CN108929609B - Packaging type modified graphene oxide/polyacrylate nano composite coating agent and preparation method thereof - Google Patents
Packaging type modified graphene oxide/polyacrylate nano composite coating agent and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 44
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 27
- 239000011248 coating agent Substances 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims abstract description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims description 40
- 238000009210 therapy by ultrasound Methods 0.000 claims description 30
- 239000003999 initiator Substances 0.000 claims description 28
- 239000000839 emulsion Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- 239000002131 composite material Substances 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 24
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 15
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 238000010907 mechanical stirring Methods 0.000 claims description 9
- 238000010008 shearing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000010985 leather Substances 0.000 abstract description 14
- 230000002209 hydrophobic effect Effects 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract 1
- 238000011160 research Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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
- 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
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
-
- 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
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Abstract
The invention relates to a preparation method of an encapsulated modified graphene oxide/polyacrylate nano-composite coating agent. At present, researches on the packaging type modified graphene oxide/polyacrylate nano composite coating agent are rarely reported. The method related by the invention is realized by the following steps: firstly, carrying out hydrophobic modification on graphene oxide by using octadecylamine to prepare hydrophobic modified graphene oxide; then preparing an encapsulated modified graphene oxide/polyacrylate nano composite coating agent by using styrene and butyl acrylate as main monomers and using hydrophobized modified graphene oxide as a functional component through a miniemulsion polymerization method; and finally, the nano composite finishing agent is applied to leather finishing, so that the water resistance of the finished leather sample is improved.
Description
Technical Field
The invention belongs to the technical field of preparation methods of waterproof leather coatings, and particularly relates to an encapsulated modified graphene oxide/polyacrylate nano-composite coating agent and a preparation method thereof.
Background
The graphene has extremely high mechanical strength, extremely large specific surface area and excellent electric and heat conducting properties, and can be used as an inorganic nano filler to be added into a polymer matrix, so that the mechanical properties, the electric and heat conducting properties, the corrosion resistance and the like of the polymer can be improved. The dispersibility of graphene in a polymer matrix is a key factor influencing the structure and performance of the composite material. However, the most common methods for preparing polymer/graphene nanocomposites are solution blending and melt blending. In the process of preparing the composite material by adopting the two methods, the graphene nanosheets are easy to agglomerate in a polymer matrix due to the strong van der Waals force and pi-pi interaction between the graphene nanosheets, so that the composite material is difficult to endow with excellent performance. Therefore, how to select a proper preparation method to enable the graphene nanosheets to be uniformly and effectively dispersed in the polymer matrix is very important for improving the application performance of the composite material.
The polyacrylate leather finishing agent has the advantages of good film forming property, flexible and elastic film forming, light resistance, aging resistance, wide raw material source, low cost and the like, and is a leather finishing material widely used at present. However, the traditional polyacrylate finishing agent also has the defect of poor water resistance of the coating, which influences the use performance of leather products to a certain extent.
Disclosure of Invention
In view of the above, the main objective of the present invention is to provide an encapsulated modified graphene oxide/polyacrylate nanocomposite coating agent and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the preparation method of the packaging type modified graphene oxide/polyacrylate nano composite finishing agent is characterized by comprising the following steps:
the method comprises the following steps: preparing hydrophobization modified graphene oxide;
step two: preparing a packaged modified graphene oxide/polyacrylate pre-emulsion;
step three: preparing the packaging type modified graphene oxide/polyacrylate nano composite finishing agent by a miniemulsion polymerization method.
