CN1028660C - Non-organic/polymer fiber composite, method of making same and use including dimensionally stable separator - Google Patents

Abstract

The present invention relates to a new composite fiber and the application thereof, and the new composite fiber is particularly to used as a diaphragm with stable size. The composite fiber comprises inorganic granules and fibrous organic polymers, and is prepared by intensively grinding or cutting granular inorganic matter and organic polymer precursor granules at high temperature. Much suitable inorganic matter exists, electron tube metal oxide is preferably used, and organic polymer fibers have good performance when containing fluorine. The composite fiber can be used as filtering materials (chromatographic column filtering fillers) or separating matter (batteries), and can be used as bearings or gaskets by compression or compressing sintering. When used as the separating matter, the composite fiber is preferably used as diaphragms of chlorine-alkali electrolytic cells and the pulp of the composite fiber can be directly deposited on porous cathodes and dried and heated.

Description

Non-organic/polymer fiber composite, method of making same and use including dimensionally stable separator

The application of resistance to chemical attack complex fiber or known already as the purposes that strengthens.On technology, known organic polymer fiber is arranged, as the extruding polytetrafluoroethylene fibre, inorfil is as carbon fiber; Natural fabric is as cotton yarn; And the mixture (floor tile) of pottery and fiber, the material that also has inorfil and organic polymer fiber mixture to make, here organic polymer fiber as " viscose glue " with inorfil " bonding " together, for example, some bibliographical informations, inorfil (as potassium titanate or zirconia) is bonded together as " viscose glue " with polytetrafluoroethylene (PTFE), makes sheet material, filter or other finished product.But this technology just " is glued these materials " each other together and is used, and the present invention then is the composite fibre that forms an a kind of inorganic polymer.

An application example of this technology is Canadian Patent No.834,895, and it has invented a kind of is inorganic material with potassium titanate, polytetrafluoroethylene (PTFE) is the battery separator that organic material is made.The Another Application example is a U.S. Patent No. 3,713,890, and it has invented one is inorganic material with zirconia, and polytetrafluoroethylene (PTFE) is the battery separator that organic material is made.In addition, be entitled as that nickel-in novel dividing plate one literary composition of batteries [being published in " international power conversion association the 16 session meeting newspaper ", XI (1981)], having introduced one is the Zircar of reinforcing agent with polytetrafluoroethylene (PTFE) ^FmBattery separator (Zirconium oxide fibre No.ZYW15 ^Tm, make by Zircar product Co., Ltd).

Also have, we know, isotropic carbon fiber of being introduced as U.S. Patent No. 992,725 of usefulness and polytetrafluoroethylene (PTFE) force together and can do people's tendon in the human body.This piece patent also proposes Zirconium oxide fibre and can replace carbon fiber to use.

We know that also in prior art, packing ring and bearing normally form with polymer powder mixing mold pressing with inorfil, and be 40～80% the polymer powder and the mixture of inorganic matter typical the composition, and these mixtures are through being hot pressed into final products.The precursor of mixture is a diameter less than 100 microns granule, may be mixed into bigger particle before mold pressing.

In all prior art application examples, the mixture of polymer and inorganic matter is not fibre morphology heterogeneous.According to former technology reality, polymer and inorganic matter are just common to be used, and does not require to generate non-isotropic intermediate, and promptly in other words composite fibre, does not generate composite fibre, and " bonding " together simply and polymer is only with inorfil.

At present, a large amount of electrolytic tanks all uses barrier film, and much the electrolytic tank with electrolytic saltwater production chlorine and caustic alkali all is a diaphragm type.This barrier film generally is directly to deposit to form on porous cathode, and the past is deposited as barrier film with the asbestos fibre slurry.This asbestos diaphragm has important disadvantages, and in use, it is very big that asbestos expand, and can stop up the space between anode and cathode up to 800%, causes electrolytic cell voltage to increase, and barrier film itself also is subjected to the loss of the gas of emitting from the anode of close proximity.

In order to reduce the expansion that is used for the conventional asbestos diaphragm of electrolytic tank that chlorine and caustic alkali produces, one of improving one's methods is with asbestos and polymer, the particularly barrier film made from fluoropolymer.For example, can be referring to U.S. Patent No. 4,410,411(Fenn etc.) and U.S. Patent No. 4,070,257(Motani etc.) the relevant technology in, also can be referring to U.S. Patent No. 3,723,264(Leduc etc.) and U.S. Patent No. 3,694,281(Leduc etc.) asbestos-membrane for polymer that is used for the electrolytic tank that alkene produces of these two pieces of patent introductions.

Also have some background technology, as U.S. Patent No. 4,354,900(Hruska etc.) asbestos diaphragm of the zirconia modification that proposes.In this piece patent, add zirconia solution or powder and only be improver, thereby not a kind of composite fibre of barrier film makes as asbestos fibre, and the mixture of asbestos fibre and polymer modification just.

Also the someone proposes superfine particle is mixed in the thermoplastic materials of fusion, again with this thermoplastic plastics shaping.For example U.S. Patent No. 4,126,536 granules of having discussed submicron order (as titanium dioxide) are added in the thermoplastic of fusion, in the process of extrusion molding, squeeze out the fiber that can be used for making barrier film, but be mixed with granule in this fiber, also promptly be sealed in the fiber, thereby the granule in the polymer has lost surface characteristic.

Afterwards, general background technology comprised that its available U.S. Patent No. 4,253,935 was as representative with the bonding barrier film of making the electrolytic tank that is used for chlorine and alkali metal oxide production of teflon (Teflon) and zirconia/magnesia.But actual the same with other background technology, this piece patent is not made the composite fibre barrier film yet, but removes to cover high polymer with inorganic matter.

Have now found that can utilize the surface characteristic of inorganic matter particulate to make inorganic matter/polymer composite fibrous, this composite fibre is made up of inorganic matter particulate and organic polymer.

As inorganic matter, fluoropolymer is the combination of our a kind of resistance to chemical attack composite fibre of adopting as organic polymer with metal oxide for superfine electron tube.Composite fibre often is dry free flowable granule, and great majority often are with color owing to contain inorganic component.Each independently fiber can both be dendritic (but not having this necessity).Sometimes inorganic matter is bonded in securely in the polymer and makes fiber be dendroid.

The present invention has summarized a kind of non-isotropic, organic composite fibre that adds inorganic non-even attitude.This fiber is made of the organic polymer of fiber shape and inorganic matter particulate tiny, infusibility.The inorganic matter particulate combines securely with polymer, enters polymer surfaces at least basically, unless so that with fiber destruction, otherwise be difficult to they are come out with physical method for separation from fiber.

The present invention also provides a kind of method of making inorganic-polymer fiber.This method for making comprises:

(1) particles of inorganic material shape material mixes mutually with the precursor granule of described polymer fiber;

(2) make this mixture place high temperature, this temperature is to being enough to make organic polymer softening and flow and do not decompose under pressure;

(3) this mixture is ground and sheared to fierceness under this temperature, its time be enough to make softening organosilane precursor particle grind and the shear pressure current downflow and in the presence of the inorganic matter particulate fibration, thereby these inorganic matter particulates and the organic polymer that softens combine in fibroplastic process securely.

Based on the person's character of inorganic matter and organic polymer, the fiber of generation demonstrates desirable stable.A purposes of composite fibre of the present invention is to make the barrier film of dimensionally stable in the chloro-alkali electrolytic tank.Composite fibre of the present invention is not only hydrophilic, and is submissive, and resistance to chemical attack, and lower than the cost of equal some organic polymers that weigh.In addition, be inorganic component with magnesium silicate or analog possibly although make this fiber, it need not to use the raw material of asbestos and so on, caused infringement to health when having avoided using asbestos fibre.

The invention provides a kind of inorganic-polymer composite fibrous dividing plate, preferably be used for the barrier film of electrolytic tank, especially produce the electrolytic tank of chlorine and caustic alkali.Composite fibre barrier film and polymer modification asbestos because its expansion is little, thereby not only strengthen its chemical resistance in the diaphragm cell environment every comparing greatly, and the variation of ability operating condition, thereby have prolonged service life.In addition, because this barrier film do not use the simple substance asbestos, also just avoided the infringement of well-known workers ' health to the contact asbestos.It is inorganic component that barrier film of the present invention also can adopt some asbestos, still, had better adopt no asbestos prescription.

