CN103013270A - 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 PDFInfo
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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
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 present widespread use, has the advantages such as good light stability, chemical-resistant, extensibility and cohesiveness.But the polyacrylic ester film forming is comparatively fine and close, has seriously stopped up the sweat that human body distributes and has diffused to extraneous passage, the sanitation performance of leather goods and snugness of fit is produced have a strong impact on.
Inorganic nano-particle is as rigid material, it is dispersed in the mechanical property that can make polymkeric substance in the polymeric matrix, resistance toheat, wear resisting property etc. is improved, simultaneously, inorganic nano-particle with specific function can also improve the performances such as antibiotic, anti-ultraviolet of polymkeric substance such as silver, zinc oxide, titanium dioxide etc.At present inorganic nano-particle is introduced the polyacrylic ester hide finishes, be used for improving the having been reported of antibiotic, the anti-ultraviolet of hide finishes, the performance such as heat-resisting [Liu Junli, Ma Jianzhong, Bao Yan, Zhu Zhenfeng. polyacrylic ester/nano-TiO
2Composite manufacture and performance [J] functional materials, 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 its lifting effect to water vapor permeability of leathers is not remarkable.
Summary of the invention
The present invention is directed to above-mentioned deficiency, a kind of preparation method of high vapor pervious type polyacrylic ester nano composite leather coating agent is provided.
In order to reach above purpose, the technical solution used in the present invention may further comprise the steps:
1) preparation hollow silica nanoparticle:
1.1) with ZnO, Tween-80, H
2O and dehydrated alcohol mix and ultra-sonic dispersion, 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 per 0.016 ~ 0.056g adds the dehydrated alcohol of 18 ~ 22mL;
1.2) in dispersion liquid, add tensio-active agent, and stir, then ultra-sonic dispersion 15 ~ 35min adds ammoniacal liquor again, and the pH value that makes the system that obtains is 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) and mixed solution in, then at room temperature stir 30min; With the reaction solution process centrifugal treating that obtains, the centrifugal lower sediment that obtains adopts distilled water and absolute ethanol washing repeatedly, obtains core/shell type zinc oxide/SiO 2 composite microsphere again; Wherein, the mass ratio of tetraethoxy and ZnO is (0.08 ~ 0.12): (0.016 ~ 0.056), and the tetraethoxy of per 0.08 ~ 0.12g and the dehydrated alcohol of 10mL are hybridly prepared into mixed solution;
1.4) at normal temperatures, core/shell type zinc oxide/SiO 2 composite microsphere is scattered in the strong acid of pH=1.0 ~ 3.0 and stirs 4 ~ 8h, centrifugal treating then, the centrifugal lower sediment that obtains is the hollow silica nanoparticle;
2) the high vapor pervious type polyacrylic ester nano composite leather coating agent of preparation:
2.1) high molecular weight water soluble polymer is joined in the distilled water, stir the solution that makes 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, add hollow silica nanoparticle, tensio-active agent, supersound process 10min; Then isothermal reaction 20min under 58 ~ 63 ℃ 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) 1/5 ~ 1/3 of esters of acrylic acid mix monomer total mass is added among the reaction solution A, then be warming up to 70 ~ 75 ℃ of reaction 30min, obtain reaction solution B; Again initiator solution and residual acrylic acid ester class mix monomer are dropped to respectively among the reaction solution B, then be warming up to 80 ~ 85 ℃ of insulation reaction 2h, namely make high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the ratio of the quality of the quality of initiator, hollow silica nanoparticle is 13.93:0.193:(0.0806 ~ 0.4030 in the esters of acrylic acid mixture total mass that adds, the initiator solution), initiator solution and residual acrylic acid ester class mix monomer drop among the reaction solution B simultaneously.
Described step 1.1) ZnO in is spherical, and 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, the sodium lauryl sulphate.
Described step 1.2) the disposable adding of ammoniacal liquor in, the mass concentration of ammoniacal liquor is 28%, the tensio-active agent of per 0.052 ~ 0.092g adds the ammoniacal liquor of 0.3 ~ 0.7mL.
Described step 1.4) strong acid in is hydrochloric acid, nitric acid or sulfuric acid.
Described step 2.1) high molecular weight water soluble polymer in is 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) the esters of acrylic acid mix monomer in is the mixture of two or more arbitrary proportions in methyl methacrylate, butyl methacrylate, ethyl propenoate, butyl acrylate, the methyl acrylate.
