CN108517024B - Preparation of polyacrylate/nano-ZnO composite leather finishing agent by Pickering miniemulsion polymerization and preparation method - Google Patents

Abstract

The invention relates to a polyacrylate/nano ZnO composite leather finishing agent prepared by a Pickering miniemulsion polymerization method and a preparation method thereof. The polyacrylate/nano ZnO composite emulsion is prepared by taking an acrylate monomer as a main raw material, replacing a traditional surfactant with nano ZnO and introducing a hydrophobic fluorine-containing monomer through the characteristic of drop nucleation by a Pickering miniemulsion polymerization method. The method overcomes the defect that the traditional surfactant brings about polyacrylate emulsion, and simultaneously overcomes the defect of poor stability of the emulsion prepared by a Pickering emulsion polymerization method. When the finishing agent is applied to the leather finishing process, the air permeability, the water vapor permeability, the hydrophobicity, the mechanical property and the dry-wet rubbing fastness of a leather sample are improved.

Description

Preparation of polyacrylate/nano-ZnO composite leather by Pickering miniemulsion polymerization Finishing agent and preparation method

technical field

The invention belongs to the technical field of leather finishing agents, and relates to a polyacrylate/nano-ZnO composite leather finishing agent prepared by a Pickering mini-emulsion polymerization method and a preparation method.

Background technique

Polyacrylate emulsions have excellent heat resistance stability, weather resistance, acid and alkali resistance, gloss retention, mechanical properties, adhesiveness and other characteristics, as well as good film-forming properties, easy availability of raw materials and relatively low cost, etc. The advantage is that it is one of the most commonly used leather finishing materials. Although the application of traditional polyacrylate finishing agents is relatively common, the water resistance of polyacrylate emulsion films is poor, which seriously affects the wet rubbing fastness of leather samples after finishing. Poor, not conducive to the maintenance of leather-like hygienic properties. These defects make it difficult to apply polyacrylate finishes to the high-end leather market. In recent years, many researchers have introduced inorganic nanoparticles into polyacrylate emulsions, and found that they can not only significantly improve the water resistance, mechanical properties, air permeability and water vapor permeability of polyacrylate emulsion films, but also impart Polyacrylate emulsion film has many properties, such as antibacterial, UV resistance, electrical conductivity, etc. Among them, nano-ZnO particles are cheap and easy to obtain, and have excellent antibacterial, photocatalytic and ultraviolet absorption properties.

However, the choice of polymerization method has a large impact on the performance of nanoparticle incorporation. The traditional emulsion polymerization method to prepare polyacrylate emulsion requires the use of a large amount of traditional small molecule surfactants, which seriously affects the water resistance of the polyacrylate emulsion film formation. At the same time, the surfactant is attached to the surface of the latex particles, which is easily affected by environmental factors and migrates. , reducing the stability of the emulsion. With the continuous improvement of polymerization theory and technology, new emulsion polymerization methods have received extensive attention from researchers, such as: soap-free emulsion polymerization, seed emulsion polymerization, core-shell emulsion polymerization, miniemulsion polymerization, Pickering emulsion polymerization and so on. Based on the characteristics of droplet nucleation, miniemulsion polymerization is very easy to polymerize highly hydrophobic monomers, easy to prepare organic/inorganic composite emulsions, and can reduce the amount of surfactants. Pickering emulsion polymerization is a polymerization method in which inorganic nanoparticles replace traditional surfactants to stabilize emulsions, which can avoid the defects caused by traditional surfactants and endow the composite emulsion with some nano-characteristics. Disadvantages such as low solid content.

SUMMARY OF THE INVENTION

In view of this, the main purpose of the present invention is to provide a kind of Pickering mini-emulsion polymerization method to prepare polyacrylate/nano ZnO composite leather finishing agent and preparation method, so as to improve the hygienic properties and mechanical properties of finished leather.

In order to achieve the above object, the technical scheme of the present invention is achieved in this way:

The method for preparing polyacrylate/nano-ZnO composite leather finishing agent by Pickering mini-emulsion polymerization is characterized in that:

Specifically include the following steps: the following are parts by mass unless otherwise specified,

Dissolve 0.24-1.44 parts of triethoxyvinylsilane in 100 parts of deionized water, add 1.44-2.88 parts of nano-ZnO particles, and ultrasonicate for 10-15 min after mixing; mix 24 parts of methacrylate and 24 parts of butyl acrylate Esters, 1.44 parts of hexafluorobutyl methacrylate, and 1.44 parts of n-butanol were mixed, emulsified at high speed for 10-15 min, and then ultrasonicated for 10-15 min to obtain a fine emulsion;

Dissolve 1.44 parts of ammonium persulfate in 100 parts of deionized water to prepare an aqueous initiator solution;

Raise the temperature to 75～85 ℃, rotate speed 300 r/min, add 1/3 volume part of the initiator aqueous solution to the three-necked flask and keep warm for 10 min, and then add the remaining initiator aqueous solution and mini-emulsion dropwise, 1.5～2 After the dropwise addition of h, the temperature was kept for 2 h, and after cooling, the material was filtered with gauze to obtain the polyacrylate/nano-ZnO composite leather finishing agent.

