CN113105588A - Method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose - Google Patents
Method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose Download PDFInfo
- Publication number
- CN113105588A CN113105588A CN202110471716.XA CN202110471716A CN113105588A CN 113105588 A CN113105588 A CN 113105588A CN 202110471716 A CN202110471716 A CN 202110471716A CN 113105588 A CN113105588 A CN 113105588A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- acrylate
- monomer
- preparing
- nanocellulose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 69
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 67
- 239000011737 fluorine Substances 0.000 title claims abstract description 67
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 56
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229920002678 cellulose Polymers 0.000 claims abstract description 19
- 239000001913 cellulose Substances 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims description 54
- 239000003999 initiator Substances 0.000 claims description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 22
- 125000000129 anionic group Chemical group 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 230000001804 emulsifying effect Effects 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 9
- 238000010907 mechanical stirring Methods 0.000 claims description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical group CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000002572 peristaltic effect Effects 0.000 claims description 6
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 3
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 description 18
- 238000007720 emulsion polymerization reaction Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 7
- 229920001400 block copolymer Polymers 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 239000004816 latex Substances 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 5
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 4
- 229920000359 diblock copolymer Polymers 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229920000469 amphiphilic block copolymer Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 206010063385 Intellectualisation Diseases 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a method for preparing fluorine-containing polyacrylate emulsion by utilizing light-responsive nano-cellulose. The invention discloses a method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose, which solves the problems that the performance of a product is reduced and the environment is polluted by a surfactant in the prior art.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose.
Background
The fluorine-containing polyacrylate not only has excellent film forming property, caking property and flexibility of polyacrylate, but also has excellent hydrophobicity and good chemical, thermal and photochemical stability of the fluorine-containing polymer. In recent years, fluorine-containing polyacrylate polymers have been widely used for biomaterials, microelectronics, and surface coatings for textiles, paper and leather, etc. due to their unique properties.
The emulsion polymerization technology is a main method for preparing the fluorine-containing polyacrylate due to the characteristics of mild conditions, simple and easily obtained raw materials, water as a reaction medium, environmental protection, safety and the like. However, the small molecule emulsifiers used in conventional emulsion polymerization easily migrate to the interface, negatively affecting the performance and environment of the material.
Pickering emulsion polymerization is the preparation of an emulsion using solid particles instead of traditional emulsifiers. Compared with the emulsion stabilized by the surfactant, the emulsion prepared by Pickering emulsion polymerization is thermodynamically more stable, is not easy to agglomerate and is easier to process. Accordingly, Pickering emulsion polymerization has attracted considerable attention in recent years. However, the Pickering stabilizers most used in Pickering emulsion polymerization are inorganic nanoparticles. With the concern of people on natural, green, rich and sustainable systems, the biodegradable Pickering stabilizer developed and obtained from renewable resources attracts the favor of the majority of researchers.
Nanocellulose (CNC) is an abundant natural nanomaterial with characteristics of low density, aspect ratio, hydrophilicity, high mechanical properties, environmental sustainability, and low cost, and is widely recognized as an ideal biomaterial. At present, many researches on CNC-stabilized Pickering emulsion polymerization are reported, however, there is no research on preparation of a fluorine-containing polyacrylate emulsion by Pickering emulsion polymerization with photoresponsive CNC as Pickering stabilizer.
Disclosure of Invention
The invention aims to provide a method for preparing fluorine-containing polyacrylate emulsion by utilizing light-responsive nano-cellulose, which solves the problems that the performance of a product is reduced and the environment is polluted by a surfactant in the prior art.
