WO2022127745A1 - 一种聚氨酯改性石墨烯微片及其制备方法 - Google Patents

一种聚氨酯改性石墨烯微片及其制备方法 Download PDF

Info

Publication number
WO2022127745A1
WO2022127745A1 PCT/CN2021/137546 CN2021137546W WO2022127745A1 WO 2022127745 A1 WO2022127745 A1 WO 2022127745A1 CN 2021137546 W CN2021137546 W CN 2021137546W WO 2022127745 A1 WO2022127745 A1 WO 2022127745A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane
modified graphene
preparation
reaction temperature
graphene
Prior art date
Application number
PCT/CN2021/137546
Other languages
English (en)
French (fr)
Inventor
冯增辉
汪洋
刘兰轩
康岩松
李冬冬
秦卫华
吴东恒
Original Assignee
武汉材料保护研究所有限公司
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 武汉材料保护研究所有限公司 filed Critical 武汉材料保护研究所有限公司
Priority to AU2021402785A priority Critical patent/AU2021402785B2/en
Publication of WO2022127745A1 publication Critical patent/WO2022127745A1/zh

Links

Images

Classifications

    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines containing two hydroxy groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3278—Hydroxyamines containing at least three hydroxy groups
    • C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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

Definitions

  • the present disclosure belongs to the field of coatings, relates to an epoxy coating modification technology, and in particular relates to a polyurethane-modified graphene microchip and a preparation method thereof.
  • solvent-free epoxy coatings are one of the most widely used varieties. Solvent-free epoxy coatings have the advantages of strong adhesion, good corrosion resistance and long service life. However, the coating viscosity is high, the mixing pot life is short, the low temperature curing speed is slow, the coating has the disadvantages of high brittleness, poor interlayer adhesion, and insignificant "labyrinth" shielding effect.
  • Graphene (Gr) is a sheet-like two-dimensional structure composed of carbon atoms, which has the characteristics of high strength, strong physical barrier and good thermal stability.
  • the precipitation properties can significantly improve the flexibility, corrosion resistance and high and low temperature resistance of the coating, but due to its large surface polarity, easy agglomeration and stacking and other defects, the actual use effect of graphene microflakes in the coating is greatly reduced.
  • the conductive channels formed by lap bonding in the closed coating further accelerate the electrochemical corrosion of the metal substrate. Therefore, the long-term dispersion stability of graphene and its compatibility with organic resins are improved by graphene. The key to the promotion and application of sexual coatings.
  • the purpose of the present disclosure is to provide a polyurethane-modified graphene microplate and a preparation method thereof, which are prepared by processes such as dehydration, addition polymerization, and purification, using polyol, isocyanate and graphene oxide as raw materials.
  • the polyurethane-modified graphene micro-sheets prepared in the present disclosure are used to modify epoxy resins, and the graphene oxide micro-sheets are modified by polyurethane prepolymers and the hydroxyl groups on the epoxy molecular chain are added and polymerized to form graphene block polymerization.
  • the present disclosure also provides a method for preparing a polyurethane-modified graphene microsheet, comprising the following steps:
  • Step (1) adding graphene oxide and polyol in the there-necked flask according to the proportioning, stirring and mixing, and simultaneously carrying out high temperature vacuum dehydration;
  • Step (2) continue mixing and stirring after the high-temperature vacuum dehydration finishes, stop heating, control the reaction temperature to be cooled to room temperature, gradually add isocyanate, monitor the reaction temperature, adjust the addition rate according to the reaction temperature, and control the reaction temperature to remain below °C;
  • Step (3) After the isocyanate is added for 10 to 30 minutes, the reaction temperature is controlled within the range of 75 to 85° C. by heating with an oil bath, and the reaction is stirred for 1.5 to 3 hours. Preparation of graphene microflakes.
  • the proportioning of described polyol, isocyanate and graphene oxide is as follows by mass:
  • the specific method of high temperature vacuum dehydration is to use oil bath heating to control the temperature within the range of 105-120°C, and use a vacuum pump to perform vacuum dehydration for 1.5-3 hours.
  • the mesh number of the filter screen is 150-250.
  • the polyol is any one or more of PTMG1000, PTMG650, PCDL1000, diethanolamine and triethanolamine.
  • the isocyanate is HDI (1,6-hexamethylene diisocyanate), MDI (diphenylmethane diisocyanate), IPDI (isophorone diisocyanate), HMDI (4,4'-dicyclohexylmethane diisocyanate) Isocyanate), TDI (toluene diisocyanate), LDI (L-lysine diisocyanate) any one or more.
  • the range of T in step (2) is 70-80°C.
  • the present disclosure also provides a polyurethane-modified graphene micro-sheet, which is prepared by any one of the preparation methods described above.
  • the present disclosure also provides a use of the polyurethane-modified graphene microsheets for the modification of solvent-free epoxy coatings.
  • the polyurethane-modified graphene micro-sheets prepared by the present disclosure are used to modify the solvent-free epoxy coating, and the specific method is as follows:
  • Step (1) according to the formula ratio, adding the polyurethane modified graphene micro-sheets into the solvent-free epoxy resin, and stirring at 60°C ⁇ 80°C for 20 ⁇ 60min to prepare the matrix resin of the coating;
  • Step (2) adding wetting and dispersing agent, anti-rust pigment and thickening agent to the matrix resin at one time in proportion, and grinding at room temperature with a sand mill.
  • Step (3) adding the defoaming agent in batches during the grinding process, and controlling the dosage not to exceed 5% of the total formula, grinding to a fineness of less than 50 ⁇ m, and using a filter screen to filter and encapsulate to obtain a coating base material;
  • Step (4) Before coating, the coating base material is stirred and aged for 30-40 minutes, and then mixed with the curing agent in the above proportion to obtain a long-lasting anti-corrosion graphene modified solvent-free epoxy coating that can be coated.
  • each component of the formula ratio is as follows in terms of mass:
  • the polyurethane-modified graphene micro-sheets are mainly prepared from polyols, isocyanates and graphene oxide through dehydration, addition polymerization and purification processes.
