultrasonicated to prepare an aqueous solution of graphene, so that graphene can play a better role in coatings.
  • This application is a green and environmentally friendly product, which not only has a strong texture, good weather resistance, water resistance, alkali resistance, and excellent stain resistance, but also has functions such as fire prevention and antibacterial, which can protect and decorate walls more lastingly.
  • Surface, zero VOC, no harmful substances such as heavy metals, suitable for walls, roofs and other parts of buildings such as industrial, civil, and public places.
  • Graphene nanosheets with a sheet diameter of 1-3 ⁇ m and a thickness of 1-5 nm are selected.
  • the concentration of the graphene aqueous solution in Examples 1-4 is between 1.2-1.4 mg/ml.
  • Example 4 The difference from Example 4 is that the graphene aqueous solution is replaced with graphene nanosheets of equivalent graphene quality, and the preparation methods of other components and coating compositions are the same as those of Example 4.
  • Example 4 The difference from Example 4 is that the graphene aqueous solution is not added, and the preparation methods of other additive components and coating compositions are the same as those of Example 4.
  • the graphene-modified water-based elastic coating of the present application has excellent weather resistance, water resistance, alkali resistance and stain resistance, and has more lasting protection for decorative walls, zero VOC, and no heavy metals. and other harmful substances, and the addition of graphene solution has no effect on the appearance of the original paint.
  • the direct addition of graphene sheets will affect the covering power of the product due to the poor dispersion of the graphene sheets, resulting in a decrease in tensile strength.
  • the graphene-modified water-based thick elastic coating of the present application also has antibacterial and lasting fire resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Plant Pathology (AREA)
  • Paints Or Removers (AREA)

Abstract

一种石墨烯改性的水性弹性涂料组合物及其制备方法，该组合物包括以质量份计的以下组分：弹性乳液38份-43份，钛白粉13份-18份，填料20份-25份，润湿剂0.2份-0.3份，分散剂0.5份-0.6份，中和剂0.1份-0.2份，消泡剂0.2份-0.4份，成膜助剂0.4份-0.6份，石墨烯水溶液2份-2.5份，水15份-30份，以及增稠剂0.5份-1份；其中石墨烯在该石墨烯水溶液中的浓度为1.2mg/ml～1.4mg/ml。

