CN114351464A - Chlorine-free durable waterproof and oil-proof agent and preparation method thereof - Google Patents
Chlorine-free durable waterproof and oil-proof agent and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 91
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 42
- 239000011737 fluorine Substances 0.000 claims abstract description 42
- 239000005871 repellent Substances 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000004744 fabric Substances 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 22
- 230000002940 repellent Effects 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 10
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000012224 working solution Substances 0.000 claims description 6
- -1 acrylic ester Chemical class 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000007730 finishing process Methods 0.000 claims 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 abstract description 13
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 13
- 238000004132 cross linking Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- 150000003254 radicals Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
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- 239000004811 fluoropolymer Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012875 nonionic emulsifier Substances 0.000 description 2
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
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- STYXVTBFUKQEKM-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F STYXVTBFUKQEKM-UHFFFAOYSA-N 0.000 description 1
- XSCRXCDDATUDLB-UHFFFAOYSA-N 2-(2-methylpropoxymethyl)prop-2-enamide Chemical compound CC(C)COCC(=C)C(N)=O XSCRXCDDATUDLB-UHFFFAOYSA-N 0.000 description 1
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Abstract
The invention discloses a chlorine-free durable waterproof and oil-proof agent, which consists of a fluorine-containing polymer and a fluorine-free polymer, wherein the mass ratio of the fluorine-containing polymer to the fluorine-free polymer is (0.1: 9.9) - (9.9): 0.1. the present invention is a binary water-and oil-repellent agent comprising a fluorine-containing polymer and a fluorine-free polymer as a carrier, wherein the fluorine-containing polymer as a main component is bonded to the fluorine-free polymer as a carrier via a crosslinking group (the bonding occurs during the baking process in which the water-and oil-repellent agent is used), the fluorine-containing polymer as a main component has a main function of water-and oil-repellency, and the fluorine-free polymer as a carrier has other functions such as durability. The invention can divide the water-proof and oil-proof functions and the durable functions into two functions on the basis of not introducing chloroethylene/vinylidene chloride, so that the water-proof and oil-proof performance and the durable performance are balanced, and the water-proof and oil-proof effects of the water-repellent and oil-repellent agent are enhanced.
Description
Technical Field
The invention belongs to the field of fabric finishing, and particularly relates to a waterproof and oil-proof agent for fabric and a preparation method thereof.
Background
In the technical field of water and oil repellent finishing of fabrics, emulsion of (methyl) acrylic acid perfluorooctyl ethyl ester polymer is used for treatment at present. For environmental reasons, the current practice is partly to use perfluorohexylethyl (meth) acrylate polymers. With increasing environmental requirements, perfluorohexylethyl (meth) acrylate polymers will occupy an increasing market share. The fluorine-free waterproof agent in the current market can only be used for single waterproof finishing of fabrics but not for waterproof and oilproof finishing because the fluorine-free waterproof agent does not have an oilproof function.
The basic synthesis method of the water and oil repellent agent comprises the following steps: the emulsion is prepared by emulsifying perfluorohexyl ethyl (meth) acrylate monomers and other functional monomers (such as other waterproof monomers, hand feeling adjusting monomers, crosslinking monomers, polarizing monomers and the like) together with an emulsifier, and then generating free radicals by an initiator to carry out free radical polymerization.
The durable water and oil repellent agent means that after the fabric is treated by the water and oil repellent agent and is washed for many times, the fabric still has a good water and oil repellent effect. To achieve durability, two methods are currently commonly used:
1. in the copolymerization process of the polymer, a certain amount of crosslinking monomers (such as N-hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, glycidyl methacrylate, isobutoxy methyl acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl methacrylate and the like) are introduced, so that the obtained polymer forms a space network structure after being cured on the fabric at high temperature, and the bonding force with the fabric fiber is increased to realize durability.
2. In the copolymerization process of the polymer, chlorine polarization containing monomers (such as vinyl chloride, vinylidene chloride and the like) are introduced, and the strong electron withdrawing property of chlorine is utilized to locally polarize in the polymer to form local dipole moment, so that the adsorption of fabric fibers is increased by utilizing the charge acting force to realize the durability.
