CN113683719A - Multifunctional water-based emulsion - Google Patents
Multifunctional water-based emulsion Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- 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
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- C09D7/60—Additives non-macromolecular
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- C08K2201/00—Specific properties of additives
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Abstract
The invention provides a multifunctional aqueous emulsion. The multifunctional aqueous emulsion comprises the following raw materials: the coating comprises a fluorine/damping functional acrylate monomer, an acrylate monomer mixture, a crosslinking monomer 1, a crosslinking monomer 2, an emulsifier, an initiator, modified nanoparticles and deionized water. Wherein, the raw materials of the acrylate monomer with the fluorine/damping function comprise: the weight ratio is 110-150: 50-60: 100-120: 550-600: 100-200: 0.01 to 1 of 2,2,3,3,4,4,5, 5-octafluoro-1-pentanol, hydroxyethyl acrylate, isophorone diisocyanate, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tetrahydrofuran and a catalyst. The multifunctional water-based emulsion has ultrahigh hydrophobic property and antifouling self-cleaning effect, and can meet the application of multifunctional damping resin.
Description
Technical Field
The invention relates to a multifunctional water-based emulsion, and belongs to the technical field of high polymer materials.
Background
The organic polymer damping paint is a special functional paint with vibration reduction, noise reduction and certain sealing property, and can be widely used for vibration reduction and noise reduction of airplanes, ships and various machines. Nowadays, damping coatings commonly used for controlling noise environment in vehicles are represented by asphalt, chloroprene rubber and nitrile rubber water-based coatings, but all have the defects of easy combustion, high environmental temperature requirement, poor adhesion to substrates, complex manufacturing process, high cost and the like, and are not convenient for mass production and use. In the damping coating, the water-based acrylic damping coating has wide application prospect due to the advantages of convenient construction coating, no environmental pollution, low cost and the like of excellent damping performance.
Generally speaking, the larger the glass transition temperature range, the more the temperature range value is consistent with the environment, and the better the damping effect is. But the single acrylate polymer has a damping temperature range of only 20-30 ℃, has a limited damping effect and is difficult to play a role. Therefore, it is desirable to broaden the effective damping temperature range by using a specific blend of low Tg polymer and high Tg acrylate polymer. Or the damping temperature range of the polymer is improved by adopting a mode of mixing the hindered phenol and the polymer, but the hindered phenol is easy to migrate from the structure of the mixed polymer material, and the damping effect is not long. In addition, the water-based damping coating used for outdoor glass has good water resistance or hydrophobicity, but the water resistance or hydrophobicity of general acrylic ester is poor. The water resistance or hydrophobicity of the acrylate is generally expressed by a water contact angle, and the water contact angle of the water-based acrylate is only 50-60 degrees and is difficult to meet the long-term outdoor use requirement. With the rapid development of the functional coatings in recent years, the market urgently needs to develop the functional coatings with high contact angles so as to meet the use requirements of the antifouling self-cleaning effect coatings.
Disclosure of Invention
The technical problem solved by the invention is as follows: the existing resin has the technical problems of poor damping performance, narrow damping temperature range, small water contact angle, poor antifouling and self-cleaning effects and the like.
In order to solve the technical problems, the invention provides a multifunctional water-based emulsion which is prepared by an emulsion polymerization method, and the preparation raw materials comprise the following components in parts by weight:
wherein, the raw materials of the acrylate monomer with the fluorine/damping function comprise the following components in a weight ratio of 110-150: 50-60: 100-120: 550-600: 100-200: 0.01 to 1 of 2,2,3,3,4,4,5, 5-octafluoro-1-pentanol, hydroxyethyl acrylate, isophorone diisocyanate, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tetrahydrofuran and a catalyst; the catalyst is dibutyltin dilaurate.
Preferably, the acrylic ester monomer mixture is a combination of any plurality of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate and cyclohexyl methacrylate.
Preferably, the crosslinking monomer 1 is diacetone acrylamide and adipic acid dihydrazide, and the mass ratio of the diacetone acrylamide to the adipic acid dihydrazide is 1-3: 1.
Preferably, the crosslinking monomer 2 is dipentaerythritol hexaacrylate, diethylene glycol diacrylate, tetrahydrofuran acrylate, pentaerythritol tetraacrylate, ethoxylated bisphenol A dimethacrylate, ditrimethylolpropane tetraacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, isobornyl acrylate, tricyclodecane dimethanol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated trimethylolpropane triacrylate, hyperbranched polyester acrylates, alkoxy acrylates, carbonate monoacrylates, imidazolyl monoacrylates, cyclic carbonate monoacrylates, epoxy silicone monomers, ethylene glycol diacrylate, ethylene glycol methacrylate, ethylene glycol, At least one of silicone acrylate and vinyl ether monomer.
