CN103396520B - A kind of nuclear shell structure nano titanium dioxide/fluorine-contaninig polyacrylate is without soap composite emulsion and preparation method thereof - Google Patents

Abstract

The invention relates to a core-shell structure nano-titanium dioxide/fluorine-containing polyacrylate soap-free composite emulsion and a preparation method thereof. At present, the method of preparing fluorine-containing polypropylene emulsion fabric finishing agent by soap-free emulsion polymerization technology has disadvantages such as large particle size of the emulsion, poor film-forming property, poor gloss and water resistance of the film, and poor stability and low solid content of the emulsion. . The invention uses reactive emulsifier, fluorine-containing acrylate monomer, (meth)acrylate monomer and double bond-containing nano-titanium dioxide as raw materials, and obtains it through a soap-free emulsion polymerization method, which can be used for fabric waterproof and oil-proof finishing agent. The invention eliminates the adverse effects of small molecule emulsifiers on fluorine-containing polyacrylate, introduces the excellent characteristics of nano-titanium dioxide into fluorine-containing polyacrylate, makes the fluorine-containing monomer in the shell layer, and obtains a fabric with excellent water and oil repellency Finishing agent, and has the advantages of low cost and environmental friendliness.

Description

A kind of core-shell structure nano-titanium dioxide/fluorine-containing polyacrylate soap-free composite emulsion and preparation method thereof

technical field

The invention relates to a preparation method of a fluorine-containing fabric finishing agent, in particular to a core-shell structure nano-titanium dioxide/fluorine-containing polyacrylate soap-free composite emulsion and a preparation method thereof.

Background technique

Due to the characteristics of fluorine element, organic fluoropolymer has excellent solvent resistance, oil resistance, weather resistance, high temperature resistance, chemical resistance, surface self-cleaning and other properties, and occupies a very important position in polymer materials. Fluorine-modified acrylic resins not only maintain the good film-forming properties, flexibility and adhesiveness of polyacrylate polymers, but also have high surface activity, high thermal stability, high chemical stability, and Water and oil repellency, it is widely used in waterproof finishing, oil repellent finishing and antifouling finishing of textiles. In recent years, based on the requirements of environmental protection and resources, water-based fluorinated polyacrylate emulsion has become a research hotspot. At present, fluorine-containing polyacrylate emulsions are mainly prepared by small-molecule emulsifiers. However, small-molecule emulsifiers are attached to the surface of latex particles by physical adsorption. Make the emulsion stability worse; during the emulsion film formation process, the emulsifier migrates to the surface of the film, which limits the enrichment of fluorine-containing components on the surface of the latex film, and reduces the adhesion, water repellency, oil repellency and antifouling properties of the film etc., and the emulsifier-containing waste liquid will pollute the environment.

Colloidal particles prepared by soap-free emulsion polymerization have the characteristics of uniform size, clean surface, and no small molecule emulsifiers. Compared with traditional emulsions, soap-free emulsion coatings have better compactness, water resistance, scrub resistance, Properties such as adhesion and gloss. At present, there are two main methods for preparing fluorine-containing polyacrylate emulsion fabric finishing agents using soap-free emulsion polymerization technology: (1) using ionic monomers to participate in copolymerization to prepare fluorine-containing polyacrylate emulsion fabric finishing agents with good performance, This method has the disadvantages of large particle size of the emulsion, poor film-forming property, poor gloss and water resistance of the film, poor stability of the emulsion and low solid content. (2) Fluoroacrylate emulsions for fabric finishing with good hydrophobicity and oleophobicity can be obtained by adding a co-solvent method. This method has the advantages of high solid content of the emulsion and fast polymerization reaction speed, etc., but the co-solvent is organic Solvents will increase the VOC value of the water emulsion (VOC is the abbreviation of volatile organic compounds), which will cause harm to the environment and the safety of operators.

Contents of the invention

The object of the present invention is to provide a kind of core-shell structure nano-titanium dioxide/fluorine-containing polyacrylate soap-free composite emulsion without small molecule emulsifier and organic co-solvent and its preparation method.