The method comprises the following specific steps:
the following are all prepared by mass portion,
the method comprises the following steps: preparation of Hydrophobically modified graphene oxide
(1) Dissolving 1.0-2.0 parts of octadecylamine in 600 parts of 300-600 parts of anhydrous ethanol to prepare a solution A, and dissolving 1.0-2.0 parts of graphene oxide in 600 parts of 300-600 parts of deionized water to prepare a solution B;
(2) adding the solution A and the solution B into a three-neck flask, stirring, reacting for 24 hours at normal temperature, performing suction filtration on a product, and performing vacuum drying to obtain hydrophobization modified graphene oxide;
step two: preparation of packaging type modified graphene oxide/polyacrylate pre-emulsion
(1) Adding 0.4-0.5 part of sodium dodecyl sulfate and 0.5-0.6 part of n-butanol into 64-65 parts of deionized water, and stirring to completely dissolve the sodium dodecyl sulfate and the n-butanol to obtain an aqueous solution of a surfactant;
(2) adding 0.045-0.047 part of the hydrophobization modified graphene oxide obtained in the step one into 20-22 parts of styrene and 24-26 parts of butyl acrylate to prepare a composite oil phase, and then carrying out ultrasonic treatment on the composite oil phase;
(3) adding the composite oil phase prepared in the step two (2) into the surfactant aqueous solution prepared in the step two (1), mechanically shearing for 0.5h, and performing ultrasonic treatment to prepare a uniform and stable pre-emulsion; the speed of the mechanical shearing is 3000 r/min;
step three: preparation of packaging type modified graphene oxide/polyacrylate nano composite finishing agent by miniemulsion polymerization method
(1) Dissolving 0.25-0.3 part of ammonium persulfate in 30-32 parts of deionized water to prepare an initiator aqueous solution C; dissolving 1.1-1.2 parts of ammonium persulfate in 55-57 parts of deionized water to prepare an initiator aqueous solution D;
(2) and (3) adding the initiator aqueous solution C into a three-neck flask with the temperature of 75-78 ℃, then simultaneously dripping the initiator aqueous solution D and the pre-emulsion prepared in the step two (3) through a constant-pressure dropping funnel, dripping for 1.5-2.0h, carrying out heat preservation reaction at the temperature of 75-78 ℃ for 2.0-3.0h after dripping, filtering and discharging to prepare the packaging type modified graphene oxide/polyacrylate nano composite coating agent.
And the stirring in the step one (2) is mechanical stirring, and the speed of the mechanical stirring is 300 r/min.
The ultrasonic treatment in the step one (2) is specifically that the requirements of ultrasonic treatment are 20-30W, ultrasonic work is 1s, the interval is 5s, and the total ultrasonic time is 0.5-1.0 h; the ultrasonic treatment in the step one (3) is specifically 300-400W ultrasonic treatment, ultrasonic work is carried out for 2s, the pause is 5s, and the total ultrasonic time is 0.5-1.0 h.
Compared with the prior art, the invention has the beneficial effects that:
firstly, carrying out hydrophobic modification on graphene oxide; and then packaging the hydrophobization modified graphene oxide in the polyacrylate emulsion particles by a miniemulsion polymerization method to obtain the packaged modified graphene oxide/polyacrylate nano composite emulsion.
Because the graphene oxide nanosheets are encapsulated inside the emulsion particles, the aggregation of the graphene oxide nanosheets in the emulsion is effectively avoided, and the excellent performance of the graphene can be exerted to the maximum extent. The nano composite finishing agent is applied to leather finishing, can keep the excellent service performance of the traditional polyacrylate leather finishing agent, can improve the defect of poor water resistance of a coating, and has obvious competitive advantage compared with similar products sold in the market.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
The invention provides a preparation method of an encapsulated modified graphene oxide/polyacrylate nano-composite coating agent, which is characterized by comprising the following steps:
the method comprises the following steps: preparing hydrophobization modified graphene oxide;
step two: preparing a packaged modified graphene oxide/polyacrylate pre-emulsion;
step three: preparing the packaging type modified graphene oxide/polyacrylate nano composite finishing agent by a miniemulsion polymerization method.