The invention provides a kind of dividing plate of dimensionally stable of porous, it is connected into textile-like by non-isotropic composite fibre heat to fusion, inorganic matter granule embedded polymer fibres surface (the single fiber front before the braiding had been done discussion).

The present invention also provide one permeable, the method for making that places the barrier film on the substrate of dimensionally stable, this barrier film is used in the electrolytic tank, method for making comprises:

(a) above-mentioned non-isotropic organic and inorganic composite fiber is made fiber pulp or fiber paste;

(b) with above-mentioned inorganic/homogeneous mixture of the compound dimension of polymer slurry utilizes pressure reduction to deposit on the substrate;

(c) deposit is heated to certain temperature, and keeps a period of time, be enough to that composite fibre is fused together and be formed with the infiltrative braided fabric of having of mechanical strength;

(d) be cooled to room temperature basically, just can obtain the barrier film of dimensionally stable under the cell operation condition.

It is to make foregoing barrier film on the substrate that the present invention also provides at the negative electrode by porous.Deposition process comprises the negative electrode that is coated with stain is dipped in the composite fibre pulp mixture, utilizes pressure reduction that the homogeneous mixture of composite fibre is deposited on the negative electrode.

So just the asbestos-free diaphragm of high-quality directly can be used on the negative electrode of chloro-alkali electrolytic tank of current common employing asbestos diaphragm, be need not electrolytic tank is redesigned.Compare with habitual asbestos, and the use in chloro-alkali electrolytic tank, asbestos-free inorganic-the membrane for polymer of dimensionally stable of the present invention also has other advantage that a lot of fronts are not enumerated: (1) is this every having long service life, (2) because heat treatment, the hardness and the intensity of barrier film are all obviously strengthened, make it when electrolytic tank loads and unloads repeatedly, do not damage so easily.(3) general asbestos diaphragm expansion rate can reach 80% in the prior art, the original thickness of polymer modification barrier film is increased about 25%, this is very harmful, and barrier film of the present invention does not expand basically in that operating condition is next, therefore just may use mechanical means (as U.S. Patent No. 3,674,676 described extendible anodes) further reduce the slit between anode and barrier film, and then reduce electrolytic cell voltage.(4) dividing plate of the present invention is suitable for pickling and removes impurity and do not cause barrier film aging.(5) barrier film of the present invention is difficult for damaging because of the current fluctuation that causes inevitably between the overtime on-stream period of factory.

The present invention also has the compression body of composite fibre in the application of others, and as filtering material, such as the filterability filler of making the column chromatography device, the also compressible and sintering of composite fibre is made bearing and packing ring; Can also in a kind of elastomer fertile material, play humidification as the reinforcing agent of elastomeric material.

Usually, the inorganic substances particle of employing generally is material or its mixture of infusibility, just under the physical condition of composite fibre machine-shaping, still keeps the integrality of particle, and simultaneously, they are inertia to polymer fiber matrix.Because the inertia of these inorganic matter particulates, in process, they only with polymer physics combine and not with the polymer chemically reactive.General difference according to the composite fibre product purpose, inorganic component can be pure or contain impurity, can be natural or synthetic, can be simple substance or compound, can be hydrate or analog, perhaps in process, change, as lose hydrate water, can adopt one or more crystalline forms, can be extremely hard (as zirconia) or not hard (as talcum).Suitable inorganic substances can be oxides, carbide, boride, silicate, sulfide, the mixture of nitride or these materials.The present invention also can suitably adopt as silicate such as magnesium silicate, alumina silicate, aluminate, and pottery, cermet, the mixture of carbon granules or these materials are inorganic component.Complex compound also can be used as inorganic component.They can be natural (as talcums), or it is synthetic (as U.S. Patent No. 4,419,278 metal oxides that proposed), also can consider to use the metal of graininess and alloy and composition thereof (for example particulate of the mixture of metal and metal oxide).Use for the majority of composite fibre, adopt valve metal oxide or its mixture for well, more particularly, the metal of forming these valve metal oxide comprises titanium, vanadium, chromium, zirconium, niobium, molybdenum, hafnium, tantalum and tungsten.Other has also being used of oxide of the metal oxide such as the aluminium of related characteristics more.The oxide of other element that is close to valve metal in the employing periodic table such as the oxide of silicon are also very suitable.Because zirconic inertia, for example in pH value is 2～14 scope with chloro-alkali electrolytic tank in the equal chemically reactive not of chemical substance, so our special recommendation with zirconia as the inorganic-polymer composite fibrous inorganic component of manufacturing.

It is the typical inorganic component that zirconia is chosen in special recommendation, also because it is present in nature with Dou zircon ore deposit, usually, the zirconia particulate is a kind of heavy white amorphous powder, exist but also have with crystalline form, fusion druse shape or form that must crystalline form, all these all can use.Natural zirconia has impurity, as containing some zircon (ZrSiO ₃) or hafnium (Hf), natural material such as zirconia pure or that contain impurity all can use in general, or mix use, as the mixture of zirconia and hafnium.Titanium oxide (TiO ₂) (because its inertia) be another kind of useful especially inorganic composition.The titanium oxide of different crystal forms is representative inorganic component.Rutile and anatase or its mixture all may be utilized.If composite fibre uses under the harsh conditions of strong acid or highly basic, adopt pure basically zirconia to leave nothing to be desired.

To the inorganic component that is adopted, any particulate in general, in small, broken bits or all can using that the certain granules size distribution is arranged.Inorganic component also may be a fine grained chippings, and they are actually very in small, broken bits, for example, general about all more than 100 orders (about 150 microns of diameter), modal is more than about 400 orders (36 microns of diameters), thereby can obtain the particulate of " micron order ".But the particulate of submicron order (promptly all particle diameters basically all less than 1 micron) at least must careful usefulness, in order to avoid this component virtually completely is sealed in the composite fibre in the fiber forming process.This a large amount of sealing function has slackened the advantage that particulate brought of fiber surface.Therefore, preferably avoid the particulate with submicron order, or with the micron particles premix or use with.In a word, used here " micron order " particulate is meant the fine particle that is coarser than " submicron order ".But, by weight, account for major part, promptly greater than 50% should be the fine particle of (about 150 microns of diameter) more than 100 orders.Here used sieve mesh is U.S.'s sieve series.Can from particle, powder, lamellar body, granule (comprising a powder), fiber, palpus crystalline substance, crystal and their mixture, select the particle of proper characteristics for use.With the inorganic oxide zirconium is prominent example, and so-called microparticles often is the powder of average diameter between the 1-16 micron, and the particulate of average diameter between 5～12 microns is more typical.Often have this situation to take place, a lot of particulates are too tiny, so that are sealed in the fiber, but because the condition of molding of composite fibre, the influence of the time that continues such as temperature and moulding, particulate just by shallow table be embedded in fiber surface.

