CN110485160B - Preparation method of efficient water-proof and oil-proof agent containing telechelic polymer - Google Patents
Preparation method of efficient water-proof and oil-proof agent containing telechelic polymer Download PDFInfo
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- CN110485160B CN110485160B CN201910701158.4A CN201910701158A CN110485160B CN 110485160 B CN110485160 B CN 110485160B CN 201910701158 A CN201910701158 A CN 201910701158A CN 110485160 B CN110485160 B CN 110485160B
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- 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
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- 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
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
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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
- 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
- D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
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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
- D06M2200/11—Oleophobic properties
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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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- 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
- D06M2200/50—Modified hand or grip properties; Softening compositions
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Abstract
The invention discloses a preparation method of a high-efficiency waterproof and oil-proof agent containing a telechelic polymer, wherein the waterproof and oil-proof agent comprises the following components in percentage by mass: 20-35% of fluorine-containing polymer, 2-8% of surfactant, 2-10% of auxiliary agent and water; the preparation method 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. The waterproof and oilproof agent provided by the invention has good waterproof and oilproof effects. Compared with the prior art, the waterproof and oilproof agent provided by the invention adopts special raw materials, and has better waterproof and oilproof effects, good hand feeling and better washing resistance.
Description
Technical Field
The invention relates to the field of textile auxiliary agents, in particular to a preparation method of a water-proof and oil-proof agent containing a telechelic polymer.
Background
The water-proof and oil-proof agent can endow the textile surface with hydrophobic and oleophobic performances. The most widely used in the market are fluorine-containing water-and oil-repellent agents. Most of the existing waterproof and oil-proof agents have the defects of poor hand feeling and poor washability, and the efficiency of waterproof and oil-proof finishing needs to be improved. These disadvantages are based on the defects in the molecular structure design of the water repellent.
The molecular structure of conventional water and oil resistant agents is exemplified by Duan Yuan Shen (Duan Yuan Shen. fluorine-containing water and oil resistant agent (I) — mechanism on water and oil resistant 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 invention aims to provide a method for preparing a high-efficiency waterproof and oil-proof agent containing a telechelic polymer, so that the waterproof and oil-proof agent can better keep the hand feeling of a fabric and has better waterproof and oil-proof effects and durability.
In order to achieve the above object, the present invention provides a method for producing a water and oil resistant agent, which comprises the following components by mass: 20-35% of fluorine-containing polymer, 2-8% of surfactant, 2-10% of auxiliary agent and the balance of water;
the fluorine-containing polymer is prepared by free radical polymerization of a fluorine-containing monomer A, a fluorine-containing monomer B, a non-fluorine monomer, a functional monomer and a telechelic polymer, wherein the fluorine-containing monomer A, the fluorine-containing monomer B, the non-fluorine monomer, the functional monomer and the telechelic polymer account for the fluorine-containing polymer in percentage by mass: 19-55% of fluorine-containing monomer A, 1-5% of fluorine-containing monomer B, 20-70% of non-fluorine monomer, 5-20% of functional monomer and 5-10% of telechelic polymer;
the fluorine-containing monomer A has a general formula CmF2m+1YCnH2nOCOCR＝CH2Wherein Y is a single chemical bond or is-NH-, -NR1-、-NH-SO2-、-NR1-SO2One or more of (A), (B), (C), and (C), R1Is C1—C4One of an alkyl group; r is H, Cl, F or CH3(ii) a m is any integer of 4, 5 and 6, and n is any integer of 1, 2, 3 and 4; it may be a single substance or a mixture of substances corresponding to the general formula.
The fluorine-containing monomer B is obtained by reacting 2mol of perfluorohexylethyl alcohol, 1mol of Hexamethylene Diisocyanate (HDI) trimer and 1mol of hydroxybutyl acrylate;
the non-fluorine monomer has a hydrocarbon hydrophobic group and a double bond, and the hydrocarbon hydrophobic group can be one or more 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 substance or a mixture of a plurality of substances;
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 double-bonded, and the other end of the telechelic polymer is pyrolysis-sealed blocked 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;
the preparation method 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.
