TWI510607B - Fluorine-containing polymer - Google Patents

Description

Fluoropolymer water repellent

The present invention relates to a water repellent, and more particularly to a water repellent of a fluoropolymer.

Water repellent is widely used in the surface treatment of paints or fabrics to prevent moisture from adhering. The fluorine polymer has the characteristics of water-repellent and oil-repellent agent, and has a high oil-repellent effect compared with the water-repellent agent of the resin-based resin.

U.S. Patent No. US Pat.3,645,990 surface with US Pat.3,859,090 classification using multiprocessing and fluoroalkyl compound (R _f group), change stone, wood, glass, ceramics, fibers, metals, plastics and the like of the substrate can The surface structure is characterized by imparting water and oil.

The Republic of China patents I301152, I302165, I304450, I304837, I325882, and I332046 also mention the use of polyfluoroalkyl R _f crystallinity or modification of other water-removing agents to improve the water-repellent agent. effect. However, the current technology is to explore how to use the combination of monomer and structure to improve the effect of water-repellent and oil-repellent agents, but does not mention the relationship between the amount of water-repellent used and the effect of water-removing, so it is necessary to The nature of the composition of the aqueous agent is evaluated.

In view of this, the main object of the present invention is to provide a fluoropolymer. The water repellent has excellent water repellency on the fabric at low dosage.

In order to achieve the above object, the fluoropolymer water repellent provided by the present invention comprises: (A) a fluorinated copolymer having an average particle diameter of 1 to 1000 nm and a cell potential of 0 to 100 mV; and (B) a cationic emulsifier of 12 to 22 carbon chain length double long carbon chain alkyl groups.

In one embodiment, the fluoropolymer is polymerized from the following monomers (a1), monomers (a2), and monomers (a3): the monomer (a1) is a fluorine-containing monomer, The general formula is R _f -YX

(wherein R _f is a perfluoroalkyl group having 2 to 20 carbon atoms; Y is a divalent organic group or a single bond or a diisocyanate group; X is -CR=CH ₂ , -C(O)OCR= CH ₂ , -OC(O)CR=CH ₂ , -OCH=CH ₂ , -OC ₂ H ₄ -OC(O)CR=CH ₂ or (R is a hydrogen atom, a methyl group or a halogen atom)); the monomer (a2) is a non-fluorinated monomer, which is a linear alkyl (meth) acrylate, a branched alkyl (meth) acrylate, And any one or more of a group consisting of a monocyclic, polycyclic or crosslinked alkyl (meth) acrylate; and the monomer (a3) is a monomer having two or more reactive groups; and the single The monomer (a2) is 1 to 300 parts by weight, and the monomer (a3) is 1 to 50 parts by weight, based on 100 parts by weight of the body (a1).

In one embodiment, the cationic emulsifier is dioctadecyl bismethyl ammonium chloride (Kao-D86P), dipoxyl ammonium chloride (Taiwan-CNA 90), bis-fatty alkyl Ethyl methyl hydroxyethyl methyl sulfate ammonium (REWOQUAT WE-18).

In one embodiment, the fluoropolymer water repellent further comprises an acid and a salt.

In one embodiment, the acid is hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid or citric acid.

The invention relates to the use of different emulsifiers and the addition of different acids, observing the average particle size and potential of the fluoropolymer, and then obtaining a water-repellent agent with a low dosage to achieve a super-water-repellent effect.

