CN106366817A - Preparation method of polyacrylate and peanut-shaped hollow zinc oxide composited leather finishing agent - Google Patents
Preparation method of polyacrylate and peanut-shaped hollow zinc oxide composited leather finishing agent Download PDFInfo
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- CN106366817A CN106366817A CN201610872058.4A CN201610872058A CN106366817A CN 106366817 A CN106366817 A CN 106366817A CN 201610872058 A CN201610872058 A CN 201610872058A CN 106366817 A CN106366817 A CN 106366817A
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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
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- 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
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- 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
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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
- 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
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- 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
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- Wood Science & Technology (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a preparation method of a polyacrylate and peanut-shaped hollow zinc oxide composited leather finishing agent. According to the preparation method, peanut-shaped hollow zinc oxide is prepared according to a sonochemical method, and is guided into a polyacrylate emulsion according to physical blending method to obtain the polyacrylate and peanut-shaped hollow zinc oxide composited leather finishing agent. Compared with leather samples coated with pure polyacrylate, leather samples coated with the prepared composite leather finishing agent has the advantages that tensile strength is improved by 103.25%, moisture permeability is improved by 27.17%, and breathability is improved by 464.32%.
Description
Technical field
The present invention relates to a kind of preparation method of composite leather coating agent, particularly to a kind of polyacrylate/peanut shape
The preparation method of hollow zinc composite leather coating agent.
Background technology
Inorganic hollow material is a kind of new material growing up in twentieth century five sixties, is widely used in medicine
The fields such as controlled release, photocatalysis, water process, biochemistry, finishing agent.At present, researcher have been able to prepare a series of
Inorganic hollow material, such as α-fe2o3、co3o4、nio、cuo、zno、sio2Deng.Wherein, hollow zno due to compound with regular structure, size can
The advantages of control, pattern are various, receives much concern in hollow material field.At present, hollow zno commonly use preparation method have hydro-thermal method,
Microwave method, template etc..Sonochemical method is a kind of novel method for synthesizing that developed recently gets up, and it has many traditional methods
Incomparable advantage, as short in preparation time, low temperature, synthesized material purity height, the homogeneous, fine size of size etc..
As one of filmogen most widely used in leather finish, its main feature has polyacrylate: excellent
Resistance to complications performance, good dry and wet wipes performance, medium embossing molding performance, medium covering power, excellent fast light, resistance to ag(e)ing
Can, and the other materials such as compatibility such as resin, pigment paste, casein finiss, casein is good.But polyacrylate film forming is fine and close, cover with paint, lacquer, colour wash, etc.
Form one layer of fine and close thin film in leather surface afterwards, block the passage that human body vapour molecule outwardly spreads, lead to wholesomeness
Can reduce, and then affect the comfort level of leather goods dress.Additionally, there is " hot sticky cold crisp " and intolerant to having in polyacrylate finishing agent
The defects such as machine solvent, limit it and apply further.Therefore, research worker is for the synthesis how improving polyacrylate coatings
Performance expands substantial amounts of work, mainly includes being combined and utilized this using inorganic nano-particle and polyacrylate dispersion
Body has the protide filmogen modified polyacrylate of good hygiene performance.
Content of the invention
It is an object of the invention to provide a kind of system of polyacrylate/peanut shape hollow zinc composite leather coating agent
Preparation Method, after being covered with paint, lacquer, colour wash, etc. using the composite leather coating agent of the method preparation, leather sample not only has good sanitation performance (vapor pervious
Property, breathability), and there is excellent resistance to water and mechanical property.
For achieving 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, comprises the following steps:
1) preparation of peanut shape hollow zinc: zinc salt is dissolved in ethylene glycol and the mixed solvent of deionized water, stirring
Dissolve to zinc salt and form aqueous solution；Adjust aqueous solution ph value to 7～9, then supersound process, washing, it is dried, obtain in peanut shape
Empty zinc oxide；
2) preparation of polyacrylate/peanut shape hollow zinc composite leather coating agent: by step 1) prepared by flower
Raw shape hollow zinc ultrasonic disperse in deionized water, obtains the suspension of peanut shape hollow zinc, is then added to gather
It is blended in acrylic acid ester emulsion, that is, obtain polyacrylate/peanut shape hollow zinc composite leather coating agent.
