阅读说明：本技术 一种防腐耐磨水性填料及其制备方法和在涂料中的应用 (Anticorrosive wear-resistant water-based filler, preparation method thereof and application thereof in coating ) 是由 王池嘉 汪怀远 王子华 高晶 李珍 刘战剑 朱艳吉 于 2020-07-27 设计创作，主要内容包括：本发明涉及一种防腐耐磨水性填料。该防腐耐磨水性填料的组分及配比按重量百分比如下：多孔固废物粉煤灰150-300份；片状功能填料10-110份；棒状功能填料15-110份；醋酸10-50份；化学偶联剂10-20份；胶黏剂1-5份。该防腐耐磨水性填料的制备方法：按比例将多孔固废物粉煤灰、片状功能填料、棒状功能填料、去离子水、乙醇溶剂、醋酸与化学偶联剂、胶黏剂搅拌均匀后,在50-300℃之间进行水热反应,经过滤洗涤干燥后、磨碎分级得到三维多孔功能性填料。本发明通过表面改性结合纳微多孔固废物粉煤灰预构建三维立体网状结构填料,添加到涂层中可提升填料在水性溶剂中的分散性,同时预交联避免了填料团聚现象,复合涂层的防腐耐磨性能得到大幅度提升。(The invention relates to an anticorrosive wear-resistant water-based filler. The anticorrosive wear-resistant water-based filler comprises the following components in percentage by weight: porous solid waste pulverized coal ash 150-300 parts; 10-110 parts of flaky functional filler; 15-110 parts of rod-shaped functional filler; 10-50 parts of acetic acid; 10-20 parts of a chemical coupling agent; 1-5 parts of an adhesive. The preparation method of the anticorrosive wear-resistant water-based filler comprises the following steps: uniformly stirring porous solid waste fly ash, flaky functional filler, rodlike functional filler, deionized water, ethanol solvent, acetic acid, chemical coupling agent and adhesive in proportion, performing hydrothermal reaction at 50-300 ℃, filtering, washing, drying, grinding and grading to obtain the three-dimensional porous functional filler. According to the invention, the surface modification is combined with the nano-micro porous solid waste fly ash to pre-construct the filler with the three-dimensional net structure, the dispersibility of the filler in an aqueous solvent can be improved when the filler is added into the coating, meanwhile, the pre-crosslinking avoids the agglomeration phenomenon of the filler, and the corrosion resistance and the wear resistance of the composite coating are greatly improved.)

1. The corrosion-resistant wear-resistant water-based filler is characterized in that: the components and the proportion are as follows according to parts by weight: porous solid waste pulverized coal ash 150-300 parts; 10-110 parts of flaky functional filler; 15-110 parts of rod-shaped functional filler; 10-50 parts of acetic acid; 10-20 parts of a chemical coupling agent; 1-5 parts of an adhesive.

2. The corrosion-resistant wear-resistant aqueous filler according to claim 1, wherein: the flaky functional filler is one or a mixture of more of graphene, graphene oxide, molybdenum disulfide, hexagonal boron nitride and montmorillonite.

3. The corrosion-resistant wear-resistant aqueous filler according to claim 1, wherein: the rod-shaped functional filler is one or a mixture of more of carbon nano tubes, carbon fibers, glass fibers and rod-shaped cerium dioxide.

4. The corrosion-resistant wear-resistant aqueous filler according to claim 1, wherein: the adhesive is one or more of phenolic aldehyde-nitrile rubber, polyurethane rubber, silicon rubber and organic silica gel; the chemical coupling agent is one or a mixture of more of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, trichloroethyl silane, tetrabutyl titanate, triisostearoyl isopropyl titanate and tri-isopropyl titanate.

5. The multiple corrosion-resistant wear-resistant aqueous functional filler according to claim 1, characterized in that: the porous solid waste fly ash is one or a mixture of more of fly ash passing through a 100-mesh screen, fly ash passing through a 250-mesh screen, fly ash passing through a 350-mesh screen, fly ash passing through a 600-mesh screen, fly ash passing through an 800-mesh screen and fly ash passing through a 1000-mesh screen.