The technical scheme adopted by the invention is a method for preparing fluorine-containing polyacrylate emulsion by utilizing light-responsive nano-cellulose, which is implemented according to the following steps:
step 1, preparing photoresponsive nanocellulose aqueous dispersion
Weighing a proper amount of anionic photoresponsive nanocellulose powder and an alkaline aqueous solution, mixing, and forming a dispersion under the action of an ultrasonic cell crusher;
step 2, preparing mixed monomer and initiator aqueous solution
Weighing a proper amount of acrylate first monomer, acrylate second monomer and fluorine-containing acrylate monomer, and mixing by a high-shear emulsifying machine to obtain a mixed monomer; uniformly mixing a proper amount of initiator and deionized water to obtain an initiator aqueous solution for later use;
step 3, preparing Pickering emulsion
Adding the mixed monomer into the dispersion, and mixing and emulsifying in an ultrasonic cell crusher to obtain Pickering emulsion for later use;
and 4, adding the Pickering emulsion into the reactor, adding an initiator aqueous solution into the reactor under the conditions of mechanical stirring and argon protection, and discharging cold water after the reaction is finished to obtain the fluorine-containing polyacrylate emulsion.
The invention is also characterized in that:
in the step 1, the mass ratio of the anionic photoresponsive nano cellulose powder to the alkaline aqueous solution is 3-18: 3250-3900; the alkaline aqueous solution is sodium hydroxide solution or potassium hydroxide solution.
In the step 1, the power of the ultrasonic cell crusher is 5-50%, and the dispersion time is 5-20 min.
In the step 2, the mass ratio of the acrylate first monomer to the acrylate second monomer to the fluorine-containing acrylate monomer is 3-63: 27-81: 1-18;
the acrylate first monomer is methyl acrylate or methyl methacrylate; the acrylate second monomer is butyl methacrylate or butyl acrylate; the fluorine-containing acrylate monomer is hexafluorobutyl methacrylate, hexafluorobutyl acrylate, 2,2, 2-trifluoroethyl methacrylate, dodecafluoroheptyl methacrylate or dodecafluoroheptyl acrylate.
In the step 2, the concentration of the initiator is 0.5-4 wt%, and the mass of the initiator is 0.6-2.0% of that of the mixed monomer;
the initiator is ammonium persulfate, potassium persulfate or sodium persulfate.
In the step 2, the rotating speed of the high-shear emulsifying machine is 500-1000 r/min.
In the step 3, the power of the ultrasonic cell crusher is 20-35%, and the emulsifying time is 5-20 min.
The step 4 specifically comprises the following steps:
step 4.1, adding the Pickering emulsion into a reactor at room temperature, placing the reactor in a water bath, and introducing argon into the reactor for 20-30 min;
and 4.2, turning on a power supply, dripping an initiator aqueous solution within 30-90 min under the condition that the mechanical stirring speed is 100-250 r/min after the temperature of the water bath is raised to 70-85 ℃, keeping the temperature and stirring for 90-120 min at 80-90 ℃, and finally discharging cold water to obtain the fluorine-containing polyacrylate emulsion.
The dropping mode of the initiator aqueous solution is dropping by a peristaltic pump or adding at one time.
The invention has the beneficial effects that:
(1) the invention relates to a method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose, which is characterized in that nanocellulose grafted by an epoxy active group-containing anionic photoresponsive amphiphilic block copolymer prepared by a reversible addition-fragmentation chain transfer polymerization (RAFT) technology is used as a Pickering emulsifier, and the fluorine-containing polyacrylate emulsion is prepared by a Pickering emulsion polymerization method, is negatively charged and has an obvious core-shell structure, wherein CNC is a shell of a latex particle, a fluorine-containing polyacrylate polymer is a core, the emulsion stability is good, and the particle size distribution of the latex particle is small;
(2) the method for preparing the fluorine-containing polyacrylate emulsion by utilizing the photo-responsive nano-cellulose has the advantages of safety and environmental protection, the nano-cellulose modified by the anionic photo-responsive amphiphilic block copolymer is used as a Pickering emulsifier to replace a micromolecule emulsifier in the preparation process, the influence of the traditional surfactant on the product performance is eliminated, the excellent performances of the functionalized nano-cellulose and the fluorine-containing polyacrylate polymer are combined together, and the performance of the polymer is favorably improved;
(3) the method for preparing the fluorine-containing polyacrylate emulsion by utilizing the light-responsive nano-cellulose adopts the light-responsive nano-cellulose as a stabilizer, introduces the light-responsive nano-cellulose into the fluorine-containing polyacrylate polymer through Pickering emulsion polymerization, realizes good dispersion of the nano-cellulose in the fluorine-containing polyacrylate emulsion, widens the application field of the nano-cellulose, and provides a new idea for intelligent application of the fluorine-containing polyacrylate emulsion.
