CN100503717C - Polymer, polymer microfiber, polymer nanofiber and applications including filter structures - Google Patents

Polymer, polymer microfiber, polymer nanofiber and applications including filter structures Download PDF

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CN100503717C
CN100503717C CNB2005101162201A CN200510116220A CN100503717C CN 100503717 C CN100503717 C CN 100503717C CN B2005101162201 A CNB2005101162201 A CN B2005101162201A CN 200510116220 A CN200510116220 A CN 200510116220A CN 100503717 C CN100503717 C CN 100503717C
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polymer
fine
fiber
fibered
nylon
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CN1765983A (en
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H·Y·钟
J·R·B·霍尔
M·A·戈金斯
D·G·克罗夫特
T·M·维克
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Donaldson Co Inc
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/52Particle separators, e.g. dust precipitators, using filters embodying folded corrugated or wound sheet material
    • B01D46/521Particle separators, e.g. dust precipitators, using filters embodying folded corrugated or wound sheet material using folded, pleated material
    • B01D46/525Particle separators, e.g. dust precipitators, using filters embodying folded corrugated or wound sheet material using folded, pleated material which comprises flutes

Abstract

Disclosed are improved polymer materials. Also disclosed are fine fiber materials that can be made from the improved polymeric materials in the form of microfiber and nanofiber structures. The microfiber and nanofiber structures can be used in a variety of useful applications including the formation of filter materials.

Description

Polymkeric substance, polymkeric substance micron/nanofiber and the purposes that comprises filtration device structure
Patent application of the present invention is that international application no is PCT/US 01/24948, international filing date is August 9 calendar year 2001, the application number that enters the China national stage is 01815165.5, denomination of invention be " polymkeric substance; polymer microfiber dimension, polymer nanofiber and comprise filtration device structure purposes " the dividing an application of application for a patent for invention.
The application is the pct international patent application of submitting in the name of August 9 calendar year 2001 with Donaldson limited-liability company (the said firm is u s company and resident), specify the All Countries except that the U.S., and require the U.S. Serial No.60/230 that submitted on September 5th, 2000,138 and the U.S. SerialNo.09/871 that submits to May 31 calendar year 2001,590 right of priority.
Technical field
The present invention relates to make and have the polymer materials that has improved the environmental stability of heat, humidity, reactive materials and mechanical stress.These materials can be used to form the stability with improvement and the fine-fibered of intensity, as micrometer fibers and nanofiber.Along with reducing of fiber size, the weather resistance of material becomes a problem day by day.These fine-fibereds can be used for various uses.In an application, filtration device structure can use this fine-fibered technology to prepare.The present invention relates to polymkeric substance, polymer composition, fiber, strainer, filtration device structure and filter method.Application of the present invention is particularly related to from fluid stream, for example filtering particle in airflow and liquid (for example non-water and the water) stream.The technology of describing relates to the structure that has one or more layers fine-fibered in filtration medium.The size of composition and fiber will be selected in conjunction with its performance and weather resistance.
Background technology
The present invention relates to have the polymer composition of the performance of improvement, it can be used for various uses, comprises forming fiber, micrometer fibers, nanofiber, fabric, fiber mat, permeable structure such as film, coating or film.Polymer materials of the present invention is the composition with certain physical properties, and it allows the polymer materials that is various physical forms and form, has to tolerate moisture, heat, air-flow, chemical reagent and mechanical stress or ballistic metamorphism.The invention still further relates to be used for filtered fluid comprise gaseous state and fluent meterial the filtration medium field.Filtration medium comprises at least base material bonded micrometer fibers or the nano fabrics layer in the filtration device structure with mechanically stable.When fluid such as gas or liquid during by filtration medium, the efficient when these layers provide good filtration, high granule capturing ability and minimum flow rate restriction together.Base material can be arranged in fluid front, back or at interior layer.In recent years, use filtration medium to be used for filtering, promptly remove the attention that unwanted particle has caused each industry from fluid such as gas or liquid.The conventional filtration method is to comprise airflow or other air-flow or remove degranulation from liquid flow such as hydraulic fluid, lubricating oil, oil fuel, current and other fluid from fluid.Such filter method is to micrometer fibers and base material requires physical strength, chemistry and physical stability.Filtration medium can be in temperature condition, humidity, mechanical vibration and the impact of wide region, and is entrained in reactive or non-reacted in the fluid, in wearing and tearing or the non-abrasion particle.And filtration medium often requires filtration medium can be in the contrary ability of carrying out self-purification in the pulse (the of short duration adverse current of fluidic is in order to remove the surface coating that degranulation constitutes) of pressing, and perhaps other can remove the mechanism of entrained particles from the filtration medium surface.Reverse purification like this can cause significantly reducing the pressure difference after pulse purifies.Pulse purifies back granule capturing efficient and generally can not improve, yet pulse purifies and can reduce pressure difference, saves the energy consumption of filter operation.Such strainer can remove from use operation down, purifies in water-based or non-aqueous cleansing composition.Such medium is generally made by extracting fine-fibered forms micrometer fibers then on porous substrate intersection fabric out.Such material is made the strainer form that needs such as cartridge type, square position formula, box, flat, packet mode and pocket type then.In these structures, medium is pleated, is rolled into volume, or places supporting structure.
In making non-woven fine fiber filter media, the various materials that comprise glass fibre, metal, pottery and many kinds of polymer compositions have been used.For making diameter little micron and nanofiber, various technology have been used.A kind of method comprises makes the material that is molten state or is in the solution that evaporates subsequently pass through tiny kapillary or perforate.Also can form fiber by " spinneret " that use is usually used in making as the synthon of nylon.The known static technology of reeling off raw silk from cocoons of also can using.This technology relates to uses hypodermic needle, nozzle, kapillary or removable projector.These structures can provide the polymer liquid liquid solution, then can be in the high tension electrostatic field it be attracted to a collecting zone.Because these materials penetrate from projector and quicken in electrostatic field, can form fibrous texture by evaporating solvent, and fiber are very thin.
