CN110485159B - Process for preparing efficient fluorine-free water repellent comprising telechelic polymer - Google Patents
Process for preparing efficient fluorine-free water repellent comprising telechelic polymer Download PDFInfo
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- CN110485159B CN110485159B CN201910831946.5A CN201910831946A CN110485159B CN 110485159 B CN110485159 B CN 110485159B CN 201910831946 A CN201910831946 A CN 201910831946A CN 110485159 B CN110485159 B CN 110485159B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of a high-efficiency fluorine-free waterproof agent containing a telechelic polymer, which comprises the following steps of (1) uniformly mixing and emulsifying 25-35% of the fluorine-free polymer, 1.5-6% of a surfactant, 1.5-9% of an auxiliary agent and water to obtain a pre-emulsion, wherein the pre-emulsion does not contain an initiator, a water-soluble monomer and a substance with a boiling point lower than the emulsification temperature; (2) adding a water-soluble monomer into the pre-emulsion obtained in the step (1), and uniformly mixing; and then adding an initiator into the mixture for reaction, adding a substance with the boiling point lower than the emulsification temperature at one time or gradually, cooling the system temperature to room temperature after the reaction is finished, and filtering to obtain a target product. The fluorine-free waterproof agent prepared by the method has a good waterproof effect, does not contain fluorine elements, is green and environment-friendly, and has a better waterproof effect, good hand feeling and better washing resistance compared with the prior art.
Description
Technical Field
The invention relates to the field of textile auxiliary agents, in particular to a preparation method of a fluorine-free waterproof agent containing a telechelic polymer.
Background
Water repellents can impart hydrophobic properties to textile surfaces. Fluorine-containing water repellent is most widely used in the market. The fluorine-containing waterproof agent is expensive, the used fluorine-containing raw material has high energy consumption and heavy pollution in production, and the carried fluorine-containing substances are difficult to degrade and have bioaccumulation toxicity. The use of fluorine-free auxiliaries is a trend.
In recent years, with the improvement of living standard and the upgrade of national industry, the demand of high-grade fluoride-free waterproof agent in the textile printing and dyeing industry is increasing. However, the existing fluoride-free waterproof agent troubles dyeing and finishing enterprises, and mainly shows that after being finished by the waterproof agent, the fabric feels hard and the durability of the waterproof effect is poor. The former is mostly solved by using a softening agent, which generally causes the reduction of water resistance; the latter is a combination of crosslinking agents or an increase in the amount of water repellent, resulting in a further reduction in hand. These disadvantages are based on the defects in the molecular structure design of the water repellent.
The molecular structure of conventional water (oil) repellent agents is exemplified by Duan Yuan Shen (Duan Yuan Shen. fluorine-containing water and oil repellent agent (I) — mechanism on water and oil repellent properties [ J ]. printing and dyeing, 1995,21 (12): 37-41): the self-crosslinking is realized through the reaction of the functional monomer in the finishing process or the reaction with the fabric and the crosslinking agent, so that the durability is improved. The functional monomer forms a short side chain with a reactive group on the main chain of the waterproof agent, and the reaction of the reactive group forms a strong constraint effect on the main chain to form a hard hand feeling; meanwhile, due to the steric effect of the main chain, many reaction groups are self-crosslinked, and do not form strong combination with the fabric, so that the durability is not obviously improved.
Disclosure of Invention
The present invention aims to provide a method for producing a highly efficient fluorine-free water repellent containing a telechelic polymer, which is capable of more retaining the hand feeling of the fabric itself and has a better water repellent effect and durability.