6. The preparation method of the multiple corrosion-resistant wear-resistant water-based functional fillers according to claim 1, characterized by comprising the following steps: uniformly stirring porous solid waste fly ash, flaky functional filler, rodlike functional filler, deionized water, ethanol solvent, acetic acid, chemical coupling agent and adhesive in proportion, performing hydrothermal reaction at 50-300 ℃, filtering, washing, drying, grinding and grading to obtain the three-dimensional porous functional filler.

7. The application of a plurality of anticorrosion wear-resistant water-based functional fillers according to claim 1 in coating, characterized in that: the anticorrosive wear-resistant water-based functional filler is used for preparing a coating, and the coating comprises the following components in parts by weight: the resin, the three-dimensional porous functional filler and the curing agent are 60-500: 12-100: 30-200.

8. The application of a plurality of anticorrosion wear-resistant water-based functional fillers according to claim 1 in coating, characterized in that: the process for preparing the coating by using the anticorrosive wear-resistant water-based functional filler comprises the following steps:

(1) dispersing the three-dimensional porous functional filler into deionized water or an ethanol solution to obtain a filler dispersion liquid;

(2) and (2) dispersing the resin and the curing agent into deionized water according to a certain proportion, adding the filler dispersion liquid obtained in the step (1) into the mixed solution after stirring, continuously stirring, and performing ultrasonic dispersion to obtain the uniformly dispersed anticorrosive wear-resistant coating emulsion.

9. The use of a plurality of corrosion and wear resistant aqueous functional fillers according to claim 8 in a coating, wherein: the resin is one of water-based epoxy resin, phenolic resin and polyurethane resin; the curing agent is a mixture of several active components selected from aliphatic diamine, aliphatic polyamine, aromatic amine, polyamide and acid anhydride.

10. The use of a plurality of corrosion and wear resistant aqueous functional fillers according to claim 8 in a coating, wherein: the weight part ratio of the three-dimensional porous functional filler in the step (1) to deionized water is 10-30: 100, respectively; the polymer resin, the curing agent and the deionized water in the step (2) have the weight part ratio of 50-80: 10-20: 50.

Technical Field

The invention relates to the field of coatings, in particular to an anticorrosive wear-resistant water-based filler, a preparation method thereof and application thereof in coatings.

Background

Metal corrosion has become a significant problem worldwide, causing a great deal of economic loss and resource waste. Therefore, it is imperative to protect metals from corrosion. In recent years, researchers have proposed various methods of preventing corrosion of metals, such as improvements in metal substrates, use of corrosion inhibitors, application of cathodic protection, and surface coating techniques. Surface coating technology has been rapidly developed for metal corrosion protection, as the coating can create an effective physical barrier between the metal substrate and the corrosive environment. The organic coating has the advantages of simple construction, wide application and the like, and is distinguished in the surface coating protection technology. With the environmental protection concept, the content of Volatile Organic Compounds (VOC) is strictly controlled, and environmental protection coatings are widely concerned.

The water-based epoxy coating and the powder coating are two environmental-friendly coatings which attract people to pay attention at present, compared with the powder coating, the water-based epoxy coating has more flexible processing conditions, and the lower construction temperature is more beneficial to industrialization. The construction process of the powder coating is complex, the spraying condition has certain requirements on temperature, and the large-scale application is difficult to realize. In the preparation process of the water-based epoxy coating, obvious micropore defects are often shown after curing, and meanwhile, the water-based epoxy coating has poor adhesion to a metal substrate and is easy to generate foaming phenomenon. Although the water paint has some defects, the development of the water paint is still an irreversible trend along with the further increase of the environmental awareness of people.

In order to solve the defect problem of the water-based paint, an effective method is to utilize the performance of the filler to make up the defects of the water-based epoxy paint, the filler can improve the compactness of a coating, the operability of the coating and the like, and the invention efficiently improves the corrosion resistance and the wear resistance of the water-based paint.

A porous filler is selected, which is originally industrial waste, has stable physicochemical properties and a high specific surface area. The porous solid waste fly ash is used as a filler, so that the corrosion resistance and the wear resistance of the water-based paint can be effectively optimized. After simple crushing treatment and surface grafting modification treatment, a large number of functional groups are obtained on the surface of the composite filler, so that the dispersibility of the filler in a coating system can be effectively improved, and on the other hand, the functional groups provide possibility for the structural optimization among the composite fillers, and are favorable for synthesizing more stable composite fillers.