The two methods for realizing the durability of the water-repellent and oil-repellent agent have the following advantages and disadvantages:
firstly, introducing a crosslinking monomer: the water-and oil-repellency is adversely affected by the crosslinking monomer, so that the use of the crosslinking monomer is limited.
Introducing vinyl chloride/vinylidene chloride: vinyl chloride/vinylidene chloride has a relatively small influence on the water-and oil-repellent properties, but does not achieve good water-resistance characteristics by virtue of the polarization of chlorine alone.
Therefore, a combination of the two methods is generally adopted to realize a durable water-and oil-repellent function. This bonding method has undoubtedly the following drawbacks:
1. introducing vinyl chloride/vinylidene chloride as a comonomer requires pressurized polymerization using a pressure vessel, and the requirements for polymerization reaction are severe.
2. Chloroethylene/vinylidene chloride has strong toxicity, safety accidents are easily caused by improper use in production, and chloroethylene/vinylidene chloride is easily remained in the finished water-repellent oil-repellent agent emulsion.
3. Whether a crosslinking monomer is introduced or vinyl chloride/vinylidene chloride is used, the crosslinking monomer or vinyl chloride/vinylidene chloride occupies a considerable proportion in the same polymer, so that the concentration of perfluoroalkyl ethyl (meth) acrylate is diluted, and the water and oil repellent performance is influenced to a greater or lesser extent.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a durable water-proof and oil-proof agent without chlorine and a preparation method thereof. The invention divides the water-proof and oil-proof functions and the durable function into two functions under the condition of not introducing vinyl chloride/vinylidene chloride, so that the water-proof and oil-proof performance and the durable performance are balanced.
In order to achieve the purpose, the invention adopts the following technical scheme:
the durable water-proof and oil-proof agent is characterized by comprising a fluorine-containing polymer and a fluorine-free polymer in a mass ratio of 0.1: 9.9-9.9: 0.1.
preferably, the fluorine-containing polymer is a polymer produced by emulsion polymerization of a fluorine-containing acrylate monomer as a main component, an emulsifier, a solvent, a chain transfer agent, and an initiator. The preparation method specifically comprises the steps of taking perfluorohexyl ethyl methacrylate as a main component, adding a small amount of octadecyl acrylate, compounding an emulsifier by a cationic emulsifier and a nonionic emulsifier, selecting propylene glycol methyl ether as a solvent, selecting dodecyl mercaptan as a chain transfer agent, and selecting V-50 as an initiator.
Preferably, the fluorine-free polymer is a polymer produced by emulsion polymerization of a fluorine-free acrylic ester as a main component, and an emulsifier, a solvent, a chain transfer agent, and an initiator. Specifically, octadecyl acrylate is taken as a main component, functional acrylate monomers are added, a cationic emulsifier and a nonionic emulsifier are compounded to form the emulsifier, propylene glycol methyl ether is taken as a solvent, dodecyl mercaptan is taken as a chain transfer agent, and V-50 is taken as an initiator.
Preferably, the mass ratio of the fluorine-containing polymer to the fluorine-free polymer is preferably 3: 7-7: 3.
The present invention is a binary water-and oil-repellent agent comprising a fluorine-containing polymer and a fluorine-free polymer as a carrier, wherein the fluorine-containing polymer as a main component is bonded to the fluorine-free polymer as a carrier via a crosslinking group (the bonding occurs during the baking process in which the water-and oil-repellent agent is used), the fluorine-containing polymer as a main component has a main function of water-and oil-repellency, and the fluorine-free polymer as a carrier has other functions such as durability.
The invention utilizes the principle that perfluoroalkyl chain segments with low surface energy tend to contact with air and migrate to the surface after being solidified into a film, divides the water and oil repellent function and the water-resistant function originally borne by the same polymer into two parts to form a binary structure, and the two polymers respectively bear different functions, wherein the two polymers comprise: a fluorine-containing polymer as a main functional unit of the water-and oil-repellent agent; the polymer containing no fluorine is used as a carrier of the fluorine-containing polymer, and the polymer has washing fastness. Neither polymer uses vinyl chloride/vinylidene chloride as a comonomer. The fluoropolymer is linked to the crosslinking groups of the non-fluorine containing polymeric support through a very small number of crosslinking groups (which may be hydroxyl, isocyanate, amide, etc.).