Preferably, the emulsifier is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, alkyl diphenyl oxide disulfonate, ethoxylated ammonium alkylphenol sulfate, nonylphenol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene ether; the initiator is ammonium persulfate and/or potassium persulfate; the modified nano particles are modified nano SiO2Modified nano TiO2And modified montmorillonite nanoparticles.
More preferably, the acrylic ester monomer mixture is prepared by mixing methyl acrylate and butyl acrylate according to a mass ratio of 30: 10 or methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate in a mass ratio of 30: 20: 10: 10 or a mixture of methyl acrylate, butyl acrylate and 2-ethylhexyl acrylate in a mass ratio of 20: 5:1, in a mixture of the components.
More preferably, the crosslinking monomer 2 is diethylene glycol diacrylate, or diethylene glycol diacrylate, ethoxylated bisphenol a dimethacrylate, ethoxylated trimethylolpropane triacrylate and hyperbranched polyester acrylate in a mass ratio of 1: 1: 0.5: 0.3 or a mixture of diethylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate in a mass ratio of 8: 1, in a mixture of the components.
More preferably, the emulsifier is a mixture of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate in a mass ratio of 1:1, or a mixture of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and nonylphenol polyoxyethylene ether in a mass ratio of 2: 2: 1 or sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and nonylphenol polyoxyethylene ether in the mass ratio of 3: 3:1, in a mixture of the components.
More preferably, the viscosity of the multifunctional aqueous emulsion is 160 to 1100 mPas, and the damping temperature range is-38 to 165 ℃ when the loss tangent tan delta is 0.3.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention relates to a multifunctional water-based emulsion, which is characterized in that firstly, a tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester compound containing four hindered phenol structures per molecule is prepared into an active acrylate macromonomer structure through a chemical reaction, and a functional acrylate monomer containing fluorine and hindered phenol structures is introduced into an acrylate polymer molecular structure through an emulsion polymerization technology to obtain the multifunctional water-based emulsion containing the fluorine structures and the hindered phenol structures at a polymer side chain, wherein the multifunctional water-based emulsion has excellent performances of good film forming performance, wide damping temperature range, good high and low temperature damping effect and the like, and the damping temperature range is-38-165 ℃, and is far higher than the damping temperature range of the existing acrylate resin of 20-30 ℃;
2. the modified nanoparticles are added into the multifunctional water-based emulsion, and are well dispersed on the surface of a film-forming object through film-forming process control, so that the micro-nano structure on the surface of the film-forming object is greatly improved, the water contact angle of a formed film is 110-;
3. the multifunctional aqueous emulsion has ultrahigh hydrophobic property and good antifouling self-cleaning effect through tests, so that the multifunctional aqueous emulsion meets the application of multifunctional damping resin in the aspects of film forming property, hydrophobicity, viscosity, antifouling property and the like.
Drawings
FIG. 1 is an infrared spectrum of the multifunctional aqueous emulsion film-forming material prepared in example 1.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
The raw materials used in the following examples are all commercially available products, and the specifications are all chemical purity. Wherein the model of the nonylphenol polyoxyethylene ether is NP-10, and the hyperbranched polyester acrylate is B574C produced by Guangdong Boxing New Material science and technology Co.
The information on the model and manufacturer of the various devices used in the following examples is as follows:
NDJ-1 rotational viscometer, Shanghai Sharp Instrument manufacturing, Inc.;
type 380 infrared chromatograph, Nicolet corporation, usa;
DMA242C dynamic mechanical thermal analyzer, german navy company;
DSA30 model contact angle tester; kruss, Germany.
Example 1
The multifunctional water-based emulsion comprises the following raw materials in parts by weight:
wherein the acrylic ester monomer mixture is prepared from methyl acrylate and butyl acrylate according to a mass ratio of 30: 10 to a mixture of the components. The crosslinking monomer 1 is diacetone acrylamide and adipic acid dihydrazide, and the mass ratio of the diacetone acrylamide to the adipic acid dihydrazide is 2.1: 1. The crosslinking monomer 2 is diethylene glycol diacrylate; the emulsifier is a mixture of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate in a mass ratio of 1: 1; the modified nano particles are modified nano SiO2(ii) a The initiator is potassium persulfate.