Owing to can envision the application that are used for the harshness of filtration medium more, require the significantly improved material of performance can stand 100~250, be up to 300 high temperature, 10~90% be up to 100%RH high humidity, gas and liquid high flow rate and can stand to filter micron and submicron particles (about more than 0.01~10 micron), from fluid, remove and grind and non-abrasive property and the strict test of active and nonactive particulate.
Therefore, need high performance polymer material, micron and nano-fiber material and filtration really, be used for filtering high temperature, high humidity, high flow rate and have described micron and the fluid of submicron particles material.
Summary of the invention
The invention provides a kind of improved polymer materials.This polymkeric substance has physics and the chemical stability that has improved.This polymeric fine fibers (micrometer fibers and nanofiber) can be made into useful product form.Nanofiber is that diameter is 0.2 micron fiber less than 200 nanometers.Micrometer fibers be diameter greater than 0.2 micron, but be not more than 10 microns fiber.These fine-fibereds can be made into the form of improved multilayer micro-filtration dielectric structure.Fine fiber layer of the present invention comprises the random distribution in conjunction with the fine-fibered that forms the intersection fabric.Mainly be since fine fiber barrier particulate path and can obtain strainability.There is thin fine paper combination base material thereon that rigidity, intensity and pleated property are provided.The fine-fibered crossover network has a key property, and relatively little space is promptly arranged between the fine-fibered of micrometer fibers or form of nanofibers.Such fiber gap is usually between about 0.01-25 micron, or about 0.1-10 micron.The filter product of the base material that comprises fine fiber layer and cellulose layer and suitably select is very thin.The filtration medium total thickness that fine-fibered makes fine-fibered add base material has increased less than 1 micron.In the use, strainer can stop contained particle by fine fiber layer, and can reach significant capture particulate area load amount.Dust or other are particles contained to form the dust filter cake rapidly at filter surfaces, and keeps high initial and overall particle to remove efficient.
Polymer materials in this announcement has significantly improved the purification of heat, humidity, high flow rate, reverse pulse purification, operational wear, submicron particles, use middle filtrator and the tolerance of other severe condition detrimental action.Having improved micrometer fibers and nanofiber performance is the result who has improved the characteristic of the polymer materials that forms micrometer fibers or nanofiber.And, use the filtration medium of the present invention of improved polymer materials of the present invention that many advantages are provided, comprise efficient, low flow restriction, the high-durability under abradability particle existence condition (with stress or environmental correclation) and the smooth outer surface that does not have loose fiber.The overall structure of filtering material provides the medium of overall thin, is improved the media area of unit volume, reduces the speed by medium, improves medium efficiency and reduces flow restriction.
A better mode of the present invention is a polymeric blends, comprises first polymkeric substance and second polymkeric substance, and described two kinds of polymkeric substance are at high temperature through the different polymkeric substance of adjusting or handle (different on polymer type, molecular weight or physicals).Described polymkeric substance miscellany can react and form single chemical substance or be blended into mixed composition by annealing process physics.Annealing means physical change, as the variation on degree of crystallinity, stress relaxation or the orientation.Material can become one matter by chemical reaction preferably, makes that disclosing through the analysis of difference formula scanning calorimeter is single polymer material.When with the preferred additives material mixing, this material can be formed on the additive surface coating on the micrometer fibers, and the stability of oleophobic property, hydrophobicity or other relevant raising can be provided when being in high temperature, high humidity with difficult operational condition.The diameter of this class fine-fibered be 2 microns to less than 0.01 micron.This fine-fibered can have and comprises the additive material different layer or the smooth surface of additive material outer covering layer, described additive material be partly dissolved on the polymer surfaces or in polymer surfaces, form alloy or two kinds all have.The preferred material that is used for mixed polymeric system comprises nylon 6, nylon 66, NYLON610, nylon (6-66-610) multipolymer and other line style aliphatics nylon composite.Analyzed the molecular weight of a kind of preferred nylon multipolymer resins (SVP-651) with terminal group titration.(J.E.Walz and Taylor, determination ofthe molecular weight of nylon, Anal.Chem.Vol.19, Number7, pp448-450 (1947)).Its number-average molecular weight (M n) be 21,500~24,800.The melting temperature phasor of the nylon 6 with about 45%, about 20% nylon 66 and these three kinds of component nylon of NYLON610 d of about 25% is estimated described composition.(the 286th page, Nylon Plastic Handbook, Melvin Kohan ed.Hanser Publisher, NewYork (1995)).
The physicals of SVP-651 is:
Performance ASTM method unit typical value
Proportion D-792--1.08
Water-absorbent (soaking 24 hours) D-570 % 2.5
Hardness D-240 Shore D 65
Fusing point DSC ℃ () 154 (309)
Tensile strength @ surrender D-638 MPa 50 (7.3)
(every square feet of kip)
D-638 % 350 is extended in fracture place
Modulus in flexure D-790 MPa 180 (26)
(every square feet of kip)
Volume resistivity D-257 ohm-cm 10 12
Hydrolysis degree is that the polyvinyl alcohol of 87.0~99.9+% can be used for this polymeric system.Suitable crosslinked and and the oleophobic property and the hydrophobic additive material mixing of significant quantity of these systems.
Another preferred mode of the present invention relates to the mixed single polymers material that compositions of additives is arranged, and this additive is work-ing life or the processing property that is used for improving fiber.The present invention this on the one hand used preferred polymers comprise nylon polymer, polyvinylidene dichloride polymkeric substance, polyvinylidene fluoride polymer, polyvinyl alcohol polymer, especially listed those materials that when they and strong oleophobic property and hydrophobic additive mix, micrometer fibers or nanofiber are had to be formed on its lip-deep coating.And the miscellany of the miscellany of these polymkeric substance such as these nylon, these polyvinyl chloride, these poly(vinylidene fluoride) in the present invention of great use.And the present invention also can imagine miscellany or the alloy that uses different polymkeric substance.In this respect, the compatible blend of polymkeric substance in forming micrometer fibers material of the present invention of great use.Can use compositions of additives as fluorosurfactant, non-ionic surface activator, low-molecular-weight resin (for example molecular weight is less than 3000 tert.-butylbenzene phenol resins).Described resin is being feature at the oligomeric bonding between the phenol core under the existence condition that does not have methylene radical bridged bond group.The hydroxyl and the tertiary butyl can be at the random sites on every side of ring.Bonding between the phenol core takes place by hydroxyl usually, rather than at random.Similarly, described polymer materials can mix with the non-linearity polymer resin that is formed by dihydroxyphenyl propane that dissolves in alcohol.This materials similar is in above-mentioned tert.-butyl phenol, and it utilizes oligomeric key directly aromatic nucleus to be connected on the aromatic nucleus to form not existing under any bridge bond group such as inferior alkene or the methylene radical condition.
