Microcapsule and kaolin composite reinforced self-lubricating fabric gasket material and its application

Abstract

The application provides a microcapsule and kaolin composite reinforced self-lubricating fabric gasket material and application thereof, and relates to the technical field of lubricating materials.The application provides a tung oil-methyl etherified melamine resin microcapsule, which comprises tung oil and methyl etherified melamine resin wrapped on the surface of the tung oil, and the methyl etherified melamine resin is formed by cross-linking polymerization of methyl etherified hexamethylol melamine.The tung oil is wrapped by the methyl etherified melamine resin, so that the excellent lubricating performance of the tung oil is retained, the dispersion problem of the tung oil in the resin is solved, and the oxidation reaction of the tung oil is inhibited.The tung oil-methyl etherified melamine resin microcapsule and amino kaolin are simultaneously introduced into the self-lubricating fabric gasket material, and the synergistic reinforcing effect of the tung oil-methyl etherified melamine resin microcapsule and the amino kaolin is exerted, so that the wear resistance and the lubricating performance of the self-lubricating fabric gasket material are effectively improved.

Description

Technical Field

[0001] This invention relates to the field of lubrication materials technology, and in particular to a microcapsule and kaolin composite reinforced self-lubricating fabric liner material and its application. Background Technology

[0002] Self-lubricating fabric gaskets are typically composite materials made by blending polytetrafluoroethylene (PTFE) fibers with reinforcing fibers and then bonding them to a resin matrix. The friction and wear properties of self-lubricating fabric gaskets are key factors in ensuring that self-lubricating spherical plain bearings possess characteristics such as self-lubrication, impact resistance, and long service life. However, under extreme application conditions such as heavy loads, self-lubricating fabric gaskets can experience resin shedding, fiber pull-out, and a decrease in the bonding force between the transfer film and the mating element, leading to lubrication failure of the fabric gasket material and severely impacting its application range and service life. Improving the lubrication performance of self-lubricating fabric gaskets remains a key issue that needs to be addressed. Summary of the Invention

[0003] In view of this, the purpose of this invention is to provide a microcapsule and kaolin composite reinforced self-lubricating fabric liner material and its application. The tung oil@methyl etherified melamine resin microcapsules provided by this invention, especially the synergistic effect of aminated kaolin, can significantly improve the tribological properties of the self-lubricating fabric liner material.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0005] This invention provides a tung oil@methyl etherified melamine resin microcapsule, comprising tung oil and methyl etherified melamine resin coated on the surface of the tung oil, wherein the methyl etherified melamine resin is cross-linked polymerized from methyl etherified hexamethyl hydroxymethyl melamine.

[0006] This invention provides a method for preparing tung oil@methyl etherified melamine resin microcapsules as described above, comprising the following steps:

[0007] Tung oil, water, and emulsifier are mixed and emulsified to obtain a tung oil emulsion.

[0008] The methyl etherified hexamethyl methacrylate (MEM) and the tung oil emulsion were mixed and subjected to emulsion polymerization to obtain the tung oil@MEM resin microcapsules.

[0009] Preferably, the emulsifier is a styrene-maleic anhydride copolymer; the tung oil and the emulsifier account for 5-10% and 1-3% of the mass of water, respectively; and the emulsification is carried out under conditions of pH 9-11.

[0010] Preferably, the mass of the methyl etherified hexamethylol melamine is 5-10% of the mass of the tung oil emulsion; the temperature of the emulsion polymerization is 45-60 DEG C, the time is 2-3 hours, the emulsion polymerization is carried out under stirring, and the stirring speed is 300-500 r / min.

[0011] The application provides a composite reinforcing filler, which comprises microcapsules and amino-modified kaolin, wherein the microcapsules are the tung oil-methyl etherified melamine resin microcapsules in the above technical solution or the tung oil-methyl etherified melamine resin microcapsules prepared by the preparation method in the above technical solution, and the amino-modified kaolin is amino-silane modified kaolin.

[0012] Preferably, the preparation method of the amino-modified kaolin comprises the following steps:

[0013] The kaolin, water and amino-silane are mixed, and a modification reaction is carried out under the condition that the pH value is 9-10, so that the amino-modified kaolin is obtained.

[0014] Preferably, the mass ratio of the microcapsules to the amino-modified kaolin is (0.5-2):(0.5-2).

[0015] The application provides an application of the composite reinforcing filler in the above technical solution in a self-lubricating fabric pad composite material.

[0016] The application provides a self-lubricating fabric pad composite material, which comprises a self-lubricating fabric and a phenolic resin composite material which is compounded on the self-lubricating fabric, wherein the phenolic resin composite material comprises a phenolic resin and a reinforcing filler which is dispersed in the phenolic resin, and the reinforcing filler is the composite reinforcing filler in the above technical solution.

[0017] The application provides an application of the self-lubricating fabric pad composite material in the above technical solution in the field of wear-reducing lubrication, and when the self-lubricating fabric pad composite material is applied, the self-lubricating fabric pad composite material is bonded on the surface of a required base material at room temperature by using an epoxy resin.