The polyacrylate/nano ZnO composite leather finishing agent is prepared by the method for preparing the polyacrylate/nano ZnO composite leather finishing agent by the Pickering mini-emulsion polymerization method.

Compared with the prior art, the beneficial effects of the present invention:

The invention adopts the Pickering mini-emulsion polymerization method, uses nano-ZnO to replace the traditional surfactant, improves the defect of poor water resistance of polyacrylate emulsion film-forming, and at the same time utilizes the characteristics of droplet nucleation of the Pickering mini-emulsion polymerization method, which is easy for fluorine-containing monomers The introduction of the composite emulsion improves the shortcoming of poor stability of the emulsion prepared by the Pickering emulsion polymerization method alone. By obtaining the coating morphology of the composite emulsion, the air permeability, water vapor permeability and mechanical properties of the film formation are improved, and the leather sample after coating is improved. Wet rub fastness and hygienic properties.

Detailed ways

The present invention will be described in detail below with reference to specific embodiments.

The invention provides a method for preparing a polyacrylate/nano ZnO composite leather finishing agent by a Pickering mini-emulsion polymerization method.

Specifically include the following steps: the following are parts by mass unless otherwise specified,

Dissolve 0.24-1.44 parts of triethoxyvinylsilane (DNS-86) in 100 parts of deionized water, add 1.44-2.88 parts of nano-ZnO particles, and ultrasonicate for 10-15 min after mixing; 24 parts of methacrylate (MMA), 24 parts of butyl acrylate (BA), 1.44 parts of hexafluorobutyl methacrylate (G02), and 1.44 parts of n-butanol were mixed, emulsified at high speed for 10 to 15 minutes, and then ultrasonicated for 10 to 15 minutes to obtain a fine emulsion ;

Dissolve 1.44 parts of ammonium persulfate (APS) in 100 parts of deionized water to prepare an aqueous initiator solution;

Raise the temperature to 75～85 ℃, rotate speed 300 r/min, add 1/3 volume part of the initiator aqueous solution to the three-necked flask and keep warm for 10 min, and then add the remaining initiator aqueous solution and mini-emulsion dropwise, 1.5～2 After the dropwise addition of h, the temperature was kept for 2 h, and after cooling, the material was filtered with gauze to obtain the polyacrylate/nano-ZnO composite leather finishing agent.

The polyacrylate/nano ZnO composite leather finishing agent is prepared by the method for preparing the polyacrylate/nano ZnO composite leather finishing agent by the Pickering mini-emulsion polymerization method.

Example 1:

Dissolve 0.24 parts by mass of triethoxyvinylsilane (DNS-86) in 100 parts by mass of deionized water, add 1.44-2.88 parts by mass of nano-ZnO particles, and ultrasonicate for 10-15 min after mixing; 24 parts by mass of methyl Acrylate (MMA), 24 parts by mass of butyl acrylate (BA), 1.44 parts by mass of hexafluorobutyl methacrylate (G02), and 1.44 parts by mass of n-butanol were mixed, emulsified at high speed for 10-15 min, and then sonicated for 10 ~15 min to obtain a fine emulsion;

Dissolve 1.44 parts by mass of ammonium persulfate (APS) in 100 parts by mass of deionized water to prepare an aqueous initiator solution;

Raise the temperature to 75～85 ℃, rotate speed 300 r/min, add 1/3 volume part of the initiator aqueous solution to the three-necked flask and keep warm for 10 min, and then add the remaining initiator aqueous solution and mini-emulsion dropwise, 1.5～2 After the dropwise addition of h, the temperature was kept for 2 h, and after cooling, the material was filtered with gauze to obtain the polyacrylate/nano-ZnO composite leather finishing agent.

Example 2:

Dissolve 0.24-1.44 parts by mass of triethoxyvinylsilane (DNS-86) in 100 parts by mass of deionized water, add 1.44 parts by mass of nano-ZnO particles, and ultrasonicate for 10-15 min after mixing; 24 parts by mass of methyl Acrylate (MMA), 24 parts by mass of butyl acrylate (BA), 1.44 parts by mass of hexafluorobutyl methacrylate (G02), and 1.44 parts by mass of n-butanol were mixed, emulsified at high speed for 10-15 min, and then ultrasonicated for 10 ~15 min to obtain a fine emulsion;

Dissolve 1.44 parts by mass of ammonium persulfate (APS) in 100 parts by mass of deionized water to prepare an aqueous initiator solution;

Raise the temperature to 75～85 ℃, rotate speed 300 r/min, add 1/3 volume part of the initiator aqueous solution to the three-necked flask and keep warm for 10 min, and then add the remaining initiator aqueous solution and mini-emulsion dropwise, 1.5～2 After the dropwise addition of h, the temperature was kept for 2 h, and after cooling, the material was filtered with gauze to obtain the polyacrylate/nano-ZnO composite leather finishing agent.

