CN115029928A - Water-repellent and oil-repellent agent composition and preparation method and application thereof - Google Patents

Water-repellent and oil-repellent agent composition and preparation method and application thereof Download PDF

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CN115029928A
CN115029928A CN202210733452.5A CN202210733452A CN115029928A CN 115029928 A CN115029928 A CN 115029928A CN 202210733452 A CN202210733452 A CN 202210733452A CN 115029928 A CN115029928 A CN 115029928A
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water
oil
repellent
surfactant
agent composition
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涂伟文
江斌
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Fuke New Materials Shanghai Co ltd
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    • 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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    • D06M2101/16—Synthetic fibres, other than mineral fibres
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Abstract

The invention relates to a water and oil repellent agent composition, a preparation method and application thereof, wherein the water and oil repellent agent composition comprises a copolymer with perfluoroalkyl, a surfactant and an aqueous medium; the copolymer with perfluoroalkyl is copolymerized by the following monomers: perfluorohexyl ethyl acrylate, perfluorohexyl ethyl methacrylate, long-chain alkyl acrylate or long-chain alkyl methacrylate with 18-30 carbon atoms, halogenated olefin and acrylate or methacrylate with blocked isocyanate groups. The water-repellent oil-repellent agent composition provided by the invention has improved water-repellent, oil-repellent and washing durability even under the condition of not additionally using a cross-linking agent, and is particularly suitable for water-repellent and oil-repellent processing of natural fiber products and natural/synthetic fiber blended products.

Description

Water-repellent and oil-repellent agent composition and preparation method and application thereof
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a water-repellent and oil-repellent agent composition, and a preparation method and application thereof.
Background
Currently, as a water-and oil-repellent agent composition for imparting water-and oil-repellent properties to a fiber product, it generally comprises: a. acrylate copolymer containing perfluoroalkyl, b. surfactant, c. aqueous medium, etc., wherein the water-repellent and oil-repellent properties are provided by the acrylate copolymer containing perfluoroalkyl.
Chinese patent CN107709505B discloses a fluorine-containing copolymer comprising perfluorohexylethyl methacrylate (C6SFMA, the same applies below), an alkyl (meth) acrylate having 20 or more carbon atoms and a monomer having a structure represented by formula (C) 2 H 4 O) and (or) (C) 4 H 8 O) group, halogenated olefin, crosslinking monomer, etc. in a specific ratio, and can impart durable water repellency to a synthetic fiber product, but the oil repellency is insufficient.
Chinese invention patent CN108017745B discloses a fluorine-containing polymer, which is prepared by copolymerizing perfluorohexylethyl acrylate, perfluorohexylethyl chloroacrylate and other non-fluorine monomers, and a water-and-oil repellent agent composition containing the polymer can endow synthetic fiber products with good water repellency, alcohol repellency, oil repellency and washing durability, but has no application of natural fibers or natural/synthetic blended fiber products.
Therefore, the water-and-oil repellent agent compositions of the prior art mainly provide water-and-oil repellent properties to synthetic fiber products, and it is difficult to satisfy the requirements for water-and-oil repellent properties, particularly the requirements for high durability, during practical use of natural fiber products or natural/synthetic blend fiber products.
Disclosure of Invention
The invention aims to provide a water-repellent and oil-repellent agent composition, a preparation method and application thereof, wherein the composition has improved water-repellent, oil-repellent and washing durability even under the condition of not additionally using a cross-linking agent, and is particularly suitable for water-repellent and oil-repellent processing of natural fiber products and natural/synthetic fiber blended products.
The invention provides a water and oil repellent agent composition, which comprises a copolymer with perfluoroalkyl, a surfactant and an aqueous medium; the copolymer with perfluoroalkyl is copolymerized by the following monomers: perfluorohexyl ethyl acrylate, perfluorohexyl ethyl methacrylate, long-chain alkyl acrylate or long-chain alkyl methacrylate with 18-30 carbon atoms, halogenated olefin and acrylate or methacrylate with blocked isocyanate groups.
The monomer is calculated by the weight portion,
Figure BDA0003714745560000011
Figure BDA0003714745560000021
the long-chain alkyl acrylate or the long-chain alkyl methacrylate with the carbon number of 18-30 is at least one of stearyl acrylate, stearyl methacrylate, behenyl acrylate and behenyl methacrylate, and the carbon number is preferably 18-22.
