A water and oil repellent finishing agent and a method for preparing the same

Abstract

The application discloses a water and oil repellent finishing agent and a preparation method thereof, and belongs to the technical field of textile auxiliaries. The water and oil repellent finishing agent comprises the following components in parts by weight: blocked isocyanate acrylate 0.1-3 parts, alkyl acrylate 5-20 parts, perfluoroalkyl ethyl acrylate 5-20 parts, thiol molecular weight regulator 0.01-0.5 parts, water-soluble azo initiator 0.01-1 part, anionic / non-ionic composite surfactant 0.5-5 parts, cosolvent 5-15 parts and deionized water 40-70 parts. The blocked isocyanate acrylate, the alkyl acrylate, the perfluoroalkyl ethyl acrylate, the thiol molecular weight regulator, the anionic / non-ionic composite surfactant and the cosolvent are added into a reaction kettle, and the deionized water is dropped into the reaction kettle to prepare a pre-emulsion; the pre-emulsion is heated in nitrogen, and then a water-soluble azo initiator solution is added; after reaction, the water and oil repellent finishing agent is obtained by cooling. The water and oil repellent finishing agent prepared by the application has excellent durability, and the textile fabric finished by the water and oil repellent finishing agent still has excellent water and oil repellency after multiple washing.

Description

Technical Field

[0001] This invention relates to the field of textile auxiliaries technology, specifically to a water- and oil-repellent finishing agent and its preparation method. Background Technology

[0002] As textile substrates demand increasingly higher water and oil repellency, current water and oil repellent finishing agents for textiles contain perfluoroalkyl ethyl compounds with 8 or more carbon atoms. However, these compounds may generate perfluorooctanoic acid (PFOA) through decomposition and metabolism. PFOA is difficult to decompose, easily leads to bioaccumulation, and is environmentally unfriendly. In recent years, research on short-chain perfluoroalkyl ethyl compounds has come into focus, but the water and oil repellency of finishing agents polymerized from these compounds is not ideal. To address these issues, this invention provides a water and oil repellent finishing agent randomly copolymerized from short-chain perfluoroalkyl ethyl compounds and its preparation method. Summary of the Invention

[0003] The purpose of this invention is to provide a water- and oil-repellent finishing agent and its preparation method. The water- and oil-repellent finishing agent is obtained by polymerization of short-chain perfluoroalkyl ethyl acrylate. Textiles treated with this water- and oil-repellent finishing agent have excellent durability and retain excellent water- and oil-repellent properties even after multiple washes.

[0004] To achieve the above objectives, the present invention provides a water- and oil-repellent finishing agent, comprising the following components by weight: 0.1-3 parts of capped isocyanate acrylate, 5-20 parts of alkyl acrylate, 5-20 parts of perfluoroalkyl ethyl acrylate, 0.01-0.5 parts of thiol molecular weight regulator, 0.01-1 parts of water-soluble azo initiator, 0.5-5 parts of cationic / non-azo composite surfactant, 5-15 parts of cosolvent, and 40-70 parts of deionized water.

[0005] Preferably, the capped isocyanate acrylate is one of 2-[(3,5-dimethyl-1-H-pyrazolyl)carboxamino]ethyl methacrylate, 2-[(3,5-dimethyl-1-H-pyrazolyl)carboxamino]ethyl acrylate, 2-[(O-(1-methylpropylimino)carboxamino]ethyl methacrylate, and 2-[(O-(1-methylpropylimino)carboxamino]ethyl acrylate], with specific structures shown in Formulas 1-4:

[0006] .

[0007] Preferably, the alkyl acrylate has 12 to 22 alkyl carbon atoms.

[0008] Preferably, the number of perfluoroalkyl carbon atoms in the perfluoroalkyl ethyl acrylate is 4 to 6.

[0009] Preferably, the thiol molecular weight regulator is one of RS-OH, wherein R is a straight-chain alkyl group with 8 to 20 carbon atoms.

[0010] Preferably, the water-soluble azo initiator is azobisisobutyramidine hydrochloride.

[0011] Preferably, in the cationic / nonionic composite surfactant, the mass ratio of cationic emulsifier to nonionic emulsifier is 1:1 to 5:1; wherein the cationic emulsifier is a quaternary ammonium salt cationic emulsifier, and the nonionic emulsifier is one of fatty alcohol polyoxyethylene ether and fatty acid polyoxyethylene ester.

[0012] Preferably, the co-solvent is one or two of propylene glycol, dipropylene glycol, tripropylene glycol, and propylene glycol methyl ether.

