CN110540614A - Water-based fluorine-containing acrylate copolymer, hybrid membrane, preparation method and application thereof - Google Patents
Water-based fluorine-containing acrylate copolymer, hybrid membrane, preparation method and application thereof Download PDFInfo
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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Abstract
The invention discloses a water-based fluorine-containing acrylate copolymer, a hybrid membrane, and a preparation method and application thereof. The water-based fluorine-containing acrylate copolymer takes the polymerization of an alkyl acrylate monomer as a core, and takes the copolymerization of the alkyl acrylate monomer, the fluorine-containing acrylate monomer and a hydroxyethyl acrylate monomer as a shell, wherein the mass percent of the alkyl acrylate monomer to the total monomer is 78.13-92.70%, the mass percent of the fluorine-containing acrylate monomer to the total monomer is 6.21-20.94%, and the mass percent of the hydroxyethyl acrylate monomer to the total monomer is 0.91-1.09%; the number of the fluorocarbon atoms is less than or equal to 6. The hybrid membrane prepared from the water-based fluorine-containing acrylate copolymer emulsion has good effects in water repellency, dirt repellency, uniform membrane formation and corrosion resistance, can be used for oil-water separation, takes water as a solvent, is green and environment-friendly, has low cost, is simple and efficient, and has good market application prospect.
Description
Technical Field
the invention relates to a water-based fluorine-containing acrylate copolymer, a hybrid membrane, and a preparation method and application thereof.
Background
The fluorine-containing polymer has excellent comprehensive properties such as chemical stability, thermal stability, surface property, lubricity, electrical insulation, aging resistance, radiation resistance, extremely low water absorption and the like due to extremely strong stability of a carbon-fluorine bond, and is widely applied to the fields of fabric finishing, functional coating, aerospace, biomedicine, microelectronics and the like. The fluorine-containing acrylate copolymer is a kind of fluorine-containing polymer obtained by copolymerizing a fluorine-containing acrylate monomer with other functional monomers, and generally has high water repellency, high film-forming property, high adhesion and the like.
in recent years, with the enhancement of environmental awareness, attention has been paid to an environmentally friendly fluorine-containing acrylic polymer emulsion. Many patent documents for preparing water-and oil-repellent finishing agents for fabrics by utilizing the superior properties of fluorine-containing compounds have been reported. Patents US6126849, US6451717 and US5344903 respectively disclose that emulsion with a conversion rate of more than 99% is prepared by mixing a fluorine-containing acrylate mixed monomer, octadecyl acrylate, N-hydroxy acrylamide and a fluorine-containing emulsifier, homogenizing and emulsifying under high pressure, and initiating by V-50, and the emulsion has good water and oil repellency. US5055538 discloses a method for preparing fluorine-containing polyacrylate emulsion by mixing and emulsifying perfluorooctyl ethyl acrylate, octadecyl acrylate, ethyl acrylate, N-hydroxy acrylamide, 1, 2-ethylene oxide vinyl methyl acrylate and a fluorine-containing emulsifier and initiating by V-50, wherein the obtained emulsion has good water and oil repellency and is water-resistant and can be compounded with other additives. CN1493601 discloses a water-emulsion water-and oil-repellent agent and a preparation method thereof, CN201010520150.7, CN200510038650.6 and the like respectively synthesize fluorine-containing polyacrylate emulsions with different performances. The problems in the above-described fluorinated polyacrylate emulsion process are mainly two-fold: firstly, most of the perfluorinated side chains of the prepared fluorine-containing polyacrylate emulsion contain fluorine and carbon atoms of more than or equal to 8, and the emulsion has biological accumulation and biological toxicity, and related laws and regulations prohibit the use; secondly, the cost of the used initiator and emulsifier is high, the large-scale popularization and application are not facilitated, and auxiliary emulsifiers such as acetone and the like are added in the emulsification process, so that the emulsifying agent has toxicity and is not environment-friendly; and thirdly, the fluorine-containing polyacrylate has a single structure and higher cost, and the popularization and application of the fluorine-containing polyacrylate are also limited.
Therefore, it is highly desirable to develop a fluorine-containing polyacrylate copolymer having a carbon-fluorine atom of less than 8, while ensuring water-and soil-repellent properties of the copolymer and reducing the amount of fluorine-containing monomer used.
Disclosure of Invention
The invention aims to solve the technical problem of providing a water-based fluorine-containing acrylate copolymer and a hybrid membrane different from the prior art, and a preparation method and application thereof. The fluorine-containing carbon atom number in the fluorine-containing acrylate copolymer in the water-based fluorine-containing acrylate copolymer is less than or equal to 6, the using amount is small, the hybrid film prepared from the water-based fluorine-containing acrylate copolymer has good effects on water repellency, dirt resistance, uniform film formation and acid and alkali resistance, can be used for oil-water separation, and the preparation method only takes water as a solvent, is green and environment-friendly, has low cost, is simple and efficient, and has better market application prospect.
The present invention solves the above technical problems by the following technical solutions.
The invention provides a core-shell type copolymer, which takes the polymerization of alkyl acrylate monomers as a core and takes the polymerization of the alkyl acrylate monomers, fluorine-containing acrylate monomers and hydroxyethyl acrylate monomers as a shell;
Wherein the mass percent of the alkyl acrylate monomer in the total monomer is 78.13-92.70%, the mass percent of the fluorine-containing acrylate monomer in the total monomer is 6.21-20.94%, and the mass percent of the hydroxyethyl acrylate monomer in the total monomer is 0.91-1.09%;
The structure of the alkyl acrylate monomer is shown as a formula 1, the structure of the fluorine-containing acrylate monomer is shown as a formula 2, and the structure of the hydroxyethyl acrylate monomer is shown as a formula 3:
r1 is C1-C18 alkyl; r2 and R3 are each independently H or CH 3; rf is CnF2n +1CH2CH2-, and n is any integer from 2 to 6.
wherein the mass of the alkyl acrylate monomer, the mass of the fluorine-containing acrylate monomer and the mass of the hydroxyethyl acrylate monomer are the mass before polymerization into a core or a shell; the total monomer mass is the total mass of the alkyl acrylate monomer, the fluorine-containing acrylate monomer and the hydroxyethyl acrylate before polymerization into a core or a shell.
in the invention, the mass percentage of the alkyl acrylate monomer in the total monomer mass can be 78.13-87.27%, the mass percentage of the fluorine-containing acrylate monomer in the total monomer mass can be 11.69-20.94%, and the mass percentage of the hydroxyethyl acrylate monomer in the total monomer mass can be 0.91-1.02%.
In the invention, CnF2n +1 in the Rf can be a linear chain structure or a branched chain structure; preferably, CnF2n +1 in Rf is a branched structure, n is 5 or 6, for example:
In the present invention, the fluorine-containing acrylate monomer may be one or more of 2- (perfluorohexyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl acrylate and 2- (perfluoro 1, 1-dimethyl-butyl) ethyl acrylate, preferably 2- (perfluorohexyl) ethyl acrylate and/or 2- (perfluoro 1, 1-dimethyl-butyl) ethyl acrylate, such as 2- (perfluoro 1, 1-dimethyl-butyl) ethyl acrylate.
in the present invention, the alkyl acrylate monomer may be an alkyl acrylate monomer conventional in the art, preferably one or more of methyl methacrylate, methyl acrylate, butyl methacrylate, butyl acrylate, isooctyl methacrylate, isooctyl acrylate, lauryl methacrylate, lauryl acrylate, stearyl methacrylate and stearyl acrylate; more preferably one or more of methyl methacrylate, butyl methacrylate and stearyl acrylate.
