CN104151564B - Shell has the preparation method of the microsphere modified polyacrylate dispersion of hollow zinc of laminated structure - Google Patents
Shell has the preparation method of the microsphere modified polyacrylate dispersion of hollow zinc of laminated structure Download PDFInfo
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Abstract
Shell has the preparation method of the microsphere modified polyacrylate dispersion of hollow zinc of laminated structure, the present invention prepares shell first with alkaline etching mechanism and Ostwald ripening mechanism and has the hollow zinc microsphere of laminated structure, then uses its modified polyacrylate emulsion by physical blending process.By ammonia or sodium hydroxide the zinc hydroxide in hydroxide zinc/zinc oxide complex microsphere preferentially etched and the self assembling process of Zinc oxide nanoparticle oriented adsorption growth forms shell and has the hollow zinc microsphere of laminated structure, preparation technology is simple, reaction condition is gentle, workable and productivity is high, the hollow zinc microsphere pattern that prepared shell has laminated structure is homogeneous.Compared with virgin pp acid esters film, improve 51% by the water vapor permeability of the polyacrylate dispersion film of the method modification of the present invention, resistance to water improves 11.61%, and tensile strength improves 60.26%.
Description
Technical field:
The present invention relates to the preparation method of a kind of modified polyacrylate emulsion, have particularly to a kind of shell
The preparation method of the microsphere modified polyacrylate dispersion of hollow zinc of laminated structure.
Technical background:
Hollow structure material is a kind of novel partculate material grown up in twentieth century five, the sixties, quilt
It is widely used in the fields such as medicine controlled releasing, light absorption, microcapsule encapsulation, water process, catalysis, biochemistry.
Zinc oxide owing to pattern is various, structure-controllable and there is numerous special physical and chemical performance, therefore in
Hollow structure Material Field receives much concern.At present, the method preparing hollow zinc mainly has template, Ao Si
Special Grindelwald ripening method and chemical etching method.For template, use Ostwald ripening method
Prepare hollow ZnO microsphere with chemical etching method and have the advantage that first, low cost, it is not necessary to mould material；
Secondly, operating process is simple, can avoid going in template the process of removing template.But both approaches institute
The hollow zinc pattern of preparation is not easy to control, especially with regard to the system of the hollow zinc of specific morphology
For being also rarely reported.
Polyacrylate is because of its wide material sources, with low cost, has good cohesiveness, resistance to tortuosity etc. excellent
Point, becomes the filmogen being most widely used in leather finishing agent.But its film forming is fine and close, causes health
Performance reduces, and then affects the comfort level of leather goods dress.Therefore, researcher is poly-for how to improve
The water vapor permeability of acrylate coatings expands substantial amounts of work.Mainly include following two aspect: one is to adopt
Use inorganic nano particle modified polyacrylate dispersion, utilize the nanoparticle with the interface of organic alternate formation to be
Coating provides more vapor channel, but the method promotes amplitude the most not quite.Two to be that utilization itself has good
The protide filmogen modified polyacrylate of good sanitation performance, thus improve the saturating of polyacrylate coatings
Steam, (Gan Changfeng, Xu Qunna, Zhou Jianhua, etc. ternary amphipathic copolymer is prepared hud typed as emulsifying agent
Modified Casein Leather finishing agent [J]. Chinese leather, 2013,42 (5): 37-41.) but protide film forming material
Material poor water resistance, rub resistance and mechanical property be not poor.
Summary of the invention:
It is an object of the invention to provide a kind of shell and there is the hollow zinc microsphere modified poly-third of laminated structure
The preparation method of olefin(e) acid ester emulsion, not only has after modified polyacrylate emulsion film prepared by employing the method
There is good water vapor permeability, and there is certain resistance to water and mechanical property.