Description

一种石墨烯改性的水性弹性涂料组合物及其制备方法 技术领域
本申请涉及涂料技术领域，特别是涉及一种石墨烯改性的水性弹性涂料组合物及其制备方法。
背景技术
外墙涂料长期暴露于户外，受到日光、雨水、风沙、冷热变化等的影响，经过一段时间后，饰面的外观发生开裂、剥落、粉化、变色、退色等现象。特别是在西北地区，气候干燥，紫外线强烈，昼夜温差大，造成墙体开裂，建筑裂缝乃当今建筑施工质量中最常见的问题，长久以来一直困扰着当今的建筑业。裂缝的出现不仅影响建筑饰面的美观，而且会对建筑物本身产生不利影响，甚至危害。
在建筑外墙涂料中，弹性涂料由于其具有弹性拉伸好、能够有效地遮盖墙体的裂纹，因而逐渐成为了外墙装饰中的主导材料。在弹性涂料中，弹性拉毛涂料具有凹凸质感和纹理，可以修补墙体裂纹，饰面效果突出，立体感强，因而受到了人们的喜爱。虽然弹性拉毛涂料立体装饰感强，能够形成强烈的视觉效果，但是其性能单一，不具备防火、抗菌等功能，同时耐沾污性能差。尤其是在环境污染日益严重的今天，大气中的灰尘以及悬浮物质较多，凹凸的纹理更容易沾染污染物而影响墙体的装饰效果。
发明概述
本申请的目的是提供一种石墨烯改性的水性弹性涂料组合物及其制备方法，以解决上述现有技术中存在的弹性拉毛涂料性能单一，不具备防火、抗菌等功能，同时耐沾污性能差的问题。
为了解决上述技术问题，本申请提供了一种石墨烯改性的水性弹性涂料组合物，所述组合物包括以质量份计的以下组分：
Figure PCTCN2021120928-appb-000001
Figure PCTCN2021120928-appb-000002
其中石墨烯在所述石墨烯水溶液中的浓度为1.2mg/ml～1.4mg/ml。在一些实施方式中，所述组合物还可以包含0.4份-0.6份的防腐剂。在一些实施方式中，所述组合物可以由以质量份计的以下组分组成：
Figure PCTCN2021120928-appb-000003
其中石墨烯在所述石墨烯水溶液中的浓度为1.2mg/ml～1.4mg/ml。
在一些实施方式中，所述弹性乳液可以为苯丙乳液、纯丙乳液、硅丙乳液或氟碳乳液或其混合物；所述钛白粉可以为金红石型钛白粉；所述填料可以为滑石粉或重钙或其混合物。
在一些实施方式中，所述润湿剂可以为聚氧烯基烷基醚类非离子型润湿剂，比如市售的SN996或科莱恩的LCN088(这是零VOC，无烷基酚聚氧乙烯醚类化合物(APEO)的环保助剂)，同时能够改善涂料的浮色发花，还具有一定的防冻性能，去除了防冻剂的添加，大大降低了VOC的含量。
在一些实施方式中，所述分散剂可以为聚羧酸钠盐，零VOC，如市售的日本诺普科SN-5027或者陶氏化学的快易。
在一些实施方式中，所述中和剂可以为2-氨基-2-甲基-1-丙醇，如市售的安格斯AMP-95或者科莱恩的KF100。
在一些实施方式中，所述消泡剂可以为矿物油类、有机硅类或聚醚类或其混合物，比如市售的如诺普科SN1360，巴斯夫A10。
所述成膜助剂可以为双酯类高沸点有机化合物比如沸点大于260摄氏度的有机化合物，例如市售伊斯曼的OE300。
在一些实施方式中，所述防腐剂可以不含甲基氯异噻唑啉酮(CIT)、可吸附有机卤素(AOX)和有机挥发物(VOC)，且所述防腐剂的活性成份可以为1,2-苯并异噻唑啉酮(BIT)和甲基异噻唑啉酮(MIT)，例如托尔的MBS或者陶氏化学的CJ-1。
在一些实施方式中，所述增稠剂可以为阴离子型疏水改性丙烯酸碱溶胀型增稠剂，如TZ-801，改善低剪切粘度方面的作用非常显著，具有高效的增稠效果和更高的假塑性，从而使涂料在施工中达到适度的立体花纹效果。
在一些实施方式中，石墨烯水溶液可以选用片径在1-3μm，厚度为1-5nm的石墨烯纳米片制备而成。
在一些实施方式中，所述石墨烯水溶液的制备方法可以包括以下步骤：在超声设备中加入水为分散介质，再加入异丙醇、聚乙烯吡咯烷酮以及石墨烯片，超声分散2-3h，静置24-48h，取上层液置于离心机中，在5000-6000r/min 转速下离心30-40min，取上层液，得石墨烯水溶液。在一些实施方式中，水可以为65wt％，异丙醇可以为5wt％，聚乙烯吡咯烷酮可以为10wt％，石墨烯可以为20wt％。
另一方面，本申请提供一种制备如上所述的石墨烯改性的水性弹性涂料组合物的方法，所述方法包括以下步骤：
先将准确称量的水加入容器比如拉缸或大罐中，在400-600r/min的低转速状态下，缓慢地依次加入分散剂、润湿剂、成膜助剂、消泡剂、中和剂和任选的防腐剂的一部分，添加完成后搅拌1-2min，提高转速至700-900r/min中速状态下，依次加入钛白粉、填料，提高转速至1000-1200r/min，高速分散30分钟，然后降低转速至400-600r/min低速状态下加入弹性乳液、任选的防腐剂的剩余部分、石墨烯水溶液，搅拌2-3min后缓慢加入增稠剂，在23±2℃条件下调整粘度至15-16mPa·s，慢速搅拌15分钟，制得石墨烯改性的水性弹性涂料组合物。
与现有技术相比，本申请选用片径在1-3μm，厚度为1-5nm的石墨烯纳米片，所述石墨烯纳米片为正六边形碳环在平面内无限拓展延伸构成，碳原子sp 2杂化形成的六边形碳环，具有高比表面积、快速导电性、优异的化学稳定性、突出的力学性能、高导热性等性能，能赋予涂料阻燃、防腐、防污效果。