The method comprises the following specific steps:
the following are all prepared by mass portion,
the method comprises the following steps: preparation of Hydrophobically modified graphene oxide
(1) Dissolving 1.0-2.0 parts of octadecylamine in 600 parts of 300-600 parts of anhydrous ethanol to prepare a solution A, and dissolving 1.0-2.0 parts of graphene oxide in 600 parts of 300-600 parts of deionized water to prepare a solution B;
(2) adding the solution A and the solution B into a three-neck flask, stirring, reacting for 24 hours at normal temperature, performing suction filtration on a product, and performing vacuum drying to obtain hydrophobization modified graphene oxide;
step two: preparation of packaging type modified graphene oxide/polyacrylate pre-emulsion
(1) Adding 0.4-0.5 part of sodium dodecyl sulfate and 0.5-0.6 part of n-butanol into 64-65 parts of deionized water, and stirring to completely dissolve the sodium dodecyl sulfate and the n-butanol to obtain an aqueous solution of a surfactant;
(2) adding 0.045-0.047 part of the hydrophobization modified graphene oxide obtained in the step one into 20-22 parts of styrene and 24-26 parts of butyl acrylate to prepare a composite oil phase, and then carrying out ultrasonic treatment on the composite oil phase;
(3) adding the composite oil phase prepared in the step two (2) into the surfactant aqueous solution prepared in the step two (1), mechanically shearing for 0.5h, and performing ultrasonic treatment to prepare a uniform and stable pre-emulsion; the speed of the mechanical shearing is 3000 r/min;
step three: preparation of packaging type modified graphene oxide/polyacrylate nano composite finishing agent by miniemulsion polymerization method
(1) Dissolving 0.25-0.3 part of ammonium persulfate in 30-32 parts of deionized water to prepare an initiator aqueous solution C; dissolving 1.1-1.2 parts of ammonium persulfate in 55-57 parts of deionized water to prepare an initiator aqueous solution D;
(2) and (3) adding the initiator aqueous solution C into a three-neck flask with the temperature of 75-78 ℃, then simultaneously dripping the initiator aqueous solution D and the pre-emulsion prepared in the step two (3) through a constant-pressure dropping funnel, dripping for 1.5-2.0h, carrying out heat preservation reaction at the temperature of 75-78 ℃ for 2.0-3.0h after dripping, filtering and discharging to prepare the packaging type modified graphene oxide/polyacrylate nano composite coating agent.
And the stirring in the step one (2) is mechanical stirring, and the speed of the mechanical stirring is 300 r/min.
The ultrasonic treatment in the step one (2) is specifically that the requirements of ultrasonic treatment are 20-30W, ultrasonic work is 1s, the interval is 5s, and the total ultrasonic time is 0.5-1.0 h; the ultrasonic treatment in the step one (3) is specifically 300-400W ultrasonic treatment, ultrasonic work is carried out for 2s, the pause is 5s, and the total ultrasonic time is 0.5-1.0 h.
Example 1:
the method comprises the following steps: preparation of Hydrophobically modified graphene oxide
According to the mass portion of the raw materials,
(1) dissolving 1.0 part of octadecylamine in 300 parts of absolute ethyl alcohol to prepare a solution A, and dissolving 1.0 part of graphene oxide in 300 parts of deionized water to prepare a solution B.
(2) And adding the solution A and the solution B into a three-neck flask, mechanically stirring, reacting for 24 hours at normal temperature, carrying out suction filtration on the product, and carrying out vacuum drying to obtain the hydrophobization modified graphene oxide. The speed of mechanical stirring was 300 r/min.
Step two: preparation of packaging type modified graphene oxide/polyacrylate pre-emulsion
According to the mass portion of the raw materials,
(1) dissolving 0.4 part of sodium dodecyl sulfate and 0.5 part of n-butanol into 64 parts of deionized water, and stirring to completely dissolve the sodium dodecyl sulfate and the n-butanol to prepare an aqueous solution of a surfactant;
(2) 0.045 part of hydrophobized modified graphene oxide was added to 20 parts of styrene and 24 parts of butyl acrylate to form a composite oil phase. And then carrying out ultrasonic treatment on the composite oil phase to uniformly disperse the hydrophobic modified graphene oxide in the composite oil phase. The requirements of ultrasonic treatment are 20W, ultrasonic work is 1s, the intermittence is 5s, and the total ultrasonic time is 0.5 h.