The especially preferred material of the present invention is that diameter is about 0.01~2 micron micrometer fibers material.Preferred Fibre diameter is 0.05~0.5 micron.This fiber with preferred size can provide good strainability, is easy to reverse pulse and purifies and others.The preferred polymeric system of the present invention has attachment characteristic, when contacting with fibrous substrate, can be with enough intensity attached on the base material, and can resist the delamination effect of reverse pulse purification techniques and other mechanical stress.In this mode, described polymer raw material must can stand to be equivalent to the pulse cleaning action power of the conventional filtration condition of process filtration except that reverse simultaneously always attached on the base material.When fiber contacts with base material or during with the fiber on heat or the pressure aftertreatment base material, this sticking power is from fibroplastic solubility effect.But, the characteristic of polymkeric substance, the particular chemical that for example is similar to hydrogen bond interacts, Tg is above or the polymkeric substance of following appearance and the contact between the base material and the polymer formulators that comprises additive, plays an important role when decision sticking power.When bonding, can improve its bounding force with solvent or water vapor plastifying polymkeric substance.
Important aspect of the present invention is to utilize this micrometer fibers or nanofiber to form filtration.In this structure, fine-fibered material of the present invention is formed on the filtering substrate and attached on the filtering substrate.Can use the fabric of the supatex fabric of natural fiber and synthon base material such as nonwoven fabric, synthon and the supatex fabric of being made by the mixture of Mierocrystalline cellulose, synthon and glass fibre, non-woven and woven glass fibre, the plasticity textile material is as extruding UF and the MF film with perforated material and organic polymer.Then flat substrates or cellulose nonwoven fabric are made filtration, be placed in the fluid that comprises airflow or liquid stream and be used for removing the particle that suspends or carry secretly in the fluid.The shape of described filtering material and structure will conform with design engineer's requirement.An important parameter after filter element forms is that it is to heat, humidity or both tolerances.An aspect of filtration medium of the present invention is the test that tolerance is immersed in the ability in the hot water for a long time to filtering material.Submergence test can provide the information of the valuable ability that stands to purify about fine-fibered tolerance wet heat condition and tolerance filtering material in the aqueous solution that mainly contains strong purification tensio-active agent and overbased materials.Preferably, fine-fibered material of the present invention can be immersed in the hot water, and still keeps at least 50% the fine-fibered that is formed at substrate surface.The retention value of fine-fibered at least 50% can keep enough fiber efficient, does not lose filtration capacity simultaneously or increases back pressure.Best is to keep 75% at least.
The fine-fibered filtration comprises two-layer or multilayered structure, and strainer comprises one or more layers fine fiber layer, and fine fiber layer combines with one or more layers synthon, cellulosic fibre or mixed goods or separated by it.
We think that the key property of fiber and micrometer fibers is relevant with temperature tolerance, humidity or moisture tolerance and solvent tolerance in the filtration, especially when micrometer fibers contacts with wet environment or solvent under elevated temperature.And second key property of material of the present invention relates to the tack of material and matrix structure.The tack of micrometer fibers layer is a key property of filtering material, the material that can make manufacturing not can with the base material layering, the micrometer fibers layer adds that base material can be processed into and comprises fold, roll and other structure, and do not have remarkable layering.Find, in the heating steps of manufacturing processed temperature rise to a kind of polymer materials melting temperature near or just be lower than this temperature, be usually less than minimum melting temperature, can obviously improve fiber each other and the sticking power between fiber and the base material.Fine-fibered is at fusing point or be higher than melting temperature and can lose its fibrous texture.The control rate of heating is also very important.Be in its Tc over a long time as fruit fiber, also can lose its fibrous texture.Careful thermal treatment also can improve polymer property, and this is owing to the cause of moving to the surface when additive materials and forming the external additive layer when fiber surface shows hydrophobicity or oleophobic property group.
The standard of performance is that material can be remained valid under various service temperatures, promptly according to final purpose, keeps 1 hour or 3 hours effectively 140,160,270 and 300, keeps 30%, 50%, 80% or 90% filtration efficiency simultaneously.Another standard to performance is that material can be remained valid under various service temperatures, promptly according to final purpose, keep 1 hour or 3 hours effectively 140,160,270 and 300, in filtering layer, keep effective fine-fibered of 30%, 50%, 80% or 90% simultaneously.Can remain valid under these temperature to very important in the water of low humidity, high humidity and saturated air.Micrometer fibers of the present invention and filtering material are considered to have water-fast minute property, and material is still remained valid after can being immersed in and being higher than 160 water, and it is about more than 5 minutes to keep efficient to grow to simultaneously.Equally, can contact with 70 solvents such as ethanol, hydrocarbon, hydraulic fluid or aromatic solvent to be longer than and still remain valid in about 5 minutes, keep the material of 50% efficient simultaneously, can reach the solvent tolerance of micrometer fibers material of the present invention and filtering material.
Fine-fibered material of the present invention can be used for various filtration applications, comprise that strainer that pulse purification and non-pulse purified is used for the collection of dust, internal combustion turbine and engine air import or induction system, heavy duty engine air intlet or induction system, light-duty vehicle engine intake or induction system; The Zee strainer, the compartment air, air in Der Gelaendewagen compartment air, the disc driver, photocopying-toning agent is removed; HAVA strainer in commercial filtration application or resident's filtration application.