The technical scheme adopted in the present invention is:

A method for preparing a core-shell structure nano-titanium dioxide/fluorine-containing polyacrylate soap-free composite emulsion, characterized in that:

Achieved by the following steps:

Step 1: In parts by mass, add 0.05~2.5 parts of nano-TiO ₂ containing double bonds, 4~6 parts of methyl methacrylate, 6~10 parts of butyl acrylate, 0.4~0.8 parts of reactive emulsification in the beaker agent and 30~40 parts of deionized water, after mixing evenly, ultrasonically disperse for 20~40min to obtain ultrasonic dispersion A;

Step 2: In parts by mass, add the ultrasonic dispersion liquid A into the reactor equipped with a stirrer, a thermometer and a feeding device, and add 2.1~6.7 parts of an initiator aqueous solution, and keep it warm at 80~85°C for 20 minutes; Add pre-emulsion A and 3.3~8.2 parts of initiator aqueous solution dropwise within ~120min. After dropping, react at 80~85°C for 60~120min; after that, add preemulsion B and 4.6~10.7 parts of initiator dropwise within 90~150min. After dripping, react at 85-90°C for 60-180min, then cool down to 45°C to obtain nano-TiO ₂ /fluorine-containing polyacrylate soap-free composite emulsion with core-shell structure;

Wherein, the preparation method of pre-emulsion A:

In terms of parts by mass, mix 5~6 parts of methyl methacrylate, 7~11 parts of butyl acrylate, 0.4~0.7 parts of reactive emulsifier and 29~36 parts of deionized water, and stir the mixture at high speed for 30~ 50min;

Preparation method of pre-emulsion B:

In terms of parts by mass, 2.5~5 parts of methyl methacrylate, 10~13 parts of acrylate or methacrylate, 3.5~6 parts of fluorine-containing acrylate, 0.6~1 part of reactive emulsifier and 25~30 Mix with 1 part deionized water, and stir the mixture at high speed for 30~50min.

In step 1 and step 2, the reactive emulsifier is selected from sodium allyloxy hydroxypropyl sulfonate, sodium acrylamido isopropyl sulfonate, sodium alkylphenol polyether sulfosuccinate monoester containing double bonds , Sodium Allyl Alkyl Sulfosuccinate Diester, Allyl Polyether Sulfate, Alkyl Allyl Phenoxy Polyether Sulfate.

In the first step, the particle size of the double bond-containing nano- _TiO2 is 20nm, and the double bond content is 0.4mmol/g.

In step 2, the acrylate is selected from butyl acrylate, isooctyl acrylate, lauryl acrylate, and octadecyl acrylate; the methacrylate is selected from lauryl methacrylate and octadecyl methacrylate.

In step 2, the fluorine-containing acrylate is selected from hexafluorobutyl acrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, perfluoroalkyl ethyl acrylate CH ₂ =CHCOOCH ₂ CH ₂ (CF ₂ ) _n F, n=4 or 6.

In step 2, the initiator is selected from potassium persulfate, sodium persulfate and ammonium persulfate in the persulfate, and the mass concentration of the initiator in the aqueous initiator solution is 1.5%.

A preparation method for a core-shell structure nano-titanium dioxide/fluorine-containing polyacrylate soap-free composite emulsion The core-shell structure nano-titanium dioxide/fluorine-containing polyacrylate soap-free composite emulsion is prepared.

The present invention has the following advantages:

The invention adopts the reactive emulsifier with emulsification and polymerization ability to prepare the core-shell structure nanometer TiO ₂ /fluorine-containing polyacrylate soap-free composite emulsion. The reactive emulsifier of the present invention can be copolymerized with (meth)acrylate monomers to permanently bond to the latex molecules, which can not only improve the stability and solid content of the soap-free emulsion, but also improve the water and oil repellency of the coating film . Simultaneously, the present invention does not use organic solvent, has avoided the harm that organic solvent brings to human health and environment, and when preparing ultrasonic dispersion liquid A, pre-emulsion A and pre-emulsion B, does not use small molecular emulsifier, eliminates small The adverse effects of molecular emulsifiers on fluorine-containing polyacrylate; so the core-shell structure nano TiO ₂ / fluorine-containing polyacrylate soap-free composite emulsion prepared by the present invention does not contain small molecule emulsifiers, and is environmentally friendly, which solves the problem of traditional methods. Defects that are hazardous to the environment and operators.

