CN115011215A - Functionalized silicon dioxide toughened epoxy resin coating and preparation method thereof - Google Patents
Functionalized silicon dioxide toughened epoxy resin coating and preparation method thereof Download PDFInfo
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Abstract
The invention provides a functionalized silicon dioxide toughened epoxy resin coating and a preparation method thereof, wherein the coating comprises the following components in parts by weight: 40-50 parts of epoxy resin, 5-10 parts of polycaprolactone functionalized silica, 5-10 parts of nano kaolin, 0.1-0.3 part of defoaming agent, 0.2-0.3 part of epoxy curing agent, 7-10 parts of wetting agent, 0.5-1 part of flatting agent, 10-15 parts of pigment and filler and 50-80 parts of water. The functional silicon dioxide toughened epoxy resin coating prepared by the invention has good toughness, salt mist resistance and wear resistance, does not contain organic solvent, has low VOC content and can meet the environmental protection requirement in the world at present.
Description
Technical Field
The invention relates to the field of chemical coatings, in particular to a functionalized silicon dioxide toughened epoxy resin coating and a preparation method thereof.
Background
Epoxy resin (EP) is an important thermosetting resin, and is a high molecular prepolymer containing 2 or more epoxy groups and having an aliphatic, alicyclic, or aromatic segment as a main chain. Has the excellent properties of high viscosity, high strength, electric insulation, good thermal stability and the like, and is widely applied to the aspects of aerospace, electronic sealing, coating and the like. However, the epoxy resin has high crosslinking degree, so that the application of the epoxy resin is limited due to poor weather resistance, large brittleness, low toughness and poor impact property of the epoxy resin, and the problems are not solved.
The toughening of epoxy resins can be classified into the following according to the toughening means: (1) introducing a dispersed phase such as a liquid crystal polymer, a rubber elastomer or a thermoplastic resin into an epoxy resin matrix; (2) preparing an interpenetrating network copolymer and a semi-interpenetrating network copolymer by using thermosetting resin or thermoplastic resin compatible with epoxy resin and epoxy resin; (3) curing epoxy resin by using a curing agent containing a flexible chain segment, introducing the flexible chain segment into a cross-linked network, and improving the flexibility of network chain molecules so as to achieve the aim of toughening; (4) adding inorganic fillers, e.g. nano SiO 2 And whiskers, and the like. The nano-ions and the whiskers have high heat resistance temperature and high modulus, toughen the epoxy resin according to a crack-rivet mechanism, and do not reduce the heat resistance and the rigidity while improving the strength.
The floor paint is an important branch of the coating industry, and has developed into a characteristic industry with a certain scale under the stimulation of large demand of the domestic floor paint market. In the prior floor paint industry in China, the epoxy floor is relatively mature in technology and development speed. Epoxy floor paint, which contains numerous floor paint varieties, such as solvent-free self-leveling floor paint, anti-corrosion floor paint, wear-resistant floor paint, anti-static floor paint, water-based floor paint and the like.
The nano particles are used as a toughening agent, the method is a new method for application development of nano composite materials appearing in recent years, how to select and prepare the nano particles and functionalize the nano materials to improve the internal structure of an epoxy resin system, and no good scheme report exists in the prior art.
Chinese patent CN 102190858A discloses an epoxy resin material toughened by nano silica and a preparation method thereof, the invention uses epoxy resin as a base material, and adds a nano silica toughening agent and a curing agent functionalized by dendritic macromolecules, the dendritic macromolecules are distributed on the surface of nano silica ions and are combined with silica through chemical bonds, but the inventor does not disclose the structure of the dendritic macromolecules.
Chinese patent CN 103113712A discloses a preparation method and application of modified nano-silica toughened epoxy resin, the inventor uses amino silane coupling agent modified nano-silica to chemically bond with low molecular weight liquid epoxy resin, thereby overcoming the problem that the toughness is enhanced and the excellent performance of the epoxy resin is reduced in the prior epoxy resin toughening modification, and the modification of nano-silica by amino silane coupling agent is a technical means commonly used by technicians in the field.