  • the solvent-free epoxy resin is any of low molecular weight modified bisphenol A epoxy, low molecular weight modified bisphenol F epoxy, low molecular weight alicyclic epoxy, and low molecular weight phenolic modified epoxy resin One or more compound resins.
  • the wetting and dispersing agent is a solvent-free associative polyurethane and/or a solvent-free acrylic dispersant.
  • the antirust pigment is a compound of any one or more of zinc phosphate, aluminum tripolyphosphate, glass flakes, iron red, and zinc powder.
  • the defoamer is a hydrophobic ion-containing silicone defoamer.
  • the thickener is any one of organic soil, fumed silica, and polyamide thickeners.
  • the curing agent is DETA (diethylenetriamine), TETA (triethylenetetramine), DEPA (triethylaminopropylamine), TEPA (tetraethylenepentamine), MDA (mantanediamine), IPDA ( Any one or more of isophorone diamine), DDS (diaminodiphenyl sulfone), and DDM (diaminodiphenylmethane).
  • DETA diethylenetriamine
  • TETA triethylenetetramine
  • DEPA triethylaminopropylamine
  • TEPA tetraethylenepentamine
  • MDA mantanediamine
  • IPDA Any one or more of isophorone diamine
  • DDS diaminodiphenyl sulfone
  • DDM diaminodiphenylmethane
  • the filter screen used in step (3) is 150-250 mesh, and the most optimal is 200 mesh.
  • the present disclosure also provides a long-term anti-corrosion graphene modified solvent-free epoxy coating, which is characterized in that: it is prepared by any one of the above preparation methods.
  • the graphene is grafted onto the epoxy molecular chain by means of chemical grafting, and the graphene micro-sheets are limited and dispersed by chemical bonds, which solves the problem of easy agglomeration and stacking of the graphene micro-sheets, and realizes the graphene micro-sheets in the Long-term stable dispersion in coatings.
  • the present disclosure utilizes the polyurethane structure to chemically graft the graphene oxide microplates onto the epoxy molecular chain, and then conduct ring-opening polymerization between the epoxy group and the amine group in the curing agent to form a dense three-dimensional network structure.
  • the graphene micro-sheets are thoroughly spread out, and the directional arrangement of the graphene micro-sheets in the coating can be realized, so that the characteristics of graphene with ultra-high specific surface area, super-hydrophobicity and high shielding can be fully reflected, which is the coating material.
  • the long-term anti-corrosion performance of the coating provides a favorable guarantee, and combined with traditional anti-rust pigments, the corrosion resistance of the coating can be further improved.
  • FIG. 1 is a low-magnification fracture topography diagram of pure epoxy resin in an embodiment of the disclosure.
  • FIG. 2 is a high-magnification fracture topography diagram of pure epoxy resin in an embodiment of the disclosure.
  • 3 is a low-magnification fracture morphology of a graphene-modified epoxy resin in an embodiment of the disclosure.
  • FIG. 4 is a high-magnification fracture morphology of graphene-modified epoxy resin in an embodiment of the disclosure.
  • Figure 6 shows the macroscopic morphology of the graphene modified solvent-free epoxy coating in the salt spray test, in which Figure 6(a) is the original morphology of the coating before the salt spray test, and Figure 6(b) is the coating after the salt spray test. corrosion morphology.
  • Figure 7 is the macroscopic topography of the solvent-free epoxy coating in the salt spray test of the comparative example, in which Figure 7(a) is the original topography of the coating before the salt spray test, and Figure 7(b) is the coating after the salt spray test. Corrosion morphology.
  • the preparation method of polyurethane-modified graphene microplates is as follows:
  • Step (1) add 1g of graphene oxide and 60g of polyol into the three-necked flask, stir and mix, use oil bath heating to control the temperature within the range of 105-120°C, and use a vacuum pump to carry out vacuum dehydration for 1.5-3h;
  • Step (2) continue mixing and stirring after the high-temperature vacuum dehydration finishes, stop heating, control the reaction temperature to be cooled to room temperature, gradually add 80g isocyanate, monitor the reaction temperature, adjust the addition rate according to the reaction temperature, and control the reaction temperature to remain below °C;
  • Step (3) After 10-30 min of isocyanate addition, the reaction temperature is controlled within the range of 75-85° C. by heating in an oil bath, the reaction is stirred for 1.5-3 h, filtered and encapsulated with a 200-mesh filter screen, and the polyurethane-modified graphene microarray is completed. Tablet preparation.
  • Step (1) add 5g graphene oxide and 70g polyol into the three-necked flask, stir and mix, use oil bath heating to control the temperature within the range of 105-120°C, and use a vacuum pump to carry out vacuum dehydration for 1.5-3h;
  • Step (2) continue mixing and stirring after the high temperature vacuum dehydration finishes, stop heating, control the reaction temperature to be cooled to room temperature, gradually add 100g of isocyanate, monitor the reaction temperature, adjust the addition rate according to the reaction temperature, and control the reaction temperature to remain below °C;
  • Step (3) After 10-30 min of isocyanate addition, the reaction temperature is controlled within the range of 75-85° C. by heating in an oil bath, the reaction is stirred for 1.5-3 h, and filtered and encapsulated with a 200-mesh filter screen to complete the polyurethane-modified graphene microarray. Tablet preparation.
  • Step (1) add 8g graphene oxide and 80g polyol into the three-necked flask, stir and mix, use oil bath heating to control the temperature within the range of 105-120°C, and use a vacuum pump to carry out vacuum dehydration for 1.5-3h;
  • Step (2) continue mixing and stirring after the high temperature vacuum dehydration finishes, stop heating, control the reaction temperature to be cooled to room temperature, gradually add 130g isocyanate, monitor the reaction temperature, adjust the addition rate according to the reaction temperature, and control the reaction temperature to remain below °C;
  • Step (3) After 10-30 min of isocyanate addition, the reaction temperature is controlled within the range of 75-85° C. by heating in an oil bath, the reaction is stirred for 1.5-3 h, and filtered and encapsulated with a 200-mesh filter screen to complete the polyurethane-modified graphene microarray. Tablet preparation.
