CN103013270B - Preparation method of high moisture permeability type polyacrylate nano-composite leather coating agent - Google Patents

Preparation method of high moisture permeability type polyacrylate nano-composite leather coating agent Download PDF

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CN103013270B
CN103013270B CN201210540281.0A CN201210540281A CN103013270B CN 103013270 B CN103013270 B CN 103013270B CN 201210540281 A CN201210540281 A CN 201210540281A CN 103013270 B CN103013270 B CN 103013270B
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solution
coating agent
acrylic acid
leather coating
composite leather
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CN103013270A (en
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鲍艳
杨永强
马建中
刘俊莉
时春华
王潇
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Abstract

The invention provides a preparation method of a high moisture permeability type polyacrylate nano-composite leather coating agent. The preparation method comprises the following steps of: firstly, using nano-zinc oxide as a template to prepare hollow silicon dioxide nano particles and subsequently using an in-situ polymerization process to copolymerize the hollow silicon dioxide nano particles with an acrylate monomer to prepare a polyacrylate nano-composite leather coating agent with high moisture permeability. The high moisture permeability type polyacrylate nano-composite leather coating agent prepared by using the method provided by the invention has the advantage of excellent performance. Compared with the pure polyacrylate leather coating agent, the moisture permeability of the high moisture permeability type polyacrylate nano-composite leather coating agent is enhanced by 530.31%, the tensile strength is enhanced by 1307.343% and the breaking elongation is enhanced by 199.73%.

Description

A kind of preparation method of high vapor pervious type polyacrylic ester nano composite leather coating agent
Technical field
The present invention relates to a kind of preparation method of polyacrylic ester nano composite leather coating agent, particularly a kind of preparation method of high vapor pervious type polyacrylic ester nano composite leather coating agent.
Technical background
Polyacrylic ester is a class hide finishes of current widespread use, has the advantages such as good light stability, chemical-resistant, extensibility and cohesiveness.But polyacrylic ester film forming is comparatively fine and close, the sweat that Severe blockage human body distributes diffuses to extraneous passage, produces have a strong impact on the sanitation performance of leather goods and snugness of fit.
Inorganic nano-particle is as rigid material, disperseed to make the mechanical property of polymkeric substance, resistance toheat, wear resisting property etc. be improved in the polymer matrix, simultaneously, there is the inorganic nano-particle of specific function, as silver, zinc oxide, titanium dioxide etc. can also improve the performances such as antibacterial, the UV resistance of polymkeric substance.At present inorganic nano-particle is introduced polyacrylic ester hide finishes, hide finishes is antibacterial for improving, the having been reported of UV resistance, the performance such as heat-resisting [Liu Junli, Ma Jianzhong, Bao Yan, Zhu Zhenfeng. polyacrylic ester/nano-TiO 2fabrication & properties [J] functional materials of matrix material, 2012,2(43): 209-212; Hafeez Ahamed; V.Senthilkumar.Experimental investigation on newly developed ultrafine-grained aluminium based nano-composites with improved mechanical properties.Materials and Design; 2012,37:182-192; Junli Liu, Jianzhong Ma, Yan Bao, Zhenfeng Zhu, Yihong Liu, Ying Zheng.Preparation of Polyacrylate/ZnONanocomposite [C] .Materials Science Forum.2011,694.430-434], but it is not remarkable to the lifting effect of water vapor permeability of leathers.
Summary of the invention
The present invention is directed to above-mentioned deficiency, provide a kind of preparation method of high vapor pervious type polyacrylic ester nano composite leather coating agent.
In order to reach above object, the technical solution used in the present invention comprises the following steps:
1) hollow silica nanoparticle is prepared:
1.1) by ZnO, Tween-80, H 2o and dehydrated alcohol mixing also ultrasonic disperse, form the dispersion liquid of stable homogeneous; Wherein, ZnO, Tween-80, H 2the mass ratio of O is (0.016 ~ 0.056): (0.052 ~ 0.092): (2 ~ 6), and the ZnO of every 0.016 ~ 0.056g adds the dehydrated alcohol of 18 ~ 22mL;
1.2) in dispersion liquid, add tensio-active agent, and stir, then ultrasonic disperse 15 ~ 35min, then add ammoniacal liquor, make the pH value of the system obtained be 8.5 ~ 10, and magnetic agitation is even, obtains mixed solution; Wherein, the mass ratio of tensio-active agent and ZnO is (0.052 ~ 0.092): (0.016 ~ 0.056);
1.3) mixed solution of tetraethoxy and dehydrated alcohol is added drop-wise to step 1.2 in 6 ~ 10h) mixed solution in, then at room temperature stir 30min; Again by the reaction solution that obtains through centrifugal treating, the centrifugal lower sediment obtained adopts distilled water and absolute ethanol washing repeatedly, obtains core/shell type zinc oxide/SiO 2 composite microsphere; Wherein, the mass ratio of tetraethoxy and ZnO is (0.08 ~ 0.12): (0.016 ~ 0.056), and the tetraethoxy of every 0.08 ~ 0.12g and the dehydrated alcohol of 10mL are hybridly prepared into mixed solution;
1.4) at normal temperatures, be scattered in by core/shell type zinc oxide/SiO 2 composite microsphere in the strong acid of pH=1.0 ~ 3.0 and stir 4 ~ 8h, then centrifugal treating, the centrifugal lower sediment obtained is hollow silica nanoparticle;
2) high vapor pervious type polyacrylic ester nano composite leather coating agent is prepared:
2.1) high molecular weight water soluble polymer is joined in distilled water, stir the solution making it to form transparent and homogeneous, and the pH value of solution is adjusted to 5 ~ 6, obtain the high molecular polymer aqueous solution; Wherein, the mass ratio of high molecular weight water soluble polymer and distilled water is (0.9 ~ 1.3): 25;
2.2) in the high molecular polymer aqueous solution, hollow silica nanoparticle, tensio-active agent is added, supersound process 10min; Then isothermal reaction 20min under 58 ~ 63 DEG C of water-baths, obtains reaction solution A; Wherein, the mass ratio of hollow silica nanoparticle, tensio-active agent, high molecular weight water soluble polymer is (0.0806 ~ 0.4030): 0.95:(0.9 ~ 1.3);
2.3) add in reaction solution A by 1/5 ~ 1/3 of esters of acrylic acid mix monomer total mass, be then warming up to 70 ~ 75 DEG C of reaction 30min, obtain reaction solution B; Again initiator solution and residual acrylic acid ester class mix monomer are dropped in reaction solution B respectively, be then warming up to 80 ~ 85 DEG C of insulation reaction 2h, be i.e. obtained high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, in the esters of acrylic acid mixture total mass added, initiator solution, the ratio of the quality of initiator, the quality of hollow silica nanoparticle is 13.93:0.193:(0.0806 ~ 0.4030), initiator solution and residual acrylic acid ester class mix monomer drop in reaction solution B simultaneously.