Disclosure of Invention
In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is to improve the internal stress of the epoxy resin and solve the problems of poor impact resistance, poor toughness of the coating film, etc.
In order to realize the purpose, the invention provides a functionalized silicon dioxide toughened epoxy resin coating and a preparation method thereof.
According to the invention, polycaprolactone functionalized silicon dioxide is adopted to modify epoxy resin, so that a buffer zone is formed mechanically to absorb certain deformation energy, silver lines and cracks are prevented from being generated, meanwhile, active hydroxyl groups and ester groups on the surface can increase the compatibility of silicon dioxide and epoxy resin, and under the condition of the presence of an epoxy curing agent, the active hydroxyl groups can participate in the ring-opening curing of epoxy resin epoxy groups to form chemical bonds which are adhered to the continuous phase of the epoxy resin, so that the deformation energy generated by strain force is further absorbed, the breakage is prevented, and the flexibility of the epoxy resin is increased.
A functional silicon dioxide toughened epoxy resin coating comprises the following components in parts by weight: 40-50 parts of epoxy resin, 5-10 parts of polycaprolactone functionalized silica, 5-10 parts of nano kaolin, 0.1-0.3 part of defoaming agent, 0.2-0.3 part of epoxy curing agent, 7-10 parts of wetting agent, 0.5-1 part of flatting agent, 10-15 parts of pigment and filler and 50-80 parts of water.
The preparation method of the functionalized silicon dioxide toughened epoxy resin coating comprises the following steps: weighing the raw materials according to the formula, uniformly mixing the epoxy resin and the polycaprolactone functionalized silicon dioxide, adding the defoaming agent, the wetting agent, the epoxy curing agent and the pigment and filler, and uniformly stirring to obtain the functionalized silicon dioxide toughened epoxy resin coating.
The preparation method comprises the following steps of (1) treating the surface of nano silicon dioxide by adopting a silane coupling agent gamma-aminopropyl triethoxysilane to obtain surface aminated silicon dioxide, bonding an initiator of ring-opening polymerization on the surface of nano silicon dioxide particles through the ring-opening reaction of glycidyl bromoisobutyrate and amino, and performing ring-opening polymerization by taking the nano silicon dioxide particles of the surface-bonded ring-opening polymerization initiator as the initiator to obtain surface-grafted polycaprolactone nano silicon dioxide ions, wherein the preparation method comprises the following steps:
(1) keeping the temperature of 12-15 mL of tetraethyl orthosilicate, 350-450 mL of absolute ethyl alcohol and 20-25 mL of ammonia water at 30-50 ℃ for 1-3 hours; adding 1-3 mL of gamma-aminopropyltriethoxysilane, and stirring for 5-7 hours; then heating to 80-100 ℃ for reflux reaction for 1-3 hours; after the reaction is finished, cooling to room temperature, and centrifugally separating a product; washing the product with absolute ethyl alcohol for 2-3 times, and washing with toluene for 2-3 times to obtain surface aminated nano silicon dioxide;
(2) stirring and mixing 20-30mL of dichloromethane, 6-10g of glycidol and 8-15g of triethylamine uniformly at 0-10 ℃ to obtain a mixed solution M1; weighing 20-30g of bromine isobutyryl bromide, and dissolving with 20-30mL of dichloromethane to obtain a mixed solution M2; dropping the mixed solution M2 into the mixed solution M1; after reacting for 2-3h, heating to 20-30 ℃ for reacting for 10-12h, and after the reaction is finished, adding water into the reaction liquid to ensure that the pH value of the mixed liquid is 6-7; standing for layering, collecting an oil phase, drying the oil phase with anhydrous magnesium sulfate for 10-12h, filtering, collecting filtrate, evaporating at 30-40 ℃ under reduced pressure to remove dichloromethane, and drying the obtained solid in a vacuum drying oven at 30-50 ℃ for 20-24h to obtain glycidyl bromoisobutyrate;