The polymer that can be used for making composite fibre generally can be can resistance to chemical attack under the operating condition of using composite fibre and any polymer, copolymer, graft polymers and their composition of mechanical strength arranged.For instance, in chloro-alkali electrolytic tank, so-called resistance to chemical attack promptly refers in the chemical substance of electrolytic tank such as caustic alkali aging.In this example, so-called mechanical strength refers to that promptly selected polymer can keep high-modulus for composite fibre, does not promptly produce inelastic deformation being higher than under the normal temperature [as 100 ℃ or higher (polytetrafluoroethylene (PTFE)-to call the PTFE polymer in the following text, approximately up to 250 ℃)].It is granular being used to manufacture inorganic-polymer composite fibrous starting polymer, comprises powder granule and agglomerate, powdery agglomerate, and the form that the powdery agglomerate can particle dispersion exists and selects for use especially with the particle that the colloidal dispersion form exists.Available polymer beads also has particle, " bar-shaped " particle, and fiber and composition thereof is as the mixture of fiber and particle.When using fibre-forming polymer, using staple fibre, rod-like fibre or the mixture that contains these fibers are for well.This what is called " rod-like fibre " is meant that its draw ratio is no more than about 100: 1 basically.Because this ratio of a lot of fibers is much smaller, as has only 10: 1 to 20: 1, therefore, in the composite fibre preparation process, fiber is easy to " growth ", also this point will be discussed specially below.For simplicity, all these polymer beads can abbreviate " forerunner's particle " of preparation polymer fiber as at this.Generally, be to use the dispersion of powdery polymer to prepare polymer fiber, particularly produce composite fibre.The granule of these dispersions has the characteristic of fine particles, its diameter range is greatly between 0.05～200 micron, for example, the about PTFE polymer dispersed thing below 0.5 micron of diameter range has commodity selling, U.S. Patent No. 4,047,537 has described this dispersion thing, and it is how a kind of hydrophilic electronegative particle diameter disperses thing at about 0.05～0.5 micron colloid shape that is suspended in the water.But when using liquid medium, can allow polymer in this liquid or liquid mixture, to be partly dissolved or swelling.Another useful typical commercial product is a fluoropolymer powdery agglomerate.The powdery agglomerate of typical commodity PTFE polymer, their average diameter of particles is greatly between 0.1～100 micron.

Forerunner's particle of polymer fiber also can consider it is the mixture of various different polymer beads, as fibre blend, the mixture of fibrid thing and particle shape, and use the particulate component mixture, as the mixture of granule, fibre-like and the fibre object of different sizes, length and composition.Term fibrid used herein and fubril are synonym basically, are illustrated in their preparation process to have stood shear action.When using mixture, mixture major part by weight is the particle of grain shaped preferably, particle just, and powder or clava comprise granule and agglomerate that fibrous and fibre-like particles only accounts for small part usually in mixture.

In available polymer, halogen-containing polymer has special advantage, comprise fluorine-containing or chloride polymer, as polyvinyl fluoride, Kynoar, polytetrafluoroethylene (PTFE), fluorinated ethylene propylene, poly-Fluoroalkyloxy ethene (often being referred to as the PFA polymer), polychlorotrifluoroethylene (generally being referred to as the PCTFE polymer), and the copolymer of CTFE and ethene (being referred to as the CTFE polymer usually), also available various acrylate copolymers such as polymethyl methacrylate, water-soluble and water-insoluble dispersion be can make and various phenoplasts (as fluosite), polyethylene used, polystyrene, acrylonitrile-vinyl chloride copolymer, polyvinylidene chloride, polyvinyl chloride; Chliorinated polyvinyl chloride, polyester, pi, polymercaptan, polysulfones and polyolefin etc.Fluoropolymer with excellent in chemical and mechanical stability can be selected the PTFE polymer for use, PCTFE polymer, CTFE polymer or PFA polymer.The PFA polymer also can be thought the copolymer of tetrafluoroethylene and perfluorovinyl ether.Resistance to chemical attack be the PTFE polymer.Used polymer is preferably unprocessed or unadulterated, for example use the most facile commodity usually, rather than for specific use without chemically treated highly finished product, be appreciated that, may contain supplementary element in the dispersion, as surfactant, but, do not use refining polymer usually for for the purpose of the economy.Like this, polymer beads is preferably without chemical treatment, as gluing, dyeing, or the painted pigment etc. that adds, also do not need to carry out machining, as grinding etc.Although not necessarily need, the polymer that also can consider to use highly finished product He have various additives also will be discussed below this puts specially.

Though processing do mixture just can successfully prepare qualified composite fibre, also can use liquid medium.Being used to prepare the normally water miscible medium of liquid medium of composite fibre, can be merely water, and typical liquid medium can be with above mentioned commercial polymer dispersion.Can consider to use qualified liquid medium.Various organic medias are arranged, comprise alcohols, hydro carbons, halohydrocarbon oils, also have liquid mixture, as water and ethanol.The dispersion of non-water-soluble like this acrylic polymer also can use as water-soluble dispersion.

Generally, the desirable any amount of polymer is combined into inorganic-polymer composite fibrous needs as long as can satisfy with the inorganic matter particulate.Used quantity is different because of the person's character and the physical aspect of polymer, and is also different different because of type, granularity and the desired composite fibre that obtains of used inorganic component.Generally, inorganic-polymer complex total amount that polymer accounts for about 1～90%, about 5～70%(commonly used all refers to the percentage by weight of butt material).The best composite fibre of performance is ZrO ₂-PTFE is polymer composite fibrous.Consider that this composite fibre final use is to make chloro-alkali diaphragm of electrolyzer, ZrO ₂Preferably account for the major part of gross weight, promptly surpass 50% of composite fibre gross weight.ZrO ₂-PTFE polymer weight ratio is that the composite fibre of making between about 8: 1 time in about 2: 1 has best hydrophily.The people who is skilled in technique knows that inorganic matter ingredients constitute advantage will give composite fibre the hydrophily of inorganic matter.According to the final use difference, also can make hydrophobic PTFE polymer have big weight ratio.

Inorganic in order to help-polymer composite fibrous moulding, preferably use a kind of matrix of fiber-induction to mix with polymer and inorganic component mixture.This matrix helps the moulding of polymer fiber or keeps the fiber attitude of polymer, thereby helps making desirable composite fibre.The matrix of this fiber-induction is solid preferably, powdery inert substance or its mixture, as not with material or its mixture of polymer or inorganic component chemically reactive.The slaine that can adopt periodic table first family or second family is as fiber-induction matrix.Usually, this mincing is emboliform, and typical matrix has NaCl, CaZrO ₃, aluminium oxide, lime, sugar, sand, graphite etc.Be added to this matrix in polymer, the inorganic component mixture and can account for the about 10～2,000% of polymer and inorganic component gross weight, in addition more, more usually about 20～500%.Thereafter, this matrix can be removed from composite fibre with the combination of any mechanical means or method, so that isolate granule from fiber, as with the method for sieving bigger matrix granule being sifted out from fiber.From final composite fibre product, remove matrix for a full due if need, preferably use dissolvable matrix, as be dissolved in the matrix (water-soluble base of NaCl and so on) of rinsing liquid, and it can separate with mechanical means earlier, and the method that washes with water is then removed from final products.

Powdered inorganic material equally also is a kind of useful matrix.Thereby a kind of useful especially matrix is the bulky grain zirconia.Because it is very hard, also being difficult for fragmentation even this oarse-grained zirconia is subjected to grinding in preparation composite fibre process, saying, has been exactly broken, this oarse-grained matrix is easy to just become composite fibre is prepared useful material, can be used as the part of inorganic component at least.Use the bulky grain zirconia also can save and do not want the washing step that saves to isolation medium is required.

No matter select which kind of matrix for use, it is favourable using the average particulate diameter matrix bigger at least 10 times than inorganic component, general all matrix granules remain on more than 100 orders (149 microns of diameters), most of particle diameter distribution from 100 microns to about more than 800 microns, typical average particulate diameter is about 150～300 microns.The most frequently used matrix average particulate diameter is minimum with the ratio of inorganic component average particulate diameter to be more than 20 times.For example, the inorganic component average diameter of particles is 10 microns, and it is common that the matrix average particulate diameter then is 200 microns.

In polymer and inorganic component, except fiber-induction matrix and liquid medium are arranged, also have multiple additives and reagent, particularly use the commercial polymer of decentralized system all the more so.Typical additive has dispersant, defoamer and wetting agent.Common reagent also comprises stabilizing agent, and as dispersion stabilizer, UV light stabilizing agent etc. also have dyestuff and other colouring agent, their most typical deliberately addings in the mixture preparation, but in the preparation commercial polymer, add.

Usually, the first step of composite fibre product method for making is the mixture of preparation inorganic component and polymers compositions, preferably prepares in suitable liquid medium.Inorganic component and polymers compositions can give mixing and make pulp or pasty consistency.