Described step 1.1) in ZnO be spherical, particle diameter is 25 ~ 35nm.
Described step 1.2) and 2.2) in tensio-active agent be the mixture of one or more arbitrary proportions in polyvinyl alcohol, PEG-4000, polyvinylpyrrolidone, Tween-80, cetyl trimethylammonium bromide, sodium lauryl sulphate.
Described step 1.2) in ammoniacal liquor is disposable adds, the mass concentration of ammoniacal liquor is 28%, and the tensio-active agent of every 0.052 ~ 0.092g adds the ammoniacal liquor of 0.3 ~ 0.7mL.
Described step 1.4) in strong acid be hydrochloric acid, nitric acid or sulfuric acid.
Described step 2.1) in high molecular weight water soluble polymer be the mixture of one or more arbitrary proportions in polyacrylic acid, polymethyl acrylic acid, polyacrylamide, diallyl dimethyl ammoniumchloride, poly-(acrylic acid-acrylamide).
Described step 2.3) in esters of acrylic acid mix monomer be the mixture of two or more arbitrary proportions in methyl methacrylate, butyl methacrylate, ethyl propenoate, butyl acrylate, methyl acrylate.
Described step 2.3) in initiator be the mixture of one or more arbitrary proportions in azo diisobutyl amidine hydrochloride, azo-bis-isobutyl cyanide, Potassium Persulphate, ammonium persulphate, Sodium Persulfate.
Described step 2.3) in initiator solution and residual acrylic acid ester class mix monomer time of dropping to reaction solution B be 2h.
Described step 2.3) in the concentration of the aqueous solution of initiator be 0.0193g/mL.
Further, preparation method of the present invention comprises the following steps:
1) hollow silica nanoparticle is prepared:
1.1) by the Tween-80 of the ZnO of 0.016 ~ 0.056g, 0.052 ~ 0.092g, the H of 2 ~ 6g 2the dehydrated alcohol mixing also ultrasonic disperse of O and 18 ~ 22mL, forms the dispersion liquid of stable homogeneous;
1.2) in dispersion liquid, add the tensio-active agent of 0.052 ~ 0.092g, and stir, then ultrasonic disperse 15 ~ 35min, then add ammoniacal liquor, make the pH value of the system obtained be 8.5 ~ 10, and magnetic agitation is even, obtains mixed solution;
1.3) mixed solution of the tetraethoxy of 0.08 ~ 0.12g and the dehydrated alcohol of 10mL is added drop-wise to step 1.2 in 6 ~ 10h) mixed solution in, then at room temperature stir 30min; Again by the reaction solution that obtains through centrifugal treating, the centrifugal lower sediment obtained adopts distilled water and absolute ethanol washing repeatedly, obtains core/shell type zinc oxide/SiO 2 composite microsphere;
1.4) at normal temperatures, be scattered in by core/shell type zinc oxide/SiO 2 composite microsphere in the strong acid of pH=1.0 ~ 3.0 and stir 4 ~ 8h, then centrifugal treating, the centrifugal lower sediment obtained is hollow silica nanoparticle;
2) high vapor pervious type polyacrylic ester nano composite leather coating agent is prepared:
2.1) high molecular weight water soluble polymer of 0.9 ~ 1.3g is joined in the distilled water of 25g, stir the solution making it to form transparent and homogeneous, and the pH value of solution is adjusted to 5 ~ 6, obtain the high molecular polymer aqueous solution;
2.2) in the high molecular polymer aqueous solution, the hollow silica nanoparticle of 0.0806 ~ 0.4030g, the tensio-active agent of 0.95g is added, supersound process 10min; Then isothermal reaction 20min under 58 ~ 63 DEG C of water-baths, obtains reaction solution A;
2.3) add in reaction solution A by 1/5 ~ 1/3 of esters of acrylic acid mix monomer total mass, be then warming up to 70 ~ 75 DEG C of reaction 30min, obtain reaction solution B; Again initiator solution and residual acrylic acid ester class mix monomer are dropped in reaction solution B respectively, be then warming up to 80 ~ 85 DEG C of insulation reaction 2h, be i.e. obtained high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the esters of acrylic acid mix monomer total mass added is 13.93g, and in the initiator solution added, the quality of initiator is 0.193g, and initiator solution and residual acrylic acid ester class mix monomer drop in reaction solution B simultaneously.