When the polymer forms a film on the surface of the fiber, the fluorine-free polymer in the system is fully crosslinked to form a space network structure, the space network structure is attached to the surface of the fiber to construct a durable substrate layer, and the fluorine-containing polymer is connected with the substrate layer through a small amount of crosslinking monomers and is distributed on the interface of the polymer film contacted with air, so that the water-repellent and oil-repellent effects are realized.
The second object of the present invention is to provide a method for preparing the durable water-and oil-repellent agent, comprising the steps of:
(1) respectively preparing fluorine-containing polymer and fluorine-free polymer by adopting a polymerization process;
(2) the mass ratio of the components is 0.1: 9.9-9.9: 0.1, mixing the fluorine-containing polymer and the fluorine-free polymer uniformly.
Wherein, the polymerization process of the fluorine-containing polymer and the fluorine-free polymer comprises the following steps:
(1) stirring and preserving heat of the ingredients except the initiator for 30 minutes at 60 ℃, shearing at high speed for 5 minutes, and homogenizing;
(2) pouring the feed liquid into a reaction bottle, and introducing nitrogen N2When the temperature is reduced to 55 ℃, the nitrogen is turned off;
(3) diluting the initiator by 10 times of water, and dropwise adding the initiator when the temperature in the reaction flask rises to 62 ℃;
(4) and (3) starting heating reaction after the initiator is dripped for 15 minutes, starting falling after the temperature rises to 68-69 ℃, keeping the temperature to 62-65 ℃ after finishing dripping the initiator for 20 minutes, continuing the reaction for 5 hours, adding the defoaming agent, starting cooling, cooling to below 35 ℃, filtering and discharging.
The third purpose of the invention is to provide a water-proof and oil-proof finishing method for fabric, which is characterized by comprising the following steps:
(1) diluting the durable water-proof and oil-proof agent, and adding a cross-linking agent to prepare a working solution;
(2) padding the fabric by using the working solution in the step (1);
(3) and (5) drying.
Further, the durable water-and oil-repellent agent in the step (1) is diluted with water at a concentration of 5%.
The cross-linking agent in the step (1) is a blocked isocyanate dispersion liquid or a polycarbodiimide cross-linking agent (in the embodiment, a commercially available blocked isocyanate dispersion liquid is selected, and the cross-linking agent TF-569 of Zhejiang province chemical union Co., Ltd.) is selected, and the addition amount of the cross-linking agent is 1%.
Further, in the step (3), baking is carried out at 180 ℃ for 120 seconds.
After the fabric is finished by the waterproof and oilproof agent, the fabric is subjected to the following standard tests (water repellency: American standard AATCC-22 corresponding to national standard GB/T4745: 2012; oil repellency: American standard AATCC-118 corresponding to national standard GB/T19977: 2014; water washing standard: water washing method in American standard AATCC-135 corresponding to national standard GB/T8630-.
The invention forms the binary water and oil repellent agent by the fluorine-containing polymer and the fluorine-free polymer, has ingenious conception and has the following beneficial effects:
1. the water-and oil-proof performance and the durability can be balanced by dividing the two functions into two on the basis of not introducing vinyl chloride/vinylidene chloride. In addition, since toxic and harmful components such as vinyl chloride/vinylidene chloride are not introduced, the method is favorable for environmental protection.
2. The process condition of pressurization is not needed any more, and the method is safe.
3. The original fluorine-containing polymer bears all functions, and the original fluorine-containing polymer is changed into two polymers which respectively bear different functions, so that the water and oil repellent effect of the water and oil repellent agent is enhanced. The fluorine-containing polymer only needs to bear the waterproof and oilproof performance, and does not need to balance more functions, so that the using amount of the (methyl) acrylic perfluoroalkyl ethyl acrylate can be greatly increased, and the waterproof and oilproof performance can be greatly improved.