The fluorinated copolymer (A) for forming a fluoropolymer water repellent of the present invention comprises the following three components: monomer (a1), monomer (a2) and monomer (a3): monomer (a1) Is a polyfluoroalkyl monomer characterized by R _f -YX (wherein R _f is a perfluoroalkyl group having 2 to 20 carbon atoms; Y is a divalent organic group or a single bond or a diisocyanate group) X; any group of the formula -CR=CH ₂ , -C(O)OCR=CH ₂ , -OC(O)CR=CH ₂ , -OCH=CH ₂ , -OC ₂ H ₄ -OC (O)CR=CH ₂ or (R is a hydrogen atom, a methyl group or a halogen atom))

A preferred embodiment of the monomer (a1) is R _f -C ₂ H ₄ -OC(O)CH=CH ₂ (wherein R _f is a linear perfluoroalkyl group having 4 to 16 carbon atoms)

Increasing the length of the fluorine segment helps to reduce the surface energy of the polymer and improve the crystallinity of the branch, which helps to improve the characteristics of the extremely low-volume fluorine water repellent. In order to maintain the equilibrium of the emulsion stability, the structure R _{f is} particularly preferred. It is 6 to 16 carbon atoms, and it is more preferable that the structure R _f is 8 to 14 carbon atoms.

The monomer (a2) is a non-fluorinated monomer comprising (a2-1) a linear alkyl (meth) acrylate, (a2-2) a branched alkyl (meth) acrylate, and (a2-3) a monocyclic, polycyclic or crosslinked alkyl (meth) acrylate. In the present embodiment, the fluoropolymer is obtained by polymerizing at least two or more kinds of repeating units of the monomer (a2) and the monomer (a1). The following is a description of the monomer (a2), and the composition of the specific examples will be described later.

(a2-1) a linear alkyl (meth) acrylate having a straight chain of a fluorine-free monomer having 2 to 30 carbon atoms, preferably a fluorine-free monomer having 12 to 22 carbon atoms, more preferably Fluorine-free monomer with 14 to 18 carbon atoms.

(a2-2) A branched alkyl (meth) acrylate having a branched chain of a fluorine-free monomer having 4 to 12 carbon atoms. Specifically, it is isooctyl (meth)acrylate and isodecyl (meth)acrylate.

(a2-3) A compound having a monocyclic, polycyclic or crosslinked alkyl group and a polymerization site, and having a fluorine-free monomer having 6 to 20 carbon atoms. For example, isobornyl (meth)acrylate, isobornyl acrylate, t-butylcyclohexyl methacrylate, dicyclopentyl (meth)acrylate, styrene, 1,3 chloromethylstyrene, 1 , 4 chloromethyl styrene and cyclohexyl methacrylate.

The monomer (a3) is a monomer having a reactive group, and the specific examples are as follows: HOC ₂ H ₄ -OC(O)CR=CH ₂ R-(OC ₂ H ₄ ) _m -OC(O)CR =CH ₂ R-(OC ₃ H ₆ ) _m -OC(O)CR=CH ₂ NH ₂ -C(O)CR=CH ₂ HOC ₂ H ₄ -NH-C(O)CR=CH ₂ C ₂ H ₆ NC ₂ H ₄ -OC(O)CR=CH ₂ C ₃ H ₉ N ⁺ (Cl ^- )C ₂ H ₄ -OC(O)CR=CH ₂ ClH ₂ CH(OH)CH ₂ OC(O)CR =CH ₂ (wherein R is a hydrogen atom or a methyl group, and m is an integer of 2 to 50.)

In the fluoropolymer, the amount of the monomer (a2) is from 1 to 300 parts by weight, based on 100 parts by weight of the monomer (a1), and the amount of the monomer (a2) is preferably from 10 to 200 parts by weight, more preferably The amount of the body (a2) is 50 to 120 parts by weight; the relative amount of the monomer (a3) is 1 to 50 parts by weight, and the amount of the monomer (a3) is preferably 10 to 40 parts by weight.

In a general polymerization mode, it is classified into solution polymerization, suspension polymerization, emulsion polymerization, and the like. The fluoropolymer of this example was prepared by emulsion polymerization.

In the emulsion polymerization method, the emulsifier (B) used is one or more APOE-free nonionic emulsifiers, cationic emulsifiers, and zwitterionic emulsifiers.