The present invention is further improved by, described step 1) in zinc salt be zinc nitrate hexahydrate, two acetate hydrate zinc, alkali
Any one in formula zinc carbonate.
The present invention is further improved by, described step 1) in supersound process power be 300～500w, ultrasonic power
For ultrasonic 2s, rest 1s batch (-type) ultrasonic, time of supersound process is 20～60min.
The present invention is further improved by, described step 1) in ethylene glycol and deionized water mixed solvent in deionization
The mass percent of water is 3～20%.
The present invention is further improved by, described step 2) in peanut shape hollow zinc and polyacrylate dispersion altogether
Mixed temperature is 75～85 DEG C, and mixing speed is 300rmp, and the time of blending is 4～6h.
The present invention is further improved by, described step 2) in deionized water quality be polyacrylate dispersion quality
50%.
The present invention is further improved by, described step 2) in polyacrylate dispersion solid content be 33%.
The present invention is further improved by, described step 2) in peanut shape hollow zinc consumption be polyacrylate
The 0.25%～1.5% of emulsion solid content.
The present invention is further improved by, described step 2) in ultrasonic disperse time be 10～20min.
Compared with prior art, the invention has the benefit that
In the present invention, sonochemical method preparation peanut shape hollow zinc, mainly uses sound cavitation effect and makes zinc oxide
Presoma hydrolyzes to form substantial amounts of zinc oxide grain, and these zinc oxide grains carry out being self-assembly of micro- with cavitation bubble for template
Ball.Under lasting ultrasonication, bubbles burst, thus form hollow zinc.Subsequently, the hydrogen bond action of ethylene glycol makes again
Two independent hollow zinc spheroids are connected, and are finally successfully prepared peanut shape hollow zinc；Peanut shape hollow zinc
Big, the special cavity structure of specific surface area, rigidity are stronger etc.；Peanut shape hollow zinc is blended with polyacrylate dispersion,
Obtain polyacrylate/peanut shape hollow zinc composite leather coating agent；This method process is simple, low cost, prepared
Peanut shape hollow zinc size is less and pattern is homogeneous, is lifted poly- using the intrinsic performance characteristics of peanut shape hollow zinc
The combination property of acrylate leather coating agent, compared with virgin pp acid esters leather finishing agent, using the painting of present invention preparation
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 breathability improves
464.32%.
Brief description
Fig. 1 is the sem photo of peanut shape hollow zinc, and the wherein amplification of Fig. 1 (a) is 50000 times, Fig. 1's (b)
Amplification is 150000 times.
Specific embodiment
Below by specific embodiment to a kind of polyacrylate of the present invention/peanut shape hollow zinc composite leather
The preparation method of finishing agent is described further.
Embodiment 1
1) preparation of peanut shape hollow zinc
4mmol bis- water zinc acetate is dissolved in the ethylene glycol of 50ml and the mixed solvent of deionized water；In mixed solvent
The mass percent of ionized water is 3%；Stir and be completely dissolved formation aqueous solution to two water zinc acetates, aqueous solution is adjusted using ammonia
Ph value to 7, be then transferred in ultrasonic cell disruptor supersound process 20min under 300w, ultrasonic power is ultrasonic 2s,
Rest 1s batch (-type) ultrasonic, you can obtain uniform white precipitate, adopt successively dehydrated alcohol and deionized water wash and from
The heart three times, drying at 60 DEG C can obtain peanut shape hollow zinc.
2) preparation of polyacrylate/peanut shape hollow zinc composite leather coating agent
By peanut shape hollow zinc ultrasonic disperse 10min in deionized water, obtain the outstanding of peanut shape hollow zinc
Supernatant liquid, is then added in polyacrylate dispersion being blended 4h at 300rmp, 75 DEG C, you can obtain 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 consumption of peanut shape hollow zinc is polyacrylate dispersion solid content
0.25%.
