WO2019214581A1 - Nanofibres de copolymère de polychlorotrifluoroéthylène, procédés de fabrication de telles nanofibres et produits fabriqués avec de telles nanofibres - Google Patents

Nanofibres de copolymère de polychlorotrifluoroéthylène, procédés de fabrication de telles nanofibres et produits fabriqués avec de telles nanofibres Download PDF

Info

Publication number
WO2019214581A1
WO2019214581A1 PCT/CN2019/085695 CN2019085695W WO2019214581A1 WO 2019214581 A1 WO2019214581 A1 WO 2019214581A1 CN 2019085695 W CN2019085695 W CN 2019085695W WO 2019214581 A1 WO2019214581 A1 WO 2019214581A1
Authority
WO
WIPO (PCT)
Prior art keywords
nanofiber
poly
vdf
ctfe
polymeric
Prior art date
Application number
PCT/CN2019/085695
Other languages
English (en)
Inventor
Tian Xia
Hanjin HUANG
Xin Zhang
Original Assignee
Honeywell Performance Materials And Technologies (China) Co., Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Honeywell Performance Materials And Technologies (China) Co., Ltd. filed Critical Honeywell Performance Materials And Technologies (China) Co., Ltd.
Publication of WO2019214581A1 publication Critical patent/WO2019214581A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
    • B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0004—Organic membrane manufacture by agglomeration of particles
    • B01D67/00042—Organic membrane manufacture by agglomeration of particles by deposition of fibres, nanofibres or nanofibrils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/32—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising halogenated hydrocarbons as the major constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
    • B01D2239/025—Types of fibres, filaments or particles, self-supporting or supported materials comprising nanofibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
    • B01D2239/0604—Arrangement of the fibres in the filtering material
    • B01D2239/0631—Electro-spun
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/10—Filtering material manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/12—Special parameters characterising the filtering material
    • B01D2239/1208—Porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/39—Electrospinning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride

Definitions

  • the present disclosure generally relates to poly-chlorotrifluoroethylene ( “PCTFE” ) copolymer nanofibers. Furthermore, the present disclosure relates to methods of manufacturing PCTFE nanofibers using electrospinning techniques and to products, such as filter membranes and textiles, made with PCTFE nanofibers.
  • PCTFE poly-chlorotrifluoroethylene
  • Polymeric nanofibers are useful in a variety of industrial applications, such as filtration devices, product packaging, medical applications, and textile protective clothing. Relatively few polymers, however, have been successfully converted into nanofiber form. These include nylon, polyester, polyacrylonitrile, polyvinyl alcohol, polyurethane, polylactic acid, for example. Each of these polymers has several drawbacks that limit the scope of their use. For example, nylon and polyester are heat sensitive, and are only suitable for use in relatively low-temperature applications (such as less than about 45 °C) . Additionally, polyacrylonitrile and polyurethane are chemically sensitive, and are not suitable for use in oxidative environments, such as halogen-containing industrial processes.
  • CTFE chlorotrifluoroethylene
  • CTFE copolymers are resistant to many chemicals, solvents, acids, and oils.
  • CTFE polymers additionally have moisture barrier properties, as well as being UV resistant.
  • CTFE polymers are heat resistant and are suitable for use in elevated temperature applications.
  • the prior art includes CTFE polymers in the form of films and coatings for a variety of industries and applications. Yet, heretofore, the prior art is devoid of any suitable method for preparing nanofibers from CTFE polymers, which would allow such polymers, with their attendant beneficial properties, to be used in the aforementioned filtration and textile applications.
  • PCTFE nanofibers and methods for manufacturing PCTFE nanofibers. Such methods desirably would be suitable for manufacturing PCTFE nanofibers on an industrial scale. Moreover, it would be desirable to provide PCTFE nanofiber products, such as filtration membranes and textiles. Furthermore, other desirable features and characteristics of the subject matter will become apparent from the subsequent detailed description of the subject matter and the appended claims, taken in conjunction with this background of the subject matter.
  • an electrospun polymeric nanofiber includes a poly (chlorotrifluoroethylene-co-vinylidenefluoride) ( “poly (CTFE-co-VDF) ” ) copolymer.
  • poly (CTFE-co-VDF) a poly (chlorotrifluoroethylene-co-vinylidenefluoride)
  • CTFE-co-VDF poly (CTFE-co-VDF) copolymer
  • Terpolymers of CTFE, VDF, and a further functional-group containing monomer are disclosed.
  • composites of poly (CTFE-co-VDF) copolymers and a secondary copolymer are disclosed.
  • a method for manufacturing a polymeric nanofiber includes the step of preparing or providing a polymeric emulsion.
  • the polymeric emulsion includes a poly (CTFE-co-VDF) copolymer and a ketone-based solvent.
  • the method further includes the step of electrospinning the polymeric emulsion to form the polymeric nanofiber using an electrospinning apparatus.
  • products made from the polymeric nanofibers are disclosed. These products may include, for example, nonwoven protective textiles and gas or liquid filtration/separation membranes. Methods for making these products are also disclosed.
  • FIG. 1 is an exemplary electrospinning apparatus and method suitable for use with embodiments of the present disclosure.
  • FIG. 2 is a flowchart illustrating a method for making products from PCTFE nanofibers in accordance with embodiments of the present disclosure.
  • Embodiments of the present disclosure are broadly directed to PCTFE nanofibers, methods of manufacturing PCTFE nanofibers, and products made with PCTFE nanofibers.
  • PCTFE includes copolymers of chlorotrifluoroethylene and other comonomers, as described in further detail below.
  • nanofiber means a fiber with a diameter of from about 50 nm to about 500 nm.
  • PCTFE nanofibers can be formed using an electrospinning process when the CTFE is copolymerized with an additional monomer (s) that aides the PCTFE in forming an emulsion, wherein the emulsion is formed using a ketone-based solvent.
  • the additional monomer is vinylidene fluoride (VDF) , although it is to be appreciated that further additional monomers may also be included in addition to the VDF.
  • VDF vinylidene fluoride
  • the present disclosure involves emulsions of poly (CTFE-co-VDF) copolymers with a ketone-based solvent.
  • poly (CFTE-co-VDF) copolymer encompasses copolymers with CFTE, VDF, and any other additional monomer-derived units.
  • the CTFE may optionallybe copolymerized with a further functional-group containing comonomer to form terpolymers of CTFE, VDF, and the further functional-group containing comonomer, for example, as will be discussed in greater detail below.
  • the poly (CTFE-co-VDF) copolymer may optionally be mixed with other polymers to form a composite emulsion, i.e., an emulsion that includes more than one type of physically separate polymer.