[0018] The application provides a tung oil methyl ether melamine resin microcapsule, which comprises tung oil and methyl ether melamine resin wrapped on the surface of the tung oil, and the methyl ether melamine resin is formed by cross-linking polymerization of methyl ether hexamethoxymethyl melamine.

[0019] The application provides a composite reinforcing filler, which comprises microcapsules and amino kaolin, wherein the microcapsules are the tung oil methyl ether melamine resin microcapsule or the tung oil methyl ether melamine resin microcapsule prepared by the preparation method.

[0020] The application provides a self-lubricating fabric liner composite material, which comprises a self-lubricating fabric and a phenolic resin composite material compounded on the self-lubricating fabric, wherein the phenolic resin composite material comprises phenolic resin and reinforcing filler dispersed in the phenolic resin, and the reinforcing filler is the composite reinforcing filler.

[0021] The application provides application of the self-lubricating fabric liner composite material in the field of friction-reducing lubrication, and the self-lubricating fabric liner composite material is bonded to the surface of a required base material at room temperature by using an epoxy resin. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 Fig. 2 is a graph of wear rate and friction coefficient of the self-lubricating fabric liner material prepared for Comparative Example 1 and Example 4, Figure 1 wherein (a) is a comparison graph of friction coefficient, and (b) is a comparison graph of wear rate;

[0023] Figure 2 Fig. 4 is a scanning electron microscope (SEM) image of the microcapsules of tung oil-methyl etherized melamine resin, Figure 2 wherein (a) is an SEM image of the microcapsules, and (b) is an SEM image of the microcapsules after rupture;

[0024] Figure 3 Fig. 6 is a scanning electron microscope (SEM) image and a transmission electron microscope (TEM) image of the aminoated kaolin, Figure 3 wherein (a) is an SEM image of the aminoated kaolin, and (b) is a TEM image of the aminoated kaolin. DETAILED DESCRIPTION

[0025] The application provides a tung oil-methyl etherized melamine resin microcapsule, which comprises tung oil and methyl etherized melamine resin wrapped on the surface of the tung oil, and the methyl etherized melamine resin is obtained by cross-linking polymerization of methyl etherized hexamethoxymethyl melamine.

[0026] The tung oil-methyl etherized melamine resin microcapsule provided by the application can not only retain the excellent lubricating performance of tung oil, but also solve the dispersion problem of tung oil in a resin and inhibit the oxidation reaction of tung oil in the subsequent process of being compounded with a resin matrix.

[0027] The application provides a preparation method of the tung oil-methyl etherized melamine resin microcapsule.

[0028] The tung oil, water and an emulsifier are emulsified to obtain a tung oil emulsion;

[0029] The methyl etherized hexamethoxymethyl melamine and the tung oil emulsion are mixed to perform emulsion polymerization, so as to obtain the tung oil-methyl etherized melamine resin microcapsule.

[0030] In the application, the raw materials involved are all commercially available products well known in the art, unless otherwise specified.

[0031] The present application mixes tung oil, water and emulsifier to emulsify, and gets the tung oil emulsion. The present application does not have special requirements for the tung oil, and the tung oil known by the person skilled in the art can be used. In the present application, the emulsifier is preferably styrene-maleic anhydride copolymer (SMA), and the mass of the tung oil and the emulsifier is preferably 5-10% and 1-3% of the mass of water, respectively, and more preferably 7-9% and 2-3%, respectively. In the present application, the emulsification is preferably carried out at a pH value of 9-11, and the pH value is more preferably 10; the present application preferably uses NaOH aqueous solution to adjust the pH value, and the mass concentration of the NaOH aqueous solution is preferably 1%. In the present application, the emulsification is carried out at a pH value of 9-11, in order to promote the hydrolysis of styrene-maleic anhydride copolymer, and the product after hydrolysis is adsorbed on the surface of the tung oil droplets to form an electrostatic layer, which is convenient for further reaction.

[0032] The present application does not have special requirements for the emulsification method, and the emulsification method known by the person skilled in the art can be used. In the present application, the emulsification is preferably carried out by means of vigorous stirring, and the speed of the vigorous stirring is preferably above 600 r / min.

[0033] In the present application, the specific operation of the emulsification is preferably as follows: the tung oil is dispersed in water, the emulsifier is added, and then the pH value of the dispersion is adjusted to 9-11 by using NaOH aqueous solution, and then the emulsion is formed by vigorous stirring.

[0034] After the tung oil emulsion is obtained, the present application mixes methyl etherified hexamethoxymethyl melamine and the tung oil emulsion to carry out emulsion polymerization, and gets the tung oil methyl etherified melamine resin microcapsule. In the present application, the mass of the methyl etherified hexamethoxymethyl melamine (HMMM) is preferably 5-10% of the mass of the tung oil emulsion, and more preferably 7-9%.