[0013] The preparation method of the above-mentioned water- and oil-repellent finishing agent includes the following steps:

[0014] S1. Add the capped isocyanate acrylate, alkyl acrylate, perfluoroalkyl ethyl acrylate, thiol molecular weight regulator, cationic / non-composite surfactant and cosolvent to the reaction vessel, and add deionized water dropwise under high speed stirring to uniformly disperse into a stable pre-emulsion.

[0015] S2. Place the pre-emulsion under a nitrogen atmosphere and heat it to 70℃~85℃. Then, add an aqueous solution of a water-soluble azo initiator dropwise to the reaction vessel. Under the condition of 70℃~85℃, a random copolymerization reaction occurs. After reacting for 2~6 hours, cool it to room temperature to obtain a water- and oil-repellent finishing agent.

[0016] Therefore, this invention employs the aforementioned water- and oil-repellent finishing agent and its preparation method. By introducing end-capped isocyanate acrylate, emulsion polymerization can be carried out in an aqueous environment. When the water- and oil-repellent finishing agent prepared by this invention is used to finish textiles, the end-capped isocyanate acrylate will be decapped after high-temperature baking, decomposing into end-capping agent and -NCO groups. The -NCO groups then react with the textiles to form covalent bonds, playing a certain positioning role, so that the branches of the polymer polymer are arranged in an orderly manner on the surface of the fabric fibers and are not easy to collapse. This gives the finished textiles excellent water- and oil-repellent properties. Moreover, the decapped -NCO groups react with the fabric to form covalent bonds, thereby making the water- and oil-repellent finishing agent firmly bonded to the textiles. The textiles have excellent durability and still have excellent water- and oil-repellent properties after multiple washes.

[0017] The technical solution of the present invention will be further described in detail below through embodiments. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not constitute a limitation thereof.

[0019] This invention provides a water- and oil-repellent finishing agent, comprising the following components by weight: 0.1-3 parts of capped isocyanate acrylate, 5-20 parts of alkyl acrylate, 5-20 parts of perfluoroalkyl ethyl acrylate, 0.01-0.5 parts of thiol molecular weight regulator, 0.01-1 parts of water-soluble azo initiator, 0.5-5 parts of cationic / non-azo composite surfactant, 5-15 parts of cosolvent, and 40-70 parts of deionized water.

[0020] The capped isocyanate acrylate is one of 2-[(3,5-dimethyl-1-H-pyrazolyl)carboxamino]ethyl methacrylate, 2-[(3,5-dimethyl-1-H-pyrazolyl)carboxamino]ethyl acrylate, 2-[(O-(1-methylpropylimino)carboxamino]ethyl methacrylate, and 2-[(O-(1-methylpropylimino)carboxamino]ethyl acrylate]; the alkyl acrylate has 12-22 alkyl carbon atoms; the perfluoroalkyl ethyl acrylate has [number of perfluoroalkyl carbon atoms missing]. 4~6; the thiol molecular weight regulator is one of RS-OH, where R is a straight-chain alkyl group with 8~20 carbon atoms; the water-soluble azo initiator is azobisisobutyramidine hydrochloride; in the cationic / nonionic composite surfactant, the mass ratio of cationic emulsifier to nonionic emulsifier is 1:1-5:1; the cationic emulsifier is a quaternary ammonium salt cationic emulsifier, and the nonionic emulsifier is one of fatty alcohol polyoxyethylene ether and fatty acid polyoxyethylene ester; the cosolvent is one or two of propylene glycol, dipropylene glycol, tripropylene glycol, and propylene glycol methyl ether.

[0021] The preparation method of the above-mentioned water- and oil-repellent finishing agent includes the following steps:

[0022] S1. Add the capped isocyanate acrylate, alkyl acrylate, perfluoroalkyl ethyl acrylate, thiol molecular weight regulator, cationic / non-composite surfactant and cosolvent to the reaction vessel, and add deionized water dropwise under high speed stirring to uniformly disperse into a stable pre-emulsion.

[0023] S2. Place the pre-emulsion under a nitrogen atmosphere and heat it to 70℃~85℃. Then, add an aqueous solution of a water-soluble azo initiator dropwise to the reaction vessel. Under the condition of 70℃~85℃, a random copolymerization reaction occurs. After reacting for 2~6 hours, cool it to room temperature to obtain a water- and oil-repellent finishing agent.

[0024] Example 1

[0025] (1) Add 5g of 2-[(3,5-dimethyl-1-H-pyrazolyl)carboxyamino]ethyl acrylate, 120g of octadecyl acrylate, 80g of perfluorohexyl ethyl acrylate, 0.5g of n-dodecyl mercaptan, 10g of octadecyltrimethylammonium chloride, 5g of fatty alcohol polyoxyethylene ether and 100g of tripropylene glycol to the reaction vessel, and add 659.5g of deionized water dropwise under high speed stirring to uniformly disperse into a stable pre-emulsion.