In order to achieve the purpose, the invention firstly provides a method for preparing a fluorine-free waterproof agent, which is characterized by comprising the following components in percentage by mass: 25-35% of fluorine-free polymer, 1.5-6% of surfactant, 1.5-9% of assistant and the balance of water;
the fluorine-free polymer is prepared by free radical polymerization of a hydrophobic monomer, a functional monomer and a telechelic polymer, wherein the hydrophobic monomer, the functional monomer and the telechelic polymer account for the fluorine-free polymer in percentage by mass: 70-90% of hydrophobic monomer, 5-20% of functional monomer and 5-10% of telechelic polymer;
the hydrophobic monomer is provided with a hydrocarbon hydrophobic group and a double bond, and the hydrocarbon hydrophobic group can be one or a mixture of linear chain, branched chain or (poly) cyclic hydrophobic alkyl;
the functional monomer is provided with a double bond and a functional group, and is a mixture of a plurality of substances;
the telechelic polymer is selected from one or a mixture of a plurality of telechelic polymers, one end of which is provided with double bonds, and the other end of which is provided with pyrolysis-sealed blocked isocyanate groups;
the surfactant is selected from nonionic and cationic surfactants;
the auxiliary agent comprises a pH adjusting auxiliary agent and an auxiliary solvent;
the free radicals are generated by thermal decomposition of an initiator;
a method for preparing a high-efficiency fluorine-free water repellent comprising a telechelic polymer comprises the steps of:
(1) uniformly mixing and emulsifying the components to obtain a pre-emulsion, wherein the pre-emulsion does not contain an initiator, a water-soluble monomer and a substance with a boiling point lower than the emulsifying temperature;
(2) adding a water-soluble monomer into the pre-emulsion obtained in the step (1), and uniformly mixing; and then adding an initiator into the mixture for reaction, adding a substance with the boiling point lower than the emulsification temperature at one time or gradually, cooling the system temperature to room temperature after the reaction is finished, and filtering to obtain a target product.
The hydrophobic group can be one or a mixture of more than one of straight chain and branched chain alkyl with the carbon number more than or equal to 8, alkyl substituted phenyl, alkyl substituted cyclohexyl and isobornyl.
The functional group of the functional monomer is selected from one or more of amino, hydroxyl, carboxyl, ketocarbonyl, trialkoxy silicon group, one or more carbon-carbon double bonds, polyoxyethylene fragment, tertiary amine group, quaternary ammonium group, chlorine-bearing element and the like.
The functional monomer is selected from one or more of acrylamide, vinyl trimethoxy silane, diacetone acrylamide and adipyl adipamide system, ethylene glycol dimethacrylate, trimethylolpropane tri (meth) acrylate, divinyl benzene, dimethylaminoethyl (meth) acrylate, (methoxy) polyethylene glycol (meth) acrylate, (meth) acryloyloxyethyl trimethyl ammonium chloride, vinyl chloride, vinylidene chloride, 3-chloro-2-hydroxy-propyl methacrylate and hydroxyethyl (meth) acrylate.
The telechelic polymer is obtained by reacting (methyl) hydroxyl acrylate, polyisocyanate, low molecular weight diol and a blocking agent, wherein one end of the telechelic polymer is a double bond, and the other end of the telechelic polymer is pyrolysis-sealed blocked isocyanate.
The synthetic telechelic polymer has a hydroxy (meth) acrylate selected from one or more of hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, and hydroxyhexyl (meth) acrylate; the polyisocyanate is selected from one or more of isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), diphenylmethane diisocyanate (MDI), HDI tripolymer, TDI tripolymer and MDI tripolymer; the low molecular weight dihydric alcohol is selected from one or more of polyethylene glycol with the molecular weight of 100-1000, polypropylene glycol, polytetrahydrofuran ether glycol, polyhexamethylene glycol adipate glycol, polybutanediol adipate glycol, polyhexamethylene glycol adipate glycol, polycaprolactone glycol and linear alkyl glycol; the blocking agent is selected from one or more of 3, 5-dimethylpyrazole, butanone oxime, phenol and diethyl malonate.
The pH adjusting auxiliary agent comprises acid, alkali or amino acid, and the pH value of the fluorine-free waterproof agent is 4-7; the auxiliary solvent is one or two mixtures of dipropylene glycol and tripropylene glycol.
The initiator is selected from one or more of persulfate, oil-soluble azo initiators or water-soluble azo initiators.
The initiator is selected from one or more of ammonium persulfate, azobisisobutyronitrile and azobisisobutyramidine hydrochloride.
A preparation method of a fluorine-free waterproof agent comprises the following steps:
(1) uniformly mixing and emulsifying the components to obtain a pre-emulsion, wherein the pre-emulsion does not contain an initiator, a water-soluble monomer and a substance with a boiling point lower than the emulsifying temperature;
(2) adding a water-soluble monomer into the pre-emulsion obtained in the step (1) and uniformly mixing. And then adding an initiator into the mixture for reaction, adding a substance with the boiling point lower than the emulsification temperature at one time or gradually, cooling the system temperature to room temperature after the reaction is finished, and filtering to obtain a target product.