  • Step (1) adding 10g graphene oxide and 100g polyol into a three-necked flask, stirring and mixing, using oil bath heating to control the temperature within the range of 105-120°C, and using a vacuum pump for vacuum dehydration for 1.5-3h;
  • Step (2) continue mixing and stirring after the high-temperature vacuum dehydration finishes, stop heating, control the reaction temperature to be cooled to room temperature, gradually add 140g isocyanate, monitor the reaction temperature, adjust the addition rate according to the reaction temperature, and control the reaction temperature to remain below °C;
  • Step (3) After 10-30 min of isocyanate addition, the reaction temperature is controlled within the range of 75-85° C. by heating in an oil bath, the reaction is stirred for 1.5-3 h, and filtered and encapsulated with a 200-mesh filter screen to complete the polyurethane-modified graphene microarray. Tablet preparation.
  • polyurethane-modified graphene micro-sheets are used for the modification of solvent-free epoxy coatings and the examples are as follows:
  • Example 5 Add 1 g of polyurethane-modified graphene microchips to 20 g of solvent-free epoxy resin, and stir for 20 to 60 min at 60°C to 80°C to prepare the matrix resin of the coating;
  • Step (2) Add 1g of wetting and dispersing agent, 1g of antirust pigment, and 1g of thickener to the matrix resin at one time, and use a sand mill to grind at room temperature, control the rotational speed at 1000-2500r/min, and grind for 2-5h;
  • Step (3) in the grinding process add 1 g of defoaming agent in batches, control the dosage not to exceed 5% of the total formula, grind to a fineness of less than 50 ⁇ m, use a 200-mesh filter screen to filter and encapsulate to obtain a coating base material;
  • Step (4) Before coating, the coating base material is stirred and aged for 30 to 40 minutes, and then mixed with 10 g of curing agent in the above proportion to obtain a long-lasting anti-corrosion graphene modified solvent-free epoxy coating that can be coated.
  • Example 6 adding 2g of polyurethane-modified graphene microchips to 25g of solvent-free epoxy resin, and stirring at 60°C to 80°C for 20 to 60 minutes to prepare the matrix resin of the coating;
  • Step (2) Add 2g wetting and dispersing agent, 1g antirust pigment and 2g thickener to the matrix resin at one time, and grind at room temperature with a sand mill, control the rotational speed at 1000 ⁇ 2500r/min, and grind for 2 ⁇ 5h;
  • Step (3) in the grinding process add 1 g of defoaming agent in batches, control the dosage not to exceed 5% of the total formula, grind to a fineness of less than 50 ⁇ m, use a 200-mesh filter screen to filter and encapsulate to obtain a coating base material;
  • Step (4) Before coating, the coating base material is stirred and aged for 30 to 40 minutes, and then mixed with 10 g of curing agent in the above proportion to obtain a long-lasting anti-corrosion graphene modified solvent-free epoxy coating that can be coated.
  • Embodiment 7 adding 10g of polyurethane-modified graphene microchips to 25g of solvent-free epoxy resin, and stirring at 60°C to 80°C for 20 to 60 minutes to prepare the matrix resin of the coating;
  • Step (2) adding 3g of anti-rust pigment and 2g of thickener to the matrix resin at one time, grinding at room temperature with a sand mill, controlling the rotational speed at 1000-2500r/min, and grinding for 2-5h;
  • Step (3) in the grinding process add 2 g of defoamer in batches, control the dosage not to exceed 5% of the total formula, grind to a fineness of less than 50 ⁇ m, and use a 200-mesh filter screen to filter and encapsulate to obtain a coating base material;
  • Step (4) Before coating, the coating base material is stirred and aged for 30 to 40 minutes, and then mixed with 10 g of curing agent in the above proportion to obtain a long-lasting anti-corrosion graphene modified solvent-free epoxy coating that can be coated.
  • Example 8 adding 15g of polyurethane-modified graphene microflakes to 50g of solvent-free epoxy resin, and stirring at 60°C to 80°C for 20 to 60 minutes to prepare the matrix resin of the coating;
  • Step (2) adding 3g of anti-rust pigment and 3g of thickener to the matrix resin at one time, grinding at room temperature with a sand mill, controlling the rotational speed at 1000-2500r/min, and grinding for 2-5h;
  • Step (3) in the grinding process add 4 g of defoamer in batches, control the dosage not to exceed 5% of the total formula, grind to a fineness of less than 50 ⁇ m, and use a 200-mesh filter screen to filter and encapsulate to obtain a coating base material;
  • Step (4) Before coating, the coating base material is stirred and aged for 30 to 40 minutes, and then mixed with 10 g of curing agent in the above proportion to obtain a long-lasting anti-corrosion graphene modified solvent-free epoxy coating that can be coated.
  • Example 9 adding 20g of polyurethane-modified graphene microchips to 70g of solvent-free epoxy resin, and stirring at 60°C to 80°C for 20 to 60 minutes to prepare the matrix resin of the coating;
  • Step (2) adding 4g of anti-rust pigment and 5g of thickener into the matrix resin at one time, and grinding at room temperature with a sand mill, controlling the rotational speed at 1000-2500r/min, and grinding for 2-5h;
  • Step (3) in the grinding process add 4 g of defoamer in batches, control the dosage not to exceed 5% of the total formula, grind to a fineness of less than 50 ⁇ m, and use a 200-mesh filter screen to filter and encapsulate to obtain a coating base material;
  • Step (4) Before coating, the coating base material is stirred and aged for 30 to 40 minutes, and then mixed with 10 g of curing agent in the above proportion to obtain a long-lasting anti-corrosion graphene modified solvent-free epoxy coating that can be coated.
  • the graphene-modified solvent-free epoxy coating prepared in Example 5 and the ring of the polyurethane-modified graphene microplatelets were coated on the Q235 steel plate.
  • Different coating samples made of oxygen coatings were tested for salt spray resistance.
  • the macroscopic morphology before and after 5000h in a neutral salt spray atmosphere is shown in the figure. It can be seen that the solvent-free polyurethane-modified graphene microsheets are added.
  • the corrosion diffusion of the epoxy coating is obviously better than that of the solvent-free epoxy coating without modified graphene microchips.
  • the evenly distributed graphene microflakes have good shielding properties, which can significantly improve the corrosion resistance of the coating.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