Described step 1.1) in ZnO be spherical, particle diameter is 25 ~ 35nm.
Described step 1.2) and 2.2) in tensio-active agent be the mixture of one or more arbitrary proportions in polyvinyl alcohol, PEG-4000, polyvinylpyrrolidone, Tween-80, cetyl trimethylammonium bromide, sodium lauryl sulphate.
Described step 1.2) in ammoniacal liquor is disposable adds, the mass concentration of ammoniacal liquor is 28%, and add-on is 0.3 ~ 0.7mL.
Described step 1.4) in strong acid be hydrochloric acid, nitric acid or sulfuric acid.
Described step 2.1) in high molecular weight water soluble polymer be the mixture of one or more arbitrary proportions in polyacrylic acid, polymethyl acrylic acid, polyacrylamide, diallyl dimethyl ammoniumchloride, poly-(acrylic acid-acrylamide).
Described step 2.3) in esters of acrylic acid mix monomer be the mixture of two or more arbitrary proportions in methyl methacrylate, butyl methacrylate, ethyl propenoate, butyl acrylate, methyl acrylate.
Described step 2.3) in initiator be the mixture of one or more arbitrary proportions in azo diisobutyl amidine hydrochloride, Potassium Persulphate, ammonium persulphate, Sodium Persulfate.
Described step 2.3) in initiator solution and residual acrylic acid ester class mix monomer time of dropping to reaction solution B be 2h.
Described step 2.3) in the initiator solution that adds be 10mL.
The present invention take nano zine oxide as Template preparation hollow silica nanoparticle, and adopts emulsion polymerization in situ the polyacrylic ester nano composite leather coating agent with high permeability to water vapour to be prepared by hollow silica nanoparticle and acrylic ester monomer copolymerization.The present invention adopts strong acid to be dissolved by the ZnO in core/shell type zinc oxide/SiO 2 composite microsphere, thus obtained hollow silica nanoparticle.Compared with prior art, its beneficial effect is embodied in following two aspects to high vapor pervious type polyacrylic ester nano composite leather coating agent prepared by the present invention:
On the one hand, the hollow structure of hollow silica nanoparticle adds the free volume number of the high vapor pervious type polyacrylic ester nano composite leather coating agent inside of preparing, provide passage for the small molecules such as steam, gas is discharged into the external world by polymeric film, the high vapor pervious type polyacrylic ester nano composite leather coating agent that the present invention is prepared can improve sanitation performance and the snugness of fit of leather goods; Compared with virgin pp acid esters hide finishes, the permeability to water vapour of the high vapor pervious type polyacrylic ester nano composite leather coating agent prepared by the present invention improves 530.31%.
On the other hand, the specific surface effect of the hollow silica nanoparticle prepared due to the present invention, quantum size effect and volume effect can improve the mechanical property of hide finishes; Compared with virgin pp acid esters hide finishes, its tensile strength improves 1307.43%, and elongation at break improves 199.73%.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of hollow silica nanoparticle prepared by the present invention.
Embodiment
Embodiment 1:
1) hollow silica nanoparticle is prepared:
1.1) by the H of Tween-80,4g of ZnO, 0.072g of 0.026g 2the dehydrated alcohol mixing also ultrasonic disperse 30min of O and 20mL, forms the dispersion liquid of stable homogeneous; Wherein, ZnO is spherical, and particle diameter is 25 ~ 35nm;
1.2) in dispersion liquid, add 0.072g polyvinylpyrrolidone (PVP), and stir, then ultrasonic disperse 30min, property adds the ammoniacal liquor that 0.5mL mass concentration is 28% again, makes the pH value of the system obtained be 9.0, and magnetic agitation 10min; Obtain mixed solution;
1.3) mixed solution of the tetraethoxy of 0.1g and the dehydrated alcohol of 10mL is added drop-wise to step 1.2 in 10h) mixed solution in, then at room temperature stir 30min; The reaction solution centrifugal treating that recycling high speed rotating whizzer will obtain, the centrifugal lower sediment obtained adopts distilled water and absolute ethanol washing 3 times repeatedly, obtains core/shell type zinc oxide/SiO 2 composite microsphere;
1.4) at normal temperatures, be scattered in the hydrochloric acid of pH=2.0 by core/shell type zinc oxide/SiO 2 composite microsphere and stir 4h, then utilize the process of high speed rotating centrifuge, the centrifugal lower sediment obtained is hollow silica nanoparticle.
