TW200829328A - Polymeric water-repellent agent - Google Patents

Abstract

An environmentally friendly hydrophobic polymeric water-repellent agent is provided. The water-repellent agent is prepared by miniemulsion polymerization. The water-repellent agent uses an extremely hydrophobic acrylic ester as a cosufactant. The cosufactant reacts with non-fluorinated monomers to form an extremely hydrophobic resin with excellent water resistance. The water-repellent agent not only is friendly to the environment, but also is widely used in many fields.

Description

200829328 1 IX. Description of the invention: [Technical field to which the invention belongs] The present invention refers to a kind of water-based tree vinegar and a preparation method thereof, and particularly, a ring (four) polymer prepared by mini-Wei polymerization. [Prior Art] The water-repellent and oil-repellent agent developed by the company is mostly a hydrophobic solvent-solvent. It is formed by using a (meth) monomer having a perfluoroalkyl group, which is polymerized by mechanical-money riding, and the m2 emulsion polymerization reaction is obtained. A large amount of material/ΓΓ, causing environmental pollution. Just because the emission reduction has become a common trend in all countries, so reducing the hydrophobic solvent-based resin and using the water-based resin will be an undeveloped domain, which can effectively reduce V0C and have low ignitability (safety). No odor and other advantages 0 The chelating reaction is a heterogeneous free radical addition polymerization reaction. The main components of this reaction include: monomer, dispersion = active agent and initiator, the first three # mixed money can form an emulsion =ulsiGn) 'After adding the initiator, the radical is decomposed by heating with a starter to initiate polymerization. After the initiation reaction, the Propagation reaction, and the termination (Terminati〇n) reaction, a very large number of polymer particles (about 1〇16~1〇19 liters) are obtained, which is the reaction. The final product, Latex. The composite particles are dispersed in the aqueous phase by the surfactant adsorbed on the surface. They are also the most important anti-emulsification polymerization. 200829328 The site should be generally pure, and the emulsion polymerization process can be: Segment: Particle core formation Period, the particle stabilizes into the growth phase and the grain is solidified. Item * long

Emulsion system - a system in which a large number of fine droplets (called a dispersed continuous phase) are uniformly distributed in a dispersion medium or a continuous phase. The diameter of some fine droplets is about 0·1~10 μιη; A surfactant adsorbed at the oil-water interface to reduce the force. In addition, it can also be stabilized by the electrostatic repulsion caused by the addition of an anionic surfactant or the surface adsorption of a droplet of water - a hydrophilic long bond ^ (for example, a nonionic surfactant). Suspended in the continuous phase. Emulsions are generally classified into three types according to their physical properties: macroemulsion (macr〇emulsi〇n), microemulsion (microenmlsion) and miniemulsion (miniemulsi〇n). The main differences of the three emulsions are shown in the following table. The mini-emulsion is an emulsion product obtained by mixing water, a surfactant (about 1-3 wt%, a co-stabilizer (an alkane or an alcohol having more than twelve carbons) and an oil by a homogenization process, a mini-emulsion. Better stability than macroemulsion' The average particle size range is ~500 faces, while the appearance is opaque emulsion. The high stability mini emulsion prepared by mini-emulsification procedure because of the surfactant dose used Less, it can prevent the disadvantage that the surface of the emulsion polymer coating is susceptible to water and poor adhesion due to the use of high concentration surfactant. In the traditional emulsification procedure, the smaller oil droplets have higher Chemical potential energy, so it is easier to dissolve in the water phase. As for the larger oil droplets, it will absorb the oil molecules dissolved in the water phase and grow. This effect is called Ostwald ripening effect. Therefore, the traditional emulsion is a thermodynamically unstable state. In the polymer preparation process, a low molecular weight and a high hydrophobicity are often added to the emulsion. Agent, because the solubility of the common stabilizer in the aqueous phase is quite low, it can provide a relatively strong osmotic pressure effect, so it can effectively prevent the aging effect of Oswald, thus making the stability of the mini emulsion more common than the traditional emulsion. South. • The job is due to the fact that the creator, based on the lack of prior art, is carefully tested and researched with a perseverance spirit to create an environmentally friendly polymer water repellent that is added by mini-emulsification polymerization. A low molecular weight, highly hydrophobic polymerizable co-stabilizer participates in the reaction together with the monomer. The selected monomer can achieve high hydrophobicity without fluorine, and the solvent is water, which is energy-saving and low-pollution. Other characteristics can reduce the use of organic solvents, not only reduce the environmental load, but also take into account the safety of preparation. The following is a brief description of the creation. Giant (conventional) emulsion mini-emulsion microemulsion monomer droplet average particle size > 1 μιη 50~500 nm 10~100 nm Main nucleation sites Micelles droplets droplets Appearance of milky white milky transparent emulsifier The amount of water is 2~3 %, the total amount is 0.5~2%, and the total amount is 15~30%. The ionic emulsifier ionic emulsifier ionic emulsifier and long-chain alcohol (burn) and short-chain alcohol• ____ 7 200829328 [Summary of the Invention] The purpose of the present invention is to provide a polymer water repellent comprising a one-pronged body. The dispersion comprises a monomer and a first acrylic acid. The monomer is selected from a fluorine-free monomer and accounts for the whole. The composition is 5-35% by weight, and the first acrylate accounts for 0.5-55% by weight of the overall composition, and is selected from the compound represented by the formula: CH2=C (RD CO〇R2, where Ri is Η or CH3, R2 is cnH2n+1, and ng 8.