  • These other polymers to be mixed with the poly (CTFE-co-VDF) copolymer may be selected based on the intended application of the nanofibers. For example, in the water- treatment industry, filtration membranes with high tolerance to chlorine are desirable. Thus, in these embodiments, other polymers to be mixed with the poly (CTFE-co-VDF) copolymer may include polyvinyl alcohol (PVA) or polyvinyl pyrrolidone (PVP) , both of which have demonstrated resistance to damage from chlorine.
  • PVA polyvinyl alcohol
  • PVP polyvinyl pyrrolidone
  • the copolymer emulsion (or the copolymer composite emulsion) is then electrospun under conditions as will also be described in greater detail below to form nanofibers. These nanofibers may be used to form products such as filtrations membranes for liquid and/or gas separation processes, or such as protective textiles.
  • the PCTFE copolymers of the present disclosure are emulsified with a ketone-based solvent to form an emulsion that is suitable for use in an electrospinning process to manufacture nanoscale fibers.
  • ketone-based solvent refers to any organic solvent that includes a ketone functional group. Suitable examples of ketone-based solvents include, but are not limited to, dimethyl ketone (acetone) and methyl ethyl ketone.
  • ketone-based solvents include acetophenone, butanone, cyclopentanone, ethyl isopropyl ketone, 2-hexanone, isopherone, methyl isobutyl ketone, methyl isopropyl ketone, 3-methyl-2-pentanone, 2-pentanone, and 3-pentanone, among others.
  • the present disclosure includes the use of poly (CTFE-co-VDF) copolymers that are capable of forming ketone-based solvent copolymer emulsions.
  • CTFE is available from Honeywell International Inc. of Morristown, NJ
  • VDF is available from Solvay S.A. of Brussels, Belgium.
  • Ketone solvents depending on the particular type, are available from many different commercial sources.
  • CTFE-co-VDF poly (CTFE-co-VDF) copolymer
  • exemplary poly (CTFE-co-VDF) copolymers contain less than about 99 weight%of a CTFE, and from about 1 to about 10 weight%, such as about 2 to about 7 weight%, of VDF.
  • CTFE may be present in an amount of from about 70 to about 95 weight%, for example from about 75 to about 94 weight%, and such as from about 80 to about 90 weight%, based upon the total weight of the poly (CTFE-co-VDF) copolymer.
  • Poly (CTFE-co-VDF) copolymers with weight-average molecular weights between about 2,000,000 and about 20,000,000 Daltons are suitable. Weight-average molecular weights less than 10,000,000 Daltons are exemplary.
  • further functional-group containing monomers may be copolymerized with the CTFE (in addition to VDF) to form terpolymers, for example, in order to aid in the emulsification of the copolymer with the ketone-based solvent.
  • CTFE in addition to VDF
  • exemplary further functional-group containing monomers include (meth) acrylic monomers, urethane-based monomers, and isocyanate-based monomers, acid-functional monomers, and hydroxyl-functional monomers.
  • the further functional-group containing monomers may be present in the copolymer in an amount from about 1 to about 10 weight%, such as about 2 to about 7 weight%.
  • the polymerization discussion that follows in reference to poly (CTFE-co-VDF) copolymers should therefore be understood to also encompass such copolymers that also include the further functional-group containing monomers.
  • the poly (CTFE-co-VDF) copolymers suitable for use in accordance with the present disclosure are polymerized by conventional free-radical polymerization methods. Any commercially available radical initiator may be used in accordance with the embodiments described herein. Suitable candidates include thermal initiators and oxidation-reduction or “redox” initiator systems.
  • Thermal initiators include: metal persulfates like potassium persulfate and ammonium persulfate; organic peroxides or hydroperoxides such as diacyl peroxides, ketone peroxides, peroxyesters, dialkyl peroxides and peroxy ketals; azo initiators such as 2, 2’ -azobisisobutyronitrile and analogues thereof; and mixtures of any of the foregoing.
  • redox initiator system Any redox initiator system known to be useful in the preparation of fluoropolymers may be used in the present disclosure.
  • exemplary redox initiator systems include: 1) an organic or inorganic oxidizing agent or mixtures thereof; and 2) an organic or inorganic reducing agent or mixtures thereof.
  • Suitable oxidizing agents include metal persulfates such as potassium persulfate and ammonium persulfate; peroxides such as hydrogen peroxide, potassium peroxide, ammonium peroxide, tertiary butyl hydroperoxide ( “TBHP” ) ( (CH 3 ) 3 COOH) , cumene hydroperoxide, and t-amyl hydroperoxide; manganese triacetate; potassium permanganate; ascorbic acid; and mixtures thereof.
  • metal persulfates such as potassium persulfate and ammonium persulfate
  • peroxides such as hydrogen peroxide, potassium peroxide, ammonium peroxide, tertiary butyl hydroperoxide ( “TBHP” ) ( (CH 3 ) 3 COOH) , cumene hydroperoxide, and t-amyl hydroperoxide
  • manganese triacetate potassium permanganate
  • ascorbic acid and mixtures thereof.
  • Suitable reducing agents include sodium sulfites such as sodium bisulfite, sodium sulfite, sodium pyrosulfite, sodium-m-bisulfite ( “MBS” ) (Na 2 S 2 O 5 ) and sodium thiosulfate; other sulfites such as ammonium bisulfite; hydroxylamine; hydrazine; ferrous irons; organic acids such as oxalic acid, malonic acid, citric acid; and mixtures thereof.