[0035] The present application preferably slowly adds the methyl etherified hexamethoxymethyl melamine into the tung oil emulsion to carry out emulsion polymerization. In the present application, the temperature of the emulsion polymerization is preferably 45-60°C, and more preferably 50-60°C, and the time is preferably 2-3h, and more preferably 2h, and the emulsion polymerization is preferably carried out under stirring, and the speed of the stirring is preferably 300-500 r / min, and more preferably 400 r / min.

[0036] After the emulsion polymerization is completed, the present application preferably sequentially carries out solid-liquid separation, solid-phase washing and drying on the obtained reaction liquid, and gets the tung oil methyl etherified melamine resin microcapsule. In the present application, the solid-liquid separation is preferably filtration, and the process of the solid-phase washing and drying is not specially limited in the present application, and the process known by the person skilled in the art can be used.

[0037] In the present application, the styrene-maleic anhydride copolymer (SMA) is hydrolyzed in an aqueous solution, and under stirring, the tung oil droplets are emulsified in the solution to form a stable droplet state; the surface of the hydrolyzed SMA is positively charged, and electrostatic attraction occurs between the positively charged SMA and the negatively charged methyl etherified melamine (HMMM), thereby initiating crosslinking polymerization of HMMM on the surface of the tung oil droplets, wrapping the tung oil droplets in the solution, and finally forming tung oil@ methyl etherified melamine resin microcapsules.

[0038] The present application provides a kind of composite reinforcing filler, including microcapsule and amino kaolin, the microcapsule is the tung oil@ methyl etherified melamine resin microcapsule described in above technical solution or the tung oil@ methyl etherified melamine resin microcapsule prepared by the preparation method described in above technical solution, and the amino kaolin is amino silane modified kaolin.

[0039] In the present application, the preparation method of the amino kaolin preferably comprises the following steps:

[0040] The kaolin, water and amino silane are mixed, and the modification reaction is carried out under the condition that the pH value is 9-10, to obtain the amino kaolin.

[0041] The present application does not have special requirements for the kaolin, and the kaolin well known to those skilled in the art can be used. In the present application, the amino silane is preferably 3-aminopropyl triethoxysilane (KH550). The present application preferably uses ammonia water to adjust the pH value. In the present application, the mass of the kaolin is preferably 1-3% of the mass of water, more preferably 2-3%, and the volume of the amino silane is preferably 2% of the volume of water.

[0042] In the present application, the specific operation of the modification reaction is preferably as follows: the kaolin is dispersed in water, amino silane is added thereto, and then ammonia water is used to adjust the pH value of the dispersion to 9-10, and the modification reaction is carried out.

[0043] In the present application, the modification reaction is preferably carried out at room temperature, and the time of the modification reaction is preferably 6-12 h, more preferably 8-10 h; the modification reaction is preferably carried out under stirring.

[0044] In the present application, after the completion of the modification reaction, the modification liquid is preferably subjected to solid-liquid separation, solid-phase washing and drying in sequence to obtain the amino kaolin. In the present application, the solid-liquid separation is preferably suction filtration, and the process of solid-phase washing and drying is not specially limited in the present application, and can be carried out according to the well known process in the art.

[0045] In this invention, the kaolin is derived from a widely available natural clay mineral resource. It is fine-grained, white, and earthy in appearance, with stable structural properties and a layered microstructure. To improve the dispersion performance of kaolin in the resin matrix, this invention employs aminosilane to perform surface modification treatment on the kaolin, obtaining aminated kaolin. In this invention, the aminated kaolin imparts abundant amino functional groups to the kaolin surface, promoting the chemical reaction between kaolin and the resin matrix, and enhancing the interfacial bonding between them.

[0046] In this invention, the mass ratio of the microcapsules to the aminated kaolin is preferably (0.5-2):(0.5-2), more preferably (0.5-1):(0.5-1), and even more preferably 1:1.

[0047] The composite reinforcing filler provided by this invention is a compound of tung oil@methyl etherified melamine resin microcapsules and aminated kaolin. The introduction of aminated kaolin leverages the excellent load-bearing and lubricating properties of layered kaolin materials, while also achieving a solid-liquid synergistic lubrication effect with the microcapsules. Simultaneously, amination of the kaolin effectively improves its dispersion properties within the fabric lining, further enhancing its reinforcing effect.

[0048] This invention provides the application of the composite reinforcing filler described in the above technical solution in self-lubricating fabric liner composite materials. This invention introduces tung oil@methyl etherified melamine resin microcapsules and aminated kaolin into self-lubricating fabric liner materials. By leveraging the synergistic reinforcing effect of the microcapsules and aminated kaolin, the wear resistance and lubrication performance of the self-lubricating fabric liner materials can be effectively improved.

[0049] The present invention provides a self-lubricating fabric liner composite material, comprising a self-lubricating fabric and a phenolic resin composite material laminated on the self-lubricating fabric, wherein the phenolic resin composite material comprises phenolic resin and reinforcing filler dispersed in the phenolic resin, and the reinforcing filler is the composite reinforcing filler described in the above technical solution.