The sheet material and the rod material are often used as fillers in the coating field by virtue of the microstructures of the sheet material and the rod material, and a skeleton structure can be molded in the polymer coating by virtue of the special structures of the sheet material and the rod material. However, the problem of dispersion of the material of a particular structure in the coating is of critical importance. Therefore, the surface of the filler can be subjected to graft modification treatment, and the dispersibility of the filler in an epoxy resin system is further improved by virtue of the specific functional group on the graft, so that the performance of the composite coating is more stable.

The porous solid waste fly ash has the defects of poor granularity uniformity, complex surface groups, unstable components and the like, but has excellent mechanical properties, and can endow a water-based coating with certain wear resistance when being added into the coating. If the porous solid waste fly ash, the lamellar material and the rod-shaped material are subjected to functional modification treatment on the surfaces, and then the multidimensional multi-scale filler is subjected to three-dimensional structure pre-construction treatment, the interface effect and the compatibility of a water-based epoxy system can be effectively improved, the phenomenon that the filler is easy to agglomerate is avoided, various advantages of the nano-micron filler are comprehensively utilized, the functional groups are utilized to react with resin and a curing agent, organic and inorganic multi-scale multidimensional three-dimensional nano-micro structures are formed inside the coating after the coating is cured, and the reticular three-dimensional structure is further crosslinked with the resin, so that the composite filler has a more stable physical form, the specific surface structure is combined, and the corrosion resistance and the wear resistance of the composite coating are greatly improved.

Disclosure of Invention

The invention provides an anticorrosive wear-resistant water-based filler, aiming at overcoming the problems of insufficient dispersibility, corrosion resistance and wear resistance of the coating of the existing water-based anticorrosive paint in the background art. The anticorrosive wear-resistant water-based filler is prepared by combining surface modification with nano-micro porous solid waste fly ash to construct a three-dimensional mesh structure filler, and the filler is added into a coating to improve the dispersibility of the filler in a water-based solvent, and meanwhile, the pre-crosslinking avoids the agglomeration of the filler, so that the anticorrosive wear-resistant performance of the composite coating is greatly improved. The invention also provides a preparation method of the anticorrosive wear-resistant water-based filler and application of the anticorrosive wear-resistant water-based filler in paint.

The invention can solve the problems by the following technical scheme: the anticorrosive wear-resistant water-based filler comprises the following components in parts by weight: porous solid waste pulverized coal ash 150-300 parts; 10-110 parts of flaky functional filler; 15-110 parts of rod-shaped functional filler; 10-50 parts of acetic acid; 10-20 parts of a chemical coupling agent; 1-5 parts of an adhesive.

The adhesive is one or more of phenolic aldehyde-nitrile rubber, polyurethane rubber, silicon rubber and organic silica gel; the chemical coupling agent is one or a mixture of more of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, trichloroethyl silane, tetrabutyl titanate, triisostearoyl isopropyl titanate and tri-isopropyl titanate.

The flaky filler is one or a mixture of more of graphene, graphene oxide, molybdenum disulfide, hexagonal boron nitride and montmorillonite; the platy filler has an excellent lamellar structure and serves as a main shielding filler inside the polymer.

The rod-shaped filler is one or a mixture of more of carbon nano tube, carbon fiber, glass fiber and rod-shaped cerium dioxide; the rod-like filler has an excellent rod-like structure and serves as a main skeletal filler within the polymer.

The porous solid waste fly ash is one or a mixture of more of fly ash passing through a 100-mesh screen, fly ash passing through a 250-mesh screen, fly ash passing through a 350-mesh screen, fly ash passing through a 600-mesh screen, fly ash passing through an 800-mesh screen and fly ash passing through a 1000-mesh screen.

The invention also provides a preparation method of the various anticorrosive wear-resistant water-based functional fillers, which comprises the steps of uniformly stirring the porous solid waste fly ash, the flaky functional fillers, the rodlike functional fillers, the deionized water, the ethanol solvent, the acetic acid, the chemical coupling agent and the adhesive in proportion, carrying out hydrothermal reaction at 50-300 ℃, filtering, washing, drying, grinding and grading to obtain the three-dimensional porous functional fillers.