本公开提供了一种聚氨酯改性石墨烯微片及其制备方法，制备方法具体为：按照配比将氧化石墨烯和多元醇加入三口烧瓶中，搅拌混合，同时进行高温真空脱水；之后高温真空脱水结束后继续混合搅拌，停止加热，控制反应温度冷却至室温，逐步加入异氰酸酯，监控反应温度，根据反应温度调整添加速率，控制反应温度保持在T℃以下；最后异氰酸酯添加完毕反应10～30min后，采用油浴加热将反应温度控制在75～85℃范围内，搅拌反应1.5-3h，采用滤网过滤封装，完成聚氨酯改性石墨烯微片制备。将本公开制备的聚氨酯改性石墨烯微片用于环氧树脂涂料中，石墨烯能在涂层中均匀的定向分布，极大的提高了涂层耐腐蚀性。

Description

一种聚氨酯改性石墨烯微片及其制备方法
相关申请的交叉引用
本公开要求于2020年12月14日提交中国专利局的申请号为CN 202011476438.9、名称为“一种聚氨酯改性石墨烯微片及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。
技术领域
本公开属涂料领域，涉及一种环氧涂料改性技术，具体涉及一种聚氨酯改性石墨烯微片及其制备方法。
背景技术
随着我国环境保护政策的日益严格，环保型长寿命防护涂料在海洋工程装备、舰船、石油化工、桥梁和重大装备等行业的应用需求日益迫切。常用的溶剂防腐涂料将逐渐被市场淘汰，无溶剂涂料的应用会越来越广泛，其中无溶剂环氧涂料是应用量最大的品种之一。无溶剂环氧涂料具有附着力强、防腐性能好、使用寿命长等优点。但涂料粘度较大、混合适用期短、低温固化速度慢，涂层存在脆性大、层间附着力差、“迷宫式”屏蔽效应不明显等缺点，与严酷环境中钢结构长效防腐保护的使用需求相比，存在着较大差距。石墨烯(Gr)是由碳原子构成的片状二维结构，具有强度高、物理阻隔性强、热稳定性好等特点，添加到无溶剂环氧涂料中，理想状态下可改善涂料的抗沉淀性能，显著提高涂层的柔韧性、耐蚀性和高低温耐受性，但由于其表面极性大、易团聚堆叠等缺陷，大大降低了石墨烯微片在涂层中的实际使用效果，更因其具有导电性在封闭涂层中搭接形成导电通道进一步加速了金属基材的电化学腐蚀，因此解决石墨烯的长期分散稳定性及其与有机树脂的相容性是石墨烯改性涂料推广应用的关键。
公开号为CN110128943A的发明专利《一种石墨烯高效能防腐涂料及其制备方法和制品》，使用溶剂型环氧树脂、防锈颜料、有机溶剂、固化剂等原料制备的石墨烯高效能防腐涂料，利用石墨烯的特性在一定程度上增强了防腐防护的长效性，但制备方法中使用了较多的溶剂和催化剂进行分散反应，环保性不高。
发明内容
本公开的目的在于提供一种聚氨酯改性石墨烯微片及其制备方法，以多元醇、异氰酸酯和氧化石墨烯为原料，经过脱水、加成聚合、提纯等工艺制备而成。将本公开制备的聚氨酯改性石墨烯微片用于改性环氧树脂，利用聚氨酯预聚体改性氧化石墨烯微片与环氧分子链上的羟基加成聚合，形成石墨烯嵌段聚合物，实现了石墨烯微片与树脂基体的化学键合，使其在树脂基体中完全定向排布，形成迷宫效应，将石墨烯微片的屏蔽性能充分发挥出来，大大提升了涂层的腐蚀防护性能。
本公开的目的是通过以下技术方案实现的：
本公开还提供了一种聚氨酯改性石墨烯微片的制备方法，包括以下步骤：
步骤(1)按照配比将氧化石墨烯和多元醇加入三口烧瓶中，搅拌混合，同时进行高温真空脱水；
步骤(2)高温真空脱水结束后继续混合搅拌，停止加热，控制反应温度冷却至室温，逐步加入异 氰酸酯，监控反应温度，根据反应温度调整添加速率，控制反应温度保持在T℃以下；
步骤(3)异氰酸酯添加完毕反应10～30min后，采用油浴加热将反应温度控制在75～85℃范围内，搅拌反应1.5-3h，采用滤网过滤封装，封装后冷却至室温，完成聚氨酯改性石墨烯微片制备。
优选的，所述多元醇、异氰酸酯和氧化石墨烯的配比按照质量计如下：
多元醇                              60～100
异氰酸酯                            80～150
氧化石墨烯                          1～10。
优选的，步骤(1)中，高温真空脱水具体方法为采用油浴加热将温度控制在105～120℃范围内，利用真空泵进行真空脱水1.5-3h。
优选的，步骤(3)中，滤网目数为150-250。
优选的，所述多元醇为PTMG1000、PTMG650、PCDL1000、二乙醇胺、三乙醇胺中的任意一种或几种。
优选的，所述异氰酸酯为HDI(1,6-己二异氰酸酯)、MDI(二苯基甲烷二异氰酸酯)、IPDI(异佛尔酮二异氰酸酯)、HMDI(4,4'-二环己基甲烷二异氰酸酯)、TDI(甲苯二异氰酸酯)、LDI(L-赖氨酸二异氰酸酯)中的任意一种或几种。
优选的，步骤(2)中所述T的范围为70-80℃。
本公开还提供一种聚氨酯改性石墨烯微片，采用上述任意一项所述制备方法制备。
本公开还提供一种聚氨酯改性石墨烯微片的用途，用于无溶剂环氧涂料的改性。将本公开制备的聚氨酯改性石墨烯微片用于改性无溶剂环氧涂料，具体方法如下：
步骤(1)按照配方比例，将聚氨酯改性石墨烯微片加入无溶剂环氧树脂中，在60℃～80℃条件下搅拌20～60min，制得涂料的基体树脂；
步骤(2)将润湿分散剂、防锈颜料、增稠剂按比例一次加入基体树脂中，采用砂磨机常温下进行研磨，转速控制在1000～2500r/min，研磨2～5h；