The halogenated olefin is at least one of chloroethylene and polyvinyl chloride.
The (meth) acrylate having a blocked isocyanate group is preferably Karenz MOI-BM (CAS No.: 78279-10-4), Karen's MOI-BP (CAS No.: 217437-44-0) produced by Showa Denko K.K., and Karen's MOI-BP is particularly preferred.
The surfactant is at least one of cationic surfactant, nonionic surfactant and amphoteric surfactant.
The cationic surfactant is at least one of an amine salt cationic surfactant, a quaternary ammonium salt cationic surfactant and an ethylene oxide addition type ammonium salt cationic surfactant. Specific examples of the cationic surfactant are not particularly limited, and include: and quaternary ammonium salt surfactants such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride.
Specific examples of the cationic surfactant include: dodecyl trimethyl ammonium acetate, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, (dodecyl methylbenzyl) trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, dodecyl methyl di (hydrogenated polyoxyethylene) ammonium chloride, dodecyl benzyl di (hydrogenated polyoxyethylene) ammonium chloride, N- [2- (diethylamino) ethyl ] oleamide hydrochloride.
The nonionic surfactant is a nonionic surfactant having an oxyalkylene group. The number of carbon atoms of the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is preferably 2 to 100 in general.
The nonionic surfactant may be an epoxide adduct of a linear and/or branched aliphatic (saturated and/or unsaturated) group, a polyalkylene glycol ester of a linear and/or branched fatty acid (saturated and/or unsaturated), a Polyoxyethylene (POE)/polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an epoxide adduct of acetylene glycol, or the like. Among them, the structure of the epoxide addition moiety and the polyalkylene glycol moiety is preferably Polyoxyethylene (POE), polyoxypropylene (POP) or POE/POP copolymer (which may be a random copolymer or a block copolymer).
In addition, from the environmental point of view (biodegradability, environmental hormone, etc.), the nonionic surfactant preferably has a structure containing no aromatic group.
The amphoteric surfactant is at least one of alanine amphoteric surfactant, imidazoline betaine amphoteric surfactant, amide betaine amphoteric surfactant and acetate betaine amphoteric surfactant. Specifically, there may be mentioned: lauryl betaine, stearyl betaine, lauryl carboxylmethyl hydroxyethyl imidazoline betaine, lauryl dimethyl amino acetic acid betaine, fatty acid amide propyl dimethyl amino acetic acid betaine, etc.
The cationic surfactant, the nonionic surfactant and the amphoteric surfactant may be 1 kind or a combination of 2 or more, respectively.
The surfactant is preferably a cationic surfactant and/or a nonionic surfactant, more preferably a combination of a cationic surfactant and a nonionic surfactant, and the ratio of the cationic surfactant to the nonionic surfactant is not particularly limited.
The amount of the surfactant may be 0.1 to 30 parts by weight, for example, 1 to 20 parts by weight, relative to 100 parts by weight of the copolymer having a perfluoroalkyl group (or the total of monomers).
The aqueous medium is a mixture of water and a water-soluble organic solvent; the water-soluble organic solvent is contained in an amount of 30% by weight or less, for example, 10% by weight or less (preferably 0.1% by weight or more).
The water-soluble organic solvent is at least one of acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol and ethanol. Dipropylene glycol and tripropylene glycol are preferred.
The amount of the aqueous medium may be 30 to 99.5 wt%, particularly 50 to 99 wt%, based on the water-and oil-repellent composition.
The invention also provides a preparation method of the water and oil repellent agent composition, which is emulsion polymerization and comprises the following steps:
in the presence of a surfactant, emulsifying a monomer in water, feeding the monomer into a reactor, replacing the monomer with nitrogen, adding a polymerization initiator, and stirring and polymerizing for 0.5-24 hours at the temperature of 40-80 ℃ to obtain the polymer.
The polymerization initiator is preferably a water solvent polymerization initiator, and examples thereof include benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, acetyl peroxide, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobisdiisopropylimidazoline, sodium peroxide, potassium persulfate, and ammonium persulfate, and particularly preferably azobisisobutylimidazoline hydrochloride. The amount of the polymerization initiator is 0.01 to 10 parts by weight, preferably 0.02 to 3 parts by weight, based on 100 parts by weight of the monomer.