According to the above concept, the polymer water repellent further comprises water, a surfactant, a buffer and a starter, wherein the water accounts for 40-80% by weight of the whole composition; the surfactant occupies the overall composition. 2 to 3% by weight; the buffer accounts for 0.02-0·1% by weight of the overall composition' and the initiator accounts for 4 to 1% by weight of the overall composition 〇·〇. According to the above concept, the surfactant is selected from one of an anionic, a cationic, an amphoteric and a nonionic surfactant. According to the above concept, the polymer water repellent is a water-dispersed polymer water repellent and is obtained by a mini emulsion polymerization reaction. According to the above concept, wherein the dispersion has an average particle size of from 50 to 500 ηπι. It is quite the above concept, wherein the single system is selected from at least one of: - (a) has an aging formula: acrylate: CH2 = C (Rl) C00R2, wherein Ri is H or CH3, and R2 is Η Any one of CnH2n+1, CnH2n〇H, and n<8; (b) a styrene and a derivative thereof; and (4) a propylamine having the following formula: CH corpse C (Rl) CONHR2, wherein & For H or cH3, ^ 8 200829328 is Η or OH. The acrylate accounts for this dispersion according to the above concept, wherein the _ body composition is 2-65% by weight. Wherein the first acrylate is a copolymerized monomer according to the above concept. According to the above concept, wherein the first propylene stabilizer is used.

Another object of the present invention is to provide another polymeric water repellent comprising a dispersion-and a boundary-active agent, the surfactant comprising 0.2 to 3% by weight of the overall composition. The dispersion comprises an acrylate which accounts for 4 to 49% by weight of the overall composition, and which has the formula: ch2 = c (Rl) C00R2, and the towel Ri is cH3 R2