步骤(3)研磨过程中将消泡剂分批加入，控制用量不超过配方总量的5％，研磨至细度达到50μm以下，采用滤网进行过滤封装，制得涂料基料；
步骤(4)涂装前将涂料基料搅拌熟化30～40min，然后与固化剂按以上比例混合即得可进行涂装的长效防腐石墨烯改性无溶剂环氧涂料。
优选的，所述配方比例的各组分以质量计如下：
Figure PCTCN2021137546-appb-000001
Figure PCTCN2021137546-appb-000002
优选的，所述聚氨酯改性石墨烯微片主要以多元醇、异氰酸酯和氧化石墨烯为原料，经过脱水、加成聚合、提纯工艺制备而成。
优选的，所述无溶剂环氧树脂为低分子量改性双酚A环氧、低分子量改性双酚F环氧、低分子量脂环族环氧、低分子量酚醛改性环氧树脂中的任意一种或多种复配树脂。
优选的，所述润湿分散剂为无溶剂缔合型聚氨酯和/或无溶剂丙烯酸分散剂。
优选的，所述防锈颜料为磷酸锌、三聚磷酸铝、玻璃鳞片、铁红、锌粉中的任意一种或多种复配。
优选的，所述消泡剂为含疏水离子的有机硅消泡剂。
优选的，所述增稠剂为有机土、气相二氧化硅、聚酰胺增稠剂中的任意一种。
优选的，所述固化剂为DETA(二乙烯三胺)、TETA(三乙烯四胺)、DEPA(三乙氨基丙胺)、TEPA(四乙烯五胺)、MDA(孟烷二胺)、IPDA(异佛尔酮二胺)、DDS(二氨基二苯基砜)、DDM(二氨基二苯基甲烷)中的任意一种或几种。
优选的，步骤(3)中采用的滤网为150-250目，最优的为200目。
本公开还提供一种长效防腐石墨烯改性无溶剂环氧涂料，其特征在于：采用上述任意一种制备方法制备。
本公开有益效果如下：
本公开通过化学接枝的方式将石墨烯嫁接到环氧分子链上，通过化学键对石墨烯微片进行限位分散，解决了石墨烯微片易团聚堆叠的问题，实现了石墨烯微片在涂料中的长久稳定分散。另外本公开利用聚氨酯结构将氧化石墨烯微片化学接枝到环氧分子链上，再通过环氧基与固化剂中的胺基开环聚合，形成致密三维网状结构，通过化学键接的方式将石墨烯微片彻底的铺展开来，可以实现石墨烯微片在涂层中的定向排布，从而将石墨烯超高比表面积、超疏水、屏蔽性高的特性充分体现出来，为涂层的长效防腐性能提供了有利保障，再结合传统防锈颜料，可以进一步提升涂层的耐蚀性。
附图说明
图1为本公开实施例中纯环氧树脂的低倍数断口形貌图。
图2为本公开实施例中纯环氧树脂的高倍数断口形貌图。
图3为本公开实施例中石墨烯改性环氧树脂的低倍数断口形貌。
图4为本公开实施例中石墨烯改性环氧树脂的高倍数断口形貌。
图5改性与未改性环氧树脂的力学性能。
图6石墨烯改性无溶剂环氧涂层盐雾试验宏观形貌图，其中图6(a)为盐雾试验前涂层的原始形貌，图6(b)为盐雾试验后涂层的腐蚀形貌。
图7为对比例无溶剂环氧涂层盐雾试验宏观形貌图，其中图7(a)为盐雾试验前涂层的原始形貌，图7(b)为盐雾试验后涂层的腐蚀形貌。
具体实施方式
下面结合附图和实施例对本公开的实施方式作进一步详细描述。以下实施例用于说明本公开，但不能用来限制本公开的范围。
聚氨酯改性石墨烯微片的制备方法如下：
实施例1：
步骤(1)将1g氧化石墨烯和60g多元醇加入三口烧瓶中，搅拌混合，采用油浴加热将温度控制在105～120℃范围内，利用真空泵进行真空脱水1.5-3h；
步骤(2)高温真空脱水结束后继续混合搅拌，停止加热，控制反应温度冷却至室温，逐步加入80g异氰酸酯，监控反应温度，根据反应温度调整添加速率，控制反应温度保持在T℃以下；
步骤(3)异氰酸酯添加完毕反应10～30min后，采用油浴加热将反应温度控制在75～85℃范围内，搅拌反应1.5-3h，采用200目滤网过滤封装，完成聚氨酯改性石墨烯微片制备。
实施例2：
步骤(1)将5g氧化石墨烯和70g多元醇加入三口烧瓶中，搅拌混合，采用油浴加热将温度控制在105～120℃范围内，利用真空泵进行真空脱水1.5-3h；
步骤(2)高温真空脱水结束后继续混合搅拌，停止加热，控制反应温度冷却至室温，逐步加入100g异氰酸酯，监控反应温度，根据反应温度调整添加速率，控制反应温度保持在T℃以下；
步骤(3)异氰酸酯添加完毕反应10～30min后，采用油浴加热将反应温度控制在75～85℃范围内，搅拌反应1.5-3h，采用200目滤网过滤封装，完成聚氨酯改性石墨烯微片制备。
实施例3：
步骤(1)将8g氧化石墨烯和80g多元醇加入三口烧瓶中，搅拌混合，采用油浴加热将温度控制在105～120℃范围内，利用真空泵进行真空脱水1.5-3h；
步骤(2)高温真空脱水结束后继续混合搅拌，停止加热，控制反应温度冷却至室温，逐步加入130g异氰酸酯，监控反应温度，根据反应温度调整添加速率，控制反应温度保持在T℃以下；
步骤(3)异氰酸酯添加完毕反应10～30min后，采用油浴加热将反应温度控制在75～85℃范围内，搅拌反应1.5-3h，采用200目滤网过滤封装，完成聚氨酯改性石墨烯微片制备。
实施例4：
步骤(1)将10g氧化石墨烯和100g多元醇加入三口烧瓶中，搅拌混合，采用油浴加热将温度控制在105～120℃范围内，利用真空泵进行真空脱水1.5-3h；
步骤(2)高温真空脱水结束后继续混合搅拌，停止加热，控制反应温度冷却至室温，逐步加入140g异氰酸酯，监控反应温度，根据反应温度调整添加速率，控制反应温度保持在T℃以下；
步骤(3)异氰酸酯添加完毕反应10～30min后，采用油浴加热将反应温度控制在75～85℃范围内，搅拌反应1.5-3h，采用200目滤网过滤封装，完成聚氨酯改性石墨烯微片制备。