In the polymerization, a chain transfer agent may be used. The molecular weight of the polymer may be varied depending on the amount of the chain transfer agent used. The chain transfer agent can be exemplified by: mercapto group-containing compounds such as lauryl mercaptan, thioglycol and thioglycerol, and inorganic salts such as sodium hypophosphite and sodium bisulfite, and lauryl mercaptan is preferred. The chain transfer agent may be used in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the total amount of the monomers.
In order to produce a water-and oil-repellent composition having excellent storage stability, it is preferable to use an emulsifying apparatus capable of imparting strong pulverization energy such as a high-pressure homogenizer or an ultrasonic cell disruptor to atomize and polymerize a monomer in water.
The invention also provides application of the water and oil repellent agent composition in preparation of natural fiber products or natural/synthetic fiber blended products.
The method comprises the following specific steps: first, the water-and oil-repellent agent composition and water are uniformly mixed to obtain a treatment liquid. The treatment liquid is then applied to the fibrous product by dipping, spraying or coating. Finally, the fiber product with the treatment liquid attached is dried and cured by heating, the heating temperature may be, for example, 100 to 200 ℃, and the heating time may be, for example, 5 seconds to 30 minutes, for example, 30 seconds to 3 minutes.
Advantageous effects
The water-repellent oil-repellent agent composition provided by the invention has improved water-repellent, oil-repellent and washing durability even under the condition of not additionally using a cross-linking agent, and is particularly suitable for water-repellent and oil-repellent processing of natural fiber products and natural/synthetic fiber blended products.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
The test method comprises the following steps:
(ii) Water repellency
Spray water repellency test was performed according to AATCC 22-2017. The spray water repellency test rating is represented by water repellency No. 2.
A glass funnel having a volume of at least 250mL and a nozzle capable of spraying 250mL of water for 25 to 30 seconds were used. The test piece frame is a metal frame with a diameter of 152.4 mm. 3 test pieces of about 20cm by 20cm in size were prepared and the sheet was secured to the test piece holder frame so that the sheet was free of wrinkles. The center of the spray was placed in the center of the sheet. The test sheet was sprayed with water at 27+ (-)1 ℃ and 250mL in a glass funnel for 25-30 seconds. The holding frame is removed from the table, and one end of the holding frame is grasped with the front surface being the lower side, and a hard object is struck. The same procedure was repeated by rotating the holding frame by 180 degrees, so that an excessive amount of water drops were dropped. Wet test sheets were scored from poor to excellent water repellency on a scale of 0, 50, 70, 80, 90, and 100 as compared to a wet comparison standard. Results were obtained by averaging the results of 3 tests.
State of water repellency
No.
100 surface of the substrate is not wetted or water drops are not attached
90 surface was not wetted, but showed a state of small water droplets adhering thereto
80 surface shows a state of small individual droplet-like wetting
70 show wetting of half of the surface, showing a small condition of individually wetting the saturated cloth
50 the entire surface showed a wet state
0 surface and rear surface showing a wet state as a whole
② oil repellency
The oil repellency test was performed according to AATCC 118-2019. The oil repellency test rating is represented by oil repellency No. 1.
The treated cloth was stored for more than 4 hours in a constant temperature and humidity cabinet with a temperature of 21+ (-)1 ℃ and a humidity of 65+ (-) 2%. The test was carried out in a constant temperature and humidity cabinet with a temperature of 21+ (-)1 ℃ and a humidity of 65+ (-) 2%. After 0.05mL of the test solution was slowly dropped onto the test cloth and left for 30+ (-)2 seconds, the test solution was regarded as acceptable if the drop remained on the test cloth. The oil repellency was set to the highest level of the test liquid that passed, and nine levels of 0, 1, 2, 3, 4, 5, 6, 7, and 8 were evaluated from a test liquid with poor oil repellency to a good level.
Oil repellency test liquid
Figure BDA0003714745560000051
(iii) durability in washing
The test cloth is repeatedly washed for 5, 10 and 20 times according to the water washing method of AATCC 135-once 2018, the test cloth is dried in a roller or laid flat for airing, and the water repellency and the oil repellency after drying are evaluated (respectively marked as HL5, HL10 and HL 20). HL0 refers to evaluation without washing.