CnH2n+i, and η=8 〇 According to the above concept, the polymer water repellent further comprises water, a surfactant, a buffer and a starter, wherein the water accounts for 40-80% by weight of the whole composition; The surfactant accounts for 0.2-3% by weight of the overall composition; the buffer accounts for the overall composition 〇〇2_〇1% by weight' and the initiator accounts for the overall composition 〇·041; [% by weight. According to the above concept, the surfactant is selected from one of an anionic, a cationic, an amphoteric and a nonionic surfactant. According to the above concept, the polymer water repellent is a water-regular hydrazine molecular water repellent and is obtained by a mini-emulsification polymerization reaction. According to the above concept, the average particle size of the dispersion is between 50 and 50 Οηπι. 9 200829328 According to the above concept, wherein the acrylate is a monomer. According to the above concept, the acrylate is a co-agent.另一 Another object of the present invention is to provide a "method of making a polymeric agent" comprising the steps of providing a mixture; subjecting the mixture to a pre-emulsification procedure and a homogenization procedure to provide a mini-emulsion; and carrying out the reaction The polymer water repellent can be obtained. The mixture comprises - an interface / a lingual agent, a water, a first acrylate and a monomer, wherein the first - __ is expressed by: CH2 = C (Ri) c 〇〇 R2 ^ 1 is 11 Or CH3, r2 is CnH2n+i, and n^8. /, _ According to the above concept, the step of carrying out the polymerization of the uranium further comprises heating the miniemulsion to a reaction temperature. According to the above concept, the reaction temperature is between 60 and 90X:. According to the above concept, the interface is one of the active ion type, the -cation type, the one-and-two type and the one-side type agent, and it occupies an overall composition of _·2_3% by weight. According to the above concept, wherein the first acrylate is a co-stabilizer in the miniemulsion. According to the above concept, wherein the first acrylate is a copolymerized monomer in the polymerization. According to the above concept, wherein the single system is selected from at least one of the following monomers (a) to (C): a second acrylate having the following formula: CH cadmium C (Rl) COOR2, wherein Ri is H or CH3, R2 is any of Η, CnH2n+1, CnH2n〇H, and 8; (8) monostyrene and its charm; and (4) acrylonitrile having the following formula: 200829328 Amine: CH2=C (Ri) CONHil2 Where Rq is H or CH3 and I is H or OH. According to the above concept, the monomer accounts for 5-35% by weight of the overall composition. 5-35%重量百分比。 The first acrylate comprises an overall composition of 0. 5-35% by weight. According to the above concept, wherein the pre-emulsification procedure is to stir the mixture uniformly. • According to the above concept, wherein the homogenization process is to fully emulsifie the mixture with a homogenizer. According to the above concept, the mini emulsion has an average particle size of from 50 to 500 nm. According to the above concept, wherein the polymerization is started by adding an initiator. According to the above concept, the polymer water repellent is a water-dispersed polymer water repellent. 10 Another object of the present invention is to provide a method for preparing another polymeric water repellent, the method comprising the steps of providing a mixture, subjecting the mixture to a pre-emulsification procedure and a homogenization procedure to provide a miniemulsion and performing a polymerization reaction. The polymer water repellent can be obtained. The mixture comprises a surfactant, monohydrate and a acrylate, wherein the acrylate is represented by the formula: CH2=C(Ri) COOR2, wherein R! is Η or CH3, and R2 is CnH2n+i, and η=8. According to the above concept, the step further comprises heating the miniemulsion to a reaction temperature before carrying out the polymerization. 11 200829328 According to the above concept, wherein the reaction temperature is between 60 and 9 (TC. According to the above concept, wherein the surfactant is selected from the group consisting of an anionic, a cationic, an amphoteric and a nonionic surfactant. - and it occupies 0.2-3% by weight of the overall composition. According to the above concept, wherein the yttrium acrylate is intended to be a co-stabilizer in the miniemulsion. According to the above concept, wherein the acrylate is in the polymerization reaction It is a monomer.