Described step 2.3) initiator in is the mixture of one or more arbitrary proportions in azo diisobutyl amidine hydrochloride, azo-bis-isobutyl cyanide, Potassium Persulphate, ammonium persulphate, the Sodium Persulfate.
Described step 2.3) to drop to the time of reaction solution B be 2h for initiator solution and residual acrylic acid ester class mix monomer in.
Described step 2.3) concentration of the aqueous solution of initiator is 0.0193g/mL in.
Further, preparation method of the present invention may further comprise the steps:
1) preparation hollow silica nanoparticle:
1.1) with Tween-80, the H of 2 ~ 6g of ZnO, the 0.052 ~ 0.092g of 0.016 ~ 0.056g
2The dehydrated alcohol of O and 18 ~ 22mL mixes and ultra-sonic dispersion, 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 ultra-sonic dispersion 15 ~ 35min adds ammoniacal liquor again, and the pH value that makes the system that obtains is 8.5 ~ 10, and magnetic agitation is even, obtains mixed solution;
1.3) mixed solution of the dehydrated alcohol of the tetraethoxy of 0.08 ~ 0.12g and 10mL is added drop-wise to step 1.2 in 6 ~ 10h) and mixed solution in, then at room temperature stir 30min; With the reaction solution process centrifugal treating that obtains, the centrifugal lower sediment that obtains adopts distilled water and absolute ethanol washing repeatedly, obtains core/shell type zinc oxide/SiO 2 composite microsphere again;
1.4) at normal temperatures, core/shell type zinc oxide/SiO 2 composite microsphere is scattered in the strong acid of pH=1.0 ~ 3.0 and stirs 4 ~ 8h, centrifugal treating then, the centrifugal lower sediment that obtains is the hollow silica nanoparticle;
2) the high vapor pervious type polyacrylic ester nano composite leather coating agent of preparation:
2.1) high molecular weight water soluble polymer of 0.9 ~ 1.3g is joined in the distilled water of 25g, stir the solution that makes 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, add the hollow silica nanoparticle of 0.0806 ~ 0.4030g, the tensio-active agent of 0.95g, supersound process 10min; Then isothermal reaction 20min under 58 ~ 63 ℃ of water-baths obtains reaction solution A;
2.3) 1/5 ~ 1/3 of esters of acrylic acid mix monomer total mass is added among the reaction solution A, then be warming up to 70 ~ 75 ℃ of reaction 30min, obtain reaction solution B; Again initiator solution and residual acrylic acid ester class mix monomer are dropped to respectively among the reaction solution B, then be warming up to 80 ~ 85 ℃ of insulation reaction 2h, namely make high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the esters of acrylic acid mix monomer total mass of adding is 13.93g, and the quality of initiator is 0.193g in the initiator solution of adding, and initiator solution and residual acrylic acid ester class mix monomer drop among the reaction solution B simultaneously.
Described step 1.1) ZnO in is spherical, and 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, the sodium lauryl sulphate.
Described step 1.2) the disposable adding of ammoniacal liquor in, the mass concentration of ammoniacal liquor is 28%, add-on is 0.3 ~ 0.7mL.
Described step 1.4) strong acid in is hydrochloric acid, nitric acid or sulfuric acid.
Described step 2.1) high molecular weight water soluble polymer in is 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) the esters of acrylic acid mix monomer in is the mixture of two or more arbitrary proportions in methyl methacrylate, butyl methacrylate, ethyl propenoate, butyl acrylate, the methyl acrylate.
Described step 2.3) initiator in is the mixture of one or more arbitrary proportions in azo diisobutyl amidine hydrochloride, Potassium Persulphate, ammonium persulphate, the Sodium Persulfate.
Described step 2.3) to drop to the time of reaction solution B be 2h for initiator solution and residual acrylic acid ester class mix monomer in.
Described step 2.3) initiator solution that adds in is 10mL.
The present invention prepares the hollow silica nanoparticle take nano zine oxide as template, and adopts emulsion polymerization in situ that hollow silica nanoparticle and acrylic ester monomer copolymerization are prepared the polyacrylic ester nano composite leather coating agent with high permeability to water vapour.The present invention adopts strong acid with the dissolving of the ZnO in core/shell type zinc oxide/SiO 2 composite microsphere, thereby makes the hollow silica nanoparticle.The high vapor pervious type polyacrylic ester nano composite leather coating agent of the present invention preparation compared with prior art, its beneficial effect is embodied in following two aspects:
On the one hand, the hollow structure of hollow silica nanoparticle has increased 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 are 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; Compare 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 that the present invention is prepared has improved 530.31%.