The hydrocarbon hydrophobic group can be one or a mixture of more than one of straight chain and branched chain alkyl (alkyl substituted) phenyl, (alkyl substituted) cyclohexyl and isobornyl with the carbon number more than or equal to 8;
the functional group of the functional monomer is selected from one or more of epoxy group, hydroxyl group, amino group, carboxyl group, ketonic carbonyl group, trialkoxy silicon group, one or more carbon-carbon double bonds, polyoxyethylene segment, tertiary amine group, quaternary ammonium group, chlorine-bearing element and the like;
the functional monomer is selected from one or more of glycidyl methacrylate, acrylamide, vinyl trimethoxy silane, diacetone acrylamide and adipyl system, ethylene glycol dimethacrylate, trimethylolpropane tri (methyl) acrylate, divinylbenzene, dimethylaminoethyl (methyl) acrylate, (methoxy) polyethylene glycol (methyl) acrylate, (methyl) acryloyloxyethyl trimethyl ammonium chloride, vinyl chloride, vinylidene chloride, 3-chloro-2-hydroxy-propyl methacrylate and hydroxyethyl (methyl) acrylate;
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 aid comprises acid, alkali or amino acid, and the pH value of the waterproof and oil-proof agent is 4-7;
the auxiliary solvent is one or two mixtures of dipropylene glycol ethyl ether and tripropylene glycol ethyl ether;
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.
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 special fluorine-containing monomer B and the telechelic polymer are adopted to synthesize the waterproof and oil-proof agent, so that the finished fabric can reflect the hand feeling of the fabric per se, and the waterproof and oil-proof performance and the washing resistance performance are better.
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.
AATCC-TEST Method l 18-2002 Method: the lowest numbered test liquid was first carefully dropped onto the sample at 0.05mL, followed by the higher numbered test liquid if no penetration and wetting occurred within 30 seconds. The experiment was continued until the test fluid was wetting the sample below or around the drop within 30 seconds. The oil repellency rating of the test specimens is represented by the highest numbered test liquid that failed to wet the test specimens in 30 seconds and is rated as follows.
TABLE 1 oil repellency test Standard solution
| Number of stages of oil-proofing | Components | Surface tension (mN/m,25 ℃ C.) |
| 1 | White mineral oil | 31.2 |
| 2 | 65 parts of white mineral oil and 35 parts of n-hexadecane | 28.7 |
| 3 | N-hexadecane | 27.1 |
| 4 | N-tetradecane | 26.1 |
| 5 | N-dodecane | 25.1 |
| 6 | N-decane | 23.5 |
| 7 | N-octane | 21.3 |
| 8 | N-heptane | 19.8 |
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 B
Completely reacting 1mol of hydroxy butyl acrylate with 1mol of Toluene Diisocyanate (TDI); adding 1mol of polycaprolactone diol 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); then adding 1mol of poly adipic acid glycol ester 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 11 g of perfluorohexyl ethyl methacrylate, 1g of a fluorine-containing monomer B (obtained by reacting 2mol of perfluorohexyl ethyl alcohol, 1mol of Hexamethylene Diisocyanate (HDI) trimer and 1mol of hydroxybutyl acrylate), 10.4 g of behenyl acrylate, 2 g of styrene, 2 g of telechelic polymer B, 5.7 g of dipropylene glycol ethyl ether, 5 g of Ethoqual C/25 (ethoxylated quaternary ammonium salt), 0.3 g of acetic acid and 58.8 g of water, heating to 55 ℃, and emulsifying at a high speed for 60 minutes to obtain a pre-emulsion; nitrogen was added for 30 minutes while controlling the temperature at 62 ℃. 0.2 g of azobisisobutyramidine hydrochloride and 3.6 g of vinyl chloride were added and the reaction was allowed to proceed for 8 hours with incubation. And finally, cooling the system to room temperature, and filtering through 300-mesh filter cloth to obtain the waterproof and oil-proof agent.
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
The water-and oil-repellent agent contains no special raw material.
Taking 12 g of perfluorohexyl ethyl methacrylate, 12.4 g of behenyl acrylate, 2 g of styrene, 5.7 g of dipropylene glycol ethyl ether, 5 g of Ethoqual C/25 (ethoxylated quaternary ammonium salt), 0.3 g of acetic acid and 58.8 g of water, heating to 55 ℃, and emulsifying at a high speed for 60 minutes to obtain a pre-emulsion; nitrogen was added for 30 minutes while controlling the temperature at 62 ℃. 0.2 g of azobisisobutyramidine hydrochloride and 3.6 g of vinyl chloride were added and the reaction was allowed to proceed for 8 hours with incubation. And finally, cooling the system to room temperature, and filtering through 300-mesh filter cloth to obtain the waterproof and oil-proof agent.
Comparative example 2
Water-and oil-repellent agents are commercially available.