(3) And (3) adding the composite oil phase prepared in the step (2) into the surfactant aqueous solution prepared in the step (1), shearing at a high speed for 0.5h, and performing ultrasonic treatment to obtain a uniform and stable pre-emulsion. The requirements of ultrasonic treatment are 400W, ultrasonic work is 2s, the intermittence is 5s, and the total ultrasonic time is 0.5 h.
Step three: preparation of packaging type modified graphene oxide/polyacrylate nano composite finishing agent by miniemulsion polymerization method
According to the mass portion of the raw materials,
(1) 0.25 part of ammonium persulfate is dissolved in 30 parts of deionized water to prepare an initiator aqueous solution C, and 1.1 part of ammonium persulfate is dissolved in 55 parts of deionized water to prepare an initiator aqueous solution D.
(2) And (3) adding the initiator aqueous solution C into a 75-DEG C three-neck flask, then simultaneously dropwise adding the pre-emulsion prepared in the step two (3) and the initiator aqueous solution D into the initiator aqueous solution C through a constant-pressure dropping funnel, dropwise adding the pre-emulsion and the initiator aqueous solution D for 1.5h, carrying out heat preservation reaction at 75 ℃ for 3.0h after the dropping is finished, filtering and discharging the mixture, and thus obtaining the packaging type modified graphene oxide/polyacrylate nano composite coating agent.
Example 2:
the method comprises the following steps: preparation of Hydrophobically modified graphene oxide
According to the mass portion of the raw materials,
(1) dissolving 1.5 parts of octadecylamine in 450 parts of absolute ethyl alcohol to prepare a solution A, and dissolving 1.5 parts of graphene oxide in 450 parts of deionized water to prepare a solution B.
(2) And adding the solution A and the solution B into a three-neck flask, mechanically stirring, reacting for 24 hours at normal temperature, carrying out suction filtration on the product, and carrying out vacuum drying to obtain the hydrophobization modified graphene oxide. The speed of mechanical stirring was 300 r/min.
Step two: preparation of packaging type modified graphene oxide/polyacrylate pre-emulsion
According to the mass portion of the raw materials,
(1) dissolving 0.45 part of sodium dodecyl sulfate and 0.55 part of n-butanol into 64.5 parts of deionized water, and mechanically stirring to completely dissolve the sodium dodecyl sulfate and the n-butanol to prepare an aqueous solution of a surfactant;
(2) 0.046 part of hydrophobized modified graphene oxide was added to 21 parts of styrene and 25 parts of butyl acrylate to form a composite oil phase. And then carrying out ultrasonic treatment on the composite oil phase to uniformly disperse the hydrophobic modified graphene oxide in the composite oil phase. The requirements of ultrasonic treatment are 20W, ultrasonic work is 1s, the intermittence is 5s, and the total ultrasonic time is 0.5 h.
(3) And (3) adding the composite oil phase prepared in the step (2) into the surfactant aqueous solution prepared in the step (1), shearing at a high speed for 0.5h, and performing ultrasonic treatment to obtain a uniform and stable pre-emulsion. The requirements of ultrasonic treatment are 400W, ultrasonic work is 2s, the intermittence is 5s, and the total ultrasonic time is 0.5 h.
Step three: preparation of packaging type modified graphene oxide/polyacrylate nano composite finishing agent by miniemulsion polymerization method
According to the mass portion of the raw materials,
(1) 0.27 part of ammonium persulfate is dissolved in 31 parts of deionized water to prepare an initiator aqueous solution C, and 1.15 parts of ammonium persulfate is dissolved in 56 parts of deionized water to prepare an initiator aqueous solution D.