On the other hand, because specific surface effect, quantum size effect and the volume effect of the hollow silica nanoparticle of the present invention's preparation can improve the mechanical property of hide finishes; Compare with virgin pp acid esters hide finishes, its tensile strength has promoted 1307.43%, and elongation at break has promoted 199.73%.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the hollow silica nanoparticle for preparing of the present invention.
Embodiment
Embodiment 1:
1) preparation hollow silica nanoparticle:
1.1) with Tween-80, the H of 4g of ZnO, the 0.072g of 0.026g
2The dehydrated alcohol of O and 20mL mixes and ultra-sonic dispersion 30min, forms the dispersion liquid of stable homogeneous; Wherein, ZnO is spherical, and particle diameter is 25 ~ 35nm;
1.2) add 0.072g polyvinylpyrrolidone (PVP) in the dispersion liquid, and stir, ultra-sonic dispersion 30min then, property adding 0.5mL mass concentration is 28% ammoniacal liquor again, the pH value that makes the system that obtains is 9.0, and magnetic agitation 10min; Obtain mixed solution;
1.3) mixed solution of the dehydrated alcohol of the tetraethoxy of 0.1g and 10mL is added drop-wise to step 1.2 in 10h) and mixed solution in, then at room temperature stir 30min; Recycling high speed rotating whizzer is the reaction solution centrifugal treating that obtains, and the centrifugal lower sediment that obtains 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, core/shell type zinc oxide/SiO 2 composite microsphere is scattered in the hydrochloric acid of pH=2.0 and stirs 4h, then utilize high speed rotating whizzer centrifugal treating, the centrifugal lower sediment that obtains is the hollow silica nanoparticle.
2) the high vapor pervious type polyacrylic ester nano composite leather coating agent of preparation:
2.1) polyacrylic acid of 1.1g is joined in the beaker that 25g distilled water is housed, stir the solution that makes 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, add the hollow silica nanoparticle of 0.1612g, the mixed surfactant of 0.95g, supersound process 10min; And the mixing solutions that obtains is transferred in the there-necked flask of 100mL, then isothermal reaction 20min under 60 ℃ of water-baths obtains reaction solution A; Wherein, mixed surfactant is to be that sodium lauryl sulphate (SDS) and the PEG-4000 (PEG-400) of 3:1 mixes by mass ratio;
2.3) 1/3 of esters of acrylic acid mix monomer total mass is joined among the reaction solution A, then be warming up to 75 ℃ of reaction 30min, obtain reaction solution B; Ammonium sulfate (APS) aqueous solution and remaining esters of acrylic acid mix monomer with 10mL drops to respectively among the reaction solution B in 2h with constant speed again, then be warming up to 80 ℃ of insulation reaction 2h, namely make high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the esters of acrylic acid mix monomer total mass that adds is 13.93g, the quality of the ammonium sulfate (APS) in ammonium sulfate (APS) aqueous solution that adds is 0.193g, ammonium sulfate (APS) aqueous solution and remaining esters of acrylic acid mix monomer drop among the reaction solution B simultaneously, and the esters of acrylic acid mix monomer is to be that methyl methacrylate and the butyl acrylate of 1:2 mixes by mass ratio.
Embodiment 2:
1) preparation hollow silica nanoparticle:
1.1) with Tween-80, the H of 3g of ZnO, the 0.052g of 0.046g
2The dehydrated alcohol of O and 18mL mixes and ultra-sonic dispersion 25min, forms the dispersion liquid of stable homogeneous; Wherein, ZnO is spherical, and particle diameter is 25 ~ 35nm;
1.2) add the sodium lauryl sulphate (SDS) of 0.092g in the dispersion liquid, and stir, ultra-sonic dispersion 15min then, property adding 0.7mL mass concentration is 28% ammoniacal liquor again, the pH value that makes the system that obtains is 10.0, and magnetic agitation 10min; Obtain mixed solution;
1.3) mixed solution of the dehydrated alcohol of the tetraethoxy of 0.12g and 10mL is added drop-wise to step 1.2 in 6h) and mixed solution in, then at room temperature stir 30min; Recycling high speed rotating whizzer is the reaction solution centrifugal treating that obtains, and the centrifugal lower sediment that obtains 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, core/shell type zinc oxide/SiO 2 composite microsphere is scattered in the hydrochloric acid of pH=2.0 and stirs 5h, then utilize high speed rotating whizzer centrifugal treating, the centrifugal lower sediment that obtains is the hollow silica nanoparticle.