The nonionic emulsifier used in this embodiment is of the formula: RX-(EO) _n -(PO) _m -H (wherein R is a linear, branched alkyl group having 8 to 30 carbon atoms, and contains an oleic acid group. X is oxygen or nitrogen; n and m are integers from 0 to 50, respectively, and the sum of n and m needs to be greater than 3.)

Examples of the nonionic emulsifier are, for example, polyoxyethylene (03) lauryl ether (Zhongri Chemical SP1203), polyoxyethylene (09) lauryl ether (Zhongri Chemical SP1209), polyoxyethylene (20) lauryl ether (medium Nippon Chemical SP1220), polyoxyethylene (07) stearyl ether (Zhongri Chemical SP1807), polyoxyethylene (30) stearyl ether (Zhongri Chemical SP1830), polyoxyethylene (13) oleate (Zhongri Chemical) SP1213)

The cationic emulsifier used in this embodiment is of the formula: (R' ₄ N ⁺ )‧X ^- (wherein R' may be a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkane having 2 to 30 carbon atoms. The base or the EO segment, the four R's may be the same or different configurations; X is a chlorine atom, an ethyl sulfate ion or an acetate ion.

Examples of the cationic emulsifier are, for example, cetyltrimethylammonium chloride (CTAC), octadecyltrimethylammonium chloride (SMTAC), dioctadecylbismethylammonium chloride (King) -D86P), dicoryl ammonium chloride (Taiwan-CNA90), bis-fatty alkyl ethyl hydroxyethyl methyl ammonium sulfate (REWOQUAT WE-18), and the like.

The zwitterionic emulsifier used in this embodiment comprises an acidic amphoteric surfactant, a polyhydric alcohol amine sulfate, an alkylamine sulfonate surfactant, and a cation. The functional groups are ammonium salts and quaternary ammonium salts, and the anionic functional groups are carboxylates, sulfates and sulfonates.

In this embodiment, in order to control the molecular weight distribution, a chain transfer agent (C) is used, which comprises an aromatic compound, a mercapto alcohol and a mercaptan, and is linear carbon tetrachloride, mercaptoethanol, and α-methylstyrene. Polymer, 2,4-diphenyl-4-methyl-1-pentene, octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, and the like.

In the polymerization reaction in this embodiment, the reactant is divided into an oil phase and an aqueous phase, and the oil phase comprises a monomer (a1), a monomer (a2), a monomer (a3), an emulsifier (B), and a chain transfer agent. (C); the aqueous phase contains water, acid, and solvent.

In this embodiment, in order to trigger the reaction, the reaction is carried out using the initiator (D), which comprises a photoinitiator, an ion initiator and a radical initiator, preferably a radical initiator, and a radical radical. The starting agent comprises a peroxide initiator and an azo initiator, more preferably an azo initiator, and the polymerization temperature is preferably 40 to 100 °C.

The above is a description of the compound involved in the reaction process for preparing a fluoropolymer according to a preferred embodiment of the present invention, and then the particle size, the cell potential and the control potential factor of the fluoropolymer are discussed to obtain a fluorine-containing compound. The polymer is used for the preferred state and lower usage of the water repellent.

In this embodiment, one or more nonionic emulsifiers, cationic emulsifiers and zwitterionic emulsifiers are used in the preparation and polymerization process; before the reaction, the oil phase and the aqueous phase are preheated and dispersed at a high speed, and then uniformly passed through a high pressure homogenizer. After dispersion, a stable uniform pre-emulsion can be obtained, and then the pre-emulsion is subjected to emulsion polymerization in a continuous or batch manner.

In this embodiment, the fluorinated copolymer is dispersed in the emulsion, and has a remarkable effect in order to achieve an extremely low dosage. The particle size of the fluorinated copolymer needs to be controlled, and the preferred average particle diameter is from 1 to 1000 nm, more preferably 1~200nm, the best is 1~100nm. In this particle size range, a good water repellency effect can be achieved without using too much water repellent.