2) high vapor pervious type polyacrylic ester nano composite leather coating agent is prepared:
2.1) polyacrylic acid of 1.1g is joined in the beaker that 25g distilled water is housed, stir the solution making it to form transparent and homogeneous, and the pH value of solution is regulated pH=6, obtain the polyacrylic acid aqueous solution;
2.2) in the polyacrylic acid aqueous solution, the hollow silica nanoparticle of 0.1612g, the mixed surfactant of 0.95g is added, supersound process 10min; And the mixing solutions obtained is transferred in the there-necked flask of 100mL, then isothermal reaction 20min under 60 DEG C of water-baths, obtains reaction solution A; Wherein, mixed surfactant is that the sodium lauryl sulphate (SDS) of 3:1 and PEG-4000 (PEG-400) mix by mass ratio;
2.3) join in reaction solution A by 1/3 of esters of acrylic acid mix monomer total mass, be then warming up to 75 DEG C of reaction 30min, obtain reaction solution B; Again ammonium sulfate (APS) aqueous solution of 10mL and remaining esters of acrylic acid mix monomer are dropped to respectively in reaction solution B with constant speed in 2h, then 80 DEG C of insulation reaction 2h are warming up to, i.e. obtained high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the esters of acrylic acid mix monomer total mass added is 13.93g, the quality of the ammonium sulfate (APS) in ammonium sulfate (APS) aqueous solution added is 0.193g, ammonium sulfate (APS) aqueous solution and remaining esters of acrylic acid mix monomer drop in reaction solution B simultaneously, and esters of acrylic acid mix monomer is that the methyl methacrylate of 1:2 and butyl acrylate mix by mass ratio.
Embodiment 2:
1) hollow silica nanoparticle is prepared:
1.1) by the H of Tween-80,3g of ZnO, 0.052g of 0.046g 2the dehydrated alcohol mixing also ultrasonic disperse 25min of O and 18mL, forms the dispersion liquid of stable homogeneous; Wherein, ZnO is spherical, and particle diameter is 25 ~ 35nm;
1.2) in dispersion liquid, add the sodium lauryl sulphate (SDS) of 0.092g, and stir, then ultrasonic disperse 15min, property adds the ammoniacal liquor that 0.7mL mass concentration is 28% again, makes the pH value of the system obtained be 10.0, and magnetic agitation 10min; Obtain mixed solution;
1.3) mixed solution of the tetraethoxy of 0.12g and the dehydrated alcohol of 10mL is added drop-wise to step 1.2 in 6h) mixed solution in, then at room temperature stir 30min; The reaction solution centrifugal treating that recycling high speed rotating whizzer will obtain, the centrifugal lower sediment obtained adopts distilled water and absolute ethanol washing 3 times repeatedly, obtains core/shell type zinc oxide/SiO 2 composite microsphere;
1.4) at normal temperatures, be scattered in the hydrochloric acid of pH=2.0 by core/shell type zinc oxide/SiO 2 composite microsphere and stir 5h, then utilize the process of high speed rotating centrifuge, the centrifugal lower sediment obtained is hollow silica nanoparticle.
2) high vapor pervious type polyacrylic ester nano composite leather coating agent is prepared:
2.1) polymethyl acrylic acid of 0.9g is joined in the beaker that 25g distilled water is housed, stir the solution making it to form transparent and homogeneous, and the pH value of solution is regulated pH=5, obtain polymethyl aqueous acid;
2.2) in polymethyl aqueous acid, the hollow silica nanoparticle of 0.0806g, the mixed surfactant of 0.95g is added, supersound process 10min; And the mixing solutions obtained is transferred in the there-necked flask of 100mL, then isothermal reaction 20min under 58 DEG C of water-baths, obtains reaction solution A; Wherein, mixed surfactant is that the polyvinyl alcohol (PVA) of 3:1 and polyvinylpyrrolidone (PVP) mix by mass ratio;
2.3) join in reaction solution A by 1/4 of esters of acrylic acid mix monomer total mass, be then warming up to 70 DEG C of reaction 30min, obtain reaction solution B; Again azo-bis-isobutyl cyanide (AIBN) aqueous solution of 10mL and remaining esters of acrylic acid mix monomer are dropped to respectively in reaction solution B with constant speed in 2h, then 82 DEG C of insulation reaction 2h are warming up to, i.e. obtained high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the esters of acrylic acid mix monomer total mass added is 13.93g, the quality of the azo-bis-isobutyl cyanide (AIBN) in azo-bis-isobutyl cyanide (AIBN) aqueous solution added is 0.193g, azo-bis-isobutyl cyanide (AIBN) aqueous solution and residual acrylic acid ester class mix monomer drop in reaction solution B simultaneously, and esters of acrylic acid mix monomer is that the methyl methacrylate of 1:2 and ethyl propenoate mix by mass ratio.
Embodiment 3:
1) hollow silica nanoparticle is prepared:
1.1) by the H of Tween-80,2g of ZnO, 0.092g of 0.016g 2the dehydrated alcohol mixing also ultrasonic disperse 35min of O and 22mL, forms the dispersion liquid of stable homogeneous; Wherein, ZnO is spherical, and particle diameter is 25 ~ 35nm;
1.2) in dispersion liquid, add the cetyl trimethylammonium bromide (CTAB) of 0.062g, and stir, then ultrasonic disperse 20min, property adds the ammoniacal liquor that 0.4mL mass concentration is 28% again, the pH value of the system obtained is made to be 8.8, and magnetic agitation 10min; Obtain mixed solution;
1.3) mixed solution of the tetraethoxy of 0.09g and the dehydrated alcohol of 10mL is added drop-wise to step 1.2 in 7h) mixed solution in, then at room temperature stir 30min; The reaction solution centrifugal treating that recycling high speed rotating whizzer will obtain, the centrifugal lower sediment obtained adopts distilled water and absolute ethanol washing 3 times repeatedly, obtains core/shell type zinc oxide/SiO 2 composite microsphere;
1.4) at normal temperatures, be scattered in the hydrochloric acid of pH=2.0 by core/shell type zinc oxide/SiO 2 composite microsphere and stir 6h, then utilize the process of high speed rotating centrifuge, the centrifugal lower sediment obtained is hollow silica nanoparticle.