But premixed is not essential.For example, inorganic and polymers compositions can be put into grinder, preliminary grinding just can make inorganic and polymers compositions is blended into pulpous state and/or pasty state, in premixed and/or blend process, can add liquid medium, also comprise the temperature that improves mixture in the process, for example, according to characteristic heated polymerizable thing and inorganic component under high temperature of used polymeric material, in grinding and/or shear, acutely grind and/or shear polymer and inorganic component simultaneously, such as using ball milling.Certainly preferably use ball mill, also can adopt shearing blender, ribbon blender, twin-screw blender, Brabender ^TMBlender, Bandnry ^TMBlender or Hobart ^TMBlender, as long as blender has heater, any violent shearing and/or Ginding process all can use, and comprise using scraper and beaker or grinding body and grind bar, their blend efficient is not high certainly.Usually, the person's character of inorganic component makes them can be used as grinding agent.Fiber-induction matrix is as (NaCl also can be used as grinding agent.In addition, the metal of loose infusibility and/or ceramic grinding media can be used for improving the grinding efficiency of ball mill as steel ball or Ceramic Balls (its representative diameter is 0.2～2 centimetre).

Usually, heating-up temperature and time should be enough to make polymer softening, can flow under pressurized, and pressurized then is not difficult for flowing, and the unlikely polymeric material that causes obviously decomposes.Typical intensification scope be about 50 ℃ to about 100 ℃, though also can reach higher temperature, shorter when being generally.Be that the heating grinder makes it to reach this temperature when adopting grinder.For example, use the PTFE polymer beads, heating-up temperature is usually at about 100～180 ℃, preferably about 130～150 ℃.But heating-up temperature is different and different according to used polymer and form thereof.Any is arranged is weight, to make the temperature that mixing fully of polymer and inorganic component reaches essential to guarantee that inorganic component combines at least basically fully with polymer exactly, just can make inorganic component and polymer scale synthesizing inorganic-polymer composite fibrous physical aspect.Heat time heating time, best was about 1 hour generally from 10 minutes to about 2 hours.3 hours or longer time also can be considered, but are uneconomic like this.Beginning preferably to use ventilation unit to drive volatile matter, as the aqueous vapor in the slurries between the period of heating.In typical 1 hour by a definite date heating process, usually at preceding 5 minutes to 30 minutes use ventilation units.

When using grinder, in the grinding or shear history of heating, heating also deficiency so that polymer becomes is easy to flow, but as be impacted and flow, thereby this polymer has ductility: if polymer is not subjected to shear just can flow (heating for example excessively heats up), just can not obtain discontinuous fiber production.Therefore, heating-up temperature remains on below the temperature that causes polymer flow, therefore aggregated particles each all be sheared independently, because it is ductile, it can be plasticated and be pulled into fubril shape (as through grinding bump), clashes into this processing and also utilizes polymer beads " growth " to become polymer fiber, and these single particles that are sheared bond mutually being heated and clashing under the mobile condition, drawing-down and growing, typical bump are ground the fiber shape that produces and are exactly liked spider or branch.The radiation shape for example paniculate or band is examined.But can expect to generate various fibrous, comprise the bar-shaped single fiber of no branch that some are short, suitable length also arranged with branch shape, with PTFE polymer one zirconia blend as the model is example, how much relevant with Ginding process dominant fiber shape is, with the bump polishing, based on the spider shape and the dendriform of generation multi-branched, and the spin finishing rule generates more single fiber.

When fiber generates and grows, inorganic component particulate and fibrous polymer substrate are bonded together securely, this bonding is due to the machining, the bonding degree is very inequality, in fact some particles are exposed to polymer surfaces, resemble a tooth in the chewing gum, just are partially submerged into, if shearing and fiber growth are continuing, other particle is then enclosed in the polymer.Have a bit very important: not every inorganic component particulate is enclosed among the polymer fiber entirely, and this point can be guaranteed cellulose and have the characteristic of inorganic component particulate.For example, use the surface of hydrophilic polymer to have hydrophobicity, make the inorganic component particle be bonded in the polymer substrate normally easy to reach widely or continuously, bonding degree difference, have plenty of loose surface and embed, but also some particle is enclosed in the polymer substrate, the difference of this bonding degree is subjected to used Ginding process, used temperature, the ratio that inorganic component is shared and the influence of milling time.For example, with regard to regard to model's PTFE polymer one zirconia, if the zirconic part by weight of inorganic component accounts for major part, use abrasive media during grinding, about 140 ℃ of heating-up temperature, grind the polymer fiber that just can produce a lot of branches in 2 hours on a polymer substrate, the bonding process is expanded down always, so that final polymer is covered by the inorganic component particle fully.Heating-up temperature is higher, will produce more single, the fiber of branch not, and the overlay capacity of inorganic component particulate is also less.Be used to make the composite fibre of chloro-alkali diaphragm of electrolyzer, coarse as in preparation and process, handling, but it is good to find that composite fibre uses, and does not find the harmful inorganic component of electrolytic tank is come off.Composite fibre is not simple mixture, but one have particle to be exposed to polymeric fiber surface, is bonded in the combination of a lot of fibers of the different physical aspects in the polymer simultaneously securely yet.Like this, do not destroy fiber, the inorganic component particulate just is difficult for separating from composite fibre.For example, even under harsh, fierce processing and service condition, composite fibre and goods thereof also can keep not separating state.

The particle overlay capacity of polymer surfaces the most directly is the influence that is subjected to inorganic component and this example of polymer.This ratio depends on the enduse of composite fibre.For example, the composite fibre of making is as chloro-alkali diaphragm of electrolyzer, and preferably polymer surfaces is virtually completely covered by particle, and the particle of enclosing in the polymer is minimum, and the particle that promptly is exposed to the outside is maximum.Thereby useful granule surface area maximum, so just strengthened the hydrophily of barrier film.Other application can push or sinter into bearing or packing ring wadding, maybe can bond and make filter paper or other paper products or as filler such as elastomeric reinforcer etc. as composite fibre.The ratio of polymer and inorganic component is different.For example in the processing of extruding or sintering, it is favourable that organic polymer is preponderated, and inorganic component only provides few surface area.As mentioned above, after processing inorganic component and polyblend are closed, can find to have generated various fibre morphology usually.

Use ball mill to clash into polishing, the intensification of operation produces dry fiber product usually, with physical method (as sieving) abrasive media is separated earlier, if product is moist, also available similar physical method for separation is gone out.Handle with physical method such as sieve and also can remove dust, as the salt of matrix and the fine dust of inorganic matter of usefulness not.Wind screening also can be used for removing these dust, and then also can be used for fiber separation, and as staple fibre is told from long fiber, other can obtain the separation method of effect same, as after the sieve etc. all can use.If when using the liquid dissolvable matrix, can remove matrix in arbitrary operating procedure washing.General any exemplary particles classification and washing step all are feasible.Promptly do not use collision medium if adopt non-bump to grind, as use the ribbon hybrid technique, can use above-mentioned separation method yet.But can save and separate this step of abrasive media.

In fact, even the draw ratio of the shortest single fiber can often be 20: 1 to 50: 1 greater than 2: 1 also, even can reach 100: 1 or bigger.

The purposes of composite fibre is a lot, comprises making filter and barrier film etc., wishes that fiber can be intertwined, so be favourable with dividing a dendritic fiber.The trunk diameter of the inorganic-polymer fiber of multi-branched is at least about 1～1000 micron, is typically 5～100 microns, and the length weak point person of single fiber is about 2 microns, and the elder is about 25,000～30,000 micron.

Composite fibre main application is to make dividing plate among the present invention, for simplicity, dividing plate described herein, non-organic component all refers to " inorganic component ", and metal and its alloy are not considered to adopt them to make dividing plate.