将上述制备的聚氨酯改性石墨烯微片用于改性无溶剂环氧涂料实施例如下：
实施例5：将1g聚氨酯改性石墨烯微片加入20g无溶剂环氧树脂中，在60℃～80℃条件下搅拌20～60min，制得涂料的基体树脂；
步骤(2)将1g润湿分散剂、1g防锈颜料、1g增稠剂一次加入基体树脂中，采用砂磨机常温下进行研磨，转速控制在1000～2500r/min，研磨2～5h；
步骤(3)研磨过程中将1g消泡剂分批加入，控制用量不超过配方总量的5％，研磨至细度达到50μm以下，采用200目滤网进行过滤封装，制得涂料基料；
步骤(4)涂装前将涂料基料搅拌熟化30～40min，然后与10g固化剂按以上比例混合即得可进行涂装的长效防腐石墨烯改性无溶剂环氧涂料。
实施例6：将2g聚氨酯改性石墨烯微片加入25g无溶剂环氧树脂中，在60℃～80℃条件下搅拌20～60min，制得涂料的基体树脂；
步骤(2)将2g润湿分散剂、1g防锈颜料、2g增稠剂一次加入基体树脂中，采用砂磨机常温下进行研磨，转速控制在1000～2500r/min，研磨2～5h；
步骤(3)研磨过程中将1g消泡剂分批加入，控制用量不超过配方总量的5％，研磨至细度达到50μm以下，采用200目滤网进行过滤封装，制得涂料基料；
步骤(4)涂装前将涂料基料搅拌熟化30～40min，然后与10g固化剂按以上比例混合即得可进行涂装的长效防腐石墨烯改性无溶剂环氧涂料。
实施例7：将10g聚氨酯改性石墨烯微片加入25g无溶剂环氧树脂中，在60℃～80℃条件下搅拌20～60min，制得涂料的基体树脂；
步骤(2)将3g防锈颜料、2g增稠剂一次加入基体树脂中，采用砂磨机常温下进行研磨，转速控制在1000～2500r/min，研磨2～5h；
步骤(3)研磨过程中将2g消泡剂分批加入，控制用量不超过配方总量的5％，研磨至细度达到50μm以下，采用200目滤网进行过滤封装，制得涂料基料；
步骤(4)涂装前将涂料基料搅拌熟化30～40min，然后与10g固化剂按以上比例混合即得可进行涂装的长效防腐石墨烯改性无溶剂环氧涂料。
实施例8：将15g聚氨酯改性石墨烯微片加入50g无溶剂环氧树脂中，在60℃～80℃条件下搅拌20～60min，制得涂料的基体树脂；
步骤(2)将3g防锈颜料、3g增稠剂一次加入基体树脂中，采用砂磨机常温下进行研磨，转速控制在1000～2500r/min，研磨2～5h；
步骤(3)研磨过程中将4g消泡剂分批加入，控制用量不超过配方总量的5％，研磨至细度达到50μm以下，采用200目滤网进行过滤封装，制得涂料基料；
步骤(4)涂装前将涂料基料搅拌熟化30～40min，然后与10g固化剂按以上比例混合即得可进行涂装的长效防腐石墨烯改性无溶剂环氧涂料。
实施例9：将20g聚氨酯改性石墨烯微片加入70g无溶剂环氧树脂中，在60℃～80℃条件下搅拌20～60min，制得涂料的基体树脂；
步骤(2)将4g防锈颜料、5g增稠剂一次加入基体树脂中，采用砂磨机常温下进行研磨，转速控制在1000～2500r/min，研磨2～5h；
步骤(3)研磨过程中将4g消泡剂分批加入，控制用量不超过配方总量的5％，研磨至细度达到50μm以下，采用200目滤网进行过滤封装，制得涂料基料；
步骤(4)涂装前将涂料基料搅拌熟化30～40min，然后与10g固化剂按以上比例混合即得可进行涂装的长效防腐石墨烯改性无溶剂环氧涂料。
对本公开实施例5中制备的聚氨酯改性石墨烯微片改性无溶剂环氧涂料和纯无溶剂环氧涂料进行电镜扫描，得到的结构如图1至图4所示，从图1至图4中可以看出，纯环氧树脂的断口形貌光滑平整，无扩散裂纹、台阶等韧性破坏特征，属于明显的脆性断裂，利用聚氨酯结构将氧化石墨烯微片化学接枝到环氧分子链后固化树脂的断口形貌，出现大量漩涡、沟渠、台阶等结构特征，说明材料在受力破坏时受到不同方向的阻力，应力破坏方向发生无规则扩散，表现出明显的韧性的断裂特征，这是由于定向排布的石墨烯微片结构比表面积大且力学性能优异，在环氧树脂中起到明显的增强作用，提高了环氧树脂的韧性，改善了环氧树脂性脆的缺陷。
参照标准GBT 228.1-2010“金属材料拉伸试验第1部分：室温试验方法”和标准GB/T 232-2010“金属材料弯曲试验方法”进行纯环氧树脂材料和实施例5中制备的石墨烯改性环氧树脂材料的拉伸性能和弯曲性能测试，其结果如图5所示，相比于纯环氧树脂，添加聚氨酯改性石墨烯微片的环氧树脂拉伸强度和弯曲强度更高，材料的综合力学性能更好。
参照标准GB/T 10125-2012“人造气氛腐蚀试验盐雾试验”在Q235钢板上涂覆实施例5中制备的石墨烯改性无溶剂环氧涂料与未加聚氨酯改性石墨烯微片的环氧涂料制得不同的涂层样板进行耐盐雾性能对比测试，置于中性盐雾氛围下5000h前后的宏观形貌如图所示，可看到添加聚氨酯改性石墨烯微片的无溶剂环氧涂层划叉部位的腐蚀扩散现象明显优于未加改性石墨烯微片的无溶剂环氧涂层，腐蚀宽度更窄，且两条划痕交叉处扩蚀更轻微，因此可判定分布均匀的石墨烯微片均有良好的屏蔽性能，可显著提升涂层的耐蚀性。
以上实施方式仅用于说明本公开，而非对本公开的限制。尽管参照实施例对本公开进行了详细说明， 本领域的普通技术人员应当理解，对本公开的技术方案进行各种组合、修改或者等同替换，都不脱离本公开技术方案的精神和范围，均应涵盖在本公开的权利要求范围当中。