[ method for measuring average molecular weight of copolymer ]
The average molecular weight of the copolymer separated by the following separation method was measured.
Method for separating copolymer
10g of the water-and oil-repellent composition was dropped into 100g of isopropyl alcohol, and stirred to precipitate a solid. The resulting solid was separated by centrifugation at 3000rpm for 5 minutes. 20g of isopropyl alcohol was again added dropwise thereto, followed by sufficient stirring. Centrifuging at the rotating speed of 3000rpm for 5 minutes, separating the obtained solid from the supernatant, and drying in vacuum at the temperature of 30-40 ℃ for 24 hours to obtain the copolymer.
Method for measuring average molecular weight
The extracted copolymer was dissolved in a mixed solvent of a fluorine-based solvent (AK-225 manufactured by AGC corporation)/tetrahydrofuran (6/4 by volume) to prepare a solution having a solid content concentration of 0.5 mass%, and the solution was passed through a 0.2um filter to prepare an analysis sample. For this sample, the data molecular weight (Mn) and mass average molecular weight (Mw) were determined. The measurement conditions are as follows.
Measurement conditions
The device comprises the following steps: HLC-8220GPC, manufactured by Tosoh corporation
Column: column of MIXED-C and 100A in series, manufactured by Polymer laboratories Inc
Measuring temperature: 37 deg.C
Injection amount: 50uL
Outflow speed: 1mL/min
Standard sample: EasiCal PS-2, a Polymer laboratory product
Eluent: fluorine-based solvent (AK-225/tetrahydrofuran, manufactured by AGC corporation) 6/4 (volume ratio)
[ method for measuring the concentration of solid component ]
Concentration of solid component
The solid content concentration of the water-and oil-repellent agent composition was calculated from the mass of the water-and oil-repellent agent composition before heating and the mass after 4 hours drying in a 120 ℃ convection type forced air drying oven, i.e., the ratio of the mass after 4 hours drying in a 120 ℃ convection type forced air drying oven to the mass before heating.
[ omission of symbols ]
Monomer
C6 SFA: perfluorohexyl ethyl acrylate
C6 SFMA: perfluorohexylethyl methacrylate
C6 SFClA: perfluorohexyl ethyl chloroacrylate
StA: stearyl acrylate
BeA: behenyl acrylate
VCM: vinyl chloride
VdCl: vinylidene chloride
MOI-BP: karenz MOI-BP (blocked isocyanate monomer, available from Showa Denko K.K.)
N-MAN: n-methylolacrylamide
Surface active agent
TMAC: stearyl trimethyl ammonium chloride, 70% of effective component
PEO-20: polyoxyethylene oleyl ether (adduct of about 26mol of ethylene oxide)
PEO-T: isotridecyl polyoxyethylene ether
P204: ethylene oxide propylene oxide Polymer (containing 40% by mass of ethylene oxide)
Aqueous medium
DPG: dipropylene glycol
Water: deionized water
Additive agent
AX-101H: blocked polyisocyanate dispersions, manufactured by Fuxisan materials (Shanghai) Co., Ltd
Molecular weight regulator:
L-SH: n-dodecyl mercaptan
Polymerization initiator:
VA-044: azobisisobutyrimidazoline hydrochloride
[ production example ]
Production example 1
20g of C6SFA, 40g C6SFMA, 19g of BeA, and 4g of MOI-BP as monomers, 4.5g of TMAC as a surfactant, 1.85g of PEO-20, 1.52g of PEO-T, and 0.48g of P204 as a surfactant, and 27g of DPG as an aqueous medium and 190g of water were placed in a glass container, and heated at 60 ℃ for 1 hour to obtain a pre-emulsion using a high-speed cutter. And (3) processing the obtained pre-emulsion at 50 ℃ by a high-pressure homogenizer under the conditions of homogenization pressure of 30MPa and 3pass to obtain the emulsion. The obtained emulsion was placed in a high-pressure reactor made of stainless steel, the temperature was lowered to 20 ℃, the gas phase was subjected to nitrogen substitution, 0.04g L-SH as a molecular weight modifier and 17g VCM as a monomer were sequentially added thereto, and after stirring for 30 minutes, 0.5gVA-044 as a polymerization initiator was further added thereto, and polymerization was carried out at 60 ℃ for 4 hours to obtain an emulsion of a copolymer (A1).
