CN111253823A - Fluorine-silicon-carbon automobile reflective heat insulation protective film and preparation method thereof - Google Patents

Fluorine-silicon-carbon automobile reflective heat insulation protective film and preparation method thereof Download PDF

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CN111253823A
CN111253823A CN202010026515.4A CN202010026515A CN111253823A CN 111253823 A CN111253823 A CN 111253823A CN 202010026515 A CN202010026515 A CN 202010026515A CN 111253823 A CN111253823 A CN 111253823A
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protective film
emulsion
insulation protective
difluoroethylene
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曲园园
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Zibo Vocational Institute
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Zibo Vocational Institute
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    • 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
    • C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/004—Reflecting paints; Signal paints
    • 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
    • C09D7/47—Levelling agents
    • 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
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    • C09D7/65—Additives macromolecular
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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Abstract

The invention relates to an automobile protective film, in particular to a fluorine-silicon-carbon automobile reflective heat-insulation protective film and a preparation method thereof. The feed is prepared from the following components in parts by mass: 50-80 parts of difluoroethylene and tetraene silane modified acrylate self-emulsifying emulsion, 2-10 parts of nano tin antimony oxide, 2-10 parts of nano indium tin oxide, 0.1-0.5 part of dispersing agent, 0.5-1.5 parts of defoaming agent, 0.2-1 part of flatting agent, 1-2 parts of protective adhesive and 55-100 parts of deionized water. According to the invention, difluoroethylene and tetraene silane modified acrylate self-emulsifying emulsion is used as a base material, so that the problems of poor sunlight radiation resistance effect and harmful gas emission of an automobile are solved; the nano antimony tin oxide and the nano indium tin oxide are selected as functional fillers, so that the protective film is safe, non-toxic and has excellent reflective heat insulation effect.

Description

Fluorine-silicon-carbon automobile reflective heat insulation protective film and preparation method thereof
Technical Field
The invention relates to an automobile protective film, in particular to a fluorine-silicon-carbon automobile reflective heat-insulation protective film and a preparation method thereof.
Background
Automobiles have been rapidly developed in recent years as a means of transportation for people going out daily. However, in hot summer, the solar radiation brings huge heat energy to the earth, the surface of the automobile body continuously absorbs the heat energy, the temperature in the automobile body is rapidly increased, and the use frequency of the automobile air conditioner is greatly improved in order to improve the comfort of the automobile. However, nowadays, energy conservation and consumption reduction become important research targets in the automobile field, and the preparation of the automobile paint capable of greatly reducing the absorption of solar energy by an automobile is an effective means for reducing the utilization rate of an automobile air conditioner and an effective way for saving energy and reducing consumption.
In addition, the production and coating of the automotive paint are carried out indoors, and the automotive paint is required to be free of volatile substances (VOC) due to factors such as production, health of coating workers and safety.
Chinese patent CN107841199A discloses an inorganic reflective heat-insulating automobile paint and a preparation method thereof, wherein the automobile paint comprises the following components in parts by weight: 8-12 parts of acrylic resin, 5-9 parts of amino resin, 36-44 parts of cellulose acetate butyrate, 4-7 parts of dispersing auxiliary agent, 6-10 parts of reflective heat-insulating pigment, 26-34 parts of solvent, 0.1-1 part of flatting agent and 0.1-1 part of UV auxiliary agent. The patent completely depends on adding inorganic reflective heat-insulating pigment to ensure that the prepared automobile paint has a reflective heat-insulating function, can not be sprayed on the parts of windows which absorb much heat, and is only sprayed on the metal parts of automobiles.
Chinese patent CN106634370A discloses an environment-friendly washable and washable automobile heat-preservation and color-preservation heat-insulation paint and a preparation method thereof. The heat insulation paint is prepared from the following components in parts by mass: 45-80 parts of carbon-silicon-fluorine colored self-emulsifying emulsion, 20-40 parts of functional filler, 0.2-1 part of wetting dispersant, 0.2-1 part of water-based organic silicon defoamer, 0.2-1 part of organic silicon flatting agent and 50-110 parts of deionized water. The automobile paint has the heat preservation and insulation functions mainly by adding the micro-fine silica aerogel and the yttrium oxide with the heat insulation function, but does not have the functions of reflecting ultraviolet light and infrared light, so the heat insulation effect is poor, and in addition, the colored paint provided by the patent cannot be coated in a whole automobile.
Chinese patent CN108456445A discloses a reflective heat-insulating automobile finish paint and a preparation method thereof. The automobile finish comprises the following components in percentage by mass: 50-65% of water-based acrylic resin, 0.5-1.5% of pH regulator, 6-10% of cosolvent, 0.3-1% of defoaming agent, 0.5-2.5% of infrared reflection component, 15-20% of double-component amino resin, 0.3-0.6% of flatting agent and 5-20% of deionized water. The film forming material of the patent adopts water-based acrylic resin which does not scatter ultraviolet light and infrared light in sunlight, and the prepared automobile finish has poor sunlight irradiation reflection effect.