The invention also provides a preparation method of the core-shell copolymer, which comprises the following steps:
Step 1, under the condition of an initiator, mixing the alkyl acrylate monomer, an emulsifier and a solvent to obtain a pre-emulsion I, and carrying out polymerization reaction to obtain a core-shell copolymer core emulsion;
Step 2, under the condition of an initiator, mixing the alkyl acrylate monomer, the fluorine-containing acrylate monomer, the hydroxyethyl acrylate monomer, an emulsifier and a solvent to obtain a pre-emulsion II, and carrying out polymerization reaction on the pre-emulsion II and the core-shell type copolymer core-shell emulsion obtained in the step 1 to obtain a core-shell type copolymer emulsion;
In the step 1, the mass percentage of the mass of the alkyl acrylate monomer to the total monomer mass is 40.84-48.46%;
In the step 2, the mass percentage of the mass of the alkyl acrylate monomer to the total monomer mass is 37.28-44.23%; the mass percentage of the mass of the fluorine-containing acrylate monomer to the total mass of the monomers is 6.21-20.95%; the mass percentage of the hydroxyethyl acrylate monomer to the total monomer is 0.92-1.08%.
In the present invention, the preparation method of the core-shell type copolymer may be a preparation method conventional in the art for such reactions, and the parameters and conditions of the preparation method of the core-shell type copolymer may be referred to those conventional in the art for such reactions.
The preparation method comprises the following steps of 1, mixing the alkyl acrylate monomer, an emulsifier and a solvent under the protection of inert gas to obtain a pre-emulsion I, and carrying out polymerization reaction on the alkyl acrylate monomer under the protection of an initiator; preferably, adding the pre-emulsion I into the reaction liquid in batches for polymerization; preferably, 1/3 the pre-emulsion I is polymerized, and after the reaction solution is blue phase, 2/3 the pre-emulsion I is dripped into the reaction solution to be polymerized.
mixing the alkyl acrylate monomer, the fluorine-containing acrylate monomer, the hydroxyethyl acrylate monomer, an emulsifier and a solvent under the protection of inert gas to obtain a pre-emulsion II, and carrying out polymerization reaction on the pre-emulsion II and the core emulsion of the core-shell type copolymer obtained in the step 1 under the protection of an initiator; preferably, an initiator and the pre-emulsion II are dropwise added to the core structure emulsion obtained in the step 1 for polymerization.
In the step 1, the mass percentage of the mass of the alkyl acrylate monomer to the mass of the total monomer can be 40.84-45.46%;
In the step 2, the mass percentage of the mass of the alkyl acrylate monomer to the mass of the total monomer can be 37.28-41.64%; the mass percentage of the mass of the fluorine-containing acrylate monomer to the mass of the total monomer can be 11.69-20.94%; the mass percentage of the hydroxyethyl acrylate monomer to the total monomer mass may be 0.92 to 1.02%.
Wherein the solvent may be a solvent conventional in the art for such reactions, preferably deionized water.
wherein, the ratio of the total mass of the solvent to the total mass of the monomers can be 1 to 5, preferably 1.8 to 2.3, and more preferably 2.0 to 2.3.
Wherein, the emulsifier can be a composite emulsifier or a reactive single emulsifier; preferably a reactive single emulsifier; more preferably 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) etherammonium sulfate (DNS-86).
The composite emulsifier can be a composition of ionic surfactant and nonionic surfactant, and preferably, the mass ratio of the ionic surfactant to the nonionic surfactant is 1:1 to 2.5.
The cationic surfactant can be one or more of dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium chloride; preferably, it is one of dodecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide and octadecyltrimethylammonium chloride.
the anionic surfactant can be one or more of sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate; preferably one of sodium lauryl sulfate, sodium lauryl sulfate and sodium dodecylbenzenesulfonate.
The nonionic surfactant can be one or more of OP (octyl phenol polyoxyethylene ether) series surfactant, NP (nonylphenol polyoxyethylene ether) series surfactant, Tween series surfactant or span series surfactant; preferably one of OP (octyl phenol polyoxyethylene ether) series surfactants, NP (nonylphenol polyoxyethylene ether) series surfactants, Tween series surfactants or span series surfactants.
Wherein, the mass percentage of the total mass of the emulsifier and the total monomer mass can be 2.1-2.4%, preferably 2.1-2.3%.
wherein the initiator may be conventional in the art for such reactions, preferably one or more of ammonium persulfate, potassium persulfate, and sodium persulfate; more preferably ammonium persulfate.
Wherein, the mass percentage of the total mass of the initiator to the total monomer mass can be 0.62-2.09%, preferably 1.17-2.09%.
Wherein, the mass percentage of the concentration of the initiator can be the conventional concentration of the reaction in the field, and is preferably 1.0-1.5%.
in step 1, the temperature for initiating the polymerization reaction may be the conventional temperature in the art, preferably 40 to 80 ℃, and more preferably 50 to 60 ℃.
In step 1, the time for initiating the polymerization reaction may be the time conventionally used in the art, and is preferably 2 to 6 hours, and more preferably 6 hours.
In step 2, the temperature of the polymerization reaction may be a conventional temperature in the art, and is preferably 70 to 80 ℃.
In step 2, the polymerization reaction time may be conventional in the art, and is preferably 2 to 6 hours.
After the step 2, the preparation method of the core-shell copolymer preferably further comprises adjusting the pH of the emulsion of the core-shell copolymer to 7-9; more preferably, the temperature of the emulsion of the core-shell copolymer is reduced to 40 ℃, and the pH is adjusted to 7-9.
Wherein, the reagent for adjusting the pH of the reaction liquid is a reagent which is conventional in the field for such reaction, and preferably ammonia water.
the mass of the alkyl acrylate monomer, the mass of the fluorine-containing acrylate monomer and the mass of the hydroxyethyl acrylate monomer are the mass before the monomers are polymerized into a core or a shell; the total monomer mass is the total mass of the alkyl acrylate monomer, the fluorine-containing acrylate monomer and the hydroxyethyl acrylate before polymerization into a core or a shell; the total mass of the solvent is the total mass of the solvent in the step 1 and the step 2; the total mass of the initiator is the total mass of the initiator in the step 1 and the step 2; and the total mass of the emulsifier is the total mass of the emulsifier in the step 1 and the step 2.
The invention also provides the core-shell copolymer prepared by the preparation method.
The invention also provides application of the core-shell copolymer in water and dirt repellency.
the invention also provides a water-repellent and dirt-repellent finishing agent which comprises the core-shell type copolymer.
The invention also provides a hybrid membrane which comprises the core-shell type copolymer, the inorganic hydrophilic nano material and the aqueous curing agent component.
The inorganic hydrophilic nano material can be a conventional material in the field, preferably hydrophilic nano silicon dioxide, hydrophilic nano titanium dioxide or hydrophilic nano zinc oxide, and more preferably hydrophilic nano silicon dioxide. The particle size of the inorganic hydrophilic nano material is preferably 10 to 50nm, and more preferably 15 to 20 nm.
the aqueous curing agent can be a conventional aqueous curing agent in the field, and is preferably an aqueous isocyanate curing agent or an aqueous amino curing agent, such as an aqueous isocyanate curing agent.
the invention also provides a preparation method of the hybrid membrane, which comprises the following steps:
Coating the hybrid membrane liquid on a base material, and curing the base material after membrane formation; wherein, the hybrid membrane liquid contains the core-shell type copolymer, inorganic hydrophilic nano material, aqueous curing agent and deionized water; preferably, the inorganic hydrophilic nano material aqueous solution with the mass percentage of 10% is mixed with the core-shell type copolymer, the water-based curing agent and the deionized water, and then the composite material is obtained.