[0050] In the present application, the self-lubricating fabric is preferably aramid fiber-polytetrafluoroethylene fiber blended fabric; the aramid fiber-polytetrafluoroethylene fiber blended fabric is preferably woven with polytetrafluoroethylene fiber as weft and aramid fiber as warp. The present application does not have special limitation on the specifications of the polytetrafluoroethylene fiber and aramid fiber, and commercially available products known in the art can be selected; in the embodiments of the present application, the fineness of the polytetrafluoroethylene fiber is specifically 400D, and the fineness of the aramid fiber is specifically 200D. In the present application, the weave structure of the aramid fiber-polytetrafluoroethylene fiber blended fabric is preferably one or several of plain weave, twill weave and satin weave; when the weave structure of the aramid fiber-polytetrafluoroethylene fiber blended fabric is several of the above, the present application does not have special limitation on the distribution ratio and mode of different weave structures, and any ratio or mode can be adopted. In the present application, the warp density of the aramid fiber-polytetrafluoroethylene fiber blended fabric is preferably 320-490 per 10 cm, and the weft density is preferably 290-350 per 10 cm. The present application does not have special limitation on the specific process of weaving, and the above warp density and weft density can be adopted according to the process known in the art.

[0051] In the present application, the mass fraction of the phenolic resin composite material in the self-lubricating fabric lining composite material is preferably 15-40%, and more preferably 20-30%; the mass fractions of the tung oil@ methyl etherified melamine resin microcapsule and the aminoated kaolin in the phenolic resin composite material are preferably 0.5-2% and 0.5-2% of the mass of the phenolic resin, respectively, and more preferably 0.5-1% and 0.5-1%, respectively. The present application does not have special requirement on the phenolic resin, and the phenolic resin known to those skilled in the art can be adopted.

[0052] In the present application, the preparation method of the self-lubricating fabric lining composite material preferably comprises the following steps:

[0053] The tung oil@ methyl etherified melamine resin microcapsule and the aminoated kaolin composite reinforcing filler are mixed with the phenolic resin solution to obtain an impregnation solution;

[0054] The self-lubricating fabric is repeatedly impregnated and dried in the impregnation solution to obtain a fabric prepreg;

[0055] The fabric prepreg is cured to obtain the self-lubricating fabric lining composite material.

[0056] The present application mixes the tung oil methyl etherified melamine resin microcapsule and the amino high clay composite reinforcing filler with a phenolic resin solution to obtain an impregnation solution. In the present application, the solvent of the phenolic resin solution is preferably at least two of ethanol, acetone and ethyl acetate, and when the solvent of the phenolic resin solution is preferably two or three of the above, the present application does not have a special limitation on the ratio of different kinds of solvents, and any ratio is acceptable. In the present application, the concentration of the phenolic resin solution is preferably 0.1-0.3 g / mL, and more preferably 0.10-0.25 g / mL. In the present application, the mass percentage of the tung oil methyl etherified melamine resin microcapsule and the amino high clay in the phenolic resin in the phenolic resin solution is the same as the above technical solution, and will not be repeated here. The present application does not have a special requirement for the mixing method, and it is only required to ensure that the components are uniformly mixed.

[0057] After obtaining the impregnation solution, the present application repeatedly performs impregnation-drying of the self-lubricating fabric in the impregnation solution to obtain a fabric prepreg. In the present application, the self-lubricating fabric is the same as the above technical solution, and will not be repeated here. Before repeatedly performing impregnation-drying, the present application preferably performs air plasma treatment on the self-lubricating fabric; the power of the air plasma treatment is preferably 40-300 W, and more preferably 100-250 W, and the treatment time is preferably 5-30 min, and more preferably 10-20 min. The present application etches the fiber surface of the self-lubricating fabric through air plasma treatment, breaks the molecular chain on the fiber surface, introduces active functional groups on the fiber surface, so as to produce a chemical bonding action between the self-lubricating fabric and the phenolic resin matrix during the impregnation process, enhance the interfacial bonding action between the self-lubricating fabric and the phenolic resin, and thus enhance the friction performance of the self-lubricating fabric lining material.

[0058] The present application does not have a special limitation on the specific process of the impregnation-drying, and the impregnation and drying are performed according to the processes well known in the art to obtain the fabric prepreg. In the embodiments of the present application, the drying mode is specifically drying. In the present application, the number of times of repeatedly performing impregnation-drying is 15-40% of the sum of the mass of the phenolic resin, the tung oil methyl etherified melamine resin microcapsule and the amino high clay to the mass of the fabric prepreg (i.e. the sizing amount). After the impregnation-drying, the mixture of the phenolic resin, the tung oil methyl etherified melamine resin microcapsule and the amino high clay is coated on the blended fabric surface as a continuous phase of the composite material.