According to the above concept, the first acrylate comprises from 4 to 49% by weight of the overall composition. According to the above concept, wherein the pre-emulsification procedure is to stir the mixture uniformly. According to the above concept, wherein the homogenization process is to emulsification the mixture in a homogenizer. According to the above concept, the mini emulsion has an average particle size of from 50 to 500 nm. According to the above concept, wherein the polymerization is started by adding an initiator. 〇 According to the above concept, the polymer water repellent is a water-dispersed polymer water repellent. The present invention will be further understood by the following detailed description: [Embodiment] Hereinafter, the present invention will be described in more detail by showing examples and comparative examples. In the examples and comparative examples, the following measurements were carried out to evaluate the effect of the water-repellent 12 200829328 % agent. Stearyl methacrylate (SMA) contains a sputum in the mini-emulsification polymerization. The stearyl methacrylate (SMA) not only inhibits the Ostwald ripening effect but also stabilizes the emulsion system. Will be incorporated into the emulsion dispersion by chemical bonding, so the co-stabilizer is also called polymerizable co-stabilizer, and its residual amount after the mini-emulsification polymerization will also affect various physical properties of the serum product. And special sex. Therefore, the concentration of SMA in the polymerized polymer was measured by 1H-NMR nuclear magnetic resonance spectroscopy, and the ratio of SMA in the dispersion after mini-emulsification polymerization was calculated to determine the proportion of SMA in the southern molecule. The measurement of the contact angle of the latex polymer can determine the surface properties of the outermost layer of the material of about 10 A, and is also an important indicator to explore the surface wettability. The wettability of the liquid to the solid surface can be determined by the contact angle. The smaller the contact angle, the better the wetness φ, indicating that the solid surface has a higher surface free energy than the droplet, and glass and metal are good examples. On the other hand, if the contact angle is larger, the harder it is to be wetted, and the solid surface has lower surface free energy than the droplets. For example, polymer resin such as Teflon (PTFE) or polyethylene (PE) belongs to this. Types of. In this experiment, after completion of the mini-emulsification polymerization reaction, the polymer was coated into a film, and the contact angle was measured by a Sessile drop method. The sessile droplet method uses a micro-syringe to directly drop droplets onto a solid surface, observes the contour of the droplet through a micro-camera, adjusts the level of the surface, and then directly measures the horn image by Detecting 13 200829328 or by CCD image Calculate the static contact angle after reaching the computer. Please refer to Figure 1, which is the flow chart of the mini emulsion preparation process. Preparing an aqueous phase comprising 2·66 πιΜ buffer sodium bicarbonate, 5 mM surfactant sodium dodecyl sulfate (SDS) and 160 g of water, and containing 40 g of monomeric methacrylate (methyl) Methacrylate (MMA) and the oil phase of the common stabilizer stearyl methacrylate (SMA). The oil phase solution was slowly poured into the aqueous phase stirred at 400 rpm and scrambled for 1 minute (pre-emulsification procedure). The pre-emulsified emulsion was homogenized by ultrasonic sonic homogenizer for 10 cycles (homogenization procedure), the shaking time was 5 minutes per cycle, and the rest was 3 minutes. After the homogenization procedure, a mini emulsion was obtained. The prepared mini-emulsion is immediately placed in a reactor heated to a reaction temperature of 75 ° C, the stirring rate in the reactor is maintained at about 250 rpm, and the temperature of the mini-emulsion reaches the reaction temperature, and 2 · 6 6 m is added. The starting agent sodium persulfate starts a polymerization reaction, and after the monomer and the co-stabilizer are fully reacted for 8 hours, a water-dispersed milk product can be obtained, that is, a polymer water repellent. The polymer water repellent comprises a dispersion having an average particle size of from 5 〇 to 5 〇〇 nm. The above method for preparing the polymer water repellent is only a preferred embodiment condition, wherein the water may comprise 40-80% by weight of the whole composition; the surfactant may comprise 0.2 to 3% by weight of the overall composition; The buffering agent may comprise an overall composition of 0·〇2~〇·1% by weight; and the initiator may comprise 0.04-1% by weight of the overall composition. The monomer may be selected from a fluorine-free monomer and occupies 5-35% by weight of the overall composition, and the common stabilizer may account for 0.5-35% by weight of the overall composition 200829328, and may be selected from the compounds represented by the following formula : CH2=C (D C00r2, where Rl is Η or CH3, r2 is

CnH2n+1, and n^8. The surfactant may be selected from one of an anionic, a cationic, an amphoteric and a nonionic honey surfactant. The reaction temperature for carrying out the polymerization is between 6 〇 and 90 ° C. Please refer to Table 1, which is a table of the preferred embodiment of the improved molecular water repellent of the present invention. According to the above method for manufacturing a polymer water repellent, 10 MMA and styrene (STY) are used as monomers for mini-emulsification polymerization, and a low-molecular-weight and high-hydrophobic polymerizable co-stabilization is required by mini-emulsification polymerization. The characteristics of the agent, the amount of the monomer fixed, the amount of SMA added and the type of the monomer were varied to produce different examples (as shown in Table 1). When the proportion of SMA increases, the average particle size of the MMA and STY monomers increases with the increase of SMA addition after polymerization. The extremely hydrophobic SMA provides a strong osmotic effect in the monomer droplets. Therefore, in the mini-emulsification polymerization with SMA as the common stabilizer, the Oswald aging effect will be reduced, and the probability of water phase nucleation will occur. Also relatively small, a partial agglomeration occurs between the more hydrophobic monomer droplets (STY), resulting in an increase in the average particle size, and the average particle size of the dispersion of STY^ is larger than that of the dispersion of the MMA. Yan Qing #表表二' is the effectiveness evaluation form for the better example of the molecular water repellent for the case. The SMA content and the contact angle size are included therein, wherein the styrene copolymer (PSTY) and the methyl methacrylate copolymer are comparative examples. Both pSTY and pMMA are polymers synthesized by a non-emulsified polymerization reaction, and nine examples are emulsion polymers synthesized by mini-emulsification polymerization with different SMA ratios. Even before the reaction 15 200829328 SMA / monomer ratio as high as SMA in the early eight (% %), after the polymerization Γΐί, containing 4 can still maintain nearly 5. ...%. Although the representative = can; it degree and single correction 4, but should be 8 ^ although ^ ^ should. The role of aging in the pre-polymerization reaction is to suppress the Oswald aging and the virgin mini-emulsion system, but slowly follow the monomer with the consumption of monomer droplets. The co-stabilizer gradually dried up and ended.