(2) And (3) adding the initiator aqueous solution C into a three-neck flask at 76 ℃, then simultaneously dropwise adding the pre-emulsion prepared in the step two (3) and the initiator aqueous solution D into the three-neck flask through a constant-pressure dropping funnel, dropwise adding the pre-emulsion and the initiator aqueous solution D for 2.0h, carrying out heat preservation reaction at 76 ℃ for 2.0h after the dropping is finished, filtering and discharging the mixture to prepare the packaging type modified graphene oxide/polyacrylate nano composite coating agent.
Example 3:
the method comprises the following steps: preparing hydrophobization modified graphene oxide according to parts by weight
According to the mass portion of the raw materials,
(1) dissolving 2.0 parts of octadecylamine in 600 parts of absolute ethyl alcohol to prepare a solution A, and dissolving 2.0 parts of graphene oxide in 600 parts of deionized water to prepare a solution B.
(2) And adding the solution A and the solution B into a three-neck flask, mechanically stirring, reacting for 24 hours at normal temperature, carrying out suction filtration on the product, and carrying out vacuum drying to obtain the hydrophobization modified graphene oxide. The speed of mechanical stirring was 300 r/min.
Step two: preparation of packaging type modified graphene oxide/polyacrylate pre-emulsion
According to the mass portion of the raw materials,
(1) dissolving 0.5 part of sodium dodecyl sulfate and 0.6 part of n-butanol into 65 parts of deionized water, and stirring to completely dissolve the sodium dodecyl sulfate and the n-butanol to prepare an aqueous solution of a surfactant;
(2) 0.047 part of hydrophobized modified graphene oxide was added to 22 parts of styrene and 26 parts of butyl acrylate to form a composite oil phase. And then carrying out ultrasonic treatment on the composite oil phase to uniformly disperse the hydrophobic modified graphene oxide in the composite oil phase. The requirements of ultrasonic treatment are 20W, ultrasonic work is 1s, the intermittence is 5s, and the total ultrasonic time is 0.5 h.
(3) And (3) adding the composite oil phase prepared in the step (2) into the surfactant aqueous solution prepared in the step (1), shearing at a high speed for 0.5h, and performing ultrasonic treatment to obtain a uniform and stable pre-emulsion. The requirements of ultrasonic treatment are 400W, ultrasonic work is 2s, the intermittence is 5s, and the total ultrasonic time is 0.5 h.
Step three: preparation of packaging type modified graphene oxide/polyacrylate nano composite finishing agent by miniemulsion polymerization method
(1) 0.3 part of ammonium persulfate is dissolved in 32 parts of deionized water to prepare an initiator aqueous solution C, and 1.2 parts of ammonium persulfate is dissolved in 57 parts of deionized water to prepare an initiator aqueous solution D.
(2) And (3) adding the initiator aqueous solution C into a three-neck flask at 78 ℃, then simultaneously dropwise adding the pre-emulsion prepared in the step two (3) and the initiator aqueous solution D into the three-neck flask through a constant-pressure dropping funnel, dropwise adding the pre-emulsion and the initiator aqueous solution D for 2.0h, carrying out heat preservation reaction at 76 ℃ for 3.0h after the dropping is finished, filtering and discharging the mixture to prepare the packaging type modified graphene oxide/polyacrylate nano composite coating agent.
Appendix 1 test method for water resistance of leather coating used in the invention:
pouring 20 g of miniemulsion into a culture dish, drying at 40 deg.C to form a film with a thickness of about 1 mm, cutting the film into samples of 1cm × 1cm, and weighing m1Soaking in deionized water at room temperature for 24 hr, taking out, drying with filter paper, and weighing to m2The water absorption of the film is:
water absorption of film formation is (m)2－ｍ1）/ｍ1×100%
The water resistance of the packaged modified graphene oxide/polyacrylate nano-composite coating agent prepared by a miniemulsion polymerization method in the film forming on the leather surface is detected, and the test method is shown in appendix 1.