The composition (parts by weight) and solid content concentration (% by mass) of the obtained emulsion are shown in the table. The proportion of each monomer unit in the copolymer (100 parts by weight) is calculated based on the monomer addition amount at the time of copolymer production. The copolymer in the emulsion was extracted by the above-mentioned method, and the average molecular weight was measured, and the results are shown in the table.
Production examples 2 to 9 and comparative production examples 1 to 3
The same was prepared by the method of reference production example 1. The composition (parts by weight), solid content concentration (% by mass), and average molecular weight test results of the obtained emulsion are shown in the table in the same manner as in production example 1.
Example 1
To the copolymer emulsion obtained in production example 1, water was added so that the solid content concentration became 30% by weight, to obtain a water/oil repellent composition.
The copolymer emulsion and the additive were mixed in the amounts (g/L) shown in the examples, and diluted with tap water to obtain a water-and oil-repellent treatment liquid.
The test cloth was immersed in the water-and oil-repellent agent treatment liquid, passed through a resin padding machine with a roll pressure of 0.5MPa and a speed of 5m/min, and then heated at 170 ℃ for 2 minutes to be dried and cured, to obtain the test cloth.
Examples 2 to 11 and comparative examples 1 to 3
The fiber product was subjected to water-and oil-repellent treatment in accordance with the method of reference example 1 to obtain a test cloth.
Figure BDA0003714745560000081
Figure BDA0003714745560000091
Among them, comparative production example 4 added an excessive amount of MOI-BP, and the copolymer was not polymerized, so that the solid content concentration and the molecular weight could not be detected.
Figure BDA0003714745560000092
Figure BDA0003714745560000101

Claims (10)

1. A water-and oil-repellent agent composition comprising a copolymer having a perfluoroalkyl group, a surfactant and an aqueous medium; the method is characterized in that: the copolymer with perfluoroalkyl is copolymerized by the following monomers: perfluorohexyl ethyl acrylate, perfluorohexyl ethyl methacrylate, long-chain alkyl acrylate or long-chain alkyl methacrylate with 18-30 carbon atoms, halogenated olefin and acrylate or methacrylate with blocked isocyanate groups.
2. The water and oil repellent composition according to claim 1, characterized in that: the monomer is calculated by the weight portion,
Figure FDA0003714745550000011
3. the water-and oil-repellent agent composition according to claim 1 or 2, characterized in that: the long-chain alkyl acrylate or the long-chain alkyl methacrylate with the carbon number of 18-30 is at least one of stearyl acrylate, stearyl methacrylate, behenyl acrylate and behenyl methacrylate.
4. The water-and oil-repellent agent composition according to claim 1 or 2, characterized in that: the halogenated olefin is at least one of chloroethylene and polyvinyl chloride.
5. The water-and oil-repellent agent composition according to claim 1, characterized in that: the surfactant is at least one of cationic surfactant, nonionic surfactant and amphoteric surfactant.
6. The water-and oil-repellent agent composition according to claim 5, characterized in that: the cationic surfactant is at least one of an amine salt cationic surfactant, a quaternary ammonium salt cationic surfactant and an ethylene oxide addition type ammonium salt cationic surfactant; the nonionic surfactant is a nonionic surfactant having an oxyalkylene group; the amphoteric surfactant is at least one of alanine amphoteric surfactant, imidazoline betaine amphoteric surfactant, amide betaine amphoteric surfactant and acetate betaine amphoteric surfactant.
7. The water and oil repellent composition according to claim 1, characterized in that: the aqueous medium is a mixture of water and a water-soluble organic solvent; wherein the weight percentage of the water-soluble organic solvent is less than 30 percent.
8. The water and oil repellent composition according to claim 7, characterized in that: the water-soluble organic solvent is at least one of acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol and ethanol.
9. A method for producing the water-and oil-repellent agent composition according to claim 1, comprising the steps of:
in the presence of a surfactant, emulsifying a monomer in water, feeding the monomer into a reactor, replacing the monomer with nitrogen, adding a polymerization initiator, and stirring and polymerizing for 0.5-24 hours at the temperature of 40-80 ℃ to obtain the polymer.
10. Use of the water-and oil-repellent agent composition according to claim 1 for producing a natural fiber product or a natural/synthetic fiber blended product.
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