Wherein the polymerization system can also contain a molecular weight regulator with the mass percentage of 0-0.3 percent of the system. The molecular weight regulator may be alkyl mercaptan, linear alpha-methyl styrene dimer, mercaptopropionic acid, etc. A linear alkyl mercaptan having 12 or more carbon atoms is preferably selected.
The invention has the beneficial effects that:
the telechelic polymer prepared by the method is synthesized into the fluorine-free waterproof agent, so that the finished fabric can reflect the hand feeling of the fabric and has better waterproof performance and washing resistance.
Detailed Description
In order to verify the water-proofing effect of the textile treated by the water-and oil-repellent agent of the present invention, the water-and oil-repellent agent can be examined by standard methods for comparison. The standard Method is to use the national standard GB 4745-2012 to examine the water-repellent effect and the oil-repellent effect is to examine AATCC-TEST Method l 18-2002, and the following is a brief introduction of the Method.
Test method of national standard GB 4745-2012.
An 18X 18cm sample was taken, held down by a holder, mounted on a fixed base at an angle of 45 degrees to the horizontal, poured quickly and smoothly into a funnel with 250mL (20. + -. 2 ℃) of distilled or deionized water, and sprayed evenly and continuously toward the center of the sample through a nozzle located above the center of the sample within 25 to 30 seconds. After the spraying, the holder was quickly removed to level the front of the sample downward, gently patted, then rotated to level the front of the sample upward, gently patted, and the degree of wetting of the sample was observed and rated by text description and by comparison with pictures. Average 2 times.
The rating standard text is:
grade 0-complete wetting of the entire sample surface.
Grade I-the drenched surface is completely wetted.
l-2 level-the surface of the sample is wetted beyond the spray point, and the wetted area is more than half of the surface to be sprayed.
Grade 2-the surface of the sample is wetted beyond the spray point, the wetted area being about half of the wetted surface.
Grade 2-3-the surface of the sample is wetted beyond the spray point, the wetted area is less than half of the wetted surface.
Grade 3-wetting of the sample surface at the spray points.
Grade 3-4-wetting of the sample surface at spray points equal to or less than half the number.
Grade 4-there is sporadic spray points on the surface of the sample to wet.
Grade 4-5-no wetting of the sample surface, with a small amount of water droplets.
Grade 5-no water drop or wetting of the sample surface.
The effect of the sample after washing with water is also examined, the washing conditions are that the standard synthetic detergent is 1g/L, the washing machine bath ratio is 1: washing at 30 deg.C, rinsing, dewatering, and drying at 100 deg.C for 3 min.
Telechelic Polymer A
1mol of acrylic acid hydroxy hexyl ester and 1mol of isophorone diisocyanate (IPDI) are taken to react completely; adding 1mol of 1, 5-hexanediol to react completely; then adding 1mol of IPDI trimer for complete reaction; and finally, adding 2mol of 3, 5-dimethylpyrazole to react to the end point to obtain the telechelic polymer A.
Telechelic Polymer A
1mol of acrylic acid hydroxy hexyl ester and 1mol of isophorone diisocyanate (IPDI) are taken to react completely; 1mol of 1, 5-pentanediol is added to react completely; then adding 1mol of IPDI trimer for complete reaction; and finally, adding 2mol of 3, 5-dimethylpyrazole to react to the end point to obtain the telechelic polymer A.
Telechelic Polymer B
Completely reacting 1mol of hydroxy butyl acrylate with 1mol of Toluene Diisocyanate (TDI); then adding 1mol of poly hexamethylene adipate glycol with the molecular weight of 500 for complete reaction; then adding 1mol of TDI tripolymer to react completely; and finally, adding 2mol of butanone oxime to react to the end point to obtain a telechelic polymer B.
Telechelic Polymer C
1mol of hydroxyethyl acrylate is taken to completely react with 1mol of isophorone diisocyanate (IPDI); adding 1mol of polycaprolactone diol with the molecular weight of 1000 for complete reaction; then adding 1mol of HDI tripolymer to react completely; and finally, adding 2mol of 3, 5-dimethylpyrazole to react to the end point to obtain the telechelic polymer C.