[0059] After obtaining the fabric prepreg, the fabric prepreg is cured to obtain the self-lubricating fabric liner composite material. In the present application, the curing pressure is preferably 0.01-3 MPa, more preferably 0.2-2.5 MPa; the curing temperature is preferably 150-250℃, more preferably 180-200℃, further preferably 185-190℃; the curing holding time is preferably 0.5-3h, more preferably 1-2.2h, further preferably 1.5-2h; the temperature rising rate to the curing temperature is preferably 3-10℃ / min, more preferably 5-8℃ / min.

[0060] The tung oil methyl etherified melamine resin microcapsule and the aminoated kaolin are simultaneously introduced into the self-lubricating fabric liner material to realize solid-liquid composite lubrication of the fabric liner material, so that the self-lubricating fabric liner composite material provided has excellent friction and wear performance.

[0061] The present application provides the application of the self-lubricating fabric liner composite material in the field of friction-reducing lubrication. In the application, the self-lubricating fabric liner composite material is bonded to the surface of a desired substrate at room temperature by using an epoxy resin. The present application does not have special requirements for the substrate, and the substrate known to those skilled in the art can be used. In the present application, the substrate is preferably a metal or a composite material, and the metal is preferably bearing steel, more preferably 9Cr18Mo, 9Cr18MoV, 9Cr18, 4Cr13 or 17-4PH. The present application does not have special limitations on the process of bonding, and the process known to those skilled in the art can be used. After bonding, room temperature curing is preferably performed, and the room temperature curing time is preferably 7 days.

[0062] The present application uses an epoxy resin to bond the self-lubricating fabric liner composite material to the surface of a substrate at room temperature, avoiding the process of high-temperature treatment of the substrate, greatly expanding the application range of the self-lubricating fabric liner material, and reducing the cost and difficulty of bonding.

[0063] In order to further illustrate the present application, the microcapsule and kaolin composite reinforced self-lubricating fabric liner material and its application provided by the present application are described in detail below with reference to examples, but they should not be understood as limiting the scope of protection of the present application.

[0064] Example 1

[0065] In 100 mL of water, 8 g of tung oil was added, and then 3 g of styrene-maleic anhydride copolymer (SMA) was added to the above solution; then, using 1 wt% NaOH aqueous solution, the above tung oil-SMA mixture was added dropwise until the pH of the mixture reached 10; under vigorous stirring, a tung oil emulsion was formed. To the above tung oil emulsion, 8 g of methyl etherified hexamethoxymethyl melamine (HMMM) was added, the solution temperature was maintained at 50°C, the stirring speed was 400 r / min, and the stirring reaction time was 2 h, and then after filtration, washing, and drying, a tung oil @ methyl etherified melamine resin microcapsule was obtained.

[0066] 3 g of kaolin was dispersed in 100 mL of water by ultrasonic stirring, then 2 mL of 3-aminopropyl triethoxysilane (KH550) was added dropwise, and ammonia water was added to the above dispersion to adjust the solution pH to 9, and the above mixture was continuously stirred for 10 h; then after filtration, washing, and drying, an aminated kaolin was obtained.

[0067] 1 g of phenolic resin was dispersed in 7 mL of a mixed solvent of ethanol-ethyl acetate-acetone with a volume ratio of 1:1:1 to obtain a phenolic resin solution; the phenolic resin solution was mixed with 0.01 g of tung oil @ methyl etherified melamine resin microcapsule and 0.01 g of aminated kaolin filler, and the mass fraction of tung oil @ methyl etherified melamine resin microcapsule and aminated kaolin in the phenolic resin was 1% and 1%, respectively, to obtain an impregnation solution;

[0068] A polytetrafluoroethylene fiber was used as weft yarn and aramid fiber as warp yarn, and a plain weave was woven according to a warp density of 400 yarns / 10 cm and a weft density of 350 yarns / 10 cm, and an air plasma modification treatment was performed for 10 min at 100 W. The obtained blended fabric was repeatedly impregnated and dried in the impregnation solution until the mass fraction of the mixture of phenolic resin, tung oil @ methyl etherified melamine resin microcapsule, and aminated kaolin in the obtained blended fabric prepreg reached 30%, and a blended fabric prepreg was obtained.

[0069] A metal clamp was used to apply pressure to the fabric liner (a polytetrafluoroethylene plate was used for isolation to prevent bonding), and the temperature was raised to 185°C at a rate of 5°C / min, and the curing was performed at 0.3 MPa for 2 h to obtain a tung oil @ methyl etherified melamine resin microcapsule and aminated kaolin mixed filler reinforced self-lubricating fabric liner material.

[0070] The self-lubricating fabric liner composite material was bonded to the surface of the required substrate using epoxy resin, and cured at room temperature for 7 days to achieve bonding and application of the liner at room temperature.