Embodiment 2
1) preparation of peanut shape hollow zinc
5mmol bis- water zinc acetate is dissolved in the ethylene glycol of 50ml and the mixed solvent of deionized water；In mixed solvent
The mass percent of ionized water is 5%；Stir and be completely dissolved formation aqueous solution to two water zinc acetates, aqueous solution is adjusted using ammonia
Ph value to 8, be then transferred in ultrasonic cell disruptor supersound process 30min under 400w, ultrasonic power is ultrasonic 2s,
Rest 1s batch (-type) ultrasonic, you can obtain uniform white precipitate, adopt successively dehydrated alcohol and deionized water wash and from
The heart three times, drying at 60 DEG C can obtain peanut shape hollow zinc.
2) preparation of polyacrylate/peanut shape hollow zinc composite leather coating agent
By peanut shape hollow zinc ultrasonic disperse 15min in deionized water, obtain the outstanding of peanut shape hollow zinc
Supernatant liquid, is then added in polyacrylate dispersion, at 300rmp, 80 DEG C be blended 5h, you can obtain 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 consumption of peanut shape hollow zinc is polyacrylate dispersion solid content
0.5%.
Embodiment 3
1) preparation of peanut shape hollow zinc
6mmol bis- water zinc acetate is dissolved in the ethylene glycol of 50ml and the mixed solvent of deionized water；In mixed solvent
The mass percent of ionized water is 10%；Stir and be completely dissolved formation aqueous solution to two water zinc acetates, adjusted using ammonia water-soluble
The ph value of liquid to 9, is then transferred in ultrasonic cell disruptor supersound process 60min under 500w, ultrasonic power is ultrasonic
2s, rest 1s batch (-type) ultrasonic, you can obtain uniform white precipitate, adopt dehydrated alcohol and deionized water wash simultaneously successively
Centrifugation three times, drying at 60 DEG C can obtain peanut shape hollow zinc.
2) preparation of polyacrylate/peanut shape hollow zinc composite leather coating agent
By peanut shape hollow zinc ultrasonic disperse 20min in deionized water, obtain the outstanding of peanut shape hollow zinc
Supernatant liquid, is then added in polyacrylate dispersion being blended 6h at 300rmp, 85 DEG C, you can obtain 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 consumption of peanut shape hollow zinc is polyacrylate dispersion solid content
1.0%.
Embodiment 4
1) preparation of peanut shape hollow zinc
4mmol bis- water zinc acetate is dissolved in the ethylene glycol of 50ml and the mixed solvent of deionized water；In mixed solvent
The mass percent of ionized water is 15%；Stir and be completely dissolved formation aqueous solution to two water zinc acetates, adjusted using ammonia water-soluble
The ph value of liquid to 7, is then transferred in ultrasonic cell disruptor supersound process 20min under 300w, ultrasonic power is ultrasonic
2s, rest 1s batch (-type) ultrasonic, you can obtain uniform white precipitate, adopt dehydrated alcohol and deionized water wash simultaneously successively
Centrifugation three times, drying at 60 DEG C can obtain peanut shape hollow zinc.
2) preparation of polyacrylate/peanut shape hollow zinc composite leather coating agent
By peanut shape hollow zinc ultrasonic disperse 10min in deionized water, obtain the outstanding of peanut shape hollow zinc
Supernatant liquid, is then added in polyacrylate dispersion being blended 4h at 300rmp, 75 DEG C, you can obtain 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 consumption of peanut shape hollow zinc is polyacrylate dispersion solid content
1.5%.