For achieving the above object, the present invention adopts the following technical scheme that:
1) by the Zn (NO of 2/3 consumption3)2·6H2O is miscible in deionized water with hexamethylenetetramine, and in
React 5min at 81～84 DEG C, be subsequently adding the sodium citrate of 2/3 consumption, after insulation reaction 1.1～1.5h, add
Enter the Zn (NO of residue 1/3 consumption3)2·6H2O and hexamethylenetetramine, and at 86～90 DEG C, react 5min
After, adding the sodium citrate of residue 1/3 consumption, after reaction 10min, regulation pH value is 9.2～10.8, then
Insulation reaction 3～5h at 86～90 DEG C, then through washing, be dried to obtain shell there is the hollow of laminated structure
ZnO microsphere；Wherein, Zn (NO3)2·6H2O, hexamethylenetetramine, the quality of total consumption of sodium citrate
Than being (0.624～1.2075): (0.2775～0.5685): (0.0225～0.2985)；
2) shell is had the hollow zinc microsphere of laminated structure in deionized water after ultrasonic disperse, add
Entering in polyacrylate dispersion, stirring also reacts 6～8h at 75～80 DEG C, obtains shell and has laminated structure
The microsphere modified polyacrylate dispersion of hollow zinc；Described shell has the hollow zinc of laminated structure
Microsphere is (0.030～0.160) with the mass ratio of polyacrylate dispersion: 30.
Described Zn (NO3)2·6H2The gross mass of O and the mass ratio of deionized water are (0.624～1.2075): 70.
Described pH value uses ammonia or sodium hydrate aqueous solution to be adjusted.
Described being dried is to be dried 8～12h under the conditions of 60～80 DEG C.
The solid content of described polyacrylate dispersion is 30%.
During described ultrasonic disperse, shell has the hollow zinc microsphere of laminated structure and the quality of deionized water
Than being (0.030～0.160): 15.
The time of described ultrasonic disperse is 10～20min.
Described mixing speed is 350～450rpm.
Compared with prior art, the invention have the benefit that
(1) present invention utilize alkaline etching mechanism and Ostwald ripening mechanism prepare shell have lamellar knot
The hollow zinc microsphere of structure, technique is simple, low cost, and reaction condition is gentle, repeatable strong and productivity
High；The hollow zinc microsphere pattern that prepared shell has laminated structure is homogeneous.
(2) by physical blending process, shell is used to have the hollow zinc microsphere of laminated structure to polypropylene
Acid esters emulsion is modified, and utilizes the Large ratio surface that its hollow structure inside, shell laminated structure intertexture is formed
And the huge interface between the intrinsic performance characteristics of roughness, zinc oxide and zinc oxide and polyacrylate, promote
The combination property of polyacrylate coatings.Compared with virgin pp acid esters film, changed by the method for the present invention
Water vapor permeability and the resistance to water of the polyacrylate dispersion film of property can improve simultaneously, and water vapor permeability carries
High by 51%, resistance to water improves 11.61%, and tensile strength improves 60.26%.
Further, by ammonia or sodium hydroxide to the zinc hydroxide in hydroxide zinc/zinc oxide complex microsphere
The self assembling process of preferential etching and the growth of Zinc oxide nanoparticle oriented adsorption forms shell and has lamellar knot
The hollow zinc microsphere of structure so that prepared shell has the hollow zinc microsphere pattern of laminated structure
Homogeneous.
Accompanying drawing illustrates:
Fig. 1 is the SEM photograph that shell has the hollow zinc microsphere of laminated structure.Wherein Fig. 1 (a) is
SEM figure under amplification is 20000 times, Fig. 1 (b) is under amplification is 50000 times
SEM schemes.
Detailed description of the invention:
The hollow zinc microsphere to shell of the present invention below by specific embodiment with laminated structure changes
The preparation method of property polyacrylate dispersion is described further.
Embodiment 1:
1) by the Zn (NO of 2/3 consumption3)2·6H2O is miscible in deionized water with hexamethylenetetramine, and in
React 5min at 81 DEG C, be subsequently adding the sodium citrate of 2/3 consumption, after insulation reaction 1.1h, add residue
Zn (the NO of 1/3 consumption3)2·6H2O and hexamethylenetetramine, and at 86 DEG C after reaction 5min, add surplus
Yu the sodium citrate of 1/3 consumption, and after reacting 10min at 86 DEG C, using ammonia regulation pH value be 9.4,
Insulation reaction 3h at 86 DEG C, then through washing, be dried 12h at 60 DEG C and obtain shell there is laminated structure
Hollow zinc microsphere；Wherein, Zn (NO3)2·6H2O, hexamethylenetetramine, total consumption of sodium citrate
Mass ratio be 0.891:0.42:0.111；Zn(NO3)2·6H2The gross mass of O and the mass ratio of deionized water
For 0.891:70.