Brief Description Of Drawings
Fig. 1 has shown the static projector drive unit that typical production fine-fibered of the present invention is used.
Fig. 2 has shown and has been used in the technology of fine-fibered formation shown in Fig. 1 fine-fibered is guided to device on the filtering substrate.
Fig. 3 compares small i.e. 2 and 5 microns particulate matter, has shown the typical internal structure of propping material and has shown fine-fibered material of the present invention separately.
Fig. 4~11st, the esca analysis spectrum relevant with embodiment 13.
Figure 12 has shown in the embodiment of the invention 5 stability of the micrometer fibers material of 0.23 micron and 0.45 micron.
Figure 13~16 have shown compares unmodified nylon copolymer solvent soluble polymeric amide, the high temperature of embodiment 5 and 6 materials and the stability of high humidity.
Figure 17~20 proved two kinds of multipolymers, a kind of nylon homopolymer and a kind of nylon copolymers mixture thermal treatment and and additive mixed after, just form the one-component material, but this material do not present the recognition feature of two kinds of polymer materialss but show be crosslinked or other modes chemically combined single-phase.
Detailed description of the Invention
Fine fibre in micron of the present invention or the nanofiber layer can be that diameter is about 0.001~2 micron, is preferably 0.05~0.5 micron fiber. The thickness of typical case's fine fibre filter course is about about 1~100 times of fibre diameter, basis weight range be about 0.01~240 microgram/centimetre2
Usually carry particulate matter in fluid such as air and the air-flow. Need to remove some or all particulate matters in the fluid. For example, enter the air stream of motor vehicle cabin, the air in the computer disk driver, the HVAC air, the ventilating air in the clean room uses the purposes of filter bag, barrier fabric, woven material, enters air automobile-used or generating equipment usefulness engine; Enter the air-flow and the air stream that enters in the various combustion furnaces of gas turbine, these air-flows often comprise particulate matter. When being the compartment air cleaner, comfortable and/or attractive in appearance in order to make the passenger, should remove particulate matter. As for the air stream and the air-flow that enter in engine, gas turbine and the combustion furnace, require to remove particulate matter, be because particle can produce substantial infringement to internal workpiece because of various relevant mechanism. In other cases, from the output gas of industrial process or engine or discharge in the gas and contain particulate matter. Can or should by upstream device with this gas discharging before the atmosphere, require fully to remove the particulate matter in these fluids.
By considering following filter medium: surface loading medium and depth media can obtain some basic principles in the air cleaner design and the general understanding of problem. These media types have been done deep research and have been widely used. For example, at U.S. patent Nos.5, some principles relevant with them have been described in 082,476,5,238,474 and 5,364,456. The content of the announcement of described three patents is in full with reference to being incorporated into this.
Usually define according to selected filter limiting pressure " service life " of filter. The pressure increase of filter will be limited on the level of application or designing institute restriction service life. Because this pressure increase is the result of load, concerning the system of same efficiency, long common and higher capacity in service life has direct relation. The tendency that efficient is characterizing the capture medium particle rather than allowing particle pass through. Usually, the efficient that filter medium is removed the particle in the air-flow is higher, and described filter medium is in general just sooner near the pressure drop (supposing that other variable keeps constant) in " service life ". In this application, term " filter effect is constant " refers to keep the efficient of particle in enough removal fluids necessary for selected purposes.
The stationery filter element is the surface loading form of medium of extensive use. Generally, the stationery parts comprise the intensive pad of cellulose, synthetic fibers or other fiber, and these fibers are identical with the air-flow orientation of particulate matter. Paper is made generally in air-flow is seen through, and has fully tiny pore-size and suitable porosity, passes through to stop the particle greater than selected size. When gas (fluid) passed through filter paper, filter paper operated by diffusion and interception in face of the air-flow face, captured and keep the particle of selected size in the air-flow (fluid). Particle is collected on the filter paper surface and is filter cake. Behind the certain hour, filter cake also begins to operate as filter, has improved efficient. This is called " timeliness (seasoning) " sometimes, and namely efficient develops into greater than initial efficient.
Simple design for filtration elements existence at least two class problems as described above. The first, the relatively simple defective of paper, namely breaking of paper can cause thrashing. The second, pile up rapidly for thin filter cake or layer at filter particulate matter on the face of air-flow, increased pressure drop. Adopted the whole bag of tricks to increase " life-span " of surface loading filtration system such as filter paper. A kind of method provides the medium of pleated structure, makes the medium that meets with air-flow larger with respect to flat its surface area of corrugationless structure. Though this method can increase the life-span, but still is restricted. Owing to this reason, the surface loading medium is mainly used in by the relatively slow application of the speed of filter medium, generally is not more than about 20-30 feet per minute clock, usually at about 10 feet per minute clocks or the less order of magnitude. Herein, term " speed " is the average speed (being volume flow/media area) by medium.
Generally, when the air velocity of the paper medium by fold improves, filter life with square the descending pro rata of flow velocity. Therefore, when using the surface loading filtration system of the paper of fold to be used for requiring the large system of air mass flow as particulate filter, need larger filter medium surface area. For example, the diameter of the conventional cylinder fold paper filter parts of the diesel truck on highway that travels is about the 9-15 inch, long 12-24 inch, and it is dark that fold is about the 1-2 inch. Therefore, the filter table area (simultaneously) of medium is generally the 30-300 foot2
Many application especially relate to those application of quite high flow, use the filter medium of another kind of type, sometimes are called " degree of depth " medium. Typical depth media comprises thicker entangled fiber material. Depth media generally characterizes with its porosity, density or percent solids. For example, the medium of 2-3% solid content is about 2-3% that fibrous material (solid) accounts for cumulative volume, and all the other are depth media pads of the fiber of air or the gas compartment.
Another the useful parameter that characterizes depth media is fibre diameter. If solid content remains unchanged, and fibre diameter (size) reduces, and the space between aperture or the fiber reduces, and namely filter becomes more effective, can more effectively capture less particle.