2) the high vapor pervious type polyacrylic ester nano composite leather coating agent of preparation:
2.1) polymethyl acrylic acid of 0.9g is joined in the beaker that 25g distilled water is housed, stir the solution that makes it to form transparent and homogeneous, and the pH value of solution is regulated pH=5, obtain the polymethyl aqueous acid;
2.2) in the polymethyl aqueous acid, add the hollow silica nanoparticle of 0.0806g, the mixed surfactant of 0.95g, supersound process 10min; And the mixing solutions that obtains is transferred in the there-necked flask of 100mL, then isothermal reaction 20min under 58 ℃ of water-baths obtains reaction solution A; Wherein, mixed surfactant is to be that polyvinyl alcohol (PVA) and the polyvinylpyrrolidone (PVP) of 3:1 mixes by mass ratio;
2.3) 1/4 of esters of acrylic acid mix monomer total mass is joined among the reaction solution A, then be warming up to 70 ℃ of reaction 30min, obtain reaction solution B; Azo-bis-isobutyl cyanide (AIBN) aqueous solution and remaining esters of acrylic acid mix monomer with 10mL drops to respectively among the reaction solution B in 2h with constant speed again, then be warming up to 82 ℃ of insulation reaction 2h, namely make high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the esters of acrylic acid mix monomer total mass that adds is 13.93g, the quality of the azo-bis-isobutyl cyanide (AIBN) in azo-bis-isobutyl cyanide (AIBN) aqueous solution that adds is 0.193g, azo-bis-isobutyl cyanide (AIBN) aqueous solution and residual acrylic acid ester class mix monomer drop among the reaction solution B simultaneously, and the esters of acrylic acid mix monomer is to be that methyl methacrylate and the ethyl propenoate of 1:2 mixes by mass ratio.
Embodiment 3:
1) preparation hollow silica nanoparticle:
1.1) with Tween-80, the H of 2g of ZnO, the 0.092g of 0.016g
2The dehydrated alcohol of O and 22mL mixes and ultra-sonic dispersion 35min, forms the dispersion liquid of stable homogeneous; Wherein, ZnO is spherical, and particle diameter is 25 ~ 35nm;
1.2) add the cetyl trimethylammonium bromide (CTAB) of 0.062g in the dispersion liquid, and stir, ultra-sonic dispersion 20min then, property adding 0.4mL mass concentration is 28% ammoniacal liquor again, the pH value that makes the system that obtains is 8.8, and magnetic agitation 10min; Obtain mixed solution;
1.3) mixed solution of the dehydrated alcohol of the tetraethoxy of 0.09g and 10mL is added drop-wise to step 1.2 in 7h) and mixed solution in, then at room temperature stir 30min; Recycling high speed rotating whizzer is the reaction solution centrifugal treating that obtains, and the centrifugal lower sediment that obtains 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, core/shell type zinc oxide/SiO 2 composite microsphere is scattered in the hydrochloric acid of pH=2.0 and stirs 6h, then utilize high speed rotating whizzer centrifugal treating, the centrifugal lower sediment that obtains is the hollow silica nanoparticle.
2) the high vapor pervious type polyacrylic ester nano composite leather coating agent of preparation:
2.1) polyacrylamide of 1.0g is joined in the beaker that 25g distilled water is housed, stir the solution that makes 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 that obtains is transferred in the there-necked flask of 100mL, then isothermal reaction 20min under 63 ℃ of water-baths obtains reaction solution A;
2.3) 1/5 of esters of acrylic acid mix monomer total mass is joined among the reaction solution A, then be warming up to 71 ℃ of reaction 30min, obtain reaction solution B; Potassium Persulphate (KPS) aqueous solution and remaining esters of acrylic acid mix monomer with 10mL drops to respectively among the reaction solution B in 2h with constant speed again, then be warming up to 81 ℃ of insulation reaction 2h, namely make high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the esters of acrylic acid mix monomer total mass that adds is 13.93g, the quality of the Potassium Persulphate (KPS) in Potassium Persulphate (KPS) aqueous solution that adds is 0.193g, Potassium Persulphate (KPS) aqueous solution and residual acrylic acid ester class mix monomer drop among the reaction solution B simultaneously, and the esters of acrylic acid mix monomer is to be that methyl methacrylate, methyl acrylate and the butyl acrylate of 2:1:1 mixes by mass ratio.