Embodiment 5
1) preparation of peanut shape hollow zinc
5mmol bis- water zinc acetate is dissolved in the ethylene glycol of 50ml and the mixed solvent of deionized water；In mixed solvent
The mass percent of ionized water is 20%；Stir and be completely dissolved formation aqueous solution to two water zinc acetates, adjusted using ammonia water-soluble
The ph value of liquid to 8, is then transferred in ultrasonic cell disruptor supersound process 30min under 400w, ultrasonic power is ultrasonic
2s, rest 1s batch (-type) ultrasonic, you can obtain uniform white precipitate, adopt dehydrated alcohol and deionized water wash simultaneously successively
Centrifugation three times, drying at 60 DEG C can obtain peanut shape hollow zinc.
2) preparation of polyacrylate/peanut shape hollow zinc composite leather coating agent
By peanut shape hollow zinc ultrasonic disperse 15min in deionized water, obtain the outstanding of peanut shape hollow zinc
Supernatant liquid, is then added in polyacrylate dispersion being blended 5h at 300rmp, 80 DEG C, you can obtain 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 consumption 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 mixed solvent of deionized water；In mixed solvent
The mass percent of deionized water is 10%；Stir and be completely dissolved formation aqueous solution to zinc nitrate hexahydrate, ultrasonic power is super
Sound 2s, rest 1s batch (-type) ultrasonic, the ph value of aqueous solution is adjusted to 8 using ammonia, is then transferred to supersonic cell and pulverizes
In machine under 400w supersound process 30min, you can obtain uniform white precipitate, adopt dehydrated alcohol and deionization to wash successively
Wash and be centrifuged three times, drying at 60 DEG C can obtain peanut shape hollow zinc.
2) preparation of polyacrylate/peanut shape hollow zinc composite leather coating agent
By peanut shape hollow zinc ultrasonic disperse 15min in deionized water, obtain the outstanding of peanut shape hollow zinc
Supernatant liquid, is then added in polyacrylate dispersion being blended 5h at 300rmp, 80 DEG C, you can obtain 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 consumption 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 mixed solvent of deionized water；In mixed solvent
The mass percent of ionized water is 10%；Stir and be completely dissolved formation aqueous solution to basic zinc carbonate, adjusted using ammonia water-soluble
The ph value of liquid to 9, is then transferred in ultrasonic cell disruptor supersound process 60min under 500w, ultrasonic power is ultrasonic
2s, rest 1s batch (-type) ultrasonic, you can obtain uniform white precipitate, adopt dehydrated alcohol and deionized water wash simultaneously successively
Centrifugation three times, drying at 60 DEG C can obtain peanut shape hollow zinc.
2) preparation of polyacrylate/peanut shape hollow zinc composite leather coating agent
By peanut shape hollow zinc ultrasonic disperse 20min in deionized water, obtain the outstanding of peanut shape hollow zinc
Supernatant liquid, is then added in polyacrylate dispersion being blended 6h at 300rmp, 85 DEG C, you can obtain 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 consumption of peanut shape hollow zinc is polyacrylate dispersion solid content
0.25%.
Fig. 1 is the sem photo of the peanut shape hollow zinc prepared by the present invention it can be seen that zinc oxide pattern is more advised
Whole, particle diameter is about 300nm, defines obvious hollow structure, and its shell is assembled by Zinc oxide nanoparticle of uniform size
Form.Table 1 polyacrylate/peanut shape hollow zinc composite leather coating agent prepared by the present invention removes from office sample after covering with paint, lacquer, colour wash, etc.
Performance.As known from Table 1, compared with leather sample after the covering with paint of virgin pp acid esters, polyacrylate/peanut shape hollow zinc Composite Skin
Sample removed from office by leather finishing agent tensile strength after covering with paint, lacquer, colour wash, etc. improves 103.25%, and water vapor permeability improves 27.17%, and breathability improves
464.32%, remove from office the resistance to water of sample and other mechanical properties are also improved to some extent.
Table 1 polyacrylate/peanut shape hollow zinc complex emulsions remove from office the performance of sample after covering with paint, lacquer, colour wash, etc.
Present disclosure is not limited to cited by embodiment, and those of ordinary skill in the art pass through to read description of the invention
And any equivalent conversion that technical solution of the present invention is taken, the claim being the present invention covered.