4. The carrier polymer not containing fluorine can impart various functions such as softness, antistatic property, flame retardancy, etc. to the polymer without affecting water and oil repellency in addition to durability.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1
According to the following mixture ratio, the fluorine-containing polymer and the fluorine-free polymer are respectively prepared by adopting a conventional free radical emulsion polymerization process.
The preparation method of the water-proof and oil-proof agent comprises the following steps:
(1) stirring and preserving heat of the ingredients except the initiator for 30 minutes at 60 ℃, shearing at high speed for 5 minutes, and homogenizing;
(2) pouring the feed liquid into a reaction bottle, and introducing nitrogen N2When the temperature is reduced to 55 ℃, the nitrogen is turned off;
(3) diluting the initiator by 10 times of water, and dropwise adding the initiator when the temperature in the reaction flask rises to 62 ℃;
(4) and (3) starting heating reaction after the initiator is dripped for 15 minutes, starting falling after the temperature rises to 68-69 ℃, keeping the temperature to 62-65 ℃ after finishing dripping the initiator for 20 minutes, continuing the reaction for 5 hours, adding the defoaming agent, starting cooling, cooling to below 35 ℃, filtering and discharging.
(5) The fluorine-containing polymer and the fluorine-free polymer are uniformly mixed according to the mass ratio of 1: 1.
Secondly, the water-proof and oil-proof finishing method of the fabric comprises the following steps:
(1) diluting the obtained durable waterproof and oil-proof agent with water according to the concentration of 5%, adding 1% of cross-linking agent (commercially available blocked isocyanate dispersion liquid, cross-linking agent TF-569 of Zhejiang province chemical union Co., Ltd.), and preparing into working solution;
(2) padding the fabric with the obtained working solution;
(3) after drying at 180 ℃ for 120 seconds, balancing at room temperature for 24 hours to be tested.
Example 2
According to the following mixture ratio, the fluorine-containing polymer and the fluorine-free polymer are respectively prepared by adopting a conventional free radical emulsion polymerization process.
The specific preparation method of the water-and oil-repellent agent was the same as in example 1.
The fluorine-containing polymer and the fluorine-free polymer are uniformly mixed according to the mass ratio of 1: 1.
The water and oil repellent finish of the fabric was the same as in example 1.
Example 3
According to the following mixture ratio, the fluorine-containing polymer and the fluorine-free polymer are respectively prepared by adopting a conventional free radical emulsion polymerization process.
The specific preparation method of the water-and oil-repellent agent was the same as in example 1.
The fluorine-containing polymer and the fluorine-free polymer are uniformly mixed according to the mass ratio of 1: 1.
The water and oil repellent finish of the fabric was the same as in example 1.
Example 4
According to the following mixture ratio, the fluorine-containing polymer and the fluorine-free polymer are respectively prepared by adopting a conventional free radical emulsion polymerization process.
The specific preparation method of the water-and oil-repellent agent was the same as in example 1.
The fluorine-containing polymer and the fluorine-free polymer are uniformly mixed according to the mass ratio of 4: 6.
The water and oil repellent finish of the fabric was the same as in example 1.
Comparative example 1 pure fluoropolymer
The pure fluorine-containing polymer is prepared by adopting a conventional free radical emulsion polymerization process according to the following mixture ratio.
The neat fluoropolymer was prepared in the same manner as in example 1.
The water and oil repellent finish of the fabric was the same as in example 1.
Comparative example 2: pure fluorine-free polymer
The pure fluorine-free polymer is prepared by adopting a conventional free radical emulsion polymerization process according to the following mixture ratio.
The pure fluorine-free polymer was prepared in the same manner as in example 1.
The water and oil repellent finish of the fabric was the same as in example 1.
Example 5
The following standard tests were carried out after the fabrics (kasuga, taffe, nylon, all cotton) were respectively finished with the water and oil repellent agents of examples 1 to 4 and comparative examples 1 to 2:
1. water repellency: american standard AATCC-22, corresponding to national standard GB/T4745: 2012;
2. oil repellency: the American standard AATCC-118 corresponds to the national standard GB/T19977: 2014;
3. and (4) water washing standard: the water washing method in American standard AATCC-135 corresponds to national standard GB/T8630-.