  • sodium sulfites such as sodium bisulfite, sodium sulfite, sodium pyrosulfite, sodium-m-bisulfite ( “MBS” ) (Na 2 S 2 O 5 ) and sodium thiosulfate
  • other sulfites such as ammonium bisulfite; hydroxylamine; hydrazine; ferrous irons; organic acids such as oxalic acid, malonic acid, citric acid; and mixtures thereof.
  • a suitable free radical initiating system is one that serves to simultaneously emulsify the polymer while initiating the polymerization, thus eliminating the need for large quantities of surfactants.
  • Redox initiator systems are suitable for this purpose.
  • Exemplary redox initiator systems use an MBS reducing agent and a TBHP oxidizing agent.
  • the redox initiator system is used in conjunction with a transition metal accelerator. Accelerators can greatly reduce the polymerization time.
  • Any commercially available transition metal may be used as an accelerator in the present disclosure.
  • Exemplary transition metals include copper, silver, titanium, ferrous iron and mixtures thereof.
  • the amount of radical initiator used in the process depends on the relative ease with which the various monomers copolymerize, the molecular weight of the polymer and the rate of reaction desired. Generally, from about 10 to about 100,000 ppm of initiator may be used, for example from about 100 to about 10,000 ppm.
  • the redox initiator system may include additional peroxide-based compounds. The amount of additional peroxide-based compound used ranges from about 10 to about 10,000 ppm, for example from about 100 to about 5,000 ppm.
  • the radical initiator may be added before, simultaneous with and/or shortly after the addition and/or consumption of the monomers CTFE and VDF (and optionally further functional-group containing monomer, if present) used to make the poly (CTFE-co-VDF) copolymer.
  • CTFE and VDF and optionally further functional-group containing monomer, if present
  • an additional peroxide-based compound it may be added at the same interval specified for the primary radical initiator.
  • the poly (CTFE-co-VDF) /ketone-based solvent emulsions of the present disclosure may be made by a two-step polymerization reaction.
  • the monomers, ketone-based solvent, and an initial charge of radical initiator are introduced into suitable polymerization vessel. Additional monomer is added throughout the reaction at a rate equal to the rate of consumption to maintain a constant pressure. Incremental additional charges of initiator are introduced into the vessel over the duration of the reaction to sustain the polymerization.
  • the reaction mixture is maintained at a controlled temperature while all reactants are being charged to the vessel and throughout the polymerization reaction.
  • the reaction vessel used to prepare the composition described herein may be capable of being pressurized and agitated.
  • Conventional commercial autoclaves that can be sealed and pressurized to the required reaction pressures (preferably in excess of 3.36 MPa (500 psig) ) are exemplary.
  • Horizontally inclined autoclaves are preferred to vertically inclined autoclaves, although both geometries can be used.
  • the ketone-based solvent medium in which the polymerization is conducted may be added to the vessel. Generally, an amount equivalent to approximately half the capacity of the vessel, such as an autoclave, is used.
  • the ratio of polymer to solvent is chosen in such a way to obtain an emulsion of about 1 to about 50%polymer solids in solvent by weight, such as about 10 to about 40%polymer solids in solvent.
  • the solvent is pre-charged to the autoclave.
  • the process may optionally include relatively lower amounts of water as part of the solvent, such as less than about 20%of the total solvent (by weight) being water, the balance being the ketone-based solvent.
  • the monomers may be charged to the reactor vessel either in a semicontinuous or a continuous manner during the course of the polymerization.
  • “Semicontinuous, ” as used herein, means that a number of batches of the monomers are charged to the reactor during the course of the polymerization reaction.
  • the batch size is determined by the desired operating pressure.
  • the molar ratio of total monomer consumed to radical initiator will depend upon the overall particle size and molecular weight desired. In an embodiment, the overall mole ratio of monomer to initiator would be from about 10 to about 10,000, for example from about 50 to about 1,000, and such as from about 100 to about 500 moles of total monomer to one mole of initiator.
  • the radical initiator is generally added incrementally over the course of the reaction.
  • “initial charge” or “initial charging” of initiator refers to a rapid, large, single or incremental addition of initiator to effect the onset of polymerization.
  • In the initial charge generally between about 10 ppm/min to about 1,000 ppm/min is added over a period of from about 3 to about 30 minutes, eitherbefore, after, or during the charging of the monomers.
  • continuous charge or “continuous charging” means the slow, small, incremental addition of initiator over a period of from about 1 hour to about 6 hours, or until polymerization has concluded.