由于石墨烯的厚度只有几个纳米，具有纳米材料颗粒之间高强的吸附性能，故很难被完全分散开，且由于纯碳材料所固有的疏水性，使得石墨烯不能够充分分散在其他材料中，直接影响其功能的充分发挥，本申请将石墨烯纳米片溶解超声后制备得到石墨烯水溶液，使得石墨烯更好的在涂料中发挥作用。
本申请为绿色环保型产品，不仅具有较强的质感，较好的耐候性、耐水性、耐碱性，优良的耐沾污性能，还具有防火、抗菌等功能，更持久的保护和装饰墙面，零VOC，不含重金属等有害物质，适用于工业、民用、公共场所等建筑物的墙体、屋顶等部位。
本申请的其它特征和优点将在随后的说明书中阐述，并且，部分地从说明书中变得显而易见，或者通过实施本申请而了解。本申请的目的和其他优 点可通过在说明书以及权利要求书中所特别指出的结构来实现和获得。
详述
现详细说明本申请的多种示例性实施方式，该详细说明不应认为是对本申请的限制，而应理解为是对本申请的某些方面、特性和实施方案的更详细的描述。
应理解本申请中所述的术语仅仅是为描述特别的实施方式，并非用于限制本申请。另外，对于本申请中的数值范围，应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本申请内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明，否则本文使用的所有技术和科学术语具有本申请所述领域的常规技术人员通常理解的相同含义。虽然本申请仅描述了优选的方法和材料，但是在本申请的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入，用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时，以本说明书的内容为准。
在不背离本申请的范围或精神的情况下，可对本申请说明书的具体实施方式做多种改进和变化，这对本领域技术人员而言是显而易见的。由本申请的说明书得到的其他实施方式对技术人员而言是显而易见得的。本申请说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等，均为开放性的用语，即意指包含但不限于。
本申请中所述的“份”如无特别说明，均按质量份计。并且，本申请所引用的原料均可市购获得。
实施例1-4
配方如表1所示。
制备方法：
制备石墨烯水溶液：
选用片径在1-3μm，厚度为1-5nm的石墨烯纳米片。在超声设备中加入65wt％的水为分散介质，再加入5wt％异丙醇、10wt％聚乙烯吡咯烷酮以及20wt％的石墨烯片，超声分散3h，静置24h，取上层液置于离心机中，在5000r/min转速下离心30min，取上层液；
石墨烯改性的水性弹性涂料组合物的制备：
先将准确称量的水加入拉缸中，在400r/min的低转速状态下，缓慢依次加入分散剂、润湿剂、成膜助剂消泡剂、中和剂、防腐剂，添加完成后搅拌2min，提高转速至700r/min中速状态下，依次加入钛白粉、填料，提高转速至1000r/min，高速分散30分钟，然后降低转速至400r/min低速状态下加入弹性乳液、防腐剂、石墨烯溶液，搅拌3min后缓慢加入增稠剂，在23±2℃条件下调整粘度至15-16mPa·s，慢速搅拌15分钟，制得石墨烯改性的水性弹性涂料组合物。
其中，实施例1-4中石墨烯水溶液的浓度在1.2-1.4mg/ml之间。
表1
Figure PCTCN2021120928-appb-000004
Figure PCTCN2021120928-appb-000005
对比例1
与实施例4的不同之处在于，将石墨烯水溶液替换为同等石墨烯质量的石墨烯纳米片，其他组分和涂料组合物的制备方法同实施例4。
对比例2
与实施例4的不同之处在于，不添加石墨烯水溶液，其他添加组分和涂料组合物的制备方法同实施例4。
根据JG/T172-2014《弹性建筑涂料》、GB24408—2009《建筑用外墙涂料中有害物质限量》共2个标准对本申请的实施例1-4以及对比例1-2的涂料进行检测，结果见表2。
表2
Figure PCTCN2021120928-appb-000006
Figure PCTCN2021120928-appb-000007
Figure PCTCN2021120928-appb-000008
根据GB/T21866-2008抗菌涂料抗菌性能测定方法和抗菌效果、HG/T 3980-2007抗菌涂料测定以及GB12441-2005饰面型防火涂料对本申请的实施例1-4以及对比例1-2的涂料组合物进行检测，结果见表3。
表3
Figure PCTCN2021120928-appb-000009
由表2可以看出，本申请石墨烯改性的水性弹性涂料的耐候性、耐水性、耐碱性、耐沾污性能优良，对装饰墙面具有更持久的保护，零VOC，不含重金属等有害物质，并且添加石墨烯溶液后对原有涂料外观状态等没有影响。而直接添加石墨烯片会因为石墨烯片分散不好，影响产品的遮盖力，导致拉伸强度下降。
由表3可以看出，本申请石墨烯改性水性厚质弹性涂料还具有抗菌以及持久的耐火性。
虽然本申请所揭露的实施方式如上，但所述的内容仅为便于理解本申请而采用的实施方式，并非用以限定本申请。任何本申请所属领域内的技术人员，在不脱离本申请所揭露的精神和范围的前提下，可以在实施的形式及细节上进行任何的修改与变化，但本申请的专利保护范围，仍须以所附的权利要求书所界定的范围为准。