At present, it is needed to provide a protective paint for automobiles, which has excellent radiation resistance and heat insulation performance, does not discharge volatile substances, and can be simultaneously sprayed on the surfaces of windshields and colored paints of automobiles.
Disclosure of Invention
The invention aims to provide a fluorine-silicon-carbon automobile reflection heat insulation protective film which has excellent radiation resistance and heat insulation performance, has no discharge of volatile substances, and can be simultaneously sprayed on the surfaces of windshields and automobile colored paint; the invention also provides a preparation method thereof.
The fluorine-silicon-carbon automobile reflective heat insulation protective film is prepared from the following components in parts by mass:
Figure BDA0002362671320000021
wherein:
the self-emulsifying emulsion of difluoroethylene and tetraene silane modified acrylate is prepared from the following components in parts by weight:
Figure BDA0002362671320000022
the preparation method of the self-emulsifying emulsion of difluoroethylene and tetraene silane modified acrylate comprises the following steps:
(1) adding 5-10 parts of tetraene silane, 3-9 parts of urea heterocyclic compound containing double bonds, 5-16 parts of 1, 1-difluoroethylene, 50-100 parts of methyl methacrylate, 30-90 parts of butyl acrylate and 0.5-4 parts of acrylic acid into a container, and uniformly stirring to obtain a mixed monomer;
(2) adding 200-500 parts of deionized water, 1-2 parts of propyleneoxypropylalkylphenol polyether sulfate, 1-3 parts of double bond-containing polyether and 0.5-2 parts of potassium persulfate into a reaction kettle, introducing nitrogen, stirring, pre-emulsifying for 2-3 hours, and heating to 83-95 ℃ to obtain a pre-emulsion;
(3) keeping the temperature of the pre-emulsion at 83-95 ℃, dropwise adding the mixed monomer obtained in the step (1) into the pre-emulsion for 4-6 hours;
(4) after the dropwise addition is finished, raising the temperature of the emulsion to 95-105 ℃, keeping the temperature for 40-80 min, and cooling to room temperature;
(5) and adjusting the pH value to 6.8-7.2 by using ammonia water to obtain the self-emulsifying emulsion of the difluoroethylene and the tetraene silane modified acrylate.
The nano antimony tin oxide and the nano indium tin oxide are preferably products of Shanghai Chaowei nanometer technology Co.
The defoaming agent is an organic modified siloxane defoaming agent, preferably ONIST DF-589 of Shanghai loyal fine chemical industry Co.
The dispersant is organosilicon modified polyether phosphate, preferably organosilicon modified polyether phosphate DISP-160 of Shanghai loyal fine chemical Co.
The flatting agent is a polyurethane type flatting agent, preferably polyurethane type LEV202 of Shanghai loyal fine chemical Co.
The protective adhesive is a methacrylic acid sodium salt polymer, preferably methacrylic acid sodium salt polymer ONIST PMA-38 of Shanghai loyalty fine chemical industry Co.
The double-bond-containing urea heterocyclic compound is preferably a double-bond-containing urea heterocyclic compound V-50M.
The propylene oxy-propyl alkylphenol polyether sulfate is an emulsifier, and is preferably propylene oxy-propyl alkylphenol polyether sulfate ONISTV-20S of Shanghai loyal fine chemical Co.
The polyether containing double bond groups is used as an emulsifier, and preferably, the double bond group-containing polyether AE320 of Shanghai loyal fine chemical Co.
The preparation method of the fluorine-silicon-carbon automobile reflective heat insulation protective film comprises the following steps:
adding the nano tin antimony oxide, the nano indium tin oxide, the dispersing agent, the leveling agent, the protective glue and the deionized water in the formula ratio into a dispersion machine for primary dispersion treatment; and then adding difluoroethylene, tetraene silane modified acrylate self-emulsifying emulsion and a defoaming agent for secondary dispersion treatment, and finally adding into a conical mill for grinding to 10-30 mu m, and discharging.
Wherein:
the first dispersion treatment is to disperse for 0.5 to 1.5 hours at a rotation speed of 450 to 550rpm, preferably for 1 hour at a rotation speed of 500rpm, and then disperse for 1.0 to 2.0 hours at a rotation speed of 2400 to 2600rpm, preferably for 1 hour at a rotation speed of 2500 rpm.
The re-dispersing treatment is performed at the rotating speed of 2400-2600 rpm for 0.5-1 hour.
According to the invention, 1-difluoroethylene is adopted to prepare the film forming material of the automobile reflective heat-insulation protective film, so that the automobile reflective heat-insulation protective film has good high temperature resistance and weather resistance, and can effectively scatter ultraviolet light and near infrared light in sunlight; the added nano tin antimony oxide has good heat insulation performance, and the nano indium tin oxide has ultraviolet rays and near infrared rays which can cut off and rapidly raise the temperature in the vehicle; in addition, the difluoroethylene and tetraethynylsilane modified acrylate self-emulsifying emulsion, the nano tin antimony oxide and the nano indium tin oxide which are used for preparing the automobile reflective heat-insulation protective film have good visible light transmittance, so that the visible light transmittance of the prepared automobile reflective heat-insulation protective film can reach over 84 percent, the automobile reflective heat-insulation protective film can be sprayed and installed on a whole automobile, the construction is easy, and the reflective heat-insulation effect is excellent.