[0071] Example 2

[0072] In 100 mL of water, 10 g of tung oil was added, and then 3 g of SMA was added to the above solution; then, using 1 wt% NaOH aqueous solution, the above tung oil-SMA mixed solution was added dropwise until the pH value of the mixed solution reached 10; under vigorous stirring, a tung oil emulsion was formed. To the above tung oil emulsion, 10 g of HMMM was added, the solution temperature was kept at 50°C, the stirring speed was 400 r / min, and the stirring reaction time was 2 h, and then after filtration, washing, and drying, a tung oil @ methyl etherified melamine resin microcapsule was obtained.

[0073] 3 g of kaolin was dispersed in 100 mL of water by ultrasonic stirring, then 2 mL of KH550 was added dropwise, and ammonia water was added to the above dispersion to adjust the pH value of the dispersion to 9, and the above mixture was continuously stirred for 10 h; after filtration, washing, and drying, an amino-functionalized kaolin was obtained.

[0074] 1 g of phenolic resin was dispersed in 7 mL of a mixed solvent of ethanol-ethyl acetate-acetone, with a volume ratio of ethanol, ethyl acetate, and acetone being 1:1:1, to obtain a phenolic resin solution; the phenolic resin solution was mixed with 0.005 g of tung oil @ methyl etherified melamine resin microcapsule and 0.01 g of amino-functionalized kaolin filler, and the mass fraction of the tung oil @ methyl etherified melamine resin microcapsule and the amino-functionalized kaolin in the phenolic resin was 0.5% and 1%, respectively, to obtain an impregnation solution;

[0075] A polytetrafluoroethylene fiber was used as weft yarn and aramid fiber was used as warp yarn, and a plain weave was woven according to a warp density of 400 yarns / 10 cm and a weft density of 350 yarns / 10 cm, and an air plasma modification treatment was performed on the obtained aramid fiber-polytetrafluoroethylene fiber blended fabric at 100 W for 10 min; the obtained blended fabric was repeatedly impregnated and dried in the impregnation solution until the mass fraction of the phenolic resin and the mixture of tung oil @ methyl etherified melamine resin microcapsule and amino-functionalized kaolin in the obtained blended fabric prepreg reached 30%, to obtain a blended fabric prepreg.

[0076] A metal clamp was used to apply pressure to the fabric liner (a polytetrafluoroethylene plate was used for isolation to prevent bonding), and the temperature was raised to 185°C at a rate of 5°C / min, and the fabric liner was cured at 0.3 MPa for 2 h, to obtain a tung oil @ methyl etherified melamine resin microcapsule and amino-functionalized kaolin mixed filler reinforced self-lubricating fabric liner material.

[0077] The self-lubricating fabric liner composite material was bonded to the surface of the required substrate using epoxy resin, and cured at room temperature for 7 days, to realize bonding and application of the liner at room temperature.

[0078] Example 3

[0079] In 100 mL of water, 8 g of tung oil was added, and then 3 g of SMA was added to the above solution; then, using 1 wt% NaOH aqueous solution, the above tung oil-SMA mixture was added dropwise until the pH of the mixture reached 10; under vigorous stirring, a tung oil emulsion was formed. To the above tung oil emulsion, 8 g of HMMM was added, the solution temperature was maintained at 50°C, the stirring speed was 400 r / min, and the stirring reaction time was 2 h, after which the tung oil @ methyl etherified melamine resin microcapsules were obtained by filtration, washing, and drying.

[0080] 2 g of kaolin was dispersed in 100 mL of water by ultrasonic stirring, then 2 mL of KH550 was added dropwise, and ammonia water was added to the above dispersion to adjust the pH of the dispersion to 9, and the above mixture was continuously stirred for 10 h; after filtration, washing, and drying, the amino-functionalized kaolin was obtained.

[0081] 1 g of phenolic resin was dispersed in 7 mL of a mixed solvent of ethanol-ethyl acetate-acetone, with a volume ratio of ethanol, ethyl acetate, and acetone of 1:1:1 to obtain a phenolic resin solution; the phenolic resin solution was mixed with 0.005 g of tung oil @ methyl etherified melamine resin microcapsules and 0.005 g of amino-functionalized kaolin filler, with the mass fraction of tung oil @ methyl etherified melamine resin microcapsules and amino-functionalized kaolin in the phenolic resin being 0.5% and 0.5%, respectively, to obtain an impregnation solution;

[0082] A polytetrafluoroethylene fiber was used as the weft yarn, and aramid fiber was used as the warp yarn, with a warp density of 400 yarns / 10 cm and a weft density of 350 yarns / 10 cm, and a plain weave was used to weave the aramid fiber-polytetrafluoroethylene fiber blended fabric, which was subjected to air plasma modification treatment for 10 min at 100 W. The obtained blended fabric was repeatedly impregnated and dried in the impregnation solution until the mass fraction of the phenolic resin and the mixture of tung oil @ methyl etherified melamine resin microcapsules and amino-functionalized kaolin in the obtained blended fabric pre-preg reached 30%, to obtain a blended fabric pre-preg.