(3) ultrasonically dispersing 10-15 g of surface aminated nano silicon dioxide and 40-60 mL of anhydrous THF for 20-40 min; adding 1-2 g of glycidyl bromoisobutyrate, reacting at 20-30 ℃ for 2-3 hours, heating to 40-50 ℃, and carrying out reflux reaction for 24-36 hours; after the reaction is finished, cooling and centrifugally separating a product; washing the product with absolute ethyl alcohol for 3-4 times, and drying the obtained product in a vacuum drying oven at 50-70 ℃ for 24-36 hours to obtain nano silicon dioxide of the bonding initiator;
(4) uniformly mixing 5-7 g of nano silicon dioxide of a bonding initiator, 25-35 g of epsilon-caprolactone and 300-350 mg of stannous isooctanoate; cooling by liquid nitrogen, vacuumizing, introducing nitrogen, unfreezing, and repeatedly and circularly performing the process for 2-3 times; sealing in a nitrogen atmosphere, and then placing in an ultrasonic cleaning instrument for ultrasonic dispersion for 5-10 minutes; after reacting for 24-30 hours at 80-90 ℃, adding 30-50 mL THF into the reaction solution, and stirring and mixing uniformly; performing centrifugal separation, collecting the precipitate, and washing the precipitate for 3-4 times by using THF; and drying in vacuum at 25-30 ℃ to obtain the polycaprolactone functionalized silicon dioxide.
The epoxy resin is any one of or a mixture of two or more of bisphenol A epoxy resin, bisphenol F epoxy resin, polyphenol glycidyl ether epoxy resin and aliphatic glycidyl ether epoxy resin.
Bisphenol A epoxy resin, which is the most widely used variety of epoxy resins with the highest yield, has high transparency, is also formed by reacting bisphenol A and epichlorohydrin in the presence of sodium hydroxide, is also called general-purpose epoxy resin, has excellent adhesive properties, has good dimensional stability and chemical resistance after curing, and has very good mechanical strength.
The defoaming agent is a polyether defoaming agent; the preferable defoaming agent is one or a mixture of two or more of aliphatic polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether, castor oil polyoxyethylene ether and fatty amine polyoxyethylene ether; further preferably, the defoaming agent is aliphatic polyoxyethylene ether.
The epoxy curing agent can be amines, tertiary amines, acid anhydrides, borides or other types of epoxy curing agents; the preferred epoxy curing agent is methylhexahydrophthalic anhydride.
The wetting agent is any one of polydimethylsiloxane and alkyl modified organic siloxane; a preferred wetting agent is polydimethylsiloxane.
The leveling agent is BYK-111.
The pigment filler is one of iron oxide red pigment, titanium dioxide pigment and phthalocyanine blue BS pigment, and the preferred pigment is rutile titanium dioxide or modified rutile titanium dioxide.
The preparation method of the modified rutile titanium dioxide comprises the following steps:
1) adding 12-20g of rutile titanium dioxide into a solution of 40-50mL of water and 20-30mL of propylene glycol, adjusting the pH value of the solution to 9-10 by using a NaOH aqueous solution with the molar concentration of 0.5-1mol/L, heating to 50-70 ℃, and stirring to obtain rutile titanium dioxide slurry;
2) adding 0.5-1g of alumina powder into the rutile titanium dioxide slurry prepared in the step 1), stirring for 30-60min, filtering, washing a filter cake with water, drying at 60-80 ℃ for 20-24h, and grinding to obtain the modified rutile titanium dioxide.