The invention has the following beneficial effects:
(1) according to the invention, the difluoroethylene and the tetraene silane are used for modifying the acrylate self-emulsifying emulsion through free radical polymerization to form a high-molecular long chain with difluoroethylene, organic silicon and acrylate chain segments, so that the difluoroethylene and tetraene silane modified acrylate self-emulsifying emulsion has the characteristics of effective scattering of ultraviolet light and near infrared light in sunlight by difluoroethylene, excellent weather resistance and washing resistance of tetraene silane and excellent weather resistance and adhesive force of acrylate;
the invention takes the difluoroethylene and tetraene silane modified acrylate self-emulsifying emulsion as the base material, solves the problem of harmful gas emission in the production and coating processes, and simultaneously provides the capability of the automobile reflective heat-insulating protective film for resisting ultraviolet radiation in sunlight.
(2) The nanometer antimony tin oxide and the nanometer indium tin oxide have higher reflectivity of ultraviolet light and near infrared light, and the nanometer antimony tin oxide and the nanometer indium tin oxide are used as functional fillers, so that the prepared automobile reflective heat-insulating protective film has excellent resistance to radiation of ultraviolet light and infrared light in sunlight.
(3) The added organic modified siloxane defoaming agent can eliminate bubbles generated in the production and spraying processes of the automobile reflective heat-insulating protective film, prevent a paint film from generating pinholes, and prevent the attractiveness and the adhesive force of the protective film from being damaged; the added dispersant can enable the inorganic filler nano tin antimony oxide and nano indium oxide to be uniformly dispersed in the automobile reflective heat insulation protective film to prevent the inorganic filler nano tin antimony oxide and nano indium oxide from settling; the added leveling agent has the function of improving the leveling performance of the automobile protective film, so that the protective film sprayed on the surface of an automobile can form a complete and uniform film; the added protective adhesive can improve the freeze-thaw resistance stability and the heat storage stability of the automobile protective film and reduce the limitation of the coating temperature of the automobile protective film.
(4) The preparation method is simple and easy to implement, and can be sprayed on the surfaces of windshields and automobile colored paint simultaneously.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The fluorine-silicon-carbon automobile reflective heat insulation protective film is prepared according to the following steps:
(1) 50 parts of difluoroethylene and tetraene silane modified acrylate self-emulsifying emulsion by mass, which comprises the following preparation steps:
a. adding 5 parts of tetraene silane, 3 parts of urea heterocyclic compound V-50M containing double bonds, 5 parts of 1, 1-difluoroethylene, 50 parts of methyl methacrylate, 30 parts of butyl acrylate and 0.5 part of acrylic acid into a four-mouth bottle, and uniformly stirring to obtain a mixed monomer;
b. adding 250 parts of deionized water, 1 part of acryloxypropyl alkylphenol polyether sulfate ONISTV-20S, 1 part of polyether AE320 containing double bond groups and 0.5 part of potassium persulfate into a reaction kettle, introducing nitrogen, starting an electric stirrer for stirring, pre-emulsifying for 2 hours, and heating to 83 ℃ to obtain pre-emulsion;
c. keeping the pre-emulsion at 83 ℃, dropwise adding the mixed monomer obtained in the step (1) into the pre-emulsion for 4 hours;
d. after the dropwise addition is finished, the temperature of the emulsion is raised to 95 ℃, kept for 40min and cooled to room temperature;
e. and adjusting the pH value to 7 by adopting 0.5 part of ammonia water to obtain the self-emulsifying emulsion of the difluoroethylene and the tetraene silane modified acrylate.
(2) Preparing a fluorine-silicon-carbon automobile reflective heat insulation protective film:
adding 2 parts of nano tin antimony oxide, 2 parts of nano indium tin oxide, 0.1 part of organic silicon modified polyether phosphate DISP-160, 0.2 part of polyurethane LEV202, 1 part of methacrylic acid sodium salt polymer ONIST PMA-38 and 60 parts of deionized water into a high-speed dispersion machine, firstly dispersing for 1 hour at the rotating speed of 500rpm, and then regulating the rotating speed to 2500rpm and dispersing for 1.0 hour; then adding 50 parts of self-emulsifying emulsion of difluoroethylene and tetraene silane modified acrylate and 0.5 part of ONIST DF-589 as an organic modified siloxane defoaming agent, dispersing for 0.5 hour at the rotating speed of 2500rpm, finally adding into a conical mill, grinding to 10-30 mu m, and discharging to obtain the fluorosilicone carbon automobile reflective heat insulation protective film.