The invention also provides application of various anticorrosive wear-resistant water-based functional fillers in a coating, which comprises the following steps:

(1) dispersing the three-dimensional porous functional filler into deionized water to obtain filler dispersion liquid;

(2) and (2) dispersing epoxy resin, phenolic resin, aliphatic diamine and polyamide into deionized water according to a ratio, adding the filler dispersion liquid obtained in the step (1) into the mixed solution after stirring, continuously stirring, and performing ultrasonic dispersion to obtain the uniformly dispersed anticorrosive wear-resistant coating emulsion.

The principle of the corrosion-resistant wear-resistant water-based filler and the preparation thereof is as follows: the porous waste fly ash filler, the flaky filler and the rodlike filler are chemically modified by different chemical coupling agents and adhesives respectively. The surface of the functionalized porous fly ash filler is provided with a certain functional group, and the surfaces of the functionalized rod-shaped filler and the functionalized sheet-shaped filler are provided with another functional group. The three fillers are subjected to vacuum high-temperature drying treatment after being fully subjected to ultrasonic dispersion and mixing, and then are subjected to slight crushing and grading treatment to obtain the filler with the three-dimensional structure. The surface groups of the fillers with various shapes are different, and the fillers and the resin adhesive can mutually generate complex crosslinking reaction to construct the fillers with three-dimensional network structures.

According to the invention, a porous particle nano material with low cost and good wear resistance is selected as a main nano-micro filler, so that the defect of micropores generated in the synthetic process of the water-based composite coating is filled, and the basic wear resistance of the coating is improved. Meanwhile, a lamellar structure filler (such as graphene, montmorillonite, molybdenum disulfide and the like) and a filler with a one-dimensional rod-like structure (such as carbon nano tubes, carbon fibers, glass fibers and the like) are selected. The filler with the three-dimensional net structure is pre-constructed by combining surface modification with the nano-micro porous solid waste fly ash, and the filler is added into the coating to improve the dispersibility of the filler in an aqueous solvent, and the pre-crosslinking avoids the agglomeration phenomenon of the filler. The corrosion resistance and the wear resistance of the composite coating are greatly improved.

The filler modification mode is that a plurality of chemical coupling agents are adopted to respectively carry out purposeful graft modification on the fillers, surface functional groups can mutually generate cross-linking reaction after the fillers are modified and can mutually generate cross-linking reaction with epoxy resin and a curing agent, the dispersibility and the stability of the three fillers in coating resin are improved, and an organic-inorganic three-dimensional network structure with physical and chemical stability is formed. By combining the special structures and special appearances of the three fillers, the coating is endowed with excellent performances of high wear resistance, high corrosion resistance and high toughness, and the performances are mutually cooperated to obtain the efficient wear-resistant and wear-resistant water-based epoxy composite coating.

Compared with the background technology, the invention has the following beneficial effects:

the invention uses functional group coupling agent modification method to graft and modify a plurality of fillers of the coating respectively, and grafts a specific functional group in the interior or on the surface of the filler, for a certain porous solid waste fly ash, the surface functional group is complex but has low activity as an industrial waste, and the dispersibility in the solvent is very poor due to the non-uniform particle size. The addition of the functional group into the coating can cause the corrosion-resistant and wear-resistant effects of the coating to be very unstable, and after the modification by the coupling agent, the surface of the coating is grafted with a large number of functional groups, so that the dispersibility of the porous solid waste fly ash in a coating system is improved, and the possibility of mutual crosslinking among fillers is provided due to the existence of the functional groups. For part of sheet layer materials and rod-shaped materials, the composite material has an excellent surface structure, if the porous solid waste flyash is combined with the sheet layer materials and the rod-shaped materials, a synergistic effect is generated among functions of a plurality of fillers, the corrosion resistance and the wear resistance of a coating are greatly improved, but serious agglomeration phenomenon exists, so that the fillers are grafted and modified by using a functional group alkane coupling agent, a large number of functional groups are grafted on the surface of the excellent structural materials, a pre-crosslinking reaction is generated among the multi-dimensional, multi-scale and multi-shape fillers by using a unique pre-crosslinking process, a three-dimensional network-shaped structural filler is built, meanwhile, the functional groups on the surface of the three-dimensional filler can be crosslinked with each other and are crosslinked with epoxy resin and a curing agent, and finally, a complex organic-inorganic network structure is combined, so that the possibility is provided for preparing the long-life aqueous corrosion-.