2) high vapor pervious type polyacrylic ester nano composite leather coating agent is prepared:
2.1) polyacrylamide of 1.0g is joined in the beaker that 25g distilled water is housed, stir the solution making it to form transparent and homogeneous, and the pH value of solution is regulated pH=5.5, obtain polyacrylamide solution;
2.2) in polyacrylamide solution, add the hollow silica nanoparticle of 0.2418g, the Tween-80 of 0.95g, supersound process 10min; And the mixing solutions obtained is transferred in the there-necked flask of 100mL, then isothermal reaction 20min under 63 DEG C of water-baths, obtains reaction solution A;
2.3) join in reaction solution A by 1/5 of esters of acrylic acid mix monomer total mass, be then warming up to 71 DEG C of reaction 30min, obtain reaction solution B; Again Potassium Persulphate (KPS) aqueous solution of 10mL and remaining esters of acrylic acid mix monomer are dropped to respectively in reaction solution B with constant speed in 2h, then 81 DEG C of insulation reaction 2h are warming up to, i.e. obtained high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the esters of acrylic acid mix monomer total mass added is 13.93g, the quality of the Potassium Persulphate (KPS) in Potassium Persulphate (KPS) aqueous solution added is 0.193g, Potassium Persulphate (KPS) aqueous solution and residual acrylic acid ester class mix monomer drop in reaction solution B simultaneously, esters of acrylic acid mix monomer be by mass ratio be the methyl methacrylate of 2:1:1, methyl acrylate and butyl acrylate mix.
Embodiment 4:
1) hollow silica nanoparticle is prepared:
1.1) by the H of Tween-80,5g of ZnO, 0.082g of 0.036g 2the dehydrated alcohol mixing also ultrasonic disperse 40min of O and 19mL, forms the dispersion liquid of stable homogeneous; Wherein, ZnO is spherical, and particle diameter is 25 ~ 35nm;
1.2) in dispersion liquid, add the poly(oxyethylene glycol) 400 (PEG-400) of 0.082g, and stir, then ultrasonic disperse 25min, property adds the ammoniacal liquor that 0.6mL mass concentration is 28% again, makes the pH value of the system obtained be 9.7, and magnetic agitation 10min; Obtain mixed solution;
1.3) mixed solution of the tetraethoxy of 0.08g and the dehydrated alcohol of 10mL is added drop-wise to step 1.2 in 9h) mixed solution in, then at room temperature stir 30min; The reaction solution centrifugal treating that recycling high speed rotating whizzer will obtain, the centrifugal lower sediment obtained adopts distilled water and absolute ethanol washing 3 times repeatedly, obtains core/shell type zinc oxide/SiO 2 composite microsphere;
1.4) at normal temperatures, be scattered in the hydrochloric acid of pH=2.0 by core/shell type zinc oxide/SiO 2 composite microsphere and stir 7h, then utilize the process of high speed rotating centrifuge, the centrifugal lower sediment obtained is hollow silica nanoparticle.
2) high vapor pervious type polyacrylic ester nano composite leather coating agent is prepared:
2.1) diallyl dimethyl ammoniumchloride of 1.2g is joined in the beaker that 25g distilled water is housed, stir the solution making it to form transparent and homogeneous, and the pH value of solution is regulated pH=5.3, obtain the diallyl dimethyl ammoniumchloride aqueous solution;
2.2) in the diallyl dimethyl ammoniumchloride aqueous solution, the hollow silica nanoparticle of 0.403g, the polyvinyl alcohol (PVA) of 0.95g is added, supersound process 10min; And the mixing solutions obtained is transferred in the there-necked flask of 100mL, then isothermal reaction 20min under 59 DEG C of water-baths, obtains reaction solution A;
2.3) join in reaction solution A by 1/4 of esters of acrylic acid mix monomer total mass, be then warming up to 72 DEG C of reaction 30min, obtain reaction solution B; Again Sodium Persulfate (SPS) aqueous solution of 10mL and remaining esters of acrylic acid mix monomer are dropped to respectively in reaction solution B with constant speed in 2h, then 84 DEG C of insulation reaction 2h are warming up to, i.e. obtained high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the esters of acrylic acid mix monomer total mass added is 13.93g, the quality of the Sodium Persulfate (SPS) in Sodium Persulfate (SPS) aqueous solution added is 0.193g, Sodium Persulfate (SPS) aqueous solution and residual acrylic acid ester class mix monomer drop in reaction solution B simultaneously, and esters of acrylic acid mix monomer is that the methyl acrylate of 2:1 and butyl acrylate mix by mass ratio.