Drawings
FIG. 1 is a transmission electron microscope photograph of fluorine-containing polyacrylate latex particles prepared by the present invention;
FIG. 2 is a graph showing the DLS test results of the fluorine-containing polyacrylate emulsion prepared according to the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose, which is implemented according to the following steps:
step 1, preparing photoresponsive nanocellulose aqueous dispersion
Weighing a proper amount of anionic photoresponsive nanocellulose powder and an alkaline aqueous solution, mixing, and forming a dispersion under the action of an ultrasonic cell crusher;
the mass ratio of the anionic photoresponsive nano-cellulose powder to the alkaline aqueous solution is 3-18: 3250-3900; the alkaline aqueous solution is sodium hydroxide solution or potassium hydroxide solution; the power of the ultrasonic cell crusher is 5-50%, and the dispersion time is 5-20 min.
Step 2, preparing mixed monomer and initiator aqueous solution
Weighing a proper amount of acrylate first monomer, acrylate second monomer and fluorine-containing acrylate monomer, and mixing by a high-shear emulsifying machine to obtain a mixed monomer; uniformly mixing a proper amount of initiator and deionized water to obtain an initiator aqueous solution for later use;
the mass ratio of the acrylate first monomer to the acrylate second monomer to the fluorine-containing acrylate monomer is 3-63: 27-81: 1-18;
the acrylate first monomer is methyl acrylate or methyl methacrylate; the acrylate second monomer is butyl methacrylate or butyl acrylate; the fluorine-containing acrylate monomer is hexafluorobutyl methacrylate, hexafluorobutyl acrylate, 2,2, 2-trifluoroethyl methacrylate, dodecafluoroheptyl methacrylate or dodecafluoroheptyl acrylate;
the concentration of the initiator is 0.5-4 wt%, and the mass of the initiator is 0.6-2.0% of that of the mixed monomer; the initiator is ammonium persulfate, potassium persulfate or sodium persulfate; the dropping mode of the initiator aqueous solution is dropping by a peristaltic pump or adding at one time;
the rotating speed of the high-shear emulsifying machine is 500-1000 r/min;
step 3, preparing Pickering emulsion
Adding the mixed monomer into the dispersion, and mixing and emulsifying in an ultrasonic cell crusher to obtain Pickering emulsion for later use;
wherein the power of the ultrasonic cell crusher is 20-35%, and the emulsifying time is 5-20 min;
step 4, adding Pickering emulsion into a reactor, adding an initiator aqueous solution into the reactor under the conditions of mechanical stirring and argon protection, and discharging cold water after the reaction is finished to obtain the fluorine-containing polyacrylate emulsion; the method specifically comprises the following steps:
step 4.1, adding the Pickering emulsion into a reactor at room temperature, placing the reactor in a water bath, and introducing argon into the reactor for 20-30 min;
and 4.2, turning on a power supply, dripping an initiator aqueous solution within 30-90 min under the condition that the mechanical stirring speed is 100-250 r/min after the temperature of the water bath is raised to 70-85 ℃, keeping the temperature and stirring for 90-120 min at 80-90 ℃, and finally discharging cold water to obtain the fluorine-containing polyacrylate emulsion.
The invention takes nano-cellulose grafted by an anionic ultraviolet-responsive amphiphilic block copolymer containing thiocarbonate end groups and epoxy active groups as a Pickering emulsifier, takes a mixture containing an acrylate first monomer, an acrylate second monomer and a fluorine-containing acrylate monomer as an oil phase to prepare a Pickering emulsion, and prepares the fluorine-containing polyacrylate emulsion by a Pickering emulsion polymerization method.