Claims (9)
1. a kind of preparation method of polyacrylate/peanut shape hollow zinc composite leather coating agent is it is characterised in that include
Following steps:
1) preparation of peanut shape hollow zinc: zinc salt is dissolved in ethylene glycol and the mixed solvent of deionized water, stirs to zinc
Salt dissolving forms aqueous solution；Adjust aqueous solution ph value to 7～9, then supersound process, washing, it is dried, obtain peanut shape hollow oxygen
Change zinc；
2) preparation of polyacrylate/peanut shape hollow zinc composite leather coating agent: by step 1) prepared by peanut shape
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 emulsion, that is, obtain polyacrylate/peanut shape hollow zinc composite leather coating agent.
2. the preparation of a kind of polyacrylate according to claim 1/peanut shape hollow zinc composite leather coating agent
Method it is characterised in that: described step 1) in zinc salt be zinc nitrate hexahydrate, two acetate hydrate zinc, appointing in basic zinc carbonate
A kind of.
3. the preparation of a kind of polyacrylate according to claim 1/peanut shape hollow zinc composite leather coating agent
Method it is characterised in that: described step 1) in supersound process power be 300～500w, ultrasonic power be ultrasonic 2s, the 1s that rests
Batch (-type) ultrasonic, time of supersound process is 20～60min.
4. the preparation of a kind of polyacrylate according to claim 1/peanut shape hollow zinc composite leather coating agent
Method it is characterised in that: described step 1) in ethylene glycol and deionized water mixed solvent in deionized water mass percent
For 3～20%.
5. the preparation of a kind of polyacrylate according to claim 1/peanut shape hollow zinc composite leather coating agent
Method it is characterised in that: described step 2) in the blending of peanut shape hollow zinc and polyacrylate dispersion temperature be 75～
85 DEG C, mixing speed is 300rmp, and the time of blending is 4～6h.
6. the preparation of a kind of polyacrylate according to claim 1/peanut shape hollow zinc composite leather coating agent
Method it is characterised in that: described step 2) in deionized water quality be polyacrylate dispersion quality 50%.
7. the preparation of a kind of polyacrylate according to claim 1/peanut shape hollow zinc composite leather coating agent
Method it is characterised in that: described step 2) in polyacrylate dispersion solid content be 33%.
8. the system of a kind of polyacrylate according to claim 1 or 7/peanut shape hollow zinc composite leather coating agent
Preparation Method it is characterised in that: described step 2) in the consumption of peanut shape hollow zinc be polyacrylate dispersion solid content
0.25%～1.5%.
9. the preparation of a kind of polyacrylate according to claim 1/peanut shape hollow zinc composite leather coating agent
Method it is characterised in that: described step 2) in ultrasonic disperse time be 10～20min.
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Cited By (5)
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| CN107345040A (en) * | 2017-08-11 | 2017-11-14 | 陕西科技大学 | A kind of preparation method of polyacrylate/spherical hollow zinc laminated film |
| CN107353753A (en) * | 2017-08-11 | 2017-11-17 | 陕西科技大学 | A kind of preparation method of polyacrylate/flower-shaped hollow zinc composite leather coating agent |
| 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 |
| CN107442099A (en) * | 2017-08-11 | 2017-12-08 | 陕西科技大学 | A kind of phonochemistry preparation method of porous zinc bloom catalysis 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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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN107345040A (en) * | 2017-08-11 | 2017-11-14 | 陕西科技大学 | A kind of preparation method of polyacrylate/spherical hollow zinc laminated film |
| CN107353753A (en) * | 2017-08-11 | 2017-11-17 | 陕西科技大学 | A kind of preparation method of polyacrylate/flower-shaped hollow zinc composite leather coating agent |
| CN107442099A (en) * | 2017-08-11 | 2017-12-08 | 陕西科技大学 | A kind of phonochemistry preparation method of porous zinc bloom catalysis material |
| 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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| Publication number | Publication date |
|---|---|
| CN106366817B (en) | 2019-02-01 |
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