Embodiment 5:
1) hollow silica nanoparticle is prepared:
1.1) by the H of Tween-80,6g of ZnO, 0.062g of 0.056g 2the dehydrated alcohol mixing also ultrasonic disperse 20min of O and 21mL, forms the dispersion liquid of stable homogeneous; Wherein, ZnO is spherical, and particle diameter is 25 ~ 35nm;
1.2) in dispersion liquid, add the cetyl trimethylammonium bromide (CTAB) of 0.052g, and stir, then ultrasonic disperse 35min, property adds the ammoniacal liquor that 0.3mL mass concentration is 28% again, the pH value of the system obtained is made to be 8.5, and magnetic agitation 10min; Obtain mixed solution;
1.3) mixed solution of the tetraethoxy of 0.11g and the dehydrated alcohol of 10mL is added drop-wise to step 1.2 in 8h) mixed solution in, then at room temperature stir 30min; The reaction solution centrifugal treating that recycling high speed rotating whizzer will obtain, the centrifugal lower sediment obtained adopts distilled water and absolute ethanol washing 3 times repeatedly, obtains core/shell type zinc oxide/SiO 2 composite microsphere;
1.4) at normal temperatures, be scattered in the hydrochloric acid of pH=2.0 by core/shell type zinc oxide/SiO 2 composite microsphere and stir 8h, then utilize the process of high speed rotating centrifuge, the centrifugal lower sediment obtained is hollow silica nanoparticle.
2) high vapor pervious type polyacrylic ester nano composite leather coating agent is prepared:
2.1) poly-(vinylformic acid-propionic acid amide) of 1.3g is joined in the beaker that 25g distilled water is housed, stir the solution making it to form transparent and homogeneous, and the pH value of solution is regulated pH=5.7, gathered (vinylformic acid-propionic acid amide) aqueous solution;
2.2) in poly-(vinylformic acid-propionic acid amide) aqueous solution, the hollow silica nanoparticle of 0.3224g, the mixed surfactant of 0.95g is added, supersound process 10min; And the mixing solutions obtained is transferred in the there-necked flask of 100mL, then isothermal reaction 20min under 62 DEG C of water-baths, obtains reaction solution A; Wherein, mixed surfactant is that the polyvinylpyrrolidone (PVP) of 3:1 and cetyl trimethylammonium bromide (CTAB) mix by mass ratio;
2.3) join in reaction solution A by 1/3 of esters of acrylic acid mix monomer total mass, be then warming up to 74 DEG C of reaction 30min, obtain reaction solution B; Again azo diisobutyl amidine hydrochloride (AIBA) aqueous solution of 10mL and remaining esters of acrylic acid mix monomer are dropped to respectively in reaction solution B with constant speed in 2h, then 85 DEG C of insulation reaction 2h are warming up to, i.e. obtained high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the esters of acrylic acid mix monomer total mass added is 13.93g, the quality of azo diisobutyl amidine hydrochloride (AIBA) in azo diisobutyl amidine hydrochloride (AIBA) aqueous solution added is 0.193g, azo diisobutyl amidine hydrochloride (AIBA) aqueous solution and residual acrylic acid ester class mix monomer drop in reaction solution B simultaneously, esters of acrylic acid mix monomer be by mass ratio be the methyl methacrylate of 2:1:1, butyl methacrylate and methyl acrylate mix.
Embodiment 6:
1) hollow silica nanoparticle is prepared:
1.1) by the H of Tween-80,5g of ZnO, 0.082g of 0.036g 2the dehydrated alcohol mixing also ultrasonic disperse 40min of O and 19mL, forms the dispersion liquid of stable homogeneous; Wherein, ZnO is spherical, and particle diameter is 25 ~ 35nm;
1.2) in dispersion liquid, add the mixed surfactant of 0.082g, and stir, then ultrasonic disperse 25min, property adds the ammoniacal liquor that 0.6mL mass concentration is 28% again, makes the pH value of the system obtained be 9.7, and magnetic agitation 10min; Obtain mixed solution; Wherein, mixed surfactant is that the polyvinyl alcohol (PVA) of 4:1 and Tween-80 mix by mass ratio;
1.3) mixed solution of the tetraethoxy of 0.08g and the dehydrated alcohol of 10mL is added drop-wise to step 1.2 in 9h) mixed solution in, then at room temperature stir 30min; The reaction solution centrifugal treating that recycling high speed rotating whizzer will obtain, the centrifugal lower sediment obtained adopts distilled water and absolute ethanol washing 3 times repeatedly, obtains core/shell type zinc oxide/SiO 2 composite microsphere;
1.4) at normal temperatures, be scattered in the sulfuric acid of pH=1.0 by core/shell type zinc oxide/SiO 2 composite microsphere and stir 7h, then utilize the process of high speed rotating centrifuge, the centrifugal lower sediment obtained is hollow silica nanoparticle.