The water-and oil-repellent agents of examples 1 to 5 and comparative examples 1 to 2 were diluted with tap water to a solid content of 5%, 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 waterproof and oil-proof agent in textiles. The application steps comprise: diluting the waterproof and oil-proof agent to 0.1-10% mass fraction, and then applying the diluted waterproof and oil-proof agent to cotton fabric subjected to low-temperature dyeing and finishing processing; then removing the excessive liquid and finally carrying out drying treatment. The water and oil repellent agent 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 waterproof and oil-proof agent components 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, and meanwhile, the functional groups brought by functional monomers in the waterproof and oil-proof agent are ensured to be fully reacted so as to achieve the optimal waterproof and oil-proof effects and durability, and the cotton fabrics are usually dried 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 (4)
1. The preparation method of the high-efficiency waterproof and oil-proof agent containing the telechelic polymer is characterized in that the high-efficiency waterproof and oil-proof agent containing the telechelic polymer comprises the following components in percentage by mass: 20-35% of fluorine-containing polymer, 2-8% of surfactant, 2-10% of auxiliary agent and the balance of water;
the fluorine-containing polymer is prepared by free radical polymerization of a fluorine-containing monomer A, a fluorine-containing monomer B, a non-fluorine monomer, a functional monomer and a telechelic polymer, wherein the fluorine-containing monomer A, the fluorine-containing monomer B, the non-fluorine monomer, the functional monomer and the telechelic polymer account for the fluorine-containing polymer in percentage by mass: 19-55% of fluorine-containing monomer A, 1-5% of fluorine-containing monomer B, 20-70% of non-fluorine monomer, 5-20% of functional monomer and 5-10% of telechelic polymer;
the fluorine-containing monomer A has a general formula CmF2m+1YCnH2nOCOCR=CH2Wherein Y is a single chemical bond or is-NH-, -NR1-、-NH-SO2-、-NR1-SO2One or more of (A), (B), (C), and (C), R1Is C1—C4One of an alkyl group; r is H, Cl, F or CH3(ii) a m is any integer of 4, 5 and 6, and n is any integer of 1, 2, 3 and 4; the fluorine-containing monomer A is selected from one substance or a mixture of substances which accord with the general formula;
the fluorine-containing monomer B is obtained by reacting 2mol of perfluorohexylethyl alcohol, 1mol of Hexamethylene Diisocyanate (HDI) trimer and 1mol of hydroxybutyl acrylate;
the non-fluorine monomer is provided with a hydrocarbon hydrophobic group and a double bond, and the hydrocarbon hydrophobic group is selected from one or more 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 substance or a mixture of a plurality of substances;
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 double-bonded, and the other end of the telechelic polymer is pyrolysis-sealed blocked isocyanate; the (methyl) acrylic acid hydroxyl ester is selected from one or more of (methyl) acrylic acid hydroxyethyl ester, (methyl) acrylic acid hydroxybutyl ester and (methyl) acrylic acid hydroxyhexyl ester; 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 surfactant is selected from nonionic and cationic surfactants;
the auxiliary agent is a pH adjusting auxiliary agent and an auxiliary solvent;
the free radicals are generated by thermal decomposition of an initiator;
the hydrocarbon hydrophobic group is selected from one or more of straight chain, branched chain alkyl, (alkyl substituted) phenyl, (alkyl substituted) cyclohexyl and isobornyl with the carbon number more than or equal to 8;
the functional monomer is selected from one or more of glycidyl methacrylate, acrylamide, vinyl trimethoxy silane, diacetone acrylamide and adipyl system, ethylene glycol dimethacrylate, trimethylolpropane tri (methyl) acrylate, divinylbenzene, dimethylaminoethyl (methyl) acrylate, (methoxy) polyethylene glycol (methyl) acrylate, (methyl) acryloyloxyethyl trimethyl ammonium chloride, vinyl chloride, vinylidene chloride, 3-chloro-2-hydroxy-propyl methacrylate and hydroxyethyl (methyl) acrylate;
the preparation method of the high-efficiency water-and-oil repellent agent containing the telechelic polymer 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), uniformly mixing, adding an initiator into the pre-emulsion for reaction, adding a substance with a boiling point lower than the emulsification temperature at one time or gradually, cooling the system 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 pH adjusting auxiliary agent is selected from one or more of acid, alkali and amino acid, and the pH value of the water and oil proofing agent is 4-7; the auxiliary solvent is one or two mixtures of dipropylene glycol ethyl ether and tripropylene glycol ethyl ether.
3. The method according to claim 2, wherein the initiator is one or more selected from a persulfate, an oil-soluble azo initiator, and a water-soluble azo initiator.