Typical case's depth media filter commonly used is dark, the medium of relatively constant (or consistent) density, and namely the solids content of depth media keeps substantially constant at its thickness. " substantially constant " herein is if refer to that it also only is quite little fluctuation that entire depth upper density at medium changes. Such variation for example is the cause that is produced slight extruding by the outer surface of the container of placing filter medium.
After deliberation the device of depth media of gradient density, for example United States Patent (USP) 4,082, described some such devices in 476,5,238,474 and 5,363,456. Generally, " load " at the granular materials of its whole volume or the degree of depth can be provided to provide substantially the device of depth media. Therefore, such device is designed to when reaching the entire life of filter, with respect to the surface loading system more substantial granular materials of loading. In gradient density system such as the above-mentioned patent those have been designed to provide significant efficient and longer life-span. In some cases, use the surface loading medium as " modifying (the polish) " filter in this sampling device.
Polymeric material has made non-woven and woven fabric, fiber and micrometer fibers. Described polymeric material provides product stability desired physical property. These materials should obviously not change dimensionally, should not reduce its molecular weight, and the pliability that should not become under sunlight, moisture, high temperature or other negative environmental consequences is relatively poor or stress crack occurs or physical degradation occurs. The present invention relates to when running into electromagnetic radiation such as ambient light, heat, moisture and other physical action, still can keep the improvement polymeric material of physical property.
The polymeric material that can be used for polymer composition of the present invention comprises addition polymers and condensation polymer such as polyolefin, polyacetals, polyamide, polyester, cellulose ether and ester, polyalkylene sulfide, polyoxygenated arylene (polyarylene oxide), polysulfones, modification polysulfones and their mixture. The preferred material that belongs to these classifications comprises with crosslinked and non-crosslinked form and the polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate (with other acrylic resin), polystyrene and their copolymer (comprising ABA block polymer) that exist with various hydrolysis degrees (87~99.5%), polyvinylidene fluoride, the inferior ethene of poly-dichloro and polyvinyl alcohol. Preferred addition polymers is (Tg is higher than room temperature) of glassy state normally. This is the situation of polyvinyl chloride and polymethyl methacrylate, polyphenylacetylene combination or alloy or polyvinylidene fluoride and the low crystallization of polyvinyl alcohol material. One class of polyamide condensation polymers is nylon material. Usually, " nylon " term is the common name of all long-chain synthesizing polyamides. Usually, nylon nomenclature comprises a series of numerals such as nylon 66, and the expression raw material is C6Diamines and C6(first digit represents C to diacid6Diamines, second digit represents C6Dicarboxylic acid compound). Another kind of nylon can be made by the epsilon-caprolactams polycondensation reaction under a small amount of water existence condition. It is the nylon 6 (being made by the cyclic lactames that is called EACA) of linear polyamide that this reaction forms. And, also can use nylon copolymer. Copolymer can be mixed various diamine compounds, various diacid compounds and various cyclic lactames structure in reactant mixture, then forms the nylon with randomly located monomer material in polyamide structure. For example, nylon 6,6-6,10 materials are by hexamethylene diamine and C6、 C 10The nylon that two acid blends are made. Nylon 6-6,6-6, the 10th, by copolymerization EACA, hexamethylene diamine and C6、 C 10The nylon that the diacid mixture material makes.
Block copolymer also can be used for method of the present invention. For this copolymer, the selection of solvent swell agent is just very important. Selected solvent is that two kinds of blocks can both be dissolved in solvent wherein. Example is ABA (styrene-EP-styrene) in the dichloromethane solvent or the AB (polymer of styrene-EP). If a kind of component is insoluble to solvent, it will form gel. The example of this block copolymer is
Figure C200510116220D0011160314QIETU
Type styrene-b-butadiene and styrene-b-hydrogenated butadiene (vinyl propylene (ethylene propylene)),
Figure C200510116220D00121
Type e-caprolactam-b-oxirane,
Figure C200510116220D00122
The polyurethane of polyester-b-oxirane and oxirane and isocyanates.
The copolymer of addition polymers such as polyvinylidene fluoride, syndiotactic polystyrene, vinylidene fluoride and hexafluoropropene, polyvinyl alcohol, poly-ethyl acetate; Copolymer, polystyrene, polyvinyl chloride and various copolymer, polymethyl methacrylate and its various copolymers of amorphous addition polymers such as polyacrylonitrile and it and acrylic acid and methacrylate can relatively carry out simply solution and reel off raw silk from cocoons, and this is because the cause that they can dissolve under low-pressure low-temperature. But high crystallinity polymer such as polyethylene and polypropylene just need the solvent of HTHP if carry out solution and reel off raw silk from cocoons. Therefore, polyethylene and polyacrylic solution reel off raw silk from cocoons very difficult. It is a kind of method of making nanofiber and micrometer fibers that electrostatic solution is reeled off raw silk from cocoons.
Find, will contain the remarkable advantage of mixed polymer composition, alloy form or cross-linking chemistry bonding structure of two or more polymeric materials. We think this polymer composition can by change polymer property such as the pliability or the chain activity that improve polymer chain, improve the bulk molecule amount and strengthen to improve its physical property by forming the polymeric material network.
In an embodiment of this idea, can mix two kinds of relevant polymeric materials for obtaining useful performance. For example, high molecular weight pvc and low-molecular-weight polyvinyl chloride is mixed. Similarly, can high molecular weight nylon material and low-molecular-weight nylon material is mixed. And, can mix different types of conventional polymer material. For example, high molecular weight styrene can be mixed with the polystyrene of low-molecular-weight, high-impact. Nylon 6 material can with nylon copolymer such as nylon 6; 6,6; 6,10 copolymers are mixed. And, the polyvinyl alcohol of low in hydrolysis degree as the polyvinyl alcohol of 87% hydrolysis can with degree of hydrolysis be 98~99.9% and higher fully or the polyvinyl alcohol of super hydrolysis mix. Can to utilize suitable mechanism of crosslinking to carry out crosslinked for these all materials in the mixture. Nylon can use the crosslinking agent of the nitrogen-atoms reaction in energy and the amido link to carry out crosslinked. Polyvinyl alcohol material can use hydroxyl activity material such as single aldehydes, and for example formaldehyde, urea, melamine-formaldehyde resin and analog thereof, boric acid and other inorganic compound, twain-aldehyde compound, two acids, urethanes class, epoxies and other known crosslinking agent carry out crosslinked. Crosslinking technological is that people know, understandable phenomenon, and therein crosslinking agent reaction also forms covalent bond between polymer chain, greatly improve molecular weight, chemical resistance, bulk strength and anti-mechanical degradation performance.