The innovation point of the invention is that the surface of the coating filler is subjected to grafting modification treatment of functional groups which can mutually generate cross-linking reaction, the porous solid waste fly ash is subjected to mesh screening normalization treatment, the porous solid waste fly ash with different meshes is subjected to different functional group modification, meanwhile, flaky and rod-shaped materials with different structures are modified by different functional groups, and a plurality of complex fillers can mutually generate cross-linking reaction to form stable three-dimensional composite filler, so that the corrosion resistance and wear resistance of the coating are greatly improved. Moreover, in the coating system, the same crosslinking reaction exists between the epoxy system and the curing agent as between the three-dimensional filler, so that the corresponding crosslinking reaction also exists between the filler and the coating system, thereby preparing the composite coating with excellent corrosion resistance and wear resistance.

The treated porous solid waste fly ash is screened by a screen mesh with a plurality of mesh intervals, and a large number of functional groups are grafted on the surfaces of fly ashes with different mesh intervals, so that the filler can be uniformly dispersed on each part of the coating, each filler particle is an anti-corrosion unit in the coating, and a large number of functional group groups are grafted on the surface of the anti-corrosion unit, thereby providing favorable conditions for the subsequent preparation of the three-dimensional composite filler.

The lamellar material and the rod-shaped material are ground and then grafted and modified by the other material, so that a large number of functional groups are obtained on the surfaces of the lamellar material and the rod-shaped material, the agglomeration phenomenon of the particles in a coating is improved, and the functional groups exist on the surfaces of the lamellar material and the rod-shaped material, so that the lamellar material and the rod-shaped material can be subjected to crosslinking reaction with the porous solid waste fly ash filler to form the three-dimensional composite filler. The crosslinked composite filler not only can provide the traditional effect of the inorganic filler, but also can increase the corrosion resistance and the wear resistance of the coating.

If the unmodified filler is mixed into the coating solution, the dispersion performance is poor, and the corrosion and wear resistance of the coating can be hindered, the innovation of the invention is that one or more functional groups capable of reacting with each other are grafted on the surfaces of various fillers, the surface functional groups and a small amount of adhesive are utilized to pre-build the three-dimensional network filler through a vacuum process, and the unreacted functional groups are all beneficial to better dispersing the fillers in the coating solution, so that the aggregation phenomenon of the fillers is avoided as much as possible, the fillers are uniformly distributed in the coating, and the three-dimensional filler can also have a crosslinking reaction with epoxy resin and a curing agent of a coating system in the curing process of the coating, so that the corrosion and wear resistance of the coating is more excellent. The corrosion resistance can be improved by 10 times and the wear resistance can be improved by three times.

The anticorrosive wear-resistant coating provided by the invention has a simple preparation process, and can achieve the aim of recycling resources by adopting the main body filler as industrial waste. By adopting the water-based paint system, the prepared coating is very environment-friendly, the resource utilization rate is improved as much as possible, and the possibility of environmental pollution is reduced.

Drawings

FIG. 1 is a scanning electron micrograph of composite filler example two;

FIG. 2 is a graph of the effect of the coating without the filler after rubbing in example two;

FIG. 3 is a diagram showing the effect of the functional filler-added coating of example two after friction;

FIG. 4 is an EIS map of an unfilled coating of example two;

FIG. 5 is an EIS map of a composite coating of example two with added functional filler;

FIG. 6 is a schematic representation of the cross-linking reaction of example two composite fillers.

The specific implementation mode is as follows:

the following examples are given to illustrate the present invention in further detail, and it should be noted that the following examples are not to be construed as limiting the scope of the present invention, and that the insubstantial modifications and variations of the present invention as disclosed above may be made by those skilled in the art without departing from the scope of the present invention.