In this embodiment, the fluorinated copolymer is dispersed in the emulsion, and the emulsifier of the double long carbon chain alkyl ester ammonium chloride type has a higher ability to push electrons and reaches a higher potential under the use of different cationic emulsifiers. The coating ability is strong, and the fluorine water repellent microcell has a smaller particle diameter; the higher potential has a larger potential difference between the fibers, and has a better attraction, and the low dosage has the same Effect; pulling the cationic emulsifier separately can only help the particle size reduction, and can not increase the potential; and the too high potential is too strong for the fiber to adsorb, which affects the continuous effect of subsequent processing. In order to achieve a very low dosage, there is a significant effect, and it is necessary to control the potential distribution of the micelles. The preferred potential distribution is 0 to 100 mV, more preferably 10 to 80 mV, and most preferably 40 to 60 mV. In this potential range, a small amount of water-repellent agent is required to achieve a good water-repellent effect.

In this embodiment, in order to control the potential distribution of the micelles dispersed in the emulsion, in addition to the emulsifier, it is also necessary to use an acid (E) and a salt to control an appropriate potential range. The commonly used acids are organic acids and inorganic acids and salts thereof. The class is preferably hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, citric acid, malic acid and salts thereof.

The above is a description of a preferred state and a lower amount of use of the fluoropolymer according to a preferred embodiment of the present invention, and then for the fluoropolymer. This is an introduction to the way of using the water repellent.

The water-repellent agent composed of the fluoropolymer of the invention can be coated on the surface of the fiber of a fabric or a fabric blend, and the processing method can be sprayed, immersed or immersed together with other kinds of auxiliary agents. The coating is a fiber surface, and then heat-treated at 100 to 200 ° C for 30 to 180 seconds to achieve the effect of water drainage.

The above is a method for using a fluoropolymer according to a preferred embodiment of the present invention when it is used as a water repellent, and then a method for measuring and evaluating the fluoropolymer when used as a water repellent is described.

A. Particle size measurement method:

A sample of 1 g of the fluorocopolymer emulsion was weighed, and 199 g of distilled water was added thereto, and the mixture was stirred with a glass rod and then used.

Device: Malvern Instruments Ltd. Zetasizer Nano ZS90

Measurement temperature: 25 ° C (sample is equilibrated at 25 ° C for 1 minute before testing)

Correction: Take 4 drops of Thermo NIST international certified standard sample, 100ml of normal saline solution, mix well, take 1~1.5ml mixture into the Size cell and confirm the Hydrodynamic Diameter needs to be in the range [58~65nm( PCS)].

Test: Take 1.5ml of diluted fluoride copolymer emulsion sample and add it to Size Cell to confirm that there are no bubbles in the side wall and corner of the Cell. Put the sample into ZS90 and start measuring the particle size. Perform five cycles of testing and take the average. value.

B. Potential measurement method:

A sample of 1 g of the fluorocopolymer emulsion was weighed, and 199 g of distilled water was added thereto, and the mixture was stirred with a glass rod and then used.

Device: Malvern Instruments Ltd. Zetasizer Nano ZS90

Measurement temperature: 25 ° C (sample is equilibrated at 25 ° C for 1 minute before testing)

Correction: Wash the Zeta potential cell rinse with alcohol, wash it twice with distilled water, and inject the potential standard into the Cell, confirm that there is no bubble in the Cell, plug the plug, put it into the ZS90 for measurement, potential range Need to be -68 ± 6.8mV.

Test: Take 1.5ml of diluted fluoride copolymer emulsion sample and add it to Zeta potential cell rinse to confirm that there are no bubbles in the side wall and corner of the Cell. Put the sample into ZS90 and start measuring the particle size for five cycles. take the average.