The light-responsive nano-cellulose is obtained by grafting an anionic ultraviolet light-responsive block copolymer which is prepared by a reversible addition-fragmentation chain transfer polymerization technology and contains a thiocarbonate end group and an epoxy active group, and the block copolymer has an amphipathic property.
The preparation method of the anionic photoresponsive nano cellulose powder comprises the following steps:
step a, preparing a diblock copolymer containing carboxyl and epoxy units
According to the mass ratio of 1: 45: 25: 713, respectively weighing 4,4' -azobis (4-cyanovaleric acid), a carboxyl-containing hydrophilic macromolecule RAFT reagent, glycidyl methacrylate and 1, 4-dioxane, placing into a three-neck flask with magnetons, and stirring and dissolving to form a mixed solution;
introducing argon into a three-neck flask for 30min at room temperature, then heating the three-neck flask to 60 ℃ to enable 4,4' -azobis (4-cyanovaleric acid), a carboxyl-containing hydrophilic macromolecule RAFT reagent and glycidyl methacrylate to react for 6h under the protection of argon to obtain a product;
precipitating and purifying the product in normal hexane, and drying in a vacuum oven to obtain a diblock copolymer containing carboxyl and epoxy units;
step b: preparation of anionic UV-responsive Block copolymer
According to the mass ratio of 1: 50: 67: 20: 1450, respectively weighing 4,4' -azobis (4-cyanovaleric acid), a diblock copolymer containing carboxyl and epoxy units, hexafluorobutyl methacrylate, 7- (2-acryloyloxy) -4-methylcoumarin and 1, 4-dioxane, fully stirring the materials in a three-neck flask with magnetons until the materials are dissolved;
introducing argon into a three-neck flask for 30min at room temperature, heating to 80 ℃, and reacting 4,4' -azobis (4-cyanovaleric acid), a diblock copolymer containing carboxyl and epoxy units, hexafluorobutyl methacrylate and 7- (2-acryloyloxy) -4-methylcoumarin for 8h under the protection of argon to obtain a product;
precipitating and purifying the product in normal hexane, and drying in a vacuum oven to obtain an anionic ultraviolet light response block copolymer;
step c: preparation of anionic ultraviolet light response block copolymer grafted nano-cellulose
According to the mass ratio of 5: 15: 20: 165 respectively weighing nano cellulose (CNC), an anionic ultraviolet response block copolymer, dimethylaminopyridine and N' N dimethylformamide into a flask; putting the flask in an oil bath, heating to 50 ℃, and fully reacting reactants in the flask for 24 hours to obtain a product;
and (3) centrifuging the obtained product by using a centrifuge, washing the product for 3-4 times by using tetrahydrofuran, and drying the product in a vacuum oven to obtain the anionic photoresponse amphiphilic nano cellulose powder.
Example 1
The invention discloses a method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose, which comprises the following steps:
(1) preparation of photo-responsive aqueous nanocellulose dispersion
According to the mass ratio of 3: 3900 weighing anionic photoresponsive nanocellulose powder and sodium hydroxide solution, mixing, and dispersing for 20min under the action of an ultrasonic cell crusher with power of 15% to form dispersion liquid;
(2) preparation of mixed monomer and initiator aqueous solution
According to the mass ratio of 14: 69: 1, respectively weighing methyl methacrylate, butyl acrylate and hexafluorobutyl acrylate, and mixing in a high-shear emulsifying machine with the rotating speed of 600r/min to obtain a mixed monomer; uniformly mixing potassium persulfate with the concentration of 0.5 wt% with deionized water to obtain an initiator aqueous solution, wherein the mass of the potassium persulfate is 0.6% of that of the mixed monomer;
(3) preparation of Pickering emulsion
Adding the mixed monomer into the dispersion, and mixing and emulsifying for 10min in an ultrasonic cell crusher with the power of 20% to obtain Pickering emulsion;
(4) preparation of fluorine-containing polyacrylate emulsion
Adding the Pickering emulsion into a three-neck flask provided with a stirrer, a condenser, a dropping funnel and an argon connecting pipe at room temperature, placing the three-neck flask into a water bath kettle, and introducing argon into the three-neck flask for 20 min;
and (3) switching on a power supply, dripping an initiator aqueous solution by using a peristaltic pump within 30min under the condition that the mechanical stirring speed is 250r/min after the temperature of the water bath kettle rises to 80 ℃, keeping the temperature and stirring at 85 ℃ for 100min, and finally discharging cold water to obtain the fluorine-containing polyacrylate emulsion.