In addition, the present invention adopts TiO2 particles containing double bonds and organic polymers to be connected in the form of covalent bonds, which increases the interfacial interaction between the inorganic phase and the organic phase, improves the compatibility between TiO2 particles and polymers and the The uniformity of dispersion in the polymer matrix allows for more efficient construction of the desired rough surface. The combination of the rough surface formed by nano-TiO2 and the fluorine-containing low-energy surface makes the modified fluorine-containing polyacrylate have excellent water and oil repellency. The core-shell structure is used in fluoropolymers, so that the acrylate monomer is in the core layer and the fluorine-containing monomer is in the shell layer, so that excellent surface properties can be obtained, the utilization rate of fluorine monomer can be improved, and the cost can be reduced.

detailed description

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

The preparation method of a kind of core-shell structure nano-titanium dioxide/fluorine-containing polyacrylate soap-free composite emulsion involved in the present invention is realized by the following steps:

Step 1: In parts by mass, add 0.05~2.5 parts of nano-TiO ₂ containing double bonds, 4~6 parts of methyl methacrylate, 6~10 parts of butyl acrylate, 0.4~0.8 parts of reactive emulsification in the beaker agent and 30~40 parts of deionized water, after mixing evenly, ultrasonically disperse for 20~40min to obtain ultrasonic dispersion A.

Among them, the reactive emulsifier is selected from sodium allyloxy hydroxypropyl sulfonate, sodium acrylamido isopropyl sulfonate, sodium alkylphenol polyether sulfosuccinate monoester containing double bonds, allyl alkyl Sodium sulfosuccinate, allyl polyether sulfate, alkylpropenylphenoxy polyether sulfate;

The particle size of the double bond-containing nano _TiO2 is 20nm, and the double bond content is 0.4mmol/g.

Step 2: In parts by mass, add the ultrasonic dispersion liquid A into the reactor equipped with a stirrer, a thermometer and a feeding device, and add 2.1~6.7 parts of an initiator aqueous solution, and keep it warm at 80~85°C for 20 minutes; Add pre-emulsion A and 3.3~8.2 parts of initiator aqueous solution dropwise within ~120min. After dropping, react at 80~85°C for 60~120min; after that, add preemulsion B and 4.6~10.7 parts of initiator dropwise within 90~150min. After dripping, react at 85-90°C for 60-180min, then lower the temperature to 45°C to obtain nano-TiO ₂ /fluorine-containing polyacrylate soap-free composite emulsion with core-shell structure.

Preparation method of pre-emulsion A:

In terms of parts by mass, mix 5~6 parts of methyl methacrylate, 7~11 parts of butyl acrylate, 0.4~0.7 parts of reactive emulsifier and 29~36 parts of deionized water, and stir the mixture at high speed for 30~ 50min.

Among them, the reactive emulsifier is selected from sodium allyloxy hydroxypropyl sulfonate, sodium acrylamido isopropyl sulfonate, sodium alkylphenol polyether sulfosuccinate monoester containing double bonds, allyl alkyl Sodium Disulfosuccinate, Allyl Polyether Sulfate, Alkyl Acrylphenoxy Polyether Sulfate.

Preparation method of pre-emulsion B:

In terms of parts by mass, 2.5~5 parts of methyl methacrylate, 10~13 parts of acrylate or methacrylate, 3.5~6 parts of fluorine-containing acrylate, 0.6~1 part of reactive emulsifier and 25~30 Mix with 1 part deionized water, and stir the mixture at high speed for 30~50min.

