CN102704273B - Preparation method of polyacrylic ester/hollow silicon dioxide nanometer composite leather finishing agent - Google Patents
Preparation method of polyacrylic ester/hollow silicon dioxide nanometer composite leather finishing agent Download PDFInfo
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- CN102704273B CN102704273B CN201210232395.9A CN201210232395A CN102704273B CN 102704273 B CN102704273 B CN 102704273B CN 201210232395 A CN201210232395 A CN 201210232395A CN 102704273 B CN102704273 B CN 102704273B
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Abstract
The invention relates to a preparation method of a polyacrylic ester/hollow silicon dioxide nanometer composite leather finishing agent. The polyacrylic ester is a kind of film forming matters most extensively applied in the leather finishing material, the polyacrylic ester has excellent optical stability, chemical resistance, extensibility and good cohesiveness, while the polyacrylic ester forms a layer of dense thin film on the leather surface to severely block the passage through which the water vapor emitted by a human body disperses to outside, so that the sanitary performance of a leather product is greatly affected. According to the invention, polystyrene microspheres are used as a template to prepare hollow silicon dioxide nanometer particles, and the hollow silicon dioxide nanometer particles are mixed with the polyacrylic ester to prepare the polyacrylic ester/hollow silicon dioxide nanometer composite leather finishing agent. Compared with the pure polyacrylic ester leather finishing agent, the composite leather finishing agent prepared by the preparation method has the advantages that the water vapor permeability is improved by 82.6%, the tensile strength is increased by 37.72% and the elongation at break is increased by 11.09%.
Description
Technical field
The present invention relates to a kind of preparation method of leather finishing agent, be specifically related to a kind of preparation method of polyacrylate/hollow silica nano composite leather coating agent.
Background technology
Leather finishing agent is a kind of macromolecule compound that is evenly coated on leather surface.It forms one or more layers film by adhesive effect at leather surface, improves the look and feel of leather, increases the function of leather, improves value-added content of product.Polyacrylate is owing to having good photostability, chemical-resistant, extensibility and good caking property, therefore become a class of consumption maximum in leather finishing agent, but polyacrylate forms the film of one deck densification at leather surface, seriously stop up the steam that human body distributes and diffused to extraneous passage, caused the sanitation performance of leather products to be subject to very big impact.
At present, people are dispersed in the mechanical property that can make polymer in polymer substrate, heat resistance, anti-wear performance etc. by inorganic nano-particle and are greatly improved, and then by inorganic nano-particle being introduced to the performances such as the mechanical property of improving leather finishing agent in polyacrylate leather finishing agent, heat resistance, antibiotic property.But the problem existing is that introduced inorganic nano-particle is fine and close solid construction, and the lifting of the sanitation performance of leather finishing agent be there is no to remarkable result.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polyacrylate/hollow silica nano composite leather coating agent, the composite leather coating agent that adopts the method to prepare has good water vapor permeability, can effectively promote the sanitation performance of leather finishing agent.
For achieving the above object, the invention provides a kind of preparation method of polyacrylate/hollow silica nano composite leather coating agent, specific implementation process is as follows:
(1) preparation of polystyrene microsphere:
The initator of the surfactant of 0.5 ~ 2.5g, 0.37 ~ 0.41g is joined in the there-necked flask that 100g distilled water is housed, stir the solution that makes it to form transparent and homogeneous.To the styrene that adds 2.0 ~ 4.0g in above-mentioned solution, stir after 30min, argon atmospher deoxygenation 1h, is warming up to 70 ~ 90 ℃, insulation reaction 22 ~ 26h.After reaction finishes, obtain the polystyrene microsphere emulsion of stable homogeneous.
(2) preparation of hollow silica nano particle:
Get 30 ~ 60g polystyrene microsphere emulsion, regulate its pH to 4.0 ~ 7.0, add 1.0 ~ 1.4g silane coupler as silica source, insulation reaction 20 ~ 25h at 50 ℃.Adopt High Rotation Speed centrifuge to its centrifugal treating, lower sediment adopts distilled water and absolute ethanol washing 3 times successively, obtain hud typed polystyrene/silica dioxide complex microsphere, then be dispersed in solvent, at 25 ~ 50 ℃, stir 18 ~ 24h, centrifugal treating obtains hollow silica nano particle.
(3) preparation of polyacrylate/hollow silica nano composite leather coating agent:
0.0718 ~ 0.3592g hollow silica nano particle is dispersed in 10mL distilled water, ultrasonic processing 5 ~ 10min, obtain the stable suspension of hollow silica nano particle, under room temperature, by itself and 19.0 ~ 20.0g polyacrylate dispersion mix and blend 20min, products obtained therefrom is polyacrylate/hollow silica nano composite leather coating agent.