Because titanium dioxide particles are spherical and uniform in size, but have a serious agglomeration phenomenon, the titanium dioxide needs to be modified, the modified titanium dioxide can improve the acid resistance and the dispersibility of the titanium dioxide, enhance the corrosion resistance under an acidic condition, improve the optical performance of the titanium dioxide, prolong the outdoor service life of the product, achieve the purposes of improving the weather resistance, the dispersibility and the dispersion stability of the pigment, and give full play to the TiO titanium dioxide particles 2 Excellent pigment performance.
Compared with the prior art, the invention has the following beneficial effects: (1) according to the invention, the nano-silica modified by the amino silane coupling agent is further modified, so that the surface activity of the nano-silica is reduced, the polycaprolactone surface grafted nano-silica is obtained through ring-opening polymerization, and the polycaprolactone chain segment is randomly interpenetrated in the epoxy resin chain segment to form an interpenetrating network structure or a semi-interpenetrating network structure, so that the defect that the nano-silica is poor in dispersibility and easy to aggregate in an epoxy resin matrix is overcome; (2) the nano kaolin and the nano silicon dioxide grafted on the surfaces of polycaprolactone in a lamellar structure are uniformly dispersed in the epoxy resin matrix, so that the problems of poor impact strength and toughness of the epoxy resin coating are solved; (3) the epoxy resin coating prepared by the invention does not contain organic solvent, has low VOC content and can meet the environmental protection requirement in the world at present.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples. The procedures, conditions, experimental methods and the like for carrying out the present invention are common knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
The sources of some of the raw materials used in the examples of the present invention are as follows, and the raw materials used in the examples can be obtained from conventional commercial sources or can be prepared by conventional methods, unless otherwise specified:
the bisphenol A epoxy resin is purchased from composite materials Limited of Yingtao, Zaoqiang county, has an epoxy value of 0.48-0.52, and is a thermosetting polymer synthetic material with good bonding, corrosion resistance, insulation, high strength and other properties.
Tetraethyl orthosilicate, purchased from New Material Inc., N.Dongyo, having a melting point of-77 deg.C, a boiling point of 165 deg.C, and a density of 0.93g/cm 3 And the model is industrial grade.
Gamma-aminopropyltriethoxysilane, KH550, was purchased from southbound tomb petro chemical limited with an active substance content of 97%.
Glycidol, also known as epoxypropanol, was purchased from Hebei Hengjing Chemicals, Inc. at a purity of 98%.
Epsilon-caprolactone is purchased from Hunan Ringren chemical new materials science and technology Limited, the purity is more than or equal to 99.9 percent, the chroma is less than or equal to 10, the acidity is less than or equal to 0.3, and the water content is less than or equal to 0.05.
Stannous isooctanoate, purchased from Shandong Huiyan chemical company Limited, with a tin content of 28% -33.5%, model number industrial grade.
The nano kaolin is purchased from Shijiazhuanda Kun mineral products Co., Ltd, the specification is 2000 meshes, and the product number is HD-00161.
Methylhexahydrophthalic anhydride, available from Shandong Liang New Material science and technology Co., Ltd, having a density of 1.17g/cm 3 And the model is LA-7Q.
Aliphatic polyoxyethylene ether, purchased from Haian petrochemical plant of Jiangsu province, model number JFC.
Polydimethylsiloxane, average molecular weight 5600, viscosity 100cP (25 ℃), purchased from Wuhan Huazhi scientific & Biotech, Inc., CAS number 9006-65-9.
BYK-111, Byk, Germany.
Rutile titanium dioxide, purchased from chemical technology ltd, denxi, crystal form, rutile type, blue light in colored light, and industrial grade in type.
Example 1
The preparation method of the functional silicon dioxide toughened epoxy resin coating comprises the following steps: weighing 50 g of bisphenol A epoxy resin, 10g of silicon dioxide, 10g of nano kaolin, 0.3g of aliphatic polyoxyethylene ether, 0.3g of methyl hexahydrophthalic anhydride, 10g of polydimethylsiloxane, 1g of BYK-111, 15g of rutile titanium dioxide and 80g of water, and uniformly stirring at 25 ℃ to obtain the functionalized silicon dioxide toughened epoxy resin coating.