Among them, the reactive emulsifier is selected from sodium allyloxy hydroxypropyl sulfonate, sodium acrylamido isopropyl sulfonate, sodium alkylphenol polyether sulfosuccinate monoester containing double bonds, allyl alkyl Sodium sulfosuccinate, allyl polyether sulfate, alkylpropenylphenoxy polyether sulfate;

The acrylate is selected from butyl acrylate, isooctyl acrylate, lauryl acrylate, and octadecyl acrylate; the methacrylate is selected from lauryl methacrylate and octadecyl methacrylate;

The fluorine-containing acrylate is selected from hexafluorobutyl acrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, perfluoroalkyl ethyl acrylate CH ₂ =CHCOOCH ₂ CH ₂ (CF ₂ ) _n F , n=4 or 6;

The initiator is selected from potassium persulfate, sodium persulfate and ammonium persulfate in persulfate, and the mass concentration of the initiator in the aqueous solution of the initiator is 1.5%.

Example 1:

Step 1: In parts by mass, add 0.05 parts of double bond-containing nano-TiO ₂ , 4 parts of methyl methacrylate, 6 parts of butyl acrylate, 0.4 parts of reactive emulsifier and 30 parts of deionized water in a beaker, After mixing evenly, ultrasonically disperse for 20 minutes to obtain ultrasonic dispersion A.

Wherein, the reactive emulsifier is selected allyloxy hydroxypropyl sodium sulfonate;

The particle size of the double bond-containing nano _TiO2 is 20nm, and the double bond content is 0.4mmol/g.

Step 2: In parts by mass, add the ultrasonic dispersion liquid A into the reactor equipped with a stirrer, a thermometer and a feeding device, and add 2.1 parts of an initiator aqueous solution, and keep it warm at 80°C for 20 minutes; Emulsion A and 3.3 parts of initiator aqueous solution, after dripping, react at 80°C for 60min; after that, add pre-emulsion B and 4.6 parts of initiator aqueous solution dropwise within 90min, after dripping, react at 85°C for 60min, then lower the temperature to 45°C to obtain the core-shell nano-TiO ₂ /fluorine-containing polyacrylate soap-free composite emulsion.

Preparation method of pre-emulsion A:

In parts by mass, 5 parts of methyl methacrylate, 7 parts of butyl acrylate, 0.4 parts of reactive emulsifier and 29 parts of deionized water were mixed, and the mixture was stirred at high speed for 30 minutes.

Wherein, the reactive emulsifier is selected from alkyl propylene phenoxy polyether sulfate.

Preparation method of pre-emulsion B:

In parts by mass, 2.5 parts of methyl methacrylate, 10 parts of acrylate, 3.5 parts of fluorine-containing acrylate, 0.6 part of reactive emulsifier and 25 parts of deionized water were mixed, and the mixture was stirred at high speed for 30 minutes.

Wherein, the reactive emulsifier is selected allyloxy hydroxypropyl sodium sulfonate;

The acrylate is selected from butyl acrylate;

The fluorine-containing acrylate is hexafluorobutyl acrylate;

The initiator is potassium persulfate in the persulfate, and the mass concentration of the initiator in the aqueous initiator solution is 1.5%.

Emulsion Stability Test:

(1) Freeze-thaw stability:

Place an appropriate amount of emulsion at -18°C for 16 hours, then at 25°C for 8 hours, and cycle 5 times without demulsification or delamination.

(2) Storage stability:

Put an appropriate amount of emulsion in a 100mL jar, place it in a thermostat at 50°C for 20 hours, and cool it at room temperature for 3 hours. No demulsification or delamination occurs.

Water and oil repellency test of emulsion:

Dilute the emulsion to 2%, then treat the cotton fabric with dipping and padding (passing rate 80%), dry at 100°C, then bake at 160°C for 3 minutes, cool to room temperature, and the waterproofness of the finished fabric reaches 85 points (refer to AATCC22-2001 standard test), oil resistance reaches level 5 (refer to AATCC118-2002 standard test).