Described surfactant is any one or two kinds of in polyvinylpyrrolidone, DTAB, softex kw, Cetyltrimethylammonium bromide.
Described initator is any in azo-bis-isobutyl cyanide, azo diisobutyl amidine hydrochloride, ammonium persulfate, potassium peroxydisulfate.
Described silane coupler is any in MTES, vinyltriethoxysilane, phenyl triethoxysilane, ethyl orthosilicate, gamma-aminopropyl-triethoxy-silane.
Described solvent is any in toluene, acetone, chloroform, oxolane, carrene.
Compared with prior art, advantage of the present invention is:
(1) the present invention utilizes the features such as skin effect, quantum size effect and bulk effect of nano silicon, improve the mechanical property of leather finishing agent, compare with virgin pp acid esters leather finishing agent, its tensile strength has promoted 37.72%, and elongation at break has promoted 11.09%.
(2) polyacrylate/hollow silica nano composite leather coating agent inside that prepared by the present invention is hollow structure, be conducive to the little molecules such as steam, gas and be discharged into the external world by silica boring structure, the vapor pervious performance of leather finishing agent gets a promotion.Compare with virgin pp acid esters leather finishing agent, its water vapor permeability has improved 82.65%.
Accompanying drawing explanation:
Fig. 1 is that the TEM of hollow silica nano particle characterizes.
The specific embodiment
Below by embodiment, the present invention is elaborated
Embodiment 1
(1) preparation of polystyrene microsphere:
The azo diisobutyl amidine hydrochloride of the polyvinylpyrrolidone of 1.5g, 0.38g is joined in the there-necked flask that 100g distilled water is housed, stir the solution that makes it to form transparent and homogeneous.To the styrene that adds 3.0g in above-mentioned solution, stir after 30min, argon atmospher deoxygenation 1h, is warming up to 70 ℃, insulation reaction 24h.After reaction finishes, obtain the polystyrene microsphere emulsion of stable homogeneous.
(2) preparation of hollow silica nano particle:
Get 30g polystyrene microsphere emulsion, regulate its pH to 4.12, add 1.33g ethyl orthosilicate, insulation reaction 24h at 50 ℃.Adopt High Rotation Speed centrifuge to its centrifugal treating, lower sediment adopts distilled water and absolute ethanol washing 3 times successively, obtain hud typed polystyrene/silica dioxide complex microsphere, then be dispersed in oxolane, at 50 ℃, stir 24h, centrifugal treating obtains hollow silica nano particle.
(3) preparation of polyacrylate/hollow silica nano composite leather coating agent:
0.0718g hollow silica nano particle is dispersed in 10mL distilled water, ultrasonic processing 5min, obtain the stable suspension of hollow silica nano particle, under room temperature, by itself and 19.8g polyacrylate dispersion mix and blend 20min, products obtained therefrom is polyacrylate/hollow silica nano composite leather coating agent.
Embodiment 2:
(1) preparation of polystyrene microsphere:
The azo-bis-isobutyl cyanide of the softex kw of 0.5g, 0.39g is joined in the there-necked flask that 100g distilled water is housed, stir the solution that makes it to form transparent and homogeneous.To the styrene that adds 4.0g in above-mentioned solution, stir after 30min, argon atmospher deoxygenation 1h, is warming up to 85 ℃, insulation reaction 23 h.After reaction finishes, obtain the polystyrene microsphere emulsion of stable homogeneous.
(2) preparation of hollow silica nano particle:
Get 37g polystyrene microsphere emulsion, regulate its pH to 4.0, add 1.0g vinyltriethoxysilane, insulation reaction 25h at 50 ℃.Adopt High Rotation Speed centrifuge to its centrifugal treating, lower sediment adopts distilled water and absolute ethanol washing 3 times successively, obtains hud typed polystyrene/silica dioxide complex microsphere, is then dispersed in acetone, at 40 ℃, stir 19h, centrifugal treating obtains hollow silica nano particle.
(3) preparation of polyacrylate/hollow silica nano composite leather coating agent:
0.2874g hollow silica nano particle is dispersed in 10mL distilled water, ultrasonic processing 7min, obtain the stable suspension of hollow silica nano particle, under room temperature, by itself and 20.0g polyacrylate dispersion mix and blend 20min, products obtained therefrom is polyacrylate/hollow silica nano composite leather coating agent.