The contact angle of a PMMA polymer surface is about 64.5. , when SMA. When the ratio of monomer/monomer rises to 丨/8, the contact angle increases significantly to about 88.5°, which indicates that the addition of SMA in the emulsion polymerization reaction can improve the hydrophobicity of the polymer, and the ratio of SMA/monomer continues to rise. To 1/2, the SMA content in the polymer after the reaction is about 32.89 %, and the contact angle can be increased to 99. Soil 3.5 indicates that the polymer surface has exhibited a low surface free energy state and has a waterproof property. However, if the ratio of SMA/monomer is further added to w 1, although the content of sMA in the polymer accounts for about 40.61%, the appearance of the contact angle tends to be flat, about 95. ~96. about. The polymer film prepared by PSTY coating has a contact angle of about 81.75°. When the ratio of SMA/monomer is slightly increased to 1J173 / 40, the contact angle rises less until the ratio is increased to 1/2. The contact angle of the STY/SMA copolymer is increased by about 10°, which is about 91.75. 1.25, at this time the content of SMA in the polymer is 34.99%, and as in the MMA / SMA copolymer, the ratio of SMA / monomer is continuously added to 1:1, although the SMA in the polymer accounts for about 50 % 'But the contact angle also tends to be gentle, no significant change, showing 16 200829328 94.75 ° ° Compared with the hydrophilic monomer of MTY, the polymer PMMA synthesized by emulsion-free polymerization has a contact angle of 64.5. The polymer PSTY synthesized by the hydrophobic monomer sty has a contact angle of about 81.75°. Therefore, the hydrophilicity of the monomer in the emulsion polymerization does affect the contact angle of the polymer surface. With the increase of SMA content, the contact angle of MMA / SMA and STY / SMA copolymers gradually increased. When the SMA content is small (SMA content is about 2.7 wt%), the contact angle is still STY / SMA copolymer. Compared with the mMA / SMA 10 copolymer, the properties reflected by the polymer surface are still dominated by the hydrophilicity of the monomer. If the SMA content is increased (SMA content is about 33.3 wt%), the MMA/SMA interpolymer is affected by the highly hydrophobic co-stabilizer SMA, and the contact angle changes rapidly, even beyond the STY / SMA copolymer. This also means that in the mini-emulsification polymerization, when the ratio of SMA/monomer is 1/2, the high hydrophobicity of the common stabilizer SMA can be fully exerted, which is also reflected on the surface of the emulsion polymer. Therefore, the originally hydrophilic PMMA high score _ sub-converted into a hydrophobic substance, and the PSTY which is originally hydrophobic can also enhance its hydrophobicity, so the addition of the common stabilizer sma can be stabilized by mini-emulsion 糸In addition, after the reaction is chemically bonded into the dispersion of the emulsion, the emulsion polymer also exhibits the high hydrophobic nature of SMA. Therefore, a highly hydrophobic common stabilizer can be added by mini-emulsification polymerization. The characteristics of the preparation of environmentally friendly water repellent. The contact angles shown in Table 2 are the surface contact angles of the polymer obtained after coating the unwashed dispersion. The contact angle is affected by the SDS, but the contact angle is irregular. However, with the increase of SMA content, the polymer surface is 17 200829328 It still has hydrophobic properties, but if the dispersion is washed with a methanol, it can exhibit the properties of the inherent polymer surface and improve its water-repellency. The monomer usable in the present invention may be selected from at least one of the following monomers (a) to (c) in addition to MMA and STY: (a) an acrylate having the following formula: CH2=C (RO C00R2 Wherein Ri is Η or CH3, R2 is any of Η, CnH2n+1, CnH2nOH, and η S8; (b) - styrene and its derivatives; and (c) an acrylamide having the following formula: CH The corpse C (Ri) CONHR2, wherein & is Η or φ CH3, and R2 is Η or OH. The polymer water repellent provided by the present invention is an aqueous resin which can be widely used in daily life, such as Adhesives, coatings, synthetic rubbers, building materials additives, aggregating agents and various modifiers, etc. In addition, they can also be used in biotechnology fields such as diagnostic tests, immunoassays and drug controlled release carriers. In addition, mini-emulsified The characteristics of the polymerization reaction, adding a common stabilizer of low molecular weight and highly hydrophobic alcohol alkanes, can not only improve the stability of the emulsion system, but also change the physical properties of the polymer, such as toughness, rheology, surface freedom. Energy, hydrophilicity, etc., large This is an increase in the scope of its commercial application. This case has been modified by people who are familiar with the art, but it is not intended to be protected by the scope of the patent application. [Simplified illustration] Figure 1: Mini emulsion in this case Flowchart of the preparation process; Table 1: Table of the formulation of the preferred embodiment of the improved molecular water repellent of the present invention; and Table 2: Evaluation form of the effect of the preferred embodiment of the improved molecular water repellent of the present invention.