C. Evaluation of water-repellent applications:

The cut fabric is a polyester cloth or nylon fabric of sanding or pongee, and a sample of the fluorine copolymer emulsion is taken, diluted with water to 0.2~2%, and the fabric is wetted by dipping, and then the pressure is 3 kg. After passing through the dyeing machine, it passes through the setting machine at 170 ° C for 60 seconds.

The water repellency of the fabric was examined by AATCC No. 22, as shown in Table 1:

The examples of the fluoropolymer of the present invention are specifically described below, but the present invention is not limited to the examples.

The following are preferred embodiments 1 to 4 of the present invention, and the composition differences of the respective embodiments are shown in bold.

Example 1 (as shown in Table 2)

A glass beaker was charged with 35.6 g of monomer (a1) R _f -C ₂ H ₂ OC(O)CH=CH ₂ (hereinafter referred to as FA), and 62.3 g of monomer (a2-1) octadecyl acrylate ( Hereinafter, SA), 25.7 g of monomer (a2-2) isooctyl methacrylate (hereinafter referred to as EHMA), 6.2 g of monomer (a2-3) isobornyl acrylate (hereinafter referred to as IBOA), 20.2 g of single (a3) N-methylol acrylamide (hereinafter referred to as N-MAM), 7.68 g of emulsifier (B-1) polyoxyethylene (30) stearyl ether (hereinafter referred to as SP1830), 2.12 g of emulsifier (B-2) Polyoxyethylene (7) stearyl ether (hereinafter referred to as SP1807), 7.3 g of emulsifier (B-3) cetyltrimethylammonium chloride (hereinafter referred to as CTAC) , 1.2 g chain The transfer agent t-dodecyl mercaptan (hereinafter referred to as TDM) and 50 g of solvent dipropylene glycol methyl ether (hereinafter referred to as DPM) are oil phase, and stirred uniformly at 40 ° C with a high speed mixer, 5 g of acetic acid (E) and 290 g of deionized The water phase was slowly added to the oil phase in the high-speed stirring. After the addition, the mixture was stirred for 20 minutes, and a uniform and stable pre-emulsion was obtained by homogenizing twice with a high-pressure homogenizer (Donghua, GYB-60-6S) at 40 MPa.

The pre-emulsion was placed in a glass four-necked flask with a stirring device, a thermometer and a condensing reflux device were set up, and after vacuuming for 2 times with nitrogen, nitrogen gas was continuously introduced, and the temperature was raised to 80 ° C, and 1.32 g of the initiator (V-50 was added). The polymerization reaction was initiated and maintained at 80 ° C for 10 hours to form 493 g of a polymer having a solid content of 28.72%.

Example 2 (as shown in Table 2)

A glass beaker was charged with 35.6 g of monomer (a1) FA, 62.3 g of monomer (a2-1) SA, 25.7 g of monomer (a2-2) EHMA, 6.2 g of monomer (a2-3) IBOA, 20.2 g. Monomer (a3) N-MAM, 7.68 g emulsifier (B-1) SP1830, 2.12 g emulsifier (B-2) SP1807, 7.68 g emulsifier (B-3) octadecyltrimethylammonium chloride (hereinafter referred to as STMAC) , 1.2g chain transfer agent TDM and 50g solvent DPM are oil phase, stir evenly at 40 ° C with high speed mixer, 5g acetic acid (E) and 290g deionized water as water phase slowly added to high speed stirring The oil phase was stirred for 20 minutes after the addition, and a uniform and stable pre-emulsion was obtained by homogenizing twice with a high pressure homogenizer at 40 MPa.

The pre-emulsion was placed in a glass four-necked flask with a stirring device, a thermometer and a condensing reflux device were set up, and after vacuuming for 2 times with nitrogen, nitrogen gas was continuously introduced, and the temperature was raised to 80 ° C, and 1.32 g of the initiator (V-50 was added). ) to trigger the polymerization at 80 ° C After maintaining for 10 hours, 486 g of a polymer was formed, and the solid content was 30.2%.