The performance test of the fluorine-silicon-carbon automobile reflective heat insulation protective film is as follows:
a the normal temperature thermal conductivity of the protective film is 0.050 W.m according to GB/T10297-1998-1·K-1；
b, the visible light transmittance of the protective film is 84%, the near infrared reflectivity is 72%, and the ultraviolet reflectivity is 71%;
c, measuring the scrubbing resistance according to GB/T9266-2009, 24900 times;
d, detecting the adhesive force according to GB/T1720-79, wherein the standard is grade 1;
e impact resistance, detected according to GB/T1732-79, with the standard of 4.9 Nm;
f, artificial weather aging resistance, according to GB/T1865-1997 detection, according to GB/T1766-1995 rating, 1000h, the damage degree, the light loss grade, the discoloration grade, the chalking grade, the cracking grade, the foaming grade, the rusting grade, the spalling grade, the mildew grade and the spot grade are all 0 grades.
Example 2
The fluorine-silicon-carbon automobile reflective heat insulation protective film is prepared according to the following steps:
(1) 60 parts of difluoroethylene and tetraene silane modified acrylate self-emulsifying emulsion by mass, which comprises the following preparation steps:
a. adding 7 parts of tetraene silane, 4 parts of urea heterocyclic compound V-50M containing double bonds, 7 parts of 1, 1-difluoroethylene, 65 parts of methyl methacrylate, 45 parts of butyl acrylate and 1 part of acrylic acid into a four-mouth bottle, and uniformly stirring to obtain a mixed monomer;
b. adding 300 parts of deionized water, 1 part of acryloxypropyl alkylphenol polyether sulfate ONISTV-20S, 1 part of polyether AE320 containing double bond groups and 0.8 part of potassium persulfate into a reaction kettle, introducing nitrogen, starting an electric stirrer for stirring, pre-emulsifying for 2.5 hours, and heating to 87 ℃ to obtain pre-emulsion;
c. keeping the temperature of the pre-emulsion at 87 ℃, dropwise adding the mixed monomer obtained in the step (1) into the pre-emulsion for 5 hours;
d. after the dropwise addition is finished, the temperature of the emulsion is increased to 97 ℃, kept for 50min and cooled to room temperature;
e. and adjusting the pH value to 7 by using 1 part of ammonia water to obtain the self-emulsifying emulsion of the difluoroethylene and the tetraene silane modified acrylate.
(2) Preparing a fluorine-silicon-carbon automobile reflective heat insulation protective film:
adding 3 parts of nano tin antimony oxide, 4 parts of nano indium tin oxide, 0.2 part of organic silicon modified polyether phosphate DISP-160, 0.5 part of polyurethane LEV202, 1 part of methacrylic acid sodium salt polymer ONIST PMA-38 and 80 parts of deionized water into a high-speed dispersion machine according to the formula ratio, firstly dispersing at the rotating speed of 500rpm for 1 hour, and then regulating the rotating speed to 2500rpm for dispersing for 1.5 hours; then 60 parts of difluoroethylene and tetraene silane modified acrylate self-emulsifying emulsion and 1 part of organic modified siloxane defoamer ONIST DF-589 are added, dispersed for 1 hour at the rotating speed of 2500rpm, and finally added into a conical mill to be ground to 20-30 mu m, and discharged, so that the fluorine-silicon-carbon automobile reflective heat-insulation protective film is obtained.
The performance test of the fluorine-silicon-carbon automobile reflective heat insulation protective film is as follows:
a the normal temperature thermal conductivity of the protective film is 0.049 W.m according to GB/T10297-1998-1·K-1；
b, the visible light transmittance of the protective film is 85%, the near infrared reflectivity is 74%, and the ultraviolet reflectivity is 73%;
c, measuring the scrubbing resistance, according to GB/T9266-2009, 24800 times;
d, detecting the adhesive force according to GB/T1720-79, wherein the standard is grade 1;
e impact resistance, detected according to GB/T1732-79, with the standard of 4.9 Nm;
f, artificial weather aging resistance, according to GB/T1865-1997 detection, according to GB/T1766-1995 grading, 1200h, wherein the damage degree, the light loss grade, the discoloration grade, the chalking grade, the cracking grade, the foaming grade, the rusting grade, the spalling grade, the mildew grade and the spot grade are all 0 grades.
Example 3
The fluorine-silicon-carbon automobile reflective heat insulation protective film is prepared according to the following steps:
(1) the self-emulsifying emulsion of difluoroethylene and tetraene silane modified acrylate comprises 80 parts by mass of the following preparation steps:
a. adding 8 parts of tetraene silane, 8 parts of urea heterocyclic compound V-50M containing double bonds, 9 parts of 1, 1-difluoroethylene, 100 parts of methyl methacrylate, 90 parts of butyl acrylate and 2 parts of acrylic acid into a four-mouth bottle, and uniformly stirring to obtain a mixed monomer;
b. adding 400 parts of deionized water, 1 part of acryloxypropyl alkylphenol polyether sulfate ONISTV-20S, 1 part of double bond-containing polyether AE320 and 1 part of potassium persulfate into a reaction kettle, introducing nitrogen, starting an electric stirrer to stir, pre-emulsifying for 3 hours, and heating to 90 ℃ to obtain pre-emulsion;
c. keeping the pre-emulsion at 90 ℃, dropwise adding the mixed monomer obtained in the step (1) into the pre-emulsion for 6 hours;
d. after the dropwise addition is finished, the temperature of the emulsion is raised to 95 ℃, kept for 60min and then cooled to room temperature;
e. and adjusting the pH value to 7 by using 1.5 parts of ammonia water to obtain the self-emulsifying emulsion of the difluoroethylene and the tetraene silane modified acrylate.