Embodiment 4:
1) preparation hollow silica nanoparticle:
1.1) with Tween-80, the H of 5g of ZnO, the 0.082g of 0.036g
2The dehydrated alcohol of O and 19mL mixes and ultra-sonic dispersion 40min, forms the dispersion liquid of stable homogeneous; Wherein, ZnO is spherical, and particle diameter is 25 ~ 35nm;
1.2) add the poly(oxyethylene glycol) 400 (PEG-400) of 0.082g in the dispersion liquid, and stir, ultra-sonic dispersion 25min then, property adding 0.6mL mass concentration is 28% ammoniacal liquor again, the pH value that makes the system that obtains is 9.7, and magnetic agitation 10min; Obtain mixed solution;
1.3) mixed solution of the dehydrated alcohol of the tetraethoxy of 0.08g and 10mL is added drop-wise to step 1.2 in 9h) and mixed solution in, then at room temperature stir 30min; Recycling high speed rotating whizzer is the reaction solution centrifugal treating that obtains, and the centrifugal lower sediment that obtains 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, core/shell type zinc oxide/SiO 2 composite microsphere is scattered in the hydrochloric acid of pH=2.0 and stirs 7h, then utilize high speed rotating whizzer centrifugal treating, the centrifugal lower sediment that obtains is the hollow silica nanoparticle.
2) the high vapor pervious type polyacrylic ester nano composite leather coating agent of preparation:
2.1) diallyl dimethyl ammoniumchloride of 1.2g is joined in the beaker that 25g distilled water is housed, stir the solution that makes 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, add the hollow silica nanoparticle of 0.403g, the polyvinyl alcohol (PVA) of 0.95g, supersound process 10min; And the mixing solutions that obtains is transferred in the there-necked flask of 100mL, then isothermal reaction 20min under 59 ℃ of water-baths obtains reaction solution A;
2.3) 1/4 of esters of acrylic acid mix monomer total mass is joined among the reaction solution A, then be warming up to 72 ℃ of reaction 30min, obtain reaction solution B; Sodium Persulfate (SPS) aqueous solution and remaining esters of acrylic acid mix monomer with 10mL drops to respectively among the reaction solution B in 2h with constant speed again, then be warming up to 84 ℃ of insulation reaction 2h, namely make high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the esters of acrylic acid mix monomer total mass that adds is 13.93g, the quality of the Sodium Persulfate (SPS) in Sodium Persulfate (SPS) aqueous solution that adds is 0.193g, Sodium Persulfate (SPS) aqueous solution and residual acrylic acid ester class mix monomer drop among the reaction solution B simultaneously, and the esters of acrylic acid mix monomer is to be that methyl acrylate and the butyl acrylate of 2:1 mixes by mass ratio.
Embodiment 5:
1) preparation hollow silica nanoparticle:
1.1) with Tween-80, the H of 6g of ZnO, the 0.062g of 0.056g
2The dehydrated alcohol of O and 21mL mixes and ultra-sonic dispersion 20min, forms the dispersion liquid of stable homogeneous; Wherein, ZnO is spherical, and particle diameter is 25 ~ 35nm;
1.2) add the cetyl trimethylammonium bromide (CTAB) of 0.052g in the dispersion liquid, and stir, ultra-sonic dispersion 35min then, property adding 0.3mL mass concentration is 28% ammoniacal liquor again, the pH value that makes the system that obtains is 8.5, and magnetic agitation 10min; Obtain mixed solution;
1.3) mixed solution of the dehydrated alcohol of the tetraethoxy of 0.11g and 10mL is added drop-wise to step 1.2 in 8h) and mixed solution in, then at room temperature stir 30min; Recycling high speed rotating whizzer is the reaction solution centrifugal treating that obtains, and the centrifugal lower sediment that obtains 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, core/shell type zinc oxide/SiO 2 composite microsphere is scattered in the hydrochloric acid of pH=2.0 and stirs 8h, then utilize high speed rotating whizzer centrifugal treating, the centrifugal lower sediment that obtains is the hollow silica nanoparticle.