The curing operation and conditions can be conventional in the art, and preferably curing is performed at 80-100 ℃ for 0.5-3 h.
Wherein the substrate may be a conventional substrate in the art, preferably one of glass, fabric, paper, nylon and metal.
In the invention, the mass ratio of the emulsion, the deionized water, the aqueous curing agent and the inorganic hydrophilic nano material can be conventional in the field, preferably 10-35: 50-80: 0.01-1: 1-10, for example 30:70:0.036: 4.
Wherein, the coating method can be a conventional coating method in the field, and is preferably spray pen coating.
The operation and condition of the spray pen coating can be conventional operation and condition in the field, preferably, the condition of the spray pen coating is that the caliber of the spray pen is 2-5 mm, the horizontal distance between the nozzle of the spray pen and the base material is 10-30 cm, and the pressure is 100-500 kPa.
Wherein, the mixing operation and conditions can be conventional in the art, and preferably mixing under ultrasound for 10-30 min.
The invention also provides application of the hybrid membrane in oil-water separation.
The preparation method of the core-shell copolymer of the present invention preferably comprises:
Step 1, 1.5g of deionized water, 0.328g of methyl methacrylate, 1.232g of butyl methacrylate and DNS-860.04g of emulsifier, and violently stirring for 0.5 hour at room temperature to form a pre-emulsion I; 1.5g of deionized water, 0.396g of methyl methacrylate, 0.528g of butyl methacrylate, 0.5g of octadecyl acrylate, 0.035g of hydroxyethyl acrylate, 0.4-0.8 g of fluorine-containing acrylate monomer and 0.5g of emulsifier DNS-860.04 are added, and the mixture is vigorously stirred at room temperature for 0.5 hour to form a pre-emulsion II. 3g of deionized water and 0.04g of ammonium persulfate are dissolved at room temperature to obtain an ammonium persulfate aqueous solution.
Step 2, adding 1/3 initiator aqueous solution, 1/3 pre-emulsion I and 1.5mL of distilled water into 0.04g of DNS-86 under the protection of nitrogen, placing at 60 ℃ and stirring at the rotating speed of 250rpm for 20 minutes, wherein the system is successfully initiated, and a blue phase appears. The temperature was gradually raised to 70 ℃ and the remaining 2/3 pre-emulsion I and 1/3 aqueous initiator solution were added dropwise slowly over 90 minutes. After the addition, the system was stirred for 2 hours. Slowly dropping the pre-emulsion II and the residual 1/3APS aqueous solution into the reaction system, wherein the dropping time is controlled to be 2 hours. After the addition, the system was stirred for 2 hours. And cooling to 40 ℃, and adjusting the pH of the system to 7-9 by using ammonia water.
the preparation method of the hybrid membrane of the invention preferably comprises the following steps:
Inorganic hydrophilic nano silicon dioxide with the grain diameter of 15 +/-5 nm is prepared into aqueous solution with the concentration of 10 percent by mass. And (3) uniformly mixing 0.3g of the obtained emulsion, 0.7g of deionized water, 0.03g of 12% aqueous curing agent in percentage by mass and 0.4g of 10% hydrophilic nano-silica aqueous solution by ultrasonic for 10-30 min. And (3) placing the emulsion into a spray pen, wherein the caliber of the spray pen is 2mm, the horizontal distance between the nozzle of the spray pen and the base material is 20cm, and the pressure is 200kPa, and spraying the emulsion onto the base material. And (3) curing the base material in an oven at the temperature of 80-100 ℃ for 1 hour to obtain the hybrid coating material.
the above preferred conditions can be combined arbitrarily to obtain preferred embodiments of the present invention without departing from the common general knowledge in the field.
The raw material 2- (perfluoro-1, 1-dimethyl-butyl) ethyl acrylate used in the invention is self-made, and other reagents and raw materials are commercially available.
the positive progress effects of the invention are as follows:
1. The fluorine-containing carbon atom number of the perfluoro side chain (Rf) of the water-based fluorine-containing polyacrylate copolymer is less than or equal to 6, the copolymer is easy to degrade and has no biotoxicity;
2. According to the water-based fluorine-containing polyacrylate copolymer, the fluorine-containing monomer is polymerized only on the shell layer, so that the water repellency and dirt repellency are guaranteed, and the usage amount of a fluorine-containing raw material is reduced;
3. the aqueous fluorine-containing polyacrylate copolymer does not change the characteristics of the base material;
4. The water-based fluorine-containing polyacrylate copolymer has the corrosion resistance of acid resistance and alkali resistance;
5. In the preparation method of the water-based fluorine-containing polyacrylate copolymer and the coating film thereof, water is used as a solvent, so that the water-based fluorine-containing polyacrylate copolymer is green, environment-friendly, economical and efficient.
Drawings
FIG. 1 is a particle size distribution diagram of core-shell latex particles of example 3, wherein 1 is a distribution curve of core emulsion particles and 2 is a distribution curve of shell emulsion particles.
FIG. 2 is a transmission electron micrograph of the core-shell latex particles of example 3, wherein (A) is an unstained core emulsion, (B) is a dyed core emulsion, (C) is an unstained core-shell emulsion, and (D) is a dyed core-shell emulsion.
FIG. 3 is a graph of the contact angle of the hybrid film on the cotton substrate in example 6 with water.
FIG. 4 is a graph of the contact angle of the hybrid membrane of example 7 with water, wherein A is the contact angle of the hybrid membrane with cotton cloth as the substrate material with water, B is the contact angle of the hybrid membrane with steel mesh (400 mesh) as the substrate material with water, C is the contact angle of the hybrid membrane with nylon mesh (400 mesh) as the substrate material with water, and D is the contact angle of the hybrid membrane with paper as the substrate material with water.
FIG. 5 is a scanning electron micrograph of the hybrid film in example 7, wherein A1 is an electron micrograph (with a scale of 50 μm) of the core-shell polymer emulsion coated on the glass substrate, A2 is an electron micrograph (with a scale of 10 μm) of the core-shell polymer emulsion coated on the glass substrate, A3 is an electron micrograph (with a scale of 50 μm) of the hybrid film solution coated on the glass substrate, and A4 is an electron micrograph (with a scale of 10 μm) of the hybrid film solution coated on the glass substrate;
B1 is an electron microscope picture (the scale is 400 μm) with cotton cloth as a base material, B2 is an electron microscope picture (the scale is 100 μm) with cotton cloth as a base material, B3 is an electron microscope picture (the scale is 400 μm) with cotton cloth as a base material coated with the hybrid membrane liquid, and B4 is an electron microscope picture (the scale is 100 μm) with cotton cloth as a base material coated with the hybrid membrane liquid;
C1 is an electron microscope picture (the scale is 400 μm) with a steel mesh as a base material, C2 is an electron microscope picture (the scale is 100 μm) with a steel mesh base material, C3 is an electron microscope picture (the scale is 400 μm) with a steel mesh as a base material coated with the hybrid membrane liquid, and C4 is an electron microscope picture (the scale is 100 μm) with a steel mesh as a base material coated with the hybrid membrane liquid;
D1 is an electron microscope picture (the scale is 400 μm) of the nylon mesh substrate, D2 is an electron microscope picture (the scale is 100 μm) of the nylon mesh substrate, D3 is an electron microscope picture (the scale is 400 μm) of the hybrid membrane liquid coated by the nylon mesh substrate, and D4 is an electron microscope picture (the scale is 100 μm) of the hybrid membrane liquid coated by the nylon mesh substrate;
E1 is an electron micrograph (scale: 400 μm) of paper as a substrate, E2 is an electron micrograph (scale: 100 μm) of paper as a substrate, E3 is an electron micrograph (scale: 400 μm) of paper as a substrate coated with the hybrid membrane solution, and E4 is an electron micrograph (scale: 100 μm) of paper as a substrate coated with the hybrid membrane solution.