Example 2
The invention discloses a method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose, which comprises the following steps:
(1) preparation of photo-responsive aqueous nanocellulose dispersion
According to the mass ratio of 18: 3250 mixing anionic photoresponsive nanocellulose powder and sodium hydroxide solution, and dispersing for 15min under the action of an ultrasonic cell crusher with power of 5% to form dispersion;
(2) preparation of mixed monomer and initiator aqueous solution
According to the mass ratio of 10: 74: 18 respectively weighing methyl acrylate, butyl methacrylate and hexafluorobutyl methacrylate, and mixing in a high-shear emulsifying machine with the rotating speed of 800r/min to obtain a mixed monomer; uniformly mixing 4 wt% of ammonium persulfate with deionized water to obtain an initiator aqueous solution, wherein the mass of the ammonium persulfate is 2% of that of the mixed monomer;
(3) preparation of Pickering emulsion
Adding the mixed monomer into the dispersion, and mixing and emulsifying in an ultrasonic cell crusher with the power of 25% for 15min to obtain Pickering emulsion;
(4) preparation of fluorine-containing polyacrylate emulsion
Adding the Pickering emulsion into a three-neck flask provided with a stirrer, a condenser, a dropping funnel and an argon connecting pipe at room temperature, placing the three-neck flask into a water bath kettle, and introducing argon into the three-neck flask for 30 min;
and (3) switching on a power supply, dripping an initiator aqueous solution by using a peristaltic pump within 60min under the condition that the mechanical stirring speed is 100r/min after the temperature of the water bath kettle rises to 85 ℃, keeping the temperature and stirring for 90min at 85 ℃, and finally discharging cold water to obtain the fluorine-containing polyacrylate emulsion.
Example 3
The invention discloses a method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose, which comprises the following steps:
(1) preparation of photo-responsive aqueous nanocellulose dispersion
According to the mass ratio of 10: 3400 weighing anionic photoresponsive nanocellulose powder and sodium hydroxide solution, mixing, and dispersing for 5min under the action of an ultrasonic cell crusher with power of 50% to form dispersion liquid;
(2) preparation of mixed monomer and initiator aqueous solution
According to the mass ratio of 36: 54: 10 respectively weighing methyl methacrylate, butyl acrylate and hexafluorobutyl acrylate, and mixing in a high-shear emulsifying machine with the rotating speed of 1000r/min to obtain a mixed monomer; uniformly mixing 1.6 wt% of potassium persulfate with deionized water to obtain an initiator aqueous solution, wherein the mass of the potassium persulfate is 1% of that of the mixed monomer;
(3) preparation of Pickering emulsion
Adding the mixed monomer into the dispersion, and mixing and emulsifying for 10min in an ultrasonic cell crusher with power of 35% to obtain Pickering emulsion;
(4) preparation of fluorine-containing polyacrylate emulsion
Adding the Pickering emulsion into a three-neck flask provided with a stirrer, a condenser, a dropping funnel and an argon connecting pipe at room temperature, placing the three-neck flask into a water bath kettle, and introducing argon into the three-neck flask for 30 min;
and (3) switching on a power supply, dripping an initiator aqueous solution by using a peristaltic pump within 90min under the condition that the mechanical stirring speed is 100r/min after the temperature of the water bath kettle rises to 80 ℃, keeping the temperature and stirring for 120min at 90 ℃, and finally discharging cold water to obtain the fluorine-containing polyacrylate emulsion.
