CN115011215B - Functionalized silica toughened epoxy resin coating and preparation method thereof - Google Patents
Functionalized silica toughened epoxy resin coating and preparation method thereof Download PDFInfo
- Publication number
- CN115011215B CN115011215B CN202210446519.7A CN202210446519A CN115011215B CN 115011215 B CN115011215 B CN 115011215B CN 202210446519 A CN202210446519 A CN 202210446519A CN 115011215 B CN115011215 B CN 115011215B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- functionalized silica
- parts
- resin coating
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention provides a functionalized silica toughened epoxy resin coating and a preparation method thereof, wherein the coating comprises the following components in parts by weight: 40 to 50 parts of epoxy resin, 5 to 10 parts of polycaprolactone functionalized silica, 5 to 10 parts of kaolin, 0.1 to 0.3 part of defoamer, 0.2 to 0.3 part of epoxy curing agent, 7 to 10 parts of wetting agent, 0.5 to 1 part of flatting agent, 10 to 15 parts of pigment and filler and 50 to 80 parts of water. The functionalized silica toughened epoxy resin coating prepared by the invention has good toughness, salt spray resistance and wear resistance, does not contain organic solvent, has low VOC content, and can meet the environmental protection requirements of the current world.
Description
Technical Field
The invention relates to the field of chemical coatings, in particular to a functionalized silica toughened epoxy resin coating and a preparation method thereof.
Background
Epoxy resins (EP) are important thermosetting resins, and are polymer prepolymers containing 2 or more epoxy groups and having aliphatic, alicyclic or aromatic segments as the main chain. Has the excellent properties of high viscosity, high strength, electric insulation, good thermal stability and the like, and can be widely applied to the aspects of aerospace, electronic sealing, paint and the like. However, the epoxy resin has high crosslinking degree, so that the epoxy resin has poor weather resistance, larger brittleness, low toughness and poor impact performance, and the application of the epoxy resin is limited, and the epoxy resin is not solved, so that the epoxy resin must be modified, and the toughening modification research is important.
The toughening of epoxy resins can be classified according to the toughening means as follows: (1) Introducing a disperse phase such as a liquid crystal polymer, a rubber elastomer or a thermoplastic resin into an epoxy resin matrix; (2) Preparing an interpenetrating network and semi-interpenetrating network structure 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 soft chain segment, introducing the soft chain segment into a crosslinked network, and improving the flexibility of network chain molecules, thereby achieving the aim of toughening; (4) Adding inorganic fillers, e.g. nano SiO 2 And whiskers, and the like. The nano ion and whisker have high heat resistance temperature and high modulus, toughen the epoxy resin according to a crack-rivet mechanism, and not reduce heat resistance and rigidity while improving strength.
Floor paint is taken as an important branch of the coating industry, and has been developed into a special industry with a certain scale under the stimulation of large domestic floor paint market demand. At present, in the domestic terrace paint industry, the epoxy terrace is relatively mature in technology and development speed. Epoxy floor paint contains a plurality of floor paint varieties, such as solvent-free self-leveling floor paint, anti-corrosion floor paint, wear-resistant floor paint, antistatic floor paint, water-based floor paint and the like.
The nano particles are taken as a toughening agent, are a new method for expanding the application of the nano composite material in recent years, and have no good proposal report in the prior art how to select and prepare the nano particles and functionalize the nano material to improve the internal structure of the epoxy resin system.
Chinese patent CN 102190858A discloses an epoxy resin material toughened by nano silicon dioxide and a preparation method thereof, the invention uses epoxy resin as a base material, adds a nano silicon dioxide toughening agent and a curing agent functionalized by dendritic macromolecules, wherein the dendritic macromolecules are distributed on the surface of nano silicon dioxide ions and are combined with silicon dioxide 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 silicon dioxide toughened epoxy resin, the inventor uses an aminosilane coupling agent to modify nano silicon dioxide and low molecular weight liquid epoxy resin to carry out chemical bonding, thereby overcoming the problem that the toughness is enhanced and the excellent performance of epoxy resin is reduced in the toughening modification of the existing epoxy resin, and the modification of nano silicon dioxide by using the aminosilane coupling agent is a common technical means for the skilled person.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to solve the problems of improving internal stress of epoxy resin, and poor impact resistance and toughness of coating film.
In order to achieve the above purpose, the invention provides a functionalized silica toughened epoxy resin coating and a preparation method thereof.