FIG. 6 is a surface element distribution diagram of a hybrid film made of glass as a substrate in example 7, wherein 1 is an XPS curve of the hybrid film made of glass as a substrate in example 7, 2 is an XPS curve of a coating film made of glass as a substrate in example 3, and 3 is an XPS curve of a coating film made of glass as a substrate in comparative example 1.
FIG. 7 is a graph showing the stain resistance of the hybrid membrane prepared in example 7 using cotton cloth as a base material.
FIG. 8 is a graph of the corrosion resistance of the hybrid film of example 7 using cotton cloth as the substrate, wherein A is a graph of the contact angle between aqueous solutions with different pH values and the hybrid film, and B is a graph of the water-proof effect of the hybrid film on the aqueous solutions with pH values of 1, 7 and 14.
FIG. 9 is a graph showing the effect of oil-water separation of the hybrid membrane of example 7 in which a nylon mesh is used as a base material.
FIG. 10 is a graph showing the oil-water separation efficiency of the hybrid membrane based on the nylon mesh of example 7.
Detailed Description
the invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
EXAMPLE 12 preparation of (perfluoro 1, 1-dimethyl-butyl) ethyl acrylate
Synthesis and characterization of Compound 2
KF (7.08g,0.12mol,1.2equiv.) and Compound 1(30.00g,0.10mol,1.0equiv.) were added to a 300mL sealed tube in this order, ethyl bromoacetate (18.37g,0.11mol,1.1equiv.), tetrabutylammonium bromide (0.50g,1.5mmol,0.015equiv.) and 100mL anhydrous DMF were added to the tube, and the tube was sealed and placed in an 80 ℃ oil bath and stirred for reaction for 24 hours. After cooling to room temperature, the reaction system was poured into ether, and the ether solution was washed with deionized water and saturated brine in this order, dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography (EtOAc: petroleum ═ 1:20) to give 31.6g of a colorless liquid product, with a yield of 78%. LCMS (EI) m/z (%): 361.1(100),406.1(2.1).
H NMR(300MHz,CDCl3)δ4.30–4.06(m,2H),3.12(s,2H),1.24(t,J＝7.1Hz,3H).
F NMR(282MHz,CDCl3)δ-63.24(p,J＝10.8Hz,6F),-80.64(t,J＝13.3Hz,3F),-
106.99–-108.13(m,2F),-123.09(tt,J＝21.2,10.5Hz,2F)。
Synthesis and characterization of Compound 3
A250 mL three-necked flask was charged with 2.4g of LiAlH4(0.63mol), and after three times replacement with argon, 40mL of anhydrous ether was added, 21.4g of Compound 1(0.053mol) was dissolved in 60mL of anhydrous ether, and the resulting solution was added dropwise to the reaction flask through a constant pressure dropping funnel at 0 ℃. Stirring for 3h at room temperature, and heating to 40 ℃ for reaction for 4 h. After cooling to room temperature, the reaction was quenched with sodium sulfate decahydrate, filtered through celite, and the filtrate was washed with deionized water and saturated brine in this order, dried over anhydrous sodium sulfate, and filtered. Distillation under reduced pressure was carried out, and fractions of 70 to 73 ℃ (35mmHg) were collected to obtain 12.9g of a colorless liquid with a yield of 67%.
LCMS(EI)m/z(％):31.1(100),363.1(2.5)。
H NMR(300MHz,Acetone-d)δ4.39–4.16(m,1H),3.86(dd,J＝13.4,6.7Hz,2H),
2.51(t,J＝7.6Hz,2H)。
F NMR(282MHz,Acetone-d)δ-65.24(p,J＝11.4Hz,6F),-81.82(t,J＝13.8Hz,
3F),-108.79(tt,J＝24.6,12.3Hz,2F),-123.88–-124.77(m,2F)。
Synthesis and characterization of Compound 4
In a 50mL three-necked flask, 10.0mL of dichloromethane, 3.64g of compound 2(0.010mol,1.0equiv.) and 1.66mL of triethylamine (0.012mol,1.2equiv.) were sequentially added under the protection of argon, the temperature was reduced to 0 ℃, 0.87mL of acryloyl chloride (0.011mol,1.1equiv.) was slowly added with stirring, and the mixture was reacted at room temperature for 8 hours. Under the ice-water bath, 5% sulfuric acid aqueous solution is added to quench the reaction, saturated ammonium chloride is added to wash the organic phase, anhydrous sodium sulfate is dried, filtered, dried, concentrated, and separated and purified by column chromatography (EtOAc: petroleum ═ 1:20), so that 3.46g of 2- (perfluoro 1, 1-dimethyl-butyl) ethyl acrylate serving as a colorless liquid product is obtained, and the yield is 83%.
LCMS(EI)m/z(％):55(100),249(7.74),418(3.94)。
H NMR(400MHz,CDCl)δ6.44(d,J＝17.3Hz,1H),6.11(dd,J＝17.3,10.5Hz,1H),
5.88(d,J＝10.4Hz,1H),4.43(t,J＝7.7Hz,2H),2.57(t,J＝7.7Hz,2H)。
F NMR(376MHz,CDCl)δ-64.05(p,J＝11.3Hz,6F),-80.24(t,J＝13.6Hz,3F),-
107.86(tt,J＝24.4,12.2Hz,2F),-123.01–-123.82(m,2F)。
example 2
(1) 1.5g of deionized water, 0.328g of methyl methacrylate, 1.232g of butyl methacrylate and 1. 860.04g of emulsifier are sequentially added into a 10mL reaction bottle, and the mixture is vigorously stirred at room temperature for 0.5 hour to form a pre-emulsion I; 1.5g of deionized water, 0.396g of methyl methacrylate, 0.528g of butyl methacrylate, 0.5g of octadecyl acrylate, 0.035g of hydroxyethyl acrylate, 0.2g of 2- (perfluoro 1, 1-dimethyl-butyl) ethyl acrylate and 0.5g of emulsifier DNS-860.04g are added in sequence into a 10mL reaction bottle, and stirred vigorously at room temperature for 0.5 hour to form pre-emulsion II. 2.7g of deionized water and 0.04g of ammonium persulfate were sequentially added to a 10mL reaction flask and dissolved at room temperature.