FIG. 1 is a transmission electron microscope photograph of fluorine-containing polyacrylate latex particles prepared by the present invention; as can be seen from FIG. 1, the particle size of the fluorine-containing polyacrylate latex particle is about 200nm, the photo-responsive nano-cellulose is located on the surface of the fluorine-containing polyacrylate latex particle, and the fluorine-containing polyacrylate polymer is wrapped in the inner layer by the photo-responsive nano-cellulose; the surface of the photoresponse nano-cellulose prepared by the method contains a reactive thiocarbonate end group, and the reactive group can continuously participate in the reaction in Pickering emulsion polymerization, so that the nano-particles are connected with the fluorine-containing polyacrylate polymer through covalent bonds.
FIG. 2 is a graph showing the DLS test results of the fluorine-containing polyacrylate emulsion prepared according to the present invention. As can be seen from fig. 2, the measured results are: 280.1nm (PDI 0.178), the diameter of the micelles measured by TEM is smaller than that measured by DLS, since the TEM samples need to be dried, during which the micelles shrink to have a size smaller than that in solution. The invention can effectively solve the problem that the nano particles and the polymer are easy to fall off due to physical adsorption combination, and can introduce the coumarin-containing anionic photoresponse nano-cellulose into the fluorine-containing polyacrylic acid polymer, thereby providing a new idea for intellectualization of the fluorine-containing polyacrylate emulsion.
Claims (9)
1. The method for preparing the fluorine-containing polyacrylate emulsion by utilizing the photoresponsive nanocellulose is characterized by comprising the following steps of:
step 1, preparing photoresponsive nanocellulose aqueous dispersion
Weighing a proper amount of anionic photoresponsive nanocellulose powder and an alkaline aqueous solution, mixing, and forming a dispersion under the action of an ultrasonic cell crusher;
step 2, preparing mixed monomer and initiator aqueous solution
Weighing a proper amount of acrylate first monomer, acrylate second monomer and fluorine-containing acrylate monomer, and mixing by a high-shear emulsifying machine to obtain a mixed monomer; uniformly mixing a proper amount of initiator and deionized water to obtain an initiator aqueous solution for later use;
step 3, preparing Pickering emulsion
Adding the mixed monomer into the dispersion, and mixing and emulsifying in an ultrasonic cell crusher to obtain Pickering emulsion for later use;
and 4, adding the Pickering emulsion into a reactor, adding the initiator aqueous solution into the reactor under the conditions of mechanical stirring and argon protection, and discharging cold water after the reaction is finished to obtain the fluorine-containing polyacrylate emulsion.
2. The method for preparing the fluorine-containing polyacrylate emulsion by using the photo-responsive nanocellulose according to claim 1, wherein in the step 1, the mass ratio of the anionic photo-responsive nanocellulose powder to the alkaline aqueous solution is 3 to 18: 3250-3900; the alkaline aqueous solution is sodium hydroxide solution or potassium hydroxide solution.
3. The method for preparing the fluorine-containing polyacrylate emulsion using photo-responsive nanocellulose according to claim 1, wherein in step 1, the power of the ultrasonic cell crusher is 5% to 50%, and the dispersion time is 5min to 20 min.
4. The method for preparing the fluorine-containing polyacrylate emulsion by using the photo-responsive nanocellulose as claimed in claim 1, wherein in step 2, the mass ratio of the acrylate first monomer, the acrylate second monomer and the fluorine-containing acrylate monomer is 3-63: 27-81: 1-18;
the acrylate first monomer is methyl acrylate or methyl methacrylate; the acrylate second monomer is butyl methacrylate or butyl acrylate; the fluorine-containing acrylate monomer is hexafluorobutyl methacrylate, hexafluorobutyl acrylate, 2,2, 2-trifluoroethyl methacrylate, dodecafluoroheptyl methacrylate or dodecafluoroheptyl acrylate.