[0026] (2) The pre-emulsion was placed under the protection of nitrogen atmosphere and heated to 80°C. Then, 20g of 5% azobisisobutyramidine hydrochloride aqueous solution was added dropwise to the reaction vessel. Random copolymerization was carried out at 80°C. After 4 hours of reaction, the temperature was lowered to room temperature to obtain a water- and oil-repellent finishing agent.

[0027] Example 2

[0028] (1) Add 10g of 2-[(3,5-dimethyl-1-H-pyrazolyl)carboxyamino]ethyl acrylate, 120g of octadecyl acrylate, 80g of perfluorohexyl ethyl acrylate, 0.5g of n-dodecyl mercaptan, 10g of octadecyltrimethylammonium chloride, 5g of fatty alcohol polyoxyethylene ether and 100g of tripropylene glycol to the reaction vessel, and add 654.5g of deionized water dropwise under high speed stirring to uniformly disperse into a stable pre-emulsion.

[0029] (2) The pre-emulsion was placed under the protection of nitrogen atmosphere and heated to 80°C. Then, 20g of 5% azobisisobutyramidine hydrochloride aqueous solution was added dropwise to the reaction vessel. Random copolymerization was carried out at 80°C. After 4 hours of reaction, the temperature was lowered to room temperature to obtain a water- and oil-repellent finishing agent.

[0030] Example 3

[0031] (1) Add 5g of 2-[(O-(1-methylpropylimino)carboxyamino]ethyl acrylate, 120g of octadecyl acrylate, 80g of perfluorohexyl ethyl acrylate, 0.5g of n-dodecyl mercaptan, 10g of octadecyltrimethylammonium chloride, 5g of fatty alcohol polyoxyethylene ether and 100g of tripropylene glycol to the reaction vessel, and add 659.5g of deionized water dropwise under high speed stirring to uniformly disperse into a stable pre-emulsion.

[0032] (2) The pre-emulsion was placed under the protection of nitrogen atmosphere and heated to 80°C. Then, 20g of 5% azobisisobutyramidine hydrochloride aqueous solution was added dropwise to the reaction vessel. Random copolymerization was carried out at 80°C. After 4 hours of reaction, the temperature was lowered to room temperature to obtain a water- and oil-repellent finishing agent.

[0033] Example 4

[0034] (1) Add 10g of ethyl 2-[(O-(1-methylpropylimino)carboxyamino]acrylate, 120g of octadecyl acrylate, 80g of perfluorohexyl ethyl acrylate, 0.5g of n-dodecyl mercaptan, 10g of octadecyltrimethylammonium chloride, 5g of fatty alcohol polyoxyethylene ether and 100g of tripropylene glycol to the reaction vessel, and add 654.5g of deionized water dropwise under high speed stirring to uniformly disperse into a stable pre-emulsion.

[0035] (2) The pre-emulsion was placed under the protection of nitrogen atmosphere and heated to 80°C. Then, 20g of 5% azobisisobutyramidine hydrochloride aqueous solution was added dropwise to the reaction vessel. Random copolymerization was carried out at 80°C. After 4 hours of reaction, the temperature was lowered to room temperature to obtain a water- and oil-repellent finishing agent.

[0036] Comparative Example 1

[0037] (1) Add 120g of octadecyl acrylate, 80g of perfluorohexyl ethyl acrylate, 0.5g of n-dodecyl mercaptan, 10g of octadecyltrimethylammonium chloride, 5g of fatty alcohol polyoxyethylene ether and 100g of tripropylene glycol to the reaction vessel, and add 664.5g of deionized water dropwise under high speed stirring to uniformly disperse into a stable pre-emulsion.

[0038] (2) The pre-emulsion was placed under the protection of nitrogen atmosphere and heated to 80°C. Then, 20g of 5% azobisisobutyramidine hydrochloride aqueous solution was added dropwise to the reaction vessel. Random copolymerization was carried out at 80°C. After 4 hours of reaction, the temperature was lowered to room temperature to obtain a water- and oil-repellent finishing agent.

[0039] The water and oil repellency and durability of the water and oil repellent finishing agent prepared above were tested under the following conditions:

[0040] Water and oil repellent finishing process: two dips and two nips; Fabric: twill cotton twill; Working solution concentration: 50g / L; Nipple pressure: 2kg / cm 2 Roller speed: 50 r / min; Baking temperature: 170℃; Baking time: 40 s.