The raw materials of the bifunctional acrylate monomer comprise: the weight ratio is 110: 50: 100: 550: 100:0.01 of 2,2,3,3,4,4,5, 5-octafluoro-1-pentanol, hydroxyethyl acrylate, isophorone diisocyanate, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tetrahydrofuran and a catalyst, wherein the catalyst is dibutyltin dilaurate.
The preparation method of the multifunctional water-based emulsion comprises the following steps:
1) 110g of isophorone diisocyanate were placed in a 2000mL round-bottom four-neck flask in N2Under protection, after controlling the temperature to 30 ℃,2,3,3,4,4,5, 5-octafluoro-1-pentanol and hydroxyethyl acrylate are added into the system dropwise at the speed of 0.01 mL/s, and then 1 drop (0.05mL) of catalyst is added dropwise. After the completion of the dropwise addition, the reaction was stirred for 2 hours. Dissolving tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid in tetrahydrofuran]And (4) pouring pentaerythritol ester into the four-neck flask, and supplementing the rest catalyst. The temperature was adjusted to 80 ℃. Stirring for 2 hours to finally obtain the transparent viscous acrylate monomer with the fluorine/damping function.
2) Adding deionized water and an emulsifier into a 500mL four-neck flask provided with a stirring paddle, a condenser tube, a dropping funnel and a thermometer, dripping a mixture of a fluorine/damping function acrylate monomer, an acrylate monomer mixture, a crosslinking monomer 1 and a crosslinking monomer 2 obtained in the step 1) into the four-neck flask at the speed of 0.1mL/s, heating to 60 ℃, adding an initiator into the four-neck flask at the speed of 0.05mL/s, reacting for 3 hours under stirring, heating to 85 ℃, reacting for 1 hour under stirring, adding modified nanoparticles, and stirring for 0.5 hour to obtain the multifunctional aqueous emulsion.
The obtained multifunctional aqueous emulsion was subjected to infrared spectroscopic analysis by an infrared chromatograph (Nicolet 380 type) to obtain an infrared spectrum of 2956.11cm as shown in FIG. 1-1is-CH3The absorption peak of stretching vibration of the middle C-H bond; 1639.32cm-1The stretching shock absorption peak of-C ═ C-has disappeared, indicating that polymerization has occurred; 1142.83cm-1Is the C-O stretching vibration absorption peak; 1449.93cm-1Is the bending vibration absorption peak of the C-H bond;
as shown above, the fluorine/damping functional acrylate monomer, the acrylate monomer mixture, the crosslinking monomer 1 and the crosslinking monomer 2 have successfully undergone polymerization reaction.
The obtained multifunctional aqueous emulsion was measured at room temperature and 25 ℃ by using an NDJ-1 rotational viscometer provided by Shanghai Ruifeng instruments & ltLtd and GB/T2794-2013, Single Cylinder rotational viscometer method for measuring adhesive viscosity, and the viscosity was 160 mPas.
The obtained multifunctional water-based emulsion is measured by using a DMA242C type dynamic mechanical thermal analyzer of Germany Chiari corporation, and the stretching mode is adopted, the testing frequency is 1Hz, the testing temperature range is-80-200 ℃, and the heating rate is 5 ℃/min. The damping temperature range of the loss tangent tan delta is 0.3 and is-15 to 139 ℃.
The multifunctional water-based emulsion is formed into a film for 7 days at room temperature, the water contact angle of the film is measured according to GB/T30693-2014, and the water contact angle of the film is 123 degrees.
And (3) antifouling property test: coating pollutants (the handwriting of a real-color-brand water color pen) on the coating film, standing for 1h, then scrubbing the pollutants back and forth 100 times by using cotton cloth dipped with a washing powder aqueous solution with the concentration of 5%, washing with water, and then drying, wherein the pollutants are clean and have no stains. The result shows that the prepared multifunctional water-based emulsion film-forming material has better antifouling effect.
Therefore, the multifunctional aqueous emulsion obtained in the embodiment 1 has wide temperature range damping characteristics, and meets the application requirements of damping resin in the aspects of film forming property, hydrophobicity, viscosity, antifouling property and the like.