Example 2
The preparation method of the functional silicon dioxide toughened epoxy resin coating comprises the following steps: weighing 50 g of bisphenol A epoxy resin, 10g of polycaprolactone functionalized silica, 10g of nano kaolin, 0.3g of aliphatic polyoxyethylene ether, 0.3g of methylhexahydrophthalic anhydride, 10g of polydimethylsiloxane, 1g of BYK-111, 15g of rutile titanium dioxide and 80g of water, and uniformly stirring at 25 ℃ to obtain the functionalized silica toughened epoxy resin coating.
The preparation method of the polycaprolactone functionalized silicon dioxide comprises the following steps:
(1) keeping the temperature of 14mL tetraethyl orthosilicate, 400mL absolute ethyl alcohol and 22mL ammonia water at 40 ℃ for 2 hours; adding 2mL of gamma-aminopropyltriethoxysilane, and stirring for 6 hours; then heating to 85 ℃ for reflux reaction for 2 hours; after the reaction is finished, cooling to room temperature, and centrifugally separating a product; washing the product with absolute ethyl alcohol for 2 times, and washing with toluene for 2 times to obtain surface aminated nano silicon dioxide;
(2) stirring and uniformly mixing 20mL of dichloromethane, 7.4g of glycidol and 10.5g of triethylamine at 0 ℃ to obtain a mixed solution M1; weighing 23g of bromine isobutyryl bromide, and dissolving the bromine isobutyryl bromide with 30mL of dichloromethane to obtain a mixed solution M2; dropping the mixed solution M2 into the mixed solution M1; after reacting for 2 hours, heating to 30 ℃ for reacting for 12 hours, after the reaction is finished, adding water into the reaction liquid to enable the pH value of the mixed liquid to be 7, standing and layering, collecting an oil phase, drying the oil phase for 12 hours by using anhydrous magnesium sulfate, filtering and collecting filtrate, evaporating dichloromethane at 30 ℃ under reduced pressure, and drying the obtained solid in a vacuum drying oven at 40 ℃ for 24 hours to obtain glycidyl bromoisobutyrate;
(3) carrying out ultrasonic dispersion on 12g of surface aminated nano silicon dioxide and 50mL of anhydrous THF for 30 min; adding 1.15g of glycidyl bromoisobutyrate, reacting at 25 ℃ for 2 hours, heating to 45 ℃, and carrying out reflux reaction for 24 hours; after the reaction is finished, cooling and centrifugally separating a product; washing the product with absolute ethyl alcohol for 4 times, and drying the obtained product in a vacuum drying oven at 60 ℃ for 24 hours to obtain nano silicon dioxide bonded with an initiator;
(4) uniformly mixing 6g of nano silicon dioxide bonded with an initiator, 30g of epsilon-caprolactone and 315mg of stannous isooctanoate; cooling with liquid nitrogen, vacuumizing, introducing nitrogen, and thawing, wherein the process is repeatedly and circularly performed for 3 times; sealing in nitrogen atmosphere, and then placing in an ultrasonic cleaning instrument for ultrasonic dispersion for 5 minutes; after reacting for 30 hours at 80 ℃, adding 40mL of THF into the reaction solution, and uniformly stirring and mixing; centrifuging, collecting precipitate, and washing the precipitate with THF for 4 times; vacuum drying at 25 ℃ to obtain the polycaprolactone functionalized silicon dioxide.
Example 3
The preparation method of the functional silicon dioxide toughened epoxy resin coating comprises the following steps: weighing 50 g of bisphenol A epoxy resin, 10g of silicon dioxide, 10g of nano kaolin, 0.3g of aliphatic polyoxyethylene ether, 0.3g of methyl hexahydrophthalic anhydride, 10g of polydimethylsiloxane, 1g of BYK-111, 15g of modified rutile titanium dioxide and 80g of water, and uniformly stirring at 25 ℃ to obtain the functional silicon dioxide toughened epoxy resin coating.