Example 3:

Dissolve 1 part by mass of triethoxyvinylsilane (DNS-86) in 100 parts by mass of deionized water, add 2 parts by mass of nano-ZnO particles, and sonicate for 10-15 min after mixing; 24 parts by mass of methacrylate (MMA), 24 parts by mass of butyl acrylate (BA), 1.44 parts by mass of hexafluorobutyl methacrylate (G02), and 1.44 parts by mass of n-butanol, emulsified at high speed for 10-15 min, and then ultrasonicated for 10-15 min min to obtain a fine emulsion;

Dissolve 1.44 parts by mass of ammonium persulfate (APS) in 100 parts by mass of deionized water to prepare an aqueous initiator solution;

Raise the temperature to 75～85 ℃, rotate speed 300 r/min, add 1/3 volume part of the initiator aqueous solution to the three-necked flask and keep warm for 10 min, and then add the remaining initiator aqueous solution and mini-emulsion dropwise, 1.5～2 After the dropwise addition of h, the temperature was kept for 2 h, and after cooling, the material was filtered with gauze to obtain the polyacrylate/nano-ZnO composite leather finishing agent.

Example 4:

Dissolve 0.24-1.44 parts by mass of triethoxyvinylsilane (DNS-86) in 100 parts by mass of deionized water, add 2.5 parts by mass of nano-ZnO particles, and ultrasonicate for 10-15 min after mixing; 24 parts by mass of methyl Acrylate (MMA), 24 parts by mass of butyl acrylate (BA), 1.44 parts by mass of hexafluorobutyl methacrylate (G02), and 1.44 parts by mass of n-butanol were mixed, emulsified at high speed for 10-15 min, and then ultrasonicated for 10 ~15 min to obtain a fine emulsion;

Dissolve 1.44 parts by mass of ammonium persulfate (APS) in 100 parts by mass of deionized water to prepare an aqueous initiator solution;

Raise the temperature to 75 °C, rotate at 300 r/min, first add 1/3 volume of the initiator aqueous solution to the three-necked flask and keep it for 10 min, and then dropwise add the remaining initiator aqueous solution and mini-emulsion for 1.5 to 2 h. After adding, keep the temperature for 2 h, and filter the material with gauze after cooling to obtain the polyacrylate/nano-ZnO composite leather finishing agent.

Example 5:

Dissolve 0.56 parts by mass of triethoxyvinylsilane (DNS-86) in 100 parts by mass of deionized water, add 1.44-2.88 parts by mass of nano-ZnO particles, and ultrasonicate for 10-15 min after mixing; 24 parts by mass of methyl Acrylate (MMA), 24 parts by mass of butyl acrylate (BA), 1.44 parts by mass of hexafluorobutyl methacrylate (G02), and 1.44 parts by mass of n-butanol were mixed, emulsified at high speed for 10-15 min, and then sonicated for 10 ~15 min to obtain a fine emulsion;

Dissolve 1.44 parts by mass of ammonium persulfate (APS) in 100 parts by mass of deionized water to prepare an aqueous initiator solution;

Raise the temperature to 80 °C, rotate at 300 r/min, first add 1/3 volume of the initiator aqueous solution to the three-necked flask and keep it warm for 10 min, and then dropwise add the remaining initiator aqueous solution and mini-emulsion for 1.5 to 2 h. After adding, keep the temperature for 2 h, and filter the material with gauze after cooling to obtain the polyacrylate/nano-ZnO composite leather finishing agent.

The content of the present invention is not limited to those listed in the embodiments, and any equivalent transformations taken by those of ordinary skill in the art to the technical solutions of the present invention by reading the description of the present invention are covered by the claims of the present invention.

Claims (2)

1. The preparation method for preparing the polyacrylate/nano ZnO composite leather finishing agent by the Pickering miniemulsion polymerization method is characterized by comprising the following steps:

   the method specifically comprises the following steps: all the components are not described separately below in parts by mass,

   dissolving 0.24-1.44 parts of triethoxyvinylsilane in 100 parts of deionized water, adding 1.44-2.88 parts of nano ZnO particles, mixing, and performing ultrasonic treatment for 10-15 min; mixing 24 parts of methacrylate, 24 parts of butyl acrylate, 1.44 parts of hexafluorobutyl methacrylate and 1.44 parts of n-butyl alcohol, carrying out high-speed shearing emulsification for 10-15 min, and carrying out ultrasonic treatment for 10-15 min to obtain a miniemulsion;

   dissolving 1.44 parts of ammonium persulfate in 100 parts of deionized water to prepare an initiator aqueous solution;

   and (3) heating the temperature to 75-85 ℃, rotating at the speed of 300 r/min, adding 1/3 parts by volume of initiator aqueous solution into a three-neck flask, preserving the temperature for 10 min, then dropwise adding the rest initiator aqueous solution and miniemulsion, completing dropwise adding for 1.5-2 h, preserving the temperature for 2 h, cooling, filtering with gauze, and discharging to obtain the polyacrylate/nano ZnO composite leather finishing agent.
2. 2. The polyacrylate/nano ZnO composite leather finishing agent prepared by the preparation method for preparing the polyacrylate/nano ZnO composite leather finishing agent by the Pickering miniemulsion polymerization method as claimed in claim 1.