  • In the continuous charge generally between about 0.1 ppm/min to about 30 ppm/min of initiator is added.
  • the sealed reactor and its contents are maintained at the desired reaction temperature, or alternately to a varying temperature profile which varies the temperature during the course of the reaction.
  • Control of the reaction temperature is a factor for establishing the final molecular weight of the poly (CTFE-co-VDF) copolymers produced.
  • polymerization temperature is inversely proportional to product molecular weight.
  • the reaction temperature may range between about 0°C to about 120°C, although temperatures above and below these values are also contemplated.
  • the reaction pressure is between from about 172 KPa to about 5.5 MPa, and for example from about 345 KPa to about 4.2 MPa. Elevated pressures and temperatures will yield greater reaction rates.
  • the polymerization is conducted under agitation to ensure proper mixing.
  • An adjustment of the agitation rate during the polymerization may be desirable to prevent premature coagulation of the particles.
  • the agitation rate and reaction time will typically depend upon the amount of poly (CTFE-co-VDF) product desired, one of ordinary skill in the art can readily optimize the conditions of the reaction without undue experimentation.
  • the agitation rate will generally be in the range of from about 5 to about 800 rpm and, for example from about 25 to about 700 rpm, depending on the geometry of the agitator and the size of the vessel.
  • the reaction time will generally range from about 1 to about 24 hours, for example from about 1 to about 8 hours.
  • the secondary polymer that is employed to impart a specific material property to the nanofibers may be provided in a solution, and then may be mixed with the poly (CTFE-co-VDF) copolymer/ketone-based solvent emulsion that has been formed as described above.
  • Suitable solvents to prepare a solution of the exemplary PVP or PVP polymers include various alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, etc.
  • the mixing/agitation rate for forming the composite emulsion may be as described above in reference to forming the poly (CTFE-co-VDF) copolymer/ketone-based solvent emulsion, namely from about 5 to about 800 rpm, for a time period of about 5 minutes to about 5 hours, depending on the overall volume of the components.
  • the secondary polymer solution may be added to the poly (CTFE-co-VDF) copolymer/ketone-based solvent emulsion in amounts that are dependent on the final desired material properties of the nanofibers.
  • the secondary polymer solution may be added to the poly (CTFE-co-VDF) copolymer/ketone-based solvent emulsion in amounts such that a weight ratio of poly (CTFE-co-VDF) copolymer solids to secondary polymer solids is from about 1: 1 to about 100: 1, such as about 2: 1 to about 50: 1, or about 5: 1 to about 20: 1.
  • a weight ratio of poly (CTFE-co-VDF) copolymer solids to secondary polymer solids is from about 1: 1 to about 100: 1, such as about 2: 1 to about 50: 1, or about 5: 1 to about 20: 1.
  • a PCTFE electrospun material 9 may be formed by electrospinning the PCTFE emulsion.
  • the PCTFE emulsion may be loaded into a controlled pumping device with a fixed conductive element which acts as the charge source 12 for the electrospinning process.
  • the conductive element may have one or several orifices, wherein the PCTFE emulsion is discharged through the orifice (s) toward a target, and the orifice (s) and target have opposing electrical charge (or the target may be at ground) .
  • a reservoir 10 may be loaded with the PCTFE emulsion.
  • a delivery system 11 (e.g., which may include one or more pumping devices) delivers the PCTFE emulsion from the reservoir 10 to the charge source 12, which may be, or may include, one or more orifices.
  • the ejection volume from the pumping device may be set to a predetermined rate that is dependent on the desired configuration of the PCTFE electrospun material 9 being made, such as the desired fiber diameters of the PCTFE electrospun material.
  • the PCTFE emulsion may be discharged through each orifice at a rate of about 0.5 microliters per minute to about 5 microliters per minute, such as about 1 microliter per minute to about 3 microliters per minute.
  • the orifice size is optionally, but not limited to, about 0.01 mm to about 3.0 mm in diameter.
  • a target (or “collection surface” ) 15 is positioned so that it is spaced apart from the charge source 12.
  • a power source 16 including (but not limited to) a DC power supply, establishes an electrical charge potential between the charge source and the target such that the spun PCTFE emulsion 14 is electrically charged opposite the target.
  • the charge source 12 may be connected to the positive side of a precision DC power supply 16.
  • the negative side of the power supply 16 may be connected to the collection surface or target 15.
  • the spun PCTFE emulsion 14 is electrostatically attracted to the target 15 and deposited thereon to form the PCTFE electrospun material 9.
  • the target/collection surface 15 may be static or in motion (e.g., it may be a continuous or near continuous material that moves through the zone of impact, such as by movement on transport rollers 17, or the like, such that the collection surface may be an endless belt, or the like, of a conveyor) .