Claims (8)

  1. 一种聚氨酯改性石墨烯微片的制备方法，其特征在于，包括以下步骤：
    步骤(1)按照配比将氧化石墨烯和多元醇加入三口烧瓶中，搅拌混合，同时进行高温真空脱水；
    步骤(2)高温真空脱水结束后继续混合搅拌，停止加热，控制反应温度冷却至室温，逐步加入异氰酸酯，监控反应温度，根据反应温度调整添加速率，控制反应温度保持在T℃以下；
    步骤(3)异氰酸酯添加完毕反应10～30min后，采用油浴加热将反应温度控制在75～85℃范围内，搅拌反应1.5-3h，采用滤网过滤封装，完成聚氨酯改性石墨烯微片制备。
  2. 如权利要求1所述聚氨酯改性石墨烯微片的制备方法，其特征在于：所述多元醇、异氰酸酯和氧化石墨烯的配比按照质量计如下：
    多元醇                               60～100
    异氰酸酯                             80～150
    氧化石墨烯                           1～10。
  3. 如权利要求1所述聚氨酯改性石墨烯微片的制备方法，其特征在于：步骤(1)中，高温真空脱水具体方法为采用油浴加热将温度控制在105～120℃范围内，利用真空泵进行真空脱水1.5-3h。
  4. 如权利要求1所述聚氨酯改性石墨烯微片的制备方法，其特征在于：步骤(3)中，滤网目数为150-250。
  5. 如权利要求1所述聚氨酯改性石墨烯微片的制备方法，其特征在于：所述多元醇为PTMG1000、PTMG650、PCDL1000、二乙醇胺、三乙醇胺中的任意一种或几种。
  6. 如权利要求1所述聚氨酯改性石墨烯微片的制备方法，其特征在于：所述异氰酸酯为HDI、MDI、IPDI、HMDI、TDI、LDI中的任意一种或几种。
  7. 如权利要求1所述聚氨酯改性石墨烯微片的制备方法，其特征在于：步骤(2)中所述T的范围为70-80℃。
  8. 一种聚氨酯改性石墨烯微片，其特征在于：采用权利要求1-7任意一项所述制备方法制备。
PCT/CN2021/137546 2020-12-14 2021-12-13 一种聚氨酯改性石墨烯微片及其制备方法 WO2022127745A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2021402785A AU2021402785B2 (en) 2020-12-14 2021-12-13 Polyurethane modified graphene microsheet and preparation method therefor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011476438.9 2020-12-14
CN202011476438.9A CN112608436A (zh) 2020-12-14 2020-12-14 一种聚氨酯改性石墨烯微片及其制备方法

Publications (1)

Publication Number Publication Date
WO2022127745A1 true WO2022127745A1 (zh) 2022-06-23

Family

ID=75234245

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/137546 WO2022127745A1 (zh) 2020-12-14 2021-12-13 一种聚氨酯改性石墨烯微片及其制备方法

Country Status (3)

Country Link
CN (1) CN112608436A (zh)
AU (1) AU2021402785B2 (zh)
WO (1) WO2022127745A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116284655A (zh) * 2023-01-10 2023-06-23 中威北化科技有限公司 一种石墨烯-有机硅协同增强聚氨酯接枝改性环氧树脂的制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112608436A (zh) * 2020-12-14 2021-04-06 武汉材料保护研究所有限公司 一种聚氨酯改性石墨烯微片及其制备方法
CN115449248A (zh) * 2022-10-14 2022-12-09 山东京博装备制造安装有限公司 一种覆土储罐外壁石墨烯重防腐涂料