In inorganic-polymer fiber when slurry that preparation is used as dividing plate, used liquid medium is the aqueous solution normally, the fiber pulp that is appreciated that any viscosity all can be used for preparing dividing plate, all can use until the paste mixture of thickness very from only containing very rare mixture that minute quantity disperses good fiber.Although other liquid except that the aqueous solution (as liquefied hydrocarbon and halogenated hydrocarbon liquid and composition thereof, comprising the mixture with water) also can be considered as liquid medium.But water is still the simplest, most economical, and qualified liquid medium may be the alkali that contains extremely low concentration, as the aqueous solution of caustic alkali, also may be synthetic or natural salt solution or electrolytic tank liquid.As contain about 15%NaCl and 15%NaOH, or the mixture of above-mentioned any material.This alkali lye usually concentration is lower than the 1%(percetage by weight) hydroxide, as alkali metal hydroxide.The concentration expressed in percentage by weight of general alkali lye is lower than 1% so that 0.01%, for the purpose of economy, preferably 0.05～0.5%, also can use dense alkali lye, as the weight percent degree of depth greater than 30%, up to 50%, so that saturated solution.Like this, concentration of lye all can use from 0.01% to saturated solution.In addition, the concentration of salt in the fiber pulp medium (NaCl) also can change in identical scope arbitrarily if desired, for example approximately from 0.01% so that saturated.Fiber-induction matrix in making as composite fibre with salt when having remaining salt to stay in the fiber, can be dissolved in the liquid medium in the dividing plate forming process.

The alkali here is hydroxide always, is typically the hydroxide of alkali metal or alkaline-earth metal, and their mixture.The most frequently used is NaOH or potassium hydroxide, and NaOH is more economical.

In addition, fiber pulp can add the composition that some are beneficial to its physical property of improvement.The general surfactant that adds can make material moistening, can add any known wetting agent, normally the surfactant of nonionic.Certainly other also can consider use.Representational nonionic surface active agent has octylphenoxy polyethoxy ethanol and dioctyl sodium sulfosuccinate, the supplementary element of this fiber pulp even can be that other fiber comprises asbestos fibre, also can add a little thickeners in fibrous medium, be typically thickener elder generation and medium blend, add composite fibre again and make it fusion, this thickener includes, but is not limited to marine alga derivative, polysaccharide, xanthan gum derivative, polyacrylamide, soluble starch modifier, animal glue, colloidal silica gel etc.When low concentration used, thickener can make fiber pulp viscosity improve 2 or 2 above orders of magnitude.And very little to its density influence, if there is not above-mentioned thickener, the viscosity of fiber pulp generally about 10 centipoises, adds suitable viscosity intensifier, and its viscosity improves greatly, as reaching 1,000,000 centipoise or higher.The thickener that adds fiber pulp weight about 0.01～10% can get the fiber pulp of desired viscosity.Use xanthan gum derivative thickener, effect is best.Fiber pulp viscosity can be by being increased to 1000 centipoises about 10 centipoises that do not add thickener originally.

Fiber pulp of the present invention contains 5～600 grams of having an appointment for general every liter, the surfactant of 50～200 gram solids (inorganic-polymer fiber adds fiber-induction matrix arbitrarily) and 0.01～0.1% weight preferably, amount of polymers is with the characteristic of polymer in the composite fibre, particularly its physical aspect is different and different, existing special argumentation the in this front.

Dividing plate can give moulding with the adoptable method of any present technique.For example, make fiber pulp, form with conventional paper technology deposition again with the prescription of system barrier film, or (normally a kind of film) makes barrier film on a kind of antiseized substrate, and then takes off with form of fabric or thin layer form and to be used for cathode of electrolytic tank, as in US Patent No 4,070, institute's opinion in 257, the slurry thing can deposit superincumbent substrate, general any available substrate thing, often be (as the screen cloth) of porous, porous plate, substrate (as film), or electrolytic negative plate.The general this barrier film negative electrode that has immerses fiber pulp earlier, again cathode can is vacuumized and makes.Barrier film being resembled deposit desirable, mainly is the cathode surface that is deposited on activation.As U.S. Patent No. 4,410, described in 411.It is good that barrier film directly is deposited on the negative electrode.Typical method is, makes inorganic uniformly-polymer composite fibrous slurry earlier, and the negative electrode that will be coated with stain is soaked into fiber pulp, can stir simultaneously, and whole then cathode can vacuumizes.Here it is is used for being prepared by fiber pulp the what is called " vacuumizing method " of barrier film.

Being generally used for making the fiber pulp vacuum moulding machine is 0 millimetres of mercury beginning as the vacuum on the negative electrode on the substrate, then can be 20～250 millimetress of mercury (being lower than 1.0～10 inches of mercury), thereafter the more high vacuum that can reach to capacity of equipment again, as 650～750 millimetress of mercury, (about 25～30 inches of mercury).The suitable time of finishing from initial low vacuum to high vacuum is about 5～30 minutes.Usually can keep capacity of equipment high vacuum in one's power 5～30 minutes.If it is longer to reach capacity of equipment vacuum required time in one's power, then keep the time of high vacuum shorter, the time that vacuumizes should be enough to make fiber pulp to be coated on the substrate surface equably, take out the substrate (as negative electrode) that so applied dry, can dry simply, but the most frequently used is the drying that heats up, as rising to about 130 ℃ from about 50 ℃.More typically intensification scope is about 70 ℃～100 ℃, and the drying time of heating up can be from half an hour to 4 hour, or longer.For the purpose of economy, be no more than 3 hours usually.With the dividing plate that this step is made, typical thickness is approximately 0.03～3 centimetre, and (about 5～500 mils) more generally are about 0.3～1.5 centimetre (about 50～250 mils).

Next step is the heating barrier film, and heating-up temperature and time are depended on the character of inorganic-polymer composite fibrous used polymers compositions.Generally, heating-up temperature and time to be enough to make inorganic-polymer composite fibrous softening with melting adhered fiber, but do not cause polymer that obvious decomposition is arranged, with the PTFE polymer is that the composite fibre of component is an example, approximately available 300～390 ℃ of the polymer melting temperatures of composite fibre, 325～370 ℃ comparatively typical.About 0.25～3 hour usually heat time heating time.About 0.25～1.5 hour comparatively economical.Be appreciated that above-mentioned drying and heating and melting can be combined into a step, can progressively improve temperature usually, beginning is dry, then makes the fibers melt of adhesion.

For instance, can place oven to heat on the negative electrode that preformed barrier film applies, make whole barrier film all reach required temperature, to guarantee polymer fusion the most completely.Heating-up temperature and time to be enough to make inorganic-polymer composite fibrously fully be fused together, generate stable mechanical performance, infiltrative " fabric " (as be coated on the negative electrode " fabric ") arranged.Because the different in kind of the polymers compositions that uses can obtain discontinuous inorganic matter-polymer composite fibrous barrier film.Negative electrode with barrier film or coating barrier film is cooled to room temperature then.The preparation chloro-alkali electrolytic tank of packing into.

The negative electrode that has the inorganic matter-polymer composite fibrous barrier film of dimensionally stable, above normally inorganic-polymer composite fibrous barrier film directly being deposited on, or preformed braiding shape barrier film is placed on it.The negative electrode that we recommend generally is to be made of the cathode tube integral body of traversing electrolytic tank, is designed to interlaced shape, and forms polynary electrode with the anode of arranged vertical.US Patent No 2,987,463 have described the example of this negative electrode.This negative electrode is that the typical case is porous, as netted, and porous chips or ductile metal.Usually make wire screen, be called the inner cathode chamber.The material that constitutes negative electrode can be the material that adopts in any this technology, as nickel, iron and alloy thereof, and steel negative electrode for example.

The product of the technology of above-mentioned high praise is the barrier film that evenly bonds, and also can be the adhesion barrier film that further directly is coated on the negative electrode.The typical weight per unit area of the barrier film that is deposited as is about 3～12 kilograms/square metre.For by the polymer composite fibrous barrier film of making of zirconia-PTFE as example, about 4～7 kilograms/square metre more common.Contain the barrier film that titanium oxide replaces zirconic composite fibre to make for other, weight per unit area is littler, as is lower than 3 kilograms/square metre even lower.Typical this barrier film is compared with the polymer modification asbestos diaphragm of producing with former technology, swelling not basically under the cell operation condition.And the common swelling about 25% of the latter.In addition, the present invention is easy to realize barrier film is deposited on the negative electrode, but go back the barrier film on the plane that the neither one mesh cathode limited basically, such barrier film can increase the effusion of hydrogen, conventional barrier film then can be by vacuum deposition steps with a part by this plane.The negative electrode of coating barrier film of the present invention is convenient to take off from negative electrode, weight limit a bit is, with the old barrier film of crossing, as the high-quality product made from PTFE polymer and zirconia, can simple being eliminated and needn't be through special treatment, and need not prevent to remove the healthhazard that conventional barrier film brings.