Claims (10)

  1. 一种石墨烯改性的水性弹性涂料组合物，所述组合物包括以质量份计的以下组分：
    Figure PCTCN2021120928-appb-100001
    其中石墨烯在所述石墨烯水溶液中的浓度为1.2mg/ml～1.4mg/ml。
  2. 根据权利要求1所述的组合物，其中所述组合物还包含0.4份-0.6份的防腐剂。
  3. 根据权利要求1所述的组合物，其中所述弹性乳液为苯丙乳液、纯丙乳液、硅丙乳液、氟碳乳液或其混合物；所述钛白粉为金红石型钛白粉；所述填料为滑石粉、重钙或其混合物。
  4. 根据权利要求1所述的组合物，其中所述润湿剂为聚氧烯基烷基醚类非离子型润湿剂。
  5. 根据权利要求1所述的组合物，其中所述分散剂为聚羧酸钠盐；所述中和剂为2-氨基-2-甲基-1-丙醇。
  6. 根据权利要求1所述的组合物，其中所述消泡剂为矿物油类、有机硅类或聚醚类或其混合物；所述成膜助剂为沸点大于260摄氏度的酯化合物。
  7. 根据权利要求2所述的组合物，其中所述防腐剂不含甲基氯异噻唑啉酮、可吸附有机卤素和有机挥发物，且所述防腐剂的活性成份为1,2-苯并异噻唑啉酮和甲基异噻唑啉酮；所述增稠剂为阴离子型疏水改性丙烯酸碱溶胀型增稠剂。
  8. 根据权利要求1所述的组合物，其中所述石墨烯水溶液选用片径在1-3μm，厚度为1-5nm的石墨烯纳米片制备而成。
  9. 根据权利要求1所述的组合物，其中所述石墨烯水溶液的制备方法包括以下步骤：
    在超声设备中加入水为分散介质，再加入异丙醇、聚乙烯吡咯烷酮以及石墨烯片，超声分散2-3h，静置24-48h，取上层液置于离心机中，离心，取上层液，得所述石墨烯水溶液；
    优选地，水为65wt％，异丙醇为5wt％，聚乙烯吡咯烷酮为10wt％，石墨烯片为20wt％，在5000-6000r/min转速下离心30-40min。
  10. 一种制备根据权利要求1-9中任一项所述的石墨烯改性的水性弹性涂料组合物的方法，所述方法包括以下步骤：
    将配方量的水加入容器中，在400-600r/min的低转速状态下，依次加入分散剂、润湿剂、成膜助剂、消泡剂、中和剂和任选的防腐剂的一部分，添加完成后搅拌1-2min，提高转速至700-900r/min中速状态下，依次加入钛白粉、填料，提高转速至1000-1200r/min，高速分散30分钟，然后降低转速至400-600r/min低速状态下加入弹性乳液、任选的防腐剂的剩余部分、石墨烯水溶液，搅拌2-3min后缓慢加入增稠剂，在23±2℃条件下调整粘度至15-16mPa·s，搅拌15分钟，制得石墨烯改性的水性弹性涂料组合物。
PCT/CN2021/120928 2021-03-25 2021-09-27 一种石墨烯改性的水性弹性涂料组合物及其制备方法 WO2022198961A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110318726.XA CN113248981A (zh) 2021-03-25 2021-03-25 一种石墨烯改性的水性弹性涂料及其制备方法
CN202110318726.X 2021-03-25

Publications (1)

Publication Number Publication Date
WO2022198961A1 true WO2022198961A1 (zh) 2022-09-29

Family

ID=77181203

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/120928 WO2022198961A1 (zh) 2021-03-25 2021-09-27 一种石墨烯改性的水性弹性涂料组合物及其制备方法

Country Status (2)