Example 3 (as shown in Table 2)

A glass beaker was charged with 35.6 g of monomer (a1) FA, 62.3 g of monomer (a2-1) SA, 25.7 g of monomer (a2-2) EHMA, 6.2 g of monomer (a2-3) IBOA, 20.2 g. Monomer (a3) N-MAM, 7.68 g emulsifier (B-1) SP1830, 2.12 g emulsifier (B-2) SP1807, 7.3 g emulsifier (B-3) dioctadecyl dimethyl chlorination Ammonium (hereinafter referred to as D86P) , 1.2g chain transfer agent TDM and 50g solvent DPM are oil phase, stir evenly at 40 ° C with high speed mixer, 5g acetic acid (E) and 290g deionized water as water phase slowly added to high speed stirring The oil phase was stirred for 20 minutes after the addition, and homogenized twice at 40 Mpa with a high pressure homogenizer to obtain a uniform and stable pre-emulsion.

The pre-emulsion was placed in a glass four-necked flask with a stirring device, a thermometer and a condensing reflux device were set up, and after vacuuming for 2 times with nitrogen, nitrogen gas was continuously introduced, and the temperature was raised to 80 ° C, and 1.32 g of the initiator (V-50 was added). The polymerization reaction was initiated and maintained at 80 ° C for 10 hours to form 486.8 g of a polymer having a solid content of 29.6%.

Example 4 (as shown in Table 2)

A glass beaker was charged with 35.6 g of monomer (a1) FA, 62.3 g of monomer (a2-1) SA, 25.7 g of monomer (a2-2) EHMA, 6.2 g of monomer (a2-3) IBOA, 20.2 g. Monomer (a3) N-MAM, 7.68 g emulsifier (B-1) SP1830, 2.12 g emulsifier (B-2) SP1807, 7.3 g emulsifier (B-3) double bovine ammonium chloride (below) It is CNA-90) , 1.2g chain transfer agent TDM and 50g solvent DPM are oil phase, stir evenly at 40 °C with high speed mixer, 5g acetic acid (E) and 290g deionized water as water phase slowly added to high speed stirring oil The phase was stirred for 20 minutes after the addition, and a uniform and stable pre-emulsion was obtained by homogenizing twice with a high pressure homogenizer at 40 MPa.

The pre-emulsion was placed in a glass four-necked flask with a stirring device, a thermometer and a condensing reflux device were set up, and after vacuuming for 2 times with nitrogen, nitrogen gas was continuously introduced, and the temperature was raised to 80 ° C, and 1.32 g of the initiator (V-50 was added). In order to trigger the polymerization reaction, it was kept at 80 ° C for 10 hours to form 496.7 g of a polymer, and the solid content was 29.28%.

Example 5 (as shown in Table 2)

A glass beaker was charged with 35.6 g of monomer (a1) FA, 62.3 g of monomer (a2-1) SA, 25.7 g of monomer (a2-2) EHMA, 6.2 g of monomer (a2-3) IBOA, 20.2 g. Monomer (a3) N-MAM, 7.68 g emulsifier (B-1) SP1830, 2.12 g emulsifier (B-2) SP1807, 7.3 g emulsifier (B-3) bis fatty alkyl ethyl ester hydroxyethyl Methyl ammonium methyl sulfate (hereinafter referred to as WE-18) , 1.2 g chain transfer agent TDM and 50 g solvent DPM are oil phase, and stirred uniformly at 40 ° C with a high speed mixer, 5 g of acetic acid (E) and 290 g of deionized water are water. The phase was slowly added to the oil phase in the high-speed stirring. After the addition, the mixture was stirred for 20 minutes, and homogenized twice at 40 Mpa in a high-pressure homogenizer to obtain a uniformly stable pre-emulsion.