(2) Preparing a fluorine-silicon-carbon automobile reflective heat insulation protective film:
adding 4 parts of nano tin antimony oxide, 5 parts of nano indium tin oxide, 0.3 part of organic silicon modified polyether phosphate DISP-160, 0.6 part of polyurethane LEV202, 2 parts of methacrylic acid sodium salt polymer ONIST PMA-38 and 70 parts of deionized water into a high-speed dispersion machine according to the formula ratio, firstly dispersing at the rotating speed of 500rpm for 1 hour, and then regulating the rotating speed to 2500rpm for dispersing for 1 hour; and then adding 80 parts of difluoroethylene and tetraene silane modified acrylate self-emulsifying emulsion and 1 part of organic modified siloxane defoamer ONIST DF-589, dispersing for 1 hour at the rotating speed of 2500rpm, finally adding into a conical mill, grinding to 10-30 mu m, and discharging to obtain the fluorosilicone automobile reflective heat insulation protective film.
The performance test of the fluorine-silicon-carbon automobile reflective heat insulation protective film is as follows:
a the normal temperature thermal conductivity of the protective film is 0.052 W.m according to GB/T10297-1998-1·K-1；
b, the visible light transmittance of the protective film is 84%, the near infrared reflectivity is 78%, and the ultraviolet reflectivity is 77%;
c, measuring the scrubbing resistance for 25500 times according to GB/T9266-;
d, detecting the adhesive force according to GB/T1720-79, wherein the standard is grade 1;
e impact resistance, detected according to GB/T1732-79, with the standard of 4.9 Nm;
f, artificial weather aging resistance, according to GB/T1865-1997 detection, according to GB/T1766-1995 rating, 1100h, breakage degree, light loss rating, discoloration rating, chalking rating, cracking rating, foaming rating, rusting rating, peeling rating, mildew rating and spot rating are all 0 grades.
Example 4
The fluorine-silicon-carbon automobile reflective heat insulation protective film is prepared according to the following steps:
(1) 60 parts of difluoroethylene and tetraene silane modified acrylate self-emulsifying emulsion by mass, which comprises the following preparation steps:
a. adding 10 parts of tetraene silane, 9 parts of urea heterocyclic compound V-50M containing double bonds, 16 parts of 1, 1-difluoroethylene, 100 parts of methyl methacrylate, 80 parts of butyl acrylate and 2 parts of acrylic acid into a four-mouth bottle, and uniformly stirring to obtain a mixed monomer;
b. adding 350 parts of deionized water, 2 parts of acryloxypropyl alkylphenol polyether sulfate ONISTV-20S, 2 parts of double bond-containing polyether AE320 and 1 part of potassium persulfate into a reaction kettle, introducing nitrogen, starting an electric stirrer to stir, pre-emulsifying for 2 hours, and heating to 85 ℃ to obtain pre-emulsion;
c. keeping the pre-emulsion at 85 ℃, dropwise adding the mixed monomer obtained in the step (1) into the pre-emulsion for 5 hours;
d. after the dropwise addition is finished, the temperature of the emulsion is raised to 95 ℃, kept for 60min and then cooled to room temperature;
e. and adjusting the pH value to 7 by using 1.2 parts of ammonia water to obtain the self-emulsifying emulsion of the difluoroethylene and the tetraene silane modified acrylate.
(2) Preparing a fluorine-silicon-carbon automobile reflective heat insulation protective film:
adding 3 parts of nano antimony tin oxide, 3 parts of nano indium tin oxide, 0.3 part of organic silicon modified polyether phosphate DISP-160, 0.4 part of polyurethane LEV202, 2 parts of methacrylic acid sodium salt polymer ONIST PMA-38 and 100 parts of deionized water into a high-speed dispersion machine, firstly dispersing for 1 hour at the rotating speed of 500rpm, and then regulating the rotating speed to 2500rpm for dispersing for 2 hours; then 60 parts of difluoroethylene and tetraene silane modified acrylate self-emulsifying emulsion and 1 part of organic modified siloxane defoamer ONIST DF-589 are added, dispersed for 1 hour at the rotating speed of 2500rpm, and finally added into a conical mill to be ground to 10-30 mu m, and discharged, so that the fluorine-silicon-carbon automobile reflective heat-insulation protective film is obtained.