2) shell is had the hollow zinc microsphere of laminated structure in deionized water through ultrasonic disperse 10min
After, add in the polyacrylate dispersion that solid content is 30%, stirring reaction at 75 DEG C under 350rpm
6h, obtains shell and has the microsphere modified polyacrylate dispersion of hollow zinc of laminated structure；Described shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of polyacrylate dispersion is 0.030:30；Shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of deionized water is 0.030:15.
Embodiment 2:
1) by the Zn (NO of 2/3 consumption3)2·6H2O is miscible in deionized water with hexamethylenetetramine, and in
React 5min at 82 DEG C, be subsequently adding the sodium citrate of 2/3 consumption, after insulation reaction 1.2h, add residue
Zn (the NO of 1/3 consumption3)2·6H2O and hexamethylenetetramine, and at 87 DEG C after reaction 5min, add surplus
Yu the sodium citrate of 1/3 consumption, and after reacting 10min at 87 DEG C, using ammonia regulation pH value be 10,
Insulation reaction 3.5h at 87 DEG C, then through washing, be dried 8h at 80 DEG C and obtain shell there is laminated structure
Hollow zinc microsphere；Wherein, Zn (NO3)2·6H2O, hexamethylenetetramine, total consumption of sodium citrate
Mass ratio be 0.7425:0.3495:0.093；Zn(NO3)2·6H2The gross mass of O and the quality of deionized water
Ratio is 0.7425:70.
2) shell is had the hollow zinc microsphere of laminated structure in deionized water through ultrasonic disperse 15min
After, add in the polyacrylate dispersion that solid content is 30%, stirring reaction at 78 DEG C under 400rpm
7h, obtains shell and has the microsphere modified polyacrylate dispersion of hollow zinc of laminated structure；Described shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of polyacrylate dispersion is 0.060:30；Shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of deionized water is 0.060:15.
Embodiment 3:
1) by the Zn (NO of 2/3 consumption3)2·6H2O is miscible in deionized water with hexamethylenetetramine, and in
React 5min at 81 DEG C, be subsequently adding the sodium citrate of 2/3 consumption, after insulation reaction 1.5h, add residue
Zn (the NO of 1/3 consumption3)2·6H2O and hexamethylenetetramine, and at 86 DEG C after reaction 5min, add surplus
Yu the sodium citrate of 1/3 consumption, and after reacting 10min at 86 DEG C, using ammonia regulation pH value be 9.8,
Insulation reaction 4h at 86 DEG C, then through washing, be dried 10h at 70 DEG C and obtain shell there is laminated structure
Hollow zinc microsphere；Wherein, Zn (NO3)2·6H2O, hexamethylenetetramine, total consumption of sodium citrate
Mass ratio be 1.2075:0.5685:0.2985；Zn(NO3)2·6H2The gross mass of O and the matter of deionized water
Amount ratio is 1.2075:70.
2) shell is had the hollow zinc microsphere of laminated structure in deionized water through ultrasonic disperse 10min
After, add in the polyacrylate dispersion that solid content is 30%, stirring reaction at 80 DEG C under 400rpm
6h, obtains shell and has the microsphere modified polyacrylate dispersion of hollow zinc of laminated structure；Described shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of polyacrylate dispersion is 0.090:30；Shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of deionized water is 0.090:15.