Find that additive material can significantly improve the performance of fine fibre form polymeric material. The existence of additive can significantly improve it to the tolerance of heat, moisture, impact, mechanical stress and other Negative environment effect. We have found that when making micrometer fibers material of the present invention as if described additive material can improve its oleophobic property, hydrophobicity and helpful to improving materials chemistry stability. We think because these additives can form protection coating, ablated surface or infiltrate the character that surperficial certain depth improves polymeric material, can improve the fine fibre of micrometer fibers form of the present invention under these oleophobic properties and hydrophobic additive existence conditions. We think that the key character of these materials is to have the strong-hydrophobicity group that also has fuel shedding quality simultaneously. The strong-hydrophobicity group comprises fluorohydrocarbon group, hydrophobic hydrocarbon based surfactants or block and mainly is the oligomeric composition of hydrocarbon. These materials are made the composition with part energy molecule compatible with described polymeric material; described molecule forms physical bond or related with polymer usually; while is related because of additive and polymer; described strong-hydrophobicity or oleophobic property group, formation are positioned at lip-deep protection top layer or become alloy or mixed with polymeric surface layer. Concerning 0.2 micrometer fibers with 10% additive capacity, if additive is moved to the surface, surface thickness calculates and is about
Figure C200510116220D00131
Because the incompatibility of oleophobic property or hydrophobic group in the integral material thinks that migration is to occur.
Figure C200510116220D00132
Thickness to the protection coating be rational thickness. Be 0.05 micron fiber to diameter,
Figure C200510116220D00133
Thickness correspond to 20 quality %. To the fiber of 2 micron thickness,
Figure C200510116220D00134
Thickness correspond to 2 quality %. The consumption of described additive material is preferably about 2~25 % by weight. The oligomer additive that uses with polymeric material of the present invention comprises that molecular weight is about the oligomer of 500-3000, should be fluorochemical, nonionic surface active agent and low-molecular-weight resin or oligomer.
The used fluorine-containing organic wetting agent of the present invention is the organic molecule that is expressed from the next:
R f-G
In the formula, RfBe fluorine-containing aliphatic free radical, G is the group that contains at least one hydrophilic radical such as cation, anion, nonionic or amphiprotic group. Preferred non-ionic material. RfBe contain at least two carbon atoms fluoridize unit price aliphatic organic free radical. It is preferably saturated perfluor aliphatic unit price organic free radical. But hydrogen atom or chlorine atom can be used as substituting group and exist on the skeletal chain. Can fully work although contain the free radical of many carbon atoms, preferably contain the compound that is no more than 20 carbon atoms, because compare short skeletal chain, the utilization ratio of the fluorine of large free radical is lower. RfShould contain 2~8 carbon atoms.
Among the present invention used useful cation group in fluorine-containing organic reagent can comprise can oxygen-free atom (for example ,-NH2) or contain amine or the quaternary ammonium salt cationic group of oxygen atom (for example, amine oxide). This amine and quaternary ammonium salt cationic hydrophilic radical can have following general formula :-NH2、-(NH 3)X、-(NH(R 2) 2)X、- (NH(R 2) 3) X or-N (R2) 2→ 0, in the formula, X is counter anion, such as halogen ion, hydroxyl, sulfate radical, bisulfate ion or carboxylate radical, R2Be H or C1-18Alkyl, and each R2Group each other can be identical or different. R2Be preferably H or C1-16Alkyl, and X is preferably halogen ion, hydroxyl or bisulfate ion.
The used useful anionic group in fluorine-containing organic wetting agent of the present invention comprises the group that can become radical anion by ionization. Described anionic group can have following general formula :-COOM ,-SO3M、- OSO 3M、-PO 3HM、-OPO 3M 2Perhaps-OPO3HM, M is H, metal ion, (NR in the formula1 4) +Or (SR1 4) +, R wherein1Be independently of one another H or replacement or do not replace C1~C 6Alkyl. M is preferably Na+Or K+ Among the present invention the anionic group of preferred fluorine-containing organic wetting agent have-COOM and-SO3The general formula of M. The organic wetting agent of anion fluoride-containing comprises the anionic polymer material, and it is made by the ethylene linkage unsaturated monocarboxylic and the diacid monomer that contain the fluorohydrocarbon side group on it usually. This material comprises the surfactant that is called FC-430 and FC-431 that obtains from 3M company.
The used useful amphiprotic group in fluorine-containing organic wetting agent of the present invention comprises the group that contains at least one above-mentioned cation group and at least one above-mentioned anionic group.
The useful non-ionic group in fluorine-containing organic wetting agent that the present invention is used comprises hydrophilic but can Ionized group under the pH condition of normal agricultural use.Described non-ionic group can have following general formula :-O (CH 2CH 2) xOH (wherein x is greater than 1) ,-SO 2NH 2,-SO 2NHCH 2CH 2OH ,-SO 2N (CH 2CH 2H) 2,-CONH 2,-CONHCH 2CH 2OH or-CON (CH 2CH 2OH) 2This examples of material comprises the material of following structure:
F(CF 2CF 2) n-CH 2CH 2O-(CH 2CH 2O) m-H
In the formula, n is 2~8, and m is 0~20.