Example 2
The multifunctional water-based emulsion comprises the following raw materials in parts by weight:
wherein the acrylate monomer mixture is prepared from methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate according to a mass ratio of 30: 20: 10: 10 to a mixture of the components. The crosslinking monomer 1 is diacetone acrylamide and adipic dihydrazide, and the diacetone acrylamide isThe mass ratio of amide to adipic acid dihydrazide was 2.5: 1. The crosslinking monomer 2 is diethylene glycol diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated trimethylolpropane triacrylate and hyperbranched polyester acrylate according to the mass ratio of 1: 1: 0.5: 0.3 of the composition of the mixture; the emulsifier is sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and nonylphenol polyoxyethylene ether in a mass ratio of 2: 2: 1; the modified nano particle is modified nano TiO2(ii) a The initiator is ammonium persulfate.
The raw materials of the acrylate monomer with the fluorine/damping function comprise: the weight ratio is 150: 60: 120: 600: 200: 1 of 2,2,3,3,4,4,5, 5-octafluoro-1-pentanol, hydroxyethyl acrylate, isophorone diisocyanate, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tetrahydrofuran and a catalyst, wherein the catalyst is dibutyltin dilaurate.
The preparation method of the multifunctional water-based emulsion comprises the following steps:
1) 130g of isophorone diisocyanate was placed in a 2000mL round-bottom four-neck flask in N2Under protection, after controlling the temperature to 32 ℃,2,3,3,4,4,5, 5-octafluoro-1-pentanol and hydroxyethyl acrylate are added into the system dropwise at the speed of 0.03 mL/s, and then 1 drop (0.05mL) of catalyst is added dropwise. After the completion of the dropwise addition, the reaction was stirred for 2 hours. Dissolving tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid in tetrahydrofuran]And (4) pouring pentaerythritol ester into the four-neck flask, and supplementing the rest catalyst. The temperature was adjusted to 83 ℃. Stirring for 2.5 hours to finally obtain the transparent viscous acrylate monomer with the fluorine/damping function.
2) Adding deionized water and an emulsifier into a 1000mL four-neck flask provided with a stirring paddle, a condenser tube, a dropping funnel and a thermometer, dripping a mixture of a fluorine/damping function acrylate monomer, an acrylate monomer mixture, a crosslinking monomer 1 and a crosslinking monomer 2 obtained in the step 1) into the four-neck flask at the speed of 0.3mL/s, heating to 70 ℃, adding an initiator into the four-neck flask at the speed of 0.07mL/s, reacting for 4 hours under stirring, heating to 87 ℃, reacting for 1.5 hours under stirring, adding modified nanoparticles, and stirring for 0.5 hour to obtain the multifunctional aqueous emulsion.
The obtained multifunctional aqueous emulsion was measured at room temperature and 25 ℃ with GB/T2794-2013 by the single cylinder rotational viscometer method for measuring the viscosity of an adhesive with the use of NDJ-1 rotational viscometer provided by Shanghai Ruifeng instruments, Ltd., and the viscosity was 1100 mPas.
The obtained multifunctional water-based emulsion is measured by using a DMA242C type dynamic mechanical thermal analyzer of Germany Chiari corporation, and the stretching mode is adopted, the testing frequency is 1Hz, the testing temperature range is-80-200 ℃, and the heating rate is 5 ℃/min. The damping temperature range of the loss tangent tan delta is 0.3 and is-38-165 ℃.
The multifunctional water-based emulsion is formed into a film for 7 days at room temperature, the water contact angle of the film is measured according to GB/T30693-2014, and the water contact angle of the film is 117 degrees.
And (3) antifouling property test: coating pollutants (the handwriting of a real-color-brand water color pen) on the coating film, standing for 1h, then scrubbing the pollutants back and forth 100 times by using cotton cloth dipped with a washing powder aqueous solution with the concentration of 5%, washing with water, and then drying, wherein the pollutants are clean and have no stains. The result shows that the prepared multifunctional water-based emulsion film-forming material has better antifouling effect.
Therefore, the multifunctional aqueous emulsion obtained in the embodiment 2 has wide temperature range damping characteristics, and meets the application requirements of damping resin in the aspects of film forming property, hydrophobicity, viscosity, antifouling property and the like.