The performance test of the fluorine-silicon-carbon automobile reflective heat insulation protective film is as follows:
a the normal temperature thermal conductivity of the protective film is 0.055 W.m according to GB/T10297-1998-1·K-1；
b, the visible light transmittance of the protective film is 85%, the near infrared reflectivity is 75%, and the ultraviolet reflectivity is 76%;
c, measuring the scrubbing resistance for 25800 times according to GB/T9266-2009;
d, detecting the adhesive force according to GB/T1720-79, wherein the standard is grade 1;
e impact resistance, detected according to GB/T1732-79, with the standard of 4.9 Nm;
f, artificial weather aging resistance, according to GB/T1865-1997 detection, according to GB/T1766-1995 rating, 1000h, the damage degree, the light loss grade, the discoloration grade, the chalking grade, the cracking grade, the foaming grade, the rusting grade, the spalling grade, the mildew grade and the spot grade are all 0 grades.
Example 5
The fluorine-silicon-carbon automobile reflective heat insulation protective film is prepared according to the following steps:
(1) the self-emulsifying emulsion of difluoroethylene and tetraene silane modified acrylate comprises 80 parts by mass of the following preparation steps:
a. adding 5 parts of tetraene silane, 8 parts of urea heterocyclic compound V-50M containing double bonds, 10 parts of 1, 1-difluoroethylene, 100 parts of methyl methacrylate, 90 parts of butyl acrylate and 4 parts of acrylic acid into a four-mouth bottle, and uniformly stirring to obtain a mixed monomer;
b. adding 450 parts of deionized water, 2 parts of acryloxypropyl alkylphenol polyether sulfate ONISTV-20S, 2 parts of double bond-containing polyether AE320 and 1 part of potassium persulfate into a reaction kettle, introducing nitrogen, starting an electric stirrer to stir, pre-emulsifying for 3 hours, and heating to 88 ℃ to obtain pre-emulsion;
c. keeping the temperature of the pre-emulsion at 88 ℃, dropwise adding the mixed monomer obtained in the step (1) into the pre-emulsion for 5 hours;
d. after the dropwise addition is finished, the temperature of the emulsion is raised to 95 ℃, kept for 60min and then cooled to room temperature;
e. and adjusting the pH value to 7 by using 1.8 parts of ammonia water to obtain the self-emulsifying emulsion of the difluoroethylene and the tetraene silane modified acrylate.
(2) Preparing a fluorine-silicon-carbon automobile reflective heat insulation protective film:
adding 3 parts of nano antimony tin oxide, 5 parts of nano indium tin oxide, 0.4 part of organic silicon modified polyether phosphate DISP-160, 0.8 part of polyurethane LEV202, 2 parts of methacrylic acid sodium salt polymer ONIST PMA-38 and 90 parts of deionized water into a high-speed dispersion machine according to the formula ratio, firstly dispersing at the rotating speed of 500rpm for 1 hour, and then regulating the rotating speed to 2500rpm for dispersing for 1.5 hours; and then adding 80 parts of self-emulsifying emulsion of difluoroethylene and tetraene silane modified acrylate and 0.5 part of ONIST DF-589 as an organic modified siloxane defoaming agent, dispersing for 1 hour at the rotating speed of 2500rpm, finally adding into a conical mill, grinding to 10-30 mu m, and discharging to obtain the fluorine-silicon-carbon automobile reflective heat-insulation protective film.
The performance test of the fluorine-silicon-carbon automobile reflective heat insulation protective film is as follows:
a the normal temperature thermal conductivity of the protective film is 0.055 W.m according to GB/T10297-1998-1·K-1；
b, the visible light transmittance of the protective film is 84%, the near infrared reflectivity is 73%, and the ultraviolet reflectivity is 76%;
c, measuring the scrubbing resistance for 25600 times according to GB/T9266-2009;
d, detecting the adhesive force according to GB/T1720-79, wherein the standard is grade 1;
e impact resistance, detected according to GB/T1732-79, with the standard of 4.9 Nm;
f, artificial weather aging resistance, according to GB/T1865-1997 detection, according to GB/T1766-1995 rating, 900h, breakage degree, light loss rating, discoloration rating, chalking rating, cracking rating, foaming rating, rusting rating, peeling rating, mildew rating and spot rating are all 0.
Comparative example 1
The same procedure as in example 1 was repeated except that 1, 1-difluoroethylene and tetraethoxysilane were not added to the acrylic ester self-emulsifying emulsion, i.e., the acrylic ester self-emulsifying emulsion was not modified.
The protective film was subjected to the following performance test:
a the normal temperature thermal conductivity of the protective film is 0.100 W.m according to GB/T10297-1998-1·K-1；
b, the visible light transmittance of the protective film is 84%, the near infrared reflectivity is 45%, and the ultraviolet reflectivity is 42%;
c, measuring the scrubbing resistance for 5000 times according to GB/T9266-;
d, detecting the adhesive force according to GB/T1720-79, wherein the standard is grade 1;
e impact resistance, measured according to GB/T1732-79, with a standard of 3.2 Nm.
f, artificial weather aging resistance, according to GB/T1865-1997 detection, according to GB/T1766-1995 grading, 300h, wherein the damage degree, the light loss grade, the discoloration grade, the chalking grade, the cracking grade, the foaming grade, the rusting grade, the spalling grade, the mildew grade and the spot grade are all 3 grades.