The representational method for making of inorganic-polymer fiber is as follows: inorganic component is put into container, add the dispersion thing of polymer again.Both thoroughly mix back adding fiber-induction matrix (as salt) and mix repeatedly, get the container that an oven dry sample is used, and claim the gross weight of mixture, are warming up to as 160 ℃ again, dry 1 hour, check the weight of mixture.Continue oven dry to remove all liq that is added in the polymer dispersed thing.The material of finish-drying and mixing is put into the ceramic pot of a preheating, should make an appointment with half to fill up abrasive media in jar, and intensification preheating (as 160 ℃ of heating 1 hour).Fill the ceramic pot 30 minutes of mixture 160 ℃ of heating.Content in the jar is put into a grinder, adjust temperature and remain on 160 ℃, grind certain hour.If grind under different temperature, the step of oven dry and preheating can be adjusted.

In order to make those skilled in the art be easy to understand the present invention and effective some optimum implementation, provide following example.

Example 1

Get 110 gram PTFE polymeric dispersions Teflon ^TMCompany of 30B(Du group, E.IDu Pont de Nemours ﹠amp; Co).Wherein contain about 60% solid (wetting agent that comprises the nonionic that accounts for solid weight about 6%) that is scattered in the water.In dispersion, the true footpath of PTFE polymer beads scope is 0.05～0.5 micron.The average diameter of most of particle is about 0.2～0.5 micron.Add above (44 microns of the diameters) ZrO of 150 grams, 325 orders ₂Powder, 800 gram NaCl and 2400 gram diameters are the steel ball of 0.5 inch (1.27 centimetres).Step is identical with example in above-mentioned " representative processes process ", and just heating-up temperature is 140 ℃.

Simultaneously, ball mill is preheated to 140 ℃, will disperse thing put into ball milling be heated to 140 ℃ 1 hour and grind it.At preceding 10 minutes of heating, ball milling will ventilate and remove aqueous vapor in the water-soluble dispersion thing.Be that the screen cloth of 0.375 inch (0.9525 centimetre) sieves with diameter then.Remove steel ball, the composition of product is the multi-branched of highly-hydrophilic, rough surface, non-isotropy, profile and crossgrained zirconia-polytetrafluoroethylene (PTFE) composite fibre and particle inorganic component that do not wait, that form differs.Generally, in fact the draw ratio of all single fibers all greater than 2: 1.A lot of trunk length are bordering on 10,000 microns, about 20 microns of diameter.The fiber of making is ecru, can flow freely, some loose granule, and hand touches drying, feel and quality softness, and the fiber proportion of malcompression is about 4～5 gram/cm ³

Example 2

The step of repeated experiments 1 is except restraining-48 to+100 purpose CaZrO with 156 ₃Replace 800 gram NaCl and with the Brabender blender ball milling in generation, product is that the zirconia-PTFE of the size shape height branch similar to example 1 product is polymer composite fibrous.

Example 3

Repeating the step of example 1, is 100 microns PTFE polymer powder but use average diameter, mixture heated to 135 ℃ rather than 140 ℃.Product is that the zirconia-PTFE of height branch is polymer composite fibrous, and its size shape is all similar to the product in the example 1 with general characteristic.

Example 4

With 45 gram PFA polymeric dispersions, 45 gram zirconias and 240 gram NaCl mix, by the step of describing in " representative processes process ", with No. 15 steel balls (0.25 inch promptly 0.635 centimetre of diameter) at this mixture of grinding in ball grinder, 110 ℃ of heating 40 minutes, ventilated in preceding 20 minutes, product is that the zirconia-PFA of the height branch similar to example 1 size shape and characteristic is polymer composite fibrous.

Example 5

Repeat the step of example 4, but restrain TiO with 45 ₂Replace ZrO ₂Product is that the zirconia-PFA of the height cladodification similar to example 1 product size shape and characteristic is polymer composite fibrous.

Example 6

Repeating the step of example 4, is not 110 ℃ but use 135 ℃ of prestige.Usually, the product draw ratio was greater than 2: 1.Zirconia-the PFA of the height cladodification that its characteristic is identical with example 1 product is polymer composite fibrous.

Example 7

The above Zirconium oxide powder of 325 orders (44 microns of diameters) of the PTFE polymeric dispersions that the example 1 of 0.4 part of weight is used and 10 parts of weight is packed into behind the mortar together, put into baking oven, 100 ℃ of heating 5 minutes, take out mortar and have gloves on immediately and firmly mix and ground 2 minutes with pestle, then the mixture in the mortar is poured in the bottle of filled with water, cover bottle cap, fierceness is swayed.After leaving standstill, residual Zirconium oxide powder sinks immediately, and the zirconia-PTFE that obtains being scattered in the water is polymer composite fibrous, as the cream-coloured fibrous particle described in the example 1.

Example 8

With 110.23 gram sodium chloride, 2 gram diameters are pre-mixed less than 53 microns boron nitride (BN) particle and the above PTFE polymer dry powder of 2 grams, 12 orders.To fill the highdensity Al of 317.3 grams ₂O ₃1.2 liters porcelain jar of ball is preheated to 125 ℃, pre-composition is poured in the porcelain jar of preheating, grinds 1 hour.Mixture reaches 148 ℃ at last.Abrasive material sieves and removes Al ₂O ₃In disperser, wash behind the bead, and on 60 purpose screen clothes, use water rinse.The rinsing thing was placed in the baking oven, 125 ℃ of oven dry 5 hours.Product is the cream-coloured fiber grain of PTFE polymer borazon composite fibre.

Example 9

With 1,315 gram NaCl, 40 gram diameters are less than 44 microns boron carbide (B ₄C) the PTFE polymer dry powder premix in powder and the 25 gram examples 8 is put into one 13 liters ceramic pot with pre-composition, fills the Al of 8.3 pounds of (3.76 kilograms) examples 8 in jar ₂O ₃Bead, and be preheated to 131 ℃ together.Mixture ground in jar 55 minutes, because heating continuously, the temperature of mixture reaches 162 ℃ at last.This abrasive material sieved remove Al ₂O ₃Bead and abrasive material fritter are washed sieving in disperser, put into baking oven, spend the night 130 ℃ of oven dry.It is polymer composite fibrous to obtain 55.42 gram boron carbide-TFE, is the loose trichoid fine fibre particle of light gray.

Example 10

With the Al in the 316 gram examples 8 ₂O ₃Bead is put into the used the sort of ceramic pot of example 8, and is preheated to 145 ℃ together, put into again mix in advance be contain the used PTFE polymeric dispersions of 110 gram NaCl, 4.45 gram examples 1 and 10.82 gram diameters less than 53 microns Al ₂O ₃Mixture.Milling time is 70 minutes.Abrasive material reaches 153 ℃ at last.Sieve with 25 purpose mesh screens again with 16 orders earlier, remove loose salt and Al ₂O ₃After screening, can obtain Al short and small, banded, branch ₂O ₃-PTFE is polymer composite fibrous.

Example 11

In example 8, put into the sort of Al of example 8 in the used ceramic pot ₂O ₃Bead, and be preheated to 130 ℃ together.Mixed 110 gram salt, 4 gram diameters of containing are in advance all packed in this preheating can less than used PTFE mixture of polymers in 45 microns active carbon powder and the 2 gram examples 8, ground 70 minutes, grinding temperature is 140 ℃ at last.Mixture through grinding sieves like that by example 8, cleans, dries.Just when cleaning, add a small amount of hydrophilic oily equilibrium index (HLB) and be the octylphenoxy polyethoxy ethanol of 13.5 liquid nonionic.The result obtains Dark grey, and fibrous charcoal-PTFE is polymer composite fibrous.

