CN106366817B - A kind of preparation method of polyacrylate/peanut shape hollow zinc composite leather coating agent - Google Patents
A kind of preparation method of polyacrylate/peanut shape hollow zinc composite leather coating agent Download PDFInfo
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- CN106366817B CN106366817B CN201610872058.4A CN201610872058A CN106366817B CN 106366817 B CN106366817 B CN 106366817B CN 201610872058 A CN201610872058 A CN 201610872058A CN 106366817 B CN106366817 B CN 106366817B
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- peanut shape
- shape hollow
- polyacrylate
- hollow zinc
- coating agent
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Classifications
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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
- 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
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Abstract
The present invention relates to a kind of polyacrylate/peanut shape hollow zinc composite leather coating agent preparation methods, peanut shape hollow zinc is prepared using sonochemical method first, then it is introduced into polyacrylate dispersion by physical blending process, obtains polyacrylate/peanut shape hollow zinc composite leather coating agent.Compared with removing from office sample after the covering with paint of virgin pp acid esters, the tensile strength that sample is removed from office after covering with paint, lacquer, colour wash, etc. using composite leather coating agent prepared by the present invention improves 103.25%, and water vapor permeability improves 27.17%, and gas permeability improves 464.32%.
Description
Technical field
The present invention relates to a kind of preparation method of composite leather coating agent, in particular to a kind of polyacrylate/peanut shape
The preparation method of hollow zinc composite leather coating agent.
Background technique
Inorganic hollow material is a kind of new material to grow up in five sixties of twentieth century, is widely used in drug
The fields such as controlled release, photocatalysis, water process, biochemistry, finishing agent.Currently, researcher have been able to prepare it is a series of
Inorganic hollow material, such as α-Fe2O3、Co3O4、NiO、CuO、ZnO、SiO2Deng.Wherein, hollow ZnO is since compound with regular structure, size can
Control, the advantages that pattern is various, are concerned in hollow material field.Currently, the hollow common preparation method of ZnO have hydro-thermal method,
Microwave method, template etc..Sonochemical method is a kind of novel method for synthesizing that developed recently gets up, with many conventional methods
Incomparable advantage, such as preparation time is short, low temperature, synthesized material purity is high, particle size is uniform, fine size.
As one of filmogen most widely used in leather finish, main feature has polyacrylate: excellent
Resistance to complications performance, good dry and wet wipe performance, medium embossing molding performance, medium covering power, excellent fast light, resistance to ag(e)ing
The compatibilities such as energy and other materials such as resin, pigment paste, casein finiss, casein are good.But polyacrylate film forming is fine and close, covers with paint, lacquer, colour wash, etc.
One layer of fine and close film is formed in leather surface afterwards, the channel that human body vapour molecule is outwardly spread is blocked, leads to wholesomeness
It can reduce, and then influence the comfort level of leather goods dress.In addition, there is " hot sticky cold crisp " and intolerant to having in polyacrylate finishing agent
The defects of solvent, limits it and further applies.Therefore, how researcher is for improve the synthesis of polyacrylate coatings
Performance expands a large amount of work, and main includes carrying out compound using inorganic nano-particle and polyacrylate dispersion and utilizing this
Body has the protide filmogen modified polyacrylate of good hygiene performance.
Summary of the invention
The purpose of the present invention is to provide a kind of polyacrylate/peanut shape hollow zinc composite leather coating agent systems
Preparation Method, leather sample not only has good sanitation performance (vapor pervious after being covered with paint, lacquer, colour wash, etc. using the composite leather coating agent of this method preparation
Property, gas permeability), and have excellent water resistance and mechanical property.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of preparation method of polyacrylate/peanut shape hollow zinc composite leather coating agent, comprising the following steps:
1) zinc salt: being dissolved in the in the mixed solvent of ethylene glycol and deionized water by the preparation of peanut shape hollow zinc, stirring
It dissolves to form aqueous solution to zinc salt；PH value of water solution is adjusted to 7~9, is then ultrasonically treated, washs, dries, obtain in peanut shape
Empty zinc oxide；
2) polyacrylate/peanut shape hollow zinc composite leather coating agent preparation: by flower prepared by step 1)
Shape hollow zinc ultrasonic disperse in deionized water is given birth to, the suspension of peanut shape hollow zinc is obtained, is then added to poly-
It is blended in acrylic acid ester emulsion to get polyacrylate/peanut shape hollow zinc composite leather coating agent is arrived.