5. The method for preparing fluorine-containing polyacrylate emulsion using photo-responsive nano-cellulose according to claim 4, wherein in step 2, the concentration of the initiator is 0.5-4 wt%, and the mass of the initiator is 0.6-2.0% of the mass of the mixed monomer;
the initiator is ammonium persulfate, potassium persulfate or sodium persulfate.
6. The method for preparing the fluorine-containing polyacrylate emulsion using the photo-responsive nano cellulose according to claim 1, wherein the rotation speed of the high shear emulsifying machine in the step 2 is 500 to 1000 r/min.
7. The method for preparing the fluorine-containing polyacrylate emulsion using photo-responsive nanocellulose according to claim 1, wherein in step 3, the power of the ultrasonic cell crusher is 20% to 35%, and the emulsification time is 5min to 20 min.
8. The method for preparing fluorine-containing polyacrylate emulsion using photo-responsive nanocellulose according to claim 1, wherein step 4 specifically comprises:
step 4.1, adding the Pickering emulsion into a reactor at room temperature, placing the reactor in a water bath, and introducing argon into the reactor for 20-30 min;
and 4.2, turning on a power supply, dripping an initiator aqueous solution within 30-90 min under the condition that the mechanical stirring speed is 100-250 r/min after the temperature of the water bath is raised to 70-85 ℃, keeping the temperature and stirring for 90-120 min at 80-90 ℃, and finally discharging cold water to obtain the fluorine-containing polyacrylate emulsion.
9. The method for preparing fluorine-containing polyacrylate emulsion using photo-responsive nanocellulose according to claim 1, wherein the aqueous initiator solution is added dropwise by using a peristaltic pump or added at one time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110471716.XA CN113105588B (en) | 2021-04-29 | 2021-04-29 | Method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110471716.XA CN113105588B (en) | 2021-04-29 | 2021-04-29 | Method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113105588A true CN113105588A (en) | 2021-07-13 |
| CN113105588B CN113105588B (en) | 2022-12-13 |
Family
ID=76721140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110471716.XA Active CN113105588B (en) | 2021-04-29 | 2021-04-29 | Method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113105588B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133591A (en) * | 2021-11-15 | 2022-03-04 | 陕西科技大学 | Preparation method of double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992421A (en) * | 2014-05-16 | 2014-08-20 | 三棵树涂料股份有限公司 | Method for preparing Pickering acrylic polymer emulsion |
| CN106749860A (en) * | 2017-01-23 | 2017-05-31 | 陕西科技大学 | The preparation method of nano-cellulose/fluorine-contaninig polyacrylate complex emulsions |
| CN108084369A (en) * | 2017-12-29 | 2018-05-29 | 陕西科技大学 | A kind of preparation method of nano-cellulose base unimolecular micelle |
| CN110684147A (en) * | 2019-10-18 | 2020-01-14 | 陕西科技大学 | Preparation method of photoresponse cellulose nanocrystalline/fluorine-containing polyacrylate self-repairing material |
| WO2020130701A2 (en) * | 2018-12-21 | 2020-06-25 | 한솔제지 주식회사 | Composite particles of cellulose nanofibers and polymer, and method for preparing same |
-
2021
- 2021-04-29 CN CN202110471716.XA patent/CN113105588B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992421A (en) * | 2014-05-16 | 2014-08-20 | 三棵树涂料股份有限公司 | Method for preparing Pickering acrylic polymer emulsion |
| CN106749860A (en) * | 2017-01-23 | 2017-05-31 | 陕西科技大学 | The preparation method of nano-cellulose/fluorine-contaninig polyacrylate complex emulsions |
| CN108084369A (en) * | 2017-12-29 | 2018-05-29 | 陕西科技大学 | A kind of preparation method of nano-cellulose base unimolecular micelle |
| WO2020130701A2 (en) * | 2018-12-21 | 2020-06-25 | 한솔제지 주식회사 | Composite particles of cellulose nanofibers and polymer, and method for preparing same |
| CN110684147A (en) * | 2019-10-18 | 2020-01-14 | 陕西科技大学 | Preparation method of photoresponse cellulose nanocrystalline/fluorine-containing polyacrylate self-repairing material |