(2) 0.04g of DNS-86 is added into a 20mL three-necked bottle, 1/3 aqueous initiator solution, 1/3 pre-emulsion I and 1.5mL of distilled water are added under the protection of nitrogen, and the mixture is stirred at the rotating speed of 250rpm for 20 minutes at the temperature of 50 ℃, so that the system is successfully initiated, and a blue phase appears. The temperature was gradually raised to 70 ℃ and the remaining 2/3 pre-emulsion I and 1/3 aqueous initiator solution were added dropwise slowly over 90 minutes. After the addition, the system was stirred for 2 hours. Slowly dropping the pre-emulsion II and the residual 1/3APS aqueous solution into the reaction system, wherein the dropping time is controlled to be 2 hours. After the addition, the system was stirred for 2 hours. Then, the temperature is reduced to 40 ℃, and a proper amount of ammonia water is added to adjust the pH value of the system to 7-9. The yield was 92%, and the solid content was 27.3%.
example 3
(1) 1.5g of deionized water, 0.328g of methyl methacrylate, 1.232g of butyl methacrylate and 1. 860.04g of emulsifier are sequentially added into a 10mL reaction bottle, and the mixture is vigorously stirred at room temperature for 0.5 hour to form a pre-emulsion I; 1.5g of deionized water, 0.396g of methyl methacrylate, 0.528g of butyl methacrylate, 0.5g of octadecyl acrylate, 0.035g of hydroxyethyl acrylate, 0.4g of 2- (perfluoro 1, 1-dimethyl-butyl) ethyl acrylate and 0.5g of emulsifier DNS-860.04g are added in sequence into a 10mL reaction bottle, and stirred vigorously at room temperature for 0.5 hour to form pre-emulsion II. 4g of deionized water and 0.04g of ammonium persulfate are sequentially added into a 10mL reaction bottle and dissolved at room temperature.
(2) 0.04g of DNS-86 is added into a 20mL three-necked bottle, 1/3 aqueous initiator solution, 1/3 pre-emulsion I and 1.5mL of distilled water are added under the protection of nitrogen, and the mixture is stirred at the rotating speed of 250rpm for 20 minutes at the temperature of 60 ℃, so that the system is successfully initiated, and a blue phase appears. The temperature was gradually raised to 80 ℃ and the remaining 2/3 pre-emulsion I and 1/3 aqueous initiator solution were added dropwise slowly over 90 minutes. After the addition, the system was stirred for 6 hours. Slowly dropping the pre-emulsion II and the residual 1/3APS aqueous solution into the reaction system, wherein the dropping time is controlled to be 2 hours. After the addition, the system was stirred for 6 hours. Then, the temperature is reduced to 40 ℃, and a proper amount of ammonia water is added to adjust the pH value of the system to 7-9. The yield was 90% and the solids content was 31.1%.
Example 4
(1) 1.5g of deionized water, 0.328g of methyl methacrylate, 1.232g of butyl methacrylate and 1. 860.04g of emulsifier are sequentially added into a 10mL reaction bottle, and the mixture is vigorously stirred at room temperature for 0.5 hour to form a pre-emulsion I; 1.5g of deionized water, 0.396g of methyl methacrylate, 0.528g of butyl methacrylate, 0.5g of octadecyl acrylate, 0.035g of hydroxyethyl acrylate, 0.6g of 2- (perfluoro 1, 1-dimethyl-butyl) ethyl acrylate and 0.5g of emulsifier DNS-860.04g are added in sequence into a 10mL reaction bottle, and stirred vigorously at room temperature for 0.5 hour to form pre-emulsion II. 4g of deionized water and 0.04g of ammonium persulfate are sequentially added into a 10mL reaction bottle and dissolved at room temperature.
(2) 0.04g of DNS-86 is added into a 20mL three-necked bottle, 1/3 aqueous initiator solution, 1/3 pre-emulsion I and 1.5mL of distilled water are added under the protection of nitrogen, and the mixture is stirred at the rotating speed of 250rpm for 20 minutes at the temperature of 60 ℃, so that the system is successfully initiated, and a blue phase appears. The temperature was gradually raised to 80 ℃ and the remaining 2/3 pre-emulsion I and 1/3 aqueous initiator solution were added dropwise slowly over 90 minutes. After the addition, the system was stirred for 6 hours. Slowly dropping the pre-emulsion II and the residual 1/3APS aqueous solution into the reaction system, wherein the dropping time is controlled to be 2 hours. After the addition, the system was stirred for 6 hours. Then, the temperature is reduced to 40 ℃, and a proper amount of ammonia water is added to adjust the pH value of the system to 7-9. The yield was 93%, and the solid content was 30.5%.
Example 5
(1) 1.5g of deionized water, 0.328g of methyl methacrylate, 1.232g of butyl methacrylate and 1. 860.04g of emulsifier are sequentially added into a 10mL reaction bottle, and the mixture is vigorously stirred at room temperature for 0.5 hour to form a pre-emulsion I; 1.5g of deionized water, 0.396g of methyl methacrylate, 0.528g of butyl methacrylate, 0.5g of octadecyl acrylate, 0.035g of hydroxyethyl acrylate, 0.8g of 2- (perfluoro 1, 1-dimethyl-butyl) ethyl acrylate and 0.8g of emulsifier DNS-860.04g are added in sequence into a 10mL reaction bottle, and stirred vigorously at room temperature for 0.5 hour to form pre-emulsion II. 4g of deionized water and 0.04g of ammonium persulfate are sequentially added into a 10mL reaction bottle and dissolved at room temperature.
(2) 0.04g of DNS-86 is added into a 20mL three-necked bottle, 1/3 aqueous initiator solution, 1/3 pre-emulsion I and 1.5mL of distilled water are added under the protection of nitrogen, and the mixture is stirred at the rotating speed of 250rpm for 20 minutes at the temperature of 60 ℃, so that the system is successfully initiated, and a blue phase appears. The temperature was gradually raised to 80 ℃ and the remaining 2/3 pre-emulsion I and 1/3 aqueous initiator solution were added dropwise slowly over 90 minutes. After the addition, the system was stirred for 6 hours. Slowly dropping the pre-emulsion II and the residual 1/3APS aqueous solution into the reaction system, wherein the dropping time is controlled to be 2 hours. After the addition, the system was stirred for 6 hours. Then, the temperature is reduced to 40 ℃, and a proper amount of ammonia water is added to adjust the pH value of the system to 7-9. The yield was 89%, and the solid content was 32.8%.
example 6
Inorganic hydrophilic silicon dioxide with the grain diameter of 15 +/-5 nm is prepared into aqueous solution with the concentration of 10 percent by mass. 0.3g of the emulsion obtained in the example 2, 0.7g of deionized water, 0.03g of 12% aqueous isocyanate and 0.4g of 10% inorganic hydrophilic silica aqueous solution are sequentially added into a container of 5mL, and the mixture is uniformly mixed by ultrasonic treatment for 10-30 min. Placing the mixed emulsion in a spray pen with an aperture of 2mm, a horizontal distance of 20cm between the nozzle and the cotton cloth substrate material, and a pressure of 200 kPa. After the spraying is finished, the base material is placed in an oven with the temperature of 80-100 ℃ for curing for 1 hour to obtain the cotton cloth base material hybrid film material.