Claims (1)

200829328 X. The scope of application for patents · · l — * water = ' it contains, the dispersion contains: 5_35% by weight; and 1 early body and the overall composition of a first acrylate, J: account for Li Li Day士A ratio 'and its choice from the following formula = compound into 〇.5. Weight CH2=C (Rj) coor2 2 *! Rl4H"CH-R^C^^n^8〇. Patent scope item 1 The polymer is cut into bismuth, which is more water-containing, which accounts for 40-80% by weight of the whole composition; a surfactant, which accounts for 0.2 to 3% by weight of the whole composition; a buffer, which accounts for 0.02- of the overall composition 0.1% by weight of the ratio and a starter, which occupies the overall composition 〇·04__1% weight, 1 patent application scope 2, the polymer water repellent agent, __ _ is selected from an anionic type, a cationic type, two One of two or two nonionic surfactants. The high-density of the high-density granules mentioned in the second section of the project, the average particle size of the polymer water-repellent agent described in the scope of the patent application is 50-500 nm. , "Knife 6 · = = profit range of the first aspect of the polymer water repellent, wherein the single system k from at least one of the following monomers (a) to (c): (a) has the following molecular formula a second acrylate: 19 200829328 CH2=C (Ri) COOR2 wherein Ri is H or CH3, R2 is any of H, CnH2n+1, CnH2nOH, and n<8; (b)-styrene and its derivatives And (c) a acrylamide having the following formula: CH2-C (R〇conhr2 wherein Ri is ruthenium or CH3, and R2 is ruthenium or OH. 7. Polymer water repellent as described in claim 1 And wherein the first acrylate comprises 2 to 5% by weight of the dispersion composition. 8. The polymer water repellent according to claim 1, wherein the first acrylate is a copolymerized monomer. The polymer water repellent according to claim 1, wherein the first acrylate is a common stabilizer. 10. A polymer water repellent comprising: a dispersion; and a surfactant , which accounts for 0.2-3% by weight of the overall composition, 10 wherein the dispersion comprises an acrylate, which accounts for 4-49% of the overall composition The ratio is expressed by the following formula: CH2=C (R〇coor2 where Ri is Η or 013, 112 is €:1111211+1, and 11=8. 1L as described in claim 10 The water composition, which further comprises: a water, which comprises 40-80% by weight of the overall composition; a buffer, which comprises 0.02-0.1% by weight of the overall composition; and a starter, which comprises 0. 04-1 20 200829328 12. The polymer water repellent according to claim 10, wherein the surfactant is selected from the group consisting of an anionic type, a cationic type, an amphoteric type and a nonionic surfactant. 13. The polymer water repellent according to claim 10, wherein the polymer water repellent is a water-dispersed polymer water repellent and is obtained by a mini-emulsification polymerization reaction. The polymer water repellent according to claim 10, wherein the dispersion has an average particle size of 50 to 500. • 15. The polymer water repellent according to claim 10 of the patent application scope, Wherein the acrylate is a monomer. 16. As described in claim 10 The polymer water repellent, wherein the acrylate is a common stabilizer. 17. The method for preparing a polymer water repellent, the method comprising: providing a mixture comprising a surfactant, a water, a first An acrylate and a monomer, wherein the first acrylate is represented by the following formula: • CH2=C (R〇coor2 wherein Ri is Η or CH3, R2 is CnH2n+1, and η-8; making the mixture a pre-preparation An emulsification procedure and a homogenization procedure to provide a miniemulsion; and a polymerization reaction to obtain the macromolecular water repellent. 18. The method of producing a polymeric water repellent according to claim 17, wherein the step of heating the cosmetic emulsion to a reaction temperature before performing the polymerization. 