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103408718A (zh) * 2013-08-05 2013-11-27 江苏大学 一种氧化石墨烯-聚氨酯发泡材料的制备方法及其应用
CN106832189A (zh) * 2017-01-24 2017-06-13 南京科孚纳米技术有限公司 一种石墨烯聚氨酯复合材料的制备方法
EP3208300A1 (en) * 2016-02-17 2017-08-23 Repsol, S.A. Polymer compositions of polyol ether and graphene oxide for polyurethane applications
CN107778449A (zh) * 2017-09-20 2018-03-09 青岛瑞利特新材料科技有限公司 一种石墨烯改性水性聚氨酯树脂及其制备方法
CN109923137A (zh) * 2016-11-09 2019-06-21 巴斯夫欧洲公司 包含石墨烯纳米结构的聚氨酯
CN111607318A (zh) * 2020-06-17 2020-09-01 林蒋 一种抗紫外、防静电的自修复水性聚氨酯改性石墨烯复合涂层的制备方法
CN112608436A (zh) * 2020-12-14 2021-04-06 武汉材料保护研究所有限公司 一种聚氨酯改性石墨烯微片及其制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104693989A (zh) * 2015-03-26 2015-06-10 东南大学 石墨烯改性聚氨酯-环氧树脂水性阻尼涂料的制备方法
CN106220826B (zh) * 2016-08-04 2019-10-11 中海油常州涂料化工研究院有限公司 一种石墨烯改性的水溶性异氰酸酯固化剂的制备方法
CN106832183B (zh) * 2016-12-14 2019-12-24 武汉科利尔新材料有限公司 一种石墨烯改性阴极聚氨酯电泳树脂及其电泳漆组合物
GB2565048B (en) * 2017-07-26 2023-04-19 Talga Tech Limited Functionalised graphene composition
CN109749582A (zh) * 2019-01-22 2019-05-14 雷洪军 一种石墨烯散热涂料及其制备方法
CN110183939B (zh) * 2019-06-26 2020-12-01 陕西科技大学 一种石墨烯/环氧树脂防腐涂料的制备方法
CN112538304A (zh) * 2019-09-20 2021-03-23 南京博科新材料产业研究院有限公司 一种改性石墨烯环氧复合防腐涂料及其制备方法
CN111410905A (zh) * 2020-04-26 2020-07-14 朱建程 一种功能化石墨烯改性聚氨酯导电防腐涂层及其制法
CN111534208A (zh) * 2020-06-12 2020-08-14 安徽开林新材料股份有限公司 一种沿海建筑防腐蚀涂料的制备工艺

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103408718A (zh) * 2013-08-05 2013-11-27 江苏大学 一种氧化石墨烯-聚氨酯发泡材料的制备方法及其应用
EP3208300A1 (en) * 2016-02-17 2017-08-23 Repsol, S.A. Polymer compositions of polyol ether and graphene oxide for polyurethane applications
CN109923137A (zh) * 2016-11-09 2019-06-21 巴斯夫欧洲公司 包含石墨烯纳米结构的聚氨酯
CN106832189A (zh) * 2017-01-24 2017-06-13 南京科孚纳米技术有限公司 一种石墨烯聚氨酯复合材料的制备方法
CN107778449A (zh) * 2017-09-20 2018-03-09 青岛瑞利特新材料科技有限公司 一种石墨烯改性水性聚氨酯树脂及其制备方法
CN111607318A (zh) * 2020-06-17 2020-09-01 林蒋 一种抗紫外、防静电的自修复水性聚氨酯改性石墨烯复合涂层的制备方法
CN112608436A (zh) * 2020-12-14 2021-04-06 武汉材料保护研究所有限公司 一种聚氨酯改性石墨烯微片及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116284655A (zh) * 2023-01-10 2023-06-23 中威北化科技有限公司 一种石墨烯-有机硅协同增强聚氨酯接枝改性环氧树脂的制备方法
CN116284655B (zh) * 2023-01-10 2024-01-09 中威北化科技有限公司 一种石墨烯-有机硅协同增强聚氨酯接枝改性环氧树脂的制备方法

Also Published As

Publication number Publication date
CN112608436A (zh) 2021-04-06
AU2021402785B2 (en) 2024-07-11
AU2021402785A1 (en) 2023-06-22

Similar Documents

Publication Publication Date Title
WO2022127745A1 (zh) 一种聚氨酯改性石墨烯微片及其制备方法
CN105925130B (zh) 一种超支化聚醚型环氧树脂/环氧树脂复合防腐涂料及其制备方法
WO2021027369A1 (zh) 一种耐磨聚脲涂料及其制备方法和应用
WO2019210528A1 (zh) 有机钛前驱体聚合物tpp-ii的制备方法及其在特种涂料中的应用
CN110028885A (zh) 一种不含溶剂的高韧性重防腐涂料及其制备方法
CN107337901B (zh) 高分子合金聚合物和涂料及其制备方法
CN109913099A (zh) 一种水性单组份环氧漆及其制备方法
CN112724774B (zh) 聚硫化合物改性环氧树脂涂料及其应用
CN110591500B (zh) 含超支化聚硅氧烷减摩抗磨阻燃型环氧粘结固体润滑材料及制备和使用方法
CN115678395A (zh) 一种高韧高强的聚脲纳米涂层
CN115353761A (zh) 一种聚合物水泥防腐涂料及其制备方法
CN115044278A (zh) 一种耐温防腐修补剂
CN109722148B (zh) 一种触变型无溶剂环氧涂料及其制备方法
WO2024109020A1 (zh) 一种聚脲组合物及其制备方法和应用
CN113004779A (zh) 一种用于蓄能电站库盆防渗的聚脲涂料及其制备方法
CN113045974A (zh) 一种用于叶轮表面抗冲击石墨烯聚脲复合涂层的制备方法
CN112538313B (zh) 一种长效防腐石墨烯改性无溶剂环氧涂料及其制备方法
CN106867377B (zh) 一种天门冬氨酸酯自流平涂料及其制备方法
CN110628324A (zh) 一种水性有机硅抗开裂防腐涂料及其制备方法
CN110240856A (zh) 一种聚合物基复合涂层材料及其制备方法
CN115124692B (zh) 一种有机硅/mdi共同改性环氧树脂及其富镁复合防腐涂料
CN114369249A (zh) 一种水性环氧树脂增韧剂及其制备方法和应用
CN112760020A (zh) 一种抗菌防腐聚脲涂料及其制备方法
CN113388323A (zh) 二硫化钼/有机硅复合改性的紫外光固化水性聚氨酯丙烯酸酯涂料、其制备方法及应用
CN114292568B (zh) 一种植物多烯酚基低粘度无溶剂防腐涂料及其制备方法及应用

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: 21905674

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021402785

Country of ref document: AU

Date of ref document: 20211213

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21905674

Country of ref document: EP

Kind code of ref document: A1