  • the collection surface 15 may be, for example, adrum (e.g., a cylinder around which an electrospun material can be wrapped) or a sheet.
  • the collection surface 15 is any material that may be coated, i.e., covered.
  • the shape, size, and geometry of the material that forms the collection surface 15 may vary.
  • the collection surface 15 can be any suitable material capable of dissipating electrical charge.
  • the collection surface 15 can be a metal, ceramic, fiberglass, graphite, or polymeric material.
  • the voltage on the power supply 16 is typically increased to the desired voltage to uniformly draw out the PCTFE emulsion.
  • the applied voltage may vary, but is optionally from about 2,000 to about 20,000 volts, such as about 10,000 to about 20,000 volts.
  • the charge induced by the connection of the power supply 16 repels the charged polymer away from the charge source 12 and attracts it to the collection surface 15.
  • the collection surface 15 may be placedperpendicular to the orifice system 12, with the fibers drawn towards the target.
  • the collection surface 15 may, in some embodiments, be rotated or otherwise moved during collection.
  • the electrospinning process may be continued until all of the PCTFE emulsion has been used up, or until a desirable amount of the PCTFE nanofiber has been formed.
  • the nanofibers as described above having been made with the poly (CTFE-co-VDF) copolymer (or composite) /ketone-based solvent emulsion and the electrospinning process, may be used to make a variety of industrially-applicable products, including but not limited to filtration/separation membranes and protective textiles.
  • electrospun nanofiber membranes may be made as highly-porous materials, wherein the “pore” size of the membrane is linearly proportional to the fiber diameter of the electrospun nanofiber, while the porosity of the mat is relatively independent of the fiber diameter and may fall in the range of about 75%to about 95%.
  • Such high porosity is responsible for a substantial improvement of permeability provided in electrospun nanofiber membranes when compared to the porosity of immersion cast membranes of similar thickness and pore size rating. These membranes may be used for filtration/separation applications including industrial liquid/gas processing.
  • protective textiles may be made with the nanofibers of the present disclosure, wherein the nanofibers are provided in the form of a nonwoven web.
  • the nonwoven web containing nanofibers may be utilized as abarrier layer.
  • the barrier layer may be disposed as an inner layer or an outer layer of a garment or clothing article.
  • the barrier layer desirably has a balance between convective air flow and barrier property.
  • the convective air flow property is effective to reduce the relative humidity within the space between the article and the wearer’s skin, while still maintain protection against the intrusion of possible harmful materials that the article may be exposed to.
  • Other products are possible in other embodiment, as known in the art.
  • FIG. 2 is a flowchart illustrating a method 100 for making PCTFE nanofiber in accordance with embodiments of the present disclosure.
  • Method 100 need not be performed in the order illustrated. Moreover, additional, non-illustrated steps may be performed in further embodiments.
  • step 102 a ketone-based solvent emulsion of a poly (CTFE-co-VDF) copolymer is prepared in accordance with the emulsion polymerization method described above.
  • the result of step 102 is a ketone-based solvent polymer emulsion that is suitable for use in an electrospinning process.
  • step 104 the method continues with a step of electrospinning the polymer emulsion onto a collection surface.
  • an electrical charge is employed in the electrospinning process to draw spun nanofibers onto the collection surface.
  • the proper viscosity and other material properties are achieved in order to allow for the electrospinning process to take place.
  • the electrospun PCTFE nanofibers are collected and made into a product, such as a separation/filtration membrane or a non-woven textile.
  • a product such as a separation/filtration membrane or a non-woven textile.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne une nanofibre polymère électrofilée. La nanofibre comprend un copolymère de poly (chlorotrifluoroéthylène-co-vinylidènefluorure) (« poly (CTFE-co-VDF) »). L'invention concerne en outre un procédé de fabrication d'une nanofibre polymère. Le procédé comprend l'étape de préparation ou de fourniture d'une émulsion polymère. L'émulsion polymère comprend un copolymère de poly (CTFE-co-VDF) et un solvant à base de cétone. Le procédé comprend en outre l'étape d'électrofilage de l'émulsion polymère pour former la nanofibre polymère à l'aide d'un appareil d'électrofilage. L'invention concerne également des produits constitués des nanofibres polymères.
PCT/CN2019/085695 2018-05-07 2019-05-06 Nanofibres de copolymère de polychlorotrifluoroéthylène, procédés de fabrication de telles nanofibres et produits fabriqués avec de telles nanofibres WO2019214581A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201862667894P 2018-05-07 2018-05-07
US62/667,894 2018-05-07