Example 7
Inorganic hydrophilic silicon dioxide with the grain diameter of 15 +/-5 nm is prepared into aqueous solution with the concentration of 10 percent by mass. 0.3g of the emulsion obtained in the step 3, 0.7g of deionized water, 0.03g of 12 mass percent aqueous curing agent and 0.4g of 10 mass percent inorganic hydrophilic silicon dioxide aqueous solution are sequentially added into a container of 5mL, and the mixture is uniformly mixed by ultrasonic treatment for 10-30 min. Placing the mixed emulsion into a spray pen, wherein the caliber of the spray pen is 2mm, the horizontal distance between the orifice of the spray pen and cotton cloth, a steel mesh (400 meshes), a nylon mesh (400 meshes) and paper serving as base materials is 20cm, and the pressure is 200 kPa. After the spraying is finished, the base material is placed in an oven with the temperature of 80-100 ℃ for curing for 1 hour, and the hybrid membrane material taking cotton cloth, steel mesh (400 meshes), nylon mesh (400 meshes) and paper as base materials is obtained.
example 8
Inorganic hydrophilic titanium dioxide with the particle size of 20nm is prepared into aqueous solution with the concentration of 10 percent by mass. 0.3g of the emulsion obtained in the example 4, 0.7g of deionized water, 0.03g of 12 mass percent aqueous curing agent and 0.4g of 10 mass percent inorganic hydrophilic titanium dioxide aqueous solution are sequentially added into a container with 5mL, and the mixture is uniformly mixed by ultrasonic treatment for 10-30 min. Placing the mixed emulsion in a spray pen, wherein the caliber of the spray pen is 2mm, the horizontal distance between the nozzle of the spray pen and the substrate material is 30cm, and the pressure is 200 kPa. And after the spraying is finished, curing the substrate material in an oven at the temperature of 80-100 ℃ for 1 hour to obtain the hybrid membrane material.
example 9
The emulsion obtained in example 5 was used to prepare a hybrid membrane material with reference to example 7.
Example 10 characterization of particle size of fluorine-containing polyacrylate emulsion
Sample preparation: fluorine-containing polyacrylate emulsion obtained in example 3
The test method comprises the following steps: diluting the emulsion ten times, and then taking a certain amount of diluted sample to test in a laser particle analyzer.
In FIG. 1,1 is a distribution curve of core emulsion particles, and 2 is a distribution curve of shell emulsion particles. As can be seen from FIG. 1, the core emulsion particles and the core-shell emulsion particles are uniformly distributed in the emulsion in a spherical shape, and the average particle size of the core emulsion particles is 90.5 nm. After the shell layer pre-emulsion is added into the core emulsion, the fluorine-containing monomer and other monomers in the shell emulsion are successfully polymerized on the particles in the core emulsion to form a core-shell structure, and the particle size of the shell layer is increased to 102.2 nm.
example 11 characterization of the core-shell Structure of a fluorinated polyacrylate emulsion
Sample preparation: fluorine-containing polyacrylate emulsion obtained in example 3
The test method comprises the following steps: and diluting the emulsion ten times, and taking a certain amount of diluted sample to perform transmission electron microscope test in a copper mesh.
In FIG. 2, (A) is an unstained core emulsion, (B) is a dyed core emulsion, (C) is an unstained core-shell emulsion, and (D) is a dyed core-shell emulsion. As can be seen from FIG. 2, the particle size was about 100nm as seen from the transmission electron micrograph, which is consistent with the results of the laser particle size analyzer. In addition, due to the difference in the permeability of electrons between the fluorine-containing shell phase and the non-fluorine-containing core phase, the core-shell structure can be clearly observed after the core-shell emulsion sample is dyed with 1% by mass of phosphotungstic acid, as shown in fig. 2(D), in which the darker area is the core phase and the lighter area is the fluorine-containing shell phase. The core-shell type copolymer emulsion prepared by the invention is proved to have a core-shell structure, wherein the shell layer is fluorine-containing polymer emulsion.
example 12
The hybrid membrane prepared from the emulsion prepared in example 2 and the cotton cloth prepared in example 2 is prepared by using the hybrid membrane prepared in example 6 as a base material, wherein the fluorine-containing acrylate monomer accounts for 6.2% of the total mass of the monomers.
The hybrid film prepared in example 6 was contacted with water, and the contact angle of the hybrid film with water was measured by a contact angle measuring instrument, and the contact angle with water after coating was more than 150 °, which was shown to be super-hydrophobic, as shown in fig. 3, and the finished cotton cloth had water repellency.
Comparative reference 1(CN105440201A) discloses a copolymer emulsion having a core-shell structure; comparative reference 2 (Zhang Qing, Zhanxianli, Chenfeng autumn. Synthesis and characterization of a fluoroacrylate-vinyl acetate terpolymer miniemulsion [ J ]. Proc. college of chemistry, 2005, 26(3): 575-. In the two references, the influence of the usage of the fluorine-containing acrylate monomer on the water and oil repellency of the latex film is examined, and the specific results are shown in table 1.
when the contact angle is used as an index for evaluating water and oil repellency, as can be seen from table 1, the core-shell structure copolymer emulsion meets biodegradation, namely the number of carbon and fluorine atoms in the fluorine-containing acrylate monomer is 6, the mass percentage of the fluorine-containing acrylate monomer to the total monomer mass is 6.2%, which is lower than 8.5% in comparative reference 1(CN 105440201A); the contact angle of the coating film prepared by the water repellent agent with water is more than 150 degrees, and is higher than the contact angle with water of 124.6 degrees in a comparative reference 1(CN105440201A), the super-hydrophobicity is shown, and the water repellent effect of the water repellent agent is superior to that of the prior art.
TABLE 1 comparison of emulsions of core-shell copolymers of the present application with emulsions of prior art copolymers
Example 13
The cotton cloth, the steel mesh (400 mesh), the nylon mesh (400 mesh) and the hybrid film using the paper as the base material obtained in example 7 were respectively contacted with water, the contact angle of the coating film with water was measured by a contact angle measuring instrument, and the contact angle is shown in fig. 4, fig. 4A is the contact angle of the hybrid film using the cotton cloth as the base material with water, fig. 4B is the contact angle of the hybrid film using the steel mesh (400 mesh) as the base material with water, fig. 4C is the contact angle of the hybrid film using the nylon mesh (400 mesh) as the base material with water, fig. 4D is the contact angle of the hybrid film using the paper as the base material with water, and the contact angles of the four base materials with water after coating are all larger than 150 degrees, and the four base materials have super-hydrophobic. Therefore, the four materials have water repellency after being coated, and the polymer emulsion has wide substrate applicability when preparing a hybrid membrane.
Example 14
The scanning electron microscope scans the glass, cotton cloth, steel mesh, nylon mesh, paper substrate, and the base material after the hybrid film obtained in example 7, respectively. In fig. 5:
a1 is an electron microscope picture (scale is 50 μm) of coating the core-shell polymer emulsion with glass as a base material, A2 is an electron microscope picture (scale is 10 μm) of coating the core-shell polymer emulsion with glass as a base material, A3 is an electron microscope picture (scale is 50 μm) of coating the hybrid membrane liquid with glass as a base material, and A4 is an electron microscope picture (scale is 10 μm) of coating the hybrid membrane liquid with glass as a base material;
B1 is an electron microscope picture (the scale is 400 μm) with cotton cloth as a base material, B2 is an electron microscope picture (the scale is 100 μm) with cotton cloth as a base material, B3 is an electron microscope picture (the scale is 400 μm) with cotton cloth as a base material coated with the hybrid membrane liquid, and B4 is an electron microscope picture (the scale is 100 μm) with cotton cloth as a base material coated with the hybrid membrane liquid;
C1 is an electron microscope picture (the scale is 400 μm) with a steel mesh as a base material, C2 is an electron microscope picture (the scale is 100 μm) with a steel mesh base material, C3 is an electron microscope picture (the scale is 400 μm) with a steel mesh as a base material coated with the hybrid membrane liquid, and C4 is an electron microscope picture (the scale is 100 μm) with a steel mesh as a base material coated with the hybrid membrane liquid;
d1 is an electron microscope picture (the scale is 400 μm) of the nylon mesh substrate, D2 is an electron microscope picture (the scale is 100 μm) of the nylon mesh substrate, D3 is an electron microscope picture (the scale is 400 μm) of the hybrid membrane liquid coated by the nylon mesh substrate, and D4 is an electron microscope picture (the scale is 100 μm) of the hybrid membrane liquid coated by the nylon mesh substrate;
E1 is an electron micrograph (scale: 400 μm) of paper as a substrate, E2 is an electron micrograph (scale: 100 μm) of paper as a substrate, E3 is an electron micrograph (scale: 400 μm) of paper as a substrate coated with the hybrid membrane solution, and E4 is an electron micrograph (scale: 100 μm) of paper as a substrate coated with the hybrid membrane solution.