The invention adopts polycaprolactone functionalized silica to modify epoxy resin, not only forms a buffer belt on mechanics to absorb certain deformation energy to prevent silver marks and cracks from generating, but also active hydroxyl and ester groups on the surface can increase the compatibility of the silica and the epoxy resin, and under the condition of the existence of an epoxy curing agent, the active hydroxyl can participate in ring-opening curing of the epoxy group of the epoxy resin to form chemical bonds to adhere in an epoxy resin continuous phase, further absorbs deformation energy generated by strain force and prevents the occurrence of fracture, thereby increasing the flexibility of the epoxy resin.
The functionalized silica toughened epoxy resin coating comprises the following components in parts by weight: 40 to 50 parts of epoxy resin, 5 to 10 parts of polycaprolactone functionalized silica, 5 to 10 parts of kaolin, 0.1 to 0.3 part of defoamer, 0.2 to 0.3 part of epoxy curing agent, 7 to 10 parts of wetting agent, 0.5 to 1 part of flatting agent, 10 to 15 parts of pigment and filler and 50 to 80 parts of water.
The preparation method of the functionalized silica 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 silica, and then adding the defoamer, the wetting agent, the epoxy curing agent and the pigment and filler to uniformly stir to obtain the functionalized silica toughened epoxy resin coating.
The preparation method comprises the steps of treating the surface of nano silicon dioxide by adopting silane coupling agent gamma-aminopropyl triethoxysilane to obtain surface aminated silicon dioxide, bonding ring-opening polymerization initiator on the surface of nano silicon dioxide particles through ring-opening reaction of bromoisobutyric acid glycidyl ester and amino, and carrying out ring-opening polymerization by taking nano silicon dioxide particles with the surface bonded with the ring-opening polymerization initiator as initiator to obtain surface grafted polycaprolactone nano silicon dioxide ions, wherein the preparation method comprises the following steps:
(1) 12-15 mL of tetraethyl orthosilicate, 350-450 mL of absolute ethyl alcohol and 20-25 mL of ammonia water are kept at 30-50 ℃ for 1-3 hours; adding 1-3 mL of gamma-aminopropyl triethoxysilane 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 toluene for 2-3 times to obtain nano silicon dioxide with aminated surface;
(2) Stirring and mixing 20-30mL of dichloromethane, 6-10g of glycidol and 8-15g of triethylamine at 0-10 ℃ uniformly to obtain a mixed solution M1; weighing 20-30g of bromoisobutyryl 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 2-3h of reaction, heating to 20-30 ℃ to react for 10-12h, and adding water into the reaction solution after the reaction is finished to enable the pH value of the mixed solution to be 6-7; standing for layering, collecting oil phase, drying the oil phase with anhydrous magnesium sulfate for 10-12h, filtering, collecting filtrate, evaporating dichloromethane under reduced pressure at 30-40deg.C, and drying the obtained solid in a vacuum drying oven at 30-50deg.C for 20-24h to obtain bromoisobutyric acid glycidyl ester;
(3) 10-15 g of nano silicon dioxide with the surface aminated and 40-60 mL of anhydrous THF are dispersed for 20-40 min by ultrasonic; adding 1-2 g of bromoisobutyric acid glycidyl ester, reacting for 2-3 hours at 20-30 ℃, 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 placing the obtained product in a vacuum drying oven at 50-70 ℃ for drying for 24-36 hours to obtain nano silicon dioxide bonded with an 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 iso-octoate; liquid nitrogen cooling-vacuumizing-introducing nitrogen-thawing, and repeating the process for 2-3 times; sealing under nitrogen atmosphere, and then placing in an ultrasonic cleaner 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, stirring and mixing uniformly; centrifugally separating, collecting precipitate, and washing the precipitate with THF for 3-4 times; vacuum drying at 25-30 deg.c to obtain the functional polycaprolactone silica.
The epoxy resin is any one or two or more than two of bisphenol A epoxy resin, bisphenol F epoxy resin, polyphenol type glycidyl ether epoxy resin and aliphatic glycidyl ether epoxy resin.
Bisphenol A type epoxy resin is the most widely used type of epoxy resin with the highest yield because of high transparency, is also produced by reacting bisphenol A and epichlorohydrin in the presence of sodium hydroxide, is also called general type epoxy resin, and has excellent bonding performance, better dimensional stability and chemical corrosion resistance after curing and very good mechanical strength.