A further improvement of the present invention lies in that zinc salt is zinc nitrate hexahydrate, acetic acid dihydrate zinc, alkali in the step 1)
Any one of formula zinc carbonate.
A further improvement of the present invention lies in that the power being ultrasonically treated in the step 1) is 300~500W, ultrasonic power
For ultrasonic 2s, the intermittent ultrasound of 1s of resting, the time of ultrasonic treatment is 20~60min.
A further improvement of the present invention lies in that in the step 1) ethylene glycol and deionized water in the mixed solvent deionization
The mass percent of water is 3~20%.
A further improvement of the present invention lies in that peanut shape hollow zinc and polyacrylate dispersion are total in the step 2)
Mixed temperature is 75~85 DEG C, mixing speed 300rmp, and the time of blending is 4~6h.
A further improvement of the present invention lies in that the quality of deionized water is polyacrylate dispersion quality in the step 2)
50%.
A further improvement of the present invention lies in that the solid content of polyacrylate dispersion is 33% in the step 2).
A further improvement of the present invention lies in that the dosage of peanut shape hollow zinc is polyacrylate in the step 2)
The 0.25%~1.5% of emulsion solid content.
A further improvement of the present invention lies in that the time of ultrasonic disperse is 10~20min in the step 2).
Compared with prior art, the invention has the benefit that
Sonochemical method prepares peanut shape hollow zinc in the present invention, mainly makes zinc oxide using sound cavitation effect
Presoma hydrolyzes to form a large amount of zinc oxide grain, these zinc oxide grains be self-assembly of using cavitation bubble as template micro-
Ball.Under lasting ultrasonication, bubbles burst, to form hollow zinc.Then, the hydrogen bond action of ethylene glycol makes again
Two independent hollow zinc spheres are connected, and are finally successfully prepared peanut shape hollow zinc；Peanut shape hollow zinc
Large specific surface area, special cavity structure, rigidity are stronger etc.；Peanut shape hollow zinc is blended with polyacrylate dispersion,
Polyacrylate/peanut shape hollow zinc composite leather coating agent is obtained；This method simple process and low cost, it is prepared
Peanut shape hollow zinc size is smaller and pattern is uniform, poly- to be promoted using the intrinsic performance characteristics of peanut shape hollow zinc
The comprehensive performance of acrylate leather coating agent, compared with virgin pp acid esters leather finishing agent, using painting prepared by the present invention
Sample is removed from office in decorations agent tensile strength after covering with paint, lacquer, colour wash, etc. improves 103.25%, and water vapor permeability improves 27.17%, and gas permeability improves
464.32%.
Detailed description of the invention
Fig. 1 is the SEM photograph of peanut shape hollow zinc, and wherein the amplification factor of Fig. 1 (a) is 50000 times, Fig. 1's (b)
Amplification factor is 150000 times.
Specific embodiment
Below by specific embodiment to a kind of polyacrylate/peanut shape hollow zinc composite leather of the present invention
The preparation method of finishing agent is described further.