19. The method for producing a polymer water repellent according to claim 18, wherein the reaction temperature is between 6 〇 and 9 〇 ° C. The method for producing a polymer water repellent according to claim 17, wherein the surfactant is selected from the group consisting of an anionic type, a cationic type, a two-type type and a nonionic surfactant. One, and it occupies the overall composition 2- 2-3% weight ratio. The method of producing a polymer water repellent according to claim 17, wherein the first acrylate is a co-stabilizer in the miniemulsion. α ς \ • A method of producing a polymer water repellent as described in the scope of claim ′ wherein the first acrylate is a copolymerized monomer in the polymerization. The method for producing a polymer water repellent according to claim 17, wherein the single system is selected from at least one of the following monomers: VIII (a) a second acrylate having the following formula : Lu CH2=zC (Ri) CO〇R2 where Ri is Η or CH3, R2 is Η, CnH2n+1, CnH2n0H any of them, and n$8; (b) styrene and its derivatives; and (c) A acrylamide having the following formula: CH2=C (R〇conhr2 ' wherein Ri is Η or CH3, and R2 is η or OH. • Preparation of a polymer water repellent as described in claim 23 The method wherein the monomer accounts for 5-35% by weight of the overall composition. The method for producing the polymer water repellent according to claim 17 of the patent application, wherein the first acrylate comprises the entire composition The method for producing a polymer water repellent according to claim 17, wherein the pre-emulsification procedure is to uniformly stir the mixture. 27. The method for preparing a polymer water repellent according to the item, wherein the homogenization process is The method of preparing the polymer water repellent according to claim 17, wherein the mini emulsion has an average particle size of 50-500 nm. The method for producing a polymer water repellent according to Item 17, wherein the polymerization is started by adding a starter. 30. The preparation of the polymer water repellent according to claim 17 of the patent application. The method, wherein the polymer water repellent is a water-dispersed polymer water repellent. 31. A method for preparing a polymer water repellent, the method comprising: providing a mixture comprising a surfactant, Monohydrate and acrylate, wherein the acrylate is represented by the formula: CH2=C (R〇coor2 • wherein R is Η or CH3, R2 is CnH2n+1, and n=8; the mixture is subjected to a pre-emulsification procedure And a homogenization process for providing a mini-emulsion; and performing a polymerization reaction to obtain the polymer water repellent agent. 32. The method for preparing a polymer water repellent agent according to claim 31, wherein the step is Before carrying out the polymerization, it further contains The method of preparing the polymer water repellent according to claim 32, wherein the reaction temperature is between 60 and 90 ° C. 23 200829328 % 34. The method for preparing a polymer water repellent according to claim 31, wherein the surfactant is selected from the group consisting of an anionic type, a cationic type, an amphoteric type and a nonionic surfactant, and It occupies 0.2-3% by weight of the overall composition. The method of producing a polymer water repellent according to claim 31, wherein the acrylate is a co-stabilizer in the miniemulsion. The method of producing a polymer water repellent according to claim 31, wherein the acrylate is a monomer in the polymerization. The method for producing a polymer water repellent according to claim 31, wherein the first acrylate comprises 4 to 49% by weight of the total composition. 3) The method for producing a polymer water repellent according to claim 31, wherein the pre-emulsification procedure is to uniformly stir the mixture. 39. The method for producing a polymer water repellent according to claim 31, wherein the homogenization procedure is to emulsifier the mixture by a homogenizer. 40. The method of preparing a polymer water repellent according to claim 31, wherein the mini emulsion has an average particle size of 50-500. The method of producing a polymer water repellent according to claim 31, wherein the polymerization is started by adding an initiator. The method for producing a polymer water repellent according to claim 31, wherein the polymer water repellent is a water-dispersible polymer water repellent. twenty four