Example 2:

Step 1: In parts by mass, add 0.5 parts of double bond-containing nano-TiO ₂ , 4 parts of methyl methacrylate, 7 parts of butyl acrylate, 0.5 parts of reactive emulsifier and 30 parts of deionized water into a beaker, After mixing evenly, ultrasonically disperse for 20 minutes to obtain ultrasonic dispersion A.

Wherein, the reactive emulsifier is sodium acrylamide isopropyl sulfonate;

The particle size of the double bond-containing nano _TiO2 is 20nm, and the double bond content is 0.4mmol/g.

Step 2: In terms of parts by mass, add the ultrasonic dispersion liquid A to the reactor equipped with a stirrer, a thermometer and a feeding device, and add 3 parts of an aqueous initiator solution, and keep it warm at 80°C for 20 minutes; Emulsion A and 4 parts of initiator aqueous solution, after dripping, react at 80°C for 70min; after that, add pre-emulsion B and 6 parts of initiator aqueous solution dropwise within 100min, after dripping, react at 85°C for 80min, then lower the temperature to 45°C to obtain the core-shell nano-TiO ₂ /fluorine-containing polyacrylate soap-free composite emulsion.

Preparation method of pre-emulsion A:

In parts by mass, 5 parts of methyl methacrylate, 8 parts of butyl acrylate, 0.5 parts of reactive emulsifier and 30 parts of deionized water were mixed, and the mixture was stirred at high speed for 35 minutes.

Among them, the reactive emulsifier is selected from allyl polyether sulfate.

Preparation method of pre-emulsion B:

In parts by mass, 3 parts of methyl methacrylate, 11 parts of acrylate, 4 parts of fluorine-containing acrylate, 0.7 part of reactive emulsifier and 26 parts of deionized water were mixed, and the mixture was stirred at high speed for 30 minutes.

Among them, the reactive emulsifier is selected from double bond-containing alkylphenol polyether sodium sulfosuccinate monoester;

The acrylate is selected from isooctyl acrylate;

The fluorine-containing acrylate is hexafluorobutyl methacrylate;

The initiator is potassium persulfate in the persulfate, and the mass concentration of the initiator in the aqueous initiator solution is 1.5%.

The test method of emulsion stability is the same as that of Example 1. The test results of freeze-thaw stability and storage stability show that the emulsion does not have demulsification or delamination. The process of emulsion treatment of cotton fabric and the test method of water and oil resistance are the same as in Example 1. The water resistance of the finished fabric reaches 90 points (refer to AATCC22-2001 standard test), and the oil repellency reaches level 6 (refer to AATCC118-2002 standard test).

Example 3:

Step 1: In parts by mass, add 1 part of nano-TiO ₂ containing double bonds, 5 parts of methyl methacrylate, 8 parts of butyl acrylate, 0.6 part of reactive emulsifier and 35 parts of deionized water in a beaker, After mixing evenly, disperse ultrasonically for 30 minutes to obtain ultrasonic dispersion A.

Among them, the reactive emulsifier is selected from double bond-containing alkylphenol polyether sodium sulfosuccinate monoester;

The particle size of the double bond-containing nano _TiO2 is 20nm, and the double bond content is 0.4mmol/g.

Step 2: In parts by mass, add the ultrasonic dispersion liquid A into the reactor equipped with a stirrer, a thermometer and a feeding device, and add 4 parts of an aqueous initiator solution, and keep it warm at 80°C for 20 minutes; Emulsion A and 5 parts of initiator aqueous solution, after dripping, react at 80°C for 80min; after that, add pre-emulsion B and 7 parts of initiator aqueous solution dropwise within 110min, after dripping, react at 85°C for 100min, then lower the temperature to 45°C to obtain the core-shell nano-TiO ₂ /fluorine-containing polyacrylate soap-free composite emulsion.

Preparation method of pre-emulsion A:

In parts by mass, 5 parts of methyl methacrylate, 9 parts of butyl acrylate, 0.6 part of reactive emulsifier and 31 parts of deionized water were mixed, and the mixture was stirred at high speed for 40 minutes.