Comparative example 2
The preparation of the acrylate self-emulsifying emulsion is carried out without adding tetraethylene silane, i.e. only 1, 1-difluoroethylene is used to modify the acrylate self-emulsifying emulsion, and the rest steps are the same as in example 1.
The protective film was subjected to the following performance test:
a the normal temperature thermal conductivity of the protective film is 0.070 W.m according to GB/T10297-1998-1·K-1；
b, the visible light transmittance of the protective film is 84%, the near infrared reflectivity is 72%, and the ultraviolet reflectivity is 76%;
c, measuring the scrubbing resistance for 18000 times according to GB/T9266-2009;
d, detecting the adhesive force according to GB/T1720-79, wherein the standard is grade 1;
e impact resistance, measured according to GB/T1732-79, with a standard of 4.0 Nm.
f, artificial weather aging resistance, according to GB/T1865-1997 detection, according to GB/T1766-1995 grading, 800h, wherein the damage degree, the light loss grade, the discoloration grade, the chalking grade, the cracking grade, the foaming grade, the rusting grade, the spalling grade, the mildew grade and the spot grade are all 1 grade.
Comparative example 3
The same procedure as in example 1 was repeated except that 1, 1-difluoroethylene was not added to the acrylic ester self-emulsifying emulsion, that is, only tetraene silane was used to modify the acrylic ester self-emulsifying emulsion.
The protective film was subjected to the following performance test:
a the normal temperature thermal conductivity of the protective film is 0.090 W.m according to GB/T10297-1998-1·K-1；
b, the visible light transmittance of the protective film is 84%, the near infrared reflectivity is 43%, and the ultraviolet reflectivity is 41%;
c, measuring the scrubbing resistance according to GB/T9266-2009, 15000 times;
d, detecting the adhesive force according to GB/T1720-79, wherein the standard is grade 1;
e impact resistance, measured according to GB/T1732-79, with a standard of 4.7 Nm.
f, artificial weather aging resistance, according to GB/T1865-1997 detection, according to GB/T1766-1995 grading, 800h, wherein the damage degree, the light loss grade, the discoloration grade, the chalking grade, the cracking grade, the foaming grade, the rusting grade, the spalling grade, the mildew grade and the spot grade are all 1 grade.
Comparative example 4
The steps are the same as those in example 1 except that nano tin antimony oxide is not added during the preparation of the fluorine silicon carbon automobile reflective heat insulation protective film.
The protective film was subjected to the following performance test:
a measurement of the normal temperature thermal conductivity of the protective film according to GB/T10297 & lt, 297 & gt, 1998, is 0.080 W.m-1·K-1；
b, the visible light transmittance of the protective film is 85%, the near infrared reflectivity is 51%, and the ultraviolet reflectivity is 49%;
c, measuring the scrubbing resistance, and performing 25000 times according to GB/T9266-;
d, detecting the adhesive force according to GB/T1720-79, wherein the standard is grade 1;
e impact resistance, measured according to GB/T1732-79, with a standard of 4.9 Nm.
f, artificial weather aging resistance, according to GB/T1865-1997 detection, according to GB/T1766-1995 rating, 1000h, the damage degree, the light loss grade, the discoloration grade, the chalking grade, the cracking grade, the foaming grade, the rusting grade, the spalling grade, the mildew grade and the spot grade are all 0 grades.
Comparative example 5
The steps of preparing the fluorinated silicon carbon reflective heat insulation protective film for the automobile are the same as those of the example 1 without adding the nano indium tin oxide.
The protective film was subjected to the following performance test:
a the normal temperature thermal conductivity of the protective film is 0.090 W.m according to GB/T10297-1998-1·K-1；
b, the visible light transmittance of the protective film is 84%, the near infrared reflectivity is 43%, and the ultraviolet reflectivity is 42%;
c, measuring the scrubbing resistance, and performing 25000 times according to GB/T9266-;
d, detecting the adhesive force according to GB/T1720-79, wherein the standard is grade 1;
e impact resistance, measured according to GB/T1732-79, with a standard of 4.9 Nm.
f, artificial weather aging resistance, according to GB/T1865-1997 detection, according to GB/T1766-1995 rating, 1000h, the damage degree, the light loss grade, the discoloration grade, the chalking grade, the cracking grade, the foaming grade, the rusting grade, the spalling grade, the mildew grade and the spot grade are all 0 grades.