2) high vapor pervious type polyacrylic ester nano composite leather coating agent is prepared:
2.1) 1.2g diallyl dimethyl ammoniumchloride is joined in the beaker that 25g distilled water is housed, stir the solution making it to form transparent and homogeneous, and the pH value of solution is regulated pH=5.3, obtain the diallyl dimethyl ammoniumchloride aqueous solution;
2.2) in the diallyl dimethyl ammoniumchloride aqueous solution, the hollow silica nanoparticle of 0.403g, the polyvinyl alcohol (PVA) of 0.95g is added, supersound process 10min; And the mixing solutions obtained is transferred in the there-necked flask of 100mL, then isothermal reaction 20min under 59 DEG C of water-baths, obtains reaction solution A;
2.3) join in reaction solution A by 1/4 of esters of acrylic acid mix monomer total mass, be then warming up to 72 DEG C of reaction 30min, obtain reaction solution B; Again Sodium Persulfate (SPS) aqueous solution of 10mL and remaining esters of acrylic acid mix monomer are dropped to respectively in reaction solution B with constant speed in 2h, then 84 DEG C of insulation reaction 2h are warming up to, i.e. obtained high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the esters of acrylic acid mix monomer total mass added is 13.93g, Sodium Persulfate (SPS) quality in Sodium Persulfate (SPS) aqueous solution added is 0.193g, Sodium Persulfate (SPS) aqueous solution and residual acrylic acid ester class mix monomer drop in reaction solution B simultaneously, and esters of acrylic acid mix monomer is that the methyl acrylate of 2:1 and butyl acrylate mix by mass ratio.
Embodiment 7:
1) hollow silica nanoparticle is prepared:
1.1) by the H of Tween-80,6g of ZnO, 0.062g of 0.056g 2the dehydrated alcohol mixing also ultrasonic disperse 20min of O and 21mL, forms the dispersion liquid of stable homogeneous; Wherein, ZnO is spherical, and particle diameter is 25 ~ 35nm;
1.2) in dispersion liquid, add the cetyl trimethylammonium bromide (CTAB) of 0.052g, and stir, then ultrasonic disperse 35min, property adds the ammoniacal liquor that 0.3mL mass concentration is 28% again, the pH value of the system obtained is made to be 8.5, and magnetic agitation 10min; Obtain mixed solution;
1.3) mixed solution of the tetraethoxy of 0.11g and the dehydrated alcohol of 10mL is added drop-wise to step 1.2 in 8h) mixed solution in, then at room temperature stir 30min; The reaction solution centrifugal treating that recycling high speed rotating whizzer will obtain, the centrifugal lower sediment obtained adopts distilled water and absolute ethanol washing 2 times repeatedly, obtains core/shell type zinc oxide/SiO 2 composite microsphere;
1.4) at normal temperatures, be scattered in the nitric acid of pH=3.0 by core/shell type zinc oxide/SiO 2 composite microsphere and stir 8h, then utilize the process of high speed rotating centrifuge, the centrifugal lower sediment obtained is hollow silica nanoparticle.
2) high vapor pervious type polyacrylic ester nano composite leather coating agent is prepared:
2.1) high molecular weight water soluble polymer of 1.3g is joined in the beaker that 25g distilled water is housed, stir the solution making it to form transparent and homogeneous, and the pH value of solution is regulated pH=5.3, obtain the high molecular polymer aqueous solution; Wherein, high molecular weight water soluble polymer is that the diallyl dimethyl ammoniumchloride of 1:3 and polyacrylic acid mix by mass ratio;
2.2) in the high molecular polymer aqueous solution, the hollow silica nanoparticle of 0.3224g, the mixed surfactant of 0.95g is added, supersound process 10min; And the mixing solutions obtained is transferred in the there-necked flask of 100mL, then isothermal reaction 20min under 62 DEG C of water-baths, obtains reaction solution A; Wherein, mixed surfactant is that the polyvinylpyrrolidone (PVP) of 3:1 and cetyl trimethylammonium bromide (CTAB) mix by mass ratio;
2.3) join in reaction solution A by 1/3 of esters of acrylic acid mix monomer total mass, be then warming up to 74 DEG C of reaction 30min, obtain reaction solution B; Again the initiator solution of 10mL and remaining esters of acrylic acid mix monomer are dropped to respectively in reaction solution B with constant speed in 2h, be then warming up to 85 DEG C of insulation reaction 2h, be i.e. obtained high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the esters of acrylic acid mix monomer total mass added is 13.93g, initiator quality in the initiator solution added is 0.193g, initiator solution and residual acrylic acid ester class mix monomer drop in reaction solution B simultaneously, esters of acrylic acid mix monomer be by mass ratio be the methyl methacrylate of 2:1:1, butyl methacrylate and methyl acrylate mix; Initiator in initiator solution is that azo diisobutyl amidine hydrochloride (AIBA) of 1:2 and ammonium sulfate (APS) mix by mass ratio.
As seen from Figure 1, the wall thickness of single hollow silica nanoparticle prepared by the present invention is 16nm, and central aperture is 23nm.
The performance data of the high vapor pervious type polyacrylic ester nano composite leather coating agent that table 1 is prepared for employing method of the present invention, as can be seen from Table 1, the high vapor pervious type polyacrylic ester nano composite leather coating agent excellent property adopting method of the present invention to prepare, compared with virgin pp acid esters hide finishes, its permeability to water vapour improves 530.31%, tensile strength improves 1307.343%, and elongation at break improves 199.73%.