As can be seen from fig. 5, the surface of the base material is very smooth before being coated with the film, and the surface of the material has a protruding structure similar to a hill after being coated with the film. From the graphs A3 and A4, it can be clearly seen that the glass surface covered by the coating film has a micro-nano multi-scale protruding surface which can endow the glass surface with super-hydrophobic performance. Further, as is clear from fig. B, C and D, the coating material does not block the micropores of the material itself, i.e., does not change some of the properties of the material itself, such as air permeability, after the soft material containing micropores is coated.
example 15
The glass-based hybrid film obtained in example 7, the emulsions obtained in example 3 and comparative example 1 were each independently coated on a glass substrate. The elemental analysis of the coating film surface shows the specific elemental contents in Table 2. As can be seen from Table 2, the measured value of the fluorine element on the surface of the hybrid membrane prepared by example 7 and using glass as a substrate is 20.6%, while the theoretical value of the fluorine element in the emulsion prepared by example 3 is 5.6%, which indicates that the fluorine-containing segment in the polymer is more prone to gather towards the surface during the film forming process, thereby reducing the surface free energy of the membrane surface and achieving better hydrophobic effect. The hybrid film prepared in example 7, which uses glass as a substrate and contains 0.12% of nano-silica particles, has a fluorine content of 0.8% and a silicon content of 12.4% on the surface of the film, which is mainly due to the fact that the detection depth of X-ray photoelectron spectroscopy (XPS) is usually 2-10nm, and the particle size of the added nano-silica is 15 + -5 nm, which indicates that the nano-silica is distributed on the surface of the film uniformly, and therefore, the signal of the fluorine element is difficult to detect.
TABLE 2 elemental composition of the surface of the coating film
In FIG. 6, 1 is the XPS curve for the hybrid film with glass as the substrate obtained in example 7, 2 is the XPS curve for the coating film with glass as the substrate obtained from the emulsion of example 3, and 3 is the XPS curve for the coating film with glass as the substrate obtained from the emulsion of comparative example 1. As shown in fig. 6, from the XPS curve of the coating film, characteristic signal peaks of F1s, O1s, C1s and Si2p appeared at 688, 529, 283 and 100eV, respectively; it can also be seen from FIG. 6 that the XPS curve of the coating film prepared from the emulsion prepared in comparative example 1 shows the characteristic signal of Si2p for elemental silicon, which is due to the silicon atoms on the glass slide of the substrate material, and this phenomenon is mainly due to the non-uniformity of the coating film caused by the dewetting phenomenon. This phenomenon was not observed in the XPS curve of the glass-based hybrid film obtained in example 7, indicating that the emulsion of the fluorocopolymer of the invention can improve the uniformity of film formation.
Example 16
different liquids such as water, fruit juice, milk, wine, ink and coffee are dropped on the hybrid film with cotton cloth as the base material obtained in example 7, and as can be seen from fig. 7, the different liquids are gathered into spherical liquid drops on the surface and cannot permeate into the cotton cloth, which shows that the cotton cloth finished by the emulsion of the core-shell copolymer has the stain repellency.
Example 17
When aqueous solutions with different pH values were contacted with the cotton cloth-based hybrid film obtained in example 7, as shown in FIG. 8A, the contact angles of the cotton cloth after finishing were respectively contacted with the acidic solution and the alkaline solution, which were both greater than 150 degrees, and the aqueous solutions showed the form of droplets when the pH values were 1, 7, and 14, respectively, as shown in FIG. 8B. Therefore, the cotton cloth finished by the emulsion of the core-shell copolymer has water repellency, and also has acid-proof and alkali-proof anticorrosion performances.
Example 18
Water and n-hexadecane were respectively dropped on the nylon mesh coated with the hybrid membrane obtained in example 7, the nylon mesh material showed a super-hydrophobic state, but hexadecane could instantly permeate through the nylon mesh. By utilizing the special property of the hybrid membrane in the nylon net, the mixed solution of water and dichloromethane is poured into a separation device provided with the nylon net coated with the hybrid membrane at the same time, and the oil-water separation function of the nylon net is explored by utilizing gravity driving. The results are shown in fig. 9, where for ease of differentiation the oil was stained red with sudan II and the water blue with methylene blue. As can be seen from FIG. 9, the methylene chloride rapidly permeates through the nylon net under the driving of gravity, and the water is always above the nylon net, which shows that the coated nylon net has the function of oil-water separation. As shown in fig. 10, the separation efficiency was measured by the weighing method to be about 98%, and the efficiency was not decreased by repeating 20 times. At present, the application firstly utilizes the fluoroacrylate polymer hybrid membrane to realize the function of oil-water separation.
comparative example 1
(1) 1.5g of deionized water, 0.328g of methyl methacrylate, 1.232g of butyl methacrylate and 1. 860.04g of emulsifier are sequentially added into a 10mL reaction bottle, and the mixture is vigorously stirred at room temperature for 0.5 hour to form a pre-emulsion I; 1.5g of deionized water, 0.396g of methyl methacrylate, 0.528g of butyl methacrylate, 0.5g of octadecyl acrylate, 0.035g of hydroxyethyl acrylate and 0.5g of emulsifier DNS-860.04g are added in sequence into a 10mL reaction bottle, and the mixture is vigorously stirred at room temperature for 0.5 hour to form a pre-emulsion II. 4g of deionized water and 0.04g of ammonium persulfate are sequentially added into a 10mL reaction bottle and dissolved at room temperature.
(2) 0.04g of DNS-86 is added into a 20mL three-necked bottle, 1/3 aqueous initiator solution, 1/3 pre-emulsion I and 1.5mL of distilled water are added under the protection of nitrogen, and the mixture is stirred at the rotating speed of 250rpm for 20 minutes at the temperature of 60 ℃, so that the system is successfully initiated, and a blue phase appears. The temperature was gradually raised to 80 ℃ and the remaining 2/3 pre-emulsion I and 1/3 aqueous initiator solution were added dropwise slowly over 90 minutes. After the addition, the system was stirred for 6 hours. Slowly dropping the pre-emulsion II and the residual 1/3APS aqueous solution into the reaction system, wherein the dropping time is controlled to be 2 hours. After the addition, the system was stirred for 6 hours. Then, the temperature is reduced to 40 ℃, and a proper amount of ammonia water is added to adjust the pH value of the system to 7-9. The yield was 97% and the solid content was 30.8%.