Example 1
Taking 18 g of acrylic acid behenyl ester, 5 g of methacrylic acid behenyl ester, 1.5 g of styrene, 2 g of telechelic polymer B, 5 g of dipropylene glycol, 3 g of Ethoqual C/25 (ethoxylated quaternary ammonium salt), 0.3 g of acetic acid and 61.5 g of water, heating to 55 ℃, and emulsifying at high speed for 60 minutes to obtain pre-emulsion; nitrogen was added for 30 minutes while controlling the temperature at 62 ℃ and 0.5 g of hydroxyethyl methacrylate was added and mixed well. Then 0.2 g of azobisisobutyramidine hydrochloride and 3 g of vinyl chloride were added and the reaction was allowed to proceed for 8 hours with heat preservation. Finally, the temperature of the system is reduced to room temperature, and the fluorine-free waterproof agent is obtained after filtering through 300-mesh filter cloth.
OTHER EMBODIMENTS
Other examples were different from example 1 in the components and the preparation process was the same as example 1, and the components of each example are shown in the attached table below.
Comparative example 1
There is no telechelic polymer in the fluorine-free water repellent.
Taking 18 g of acrylic acid behenyl ester, 5 g of methacrylic acid behenyl ester, 3.5 g of styrene, 5 g of dipropylene glycol, 3 g of Ethoqual C/25 (ethoxylated quaternary ammonium salt) and 0.3 g of acetic acid, heating to 55 ℃, melting and uniformly stirring, adding 61.5 water, and emulsifying for 60 minutes under high pressure to obtain a pre-emulsion. Then nitrogen is introduced for 30 minutes, the temperature is controlled to be 62 ℃, and 0.5 g of hydroxyethyl methacrylate is added and stirred uniformly. Then 0.2 g of azobisisobutyramidine hydrochloride and 1.5 g of vinyl chloride were added and the reaction was allowed to proceed for 8 hours with incubation. Finally, the temperature of the system is reduced to room temperature, and the fluorine-free waterproof agent is obtained after filtering through 300-mesh filter cloth.
Comparative example 2
Fluorine-free water repellent agents are commercially available.
The fluorine-free water repellent of examples 1 to 5 and comparative examples 1 to 2 was diluted with tap water to a solid content of 10%, a woven cotton fabric was taken, dipped and rolled, dried at 100 ℃ and heat-treated at 180 ℃ for 30 seconds, and the water repellent effect was measured after cooling to room temperature.
In addition, the hand of the cloth samples finished by the examples 1 to 5 is closer to that of the cloth samples before finishing, while the cloth samples finished by the comparative examples have obviously stiff hand.
The invention also provides an application of the fluorine-free waterproof agent in textiles. The application steps comprise: firstly, diluting the fluorine-free waterproof agent to 0.1-10% by mass, and then applying the fluorine-free waterproof agent to cotton fabric subjected to low-temperature dyeing and finishing processing; then removing the excessive liquid and finally carrying out drying treatment. The fluorine-free water repellent can be applied to the cotton fabric finished by low temperature dyeing and finishing by coating, spraying, roll coating, padding, dipping, and the like, and combinations thereof. Through detection, the mass proportion of the fluorine-free waterproof agent component attached to the cotton fabric subjected to the low-temperature dyeing and finishing processing is 0.01-10%. In the drying treatment, the drying conditions are different according to the types of cotton fabrics subjected to low-temperature dyeing and finishing processing, and meanwhile, the full reaction of functional groups brought by functional monomers in the fluorine-free waterproof agent is ensured to achieve the optimal waterproof effect and durability, and the drying is usually carried out at 100-200 ℃ for 0.1-90 minutes.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several changes, improvements and modifications can be made without departing from the spirit of the present invention, and these changes, improvements and modifications should also be construed as the protection scope of the present invention.