The defoaming agent is a polyether defoaming agent; the preferred defoaming agent is one or 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 may be an amine, tertiary amine, anhydride, boride or other type of epoxy curing agent; the preferred epoxy curing agent is methyl hexahydrophthalic anhydride.
The wetting agent is any one of polydimethylsiloxane and alkyl modified organosiloxane; the preferred wetting agent is polydimethylsiloxane.
The leveling agent is BYK-111.
The pigment and filler is one of iron oxide red pigment, titanium pigment and phthalocyanine BS pigment, and the preferable pigment is rutile titanium pigment or modified rutile titanium pigment.
The preparation method of the modified rutile titanium dioxide comprises the following steps:
1) Adding 12-20g of rutile titanium dioxide into 40-50mL of water and 20-30mL of propylene glycol, regulating the pH value of the solution to 9-10 by using 0.5-1mol/L NaOH aqueous solution, 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 the titanium dioxide particles are spherical and have uniform size but serious agglomeration phenomenon, the titanium dioxide needs to be modified, and the modified titanium dioxide can improve the acid resistance and the dispersibility, enhance the corrosion resistance under the acid condition and also improve the corrosion resistanceThe optical performance of the pigment is improved, the outdoor service life of the product is prolonged, the purposes of improving the weather resistance, the dispersibility and the dispersion stability of the pigment are achieved, and the TiO is fully exerted 2 Excellent pigment properties.
Compared with the prior art, the invention has the beneficial effects that: (1) According to the invention, the nano silicon dioxide modified by the aminosilane coupling agent is further modified, so that the surface activity of the nano silicon dioxide is reduced, the polycaprolactone surface grafted nano silicon dioxide is obtained through ring-opening polymerization, and the polycaprolactone chain segments are inserted into the epoxy resin chain segments irregularly to form an interpenetrating network structure or a semi-interpenetrating network structure, so that the defect that the nano silicon dioxide is poor in dispersibility in an epoxy resin matrix and easy to aggregate is overcome; (2) The nano kaolin with a lamellar structure and the nano silicon dioxide grafted on the surface of the polycaprolactone are uniformly dispersed in the epoxy resin matrix, so that the problem of poor impact strength and toughness of the epoxy resin coating is 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 of the current world.
Detailed Description
The invention will be described in further detail with reference to specific examples. The procedures, conditions, experimental methods, etc. for carrying out the present invention are common general knowledge and knowledge in the art, except for the following specific references, and the present invention is not particularly limited.
The sources of some of the raw materials in the examples of the present invention are as follows, and the raw materials used in the examples are all available from conventional commercial sources or can be prepared by conventional methods unless specifically indicated otherwise:
bisphenol A type epoxy resin, purchased from Zaoqiang county composite materials Inc., has an epoxy value of 0.48-0.52, and is a thermosetting polymer composite material with good adhesion, corrosion resistance, insulation, high strength and other properties.
Tetraethyl orthosilicate, which is also called tetraethyl silicate, purchased from Shandong Xin Yingning New material Co., ltd, has a melting point of-77 ℃, a boiling point of 165 ℃ and a density of 0.93g/cm 3 The model is industrial grade.
Gamma-aminopropyl triethoxysilane, KH550, purchased from the company of petrochemical industry, south tongshun, has an active substance content of 97%.
Glycidol, also known as glycidol, is purchased from Hubei Heng Jing Rui chemical Co., ltd and has a purity of 98%.
Epsilon-caprolactone purchased from Hunan polykernel chemical new material technology Co., ltd. With purity of not less than 99.9%, chromaticity of not more than 10, acidity of not more than 0.3 and moisture of not more than 0.05.
Stannous iso-octoate purchased from Shandong Hui An chemical Co., ltd, with a tin content of 28% -33.5% and model grade.
Nanometer kaolin is purchased from Shijia Dakun mineral products limited company, with the specification of 2000 meshes and the product number of HD-00161.
Methyl hexahydrophthalic anhydride, purchased from Shandong Liang New Material technology Co., ltd, density 1.17g/cm 3 Model is LA-7Q.
The aliphatic polyoxyethylene ether is purchased from Jiangsu province sea-An petrochemical plant, and the model is JFC.
Polydimethylsiloxane, average molecular weight 5600, viscosity 100cP (25 ℃ C.), commercially available from Wuhan Hua Xiangke Biotechnology Inc., CAS number 9006-65-9.
BYK-111, pick, germany.