The performance data of table 1 high vapor pervious type polyacrylic ester nano composite leather coating agent

Claims (6)

1. a preparation method for high vapor pervious type polyacrylic ester nano composite leather coating agent, is characterized in that comprising the following steps:
1) hollow silica nanoparticle is prepared:
1.1) by ZnO, Tween-80, H 2o and dehydrated alcohol mixing also ultrasonic disperse, form the dispersion liquid of stable homogeneous; Wherein, ZnO, Tween-80, H 2the mass ratio of O is (0.016 ~ 0.056): (0.052 ~ 0.092): (2 ~ 6), and the ZnO of every 0.016 ~ 0.056g adds the dehydrated alcohol of 18 ~ 22mL; ZnO is spherical, and particle diameter is 25 ~ 35nm;
1.2) in dispersion liquid, add tensio-active agent, and stir, then ultrasonic disperse 15 ~ 35min, then add ammoniacal liquor, make the pH value of the system obtained be 8.5 ~ 10, and magnetic agitation is even, obtains mixed solution; Wherein, the mass ratio of tensio-active agent and ZnO is (0.052 ~ 0.092): (0.016 ~ 0.056); Wherein, tensio-active agent is the mixture of one or more arbitrary proportions in polyvinyl alcohol, PEG-4000, polyvinylpyrrolidone, Tween-80, cetyl trimethylammonium bromide, sodium lauryl sulphate;
1.3) mixed solution of tetraethoxy and dehydrated alcohol is added drop-wise to step 1.2 in 6 ~ 10h) mixed solution in, then at room temperature stir 30min; Again by the reaction solution that obtains through centrifugal treating, the centrifugal lower sediment obtained adopts distilled water and absolute ethanol washing repeatedly, obtains core/shell type zinc oxide/SiO 2 composite microsphere; Wherein, the mass ratio of tetraethoxy and ZnO is (0.08 ~ 0.12): (0.016 ~ 0.056), and the tetraethoxy of every 0.08 ~ 0.12g and the dehydrated alcohol of 10mL are hybridly prepared into mixed solution;
1.4) at normal temperatures, be scattered in by core/shell type zinc oxide/SiO 2 composite microsphere in the strong acid of pH=1.0 ~ 3.0 and stir 4 ~ 8h, then centrifugal treating, the centrifugal lower sediment obtained is hollow silica nanoparticle;
2) high vapor pervious type polyacrylic ester nano composite leather coating agent is prepared:
2.1) high molecular weight water soluble polymer is joined in distilled water, stir the solution making it to form transparent and homogeneous, and the pH value of solution is adjusted to 5 ~ 6, obtain the high molecular polymer aqueous solution; Wherein, the mass ratio of high molecular weight water soluble polymer and distilled water is (0.9 ~ 1.3): 25; High molecular weight water soluble polymer is the mixture of one or more arbitrary proportions in polyacrylic acid, polymethyl acrylic acid, polyacrylamide, diallyl dimethyl ammoniumchloride, poly-(acrylic acid-acrylamide);
2.2) in the high molecular polymer aqueous solution, hollow silica nanoparticle, tensio-active agent is added, supersound process 10min; Then isothermal reaction 20min under 58 ~ 63 DEG C of water-baths, obtains reaction solution A; Wherein, the mass ratio of hollow silica nanoparticle, tensio-active agent, high molecular weight water soluble polymer is (0.0806 ~ 0.4030): 0.95:(0.9 ~ 1.3); Wherein, tensio-active agent is the mixture of one or more arbitrary proportions in polyvinyl alcohol, PEG-4000, polyvinylpyrrolidone, Tween-80, cetyl trimethylammonium bromide, sodium lauryl sulphate;
2.3) add in reaction solution A by 1/5 ~ 1/3 of esters of acrylic acid mix monomer total mass, be then warming up to 70 ~ 75 DEG C of reaction 30min, obtain reaction solution B; Again initiator solution and residual acrylic acid ester class mix monomer are dropped in reaction solution B respectively, be then warming up to 80 ~ 85 DEG C of insulation reaction 2h, be i.e. obtained high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, in the esters of acrylic acid mixture total mass added, initiator solution, the ratio of initiator quality, hollow silica nanoparticle quality is 13.93:0.193:(0.0806 ~ 0.4030), initiator solution and residual acrylic acid ester class mix monomer drop in reaction solution B simultaneously;
Described step 2.3) in esters of acrylic acid mix monomer be the mixture of two or more arbitrary proportions in methyl methacrylate, butyl methacrylate, ethyl propenoate, butyl acrylate, methyl acrylate.
2. the preparation method of high vapor pervious type polyacrylic ester nano composite leather coating agent according to claim 1, it is characterized in that: described step 1.2) in ammoniacal liquor is disposable adds, the mass concentration of ammoniacal liquor is 28%, and the tensio-active agent of every 0.052 ~ 0.092g adds the ammoniacal liquor of 0.3 ~ 0.7mL.
3. the preparation method of high vapor pervious type polyacrylic ester nano composite leather coating agent according to claim 1, is characterized in that: described step 1.4) in strong acid be hydrochloric acid, nitric acid or sulfuric acid.
4. the preparation method of high vapor pervious type polyacrylic ester nano composite leather coating agent according to claim 1, is characterized in that: described step 2.3) in initiator be the mixture of one or more arbitrary proportions in azo diisobutyl amidine hydrochloride, azo-bis-isobutyl cyanide, Potassium Persulphate, ammonium persulphate, Sodium Persulfate.
5. the preparation method of the high vapor pervious type polyacrylic ester nano composite leather coating agent according to claim 1 or 4, is characterized in that: described step 2.3) in initiator solution and residual acrylic acid ester class mix monomer time of dropping to reaction solution B be 2h.
6. the preparation method of high vapor pervious type polyacrylic ester nano composite leather coating agent according to claim 1, is characterized in that: described step 2.3) in the concentration of the aqueous solution of initiator be 0.0193g/mL.
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