Wherein, the reactive emulsifier is selected from allyl alkyl sulfosuccinic acid diester sodium.

Preparation method of pre-emulsion B:

In parts by mass, 3.5 parts of methyl methacrylate, 12 parts of acrylate, 4.5 parts of fluorine-containing acrylate, 0.8 part of reactive emulsifier and 27 parts of deionized water were mixed, and the mixture was stirred at high speed for 40 minutes.

Wherein, reactive emulsifier selects allyl polyether sulfate;

The acrylate is lauryl acrylate;

The fluorine-containing acrylate is selected from dodecafluoroheptyl methacrylate;

The initiator is sodium persulfate in the persulfate, and the mass concentration of the initiator in the aqueous initiator solution is 1.5%.

The test method of emulsion stability is the same as that of Example 1. The test results of freeze-thaw stability and storage stability show that the emulsion does not have demulsification or delamination. The process of emulsion treatment of cotton fabric and the test method of water and oil resistance are the same as in Example 1. The water resistance of the finished fabric reaches 90 points (refer to AATCC22-2001 standard test), and the oil repellency reaches level 5 (refer to AATCC118-2002 standard test).

Example 4:

Step 1: in parts by mass, add 1.5 parts of double bond-containing nano TiO ₂ , 5 parts of methyl methacrylate, 9 parts of butyl acrylate, 0.7 part of reactive emulsifier and 35 parts of deionized water in a beaker, After mixing evenly, disperse ultrasonically for 30 minutes to obtain ultrasonic dispersion A.

Among them, the reactive emulsifier is selected from allyl alkyl sulfosuccinate diester sodium;

The particle size of the double bond-containing nano _TiO2 is 20nm, and the double bond content is 0.4mmol/g.

Step 2: In parts by mass, add the ultrasonic dispersion liquid A into the reactor equipped with a stirrer, a thermometer and a feeding device, and add 5 parts of an aqueous initiator solution, and keep it warm at 85°C for 20 minutes; Emulsion A and 6 parts of initiator aqueous solution, after dripping, react at 85°C for 90min; after that, add pre-emulsion B and 8 parts of initiator aqueous solution dropwise within 120min, after dripping, react at 90°C for 120min, then lower the temperature to 45°C to obtain the core-shell nano-TiO ₂ /fluorine-containing polyacrylate soap-free composite emulsion.

Preparation method of pre-emulsion A:

In parts by mass, 6 parts of methyl methacrylate, 10 parts of butyl acrylate, 0.6 parts of reactive emulsifier and 32 parts of deionized water were mixed, and the mixture was stirred at high speed for 45 minutes.

Among them, the reactive emulsifier is sodium alkylphenol polyether monosulfosuccinate containing double bonds.

Preparation method of pre-emulsion B:

In parts by mass, 4 parts of methyl methacrylate, 12 parts of acrylate, 5 parts of fluorine-containing acrylate, 0.9 part of reactive emulsifier and 28 parts of deionized water were mixed, and the mixture was stirred at high speed for 40 minutes.

Wherein, the reactive emulsifier is sodium acrylamide isopropyl sulfonate;

The acrylate is selected from octadecyl acrylate;

The fluorine-containing acrylate is selected from perfluoroalkyl ethyl acrylate CH ₂ =CHCOOCH ₂ CH ₂ (CF ₂ ) _n F, n=4;

The initiator is sodium persulfate in the persulfate, and the mass concentration of the initiator in the aqueous initiator solution is 1.5%.

The test method of emulsion stability is the same as that of Example 1. The test results of freeze-thaw stability and storage stability show that the emulsion does not have demulsification or delamination. The process of emulsion treatment of cotton fabric and the waterproof and oil-proof test method are the same as in Example 1. The water resistance of the finished fabric reaches 85 points (refer to AATCC22-2001 standard test), and the oil repellency reaches level 4 (refer to AATCC118-2002 standard test).

Example 5:

Step 1: in parts by mass, add 2 parts of nano-TiO ₂ containing double bonds, 6 parts of methyl methacrylate, 10 parts of butyl acrylate, 0.8 parts of reactive emulsifier and 40 parts of deionized water in a beaker, After mixing evenly, disperse ultrasonically for 40 minutes to obtain ultrasonic dispersion A.

Wherein, reactive emulsifier selects allyl polyether sulfate;

The particle size of the double bond-containing nano _TiO2 is 20nm, and the double bond content is 0.4mmol/g.

Step 2: In parts by mass, add the ultrasonic dispersion liquid A into the reactor equipped with a stirrer, a thermometer and a feeding device, and add 6 parts of an aqueous initiator solution, and keep it warm at 85°C for 20 minutes; Emulsion A and 7 parts of initiator aqueous solution, after dripping, react at 85°C for 100min; after that, add pre-emulsion B and 9 parts of initiator aqueous solution dropwise within 130min, after dripping, react at 90°C for 140min, then lower the temperature to 45°C to obtain the core-shell nano-TiO ₂ /fluorine-containing polyacrylate soap-free composite emulsion.

Preparation method of pre-emulsion A:

In parts by mass, 6 parts of methyl methacrylate, 11 parts of butyl acrylate, 0.7 parts of reactive emulsifier and 33 parts of deionized water were mixed, and the mixture was stirred at high speed for 50 minutes.

Wherein, the reactive emulsifier is sodium acrylamide isopropyl sulfonate.

Preparation method of pre-emulsion B:

In parts by mass, 4.5 parts of methyl methacrylate, 13 parts of methacrylate, 5.5 parts of fluorine-containing acrylate, 1 part of reactive emulsifier and 29 parts of deionized water were mixed, and the mixture was stirred at high speed for 50 minutes.

Among them, the reactive emulsifier is selected from allyl alkyl sulfosuccinate diester sodium;

The methacrylate is lauryl methacrylate;

The fluorine-containing acrylate is selected from perfluoroalkyl ethyl acrylate CH ₂ =CHCOOCH ₂ CH ₂ (CF ₂ ) _n F, n=6;

The initiator is ammonium persulfate in the persulfate, and the mass concentration of the initiator in the aqueous initiator solution is 1.5%.

The test method of emulsion stability is the same as that of Example 1. The test results of freeze-thaw stability and storage stability show that the emulsion does not have demulsification or delamination. The process of emulsion treatment of cotton fabric and the test method of water and oil resistance are the same as in Example 1. The water resistance of the finished fabric reaches 90 points (refer to AATCC22-2001 standard test), and the oil repellency reaches level 6 (refer to AATCC118-2002 standard test).

Embodiment 6:

Step 1: in parts by mass, add 2.5 parts of nano-TiO ₂ containing double bonds, 6 parts of methyl methacrylate, 10 parts of butyl acrylate, 0.8 parts of reactive emulsifier and 40 parts of deionized water in a beaker, After mixing evenly, disperse ultrasonically for 40 minutes to obtain ultrasonic dispersion A.

Wherein, the reactive emulsifier is selected from alkyl propylene phenoxy polyether sulfate;

The particle size of the double bond-containing nano _TiO2 is 20nm, and the double bond content is 0.4mmol/g.

Step 2: In parts by mass, add the ultrasonic dispersion liquid A into the reactor equipped with a stirrer, a thermometer and a feeding device, and add 6.7 parts of an initiator aqueous solution, and keep it warm at 85°C for 20 minutes; Emulsion A and 8.2 parts of initiator aqueous solution, after dripping, react at 85°C for 120min; after that, add pre-emulsion B and 10.7 parts of initiator aqueous solution dropwise within 150min, after dripping, react at 90°C for 180min, then lower the temperature to 45°C to obtain the core-shell nano-TiO ₂ /fluorine-containing polyacrylate soap-free composite emulsion.

Preparation method of pre-emulsion A:

In parts by mass, 6 parts of methyl methacrylate, 11 parts of butyl acrylate, 0.7 parts of reactive emulsifier and 36 parts of deionized water were mixed, and the mixture was stirred at high speed for 50 minutes.

Wherein, the reactive emulsifier is sodium allyloxy hydroxypropyl sulfonate.

Preparation method of pre-emulsion B:

In parts by mass, 5 parts of methyl methacrylate, 13 parts of methacrylate, 6 parts of fluorine-containing acrylate, 1 part of reactive emulsifier and 30 parts of deionized water were mixed, and the mixture was stirred at high speed for 50 minutes.

Wherein, the reactive emulsifier is selected from alkyl propylene phenoxy polyether sulfate;

Methacrylate selects octadecyl methacrylate;

The fluorine-containing acrylate is selected from perfluoroalkyl ethyl acrylate CH ₂ =CHCOOCH ₂ CH ₂ (CF ₂ ) _n F, n=6;

The initiator is ammonium persulfate in the persulfate, and the mass concentration of the initiator in the aqueous initiator solution is 1.5%.

The test method of emulsion stability is the same as that of Example 1. The test results of freeze-thaw stability and storage stability show that the emulsion does not have demulsification or delamination. The process of emulsion treatment of cotton fabric and the test method of water and oil resistance are the same as in Example 1. The water resistance of the finished fabric reaches 90 points (refer to AATCC22-2001 standard test), and the oil repellency reaches level 5 (refer to AATCC118-2002 standard test).

The content of the present invention is not limited to the examples listed, and any equivalent transformation of the technical solution of the present invention adopted by those of ordinary skill in the art by reading the description of the present invention is covered by the claims of the present invention.

Claims (1)

1. nuclear shell structure nano titanium dioxide/fluorine-contaninig polyacrylate is without a preparation method for soap composite emulsion, it is characterized in that:

Realized by following steps:

Step one: according to the mass fraction, adds 1 part of double bond containing nano-TiO in beaker ₂, 5 parts of methyl methacrylates, 8 parts of butyl acrylates, 0.6 part of reactive emulsifier and 35 parts of deionized waters, after mixing, ultrasonic disperse 30min, obtains ultrasonic disperse liquid A;

Wherein, reactive emulsifier chooses double bond containing alkyl phenol polyether sulfosuccinic acid monoesters sodium;

Double bond containing nano-TiO ₂particle diameter be 20nm, double bond content is 0.4mmol/g;

Step 2: according to the mass fraction, joins ultrasonic disperse liquid A and agitator is housed, temperature is taken into account in the reactor of feeding device, and add 4 parts of initiator solutions, at 80 DEG C of insulation 20min; In 80min, drip pre-emulsion A and 5 part initiator solution, after dripping off, at 80 DEG C, react 80min; Afterwards, in 110min, drip pre-emulsion B and 7 part initiator solution, after dripping off, at 85 DEG C, react 100min, be then cooled to 45 DEG C, obtain nuclear shell structure nano TiO ₂/ fluorine-contaninig polyacrylate is without soap composite emulsion;

The preparation method of pre-emulsion A:

According to the mass fraction, by 5 parts of methyl methacrylates, 9 parts of butyl acrylates, 0.6 part of reactive emulsifier and 31 parts of deionized water mixing, by mixed solution high-speed stirring 40min;

Wherein, reactive emulsifier chooses allyl alkyl sulfo-succinic acid diesteras;

The preparation method of pre-emulsion B:

According to the mass fraction, by 3.5 parts of methyl methacrylates, 12 parts of acrylate, 4.5 parts of fluorinated acrylates, 0.8 part of reactive emulsifier and 27 parts of deionized water mixing, by mixed solution high-speed stirring 40min;

Wherein, reactive emulsifier chooses allyl polyether vitriol;

Dodecyl acrylate chosen by acrylate;

Fluorinated acrylate chooses dodecafluoroheptyl methacrylate;

The Sodium Persulfate in persulphate chosen by initiator, and in initiator solution, the mass concentration of initiator is 1.5%.