[0083] A metal clamp was used to apply pressure to the fabric liner (a polytetrafluoroethylene plate was used for isolation to prevent bonding), and the temperature was raised to 185°C at a rate of 5°C / min, and the fabric liner was cured at 0.3 MPa for 2 h to obtain a tung oil @ methyl etherified melamine resin microcapsule and amino-functionalized kaolin mixed filler reinforced self-lubricating fabric liner material.

[0084] The self-lubricating fabric liner composite material was bonded to the surface of the desired substrate using epoxy resin, and cured at room temperature for 7 days to achieve bonding and application of the liner at room temperature.

[0085] Example 4

[0086] In 100 mL of water, 8 g of tung oil was added, and then 3 g of SMA was added to the above solution; then, using 1 wt% NaOH aqueous solution, the above tung oil-SMA mixed solution was added dropwise until the pH value of the mixed solution reached 10; under vigorous stirring, a tung oil emulsion was formed. To the above tung oil emulsion, 8 g of HMMM was added, the solution temperature was kept at 50°C, the stirring speed was 400 r / min, and the stirring reaction time was 2 h, and then after filtration, washing, and drying, a tung oil @ methyl etherified melamine resin microcapsule was obtained.

[0087] 3 g of kaolin was dispersed in 100 mL of water by ultrasonic stirring, then 2 mL of KH550 was added dropwise, and ammonia water was added to the above dispersion to adjust the solution pH value to 9, and the above mixture was continuously stirred for 10 h; after filtration, washing, and drying, an amino-functionalized kaolin was obtained.

[0088] 1 g of phenolic resin was dispersed in 7 mL of a mixed solvent of ethanol-ethyl acetate-acetone, with a volume ratio of ethanol, ethyl acetate, and acetone being 1:1:1, to obtain a phenolic resin solution; the phenolic resin solution was mixed with 0.01 g of tung oil @ methyl etherified melamine resin microcapsule and 0.01 g of amino-functionalized kaolin filler, and the mass fraction of the tung oil @ methyl etherified melamine resin microcapsule and the amino-functionalized kaolin in the phenolic resin was 1% and 1%, respectively, to obtain an impregnation solution;

[0089] A polytetrafluoroethylene fiber was used as weft yarn, and aramid fiber was used as warp yarn, and a plain weave was woven according to a warp density of 400 yarns / 10 cm and a weft density of 350 yarns / 10 cm, and an air plasma modification treatment was performed on the obtained aramid fiber-polytetrafluoroethylene fiber blended fabric at 200 W for 10 min, and the obtained blended fabric was repeatedly impregnated and dried in the impregnation solution until the mass fraction of the phenolic resin and the tung oil @ methyl etherified melamine resin microcapsule, amino-functionalized kaolin mixture in the obtained blended fabric prepreg reached 20%, to obtain a blended fabric prepreg.

[0090] A metal clamp was used to apply pressure to the fabric liner (polytetrafluoroethylene plate was used for isolation to prevent bonding), and the temperature was raised to 190°C at a rate of 5°C / min, and the fabric liner was cured at 0.3 MPa for 2 h, to obtain a tung oil @ methyl etherified melamine resin microcapsule, amino-functionalized kaolin mixed filler reinforced self-lubricating fabric liner material.

[0091] The self-lubricating fabric liner composite material was bonded to the surface of the required substrate using epoxy resin, and cured at room temperature for 7 days, to realize bonding and application of the liner at room temperature.

[0092] Comparative Example 1

[0093] The difference from Example 1 is only that the preparation process of the tung oil methyl etherified melamine resin microcapsule and the amino kaolin filler and the mixing process of the tung oil methyl etherified melamine resin microcapsule and the amino kaolin filler with the phenolic resin solution are omitted, and a self-lubricating fabric gasket material loaded only with the tung oil methyl etherified melamine resin microcapsule filler is prepared.

[0094] Comparative Example 2

[0095] The difference from Example 1 is only that the preparation process of the amino kaolin filler and the mixing process of the amino kaolin filler with the phenolic resin solution are omitted, and a self-lubricating fabric gasket material loaded only with the tung oil methyl etherified melamine resin microcapsule filler is prepared.

[0096] Performance test

[0097] (1) The tung oil methyl etherified melamine resin microcapsule, the amino kaolin filler enhanced self-lubricating fabric gasket material prepared in Examples 1-4 and the self-lubricating fabric gasket materials of Comparative Examples 1-2 were respectively subjected to friction and wear performance test, the test method: the test conditions were: pressure 102 MPa, sliding friction linear velocity 0.26 m / s, time 120 min, temperature room temperature, basalt No. 3 friction and wear tester was used, and 45 steel with a diameter of 2 mm was used as the friction pair. The friction coefficient was automatically output after the data collected by the connected computer was processed. The wear depth of the self-lubricating fabric gasket material was measured by using the digital height gauge, and then the wear volume of the fabric gasket was calculated. The specific wear rate of the fabric gasket material was calculated by using the formula K=ΔV / P·L, and the friction coefficient was automatically derived from the instrument, wherein K-specific wear rate; ΔV-wear volume; P-applied load; L-sliding distance. The test results are shown in Table 1.