Example 3
The multifunctional water-based emulsion comprises the following raw materials in parts by weight:
wherein the acrylic ester monomer mixture is methyl acrylate, butyl acrylate and 2-ethylhexyl acrylate according to the mass ratio of 20: 5: 1; the crosslinking monomer 1 is diacetone acrylamide and adipic acid dihydrazide, and the mass ratio of the diacetone acrylamide to the adipic acid dihydrazide is 3: 1; the crosslinking monomer 2 is diethylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate according to the mass ratio of 8: 1; the emulsifier is sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and nonylphenol polyoxyethylene ether in a mass ratio of 3: 3: 1; the modified nano particles are modified nano SiO2Modified nano TiO2A mixture which is composed of the components according to the mass ratio of 1: 1; the initiator is ammonium persulfate.
The raw materials of the acrylate monomer with the fluorine/damping function comprise: the weight ratio is 130: 55: 110: 570: 150: 0.06 parts of 2,2,3,3,4,4,5, 5-octafluoro-1-pentanol, hydroxyethyl acrylate, isophorone diisocyanate, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tetrahydrofuran and a catalyst which is dibutyltin dilaurate.
The preparation method of the multifunctional water-based emulsion comprises the following steps:
1) 150g of isophorone diisocyanate was placed in a 2000mL round bottom four-neck flask in N2Under protection, after controlling the temperature to 35 ℃,2,3,3,4,4,5, 5-octafluoro-1-pentanol and hydroxyethyl acrylate are added into the system dropwise at the speed of 0.05mL/s, and then 1 drop (0.05mL) of catalyst is added dropwise. After the completion of the dropwise addition, the reaction was stirred for 2 hours. Dissolving tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid in tetrahydrofuran]And (4) pouring pentaerythritol ester into the four-neck flask, and supplementing the rest catalyst. The temperature was adjusted to 85 ℃. Stirring for 3 hours to finally obtain the transparent viscous acrylate monomer with the fluorine/damping function.
2) Adding deionized water and an emulsifier into a 1000mL four-neck flask provided with a stirring paddle, a condenser tube, a dropping funnel and a thermometer, dripping a mixture of a fluorine/damping function acrylate monomer, an acrylate monomer mixture, a crosslinking monomer 1 and a crosslinking monomer 2 obtained in the step 1) into the four-neck flask at the speed of 0.5mL/s, heating to 75 ℃, adding an initiator into the four-neck flask at the speed of 0.1mL/s, reacting for 5 hours under stirring, heating to 90 ℃, reacting for 2 hours under stirring, adding modified nanoparticles, and stirring for 0.5 hour to obtain the multifunctional aqueous emulsion.
The obtained multifunctional aqueous emulsion was measured at room temperature and 25 ℃ by using an NDJ-1 rotational viscometer provided by Shanghai Ruifeng instruments & ltLtd and GB/T2794-2013, Single Cylinder rotational viscometer method for measuring adhesive viscosity, and the viscosity was 630 mPas.
The obtained multifunctional water-based emulsion is measured by using a DMA242C type dynamic mechanical thermal analyzer of Germany Chiari corporation, and the stretching mode is adopted, the testing frequency is 1Hz, the testing temperature range is-80-200 ℃, and the heating rate is 5 ℃/min. The damping temperature range of the loss tangent tan delta is 0.3 and is-10 to 147 ℃.
The multifunctional water-based emulsion is formed into a film for 7 days at room temperature, the water contact angle of the film is measured according to GB/T30693-2014, and the water contact angle of the film is 110 degrees.
And (3) antifouling property test: coating pollutants (the handwriting of a real-color-brand water color pen) on the coating film, standing for 1h, then scrubbing the pollutants back and forth 100 times by using cotton cloth dipped with a washing powder aqueous solution with the concentration of 5%, washing with water, and then drying, wherein the pollutants are clean and have no stains. The result shows that the prepared multifunctional water-based emulsion film-forming material has better antifouling effect.
Therefore, the multifunctional aqueous emulsion obtained in the embodiment 3 has wide temperature range damping characteristics, and meets the application requirements of damping resin in the aspects of film forming property, hydrophobicity, viscosity, antifouling property and the like.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (9)
1. The multifunctional water-based emulsion is characterized by being prepared by an emulsion polymerization method, and the preparation raw materials comprise the following components in parts by weight:
wherein, the raw materials of the acrylate monomer with the fluorine/damping function comprise the following components in a weight ratio of 110-150: 50-60: 100-120: 550-600: 100-200: 0.01 to 1 of 2,2,3,3,4,4,5, 5-octafluoro-1-pentanol, hydroxyethyl acrylate, isophorone diisocyanate, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tetrahydrofuran and a catalyst; the catalyst is dibutyltin dilaurate.