Embodiment 1
1) preparation of peanut shape hollow zinc
Bis- water zinc acetate of 4mmol is dissolved in the ethylene glycol of 50mL and the in the mixed solvent of deionized water；In the mixed solvent is gone
The mass percent of ionized water is 3%；Stirring to two water zinc acetates are completely dissolved to form aqueous solution, adjust aqueous solution using ammonium hydroxide
PH value to 7, be then transferred in ultrasonic cell disruptor at 300W and be ultrasonically treated 20min, ultrasonic power be ultrasound 2s,
Rest the intermittent ultrasound of 1s, can be obtained uniform white precipitate, successively washed using dehydrated alcohol and deionized water and from
Three times, drying can be obtained peanut shape hollow zinc to the heart at 60 DEG C.
2) polyacrylate/peanut shape hollow zinc composite leather coating agent preparation
By peanut shape hollow zinc ultrasonic disperse 10min in deionized water, the outstanding of peanut shape hollow zinc is obtained
Supernatant liquid is then added into polyacrylate dispersion and 4h is blended at 300rmp, 75 DEG C, can be obtained polyacrylate/
Peanut shape hollow zinc composite leather coating agent.Wherein, the quality of deionized water is the 50% of polyacrylate dispersion quality,
The solid content of polyacrylate dispersion is 33%, and the dosage of peanut shape hollow zinc is polyacrylate dispersion solid content
0.25%.
Embodiment 2
1) preparation of peanut shape hollow zinc
Bis- water zinc acetate of 5mmol is dissolved in the ethylene glycol of 50mL and the in the mixed solvent of deionized water；In the mixed solvent is gone
The mass percent of ionized water is 5%；Stirring to two water zinc acetates are completely dissolved to form aqueous solution, adjust aqueous solution using ammonium hydroxide
PH value to 8, be then transferred in ultrasonic cell disruptor at 400W and be ultrasonically treated 30min, ultrasonic power be ultrasound 2s,
Rest the intermittent ultrasound of 1s, can be obtained uniform white precipitate, successively washed using dehydrated alcohol and deionized water and from
Three times, drying can be obtained peanut shape hollow zinc to the heart at 60 DEG C.
2) polyacrylate/peanut shape hollow zinc composite leather coating agent preparation
By peanut shape hollow zinc ultrasonic disperse 15min in deionized water, the outstanding of peanut shape hollow zinc is obtained
Supernatant liquid is then added into polyacrylate dispersion, and 5h is blended at 300rmp, 80 DEG C, can be obtained polyacrylate/
Peanut shape hollow zinc composite leather coating agent.Wherein, the quality of deionized water is the 50% of polyacrylate dispersion quality,
The solid content of polyacrylate dispersion is 33%, and the dosage of peanut shape hollow zinc is polyacrylate dispersion solid content
0.5%.
Embodiment 3
1) preparation of peanut shape hollow zinc
Bis- water zinc acetate of 6mmol is dissolved in the ethylene glycol of 50mL and the in the mixed solvent of deionized water；In the mixed solvent is gone
The mass percent of ionized water is 10%；Stirring to two water zinc acetates are completely dissolved to form aqueous solution, are adjusted using ammonium hydroxide water-soluble
The pH value of liquid is then transferred in ultrasonic cell disruptor at 500W to 9 and is ultrasonically treated 60min, ultrasonic power is ultrasound
2s, the intermittent ultrasound of 1s of resting, can be obtained uniform white precipitate, successively be washed simultaneously using dehydrated alcohol and deionized water
Three times, drying can be obtained peanut shape hollow zinc at 60 DEG C for centrifugation.
2) polyacrylate/peanut shape hollow zinc composite leather coating agent preparation
By peanut shape hollow zinc ultrasonic disperse 20min in deionized water, the outstanding of peanut shape hollow zinc is obtained
Supernatant liquid is then added into polyacrylate dispersion and 6h is blended at 300rmp, 85 DEG C, can be obtained polyacrylate/
Peanut shape hollow zinc composite leather coating agent.Wherein, the quality of deionized water is the 50% of polyacrylate dispersion quality,
The solid content of polyacrylate dispersion is 33%, and the dosage of peanut shape hollow zinc is polyacrylate dispersion solid content
1.0%.