Rutile titanium dioxide is purchased from Jinan river chemical engineering Co., ltd, crystal form, rutile type, blue light of chromatic light and industrial grade.
Example 1
The preparation method of the functionalized silica toughened epoxy resin coating comprises the following steps: 50g 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 are weighed and stirred uniformly at 25 ℃ to obtain the functionalized silicon dioxide toughened epoxy resin coating.
Example 2
The preparation method of the functionalized silica toughened epoxy resin coating comprises the following steps: 50g of bisphenol A epoxy resin, 10g of polycaprolactone functionalized silica, 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 are weighed and uniformly stirred at 25 ℃ to obtain the functionalized silica toughened epoxy resin coating.
The preparation method of the polycaprolactone functionalized silica comprises the following steps:
(1) 14mL of tetraethyl orthosilicate, 400mL of absolute ethyl alcohol and 22mL of ammonia water are subjected to heat preservation for 2 hours at 40 ℃; 2mL of gamma-aminopropyl triethoxysilane is added and stirred 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 nano silicon dioxide with aminated surface;
(2) Stirring and mixing 20mL of dichloromethane, 7.4g of glycidol and 10.5g of triethylamine at 0 ℃ uniformly to obtain a mixed solution M1; 23g of bromoisobutyryl bromide is weighed and dissolved by 30mL of dichloromethane to obtain a mixed solution M2; dropping the mixed solution M2 into the mixed solution M1; after 2h of reaction, heating to 30 ℃ for reaction for 12h, adding water into the reaction liquid to enable the pH value of the mixed liquid to be 7 after the reaction is finished, standing for layering, collecting an oil phase, drying the oil phase for 12h by using anhydrous magnesium sulfate, filtering and collecting filtrate, decompressing and steaming at 30 ℃ to remove dichloromethane, and placing the obtained solid in a 40 ℃ vacuum drying box for drying for 24h to obtain bromoisobutyric acid glycidyl ester;
(3) Dispersing 12g of nano silicon dioxide with an aminated surface and 50mL of anhydrous THF for 30min by ultrasonic; 1.15g of bromoisobutyric acid glycidyl ester is added for reaction for 2 hours at 25 ℃, and then the temperature is raised 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 placing the obtained product in a vacuum drying oven at 60 ℃ for drying 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 iso-octoate; liquid nitrogen cooling-vacuumizing-introducing nitrogen-thawing, and repeating the process for 3 times; sealing under nitrogen atmosphere, and then placing in an ultrasonic cleaner for ultrasonic dispersion for 5 minutes; after reacting for 30 hours at 80 ℃, adding 40mL of THF into the reaction solution, and stirring and mixing uniformly; centrifuging, collecting precipitate, and washing the precipitate with THF for 4 times; and (3) drying in vacuum at 25 ℃ to obtain the polycaprolactone functionalized silica.
Example 3
The preparation method of the functionalized silica toughened epoxy resin coating comprises the following steps: 50g 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 are weighed and uniformly stirred at 25 ℃ to obtain the functionalized 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 40mL of water and 20mL of propylene glycol solution, regulating the pH value of the solution to 10 by using 1mol/L NaOH aqueous solution, 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 silica toughened epoxy resin coating comprises the following steps: 50g of bisphenol A epoxy resin, 10g of polycaprolactone functionalized silica, 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 are weighed and uniformly stirred at 25 ℃ to obtain the functionalized silica toughened epoxy resin coating.