Publications (1)

Publication Number Publication Date
WO2019214581A1 true WO2019214581A1 (fr) 2019-11-14

Family

ID=68467734

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/085695 WO2019214581A1 (fr) 2018-05-07 2019-05-06 Nanofibres de copolymère de polychlorotrifluoroéthylène, procédés de fabrication de telles nanofibres et produits fabriqués avec de telles nanofibres

Country Status (1)

Country Link
WO (1) WO2019214581A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090291243A1 (en) * 2005-06-17 2009-11-26 Takahiro Kitahara Multilayer body
CN103437071A (zh) * 2013-09-11 2013-12-11 浙江伟星实业发展股份有限公司 一种静电纺纳米纤维膜及其制备方法
CN104289042A (zh) * 2014-09-05 2015-01-21 东华大学 一种静电纺纳米纤维驻极过滤材料及其制备方法
CN104452109A (zh) * 2014-12-09 2015-03-25 东华大学 一种高透湿通量的纤维基防水透湿膜的静电纺丝方法及其装置
CN105002656A (zh) * 2014-12-29 2015-10-28 中国科学院烟台海岸带研究所 一种具有自清洁功能的疏水膜及其制备方法和应用
CN105200539A (zh) * 2015-09-29 2015-12-30 东华大学 一种静电纺丝方法及其制备的纳米纤维/纺粘无纺布复合过滤材料
CN107939266A (zh) * 2017-10-25 2018-04-20 汪涛 一种净化空气的纱网及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090291243A1 (en) * 2005-06-17 2009-11-26 Takahiro Kitahara Multilayer body
CN103437071A (zh) * 2013-09-11 2013-12-11 浙江伟星实业发展股份有限公司 一种静电纺纳米纤维膜及其制备方法
CN104289042A (zh) * 2014-09-05 2015-01-21 东华大学 一种静电纺纳米纤维驻极过滤材料及其制备方法
CN104452109A (zh) * 2014-12-09 2015-03-25 东华大学 一种高透湿通量的纤维基防水透湿膜的静电纺丝方法及其装置
CN105002656A (zh) * 2014-12-29 2015-10-28 中国科学院烟台海岸带研究所 一种具有自清洁功能的疏水膜及其制备方法和应用
CN105200539A (zh) * 2015-09-29 2015-12-30 东华大学 一种静电纺丝方法及其制备的纳米纤维/纺粘无纺布复合过滤材料
CN107939266A (zh) * 2017-10-25 2018-04-20 汪涛 一种净化空气的纱网及其制备方法

Similar Documents

Publication Publication Date Title
US7728087B2 (en) Fluoropolymer dispersion and method for making the same
CA2956703C (fr) Articles produits a partir de polymeres vdf-co-(tfe ou trfe)
US3920599A (en) Latices of dially dimethyl ammonium chloride/acrylamide polymers
TW201341046A (zh) 高分子多孔質膜
CN103619891B (zh) 含氟聚合物、含氟聚合物的制造方法以及高分子多孔质膜
JP6075452B2 (ja) 組成物、高分子多孔質膜及び親水化剤
EP1287046B1 (fr) Copolymere de tetrafluoroethylene / perfluoro (alkyl-vinyl-ether) et son procede de fabrication
EP2898147B1 (fr) Substrats revêtus de chlorofluoropolymère et leurs procédés de production
CA1139046A (fr) Copolymeres de vinyle a reticulation croisee contenant des groupements hydroxydes
CN112105706A (zh) 拨水拨油剂和纤维制品
EP3252086A1 (fr) Agent d'hydrophilisation, composition contenant ledit agent d'hydrophilisation, et film polymère poreux
US2858290A (en) Preparation and use of acrylonitrile polymer dissolved in dimethyl sulfoxide
CN115135718A (zh) 分散液
WO2019214581A1 (fr) Nanofibres de copolymère de polychlorotrifluoroéthylène, procédés de fabrication de telles nanofibres et produits fabriqués avec de telles nanofibres
US5780553A (en) Heterogeneous polymerizations in carbon dioxide
WO1988006585A1 (fr) Polymeres bloc d'acrylate de pyrrolidonyle
DE2521766A1 (de) Ischpolymer und verfahren zu dessen herstellung
CN114616296B (zh) 拒液剂组合物、其制造方法和物品
US3253058A (en) Process for preparing film-forming polymers of olefinically-unsaturated nitriles andpolyalkenyl compounds and products thereof
CN107043438B (zh) 油酸-丙烯腈共聚物及其制备方法
US3002956A (en) Polymerization process
AU2016233336B2 (en) Coalescing elements in copper production
US2616882A (en) Shortstopping vinyl chloride polymerizations with vinyl pyridines
CN113856487A (zh) 一种超亲水/水下超疏油的分离膜的制备方法
JPS5889901A (ja) 液体混合物の分離方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19800216

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19800216

Country of ref document: EP

Kind code of ref document: A1