The test results are given in the following table:
from the test results it can be seen that: the fabric treated by the water-proof and oil-proof agent has good water-proof and oil-proof effects because the water-proof and oil-proof film uniformly covers the surface of the fabric, and the water-proof and oil-proof film is still firmly attached to the fabric after 5 times of water washing, so that the water-proof and oil-proof performance of the fabric is obviously superior to that of the fabric treated by the fluorine-containing polymer or the pure fluorine-free polymer.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. The durable water-proof and oil-proof agent is characterized by comprising a fluorine-containing polymer and a fluorine-free polymer in a mass ratio of 0.1: 9.9-9.9: 0.1.
2. the durable water-and oil-repellent agent according to claim 1, wherein the fluorine-containing polymer is a polymer produced by emulsion polymerization of a fluorine-containing acrylate monomer as a main component, an emulsifier, a solvent, a chain transfer agent and an initiator.
3. The durable water-and oil-repellent agent according to claim 1, wherein the fluorine-free polymer is a polymer produced by emulsion polymerization using a fluorine-free acrylic ester as a main component and an emulsifier, a solvent, a chain transfer agent and an initiator.
4. The durable water-and oil-repellent agent according to claim 1, wherein the mass ratio of the fluorine-containing polymer to the fluorine-free polymer is 3: 7 to 7:3
5. A process for preparing a durable water-and oil-repellent agent according to any one of claims 1 to 4, which comprises the steps of:
(1) respectively preparing fluorine-containing polymer and fluorine-free polymer by adopting a polymerization process;
(2) the mass ratio of the components is 0.1: 9.9-9.9: 0.1, mixing the fluorine-containing polymer and the fluorine-free polymer uniformly.
6. The method according to claim 5, wherein the polymerization process of the fluorine-containing polymer and the fluorine-free polymer is specifically:
(1) stirring and preserving heat of the ingredients except the initiator for 30 minutes at 60 ℃, shearing at high speed for 5 minutes, and homogenizing;
(2) pouring the feed liquid into a reaction bottle, and introducing nitrogen N2When the temperature is reduced to 55 ℃, the nitrogen is turned off;
(3) diluting the initiator by 10 times of water, and dropwise adding the initiator when the temperature in the reaction flask rises to 62 ℃;
(4) and (3) starting heating reaction after the initiator is dripped for 15 minutes, starting falling after the temperature rises to 68-69 ℃, keeping the temperature to 62-65 ℃ after finishing dripping the initiator for 20 minutes, continuing the reaction for 5 hours, adding the defoaming agent, starting cooling, cooling to below 35 ℃, filtering and discharging.
7. The water-proof and oil-proof finishing method of the fabric is characterized by comprising the following steps:
(1) diluting the durable water-proof and oil-proof agent of any one of claims 1 to 4, and adding a cross-linking agent to prepare a working solution;
(2) padding the fabric by using the working solution in the step (1);
(3) and (5) drying.
8. The water and oil repellent finishing process according to claim 7, characterized in that the durable water and oil repellent agent in the step (1) is diluted with water at a concentration of 5%.
9. The method according to claim 7, characterized in that the crosslinking agent in step (1) is blocked isocyanate dispersion or polycarbodiimide crosslinking agent, and the addition amount of the crosslinking agent is 1%.
10. The method according to claim 7, characterized in that the step (3) is carried out by baking at 180 ℃ for 120 seconds.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102159605A (en) * | 2008-09-15 | 2011-08-17 | 大金工业株式会社 | Aqueous polymer dispersion composition and surface treatment agent |
| CN103628317A (en) * | 2013-12-02 | 2014-03-12 | 广东德美精细化工股份有限公司 | Water-proof and oil-proof agent composition and preparation method thereof as well as textile |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102159605A (en) * | 2008-09-15 | 2011-08-17 | 大金工业株式会社 | Aqueous polymer dispersion composition and surface treatment agent |
| CN103628317A (en) * | 2013-12-02 | 2014-03-12 | 广东德美精细化工股份有限公司 | Water-proof and oil-proof agent composition and preparation method thereof as well as textile |
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