The preparation method of the polycaprolactone functionalized silica comprises the following steps:
(1) 14mL of tetraethyl orthosilicate, 400mL of absolute ethyl alcohol and 22mL of ammonia water are subjected to heat preservation for 2 hours at 40 ℃; 2mL of gamma-aminopropyl triethoxysilane is added and stirred 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 nano silicon dioxide with aminated surface;
(2) Stirring and mixing 20mL of dichloromethane, 7.4g of glycidol and 10.5g of triethylamine at 0 ℃ uniformly to obtain a mixed solution M1; 23g of bromoisobutyryl bromide is weighed and dissolved by 30mL of dichloromethane to obtain a mixed solution M2; dropping the mixed solution M2 into the mixed solution M1; after 2h of reaction, heating to 30 ℃ for reaction for 12h, adding water into the reaction liquid to enable the pH value of the mixed liquid to be 7 after the reaction is finished, standing for layering, collecting an oil phase, drying the oil phase for 12h by using anhydrous magnesium sulfate, filtering and collecting filtrate, decompressing and steaming at 30 ℃ to remove dichloromethane, and placing the obtained solid in a 40 ℃ vacuum drying box for drying for 24h to obtain bromoisobutyric acid glycidyl ester;
(3) Dispersing 12g of nano silicon dioxide with an aminated surface and 50mL of anhydrous THF for 30min by ultrasonic; 1.15g of bromoisobutyric acid glycidyl ester is added for reaction for 2 hours at 25 ℃, and then the temperature is raised 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 placing the obtained product in a vacuum drying oven at 60 ℃ for drying 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 iso-octoate; liquid nitrogen cooling-vacuumizing-introducing nitrogen-thawing, and repeating the process for 3 times; sealing under nitrogen atmosphere, and then placing in an ultrasonic cleaner for ultrasonic dispersion for 5 minutes; after reacting for 30 hours at 80 ℃, adding 40mL of THF into the reaction solution, and stirring and mixing uniformly; centrifuging, collecting precipitate, and washing the precipitate with THF for 4 times; and (3) drying in vacuum at 25 ℃ to obtain the polycaprolactone functionalized silica.
The preparation method of the modified rutile titanium dioxide comprises the following steps:
1) Adding 15g of rutile titanium dioxide into 40mL of water and 20mL of propylene glycol solution, regulating the pH value of the solution to 10 by using 1mol/L NaOH aqueous solution, 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 functionalized silica toughened epoxy resin paint prepared in the embodiment 1-4 of the invention is coated on tin plate with the size of 155mm multiplied by 70mm multiplied by 0.20mm, is placed at 50 ℃ for curing for 10 hours, and is cooled to obtain the cured functionalized silica toughened epoxy resin paint, the pencil hardness of the paint is tested by using an HT-1086 pencil hardness tester according to the test 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 test method of the standard GB/T1732-2020, and the neutral salt fog resistance of the paint is tested according to the test method of the standard GB/T1771-2007. For each example, 3 samples were tested and the results averaged, the test data are shown in table 1:
table 1: performance of functionalized silica toughened epoxy resin coating
Abrasion resistance test: and (5) carrying out wear resistance test by using an MPX-2000 type friction and wear testing machine. Adopting a ring disk counter-grinding mode, counter-grinding a grinding disk by adopting a rubber material and respectively carrying out counter-grinding on the ring sample with the ring samples in the embodiments 1-4, wherein in the experimental process, the ring sample and the rubber counter-grinding disk are immersed in clean water so as to facilitate timely heat dissipation, the normal load value of the ring disk counter-grinding is selected to be 100N, the relative rotating speed of the ring disk is 580r/min, the total rotating speed is 2000r, the friction resistance is recorded, the friction coefficient is calculated, and the induction quantity is 10 -4 The analytical balance of (2) weighed the ring samples before and after abrasion, calculated the abrasion loss weight, 3 samples were tested for each set of data, and the average was taken, and the test data are shown in table 2:
table 2: abrasion loss per gram of epoxy paint
| Wear amount/g | |
| Example 1 | 0.402 |
| Example 2 | 0.321 |
| Example 3 | 0.347 |
| Example 4 | 0.302 |
The smaller the abrasion loss, the better the abrasion resistance of the material. The essence of abrasion is that when the composite material slides and rubs on a rough surface, a paint film in a small area is torn by local overlarge stress and is torn away from a body to form independent small particles, the strength of silicon dioxide is high, cracking is difficult to occur, and the silicon dioxide is well modified and uniformly dispersed in an epoxy resin paint together with nano kaolin with a lamellar structure and modified rutile titanium dioxide, so that the paint film is difficult to separate from a matrix, and the abrasion resistance of the paint film is improved.