2. The multifunctional aqueous emulsion of claim 1 wherein the acrylic monomer mixture is a combination of any of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, and cyclohexyl methacrylate.
3. The multifunctional aqueous emulsion according to claim 1, wherein the crosslinking monomer 1 is diacetone acrylamide and adipic acid dihydrazide, and the mass ratio of the diacetone acrylamide to the adipic acid dihydrazide is 1-3: 1.
4. The multifunctional aqueous emulsion of claim 1 wherein the crosslinking monomer 2 is dipentaerythritol hexaacrylate, diethylene glycol diacrylate, tetrahydrofuran acrylate, pentaerythritol tetraacrylate, ethoxylated bisphenol A dimethacrylate, ditrimethylolpropane tetraacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, isobornyl acrylate, tricyclodecane dimethanol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated trimethylolpropane triacrylate, hyperbranched polyester acrylates, alkoxy acrylates, carbonate monoacrylates, imidazolyl monoacrylates, crosslinked copolymers of ethylene glycol and propylene glycol, and mixtures thereof, At least one of cyclic carbonate monoacrylate, epoxy silicone monomer, silicone acrylate, and vinyl ether monomer.
5. The multifunctional aqueous emulsion of claim 1 wherein the emulsifier is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, alkyldiphenyl oxide disulfonate, ethoxylated ammonium alkyl phenol sulfate, nonylphenol polyoxyethylene ether, and isotridecyl alcohol polyoxyethylene ether; the initiator is ammonium persulfate and/or potassium persulfate; the modified nano particles are modified nano SiO2Modified nano TiO2And modified montmorillonite nanoparticles.
6. The multifunctional aqueous emulsion according to claim 2, wherein the acrylic ester monomer mixture is methyl acrylate and butyl acrylate in a mass ratio of 30: 10 or methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate in a mass ratio of 30: 20: 10: 10 or a mixture of methyl acrylate, butyl acrylate and 2-ethylhexyl acrylate in a mass ratio of 20: 5:1, in a mixture of the components.
7. The multifunctional aqueous emulsion according to claim 4, wherein the crosslinking monomer 2 is diethylene glycol diacrylate, or diethylene glycol diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated trimethylolpropane triacrylate and hyperbranched polyester acrylate in a mass ratio of 1: 1: 0.5: 0.3 or a mixture of diethylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate in a mass ratio of 8: 1, in a mixture of the components.
8. The multifunctional aqueous emulsion according to claim 5, wherein the emulsifier is a mixture of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate in a mass ratio of 1:1, or a mixture of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and nonylphenol polyoxyethylene ether in a mass ratio of 2: 2: 1 or sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and nonylphenol polyoxyethylene ether in the mass ratio of 3: 3:1, in a mixture of the components.
9. The multifunctional aqueous emulsion according to any one of claims 1 to 8, wherein the multifunctional aqueous emulsion has a viscosity of 160 to 1100mPa · s and a damping temperature range of-38 to 165 ℃ at a loss tangent tan δ of 0.3.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391410A (en) * | 2011-09-10 | 2012-03-28 | 中国十七冶集团有限公司 | Inorganic nano particle modified composite waterproof emulsion and preparation method thereof |
| CN107267034A (en) * | 2017-06-16 | 2017-10-20 | 上海应用技术大学 | A kind of long-acting weather-resistant type anticorrosive paint water-base resin and preparation method thereof |
| CN109438613A (en) * | 2018-10-23 | 2019-03-08 | 上海应用技术大学 | A kind of damping resin emulsion and preparation method thereof |
| CN112480304A (en) * | 2020-12-04 | 2021-03-12 | 上海应用技术大学 | Functional emulsion and preparation method thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391410A (en) * | 2011-09-10 | 2012-03-28 | 中国十七冶集团有限公司 | Inorganic nano particle modified composite waterproof emulsion and preparation method thereof |
| CN107267034A (en) * | 2017-06-16 | 2017-10-20 | 上海应用技术大学 | A kind of long-acting weather-resistant type anticorrosive paint water-base resin and preparation method thereof |
| CN109438613A (en) * | 2018-10-23 | 2019-03-08 | 上海应用技术大学 | A kind of damping resin emulsion and preparation method thereof |
| CN112480304A (en) * | 2020-12-04 | 2021-03-12 | 上海应用技术大学 | Functional emulsion and preparation method thereof |
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