Embodiment 3:
(1) preparation of polystyrene microsphere:
The ammonium persulfate of the DTAB of 2.5g, 0.41g is joined in the there-necked flask that 100g distilled water is housed, stir the solution that makes it to form transparent and homogeneous.To the styrene that adds 2.0g in above-mentioned solution, stir after 30min, argon atmospher deoxygenation 1h, is warming up to 80 ℃, insulation reaction 25h.After reaction finishes, obtain the polystyrene microsphere emulsion of stable homogeneous.
(2) preparation of hollow silica nano particle:
Get 60g polystyrene microsphere emulsion, regulate its pH to 6.0, add 1.4g MTES, insulation reaction 20h at 50 ℃.Adopt High Rotation Speed centrifuge to its centrifugal treating, lower sediment adopts distilled water and absolute ethanol washing 3 times successively, obtain hud typed polystyrene/silica dioxide complex microsphere, then be dispersed in chloroform, at 30 ℃, stir 18h, centrifugal treating obtains hollow silica nano particle.
(3) preparation of polyacrylate/hollow silica nano composite leather coating agent:
0.1436g hollow silica nano particle is dispersed in 10mL distilled water, ultrasonic processing 9min, obtain the stable suspension of hollow silica nano particle, under room temperature, by itself and 19.2g polyacrylate dispersion mix and blend 20min, products obtained therefrom is polyacrylate/hollow silica nano composite leather coating agent.
Embodiment 4:
(1) preparation of polystyrene microsphere:
The potassium peroxydisulfate of the polyvinylpyrrolidone of 1.0g, 0.40g is joined in the there-necked flask that 100g distilled water is housed, stir the solution that makes it to form transparent and homogeneous.To the styrene that adds 3.5g in above-mentioned solution, stir after 30min, argon atmospher deoxygenation 1h, is warming up to 75 ℃, insulation reaction 26h.After reaction finishes, obtain the polystyrene microsphere emulsion of stable homogeneous.
(2) preparation of hollow silica nano particle:
Get 50g polystyrene microsphere emulsion, regulate its pH to 5.0, add 1.38g gamma-aminopropyl-triethoxy-silane, insulation reaction 23h at 50 ℃.Adopt High Rotation Speed centrifuge to its centrifugal treating, lower sediment adopts distilled water and absolute ethanol washing 3 times successively, obtains hud typed polystyrene/silica dioxide complex microsphere, is then dispersed in toluene, at 35 ℃, stir 20h, centrifugal treating obtains hollow silica nano particle.
(3) preparation of polyacrylate/hollow silica nano composite leather coating agent:
0.2155g hollow silica nano particle is dispersed in 10mL distilled water, ultrasonic processing 8min, obtain the stable suspension of hollow silica nano particle, under room temperature, by itself and 19.4g polyacrylate dispersion mix and blend 20min, products obtained therefrom is polyacrylate/hollow silica nano composite leather coating agent.
Embodiment 5:
(1) preparation of polystyrene microsphere:
The azo-bis-isobutyl cyanide of the Cetyltrimethylammonium bromide of 2.0g, 0.37g is joined in the there-necked flask that 100g distilled water is housed, stir the solution that makes it to form transparent and homogeneous.To the styrene that adds 2.5g in above-mentioned solution, stir after 30min, argon atmospher deoxygenation 1h, is warming up to 90 ℃, insulation reaction 22h.After reaction finishes, obtain the polystyrene microsphere emulsion of stable homogeneous.
(2) preparation of hollow silica nano particle:
Get 45g polystyrene microsphere emulsion, regulate its pH to 7.0, add 1.30g phenyl triethoxysilane, insulation reaction 22h at 50 ℃.Adopt High Rotation Speed centrifuge to its centrifugal treating, lower sediment adopts distilled water and absolute ethanol washing 3 times successively, obtain hud typed polystyrene/silica dioxide complex microsphere, then be dispersed in carrene, at 25 ℃, stir 22h, centrifugal treating obtains hollow silica nano particle.
(3) preparation of polyacrylate/hollow silica nano composite leather coating agent:
0.3592g hollow silica nano particle is dispersed in 10mL distilled water, ultrasonic processing 6min, obtain the stable suspension of hollow silica nano particle, under room temperature, by itself and 19.6g polyacrylate dispersion mix and blend 20min, products obtained therefrom is polyacrylate/hollow silica nano composite leather coating agent.
Polyacrylate/hollow silica nano composite leather coating agent the sanitation performance that utilizes preparation method of the present invention to prepare is good, water vapor permeability compared with virgin pp acid esters finishing agent has improved 82.65%, tensile strength has promoted 37.72%, and elongation at break has promoted 11.09%.(experimental data is in Table 1).