Other fluorine-containing organic wetting agent comprises for example United States Patent(USP) Nos. 2,764,602,2,764,603,3,147,064 and 4,069, those cationic fluorochemical chemical reagent described in 158.The fluorine-containing organic wetting agent of this both sexes comprises for example United States Patent(USP) Nos. 2,764,602,4,042,522,4,069,158,4,069,244,4,090,967,4,161,590 and 4,161, the fluorine-containing chemical reagent of those both sexes described in 602.The organic wetting agent of this anion fluoride-containing comprises for example United States Patent(USP) Nos. 2,803,656,3,255,131,3,450,755 and 4,090, the anion fluoride-containing chemical reagent described in 967.
This examples of material is duPont Zonyl FSN and duPont Zonyl FSO nonionogenic tenside.Can be used for polymkeric substance of the present invention additive comprise low molecular weight propylene acid fluorohydrocarbon ester material on the other hand, as have following the Scotchgard material of 3M company of structure:
CF3 (CX 2) n-vinylformic acid
In the formula, X is-F or-CF 3, n is 1~7.
And, comprise that the nonionic alkylene based surfactants of lower aliphatic alcohol ethoxylate, fatty acid ethoxylate and nonyl phenol ethoxylate etc. also can be used as the additive material that the present invention uses.The example of these additive materials comprises Triton X-100 and Triton N-101.
Useful materials as additive material in the present composition is the tert.-butyl phenol oligopolymer.This material aromatic series resol that molecular weight is lower often.This resin is the novolac polymer by enzymatic oxidation coupling preparation.Do not exist the methylene radical bridged bond to produce unique chemical and physical stability.These resol can with various amine and epoxy crosslinked and compatible with various polymer materialss.These materials are illustrated by following general structure usually, it is characterized by that there is not the methylene radical bridged bond with phenolic aldehyde and aromatic group in repeating unit in the phenolic materials:
Figure C200510116220D00151
In the formula, n is 2~20.The example of these phenolic materials comprises Enzo-BPA, Enzo-BPA/ phenol, Enzo-COP, and other relevant phenolic material can be from Enzymol International Inc., Columbus, and Ohio obtains.
Should be understood that to different purposes and have a variety of fiber filter medias.Durable nanofiber of the present invention and micrometer fibers can add in any medium.Fiber of the present invention also can be used for replacing the fibre fractionation in these known media, because its diameter is little, the remarkable advantage of improvement performance (raise the efficiency and/or reduce pressure drop) can be arranged, and has weather resistance preferably simultaneously.
Polymer nanofiber and micrometer fibers are known, but because its fragility to mechanical stress, and owing to the very high chemometamorphism that is easy to of ratio of its surface area/volume, its purposes is very restricted.Fiber of the present invention solves these problems, and therefore can be used for various filtrations, fabric, the pellicle application different with other.
Filter media construction of the present invention comprises the permeable robust fibre medium layer of the first layer or the base material of first surface is arranged.The first layer fine fiber media layer is fixed on the first surface of the permeable robust fibre medium layer of the first layer.Preferably, be that mean diameter is at least 10 microns fiber in the permeable robust fibre material layer of the first layer, better be about 12 (or 14)-30 micron.Permeable coarse-fibred the first layer should be that basic weight is not more than about 200 gram/rice 2, better be about 0.5-150 gram/rice 2, preferably be at least 8 gram/rice 2Medium.The thickness of permeable robust fibre medium the first layer better is at least 0.0005 inch (12 microns), better is about 0.001-0.030 inch (25-800 micron).
In the preferred device, permeable robust fibre material the first layer is a kind of material, if test with this material that the rest part of Frazier permeability test method pair and structure separates, this material just has at least 1 meter/minute rate of permeation, better be about 2-900 rice/minute.At this, when mentioning efficient, unless otherwise indicated, be meant the efficient of measuring gained according to ASTM-1215-89 with the air-flow of 0.78 micron monodisperse polystyrene spheroidal particle with the speed of 20fpm (6.1 meters/minute).
The fine-fibered material layer that is fixed on the first surface of permeable robust fibre medium layer is preferably nanofiber media and micrometer fibers medium, wherein the mean diameter of fiber is not more than about 2 microns, generally be not more than about 1 micron, better less than 0.5 micron, and at about 0.05-05 micrometer range.Be fixed on the first layer fine-fibered material on the first surface of the first layer of permeable robust fibre material, its total thickness better is not more than about 30 microns, better be not more than 20 microns, preferably be not more than about 10 microns, be more preferably the about 1-8 times of scope (better being not more than 5 times) of this layer fine-fibered mean diameter usually.
Some preferred embodiment of the present invention comprises filtration medium, and it generally is generally indicated in total filtration.Some preferred embodiment to such purposes comprise with cylindrical having general some folds that extend by the longitudinal axis equidirectional of promptly vertical and cylinder.To such device, can be as conventional strainer, medium is embedded in two end caps.To typical conventional purpose, if desired, such device can comprise the lining of upstream and downstream.
During some were used, medium of the present invention can be used in combination with other type media such as conventional medium, to improve total strainability or life-span.For example, medium of the present invention can be laminated on the conventional media, uses with the form of piling up; Or join in the dielectric structure that comprises one or more conventional media zone.Medium of the present invention can use the front of conventional media to reach well loaded; And/or be applied in the back of conventional media, be used as modified filter efficiently.
Devices more of the present invention also can be used for the liquid filter system, and promptly being needs filtering particulate material to be stated from a kind of liquid.The present invention also has some devices to can be used for mist collector, for example, is used for the filtrated air mist.
The invention provides filter method.These methods relate generally to use described medium to filter preferably.By described and following embodiment as can be known, medium of the present invention can design and construct especially, to help better providing the long life-span in the efficient system.