Example 12

With Al used in the example 9 ₂O ₃Bead is put into the used ceramic pot of example 9, is preheated to 130 ℃ together.Mixed in advance contain 1315 gram salt, 60 gram talcums (being natural magnesium silicate ore) and 200 gram examples, 8 used PTFE mixture of polymers are put into jar, ground 60 minutes, reach 154 ℃ at last.Through screening out loose salt and free talcum, clean oven dry then like that by example 9.It is polymer composite fibrous that the result obtains the talcum-PTFE of 59.4 grammeter yellow.

Example 13

Do two positive mold of polishing fabulous cold rolling steel, in order to moulding.Die face 2-1/4 inch (5.72 centimetres) dabs each die face with the antiseized powder of magnesium stearate mould.Formpiston be inserted in one high in the mould tube of 2-3/4 inch (6.99 centimetres), male mould face is upwards put zirconia-PTFE composite fibre that 10 grams make with the method for example 1 to the die face of inserting, and makes it dispersion with an agitator.Second positive mold faced down insert the mould tube fiber sample is completely enclosed among two moulds.

With hydraulic press with 10 kip/inches ²(KPST) it is maximum that pressure extrusion sample, pressure reached in 20 seconds.Decompression (nothing keep-ups pressure the time) immediately then.It is 3,05 gram per centimeters that the result is pressed into 5.72 * 0.117 inches big or small density ²Disk.Disk is 350 ℃ of sintering 1 hour, generates a kind of tough and tensile and solid tablet.Similarly the disk product is under 25.4 centimetres of (mercury pressure table) vacuums, at diameter is to form with vacuum moulding machine on 710 microns the screen cloth, and squeezes without hydraulic press.This disk is cut into thick 0.114 centimetre, 6.35 centimetres of internal diameters, the annulus that external diameter is 8.26 centimetres.This annulus is as the packing ring under the ball grinder top cover of 1.2 liters of volumes.This annulus packing ring can successfully use repeatedly and physical property does not descend, and provides very desirable sealing for ball milling.

Example 14

With 1 the gram pale brown look Powdered xanthan gum derivative [its pH value in the deionized water of weight concentration 1% is 5.0～6.6; (Kelzan ^TMS, Kelco company sells)] be scattered in 1 premium on currency, make pasty media, and continue to mix 15 minutes.With 275 grams (fibrid of 50% weight adds salt residue) inorganic-after polymer composite fibrous and salt mixture mixes, be added in the water slurry of this 1 liter of thickness.The composition of this fibrid mixture is to be inorganic component with the zirconia, and polytetrafluoroethylene (PTFE) is that polymers compositions and remaining salt are made with said method.Continue to mix 10 minutes to 1 hour with disperser, obtain uniform fibers slurry.

The aperture is the steel wire negative electrode of 0.093 inch (0.236 centimetre), be pressed into 0.155 inch (0.394 centimetre) thick, be placed horizontally at the bottom of the deposition box.The negative electrode that fiber pulp is put in the deposition box pushes up, and vacuumizes on the negative electrode opposite.Vacuum was increased to 17 inches (0～43 centimetre of mercury table) from 0 in 11 minutes, kept high vacuum 10 minutes, will deposit the negative electrode that covers then and put baking oven into, dried 3 hours at 95 ℃.And be warmed up to 345 ℃, and heated 1 hour, make the barrier film fusion.The softening back of the polymer of composite fibre also is coated on the negative electrode, forms the porous polymer coating.At high temperature, the contact point of adjacent fiber bonds together, and forms the coating of braiding shape, at the staggered fiber surface reservation organic component particle of " fabric ".The result a kind of discontinuous inorganic-polymer composite fibrous being coated on the cathode surface.The negative electrode of this coating barrier film is cooled to the room temperature electrolytic tank of can packing into.The product of above-mentioned technical process is a kind of sticking barrier film that adheres to uniformly that directly is coated on the negative electrode.Compare with the polymer modification asbestos in the prior art, this coating is in the operating condition of electrolytic tank swelling not basically.The negative electrode of the coating barrier film of making is like this adorned with liner, is contained in the desk-top electrolytic cell anode opposite, laboratory of dimensionally stable then.This electrolytic tank adopts the slit configuration, uses saturated brine as anolyte.About 90 ℃ of serviceability temperature.This electrolytic tank that has above-mentioned barrier film comes into operation, and not only performance is better than having conventional modified asbestos diaphragm cell, and longer service life, operate saferly, has the ability of stronger anti-operating condition change.Show in the I below the results are summarized in.

Example 15

According to the general step of example 14, just zirconia-polytetrafluoroethylene (PTFE) composite fibre is to make with ribbon mixer, rather than uses ball mill.Deposit fiber is added every premium on currency to be contained 0.9 gram xanthan gum derivative and does with vacuum fiber directly to be deposited on the negative electrode of porous in the water slurry of thickener.Press the method oven dry of example 14, heating is then used.Product is the zirconia-PTFE composite fibre of height cladodification, in using the chloro-alkaline cell, uses 39 days after the fusion.Average behavior is as follows: voltage is 3.09v, and electric Liu Midu is 1 ampere/inch ²; Current efficiency is 91.2%, can produce every liter of NaOH solution that contains 133 gram concentration, and the power consumption of per hectare NaOH is 2270 kilowatt-hours.The results are summarized in the table I.

Example 16

At volume is to add in 20 liters the vertical sedimentation basin to contain 1 with every liter to restrain the xanthan gum derivative be the thickness water slurry of thickener.As example 14, add 4000 grams inorganic-mixture of polymer composite fibrous and salt.Mix with disperser.Before deposition, stir slurries, to keep its uniformity with air atomizer.To there be the cathode can of negative electrode to put into below the sedimentation basin, make the complete covered cathode jar of slurries.Vacuum increases to 17 inches (0～43 centimetres) from 0 and kept 17 inches high vacuum again 10 minutes in 10 minutes.

The negative electrode that deposition is good places in the oven, spend the night 100 ℃ of oven dry, and be heated to 350 ℃ 1 hour, make the barrier film fusion.Use the results are shown in Table I.

Example 17

Add water slurry and the salt in the 275 gram examples 14 and the mixture of composite fibre of 2.5 gram xanthan gum derivatives in every premium on currency, mix by means of disperser, vacuum increases to 17 inches (0～43 centimetres) and remained on 17 inches high vacuum 7 hours from 0 in 7 minutes.The barrier film that generates is 104 ℃ of oven dry 3 hours, be heated to again 345 ℃ 15 minutes, make its fusion.Use the results are shown in Table I.

Example 18

After containing the abundant mixing of water slurry (as example 14 samples) that salt that 0.9 gram xanthan gum derivative mixes with 275 grams and composite fibre form by every premium on currency, then be deposited on the negative electrode, vacuum increases to 17 inches vacuum of 17 inches (0～43 centimetre) maintenance 15 minutes from 0 in 10 minutes, barrier film is 115 ℃ of oven dry 2 hours and 345 ℃ of roastings 1/2 hour, and the electrolytic tank performance that constitutes with this negative electrode sees Table I.

Example 20

The water slurry that contains 1.0 gram xanthan gum derivatives and 275 gram salt and composite fibre mixture as every liter of example 14 preparation, method is to stir the water of thickness with disperser, add salt simultaneously and the composite fibre mixture is made the fiber water slurry, with 0～17 inch (0～43 centimetre) vacuum moulding machine 12 minutes.Extract unnecessary filtrate out from the place ahead, last high vacuum keeps a short time, and cathode can and barrier film be 120 ℃ of oven dry 1 hour, 350 ℃ of roastings 1.2 hours, with the electrolytic tank results of property of this negative electrode in showing I.

(the table I is seen the literary composition back)

Example 21

Other 4 with the use current efficiency of the barrier film of the similar methods preparation of example 14 with by U.S. Patent No. 4,444,640 made " SM-2 arranged ^TM" the chloro-alkali electrolytic tank of asbestos and polytetrafluoroethylene (PTFE) barrier film compares in the average current efficient of manufacturer, the result is reported in the following table II.