Claims (8)
1. A preparation method of a high-efficiency fluorine-free water repellent containing a telechelic polymer is characterized in that the high-efficiency fluorine-free water repellent containing the telechelic polymer comprises the following components in percentage by mass:
25-35% of fluorine-free polymer, 1.5-6% of surfactant, 1.5-9% of assistant and the balance of water; the fluorine-free polymer is prepared by free radical polymerization of a hydrophobic monomer, a functional monomer and a telechelic polymer, wherein the hydrophobic monomer, the functional monomer and the telechelic polymer account for the fluorine-free polymer in percentage by mass: 70-90% of hydrophobic monomer, 5-20% of functional monomer and 5-10% of telechelic polymer; the hydrophobic monomer is provided with a hydrocarbon hydrophobic group and a double bond, and the hydrocarbon hydrophobic group is one or a mixture of linear chain, branched chain or cyclic hydrophobic alkyl; the functional monomer is provided with a double bond and a functional group, and is a mixture of a plurality of substances; the telechelic polymer is obtained by reacting hydroxyl acrylate, polyisocyanate, low molecular weight diol and a blocking agent, wherein one end of the telechelic polymer is a double bond, and the other end of the telechelic polymer is pyrolysis-sealed type closed isocyanate; the surfactant is selected from nonionic and cationic surfactants; the auxiliary agent comprises a pH adjusting auxiliary agent and an auxiliary solvent; the free radicals are generated by thermal decomposition of an initiator;
a method for preparing a high-efficiency fluorine-free water repellent comprising a telechelic polymer comprises the steps of:
(1) uniformly mixing and emulsifying the components to obtain a pre-emulsion, wherein the pre-emulsion does not contain an initiator, a water-soluble monomer and a substance with a boiling point lower than the emulsifying temperature;
(2) adding a water-soluble monomer into the pre-emulsion obtained in the step (1), and uniformly mixing; and then adding an initiator into the mixture for reaction, adding a substance with the boiling point lower than the emulsification temperature at one time or gradually, cooling the system temperature to room temperature after the reaction is finished, and filtering to obtain a target product.
2. The preparation method according to claim 1, wherein the hydrophobic group is one or more of a linear chain alkyl group, a branched chain alkyl group with a carbon number of 8 or more, an alkyl-substituted phenyl group, an alkyl-substituted cyclohexyl group and an isobornyl group.
3. The method according to claim 1, wherein the functional group of the functional monomer is selected from one or more of amino group, hydroxyl group, carboxyl group, ketocarbonyl group, trialkoxysilyl group, carbon-carbon double bond, polyoxyethylene segment, tertiary amine group, quaternary ammonium group, and chlorine-containing element.
4. The method according to claim 3, wherein the functional monomer is selected from one or more of acrylamide, vinyltrimethoxysilane, diacetone acrylamide complex adipamide system, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, divinylbenzene, dimethylaminoethyl acrylate, methoxypolyethylene glycol acrylate, methacryloyloxyethyl trimethyl ammonium chloride, vinyl chloride, vinylidene chloride, 3-chloro-2-hydroxy-propyl methacrylate, and hydroxyethyl methacrylate.
5. The method according to claim 1, wherein the hydroxy acrylate is one or more selected from the group consisting of hydroxyethyl acrylate, hydroxybutyl acrylate and hydroxyhexyl acrylate; the polyisocyanate is selected from one or more of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, HDI tripolymer, TDI tripolymer and MDI tripolymer; the low molecular weight dihydric alcohol is selected from one or more of polyethylene glycol with the molecular weight of 100-1000, polypropylene glycol, polytetrahydrofuran ether glycol, polyhexamethylene glycol adipate glycol, polybutanediol adipate glycol, polyhexamethylene glycol adipate glycol, polycaprolactone glycol and linear alkyl glycol; the blocking agent is selected from one or more of 3, 5-dimethylpyrazole, butanone oxime, phenol and diethyl malonate.
6. The preparation method according to claim 1, wherein the pH adjusting aid comprises an acid, a base or an amino acid, and the pH value of the fluorine-free waterproof agent is 4-7; the auxiliary solvent is one or two mixtures of dipropylene glycol and tripropylene glycol.
7. The method according to claim 1, wherein the initiator is one or more selected from persulfate, oil-soluble azo-based initiator, and water-soluble azo-based initiator.
8. The preparation method according to claim 7, wherein the initiator is selected from one or more of ammonium persulfate, azobisisobutyronitrile and azobisisobutyramidine hydrochloride.
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| CN109763345B (en) * | 2018-12-20 | 2021-04-02 | 上海开米科技有限公司 | Fluorine-free anti-splashing fabric spray and preparation method thereof |
| CN110527014A (en) * | 2019-08-22 | 2019-12-03 | 浙江工业职业技术学院 | A kind of free-floride cationic polyacrylate waterproofing agent and preparation method thereof |
| EP4058500A1 (en) * | 2019-11-15 | 2022-09-21 | BASF Coatings GmbH | A blocked polyisocyanate crosslinking agent, its preparation method and a coating composition comprising the same |
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| CN107700214A (en) | 2018-02-16 |
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