4. The preparation method according to claim 3, wherein the initiator is selected from one or more of ammonium persulfate, azobisisobutyronitrile and azobisisobutyramidine hydrochloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910701158.4A CN110485160B (en) | 2017-10-24 | 2017-10-24 | Preparation method of efficient water-proof and oil-proof agent containing telechelic polymer |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710999753.1A CN107653681B (en) | 2017-10-24 | 2017-10-24 | High-effective water-proof oil-proofing agent and preparation method comprising telechelic polymer |
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| CN110670359B (en) * | 2019-10-10 | 2022-02-11 | 广东中联邦精细化工有限公司 | Low-temperature type waterproof and oil-proof agent and preparation method thereof |
| CN111877017A (en) * | 2020-07-10 | 2020-11-03 | 温州厚德服饰有限公司 | Waterproof cotton-padded clothes |
| CN112538760A (en) * | 2020-11-24 | 2021-03-23 | 京准化工技术(上海)有限公司 | Six-carbon fluorine-series high-washing-resistance waterproof and oil-proof agent and preparation method thereof |
| CN113089325B (en) * | 2021-06-08 | 2022-06-10 | 广东德美精细化工集团股份有限公司 | Durable short-chain fluorine-containing water and oil repellent agent and preparation method thereof |
| CN114687210A (en) * | 2021-12-22 | 2022-07-01 | 浙江科峰新材料有限公司 | Environment-friendly washable waterproof and oil-proof agent and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296503A (en) * | 1998-04-09 | 2001-05-23 | 克拉瑞特金融(Bvi)有限公司 | Blocked oligomeric isocyanates, their production and use |
| CN1509361A (en) * | 2001-05-15 | 2004-06-30 | ��Ļ���Ű˾ | High-durability low-yellowing water-and oil-repellent for textiles |
| CN1882622A (en) * | 2003-11-18 | 2006-12-20 | 纳幕尔杜邦公司 | Fluorine efficient finishes for textiles |
| CN1993443A (en) * | 2004-06-04 | 2007-07-04 | 优迈特株式会社 | Method for producing water-and-oil repellent agent |
| CN101679840A (en) * | 2007-06-12 | 2010-03-24 | 旭硝子株式会社 | Water-repellent/oil-repellent composition, method for producing the same, and article |
| CN102666971A (en) * | 2009-11-20 | 2012-09-12 | 大金工业株式会社 | Fluoropolymers and treatment agent |
| CN105339398A (en) * | 2013-06-25 | 2016-02-17 | 优迈特株式会社 | Aqueous dispersion of fluorinated copolymer |
| CN106758232A (en) * | 2016-11-29 | 2017-05-31 | 广东德美高新材料有限公司 | Bafta special-purpose water-proof oil-proofing agent, preparation method and its bafta processed through full low-temperature dyeing and finishing |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH286872D (en) * | 1971-03-08 | |||
| JPH01131135A (en) * | 1987-11-16 | 1989-05-24 | Asahi Chem Ind Co Ltd | Perfluropolyether diacrylate |
| EP2103635B1 (en) * | 2007-01-17 | 2012-09-12 | Asahi Glass Company, Limited | Oil-repellent copolymer, method for producing the same and oil-repellent processing liquid |
| CN102002129B (en) * | 2010-10-25 | 2012-10-03 | 江苏梅兰化工有限公司 | Method for preparing fluorine-containing acrylate copolymer textile finishing agent |
| CN103266482B (en) * | 2013-03-23 | 2015-02-04 | 广东德美精细化工股份有限公司 | Wax-containing water-and-oil repellent agent and textile |
-
2017
- 2017-10-24 CN CN201910701158.4A patent/CN110485160B/en active Active
- 2017-10-24 CN CN201710999753.1A patent/CN107653681B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296503A (en) * | 1998-04-09 | 2001-05-23 | 克拉瑞特金融(Bvi)有限公司 | Blocked oligomeric isocyanates, their production and use |
| CN1509361A (en) * | 2001-05-15 | 2004-06-30 | ��Ļ���Ű˾ | High-durability low-yellowing water-and oil-repellent for textiles |
| CN1882622A (en) * | 2003-11-18 | 2006-12-20 | 纳幕尔杜邦公司 | Fluorine efficient finishes for textiles |
| CN1993443A (en) * | 2004-06-04 | 2007-07-04 | 优迈特株式会社 | Method for producing water-and-oil repellent agent |
| CN101679840A (en) * | 2007-06-12 | 2010-03-24 | 旭硝子株式会社 | Water-repellent/oil-repellent composition, method for producing the same, and article |
| CN102666971A (en) * | 2009-11-20 | 2012-09-12 | 大金工业株式会社 | Fluoropolymers and treatment agent |
| CN105339398A (en) * | 2013-06-25 | 2016-02-17 | 优迈特株式会社 | Aqueous dispersion of fluorinated copolymer |
| CN106758232A (en) * | 2016-11-29 | 2017-05-31 | 广东德美高新材料有限公司 | Bafta special-purpose water-proof oil-proofing agent, preparation method and its bafta processed through full low-temperature dyeing and finishing |
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| CN110485160A (en) | 2019-11-22 |
| CN107653681A (en) | 2018-02-02 |
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