Claims (10)
1. The core-shell copolymer is characterized in that the core-shell copolymer takes the polymerization of alkyl acrylate monomers as a core and takes the copolymerization of the alkyl acrylate monomers, fluorine-containing acrylate monomers and hydroxyethyl acrylate monomers as a shell;
Wherein the mass percent of the alkyl acrylate monomer in the total monomer is 78.13-92.70%, the mass percent of the fluorine-containing acrylate monomer in the total monomer is 6.21-20.94%, and the mass percent of the hydroxyethyl acrylate monomer in the total monomer is 0.91-1.09%;
The structure of the alkyl acrylate monomer is shown as a formula 1, the structure of the fluorine-containing acrylate monomer is shown as a formula 2, and the structure of the hydroxyethyl acrylate monomer is shown as a formula 3:
R1 is C1-C18 alkyl; r2 and R3 are each independently H or CH 3; rf is CnF2n +1CH2CH2-, and n is any integer from 2 to 6.
2. The core-shell copolymer according to claim 1, wherein the mass percentage of the alkyl acrylate monomer to the total monomer mass is 78.13 to 87.27%, the mass percentage of the fluorine-containing acrylate monomer to the total monomer mass is 11.69 to 20.94%, and the mass percentage of the hydroxyethyl acrylate monomer to the total monomer mass is 0.91 to 1.02%;
And/or, CnF2n +1 in said Rf is a linear structure or a branched structure; preferably, CnF2n +1 in Rf is a branched structure, n is 5 or 6;
And/or the fluorine-containing acrylate monomer is one or more of 2- (perfluorohexyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl acrylate and 2- (perfluoro 1, 1-dimethyl-butyl) ethyl acrylate, preferably 2- (perfluorohexyl) ethyl acrylate and/or 2- (perfluoro 1, 1-dimethyl-butyl) ethyl acrylate;
And/or the alkyl acrylate monomer is one or more of methyl methacrylate, methyl acrylate, butyl methacrylate, butyl acrylate, isooctyl methacrylate, isooctyl acrylate, lauryl methacrylate, lauryl acrylate, stearyl methacrylate and stearyl acrylate; preferably one or more of methyl methacrylate, butyl methacrylate and stearyl acrylate.
3. A method for preparing a core-shell copolymer, comprising the steps of:
Step 1, under the condition of an initiator, mixing an alkyl acrylate monomer, an emulsifier and a solvent to obtain a pre-emulsion I, and carrying out polymerization reaction to obtain a core-shell copolymer core emulsion;
Step 2, under the condition of an initiator, mixing an alkyl acrylate monomer, a fluorine-containing acrylate monomer, a hydroxyethyl acrylate monomer, an emulsifier and a solvent to obtain a pre-emulsion II, and carrying out polymerization reaction on the pre-emulsion II and the core-shell type copolymer core-shell emulsion obtained in the step 1 to obtain a core-shell type copolymer emulsion;
In the step 1, the mass percentage of the mass of the alkyl acrylate monomer to the total monomer mass is 40.84-48.46%;
In the step 2, the mass percentage of the mass of the alkyl acrylate monomer to the total monomer mass is 37.28-44.23%; the mass percentage of the mass of the fluorine-containing acrylate monomer to the total mass of the monomers is 6.21-20.95%; the mass percentage of the hydroxyethyl acrylate monomer to the total monomer is 0.92-1.08%;
the species of the alkyl acrylate monomer is as defined in claim 1 or 2; the kind of the fluorine-containing acrylate monomer is as defined in claim 1 or 2; the hydroxyethyl acrylate monomer is defined in claim 1.
4. The preparation method according to claim 3, wherein the step 1 comprises mixing the alkyl acrylate monomer, the emulsifier and the solvent under the protection of inert gas to obtain a pre-emulsion I, and polymerizing the alkyl acrylate monomer under the protection of the initiator; preferably, adding the pre-emulsion I into the reaction liquid in batches for polymerization; preferably, 1/3 the pre-emulsion I is polymerized, and 2/3 the pre-emulsion I is dripped into the reaction liquid to be polymerized after the reaction liquid is in a blue phase;
And/or, the step 2 comprises mixing the alkyl acrylate monomer, the fluorine-containing acrylate monomer, the hydroxyethyl acrylate monomer, an emulsifier and a solvent under the protection of inert gas to obtain a pre-emulsion II, and carrying out polymerization reaction on the pre-emulsion II and the core emulsion of the core-shell type copolymer obtained in the step 1 under the protection of an initiator; preferably, an initiator and the pre-emulsion II are dropwise added to the core structure emulsion obtained in the step 1 for polymerization; more preferably, after the step 2 is finished, the method comprises the step of adjusting the pH of the emulsion of the core-shell copolymer to 7-9.
5. The method according to claim 3, wherein in step 1, the mass percentage of the mass of the alkyl acrylate monomer to the total mass of the monomers is 40.84 to 45.46%;
In the step 2, the mass percentage of the mass of the alkyl acrylate monomer to the mass of the total monomer is 37.28-41.64%; the mass percentage of the mass of the fluorine-containing acrylate monomer to the mass of the total monomer is 11.69-20.94%; the mass percentage of the hydroxyethyl acrylate monomer to the total monomer is 0.92-1.02%;
and/or the solvent is deionized water;
And/or the ratio of the total mass of the solvent to the total mass of the monomers is 1 to 5, preferably 1.8 to 2.3, more preferably 2.0 to 2.3;
and/or the emulsifier is a composite emulsifier or a reactive single emulsifier; preferably a reactive single emulsifier; more preferably 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ammonium ethersulfate;
and/or the mass percentage of the total mass of the emulsifier to the total monomer mass is 2.1-2.4%, preferably 2.1-2.3%;
And/or the initiator is one or more of ammonium persulfate, potassium persulfate and sodium persulfate; preferably ammonium persulfate;
And/or the mass percentage of the total mass of the initiator to the total monomer mass is 0.62-2.09%, preferably 1.17-2.09%;
and/or the concentration of the initiator is 1.0-1.5% by mass;
And/or, in the step 1, the temperature for initiating the polymerization reaction is 40-80 ℃, preferably 50-60 ℃;
And/or, in the step 1, the time for initiating the polymerization reaction is 2-6 hours, preferably 6 hours;
And/or in the step 2, the temperature of the polymerization reaction is 70-80 ℃;
and/or in the step 2, the time of the polymerization reaction is 2-6 hours.
6. A core-shell type copolymer obtained by the production method according to any one of claims 3 to 5.
7. use of the core-shell copolymer according to any one of claims 1,2 and 6 for water and soil repellency.
8. a water and soil repellent finish comprising the core-shell type copolymer according to any one of claims 1,2 and 6.
9. a hybrid membrane comprising the core-shell copolymer of any one of claims 1,2 and 6, an inorganic hydrophilic nanomaterial, and an aqueous curing agent component.
10. A method for preparing the hybrid membrane according to claim 9, comprising the steps of:
coating the hybrid membrane liquid on a base material, and curing the base material after membrane formation; wherein, the hybrid membrane liquid is the core-shell type copolymer, the inorganic hydrophilic nano material, the water-based curing agent and the deionized water which are contained in any one of the claims 1,2 and 6; preferably, 10% by mass of an aqueous solution of inorganic hydrophilic nanomaterial is mixed with the core-shell copolymer according to any one of claims 1,2 and 6, the aqueous curing agent and deionized water.
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