[0098] Table 1 Friction data of the self-lubricating fabric gasket materials prepared in Examples 1-4 and Comparative Examples 1-2

[0099]

[0100]

[0101] As can be seen from Table 1, the wear rate and friction coefficient of the self-lubricating fabric gasket material of Example 4 prepared by loading the tung oil methyl etherified melamine resin microcapsule and the amino kaolin filler are 0.73×10 -14 m 3 (Nm) -1 , 0.060, which are respectively reduced by 65.6%, 28.6% compared with Comparative Example 1, and the wear resistance and lubrication performance of the self-lubricating fabric gasket are significantly improved.

[0102] Figure 1The wear rate and friction coefficient diagram of the self-lubricating fabric liner material prepared for Comparative Example 1 and Example 4, wherein (a) is a friction coefficient comparison diagram, and (b) is a wear rate comparison diagram. Figure 1 It can be seen that after the self-lubricating fabric liner is enhanced by the tung oil methyl etherized melamine resin microcapsule and the aminated kaolin filler, the lubrication and wear resistance of the fabric liner material are effectively improved.

[0103] (2) The morphology of the tung oil methyl etherized melamine resin microcapsule and the aminated kaolin prepared in Example 1 is characterized, and the results are shown in Figure 2 and Figure 3 .

[0104] Figure 2 The scanning electron microscope photos of the tung oil methyl etherized melamine resin microcapsule are shown in Figure 2 , wherein (a) is a scanning electron microscope photo of the microcapsule, and (b) is a scanning electron microscope photo of the microcapsule after being broken. From Figure 2 It can be seen that the tung oil is completely wrapped by the methyl etherized melamine resin to form spherical microcapsules.

[0105] Figure 3 The scanning electron microscope photos and the transmission electron microscope photos of the aminated kaolin are shown in Figure 3 , wherein (a) is a scanning electron microscope photo of the aminated kaolin, and (b) is a transmission electron microscope photo of the aminated kaolin. Under the transmission photo condition, the kaolin presents a layered structure.

[0106] The above only describes the preferred embodiments of the present application, and does not limit the present application in any form. It should be noted that for ordinary skilled persons in the art, several improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A tung oil@methyl etherified melamine resin microcapsule, comprising tung oil and methyl etherified melamine resin coated on the surface of the tung oil, wherein the methyl etherified melamine resin is cross-linked polymerized from methyl etherified hexamethyl hydroxymethyl melamine.

2. The method for preparing tung oil@methyl etherified melamine resin microcapsules according to claim 1, characterized in that, Includes the following steps: Tung oil, water, and an emulsifier are mixed and emulsified to obtain a tung oil emulsion; the emulsifier is a styrene-maleic anhydride copolymer. The methyl etherified hexamethyl methacrylate (MEM) and the tung oil emulsion were mixed and subjected to emulsion polymerization to obtain the tung oil@MEM resin microcapsules.

3. The preparation method according to claim 2, characterized in that, The tung oil and emulsifier are respectively 5-10% and 1-3% of the mass of water; the emulsification is carried out under conditions of pH 9-11.

4. The preparation method according to claim 2, characterized in that, The mass of the methyl etherified hexahydroxymethyl melamine is 5-10% of the mass of the tung oil emulsion; the emulsion polymerization temperature is 45-60℃, the time is 2-3h, and the emulsion polymerization is carried out under stirring conditions, with a stirring speed of 300-500r / min.

5. A composite reinforced filler, characterized in that, The product includes microcapsules and aminated kaolin, wherein the microcapsules are the tung oil@methyl etherified melamine resin microcapsules of claim 1 or the tung oil@methyl etherified melamine resin microcapsules prepared by the preparation method of any one of claims 2 to 4, and the aminated kaolin is aminosilane modified kaolin. The preparation method of the aminated kaolin includes the following steps: Kaolin, water, and aminosilane are mixed and modified under pH conditions of 9-10 to obtain the aminated kaolin.

6. The composite reinforced filler according to claim 5, characterized in that, The mass ratio of the microcapsules to the aminated kaolin is (0.5~2):(0.5~2).

7. The application of the composite reinforcing filler according to any one of claims 5 to 6 in self-lubricating fabric liner composite materials.

8. A self-lubricating fabric liner composite material, characterized in that, The invention includes a self-lubricating fabric and a phenolic resin composite material laminated on the self-lubricating fabric. The phenolic resin composite material includes phenolic resin and reinforcing filler dispersed in the phenolic resin. The reinforcing filler is the composite reinforcing filler according to any one of claims 5 to 6.

9. The application of the self-lubricating fabric pad composite material of claim 8 in the field of friction reduction and lubrication, wherein the self-lubricating fabric pad composite material is bonded to the surface of the desired substrate at room temperature using epoxy resin.

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