[0041] Durability testing process: Water washing process: 40℃ warm water, 15min / time, 1g / L laundry detergent, rinse with clean water, 60℃ dry, water washing ten times.

[0042] Water and oil repellency test standard: AATCC22; Oil repellency test standard: AATCC118

[0043] The results of the water and oil repellency tests are shown in Table 1, and the results of the durability tests are shown in Table 2.

[0044] Table 1

[0045]

[0046] Table 2

[0047]

[0048] As can be seen from the data in Tables 1 and 2, the water-repellent and oil-repellent finishing agent prepared by the present invention incorporates end-capped isocyanate acrylate for polymerization, and the resulting water-repellent and oil-repellent finishing agent has excellent water-repellent and oil-repellent properties as well as excellent durability.

[0049] This invention discloses a water- and oil-repellent finishing agent and its preparation method. It is formed by random copolymerization of short-chain perfluoroalkyl ethyl compounds. By introducing end-capped isocyanate acrylates, emulsion polymerization can be carried out in an aqueous environment. When this water- and oil-repellent finishing agent is used to finish textiles, the end-capped isocyanate acrylates are decapped after high-temperature baking, releasing the end-capping agent and -NCO groups. The -NCO groups then react with the textiles to form covalent bonds, playing a certain positioning role. This ensures that the polymer's branches are arranged orderly on the fabric fiber surface, preventing them from collapsing. This imparts excellent water- and oil-repellent properties to the finished textiles. Furthermore, the decapped -NCO groups react with the fabric to form covalent bonds, thus firmly bonding the water- and oil-repellent finishing agent to the textiles. The textiles exhibit excellent durability, retaining excellent water- and oil-repellent properties even after multiple washes.

[0050] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a water- and oil-repellent finishing agent, characterized in that, The water- and oil-repellent finishing agent comprises, by weight, the following components: 0.1-3 parts of capped isocyanate acrylate, 5-20 parts of alkyl acrylate, 5-20 parts of perfluoroalkyl ethyl acrylate, 0.01-0.5 parts of thiol molecular weight regulator, 0.01-1 parts of water-soluble azo initiator, 0.5-5 parts of cationic / non-cationic composite surfactant, 5-15 parts of cosolvent, and 40-70 parts of deionized water; The terminated isocyanate acrylate is one of 2-[(3,5-dimethyl-1-H-pyrazolyl)carboxamino]ethyl methacrylate, 2-[(3,5-dimethyl-1-H-pyrazolyl)carboxamino]ethyl acrylate, 2-[(O-(1-methylpropylimino)carboxamino]ethyl methacrylate, and 2-[(O-(1-methylpropylimino)carboxamino]ethyl acrylate], with specific structures shown in Formulas 1-4: The perfluoroalkyl group in the perfluoroalkyl ethyl acrylate has 4 to 6 carbon atoms; The alkyl acrylate has 12 to 22 alkyl carbon atoms; The preparation method of the water- and oil-repellent finishing agent includes the following steps: S1. Add the capped isocyanate acrylate, alkyl acrylate, perfluoroalkyl ethyl acrylate, thiol molecular weight regulator, cationic / non-composite surfactant and cosolvent to the reaction vessel, and add deionized water dropwise under high speed stirring to uniformly disperse into a stable pre-emulsion. S2. The pre-emulsion is placed under a nitrogen atmosphere and heated to 70℃~85℃. Then, an aqueous solution of a water-soluble azo initiator is added dropwise to the reaction vessel. Random copolymerization occurs at 70℃~85℃. After reacting for 2~6 hours, the temperature is lowered to room temperature to obtain a water- and oil-repellent finishing agent.

2. The method for preparing a water- and oil-repellent finishing agent according to claim 1, characterized in that: The thiol molecular weight regulator is one of RS-OH, wherein R is a straight-chain alkyl group with 8 to 20 carbon atoms.

3. The method for preparing a water- and oil-repellent finishing agent according to claim 1, characterized in that: The water-soluble azo initiator is azobisisobutyramidine hydrochloride.

4. The method for preparing a water- and oil-repellent finishing agent according to claim 1, characterized in that: In the cationic / nonionic composite surfactant, the mass ratio of cationic emulsifier to nonionic emulsifier is 1:1 to 5:1; wherein the cationic emulsifier is a quaternary ammonium salt cationic emulsifier, and the nonionic emulsifier is one of fatty alcohol polyoxyethylene ether and fatty acid polyoxyethylene ester.

5. The method for preparing a water- and oil-repellent finishing agent according to claim 1, characterized in that: The co-solvent is one or two of propylene glycol, dipropylene glycol, tripropylene glycol, and propylene glycol methyl ether.

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