Embodiment 4
1) preparation of peanut shape hollow zinc
Bis- water zinc acetate of 4mmol is dissolved in the ethylene glycol of 50mL and the in the mixed solvent of deionized water；In the mixed solvent is gone
The mass percent of ionized water is 15%；Stirring to two water zinc acetates are completely dissolved to form aqueous solution, are adjusted using ammonium hydroxide water-soluble
The pH value of liquid is then transferred in ultrasonic cell disruptor at 300W to 7 and is ultrasonically treated 20min, ultrasonic power is ultrasound
2s, the intermittent ultrasound of 1s of resting, can be obtained uniform white precipitate, successively be washed simultaneously using dehydrated alcohol and deionized water
Three times, drying can be obtained peanut shape hollow zinc at 60 DEG C for centrifugation.
2) polyacrylate/peanut shape hollow zinc composite leather coating agent preparation
By peanut shape hollow zinc ultrasonic disperse 10min in deionized water, the outstanding of peanut shape hollow zinc is obtained
Supernatant liquid is then added into polyacrylate dispersion and 4h is blended at 300rmp, 75 DEG C, can be obtained polyacrylate/
Peanut shape hollow zinc composite leather coating agent.Wherein, the quality of deionized water is the 50% of polyacrylate dispersion quality,
The solid content of polyacrylate dispersion is 33%, and the dosage of peanut shape hollow zinc is polyacrylate dispersion solid content
1.5%.
Embodiment 5
1) preparation of peanut shape hollow zinc
Bis- water zinc acetate of 5mmol is dissolved in the ethylene glycol of 50mL and the in the mixed solvent of deionized water；In the mixed solvent is gone
The mass percent of ionized water is 20%；Stirring to two water zinc acetates are completely dissolved to form aqueous solution, are adjusted using ammonium hydroxide water-soluble
The pH value of liquid is then transferred in ultrasonic cell disruptor at 400W to 8 and is ultrasonically treated 30min, ultrasonic power is ultrasound
2s, the intermittent ultrasound of 1s of resting, can be obtained uniform white precipitate, successively be washed simultaneously using dehydrated alcohol and deionized water
Three times, drying can be obtained peanut shape hollow zinc at 60 DEG C for centrifugation.
2) polyacrylate/peanut shape hollow zinc composite leather coating agent preparation
By peanut shape hollow zinc ultrasonic disperse 15min in deionized water, the outstanding of peanut shape hollow zinc is obtained
Supernatant liquid is then added into polyacrylate dispersion and 5h is blended at 300rmp, 80 DEG C, can be obtained polyacrylate/
Peanut shape hollow zinc composite leather coating agent.Wherein, the quality of deionized water is the 50% of polyacrylate dispersion quality,
The solid content of polyacrylate dispersion is 33%, and the dosage of peanut shape hollow zinc is polyacrylate dispersion solid content
0.25%.
Embodiment 6
1) preparation of peanut shape hollow zinc
5mmol zinc nitrate hexahydrate is dissolved in the ethylene glycol of 50mL and the in the mixed solvent of deionized water；In the mixed solvent
The mass percent of deionized water is 10%；Stirring is completely dissolved to form aqueous solution to zinc nitrate hexahydrate, and ultrasonic power is super
Sound 2s, the intermittent ultrasound of 1s of resting, the pH value for adjusting aqueous solution using ammonium hydroxide are then transferred to supersonic cell crushing to 8
It is ultrasonically treated 30min at 400W in machine, can be obtained uniform white precipitate, is successively washed using dehydrated alcohol and deionization
It washs and is centrifuged three times, drying can be obtained peanut shape hollow zinc at 60 DEG C.