The preparation method of the modified rutile titanium dioxide comprises the following steps:
1) adding 15g of rutile titanium dioxide into a solution of 40mL of water and 20mL of propylene glycol, adjusting the pH value of the solution to 10 by using a NaOH aqueous solution with the molar concentration of 1mol/L, heating to 70 ℃, and stirring to obtain rutile titanium dioxide slurry;
2) adding 1g of alumina powder into the rutile titanium dioxide slurry prepared in the step 1), stirring for 60min, filtering, washing a filter cake with water, drying at 80 ℃ for 24h, and grinding to obtain the modified rutile titanium dioxide.
Example 4
The preparation method of the functionalized silicon dioxide toughened epoxy resin coating comprises the following steps: weighing 50 g of bisphenol A epoxy resin, 10g of polycaprolactone functionalized silica, 10g of nano kaolin, 0.3g of aliphatic polyoxyethylene ether, 0.3g of methylhexahydrophthalic anhydride, 10g of polydimethylsiloxane, 1g of BYK-111, 15g of modified rutile titanium dioxide and 80g of water, and uniformly stirring at 25 ℃ to obtain the functionalized silica toughened epoxy resin coating.
The preparation method of the polycaprolactone functionalized silicon dioxide comprises the following steps:
(1) keeping the temperature of 14mL tetraethyl orthosilicate, 400mL absolute ethyl alcohol and 22mL ammonia water at 40 ℃ for 2 hours; adding 2mL of gamma-aminopropyltriethoxysilane, and stirring for 6 hours; then heating to 85 ℃ for reflux reaction for 2 hours; after the reaction is finished, cooling to room temperature, and centrifugally separating a product; washing the product with absolute ethyl alcohol for 2 times and toluene for 2 times to obtain the nano silicon dioxide with aminated surface;
(2) stirring and uniformly mixing 20mL of dichloromethane, 7.4g of glycidol and 10.5g of triethylamine at 0 ℃ to obtain a mixed solution M1; weighing 23g of bromine isobutyryl bromide, and dissolving the bromine isobutyryl bromide with 30mL of dichloromethane to obtain a mixed solution M2; dropping the mixed solution M2 into the mixed solution M1; after reacting for 2 hours, heating to 30 ℃ for reacting for 12 hours, after the reaction is finished, adding water into the reaction liquid to enable the pH value of the mixed liquid to be 7, standing and layering, collecting an oil phase, drying the oil phase for 12 hours by using anhydrous magnesium sulfate, filtering and collecting filtrate, evaporating dichloromethane at 30 ℃ under reduced pressure, and drying the obtained solid in a vacuum drying oven at 40 ℃ for 24 hours to obtain glycidyl bromoisobutyrate;
(3) carrying out ultrasonic dispersion on 12g of surface aminated nano silicon dioxide and 50mL of anhydrous THF for 30 min; adding 1.15g of glycidyl bromoisobutyrate, reacting at 25 ℃ for 2 hours, and heating to 45 ℃ for reflux reaction for 24 hours; after the reaction is finished, cooling and centrifugally separating a product; washing the product with absolute ethyl alcohol for 4 times, and drying the obtained product in a vacuum drying oven at 60 ℃ for 24 hours to obtain nano silicon dioxide bonded with an initiator;
(4) uniformly mixing 6g of nano silicon dioxide bonded with an initiator, 30g of epsilon-caprolactone and 315mg of stannous isooctanoate; cooling with liquid nitrogen, vacuumizing, introducing nitrogen, and thawing, wherein the process is repeatedly and circularly performed for 3 times; sealing in nitrogen atmosphere, and then placing in an ultrasonic cleaning instrument for ultrasonic dispersion for 5 minutes; after reacting for 30 hours at 80 ℃, adding 40mL of THF into the reaction solution, and uniformly stirring and mixing; centrifuging, collecting precipitate, and washing the precipitate with THF for 4 times; and drying in vacuum at 25 ℃ to obtain the polycaprolactone functionalized silicon dioxide.