(the table II is seen the literary composition back)

The table I

Inorganic-polymer composite fibrous barrier film operating data

Instance number on-Line Voltage (v) CE ^*The NaOH power consumption ^*The salt hydraulic head

(No.) % concentration kilowatt-hour/(inch) fate 1(ASI)

G/l NaOH per ton

14 75 2.87 91.0 130 2113 1.9

15 39 3.09 91.2 130 2270 3.5

16 117 3.10 93.3 134 2226 2.0

17 82 2.97 92.5 130 2151 0.8

18 181 3.29 90.0 134 2449 0.8

19 31 3.20 90.5 130 2369 2.75

20 133 3.02 90.4 130 2238 4.0

* 1ASI(ampere/inch) ²=6.45 amperes of/centimetre CE=current efficiency

The kilowatt-hour meter that power consumption in the * table I is consumed with per metric ton NaOH.

The table II

Inorganic-polymer composite fibrous barrier film operating data (subordinate list)

Barrier film weight GAP ^*Voltage ^*The salt hydraulic head ^*% CCE ^*KWH ^*Per ton

（v） Cl ₂

0 2.78 0.18 inch 90.4 2109 of 131,661,021 170 gram

0.82 inch 89.9 2166 of 131,661,172 140 grams, 1/8 in2 .84

0.84 inch 91.9 2164 of 131,661,191 138 grams, 1/8 in2 .90

0 2.99 0.70 inch 93.9 2184 of 131,661,241 128 gram

SM-2AVG ^*36 grams, 1/8 in2 .97 4-10 inch 93.1 2188

^*Be 1 ampere/inch of current density ², 95 ℃ are down used the production concentration is the corrected value of the NaOH of 135 gram/tons, and the salt hydraulic head is in inch, and KWH is kilowatt-hour, and CCE is the current efficiency of correction, G=restrains, AVG=mean value.

^*GAP is the space between anode and membrane surface.The normal space that is used to produce is 1/8 inch (0.3175 centimetre).But the membrane surface of the dimensionally stable that the present invention is made can be by going up anode, or " gap is 0 ".The gap is reduced to 0 from 1/8 inch, generally can saves about 50 millivolts of electricity, or every short ton of (2000 pounds) chlorine is saved 35 kilowatt-hours.

Claims (33)

1, a kind of composite fibre, wherein having superfine refractory inorganic particle is combined on the described polymer securely, at least be securely in conjunction with in its surface, in case the generation physical damage, it is characterized in that this fiber be have inhomogeneous form, to the small part fiber by the fibrillation non-isotropy fiber of branching.

2, composite fibre according to claim 1, wherein said inorganic particle partly are sealed among the said polymer fiber and are embedded on the surface of polymer fiber.

3, composite fibre according to claim 1, the inorganic particle that wherein is combined in securely on the polymeric fiber surface comprises the particle of mechanical impact in polymeric fiber surface.

4, composite fibre according to claim 1 is to be selected from the polymer beads that comprises powder, particle, polymer clump and agglomerate, fragment, rod-like fibre and their mixture with the organic polymer fiber of inorganic particle strong bonded under mechanism wherein.

5, composite fibre according to claim 1, wherein the diameter of organic polymer fiber is 1 micron to about 1000 microns.

6, composite fibre according to claim 1, wherein the particle diameter of most of inorganic particles is less than about 150 microns.

7, composite fibre according to claim 6 is characterized in that the inorganic particle because of be sealed in polymer fiber at the polymeric fiber surface bump is a minimum part.

8, composite fibre according to claim 1 is characterized in that organic polymer fiber is prepared by undressed organic polymer.

9, composite fibre according to claim 1, wherein inorganic particle comprises the superfine sub that is selected from metal oxide, metal carbides, metal boride, metal silicide, metal sulfide, metal nitride, silicate, aluminate, pottery, cermet, carbon, metal, alloy or their mixture.

10, composite fibre according to claim 9, wherein inorganic particle is to be selected from valve metal oxide and their mixture.

11, composite fibre according to claim 1, wherein organic polymer comprises at least a halogen-containing polymer, this halogen-containing polymer comprises fluoropolymer.

12, composite fibre according to claim 1, wherein the trunk length of branching fiber is 1 micron to about 30,000 microns, the length of composite fibre is greater than 2/1.

13, composite fibre according to claim 1, wherein this composite fibre also comprises fiber-induction matrix.

14, composite fibre according to claim 13, wherein fiber-induction matrix is a solid-state Powdered inert substance.

15, composite fibre according to claim 14, wherein fiber-induction matrix is selected from salt, CaZrO ₃, aluminium oxide, lime stone, sand, graphite or their mixture.

16, composite fibre according to claim 1, wherein this composite fibre is soft and easily mobile, the loose and dried particulate material of ecru quality, is combined in the surface of halogen-containing organic polymer fiber securely and is formed by superfine zirconia particles.

17, a kind of preparation method of the composite fibre of inorganic particle and fibrous organic polymer strong bonded wherein according to claim 1, the method comprises:

(1) the forerunner's particle with particulate inorganic thing and organic polymer mixes;

(2) mixture is placed high temperature adding to depress, its temperature is enough to make organic polymer to soften and to produce to flow, but can not make polymer produce substantial decomposition;

(3) at high temperature acutely grind (or shearing) this mixture, its time is enough to make the moving particle of softening organosilane precursor grinding scissors pressure current downflow and form fiber in the presence of particulate material.Thus, particulate matter combines securely with the polymer that softens in the forming process of fiber.

18, method according to claim 17 is characterized in that said mixing also comprises the mixing of liquid medium.

19, method according to claim 18, the weight ratio that it is characterized in that polymer and inorganic particulate material is 1～90%, except the liquid medium.

20, method according to claim 18 is characterized in that said method also comprises method of ventilation, promptly disperses its contained volatile materials when the temperature of rising mixture.

21, method according to claim 17, it is characterized in that heating up should be maintained at about between 50 ℃ to about 200 ℃, and the time can reach about 2 hours.

22, method according to claim 17, the polymer beads that it is characterized in that comprising the particle that is about 0.05 to 200 micron size and major part are that the inorganic particulate material less than about 150 microns sizes mixes mutually.

23, method according to claim 17 is characterized in that this mixing comprises that also cellulose induces the mixing of matrix.

24, method according to claim 23 is characterized in that this mixing comprises that also mean particle size is at least than the fiber-induction matrix to 10 times of the mean particle sizes of inorganic particulate material.

25, method according to claim 17, it is characterized in that grinding or shearing when beginning is that inorganic particle material and organic polymer particles are mixed, and produces slurry or pastel.

26, method according to claim 17 is characterized in that the bonding slurry that is pre-mixed that becomes of particulate inorganic material and organic polymer particles.

27, method according to claim 17 is characterized in that with the particulate inorganic material as grinding agent.

28, method according to claim 23 is characterized in that with fiber-induction matrix as grinding agent.

29, method according to claim 17 is characterized in that grinding or shear action is carried out in blender or mill, and the infusibility bump abrasive media of discrete particles shape is arranged in this mixture or the mill.

30, make the method for the composite fibre of claim 1, wherein inorganic particle is combined on the fibrous organic polymer securely, it is characterized in that the method comprises:

(1) granular inorganic, polybenzazole precursor particle and comminuted fibres are induced matrix (with inorganic matter by same forming) mix mutually, about at least 10 times of the mean particle sizes that this comminuted fibres is induced matrix than the mean particle size of inorganic matter,

(2) mixture is placed high temperature adding to depress, this temperature is enough to make organic polymer softening and produce and flow, but deficiency is so that polymer produces substantial decomposition,

(3) at high temperature acutely grind to form sheared mixt, its time is enough to make softening organosilane precursor particle to produce mobile under grinding or shear pressure and forms fiber in the presence of the particulate inorganic material, and the particulate inorganic thing combines securely with the polymer that softens in the forming process of fiber.

31, a kind of organic/inorganic complex of compression is comprising the composite fibre of the compressed format of claim 1.

32, complex according to claim 31 is characterized in that its compressed format is a sintering.

33, a kind of fibre reinforced materials is comprising the elastomeric matrices that strengthens with the composite fibre of claim 1.