2) polyacrylate/peanut shape hollow zinc composite leather coating agent preparation
By peanut shape hollow zinc ultrasonic disperse 15min in deionized water, the outstanding of peanut shape hollow zinc is obtained
Supernatant liquid is then added into polyacrylate dispersion and 5h is blended at 300rmp, 80 DEG C, can be obtained polyacrylate/
Peanut shape hollow zinc composite leather coating agent.Wherein, the quality of deionized water is the 50% of polyacrylate dispersion quality,
The solid content of polyacrylate dispersion is 33%, and the dosage of peanut shape hollow zinc is polyacrylate dispersion solid content
0.25%.
Embodiment 7
1) preparation of peanut shape hollow zinc
6mmol basic zinc carbonate is dissolved in the ethylene glycol of 50mL and the in the mixed solvent of deionized water；In the mixed solvent is gone
The mass percent of ionized water is 10%；Stirring is completely dissolved to form aqueous solution to basic zinc carbonate, is adjusted using ammonium hydroxide water-soluble
The pH value of liquid is then transferred in ultrasonic cell disruptor at 500W to 9 and is ultrasonically treated 60min, ultrasonic power is ultrasound
2s, the intermittent ultrasound of 1s of resting, can be obtained uniform white precipitate, successively be washed simultaneously using dehydrated alcohol and deionized water
Three times, drying can be obtained peanut shape hollow zinc at 60 DEG C for centrifugation.
2) polyacrylate/peanut shape hollow zinc composite leather coating agent preparation
By peanut shape hollow zinc ultrasonic disperse 20min in deionized water, the outstanding of peanut shape hollow zinc is obtained
Supernatant liquid is then added into polyacrylate dispersion and 6h is blended at 300rmp, 85 DEG C, can be obtained polyacrylate/
Peanut shape hollow zinc composite leather coating agent.Wherein, the quality of deionized water is the 50% of polyacrylate dispersion quality,
The solid content of polyacrylate dispersion is 33%, and the dosage of peanut shape hollow zinc is polyacrylate dispersion solid content
0.25%.
Fig. 1 is the SEM photograph of peanut shape hollow zinc prepared by the present invention, it can be seen that zinc oxide pattern is more advised
Whole, partial size is about 300nm, forms apparent hollow structure, and its shell is assembled by Zinc oxide nanoparticle of uniform size
It forms.Table 1 is to remove from office sample after polyacrylate/peanut shape hollow zinc composite leather coating agent prepared by the present invention is covered with paint, lacquer, colour wash, etc.
Performance.As known from Table 1, compared with removing from office sample after the covering with paint of virgin pp acid esters, polyacrylate/peanut shape hollow zinc Composite Skin
Leather finishing agent removes from office sample tensile strength after covering with paint, lacquer, colour wash, etc. improves 103.25%, and water vapor permeability improves 27.17%, and gas permeability improves
464.32%, the water resistance and other mechanical properties for removing from office sample are also improved to some extent.
1 polyacrylate of table/peanut shape hollow zinc multiple emulsion removes from office the performance of sample after covering with paint, lacquer, colour wash, etc.
The contents of the present invention are not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention
And to any equivalent transformation that technical solution of the present invention is taken, all are covered by the claims of the invention.
Claims (8)
1. a kind of polyacrylate/peanut shape hollow zinc composite leather coating agent preparation method, which is characterized in that including
Following steps:
1) zinc salt the preparation of peanut shape hollow zinc: is dissolved in the in the mixed solvent of ethylene glycol and deionized water, stirring to zinc
Salt dissolves to form aqueous solution；PH value of water solution is adjusted to 7~9 using ammonium hydroxide, is then ultrasonically treated, washs, dries, obtain peanut
Shape hollow zinc；Wherein, the power of ultrasonic treatment is 300~500W, and ultrasonic power is ultrasound 2s, the intermittent of 1s that rest surpasses
Sound, the time of ultrasonic treatment are 20~60min；
2) polyacrylate/peanut shape hollow zinc composite leather coating agent preparation: by peanut shape prepared by step 1)
Hollow zinc ultrasonic disperse in deionized water, obtains the suspension of peanut shape hollow zinc, is then added to polypropylene
It is blended in acid esters lotion to get polyacrylate/peanut shape hollow zinc composite leather coating agent is arrived.