The preparation method of the modified rutile titanium dioxide comprises the following steps:
1) adding 15g of rutile titanium dioxide into a solution of 40mL of water and 20mL of propylene glycol, adjusting the pH value of the solution to 10 by using a NaOH aqueous solution with the molar concentration of 1mol/L, heating to 70 ℃, and stirring to obtain rutile titanium dioxide slurry;
2) adding 1g of alumina powder into the rutile titanium dioxide slurry prepared in the step 1), stirring for 60min, filtering, washing a filter cake with water, drying at 80 ℃ for 24h, and grinding to obtain the modified rutile titanium dioxide.
Test example 1
The functional silica toughened epoxy resin paint prepared in the embodiments 1-4 of the invention is coated on a tinplate with the size of 155mm × 70mm × 0.20mm, is placed at 50 ℃ for curing for 10 hours, and is cooled to obtain the cured functional silica toughened epoxy resin paint, the pencil hardness of the paint is tested by using an HT-1086 pencil hardness tester according to the testing method of the standard GB/T6739-2006, the impact strength of the paint is tested by using a GS-CJQD impact strength tester according to the testing method of the standard GB/T1732-2020, and the neutral salt fog resistance of the paint is tested according to the testing method of the standard GB/T1771-2007. 3 samples were taken from each example and the results averaged, with the test data shown in Table 1:
table 1: performance of functional silicon dioxide toughened epoxy resin paint
And (3) testing the wear resistance: the wear resistance test was carried out by using MPX-2000 type friction wear testing machine. Adopts a ring disc opposite grinding mode, and adopts rubber material for the grinding discIn the experimental process, the ring sample and the rubber counter grinding disc are immersed in clear water to facilitate timely heat dissipation, the normal load value of the ring disc counter grinding is selected to be 100N, the relative rotating speed of the ring disc is 580r/min, the total revolution is 2000r, the frictional resistance is recorded, the friction coefficient is calculated, and the induction quantity is 10 -4 The analytical balance weighs the ring sample before and after abrasion, calculates abrasion weight loss, tests 3 samples per group of data, and takes an average value, and the test data is shown in table 2:
table 2: abrasion loss/g of epoxy resin varnish
| Abrasion loss per gram | |
| Example 1 | 0.402 |
| Example 2 | 0.321 |
| Example 3 | 0.347 |
| Example 4 | 0.302 |
The smaller the abrasion loss, the better the wear resistance of the material. The essence of abrasion is that when the composite material is subjected to sliding friction on a rough surface, a paint film in a small area is torn by local overlarge stress and is pulled away from a body to form single small particles, the strength of silicon dioxide is high, and the silicon dioxide is difficult to break, and in addition, the silicon dioxide, the nano kaolin with a lamellar structure and the modified rutile titanium dioxide are uniformly dispersed in the epoxy resin coating through good modification, so that the paint film is difficult to separate from a matrix, and the abrasion resistance of the paint film is improved.
Claims (7)
1. The functional silicon dioxide toughened epoxy resin coating is characterized by comprising the following components in parts by weight: 40-50 parts of epoxy resin, 5-10 parts of polycaprolactone functionalized silica, 5-10 parts of nano kaolin, 0.1-0.3 part of defoaming agent, 0.2-0.3 part of epoxy curing agent, 7-10 parts of wetting agent, 0.5-1 part of flatting agent, 10-15 parts of pigment and filler and 50-80 parts of water.
2. The functionalized silica-toughened epoxy resin coating according to claim 1, wherein the epoxy resin is any one of or a mixture of two or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, and aliphatic glycidyl ether epoxy resin.