Non-Patent Citations (1)
| Title |
|---|
| 周建华等: "阳离子型含氟聚丙烯酸酯无皂乳液的合成及性能", 《精细化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133591A (en) * | 2021-11-15 | 2022-03-04 | 陕西科技大学 | Preparation method of double self-repairing cellulose nanocrystal/fluorine-containing polyacrylate composite emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113105588B (en) | 2022-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102604006B (en) | Preparation method for acidic silica sol in-situ modified acrylate emulsion | |
| CN107118650B (en) | Silica sol/polyacrylate emulsion containing hydroxyl-amino resin baking varnish and preparation method thereof | |
| CN108752540B (en) | Amphiphilic multifunctional hybrid nano particle, and preparation method and application thereof | |
| CN101033360A (en) | Method of preparing organic/inorganic hybridization reactivity semi-interpenetrating network structure emulsion | |
| CN104530302A (en) | Silica sol/polyacrylic ester emulsion with high silicon content and preparation method of silica sol/polyacrylic ester emulsion | |
| CN101372527A (en) | Nano-zinc oxide/acrylic ester grafting composite emulsion and preparation thereof | |
| CN101982478A (en) | Polymer surfactant and core-shell amphiphilic polymer microsphere as well as preparation method thereof | |
| CN108676116A (en) | A kind of modified manometer silicon dioxide and the organic inorganic hybridization polyacrylate dispersion using the modified manometer silicon dioxide | |
| CN101210053B (en) | Amphiphilic starch derivative fine particles and preparing method thereof | |
| WO2023123580A1 (en) | Graphene oxide modified styrene-acrylic pickering emulsion and composite emulsion, and preparation methods therefor and applications thereof | |
| CN113105588B (en) | Method for preparing fluorine-containing polyacrylate emulsion by utilizing photoresponsive nanocellulose | |
| CN109627370A (en) | The preparation method of a kind of nitrogen-containing functional group polyalcohol stephanoporate microballoons | |
| CN103665242B (en) | A kind of Silica sol/acrylate nano core-shell compound emulsion and preparation method thereof | |
| CN100417686C (en) | High molecule/calcium carbonate nanometer particles, functional particles and prepn. method thereof | |
| CN103467678A (en) | Preparation method of pomegranate-shaped organic-inorganic nano-composite microspheres | |
| CN111548444A (en) | Preparation method of surface ionic liquid functionalized polymer microspheres | |
| CN101407565A (en) | Soy protein / emulsion polymerization high polymer nano composite material, and preparation and use thereof | |
| CN108219186B (en) | Preparation of micro-aperture fluorine-containing porous material based on polylactic acid induced thickening effect | |
| CN108084348B (en) | Preparation method of strawberry type complex colloidal particle cluster emulsion for super-hydrophobic nano coating | |
| CN103936939A (en) | Interpenetrating polymer network core-shell emulsion and preparation method thereof | |
| CN111087548B (en) | High-gloss quick-drying high-solid-content low-viscosity acrylate emulsion and preparation method thereof | |
| CN1772366A (en) | Hollow microcapsule preparing process | |
| CN108003272B (en) | Preparation method of nano-cellulose/fluorine-containing polyacrylate soap-free emulsion | |
| CN1974619A (en) | Prepn and application of reactive polyacrylate microgel | |
| CN111393720A (en) | Nano zinc oxide modified nanocrystalline cellulose reinforced natural rubber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240805 Address after: No. 1912, 19th Floor, Block A, Zhongdeng Building, No. 138 Weiyang Road, Xi'an Economic and Technological Development Zone, Shaanxi Province 710000 Patentee after: Shaanxi Puerkang Chemical Technology Co.,Ltd. Country or region after: China Address before: 710021 Shaanxi city of Xi'an province Weiyang University Park Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY Country or region before: China |