2. a kind of preparation of polyacrylate according to claim 1/peanut shape hollow zinc composite leather coating agent
Method, it is characterised in that: zinc salt is zinc nitrate hexahydrate, acetic acid dihydrate zinc, appointing in basic zinc carbonate in the step 1)
It is a kind of.
3. a kind of preparation of polyacrylate according to claim 1/peanut shape hollow zinc composite leather coating agent
Method, it is characterised in that: the mass percent of the in the mixed solvent deionized water of ethylene glycol and deionized water in the step 1)
It is 3~20%.
4. a kind of preparation of polyacrylate according to claim 1/peanut shape hollow zinc composite leather coating agent
Method, it is characterised in that: the temperature that peanut shape hollow zinc is blended with polyacrylate dispersion in the step 2) be 75~
85 DEG C, mixing speed 300rmp, the time of blending is 4~6h.
5. a kind of preparation of polyacrylate according to claim 1/peanut shape hollow zinc composite leather coating agent
Method, it is characterised in that: the quality of deionized water is the 50% of polyacrylate dispersion quality in the step 2).
6. a kind of preparation of polyacrylate according to claim 1/peanut shape hollow zinc composite leather coating agent
Method, it is characterised in that: the solid content of polyacrylate dispersion is 33% in the step 2).
7. a kind of preparation of polyacrylate according to claim 1/peanut shape hollow zinc composite leather coating agent
Method, it is characterised in that: the dosage of peanut shape hollow zinc is polyacrylate dispersion solid content in the step 2)
0.25%~1.5%.
8. a kind of preparation of polyacrylate according to claim 1/peanut shape hollow zinc composite leather coating agent
Method, it is characterised in that: the time of ultrasonic disperse is 10~20min in the step 2).
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| CN107385935A (en) * | 2017-06-28 | 2017-11-24 | 常州创索新材料科技有限公司 | A kind of preparation method of high-strength flooring laminate material |
| CN107353753B (en) * | 2017-08-11 | 2019-09-13 | 陕西科技大学 | A kind of preparation method of polyacrylate/flower-shaped hollow zinc composite leather coating agent |
| CN107345040B (en) * | 2017-08-11 | 2019-09-10 | 陕西科技大学 | A kind of preparation method of polyacrylate/spherical hollow zinc laminated film |
| CN107442099B (en) * | 2017-08-11 | 2020-09-08 | 陕西科技大学 | Sonochemistry preparation method of porous zinc oxide photocatalytic material |
| CN110894387A (en) * | 2019-12-11 | 2020-03-20 | 江西省东鹏鞋业有限公司 | Preparation method of yellowing-resistant polyacrylate nano ZnO leather finishing agent |
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| CN103013270A (en) * | 2012-12-13 | 2013-04-03 | 陕西科技大学 | Preparation method of high moisture permeability type polyacrylate nano-composite leather coating agent |
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| CN104177537A (en) * | 2014-08-04 | 2014-12-03 | 陕西科技大学 | Method for preparing composite polyacrylate/cylindrical hollow zinc oxide emulsion for leather |
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| CN101817548A (en) * | 2010-04-27 | 2010-09-01 | 中山大学 | Method for preparing zinc oxide hollow spheres |
| CN103013270A (en) * | 2012-12-13 | 2013-04-03 | 陕西科技大学 | Preparation method of high moisture permeability type polyacrylate nano-composite leather coating agent |
| CN104151564A (en) * | 2014-08-04 | 2014-11-19 | 陕西科技大学 | Preparation method of polyacrylic ester emulsion modified by hollow zinc oxide microspheres with shell layers adopting sheet structures |
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