Country Link
CN (1) CN113248981A (zh)
WO (1) WO2022198961A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110964385A (zh) * 2019-11-27 2020-04-07 河北晨阳工贸集团有限公司 一种水性防火功能质感涂料及其制备方法
CN115449090A (zh) * 2022-10-08 2022-12-09 浙江建工装饰材料有限公司 一种氟碳树脂乳液改性硅丙乳液及其生产工艺
CN117511287A (zh) * 2023-11-29 2024-02-06 亚士创能科技(上海)股份有限公司 弹性涂料及其制备方法和应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113248981A (zh) * 2021-03-25 2021-08-13 龙牌涂料(北京)有限公司 一种石墨烯改性的水性弹性涂料及其制备方法
CN113105791A (zh) * 2021-04-02 2021-07-13 河北晨阳工贸集团有限公司 一种石墨烯改性水性厚质弹性涂料及其制备方法
CN113975849A (zh) * 2021-10-26 2022-01-28 龙牌涂料(北京)有限公司 一种中草药除臭剂及其制备方法、中草药除臭涂料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105368219A (zh) * 2015-12-22 2016-03-02 青岛博泰美联化工技术有限公司 一种弹性建筑外墙涂料
CN106752532A (zh) * 2016-12-29 2017-05-31 三棵树涂料股份有限公司 一种耐沾污耐候型外墙弹性拉毛漆及其制备方法
CN110591525A (zh) * 2019-09-25 2019-12-20 河北晨阳工贸集团有限公司 一种添加石墨烯的水性涂料及其制备方法
CN113248981A (zh) * 2021-03-25 2021-08-13 龙牌涂料(北京)有限公司 一种石墨烯改性的水性弹性涂料及其制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109777220B (zh) * 2018-12-07 2021-02-12 宁波墨西科技有限公司 一种石墨烯复合水包水多彩涂料及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105368219A (zh) * 2015-12-22 2016-03-02 青岛博泰美联化工技术有限公司 一种弹性建筑外墙涂料
CN106752532A (zh) * 2016-12-29 2017-05-31 三棵树涂料股份有限公司 一种耐沾污耐候型外墙弹性拉毛漆及其制备方法
CN110591525A (zh) * 2019-09-25 2019-12-20 河北晨阳工贸集团有限公司 一种添加石墨烯的水性涂料及其制备方法
CN113248981A (zh) * 2021-03-25 2021-08-13 龙牌涂料(北京)有限公司 一种石墨烯改性的水性弹性涂料及其制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110964385A (zh) * 2019-11-27 2020-04-07 河北晨阳工贸集团有限公司 一种水性防火功能质感涂料及其制备方法
CN115449090A (zh) * 2022-10-08 2022-12-09 浙江建工装饰材料有限公司 一种氟碳树脂乳液改性硅丙乳液及其生产工艺
CN115449090B (zh) * 2022-10-08 2023-12-08 浙江建工装饰材料有限公司 一种氟碳树脂乳液改性硅丙乳液及其生产工艺
CN117511287A (zh) * 2023-11-29 2024-02-06 亚士创能科技(上海)股份有限公司 弹性涂料及其制备方法和应用

Also Published As

Publication number Publication date
CN113248981A (zh) 2021-08-13

Similar Documents

Publication Publication Date Title
WO2022198961A1 (zh) 一种石墨烯改性的水性弹性涂料组合物及其制备方法
CN101067062B (zh) 高性能外墙涂料的制备方法
CN100534956C (zh) 石材防护剂及其制备方法
CN103242722B (zh) 一种多功能复合内墙保温涂料及其制备方法
CN101851450B (zh) 一种水性氟碳质感涂料及其制备方法和应用
CN104250498A (zh) 一种水性耐候、耐沾污的热反射隔热涂料及其制备方法
CN105295623A (zh) 一种室外防水涂料及其制备方法
CN102732079A (zh) 一种外墙涂料及其制备方法
CN106280749B (zh) 保温隔热水性氟碳涂料及其制备方法
CN1844281A (zh) 环境友好耐沾污耐候型热反射隔热涂料及其制备方法
CN104031508A (zh) 一种三防型真石漆及其制备方法
CN109294382B (zh) 一种超耐候耐酸雨耐沾污水性无机纳米陶瓷涂料及其制备方法
CN105419504A (zh) 一种水性自清洁罩面漆及其制备方法
CN104327655A (zh) 一种水性罩面漆及其制备方法
CN103980788B (zh) 一种水性环保型硅丙真石外墙涂料及其制备方法
CN105176232A (zh) 一种耐候防水外墙乳胶漆
CN112680047A (zh) 一种汽车用可烘烤厚浆型水性阻尼涂料及其制备方法
CN100392032C (zh) 纳米复合水性仿幕墙外墙涂料的制备方法
CN116535909B (zh) 一种二氧化硅气凝胶水性涂料及其制备方法和应用
CN114316707A (zh) 一种多功能清水混凝土表面防护涂装材料及其制备方法
CN112680014B (zh) 一种反射隔热水包砂涂料及其制备方法
CN106833368A (zh) 一种水性有机硅石材防护剂的制备方法
CN113105791A (zh) 一种石墨烯改性水性厚质弹性涂料及其制备方法
CN104592792B (zh) 一种无机抗裂耐老化涂料及其制备方法
CN104073164B (zh) 弹性隔热耐候保护漆

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21932571

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21932571

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 10/07/2024)

122 Ep: pct application non-entry in european phase

Ref document number: 21932571

Country of ref document: EP

Kind code of ref document: A1