2) the high vapor pervious type polyacrylic ester nano composite leather coating agent of preparation:
2.1) poly-(vinylformic acid-propionic acid amide) of 1.3g joined in the beaker that 25g distilled water is housed, stir the solution that makes 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, add the hollow silica nanoparticle of 0.3224g, the mixed surfactant of 0.95g, supersound process 10min; And the mixing solutions that obtains is transferred in the there-necked flask of 100mL, then isothermal reaction 20min under 62 ℃ of water-baths obtains reaction solution A; Wherein, mixed surfactant is to be that polyvinylpyrrolidone (PVP) and the cetyl trimethylammonium bromide (CTAB) of 3:1 mixes by mass ratio;
2.3) 1/3 of esters of acrylic acid mix monomer total mass is joined among the reaction solution A, then be warming up to 74 ℃ of reaction 30min, obtain reaction solution B; Azo diisobutyl amidine hydrochloride (AIBA) aqueous solution and remaining esters of acrylic acid mix monomer with 10mL drops to respectively among the reaction solution B in 2h with constant speed again, then be warming up to 85 ℃ of insulation reaction 2h, namely make high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the esters of acrylic acid mix monomer total mass that adds is 13.93g, the quality of the azo diisobutyl amidine hydrochloride (AIBA) in azo diisobutyl amidine hydrochloride (AIBA) aqueous solution that adds is 0.193g, azo diisobutyl amidine hydrochloride (AIBA) aqueous solution and residual acrylic acid ester class mix monomer drop among the reaction solution B simultaneously, and the esters of acrylic acid mix monomer is to be that methyl methacrylate, butyl methacrylate and the methyl acrylate of 2:1:1 mixes by mass ratio.
Embodiment 6:
1) preparation hollow silica nanoparticle:
1.1) with Tween-80, the H of 5g of ZnO, the 0.082g of 0.036g
2The dehydrated alcohol of O and 19mL mixes and ultra-sonic dispersion 40min, forms the dispersion liquid of stable homogeneous; Wherein, ZnO is spherical, and particle diameter is 25 ~ 35nm;
1.2) add the mixed surfactant of 0.082g in the dispersion liquid, and stir, ultra-sonic dispersion 25min then, property adding 0.6mL mass concentration is 28% ammoniacal liquor again, the pH value that makes the system that obtains is 9.7, and magnetic agitation 10min; Obtain mixed solution; Wherein, mixed surfactant is to be that polyvinyl alcohol (PVA) and the Tween-80 of 4:1 mixes by mass ratio;
1.3) mixed solution of the dehydrated alcohol of the tetraethoxy of 0.08g and 10mL is added drop-wise to step 1.2 in 9h) and mixed solution in, then at room temperature stir 30min; Recycling high speed rotating whizzer is the reaction solution centrifugal treating that obtains, and the centrifugal lower sediment that obtains 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, core/shell type zinc oxide/SiO 2 composite microsphere is scattered in the sulfuric acid of pH=1.0 and stirs 7h, then utilize high speed rotating whizzer centrifugal treating, the centrifugal lower sediment that obtains is the hollow silica nanoparticle.
2) the high vapor pervious type polyacrylic ester nano composite leather coating agent of preparation:
2.1) the 1.2g diallyl dimethyl ammoniumchloride is joined in the beaker that 25g distilled water is housed, stir the solution that makes 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, add the hollow silica nanoparticle of 0.403g, the polyvinyl alcohol (PVA) of 0.95g, supersound process 10min; And the mixing solutions that obtains is transferred in the there-necked flask of 100mL, then isothermal reaction 20min under 59 ℃ of water-baths obtains reaction solution A;
2.3) 1/4 of esters of acrylic acid mix monomer total mass is joined among the reaction solution A, then be warming up to 72 ℃ of reaction 30min, obtain reaction solution B; Sodium Persulfate (SPS) aqueous solution and remaining esters of acrylic acid mix monomer with 10mL drops to respectively among the reaction solution B in 2h with constant speed again, then be warming up to 84 ℃ of insulation reaction 2h, namely make high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the esters of acrylic acid mix monomer total mass that adds is 13.93g, Sodium Persulfate (SPS) quality in Sodium Persulfate (SPS) aqueous solution that adds is 0.193g, Sodium Persulfate (SPS) aqueous solution and residual acrylic acid ester class mix monomer drop among the reaction solution B simultaneously, and the esters of acrylic acid mix monomer is to be that methyl acrylate and the butyl acrylate of 2:1 mixes by mass ratio.