Claims (6)
1. The functionalized silica 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 defoamer, 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 polycaprolactone functionalized silica comprises the following steps:
(1) Preserving heat for 1-3 hours at the temperature of 30-50 ℃ by using 12-15 mL of tetraethyl orthosilicate, 350-450 mL of absolute ethyl alcohol and 20-25 mL of ammonia water; adding 1-3 mL of gamma-aminopropyl triethoxysilane, 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 toluene for 2-3 times to obtain nano silicon dioxide with an aminated surface;
(2) Stirring and mixing 20-30mL of dichloromethane, 6-10g of glycidol and 8-15g of triethylamine at 0-10 ℃ uniformly to obtain a mixed solution M1; weighing 20-30g of bromoisobutyryl 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 2-3h of reaction, heating to 20-30 ℃ to react for 10-12h, and adding water into the reaction solution after the reaction is finished to enable the pH value of the mixed solution to be 6-7; standing for layering, collecting oil phase, drying the oil phase with anhydrous magnesium sulfate for 10-12h, filtering, collecting filtrate, evaporating dichloromethane under reduced pressure at 30-40deg.C, and drying the obtained solid in a vacuum drying oven at 30-50deg.C for 20-24h to obtain bromoisobutyric acid glycidyl ester;
(3) Dispersing 10-15 g of surface aminated nano silicon dioxide and 40-60 mL of anhydrous THF in an ultrasonic manner for 20-40 min; adding 1-2 g of bromoisobutyric acid glycidyl ester, reacting for 2-3 hours at 20-30 ℃, 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 placing the obtained product in a vacuum drying oven at 50-70 ℃ for drying for 24-36 hours to obtain nano silicon dioxide bonded with an initiator;
(4) Uniformly mixing 5-7 g of nano silicon dioxide of a bonding initiator, 25-35 g of ɛ -caprolactone and 300-350 mg of stannous isooctanoate; liquid nitrogen cooling, vacuumizing, introducing nitrogen and thawing, wherein the process is repeatedly and circularly carried out for 2-3 times; sealing in a nitrogen atmosphere, and then performing ultrasonic dispersion for 5-10 minutes; after reacting for 24-30 hours at 80-90 ℃, adding 30-50 mL of THF into the reaction solution, and stirring and mixing uniformly; centrifugally separating, collecting a precipitate, and washing the precipitate with THF for 3-4 times; vacuum drying at 25-30 ℃ to obtain the polycaprolactone functionalized silica;
the pigment and filler is modified rutile titanium dioxide, and the preparation method comprises the following steps:
1) Adding 12-20g rutile titanium dioxide into 40-50mL of water and 20-30mL of propylene glycol, regulating the pH value of the solution to 9-10 by using 0.5-1mol/L NaOH aqueous solution, heating to 50-70 ℃, and stirring to obtain rutile titanium dioxide slurry;
2) Adding 0.5-1. 1g 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.
2. The functionalized silica toughened epoxy resin coating according to claim 1, wherein said epoxy resin is any one or a mixture of two or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, aliphatic glycidyl ether epoxy resin.
3. The functionalized silica toughened epoxy resin coating of claim 1 wherein: the defoamer is polyether defoamer.
4. The functionalized silica toughened epoxy resin coating of claim 1 wherein: the epoxy curing agent may be tertiary amines, anhydrides, borides or other types of epoxy curing agents.
5. The functionalized silica toughened epoxy resin coating according to claim 1 wherein said wetting agent is any of alkyl modified organosiloxanes.
6. The method for preparing the functionalized silica toughened epoxy resin coating according to any one of claims 1 to 5, comprising the following steps: weighing the raw materials according to the formula, uniformly mixing the epoxy resin and the polycaprolactone functionalized silica, and then adding the defoamer, the wetting agent, the epoxy curing agent and the pigment and filler to uniformly stir to obtain the functionalized silica toughened epoxy resin coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210446519.7A CN115011215B (en) | 2022-04-26 | 2022-04-26 | Functionalized silica toughened epoxy resin coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210446519.7A CN115011215B (en) | 2022-04-26 | 2022-04-26 | Functionalized silica toughened epoxy resin coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115011215A CN115011215A (en) | 2022-09-06 |
| CN115011215B true CN115011215B (en) | 2023-08-25 |
Family
ID=83067712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210446519.7A Active CN115011215B (en) | 2022-04-26 | 2022-04-26 | Functionalized silica toughened epoxy resin coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115011215B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115975235A (en) * | 2022-12-23 | 2023-04-18 | 温州大学苍南研究院 | Anti-slip woven bag |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580570A (en) * | 2009-06-17 | 2009-11-18 | 厦门大学 | Siloxane-acrylate copolymer/nano-silicon dioxide organic/inorganic hybrid nano-material and preparation method thereof |