Embodiment 4:
1) by the Zn (NO of 2/3 consumption3)2·6H2O is miscible in deionized water with hexamethylenetetramine, and in
React 5min at 83 DEG C, be subsequently adding the sodium citrate of 2/3 consumption, after insulation reaction 1.4h, add residue
Zn (the NO of 1/3 consumption3)2·6H2O and hexamethylenetetramine, and at 88 DEG C after reaction 5min, add surplus
Yu the sodium citrate of 1/3 consumption, and after reacting 10min at 88 DEG C, using ammonia regulation pH value be 10.4,
Insulation reaction 3.5h at 88 DEG C, then through washing, be dried 11h at 75 DEG C and obtain shell there is lamellar knot
The hollow zinc microsphere of structure；Wherein, Zn (NO3)2·6H2O, hexamethylenetetramine, total use of sodium citrate
The mass ratio of amount is 0.636:0.30:0.039；Zn(NO3)2·6H2The gross mass of O and the quality of deionized water
Ratio is 0.636:70.
2) shell is had the hollow zinc microsphere of laminated structure in deionized water through ultrasonic disperse 20min
After, add in the polyacrylate dispersion that solid content is 30%, stirring reaction at 75 DEG C under 350rpm
8h, obtains shell and has the microsphere modified polyacrylate dispersion of hollow zinc of laminated structure；Described shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of polyacrylate dispersion is 0.120:30；Shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of deionized water is 0.120:15.
Embodiment 5:
1) by the Zn (NO of 2/3 consumption3)2·6H2O is miscible in deionized water with hexamethylenetetramine, and in
React 5min at 82 DEG C, be subsequently adding the sodium citrate of 2/3 consumption, after insulation reaction 1.3h, add residue
Zn (the NO of 1/3 consumption3)2·6H2O and hexamethylenetetramine, and at 87 DEG C after reaction 5min, add surplus
Yu the sodium citrate of 1/3 consumption, and after reacting 10min at 87 DEG C, using ammonia regulation pH value be 9.2,
Insulation reaction 3h at 87 DEG C, then through washing, be dried 12h at 60 DEG C and obtain shell there is laminated structure
Hollow zinc microsphere；Wherein, Zn (NO3)2·6H2O, hexamethylenetetramine, total consumption of sodium citrate
Mass ratio be 1.068:0.504:0.1335；Zn(NO3)2·6H2The gross mass of O and the quality of deionized water
Ratio is 1.068:70.
2) shell is had the hollow zinc microsphere of laminated structure in deionized water through ultrasonic disperse 10min
After, add in the polyacrylate dispersion that solid content is 30%, stirring reaction at 78 DEG C under 450rpm
7.5h, obtains shell and has the microsphere modified polyacrylate dispersion of hollow zinc of laminated structure；Described shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of polyacrylate dispersion is 0.030:30；Shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of deionized water is 0.030:15.
Embodiment 6:
1) by the Zn (NO of 2/3 consumption3)2·6H2O is miscible in deionized water with hexamethylenetetramine, and in
React 5min at 84 DEG C, be subsequently adding the sodium citrate of 2/3 consumption, after insulation reaction 1.1h, add residue
Zn (the NO of 1/3 consumption3)2·6H2O and hexamethylenetetramine, and at 90 DEG C after reaction 5min, add surplus
Yu the sodium citrate of 1/3 consumption, and after reacting 10min at 90 DEG C, use sodium hydrate aqueous solution regulation
PH value is 10.8, insulation reaction 4.5h at 90 DEG C, then through washing, be dried 11h at 65 DEG C and obtain shell
Layer has the hollow zinc microsphere of laminated structure；Wherein, Zn (NO3)2·6H2O, hexamethylenetetramine, lemon
The mass ratio of total consumption of lemon acid sodium is 0.7125:0.336:0.0225；Zn(NO3)2·6H2The gross mass of O with
The mass ratio of deionized water is 0.7125:70.
2) shell is had the hollow zinc microsphere of laminated structure in deionized water through ultrasonic disperse 15min
After, add in the polyacrylate dispersion that solid content is 30%, stirring reaction at 76 DEG C under 450rpm
7h, obtains shell and has the microsphere modified polyacrylate dispersion of hollow zinc of laminated structure；Described shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of polyacrylate dispersion is 0.060:30；Shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of deionized water is 0.060:15.
Embodiment 7:
1) by the Zn (NO of 2/3 consumption3)2·6H2O is miscible in deionized water with hexamethylenetetramine, and in
React 5min at 83 DEG C, be subsequently adding the sodium citrate of 2/3 consumption, after insulation reaction 1.3h, add residue
Zn (the NO of 1/3 consumption3)2·6H2O and hexamethylenetetramine, and at 88 DEG C after reaction 5min, add surplus
Yu the sodium citrate of 1/3 consumption, and after reacting 10min at 88 DEG C, use sodium hydrate aqueous solution regulation
PH value is 10.6, insulation reaction 5h at 88 DEG C, then through washing, be dried 9h at 60 DEG C and obtain shell
There is the hollow zinc microsphere of laminated structure；Wherein, Zn (NO3)2·6H2O, hexamethylenetetramine, Fructus Citri Limoniae
The mass ratio of total consumption of acid sodium is 0.624:0.2775:0.027；Zn(NO3)2·6H2The gross mass of O with go
The mass ratio of ionized water is 0.624:70.
2) shell is had the hollow zinc microsphere of laminated structure in deionized water through ultrasonic disperse 20min
After, add in the polyacrylate dispersion that solid content is 30%, stirring reaction at 80 DEG C under 370rpm
8h, obtains shell and has the microsphere modified polyacrylate dispersion of hollow zinc of laminated structure；Described shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of polyacrylate dispersion is 0.160:30；Shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of deionized water is 0.160:15.
Embodiment 8
1) by the Zn (NO of 2/3 consumption3)2·6H2O is miscible in deionized water with hexamethylenetetramine, and in
React 5min at 81 DEG C, be subsequently adding the sodium citrate of 2/3 consumption, after insulation reaction 1.5h, add residue
Zn (the NO of 1/3 consumption3)2·6H2O and hexamethylenetetramine, and at 86 DEG C after reaction 5min, add surplus
Yu the sodium citrate of 1/3 consumption, and after reacting 10min at 86 DEG C, use sodium hydrate aqueous solution regulation
PH value is 9.2, insulation reaction 5h at 86 DEG C, then through washing, be dried 12h at 60 DEG C and obtain shell
There is the hollow zinc microsphere of laminated structure；Wherein, Zn (NO3)2·6H2O, hexamethylenetetramine, Fructus Citri Limoniae
The mass ratio of total consumption of acid sodium is 0.935:0.481:0.15；Zn(NO3)2·6H2The gross mass of O with go from
The mass ratio of sub-water is 0.935:70.
2) shell is had the hollow zinc microsphere of laminated structure in deionized water through ultrasonic disperse 20min
After, add in the polyacrylate dispersion that solid content is 30%, stirring reaction at 75 DEG C under 450rpm
8h, obtains shell and has the microsphere modified polyacrylate dispersion of hollow zinc of laminated structure；Described shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of polyacrylate dispersion is 0.030:30；Shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of deionized water is 0.030:15.
Embodiment 9
1) by the Zn (NO of 2/3 consumption3)2·6H2O is miscible in deionized water with hexamethylenetetramine, and in
React 5min at 84 DEG C, be subsequently adding the sodium citrate of 2/3 consumption, after insulation reaction 1.1h, add residue
Zn (the NO of 1/3 consumption3)2·6H2O and hexamethylenetetramine, and at 90 DEG C after reaction 5min, add surplus
Yu the sodium citrate of 1/3 consumption, and after reacting 10min at 90 DEG C, use sodium hydrate aqueous solution regulation
PH value is 10.8, insulation reaction 3h at 90 DEG C, then through washing, be dried 8h at 80 DEG C and obtain shell
There is the hollow zinc microsphere of laminated structure；Wherein, Zn (NO3)2·6H2O, hexamethylenetetramine, Fructus Citri Limoniae
The mass ratio of total consumption of acid sodium is 1.2075:0.5685:0.135；Zn(NO3)2·6H2The gross mass of O with
The mass ratio of deionized water is 1.2075:70.
2) shell is had the hollow zinc microsphere of laminated structure in deionized water through ultrasonic disperse 15min
After, add in the polyacrylate dispersion that solid content is 30%, stirring reaction at 75 DEG C under 400rpm
7h, obtains shell and has the microsphere modified polyacrylate dispersion of hollow zinc of laminated structure；Described shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of polyacrylate dispersion is 0.16:30；Shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of deionized water is 0.16:15.
Embodiment 10
1) by the Zn (NO of 2/3 consumption3)2·6H2O is miscible in deionized water with hexamethylenetetramine, and in
React 5min at 82 DEG C, be subsequently adding the sodium citrate of 2/3 consumption, after insulation reaction 1.5h, add residue
Zn (the NO of 1/3 consumption3)2·6H2O and hexamethylenetetramine, and at 88 DEG C after reaction 5min, add surplus
Yu the sodium citrate of 1/3 consumption, and after reacting 10min at 88 DEG C, use sodium hydrate aqueous solution regulation
PH value is 10, insulation reaction 4h at 88 DEG C, then through washing, be dried 10h at 70 DEG C and obtain shell
There is the hollow zinc microsphere of laminated structure；Wherein, Zn (NO3)2·6H2O, hexamethylenetetramine, Fructus Citri Limoniae
The mass ratio of total consumption of acid sodium is 1.132:0.53:0.076；Zn(NO3)2·6H2The gross mass of O with go from
The mass ratio of sub-water is 1.132:70.
2) shell is had the hollow zinc microsphere of laminated structure in deionized water through ultrasonic disperse 10min
After, add in the polyacrylate dispersion that solid content is 30%, stirring reaction at 80 DEG C under 350rpm
6.5h, obtains shell and has the microsphere modified polyacrylate dispersion of hollow zinc of laminated structure；Described shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of polyacrylate dispersion is 0.09:30；Shell
Having the hollow zinc microsphere of laminated structure with the mass ratio of deionized water is 0.09:15.
Fig. 1 is the SEM photograph that shell has the hollow zinc microsphere of laminated structure, from Fig. 1 (a) and figure
1 (b) can be seen that the ZnO microsphere appearance and size using the present invention to prepare is homogeneous, in defining significantly
Hollow structure, and its shell has laminated structure.
Table 1 has the property of the hollow zinc microsphere modified polyacrylate dispersion film of laminated structure for shell
Energy.Refer to table 1 below.
Table 1 shell has the performance of the hollow zinc microsphere modified polyacrylate dispersion film of laminated structure
As known from Table 1 compared with virgin pp acid esters emulsion film, the modified polypropene prepared according to the present invention
The water vapor permeability of acid esters emulsion film improves 51.33%, and resistance to water improves 11.61%, and tensile strength promotes
60.26%.
The present invention prepares shell first with alkaline etching mechanism and Ostwald ripening mechanism and has lamellar knot
The hollow zinc microsphere of structure, then uses its modified polyacrylate emulsion by physical blending process.Pass through
Zinc hydroxide in hydroxide zinc/zinc oxide complex microsphere is preferentially etched and zinc oxide by ammonia or sodium hydroxide
The hollow zinc that the self assembling process formation shell of nano-particle oriented adsorption growth has laminated structure is micro-
Ball, preparation technology is simple, and reaction condition is gentle, workable and productivity is high, and prepared shell has
The hollow zinc microsphere pattern of laminated structure is homogeneous.Compared with virgin pp acid esters film, pass through the present invention
The water vapor permeability of the modified polyacrylate dispersion film of method improve 51%, resistance to water improves
11.61%, tensile strength improves 60.26%.
Present disclosure is not limited to cited by embodiment, and those of ordinary skill in the art are by reading the present invention
Description and the conversion of any equivalence of taking technical solution of the present invention, be the claim institute of the present invention
Contain.
Claims (7)
1. shell has the preparation method of the microsphere modified polyacrylate dispersion of hollow zinc of laminated structure, its
It is characterised by, comprises the following steps:
1) by the Zn (NO of 2/3 consumption3)2·6H2O is miscible in deionized water with hexamethylenetetramine, and in
React 5min at 81～84 DEG C, be subsequently adding the sodium citrate of 2/3 consumption, after insulation reaction 1.1～1.5h, add
Enter the Zn (NO of residue 1/3 consumption3)2·6H2O and hexamethylenetetramine, and at 86～90 DEG C, react 5min
After, adding the sodium citrate of residue 1/3 consumption, after reaction 10min, regulation pH value is 9.2～10.8, then
Insulation reaction 3～5h at 86～90 DEG C, then through washing, be dried to obtain shell there is the hollow of laminated structure
ZnO microsphere；Wherein, Zn (NO3)2·6H2O, hexamethylenetetramine, the quality of total consumption of sodium citrate
Than being (0.624～1.2075): (0.2775～0.5685): (0.0225～0.2985)；Wherein, described pH value is
Ammonia or sodium hydrate aqueous solution is used to be adjusted；
2) shell is had the hollow zinc microsphere of laminated structure in deionized water after ultrasonic disperse, add
Entering in polyacrylate dispersion, stirring also reacts 6～8h at 75～80 DEG C, obtains shell and has laminated structure
The microsphere modified polyacrylate dispersion of hollow zinc；Described shell has the hollow zinc of laminated structure
Microsphere is (0.030～0.160) with the mass ratio of polyacrylate dispersion: 30.
Shell the most according to claim 1 has the microsphere modified polypropylene of hollow zinc of laminated structure
The preparation method of acid esters emulsion, it is characterised in that described Zn (NO3)2·6H2The gross mass of O and deionized water
Mass ratio is (0.624～1.2075): 70.
Shell the most according to claim 1 has the microsphere modified polypropylene of hollow zinc of laminated structure
The preparation method of acid esters emulsion, it is characterised in that described being dried is to be dried 8～12h under the conditions of 60～80 DEG C.
Shell the most according to claim 1 has the microsphere modified polypropylene of hollow zinc of laminated structure
The preparation method of acid esters emulsion, it is characterised in that the solid content of described polyacrylate dispersion is 30%.
Shell the most according to claim 1 has the microsphere modified polypropylene of hollow zinc of laminated structure
The preparation method of acid esters emulsion, it is characterised in that during described ultrasonic disperse, shell has in laminated structure
Empty ZnO microsphere is (0.030～0.160) with the mass ratio of deionized water: 15.
Shell the most according to claim 1 has the microsphere modified polypropylene of hollow zinc of laminated structure
The preparation method of acid esters emulsion, it is characterised in that the time of described ultrasonic disperse is 10～20min.
Shell the most according to claim 1 has the microsphere modified polypropylene of hollow zinc of laminated structure
The preparation method of acid esters emulsion, it is characterised in that described mixing speed is 350～450rpm.
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|---|---|---|---|---|
| CN104177537B (en) * | 2014-08-04 | 2016-05-18 | 陕西科技大学 | A kind of preparation method of polyacrylate/columnar hollow zinc oxide complex emulsions for leather |
| CN106366817B (en) * | 2016-09-30 | 2019-02-01 | 陕西科技大学 | A kind of preparation method of polyacrylate/peanut shape hollow zinc composite leather coating agent |
| CN107376955B (en) * | 2017-07-28 | 2020-05-29 | 浙江师范大学 | Photocatalytic antibacterial material and preparation method thereof |
-
2014
- 2014-08-04 CN CN201410380206.1A patent/CN104151564B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| "Fabrication of monodisperse hollow silica spheres and effect on water";Yan Bao et al.;《Journal of Colloid and Interface Science》;20130627;第407卷;第155-163页 * |
| "Trisodium citrate assisted synthesis of ZnO hollow spheres via a facile precipitation route and their application as gas sensor";Lan Ge et al.;《Journal of Materials Chemistry》;20110620;第21卷;第10750-10754页 * |
| "氧化锌纳米梭酒精敏感性能的研究";张春宇等;《哈尔滨理工大学学报》;20140630;第19卷(第3期);第15-19页 * |
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| CN104151564A (en) | 2014-11-19 |
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