Embodiment 7:
1) preparation hollow silica nanoparticle:
1.1) with Tween-80, the H of 6g of ZnO, the 0.062g of 0.056g
2The dehydrated alcohol of O and 21mL mixes and ultra-sonic dispersion 20min, forms the dispersion liquid of stable homogeneous; Wherein, ZnO is spherical, and particle diameter is 25 ~ 35nm;
1.2) add the cetyl trimethylammonium bromide (CTAB) of 0.052g in the dispersion liquid, and stir, ultra-sonic dispersion 35min then, property adding 0.3mL mass concentration is 28% ammoniacal liquor again, the pH value that makes the system that obtains is 8.5, and magnetic agitation 10min; Obtain mixed solution;
1.3) mixed solution of the dehydrated alcohol of the tetraethoxy of 0.11g and 10mL is added drop-wise to step 1.2 in 8h) and mixed solution in, then at room temperature stir 30min; Recycling high speed rotating whizzer is the reaction solution centrifugal treating that obtains, and the centrifugal lower sediment that obtains 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, core/shell type zinc oxide/SiO 2 composite microsphere is scattered in the nitric acid of pH=3.0 and stirs 8h, then utilize high speed rotating whizzer centrifugal treating, the centrifugal lower sediment that obtains is the hollow silica nanoparticle.
2) the high vapor pervious type polyacrylic ester nano composite leather coating agent of preparation:
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 that makes 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 to be that diallyl dimethyl ammoniumchloride and the polyacrylic acid of 1:3 mixes by mass ratio;
2.2) in the high molecular polymer aqueous solution, add the hollow silica nanoparticle of 0.3224g, the mixed surfactant of 0.95g, supersound process 10min; And the mixing solutions that obtains is transferred in the there-necked flask of 100mL, then isothermal reaction 20min under 62 ℃ of water-baths obtains reaction solution A; Wherein, mixed surfactant is to be that polyvinylpyrrolidone (PVP) and the cetyl trimethylammonium bromide (CTAB) of 3:1 mixes by mass ratio;
2.3) 1/3 of esters of acrylic acid mix monomer total mass is joined among the reaction solution A, then be warming up to 74 ℃ of reaction 30min, obtain reaction solution B; Initiator solution and remaining esters of acrylic acid mix monomer with 10mL drops to respectively in 2h among the reaction solution B with constant speed again, then is warming up to 85 ℃ of insulation reaction 2h, namely makes high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the esters of acrylic acid mix monomer total mass that adds is 13.93g, initiator quality in the initiator solution that adds is 0.193g, initiator solution and residual acrylic acid ester class mix monomer drop among the reaction solution B simultaneously, and the esters of acrylic acid mix monomer is to be that methyl methacrylate, butyl methacrylate and the methyl acrylate of 2:1:1 mixes by mass ratio; Initiator in the initiator solution is to be that azo diisobutyl amidine hydrochloride (AIBA) and the ammonium sulfate (APS) of 1:2 mixes by mass ratio.
As seen from Figure 1, the wall thickness of the single hollow silica nanoparticle of the present invention's preparation is 16nm, and central aperture is 23nm.
Table 1 is the performance data of the high vapor pervious type polyacrylic ester nano composite leather coating agent of employing method preparation of the present invention, as can be seen from Table 1, adopt the high vapor pervious type polyacrylic ester nano composite leather coating agent excellent property of method preparation of the present invention, compare with virgin pp acid esters hide finishes, its permeability to water vapour has promoted 530.31%, tensile strength has promoted 1307.343%, and elongation at break has promoted 199.73%.