| CN102190858A (en) * | 2010-03-19 | 2011-09-21 | 包海峰 | Epoxy resin material toughened by nanometer silica and preparation method thereof |
| CN112898869A (en) * | 2021-01-22 | 2021-06-04 | 杜磊 | Polycaprolactone functionalized silicon dioxide toughened epoxy resin floor paint and preparation method thereof |
| CN114058153A (en) * | 2020-12-21 | 2022-02-18 | 中国科学院兰州化学物理研究所 | SiO (silicon dioxide)2-PGMA reinforced epoxy resin composite material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008051616A2 (en) * | 2006-10-27 | 2008-05-02 | The University Of Akron | Organic-inorganic hybrid nanomaterials and method for synthesizing same |
-
2022
- 2022-04-26 CN CN202210446519.7A patent/CN115011215B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580570A (en) * | 2009-06-17 | 2009-11-18 | 厦门大学 | Siloxane-acrylate copolymer/nano-silicon dioxide organic/inorganic hybrid nano-material and preparation method thereof |
| CN102190858A (en) * | 2010-03-19 | 2011-09-21 | 包海峰 | Epoxy resin material toughened by nanometer silica and preparation method thereof |
| CN114058153A (en) * | 2020-12-21 | 2022-02-18 | 中国科学院兰州化学物理研究所 | SiO (silicon dioxide)2-PGMA reinforced epoxy resin composite material and preparation method thereof |
| CN112898869A (en) * | 2021-01-22 | 2021-06-04 | 杜磊 | Polycaprolactone functionalized silicon dioxide toughened epoxy resin floor paint and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115011215A (en) | 2022-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107722792B (en) | Preparation method of epoxy resin coating with high corrosion resistance | |
| CN109749087B (en) | Semi-closed cage-shaped trifunctional epoxy ether POSS and preparation method thereof | |
| CN109851759B (en) | Organic silicon modified epoxy resin, preparation method thereof and organic silicon modified epoxy resin adhesive | |
| CN108892929B (en) | Toughened and reinforced epoxy resin composition | |
| CN112876983A (en) | Fluorine-free super-hydrophobic modified silicon dioxide composite resin coating and preparation method thereof | |
| CN110591288B (en) | Hyperbranched silicon-phosphorus synergistic flame retardant modified epoxy resin and preparation method thereof | |
| CN109824903B (en) | High-refractive-index boron-containing organic silicon tackifier and preparation method thereof | |
| CN115011215B (en) | Functionalized silica toughened epoxy resin coating and preparation method thereof | |
| CN112500553B (en) | Waterborne epoxy back-screen adhesive curing agent, preparation method thereof and back-screen adhesive | |
| CN112226101B (en) | Preparation method of tannin grafted glass flakes and application of tannin grafted glass flakes in high-solid anticorrosive paint | |
| CN111944387A (en) | Graphene anticorrosive paint | |
| CN115029046B (en) | Epoxy resin coating and preparation method thereof | |
| CN105461963B (en) | A kind of boron nitride powder of surface organic modification and its preparation method and application | |
| CN109836557B (en) | Toughened hydrophobic epoxy resin and preparation method thereof | |
| CN109486345B (en) | Nano modified epoxy resin floor coating and preparation method thereof | |
| CN114181589A (en) | High-salt-spray-resistance water-based tower barrel coating and preparation method thereof | |
| CN108129974B (en) | Polysiloxane finish paint for rolling stock and preparation method thereof | |
| CN101463223B (en) | Epoxy enhanced tough organosilicon coating | |
| CN115093768B (en) | Solvent-free modified epoxy anti-corrosion coating and preparation method and application thereof | |
| CN114702899A (en) | Water-based one-component baking type polysiloxane coating and preparation method thereof | |
| CN113755035B (en) | Epoxy silane modified nano alumina and polymer cement-based waterproof coating | |
| CN113045919B (en) | Low-temperature curing high-solid epoxy coating and preparation method thereof | |
| CN114525045A (en) | Preparation method of efficient anti-yellowing modified silicon dioxide powder | |
| CN110484025B (en) | Method for improving settling resistance and dispersibility of silicon micro powder in organic silicon pouring sealant | |
| CN114262528B (en) | Surface modification method and application of silicon dioxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230802 Address after: 430000 Room 301, building 2, jinshikai laser Industrial Park, Guanshan Second Road, Donghu Development Zone, Wuhan, Hubei Province Applicant after: Wuhan Changwei Electric Co.,Ltd. Address before: Room 1303, Unit 2, Building 1, Guoxing New Century, Chengjiang Town, Taihe County, Ji'an City, Jiangxi Province 343700 Applicant before: Jiangxi Dingchun Construction Engineering Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |