CN101869815A - Preparation of hybrid fluorine-containing surfactant and its application in weak cationic fabric three-proof finishing agent - Google Patents

Abstract

Preparation of hybrid fluorine-containing surfactant and its application in weak cationic fabric three-proof finishing agent. Hybrid fluorine-containing surfactant, the surface tension of 0.001wt% aqueous solution is ~ 30mNm ^-1 , and 0.01wt% is ~ 24mNm ^-1 ; the weak cationic fabric three-proof finishing agent prepared with this surfactant has a water repellency of 9 Grade, after washing 5 times, there is no obvious change in hydrophobicity, and there is no leakage on the back; oil repellency ≥ grade 7, after washing 5 times, the remaining oil repellency is ≥ grade 5. The finishing agent does not use long-chain fluorine-containing alkyl compound PFOS/A, but uses perfluorobutyl or perfluorohexyl fluorine-containing monomers, and uses "hybrid" type fluorine-containing surfactants to overcome short-chain fluorine-containing monomers. The activity is not as good as PFOS /A defect, keep the performance of fabric finishing agent close to or even reach the original product level.

Description

Preparation of hybrid fluorine-containing surfactant and its application in weak cationic fabric three-proof finishing agent

technical field

The invention relates to the technical field of three-proof finishing agent for fluorine-containing fabrics, in particular to a three-proof finishing agent for weak cationic fabrics prepared by using a hybrid fluorine-containing surfactant.

Background technique

Fluorine-based fabric finishing agents have better water-repelling, oil-repelling, and stain-repelling "three defense" effects than other types of fabric finishing agents (as shown in Table 1), and are currently the most recommended product type of fabric finishing agents on the market , The focus of application is rainproof outerwear fabrics, curtains, overalls, carpets, etc. American 3M, DuPont, Japan Asahi Glass, Daikin and other companies have developed and produced a variety of brands of fluorine-containing fabric finishing agents, all of which involve long-chain fluorine-containing alkyl compounds (PFOS/A), but PFOS/A is used in various Under such environmental physical and chemical conditions, almost no observable decomposition occurs, and it has high bioaccumulation and human multiple organ toxicity. Studies have shown that PFOS/A substitutes - perfluorobutyl/hexyl sulfonates have no bioaccumulation effect, and the US NIOSH and the EU classify them as no obvious hazardous substances.

Strictly speaking, fluorine-containing fabric finishing agent is a kind of polymer coating material with fluorine resin as the main film-forming substance. The fluororesin is a general term for a class of resins containing more C-F chemical bonds in the molecular structure obtained by homopolymerization or copolymerization of fluorine-containing olefins or monomers containing fluorocarbon bonds in the side chains. The fluorine-containing fabric finishing agent not only has the effect of water repellency and oil repellency, but also has the function of antifouling and easy decontamination. The fabrics treated with fluorine-containing fabric finishing agents can still maintain the original color, feel, air permeability, and wearing comfort of the fabrics, and show oil repellency and water resistance that are not possessed by general hydrocarbon or silicone water repellents. Friction and corrosion resistance make fluorine-containing fabric finishing agents popular and popularized rapidly.

Table 1 Performance comparison between fluorine-containing fabric finishing agent and common fabric finishing agent

Note: ○Excellent △General ×Poor

Cationic perfluoroalkyl acrylate (Perfluoroalkyl acrylate, FA) copolymers are positively charged, and have incomparable advantages over anionic fluoropolymers in terms of water and oil repellency for fabrics and paper. When it is used to treat the surface of negatively charged paper, fabric, etc., the electrostatic effect is more conducive to its combination with the substrate, and at the same time endows the substrate with "hydrophobic and oil-repellent" amphiphobic properties, which has potential application value. However, due to the high density of the FA monomer itself (when the C number in the perfluoroalkyl side chain is 6-10, it is waxy at room temperature and needs to be dissolved in an organic solvent), it is difficult to emulsify, low in reactivity, and difficult to dissolve in the water phase. Diffusion, so that the preparation of cationic perfluoroalkyl acrylate copolymer is limited, and many problems also appeared in the polymerization process, such as incomplete polymerization, unstable latex particles to produce oily layer, powdery precipitation, etc., the polymerization rate Wait a minute.

Initially, people used cationic initiator fragments to provide cationic properties. In the report, initiator 2,2'-azo-2-methylpropylamidine-dihydrochloride (V-50) and emulsifier octadecane Trimethyl ammonium chloride is mostly used. For example, Linemann et al. successfully prepared a cationic perfluoroalkyl acrylate copolymer emulsion through conventional emulsion polymerization under the combined action of cationic emulsifier octadecyltrimethylammonium chloride and cationic initiator V-50. Jong-Wook Ha et al. prepared a cationic perfluoroalkyl acrylate polymer emulsion with PS as the core and FA as the core-shell structure by seed emulsion polymerization.

In addition to the initiator fragmentation method, Wang Haiwei and others introduced cationic groups through the cationic monomer methacryloyloxyethyltrimethylammonium chloride (DMC) to provide cationic properties, and prepared cationic soap-free Fluorinated acrylate emulsion.

It has been found in practice that long-chain perfluoroalkyl chains, especially perfluoroalkyl acrylates derived from perfluorooctyl (C8) have the best hydrophobic and oil-repellent properties, so C8-based FA monomers are all Fluorine fabric finishing agent is the most widely used. However, the excellent stability of C8 FA monomers is a double-edged sword like Freon CFC. Various monitoring data show that it is one of the most difficult to degrade organic pollutants found in the world at present. Cumulative, long-distance migration, etc., causing lasting impact and harm to humans and the environment. On November 11, 2004, the "Stockholm Convention on Persistent Organic Pollutants" officially entered into force in my country, and perfluorooctyl pollution has been detected in groundwater, surface water and seawater in my country, and no perfluorooctyl has been found so far. Any signs of decomposition in the environment and in vivo.

references:

[1] Linemann R., Malner T., Brandsch R., et al. Latex blends of fluorinated and fluorine freeacrylates: Emulsion polymerization and tapping mode atomic force microscopy of film formation. Macromolecules, 1999, 32(6): 1715-1721.

[2] Wang Haiwei, Yuan Qiaolong, Wu Shusen. Synthesis and surface properties of cationic fluorinated acrylates. Journal of Functional Polymers, 2007, 2: 184-192.

[3] Motoshin Kubo. Fluorine-containing water and oil repellent II: Fiber characteristics and waterproof processing. Printing and Dyeing, 1996, 22(4): 40-43.

S.，Guittard F.，Guimon C.，et al.Synthesis and characterization of copolymers basedon styrene and partially fluorinated acrylates[J].European Polymer Journal，2006，42(3)：702-710.[4]

S., Guittard F., Guimon C., et al. Synthesis and characterization of copolymers based on styrene and partially fluorinated acrylates [J]. European Polymer Journal, 2006, 42(3): 702-710.

[5] D Danino, D Weihs, R Zana, M Abe, et al. Microstructures in the aqueous solutions of ahybrid anionic fluorocarbon/hydrocarbon surfactant, J Colloid Interface Sci, 2003, 259: 383.

Contents of the invention

The object of the present invention is to provide a novel three-proof finishing agent for weak cationic fabrics. Avoid the use of long-chain fluorine-containing alkyl compounds PFOS/A, but use perfluorobutyl or perfluorohexyl fluorine-containing monomers that meet environmental and health requirements, and use "hybrid" fluorine-containing surfactants to overcome their short-chain fluorine-containing surfactants. The activity of fluorine monomer is not as good as that of PFOS/A, and the performance of fabric finishing agent can be kept close to or even reach the original product level. The safety, sanitation and technical performance requirements of the treated cotton fabric fully comply with the national standard GB12799-1991:

1. The "hybrid" type fluorine-containing surfactant should meet the following performance indicators: pH 6-8, the measured dynamic surface tension at the concentration of 0.001% by weight is ~30mN m ^-1 , and the dynamic surface tension at the concentration of 0.01% by weight is ~ 24mN m ^-1 ;

2. According to the method of 3M-II-1988, the hydrophobicity test is carried out. The initial contact angle of pure water on the surface is ≥130°, and the water repellency reaches level 9. After washing for 5 times, the hydrophobicity has no obvious change, and there is no seepage on the back;

3. Use FZ/T 01067-1999 method for oil repellency test, the initial surface CH ₂ I ₂ contact angle is about 120°, oil repellency ≥ 7 grades, and remaining oil repellency ≥ 5 grades after washing 5 times.

The novel weak cationic fabric three-proof finishing agent for realizing the purpose of the present invention is an emulsion-type weak cationic fabric three-proof finishing agent, avoiding the use of long-chain fluorine-containing alkyl compounds, and adopting perfluorobutyl or perfluorohexyl compounds that meet environmental protection and health requirements Fluorine-containing monomers, using "hybrid" type fluorine-containing surfactants to overcome the short-chain fluorine-containing monomer activity is not as good as PFOS/A defect, keep the performance of fabric finishing agents close to or even reach the original product level, water droplets after being treated by it The contact angle on the cotton cloth can reach up to 150°, and the relevant technical indicators are shown in Table 2.

Table 2 Technical indicators of three-proof environmental protection fabric finishing agent

The molecular structure of the hybrid fluorosurfactant of the present invention is as shown in formula 1. The same molecule contains a fluorocarbon chain and a hydrocarbon chain. It not only has a high ability to reduce the surface tension of aqueous solution, but also can Greatly reduces the tension at the oil-water interface,

In the formula, m=4, 8, 10, 14; n=4, 6.

The preparation method of hybrid fluorosurfactant of the present invention is carried out as follows:

In the reaction formula, acid is I ₂ or dilute hydrochloric acid; Ethanol is ethanol.

Preparation includes the following steps:

1. According to the percentage by weight, pour 30%-65% of the solvent into the reaction kettle, raise the temperature to 110-150°C, and reflux the solvent for 30 minutes; at the same time, add 15%-30% of F(CF ₂ ) _n SO ₂ N( After mixing C ₂ H ₅ )(CH ₂ ) ₂ OH, 30%-45% hydrogen iodide and 1%-10% catalyst evenly, carry out solution polymerization at 110-150°C for 6-12h;

2. Synthesis: According to weight percentage, pour 30%-65% solvent into the reaction kettle, heat up to solvent reflux temperature; at the same time, add 15%-30% F(CF ₂ ) _n SO ₂ N(C ₂ H ₅ ) After (CH ₂ ) ₂ I, 30%-45% of N(C ₂ H ₅ ) ₂ (CH ₂ ) _mOH are mixed evenly, solution polymerization is carried out for 24-72h;

Wherein, the solvent is: toluene, xylene, dimethylformamide, acetone, ethanol or butanol;

The catalyst is: _I2 or dilute hydrochloric acid.

The application of the "hybrid" type fluorine-containing surfactant of the present invention is characterized in that it is used to prepare a weak cationic fluorine-containing fabric finishing agent, and the preparation method comprises the following steps:

In a four-necked bottle equipped with an electric stirrer, a condenser tube, a _N2 introduction tube and a thermometer, add 65-80% by weight of deionized water, 0.2-1.0% by weight of the compound emulsification system, and in the compound emulsification system""Hybrid" type fluorine-containing surfactant accounts for 25%-67% of the total weight of the composite emulsification system, 0.5%-2% by weight of acrylic acid or chlorine-containing monomer, 1.5%-5% by weight of perfluoroalkyl acrylate, 3%-10% by weight acrylate monomer or methacrylate monomer, 0.1%-0.5% by weight cross-linking agent, add 5%-20% by weight co-solvent to ensure that the above-mentioned mixing is uniform, and then add 0.05 %-0.2% by weight initiator, heat up to 70°C for emulsion polymerization, keep warm for 3-6 hours, and cool to obtain the product.

Weak cationic fluorine-containing fabric finishing agent is made from the following raw materials by weight:

Perfluoroalkyl acrylate monomer 1.5-5%

(meth)acrylate monomer 3-10%

Chlorine-containing monomers 0.5-2%

Cross-linking agent 0.1-0.5%

Emulsifier 0.2-1.0%

Initiator 0.05-0.2%

Co-solvent 5-20%

Deionized water 65-80%;

The chlorine-containing monomer includes: vinyl chloride, or vinylidene chloride, or p-chloromethylstyrene, or methacryloyloxyethyltrimethylammonium chloride; the crosslinking agent includes: methyl methylol acrylate, or nitrogen methylol acrylamide, or diacetone acrylamide; the emulsifier includes: octadecyltrimethylammonium bromide, or polyvinyl alcohol, or fatty alcohol polyoxyethylene ether, Or self-made hybrid fluorine-containing emulsifier, the composite emulsification system is a combination of the above emulsifiers; the initiator is 2,2'-azo-2-methylpropylamidine-dihydrochloride or tert-butyl Perbenzoic acid; the co-solvent is acetone, or isopropanol, or tetrahydrofuran.

The weak cationic fabric three-proof finishing agent prepared by using the "hybrid" type fluorine-containing surfactant is emulsion type, and its most important component is fluorine-containing polymer latex. Depending on the final design of the polymer, the fluorine-free acrylate monomers copolymerized with fluorine-containing monomers, in addition to the common methyl and butyl acrylic acid, methyl and butyl methacrylate, the length of C _8-18 Acrylates of chain fatty alcohols, methacrylates are also frequently used as comonomers. In order to reduce costs and endow polymers with other properties, such as durability, monomers such as vinyl chloride, vinylidene chloride, styrene or acrylonitrile are also introduced into the formulation of fluorine-containing copolymers; methylol compounds on the polymer molecular chain And the introduction of acrylamide cross-linking monomers, such as hydroxyethyl methacrylate and diacetone acrylamide, can effectively improve the durability of polymers. The molecular structure of common fluorine-containing fabric finishing agents is shown in 2.

2

Description of drawings

Fig. 1 is the effect diagram of 1% by weight fluorine-containing fabric finishing agent treating paper, fabric

In the figure: A: paper treated with 1% by weight DuPont FC-43; B: paper before coating; C/D: self-made sample with 1% by weight of paper; E: sample coated with 1% by weight of cotton gauze.

Fig. 2 is the SEM contrast chart before and after treating paper and fabric with 1% by weight fluorine-containing fabric finishing agent

In the figure: a: gray cloth before treatment (completely wet); b: gray cloth after treatment (142°); c: paper before treatment (109°); d: paper after treatment (129°).

Detailed ways

Preparation of "hybrid" type fluorosurfactant

1. According to the percentage by weight, pour 30%-65% of the solvent into the reaction kettle, raise the temperature to 110-150°C, and reflux the solvent for 30 minutes; at the same time, add 15%-30% of F(CF ₂ ) _n SO ₂ N( After C ₂ H ₅ )(CH ₂ ) ₂ OH, 30%-45% hydrogen iodide and 1%-10% catalyst are mixed evenly, solution polymerization is carried out at 110-150°C for 6-12h, solid F( CF ₂ ) _n SO ₂ N(C ₂ H ₅ )(CH ₂ ) ₂ I yield is higher than 90%;

2. Synthesis, according to the weight percentage, first pour 30%-65% of the solvent into the reaction kettle, heat up to the solvent reflux temperature; at the same time, add 15%-30% of F(CF ₂ ) _n SO ₂ N(C ₂ H ₅ )(CH ₂ ) ₂ I, 30%-45% of N(C ₂ H ₅ ) ₂ (CH ₂ ) _mOH are mixed uniformly, then solution polymerization is carried out for 24-72h, and the solid product is a hybrid fluorosurfactant The yield is higher than 80%.

Example 1

Preparation of "hybrid" type fluorosurfactant

First, pour 50% by weight of the solvent into the reactor, raise the temperature to about 120°C, and reflux the solvent for 30 minutes; at the same time, add 15% by weight of F(CF ₂ ) _n SO ₂ N(C ₂ H ₅ )(CH ₂ ) ₂ OH, 30% by weight of hydrogen iodide and 5% by weight of catalyst are uniformly mixed, and the solution polymerization is carried out at 120°C for 6-12h, and the solid F(CF ₂ ) _n SO ₂ N(C ₂ H ₅ )(CH ₂ ) ₂ I yield is 94.5%; in the second step of synthesis, 55% by weight of the solvent is first poured into the reactor, and the temperature is raised to the reflux temperature of the solvent; simultaneously, 15% by weight of F(CF ₂ ) _n SO ₂ N(C ₂ H ₅ )(CH ₂ ) ₂ I, 30% by weight of N(C ₂ H ₅ ) ₂ (CH ₂ ) _m OH mixed uniformly, then solution polymerized for 24 hours, the solid product hybrid type The yield of fluorine-containing surfactant was 85.2%.

Example 2

Preparation of "hybrid" type fluorosurfactant

First, pour 35% by weight of the solvent into the reactor, raise the temperature to 110°C, and reflux the solvent for 30 minutes; at the same time, add 15% by weight of F(CF ₂ ) _n SO ₂ N(C ₂ H ₅ )(CH ₂ ) ₂ OH, 45% by weight of hydrogen iodide and 5% by weight of catalyst are mixed evenly, and solution polymerization is carried out at 110°C for 6-12h, and solid F(CF ₂ ) _n SO ₂ N(C ₂ H ₅ ) The yield of (CH ₂ ) ₂ I is 95.2%; in the second step of synthesis, first pour 40% by weight of the solvent into the reactor, and heat up to the reflux temperature of the solvent; simultaneously add 15% by weight of F(CF ₂ ) _n SO ₂ N(C ₂ H ₅ )(CH ₂ ) ₂ I, 45% by weight of N(C ₂ H ₅ ) ₂ (CH ₂ ) _m OH were mixed evenly, and solution polymerization was carried out for 24 hours, and the solid product hybrid type contained The yield of fluorosurfactant was 89.4%.

Example 3

Preparation of "hybrid" type fluorosurfactant

First, pour 35% by weight of the solvent into the reactor, raise the temperature to 150°C, and reflux the solvent for 30 minutes; at the same time, add 30% by weight of F(CF ₂ ) _n SO ₂ N(C ₂ H ₅ )(CH ₂ ) ₂ OH, 30% by weight of hydrogen iodide and 5% by weight of catalyst were mixed evenly, and solution polymerization was carried out at 150°C for 12 hours, and solid F(CF ₂ ) _n SO ₂ N(C ₂ H ₅ )(CH ₂ ) The yield of ₂ I is 91.2%; in the second step of synthesis, first pour 55% by weight of the solvent into the reactor, and heat up to the reflux temperature of the solvent; at the same time, sequentially add 15% by weight of F(CF ₂ ) _n SO ₂ N(C ₂ H ₅ )(CH ₂ ) ₂ I, 30% by weight of N(C ₂ H ₅ ) ₂ (CH ₂ ) _m OH are mixed evenly, and solution polymerization is carried out for 24-72 hours, and the solid product hybrid type contains The yield of fluorosurfactant was 84.6%.

Example 4

The dynamic surface tension of a certain concentration of hybrid fluorine-containing surfactant aqueous solution at room temperature was measured on a German Kruss K12 interfacial tensiometer by the hanging method, and the water was deionized water.

An appropriate amount of the hybrid fluorine-containing surfactant recrystallized and refined in Example 1 was dissolved in deionized water and left to stand overnight. The measured dynamic surface tension is ~30mN m ^-1 when the concentration is 0.001% by weight, and ~24mN m ^-1 when the concentration is 0.01% by weight.

Example 5

Application example 1:

In a four-neck flask equipped with an electric stirrer, a condenser tube, a _N2 introduction tube, and a thermometer, add 120 mL of deionized water, 0.36 g of octadecyltrimethylammonium bromide, 0.20 g of OS, and 0.10 g of "hybridization "Type fluorosurfactant, 1.0g of acrylic acid is fully dissolved. 3.0g of perfluoroalkyl acrylate and 6.0g of octadecyl methacrylate monomers were first dissolved in 20mL of acetone, then mixed with 10.0g of methyl methacrylate and an appropriate amount of hydroxyethyl methacrylate, etc., and then added . Pass _N2 to deoxygenate, and stir mechanically at a high speed for 30 min at 45°C. Add the initiator 2,2'-azo-2-methylpropylamidine-dihydrochloride (AIBA) aqueous solution (0.2g AIBA/20mL H ₂ O), and raise the temperature to above 70°C to initiate. After the end of the heating process, keep the reaction at about 73°C for 3-6h. The solid content of the discharged emulsion was 11.25wt%.

The molecular structure of the "hybrid" type fluorosurfactant in this example is shown in formula 1, m=4,8,10,14; n=4,6. The perfluoroalkyl side chain of the perfluoroalkyl acrylate monomer includes the following structures: -CF2CF2CF2CF3, -CF2CF2CF2CF2CF2CF3, -CF2CFHCF3, -CF(CF3)CFHCF(CF3)CF3.

Example 6

Application example 2:

In a four-neck flask equipped with an electric stirrer, condenser tube, _N2 introduction tube and thermometer, add 200 mL of deionized water, 0.8 g of self-made "hybrid" type fluorosurfactant, 0.4 g of polyvinyl alcohol and 2.0 g of Acrylic acid dissolves well. 5.0g of perfluoroalkyl acrylate, 10.0g of octadecyl methacrylate monomers were first dissolved in 30mL of acetone, and then mixed with 25.0g of methyl methacrylate and an appropriate amount of hydroxymethyl methacrylate or nitrogen hydroxymethyl Add acrylamide after mixing evenly. Pass N ₂ to deoxygenate, and stir with high-speed machinery for 30 minutes. Add the initiator 2,2'-azo-2-methylpropylamidine-dihydrochloride (AIBA) aqueous solution (0.3gAIBA/20mL H ₂ O), and raise the temperature to above 70°C to initiate. After the end of the heating process, keep the reaction at about 73°C for 3 hours, and add 0.1g of initiator AIBA to continue the reaction for 2-3 hours. The solid content of the discharged emulsion was 14.69wt%.

The molecular structure of the "hybrid" type fluorosurfactant in this example is shown in formula 1, m=4,8,10,14; n=4,6. The perfluoroalkyl side chain of the perfluoroalkyl acrylate monomer includes the following structures: -CF2CF2CF2CF3, -CF2CF2CF2CF2CF2CF3, -CF2CFHCF3, -CF(CF3)CFHCF(CF3)CF3.

Example 7

Application example 3:

In a four-necked flask equipped with an electric stirrer, condenser tube, _N2 introduction tube and thermometer, add 220 mL of deionized water, 0.8 g of self-made "hybrid" type fluorosurfactant, 0.4 g of polyvinyl alcohol and 1.0 g of Acrylic acid, 1.0g of methacryloyloxyethyltrimethylammonium chloride was fully dissolved. 10.0g perfluoroalkyl acrylate, 15.0g octadecyl methacrylate monomers were first dissolved in 40mL acetone, and then mixed with 30.0g methyl methacrylate and an appropriate amount of crosslinking agent (hydroxymethyl methacrylate, or nitrogen methylol acrylamide, or diacetone acrylamide), etc., mix well and then add. Pass _N2 to deoxygenate, high-speed mechanical stirring for 30 minutes, and ultrasonic homogenization for 15 minutes. Add 0.4 g of initiator tert-butylperbenzoic acid, and raise the temperature to above 70°C to initiate. After the end of the heating process, keep the reaction at about 73°C for 3 hours, and add 0.2g of initiator AIBA to continue the reaction for 2-3 hours. The solid content of the discharged emulsion was 14.69wt%.

The molecular structure of the "hybrid" type fluorosurfactant in this example is shown in formula 1, m=4,8,10,14; n=4,6. The perfluoroalkyl side chain of the perfluoroalkyl acrylate monomer includes the following structures: -CF2CF2CF2CF3, -CF2CF2CF2CF2CF2CF3, -CF2CFHCF3, -CF(CF3)CFHCF(CF3)CF3.

Example 8

Waterproof and oilproof test:

Take a 10×10cm ² gray cloth or paper soaked in 1wt% fluorine-containing fabric finishing agent for 2 hours, take out and control the excess finishing agent residual liquid attached to the gray cloth or paper surface, and hang it to dry naturally. Then anneal at a high temperature of 160°C for 3-5 minutes for testing.

1. Hydrophobicity test

Test according to 3M-II-1988 method. Prepare a series of mixtures of isopropanol and water as the test solvent, drop the solvent on the textile sample, and observe its wetting condition. The hydrophobic level is the level corresponding to the highest level of droplets. Hydrophobicity is divided into 12 grades, with grade 12 being the highest.

2. Oil repellency test

Tested by FZ/T 01067-1999 method. It takes 8 kinds of liquid homologues whose surface tension decreases in turn as the standard, use a dropper to drop various standard test solutions on the surface of the fabric, and observe its wetting condition. The grade corresponding to the last unwetted alkane is the oleophobic grade of the test fabric. The oil-repellent grade is divided into 8 grades, with grade 8 being the highest.

The fabric finishing agent is used for the surface treatment of fabrics and paper, and compared (A) with the DuPont similar product FC-43 in the United States, as shown in Figure 1 and Figure 2. After the paper is treated with 1wt% fluorine-silicon copolymer emulsion, the hydrophobic performance of its surface is significantly increased (B), and the water droplet shrinks on its surface to form a spherical shape, which is easy to roll (C, D), and its hydrophobic effect reaches or exceeds that of foreign countries. level of similar products. Moreover, after the ordinary gauze is treated with 1wt% fluorine-silicon copolymer emulsion, its surface tension decreases obviously, and it can support a certain quality of water liquid without leakage (E).

Claims (5)

1. " hybridization " type fluorine-containing surfactant is characterized in that having as shown in the formula 1 molecular structure,

M=4 in the formula, 8,10,14; N=4,6.

2. the preparation method of claim 1 described " hybridization " type fluorine-containing surfactant is characterized in that, carries out according to the following procedure:

In the reaction equation, acid is I ₂Perhaps watery hydrochloric acid; Ethanol is an ethanol.

3. the preparation method of " hybridization " as claimed in claim 2 type fluorine-containing surfactant is characterized in that, comprises the steps:

1), by weight percentage, the solvent of 30%-65% is poured in the reactor, be warming up to 110-150 ℃, solvent refluxing 30min; F (the CF that adds simultaneously 15%-30% successively ₂) _nSO ₂N (C ₂H ₅) (CH ₂) ₂OH after the hydrogen iodide of 30%-45% and the catalyst mix of 1%-10% are even, carries out polymerisation in solution 6-12h under 110-150 ℃ of temperature;

2), by weight percentage, the solvent of 30%-65% is poured in the reactor, be warming up to the solvent refluxing temperature; F (the CF that adds simultaneously 15%-30% successively ₂) _nSO ₂N (C ₂H ₅) (CH ₂) ₂I, the N (C of 30%-45% ₂H ₅) ₂(CH ₂) _mAfter OH mixes, carry out polymerisation in solution 24-72h;

Wherein, described solvent is: toluene, dimethylbenzene, dimethyl formamide, acetone, ethanol or butanols;

Described catalyst is: I ₂Perhaps watery hydrochloric acid.

4. the application of claim 1 described " hybridization " type fluorine-containing surfactant is characterized in that, be used to prepare the weak cation fluorine-containing textile finishing agent, described fluorine-containing textile finishing agent has as shown in the formula the molecular structure shown in 2,

5. the application of claim 1 described " hybridization " type fluorine-containing surfactant is characterized in that be used to prepare the weak cation fluorine-containing textile finishing agent, the method for preparing the weak cation fluorine-containing textile finishing agent comprises the following steps:

Electric mixer, condenser pipe, N are being housed ₂In the four-necked bottle of ingress pipe and thermometer, by weight percentage, the deionized water that adds 65%-80% successively, 0.2%-1.0% composite emulsifying system, " hybridization " type fluorine-containing surfactant accounts for the 25%-67% of composite emulsifying system gross weight in the composite emulsifying system, the acrylic acid of 0.5%-2% or chloride monomer, 1.5%-5% perfluoroalkyl acrylate, 3%-10% acrylate monomer or methacrylate monomers, the 0.1%-0.5% crosslinking agent, add the 5%-20% cosolvent, guarantee above-mentioned mixing, add the 0.05%-0.2% initator then, be warming up to 70 ℃ and carry out emulsion polymerisation, insulation reaction 3-6h, cool off product

Described chloride monomer comprises: vinyl chloride or vinylidene chloride or p-chloromethyl styrene, or methylacryoyloxyethyl trimethyl ammonium chloride; Described crosslinking agent comprises: hydroxy methyl methacrylate, or nitrogen NMA, or DAAM; Described emulsifying agent comprises: octadecyl trimethylammonium bromide, or polyvinyl alcohol, or AEO, or hybrid fluorine-containing emulsifying agent, and the composite emulsifying system is the combination of mentioned emulsifier; Described initator is 2,2 '-azo-2-methyl-propyl amidine-dihydrochloride or tert-butyl group benzylhydroperoxide; Described cosolvent is an acetone, or isopropyl alcohol, or oxolane.

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