The performance of table 1 polyacrylate/hollow silica nano composite leather coating agent
Claims (4)
1. a preparation method for polyacrylate/hollow silica nano composite leather coating agent, is characterized in that step is as follows:
(1) preparation of polystyrene microsphere:
The initator of the surfactant of 0.5 ~ 2.5g, 0.37 ~ 0.41g is joined in the there-necked flask that 100g distilled water is housed, stirring makes it to form the solution of transparent and homogeneous, to the styrene that adds 2.0 ~ 4.0g in above-mentioned solution, stir after 30min, argon atmospher deoxygenation 1h, is warming up to 70 ~ 90 ℃, insulation reaction 22 ~ 26h, after reaction finishes, obtain the polystyrene microsphere emulsion of stable homogeneous;
Wherein, surfactant is any one or two kinds of in polyvinylpyrrolidone, DTAB, softex kw, Cetyltrimethylammonium bromide;
(2) preparation of hollow silica nano particle:
Get 30 ~ 60g polystyrene microsphere emulsion, regulate its pH to 4.0 ~ 7.0, add 1.0 ~ 1.4g silane coupler as silica source, insulation reaction 20 ~ 25h at 50 ℃, adopts High Rotation Speed centrifuge to its centrifugal treating, and lower sediment adopts distilled water and absolute ethanol washing 3 times successively, obtain hud typed polystyrene/silica dioxide complex microsphere, then be dispersed in solvent, at 25 ~ 50 ℃, stir 18 ~ 24h, centrifugal treating obtains hollow silica nano particle;
(3) preparation of polyacrylate/hollow silica nano composite leather coating agent:
0.0718 ~ 0.3592g hollow silica nano particle is dispersed in 10mL distilled water, ultrasonic processing 5 ~ 10min, obtain the stable suspension of hollow silica nano particle, under room temperature, by itself and 19.0 ~ 20.0g polyacrylate dispersion mix and blend 20min, products obtained therefrom is polyacrylate/hollow silica nano composite leather coating agent.
2. the preparation method of a kind of polyacrylate/hollow silica nano composite leather coating agent according to claim 1, is characterized in that: the initator described in step (1) is any in azo-bis-isobutyl cyanide, azo diisobutyl amidine hydrochloride, ammonium persulfate, potassium peroxydisulfate.
3. the preparation method of a kind of polyacrylate/hollow silica nano composite leather coating agent according to claim 1, is characterized in that: the silane coupler described in step (2) is any in MTES, vinyltriethoxysilane, phenyl triethoxysilane, ethyl orthosilicate, gamma-aminopropyl-triethoxy-silane.
4. the preparation method of a kind of polyacrylate/hollow silica nano composite leather coating agent according to claim 1, is characterized in that: the solvent described in step (2) is any in toluene, acetone, chloroform, oxolane, carrene.
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| CN103013270B (en) * | 2012-12-13 | 2015-06-24 | 陕西科技大学 | Preparation method of high moisture permeability type polyacrylate nano-composite leather coating agent |
| CN104761740B (en) * | 2015-04-17 | 2018-05-15 | 陕西科技大学 | The preparation method of hollow silica/polyacrylate laminated film |
| CN104761741B (en) * | 2015-04-17 | 2017-12-26 | 陕西科技大学 | The preparation method of hollow titanium dioxide with heat-insulating property/polyacrylate laminated film |
| CN106866992B (en) * | 2017-03-31 | 2019-05-17 | 陕西科技大学 | A kind of preparation method of the titania modified polyacrylate dispersion of hollow spheres |
| CN110156027A (en) * | 2019-05-23 | 2019-08-23 | 华南理工大学 | A kind of double layer hollow silica nanometer heat-insulating material and preparation method thereof |
| CN110591543B (en) * | 2019-09-12 | 2021-02-12 | 陕西科技大学 | Silicon dioxide loaded chitosan modified waterborne polyurethane acrylate composite emulsion and preparation method and application thereof |
| CN111234699B (en) * | 2020-03-10 | 2022-03-18 | 苏州和福汽车饰件有限公司 | Preparation process of antibacterial waterproof composite leather for automobile ornaments |
| CN112795264B (en) * | 2021-01-28 | 2021-09-24 | 河南大学 | Hollow nano titanium dioxide @ lauryl sodium sulfate modified graphene/fluorinated copolymer composite leather finishing agent and preparation method thereof |
| CN114213948A (en) * | 2021-12-20 | 2022-03-22 | 江南大学 | Contains hollow SiO2@TiO2Preparation method of microsphere photocuring waterborne polyurethane heat-insulating coating |
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