Test results show that compared with a pure polyacrylate leather coating, the water absorption rate of the packaging type modified graphene oxide/polyacrylate nano-composite leather coating after being soaked in water for 24 hours is only 6.8%, which is obviously lower than the water absorption rate of the pure polyacrylate leather coating after being soaked in water for 24 hours by 10.2%, and the packaging type modified graphene oxide/polyacrylate nano-composite finishing agent has excellent water resistance when forming a film on the surface of leather.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (3)
1. A preparation method of an encapsulated modified graphene oxide/polyacrylate nano-composite coating agent is characterized by comprising the following steps:
the following are all prepared by mass portion,
the method comprises the following steps: preparation of Hydrophobically modified graphene oxide
(1) Dissolving 1.0-2.0 parts of octadecylamine in 600 parts of 300-600 parts of anhydrous ethanol to prepare a solution A, and dissolving 1.0-2.0 parts of graphene oxide in 600 parts of 300-600 parts of deionized water to prepare a solution B;
(2) adding the solution A and the solution B into a three-neck flask, stirring, reacting for 24 hours at normal temperature, performing suction filtration on a product, and performing vacuum drying to obtain hydrophobization modified graphene oxide;
step two: preparation of packaging type modified graphene oxide/polyacrylate pre-emulsion
(1) Adding 0.4-0.5 part of sodium dodecyl sulfate and 0.5-0.6 part of n-butanol into 64-65 parts of deionized water, and stirring to completely dissolve the sodium dodecyl sulfate and the n-butanol to obtain an aqueous solution of a surfactant;
(2) adding 0.045-0.047 part of the hydrophobization modified graphene oxide obtained in the step one into 20-22 parts of styrene and 24-26 parts of butyl acrylate to prepare a composite oil phase, and then carrying out ultrasonic treatment on the composite oil phase;
(3) adding the composite oil phase prepared in the step two (2) into the surfactant aqueous solution prepared in the step two (1), mechanically shearing for 0.5h, and performing ultrasonic treatment to prepare a uniform and stable pre-emulsion; the speed of the mechanical shearing is 3000 r/min;
step three: preparation of packaging type modified graphene oxide/polyacrylate nano composite finishing agent by miniemulsion polymerization method
(1) Dissolving 0.25-0.3 part of ammonium persulfate in 30-32 parts of deionized water to prepare an initiator aqueous solution C; dissolving 1.1-1.2 parts of ammonium persulfate in 55-57 parts of deionized water to prepare an initiator aqueous solution D;
(2) and (3) adding the initiator aqueous solution C into a three-neck flask with the temperature of 75-78 ℃, then simultaneously dripping the initiator aqueous solution D and the pre-emulsion prepared in the step two (3) through a constant-pressure dropping funnel, dripping for 1.5-2.0h, carrying out heat preservation reaction at the temperature of 75-78 ℃ for 2.0-3.0h after dripping, filtering and discharging to prepare the packaging type modified graphene oxide/polyacrylate nano composite coating agent.
2. The preparation method of the encapsulated modified graphene oxide/polyacrylate nanocomposite coating agent according to claim 1, wherein the preparation method comprises the following steps: and the stirring in the step one (2) is mechanical stirring, and the speed of the mechanical stirring is 300 r/min.
3. The preparation method of the encapsulated modified graphene oxide/polyacrylate nanocomposite coating agent according to claim 1, wherein the preparation method comprises the following steps: the ultrasonic treatment in the second step (2) is specifically that the requirements of ultrasonic treatment are 20-30W, ultrasonic work is 1s, the interval is 5s, and the total ultrasonic time is 0.5-1.0 h; the ultrasonic treatment in the step two (3) is specifically 300-400W ultrasonic treatment, ultrasonic work is carried out for 2s, the pause is 5s, and the total ultrasonic time is 0.5-1.0 h.
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