The pre-emulsion was placed in a glass four-necked flask with a stirring device, a thermometer and a condensing reflux device were set up, and after vacuuming for 2 times with nitrogen, nitrogen gas was continuously introduced, and the temperature was raised to 80 ° C, and 1.32 g of the initiator (V-50 was added). ) to trigger the polymerization at 80 ° C After maintaining for 10 hours, 497.2 g of a polymer was formed, and the solid content was 29.46%.

The above is the preferred examples 1 to 5 of the present invention, the difference of the composition is that different cationic emulsifiers are added, and then the fluorinated copolymer obtained by polymerizing the respective examples is used to measure the particle diameter and the potential, and the results are shown in the table. 2 is shown.

The following are preferred embodiments 6-8 of the present invention, and the composition differences of the respective embodiments are indicated in bold.

Example 6 (as shown in Table 3)

A glass beaker was charged with 35.6 g of monomer (a1) FA, 62.3 g of monomer (a2-1) SA, 25.7 g of monomer (a2-2) EHMA, 6.2 g of monomer (a2-3) IBOA, 20.2 g. Monomer (a3) N-MAM, 7.68 g emulsifier (B-1) SP1830, 2.12 g emulsifier (B-2) SP1807, 7.3 g emulsifier (B-3) dipoxyl ammonium chloride (CNA- 90), 1.2g chain transfer agent TDM and 50g solvent DPM are oil phase, stirred at 40 ° C with a high speed mixer, 3g citric acid (E) and 292g deionized water for the aqueous phase is slowly added to the oil phase in high speed stirring. After the addition was completed, the mixture was stirred for 20 minutes, and homogenized twice at 40 Mpa with a high pressure homogenizer to obtain a uniformly stable pre-emulsion.

The pre-emulsion was placed in a glass four-necked flask with a stirring device, a thermometer and a condensing reflux device were set up, and after vacuuming for 2 times with nitrogen, nitrogen gas was continuously introduced, and the temperature was raised to 80 ° C, and 1.32 g of the initiator (V-50 was added). The polymerization reaction was initiated and maintained at 80 ° C for 10 hours to form 486.8 g of a polymer having a solid content of 29.6%.

Example 7 (as shown in Table 3)

A glass beaker was charged with 35.6 g of monomer (a1) FA, 62.3 g of monomer (a2-1) SA, 25.7 g of monomer (a2-2) EHMA, 6.2 g of monomer (a2-3) IBOA, 20.2 g. Monomer (a3) N-MAM, 7.68 g emulsifier (B-1) SP1830, 2.12 g emulsifier (B-2) SP1807, 7.3 g emulsifier (B-3) dipoxyl ammonium chloride (CNA- 90), 1.2g chain transfer agent TDM and 50g solvent DPM are oil phase, stir evenly at 40 ° C with high speed mixer, 3g hydrochloric acid (E) and 292g deionized water as water phase slowly added to the oil phase in high speed stirring, add After completion, the mixture was stirred for 20 minutes, and homogenized twice at a high pressure homogenizer to obtain a uniform and stable pre-emulsion.

The pre-emulsion was placed in a glass four-necked flask with a stirring device, a thermometer and a condensing reflux device were set up, and after vacuuming for 2 times with nitrogen, nitrogen gas was continuously introduced, and the temperature was raised to 80 ° C, and 1.32 g of the initiator (V-50 was added). The polymerization reaction was initiated and maintained at 80 ° C for 10 hours to form 486.8 g of a polymer having a solid content of 29.6%.