Claims (10)

1. The fluorine-silicon-carbon automobile reflective heat insulation protective film is characterized by being prepared from the following components in parts by mass:
Figure FDA0002362671310000011
2. the fluorosilicone carbon automobile reflective insulation protective film according to claim 1, characterized in that: the self-emulsifying emulsion of difluoroethylene and tetraene silane modified acrylate is prepared from the following components in parts by weight:
Figure FDA0002362671310000012
3. the fluorosilicone carbon automobile reflective insulation protective film according to claim 2, characterized in that: the preparation method of the self-emulsifying emulsion of difluoroethylene and tetraene silane modified acrylate comprises the following steps:
(1) adding 5-10 parts of tetraene silane, 3-9 parts of urea heterocyclic compound containing double bonds, 5-16 parts of 1, 1-difluoroethylene, 50-100 parts of methyl methacrylate, 30-90 parts of butyl acrylate and 0.5-4 parts of acrylic acid into a container, and uniformly stirring to obtain a mixed monomer;
(2) adding 200-500 parts of deionized water, 1-2 parts of propyleneoxypropylalkylphenol polyether sulfate, 1-3 parts of double bond-containing polyether and 0.5-2 parts of potassium persulfate into a reaction kettle, introducing nitrogen, stirring, pre-emulsifying for 2-3 hours, and heating to 83-95 ℃ to obtain a pre-emulsion;
(3) keeping the temperature of the pre-emulsion at 83-95 ℃, dropwise adding the mixed monomer obtained in the step (1) into the pre-emulsion for 4-6 hours;
(4) after the dropwise addition is finished, raising the temperature of the emulsion to 95-105 ℃, keeping the temperature for 40-80 min, and cooling to room temperature;
(5) and adjusting the pH value to 6.8-7.2 by using ammonia water to obtain the self-emulsifying emulsion of the difluoroethylene and the tetraene silane modified acrylate.
4. The fluorosilicone carbon automobile reflective insulation protective film according to claim 1, characterized in that: the defoaming agent is an organic modified siloxane defoaming agent.
5. The fluorosilicone carbon automobile reflective insulation protective film according to claim 1, characterized in that: the dispersing agent is organic silicon modified polyether phosphate.
6. The fluorosilicone carbon automobile reflective insulation protective film according to claim 1, characterized in that: the leveling agent is a polyurethane type leveling agent.
7. The fluorosilicone carbon automobile reflective insulation protective film according to claim 1, characterized in that: the protective glue is a methacrylic acid sodium salt polymer.
8. A preparation method of the fluorinated silicone carbon automobile reflective insulation protective film according to any one of claims 1 to 7, characterized by comprising the following steps:
adding the nano tin antimony oxide, the nano indium tin oxide, the dispersing agent, the leveling agent, the protective glue and the deionized water in the formula ratio into a dispersion machine for primary dispersion treatment; and then adding difluoroethylene and tetraene silane modified acrylate self-emulsifying emulsion and a defoaming agent for secondary dispersion treatment, and finally adding into a conical mill for grinding to 10-30 mu m, and discharging.
9. The preparation method of the fluorosilicone carbon automobile reflective insulation protective film according to claim 8, characterized in that: the primary dispersing treatment is to firstly disperse for 0.5 to 1.5 hours at the rotating speed of 450 to 550rpm, and then disperse for 1.0 to 2.0 hours at the rotating speed of 2400 to 2600 rpm.
10. The preparation method of the fluorosilicone carbon automobile reflective insulation protective film according to claim 8, characterized in that: the re-dispersing treatment is performed at the rotating speed of 2400-2600 rpm for 0.5-1 hour.
CN202010026515.4A 2020-01-10 2020-01-10 Fluorine-silicon-carbon automobile reflective heat insulation protective film and preparation method thereof Pending CN111253823A (en)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
CN101629041A (en) * 2009-02-26 2010-01-20 深圳市德厚科技有限公司 Transparent heat-insulated paint based on nano spectral selectivity compound oxide
CN106634370A (en) * 2016-10-11 2017-05-10 淄博职业学院 Environment-friendly scrubbing-resistant automobile heat-preservation color-retention heat-insulation paint and preparation method thereof
CN106752526A (en) * 2016-12-23 2017-05-31 沈阳化工研究院有限公司 A kind of aqueous light reflection industrial heat preservation coating and preparation method thereof
CN109354939A (en) * 2018-11-02 2019-02-19 浙江华德新材料有限公司 Low-VOC aqueous insulating glass coating of environment-friendly type and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101629041A (en) * 2009-02-26 2010-01-20 深圳市德厚科技有限公司 Transparent heat-insulated paint based on nano spectral selectivity compound oxide
CN106634370A (en) * 2016-10-11 2017-05-10 淄博职业学院 Environment-friendly scrubbing-resistant automobile heat-preservation color-retention heat-insulation paint and preparation method thereof
CN106752526A (en) * 2016-12-23 2017-05-31 沈阳化工研究院有限公司 A kind of aqueous light reflection industrial heat preservation coating and preparation method thereof
CN109354939A (en) * 2018-11-02 2019-02-19 浙江华德新材料有限公司 Low-VOC aqueous insulating glass coating of environment-friendly type and preparation method thereof

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