3. The functionalized silica toughened epoxy resin coating of claim 1 wherein the polycaprolactone functionalized silica is prepared by the following method:
(1) keeping the temperature of 12-15 mL of tetraethyl orthosilicate, 350-450 mL of absolute ethyl alcohol and 20-25 mL of ammonia water at 30-50 ℃ for 1-3 hours; adding 1-3 mL of gamma-aminopropyltriethoxysilane, and stirring for 5-7 hours; then heating to 80-100 ℃ for reflux reaction for 1-3 hours; after the reaction is finished, cooling to room temperature, and centrifugally separating a product; washing the precipitate with absolute ethyl alcohol for 2-3 times, and washing with toluene for 2-3 times to obtain surface aminated nano silicon dioxide;
(2) stirring and mixing 20-30mL of dichloromethane, 6-10g of glycidol and 8-15g of triethylamine uniformly at 0-10 ℃ to obtain a mixed solution M1; weighing 20-30g of bromine isobutyryl bromide, and dissolving with 20-30mL of dichloromethane to obtain a mixed solution M2; dropping the mixed solution M2 into the mixed solution M1; after reacting for 2-3h, heating to 20-30 ℃ for reacting for 10-12h, and after the reaction is finished, adding water into the reaction liquid to ensure that the pH value of the mixed liquid is 6-7; standing for layering, collecting an oil phase, drying the oil phase with anhydrous magnesium sulfate for 10-12h, filtering, collecting a filtrate, distilling at 30-40 ℃ under reduced pressure to remove dichloromethane, and drying the obtained solid in a vacuum drying oven at 30-50 ℃ for 20-24h to obtain glycidyl bromoisobutyrate;
(3) ultrasonically dispersing 10-15 g of surface aminated nano silicon dioxide and 40-60 mL of anhydrous THF for 20-40 min; adding 1-2 g of glycidyl bromoisobutyrate, reacting at 20-30 ℃ for 2-3 hours, heating to 40-50 ℃, and carrying out reflux reaction for 24-36 hours; after the reaction is finished, cooling and centrifugally separating a product; washing the product with absolute ethyl alcohol for 3-4 times, and drying the obtained product in a vacuum drying oven at 50-70 ℃ for 24-36 hours to obtain nano silicon dioxide of the bonding initiator;
(4) uniformly mixing 5-7 g of nano silicon dioxide of a bonding initiator, 25-35 g of epsilon-caprolactone and 300-350 mg of stannous isooctanoate; cooling by liquid nitrogen, vacuumizing, introducing nitrogen, unfreezing, and repeatedly and circularly performing the process for 2-3 times; sealing in a nitrogen atmosphere, and then carrying out ultrasonic dispersion for 5-10 minutes; after reacting for 24-30 hours at 80-90 ℃, adding 30-50 mL THF into the reaction solution, and stirring and mixing uniformly; performing centrifugal separation, collecting precipitate, and washing the precipitate with THF for 3-4 times; and drying in vacuum at 25-30 ℃ to obtain the polycaprolactone functionalized silicon dioxide.
4. The functionalized silica toughened epoxy resin coating of claim 1, wherein: the defoaming agent is a polyether defoaming agent.
5. The functionalized silica toughened epoxy resin coating of claim 1, wherein: the epoxy curing agent may be an amine, tertiary amine, anhydride, boride or other type of epoxy curing agent.
6. The functionalized silica toughened epoxy resin coating of claim 1 wherein the wetting agent is any one of polydimethylsiloxane and alkyl modified organosiloxane.
7. The method for preparing the functionalized silica toughened epoxy resin coating according to any one of claims 1 to 6, comprising the following steps: weighing the raw materials according to the formula, uniformly mixing the epoxy resin and the polycaprolactone functionalized silica, adding the defoaming agent, the wetting agent, the epoxy curing agent and the pigment and filler, and uniformly stirring to obtain the functionalized silica toughened epoxy resin coating.
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