Example 8 (as shown in Table 3)

A glass beaker was charged with 35.6 g of monomer (a1) FA, 62.3 g of monomer (a2-1) SA, 25.7 g of monomer (a2-2) EHMA, 6.2 g of monomer (a2-3) IBOA, 20.2 g. Monomer (a3) N-MAM, 7.68 g emulsifier (B-1) SP1830, 2.12 g emulsifier (B-2) SP1807, 7.3 g emulsifier (B-3) dipoxyl ammonium chloride (CNA- 90), 1.2g chain transfer agent TDM and 50g solvent DPM are oil phase, stir evenly at 40 °C with high speed mixer, 3g phosphoric acid (E) and 292g deionized water as water phase slowly added to the oil phase in high speed stirring, add After completion, the mixture was stirred for 20 minutes, and homogenized twice at a high pressure homogenizer to obtain a uniform and stable pre-emulsion.

The pre-emulsion was placed in a glass four-necked flask with a stirring device, a thermometer and a condensing reflux device were set up, and after vacuuming for 2 times with nitrogen, nitrogen gas was continuously introduced, and the temperature was raised to 80 ° C, and 1.32 g of the initiator (V-50 was added). The polymerization reaction was initiated and maintained at 80 ° C for 10 hours to form 486.8 g of a polymer having a solid content of 29.6%.

The above are preferred examples 6 to 8 of the present invention, wherein the difference in composition is that different acids are added, and then the fluorine-containing copolymer obtained by polymerization in each example is measured for particle diameter and potential, and the results are shown in Table 3. Show.

The above description is only for the preferred embodiments of the present invention, and the equivalent composition and manufacturing method of the present invention and the scope of the patent application are intended to be included in the scope of the present invention.

Claims (9)

A fluoropolymer water repellent comprising: (A) a fluorinated copolymer having an average particle diameter of from 1 to 1000 nm in an aqueous solution and a cell potential of from 0 to 100 mV; The monomer (a1), the monomer (a2) and the monomer (a3) are polymerized, wherein: the monomer (a1) is a fluorine-containing monomer, and the general formula is R _f -YX wherein R _f is a perfluoroalkyl group having 8 to 20 carbon atoms; Y is a divalent organic group or a single bond or a diisocyanate group; X is -CR=CH ₂ , -C(O)OCR=CH ₂ , -OC ( O) CR=CH ₂ , -OCH=CH ₂ , -OC ₂ H ₄ -OC(O)CR=CH ₂ or (R is a hydrogen atom, a methyl group or a halogen atom); the monomer (a2) is a non-fluorinated monomer, which is a linear alkyl (meth) acrylate, a branched alkyl (meth) acrylate, and Any one or more of the group consisting of a monocyclic, polycyclic or crosslinked alkyl (meth) acrylate; and the monomer (a3) is a monomer having two reactive groups or more; relative to the single The monomer (a2) is 1 to 300 parts by weight, the monomer (a3) is 1 to 50 parts by weight, and (B) 12 to 22 carbon chain length double long carbons, in terms of 100 parts by weight of the body (a1). a cationic emulsifier of an alkyl group; and (C) an acid or a salt thereof. The fluoropolymer water repellent according to claim 1, wherein the cationic emulsifier It is dioctadecyl dimethylammonium chloride (Kao-D86P), dipoxyl ammonium chloride (Taiwan-CNA90) or bis-fatty alkyl ethyl hydroxyethyl methyl ammonium sulfate (REWOQUAT) WE-18). The fluoropolymer water repellent according to claim 1, wherein the fluoropolymer has an average particle diameter of from 1 to 200 nm. The fluoropolymer water repellent according to claim 3, wherein the fluoropolymer has an average particle diameter of from 1 to 100 nm. The method for producing a fluoropolymer according to claim 1, wherein the fluoropolymer has a microcell potential of 10 to 80 mV. The method for producing a fluoropolymer according to claim 5, wherein the fluoropolymer has a cell potential of 30 to 60 mV. The fluoropolymer water repellent according to claim 1, wherein the acid is an organic acid or an inorganic acid. The fluoropolymer water repellent according to claim 7, wherein the inorganic acid is hydrochloric acid, phosphoric acid or sulfuric acid. The fluoropolymer water repellent according to claim 7, wherein the organic acid is acetic acid or citric acid.