The performance data of the high vapor pervious type of table 1 polyacrylic ester nano composite leather coating agent
Claims (10)
1. the preparation method of one kind high vapor pervious type polyacrylic ester nano composite leather coating agent is characterized in that may further comprise the steps:
1) preparation hollow silica nanoparticle:
1.1) with ZnO, Tween-80, H
2O and dehydrated alcohol mix and ultra-sonic dispersion, 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 per 0.016 ~ 0.056g adds the dehydrated alcohol of 18 ~ 22mL;
1.2) in dispersion liquid, add tensio-active agent, and stir, then ultra-sonic dispersion 15 ~ 35min adds ammoniacal liquor again, and the pH value that makes the system that obtains is 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) and mixed solution in, then at room temperature stir 30min; With the reaction solution process centrifugal treating that obtains, the centrifugal lower sediment that obtains adopts distilled water and absolute ethanol washing repeatedly, obtains core/shell type zinc oxide/SiO 2 composite microsphere again; Wherein, the mass ratio of tetraethoxy and ZnO is (0.08 ~ 0.12): (0.016 ~ 0.056), and the tetraethoxy of per 0.08 ~ 0.12g and the dehydrated alcohol of 10mL are hybridly prepared into mixed solution;
1.4) at normal temperatures, core/shell type zinc oxide/SiO 2 composite microsphere is scattered in the strong acid of pH=1.0 ~ 3.0 and stirs 4 ~ 8h, centrifugal treating then, the centrifugal lower sediment that obtains is the hollow silica nanoparticle;
2) the high vapor pervious type polyacrylic ester nano composite leather coating agent of preparation:
2.1) high molecular weight water soluble polymer is joined in the distilled water, stir the solution that makes 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, add hollow silica nanoparticle, tensio-active agent, supersound process 10min; Then isothermal reaction 20min under 58 ~ 63 ℃ 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) 1/5 ~ 1/3 of esters of acrylic acid mix monomer total mass is added among the reaction solution A, then be warming up to 70 ~ 75 ℃ of reaction 30min, obtain reaction solution B; Again initiator solution and residual acrylic acid ester class mix monomer are dropped to respectively among the reaction solution B, then be warming up to 80 ~ 85 ℃ of insulation reaction 2h, namely make high vapor pervious type polyacrylic ester nano composite leather coating agent; Wherein, the ratio of initiator quality, hollow silica nanoparticle quality is 13.93:0.193:(0.0806 ~ 0.4030 in the esters of acrylic acid mixture total mass that adds, the initiator solution), initiator solution and residual acrylic acid ester class mix monomer drop among the reaction solution B simultaneously.
2. the preparation method of high vapor pervious type polyacrylic ester nano composite leather coating agent according to claim 1 is characterized in that: the ZnO described step 1.1) is for spherical, and particle diameter is 25 ~ 35nm.
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 1.2) 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, the sodium lauryl sulphate.
4. according to claim 1 or the preparation method of 3 described high vapor pervious type polyacrylic ester nano composite leather coating agents, it is characterized in that: the disposable adding of ammoniacal liquor described step 1.2), the mass concentration of ammoniacal liquor is 28%, and the tensio-active agent of per 0.052 ~ 0.092g adds the ammoniacal liquor of 0.3 ~ 0.7mL.
5. the preparation method of high vapor pervious type polyacrylic ester nano composite leather coating agent according to claim 1, it is characterized in that: the strong acid described step 1.4) is hydrochloric acid, nitric acid or sulfuric acid.
6. the preparation method of high vapor pervious type polyacrylic ester nano composite leather coating agent according to claim 1 is characterized in that: the high molecular weight water soluble polymer described step 2.1) is the mixture of one or more arbitrary proportions in polyacrylic acid, polymethyl acrylic acid, polyacrylamide, diallyl dimethyl ammoniumchloride, poly-(acrylic acid-acrylamide).
7. the preparation method of high vapor pervious type polyacrylic ester nano composite leather coating agent according to claim 1, it is characterized in that: the esters of acrylic acid mix monomer described step 2.3) is the mixture of two or more arbitrary proportions in methyl methacrylate, butyl methacrylate, ethyl propenoate, butyl acrylate, the methyl acrylate.
8. the preparation method of high vapor pervious type polyacrylic ester nano composite leather coating agent according to claim 1, it is characterized in that: the initiator described step 2.3) is the mixture of one or more arbitrary proportions in azo diisobutyl amidine hydrochloride, azo-bis-isobutyl cyanide, Potassium Persulphate, ammonium persulphate, the Sodium Persulfate.
9. according to claim 1, the preparation method of 7 or 8 described high vapor pervious type polyacrylic ester nano composite leather coating agents, it is characterized in that: to drop to the time of reaction solution B be 2h for initiator solution and residual acrylic acid ester class mix monomer described step 2.3).
10. it is characterized in that according to claim 1 or the preparation method of 8 described high vapor pervious type polyacrylic ester nano composite leather coating agents: the concentration of the aqueous solution of initiator is 0.0193g/mL described step 2.3).
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