The each side of the filtration device structure of the open and claimed various designs of using filtering material in each patent.Authorize people's such as Engel United States Patent (USP) 4,720,292 disclose a kind of radial seal design that is used for filter assemblies, and this filter assemblies has the cylindrical filter element design, and this filter element is with the relatively soft rubber-like end cap seal of cylindrical radial to internal surface arranged.The United States Patent (USP) 5,082,476 of authorizing people such as Kahlbaugh has disclosed the filter design of using depth media, and described depth media includes the foamed substrate with the micrometer fibers material bonded fold parts of this patented invention.People's such as Stifelman United States Patent (USP) 5,104,537 relates to a kind of filtration device structure that can be used for the medium of filter liquide.Liquid entrainment enters into filter body, enters in the inner loop core by the strainer outside, returns active use the in this structure then.Such strainer is particularly useful to the filtered liquid hydraulic fluid.People's such as Engel United States Patent (USP) 5,613,992 provides a kind of air intake filtration structure of typical diesel engine.This structure obtains air from the outside of housing, contains or do not contain the moisture of carrying secretly in the air.Air is by strainer, and moisture leads to housing bottom and discharges from this housing simultaneously.People's such as Gillingham United States Patent (USP) 5,820,646 disclose a kind of Z-shaped filtration device structure, and this structure is used and related to the inaccessible specific folded filter design of passage, this passage requires fluid to pass through one deck filtration medium at least with Z-shaped path, obtains suitable strainability.The filtration medium that forms folded Z-shaped pattern can comprise the fine-fibered of this invention.People's such as Glen United States Patent (USP) 5,853,442 disclosed bag room structures have the filter element that comprises this invention fine fiber structure.People's such as Berkhoel United States Patent (USP) 5,954,849 has shown to be dust collection, is used for processing work produce a large amount of dust in environment after, is handled the big typical air of dust load, and Chalk-dust filtering is useful from airflow.At last, U.S.'s design patent 425,189 of Gillingham discloses a kind of plate filter that uses Z-shaped filtration device structure.
The detailed description of some accompanying drawing
Micrometer fibers in the unit or nanofiber can be formed by the static method of reeling off raw silk from cocoons.Figure 1 illustrates the appropriate device that is used to form described fiber.This device comprises storage tank 80, pump 81 that the polymers soln that forms fine-fibered wherein is housed and rotary-type launching device or the projector 40 that polymers soln is pumped.Described projector 40 is usually by swivel joint 41, the turning unit 42 that comprises many offset holes 44 and be used to connect the axle 43 of preposition face component and swivel joint.Described swivel joint 41 is used for polymers soln is guided to preposition face component 42 by quill shaft 43.Described hole 44 is along the circumferential distribution of described preposition face component 42.Described turning unit 42 can be immersed in the polymkeric substance storage tank by storage tank 80 and pump 81 chargings.Turning unit 42 obtains polymkeric substance from storage tank then, and when it rotated in electrostatic field, solution droplets will as described belowly be quickened by electrostatic field, flew on the trapping medium 70.
In the face of projector 40 but leave with it at interval be abundant flat grid, be fixed with trapping medium 70 (be substrate or mixed base at the bottom of) on it.Air can aspirate by grid.Described trapping medium 70 moves around the cylinder 71 and 72 that is fixed on grid 60 two ends.Use suitable electrostatic potential source 61 and be connected to grid 60 and projector 40 on line 62 and 63, between projector 40 and grid 60, keep high electrostatic potential.
In use, polymers soln is pumped into swivel joint 41 or the storage tank from storage tank 80.42 rotations of preposition face component, liquid left hole 44 or extracted out from storage tank this moment, moved to the trapping medium 70 that is fixed on the grid 60 from the outer rim of projector.Specifically, the electrostatic potential between grid 60 and the projector 40 makes electric charge on the material band, causes liquid therefrom to emit as the fine-fibered of extracting out to grid 60, is collected on base material 12 or the effective layer 14.For the polymkeric substance in the solution, when they flew to grid 60, the solvent evaporation on the fiber was removed.The fine-fibered that is bonded on the basilar fibers is at first run into grid 60.Select electrostatic field intensity with guarantee when polymer materials from projector when trapping medium 70 quickens, its acceleration is enough to make very thin micrometer fibers or the nanofibrous structures of polymer materials formation.The speed that raising or reduction trapping medium move can form the more or less fiber of deposition on the medium, controls the thickness of sedimentary each thin layer on it thus.Described turning unit 42 can have various useful positions.Described turning unit 42 can place on the plane of rotation with trapping medium 70 Surface Vertical, perhaps be positioned at arbitrarily angled on.Described rotating media can positioned parallel, perhaps parallel deviate direction a little.
Fig. 2 is the synoptic diagram that is used for forming the apparatus and method of fine fiber layer on sheet form base or medium.In Fig. 2, sheet form base is launched by volume on device 20.Sheet form base 20a is directed to engagement device 21 then, here will be joined together at the bottom of many segment bases for carrying out the line operation.The sheet form base of the continuous length fine-fibered process unit 22 that leads again, comprising the process unit that reels off raw silk from cocoons of Fig. 1, this spinning unit forms fine-fibered and fine-fibered is deposited on and forms filtering layer on the sheet form base.When form fine fiber layer on sheet form base in formation zone 22 after, fine fiber layer and substrate-guided thermal treatment unit 23 carry out suitable processing.In efficient monitor 24, test sheet form base and fine fiber layer then, and if necessary, in planishing device 25, planish.With sheet form base and the suitable wind2 of fine fiber layer guiding, will reel on the wherein suitable spindle then for further handling 26 and 27.
Fig. 3 shows that diameter is about 2 and 5 microns typical dust granule and scanning electron microscope diagram in typical fibers medium and typical fine fiber structure mesoporosity size relativity.In Fig. 3 A, shown at hole obviously greater than 2 micron particle 31 in the fiber medium 33 of typical particle diameter and 5 micron particle 32.What form sharp contrast in Fig. 3 B is, 2 micron particle are approximately equal to or greater than typical hole between the fiber in fine-fibered knitmesh 35, and 5 micron particle 32 are greater than all holes in the fine-fibered knitmesh 35.
More than the useful filtration of polymer materials of the present invention, the fine-fibered material that the present invention includes micrometer fibers and nanofiber and fine-fibered material of the present invention is made the general remark of each side, the understanding of the present invention being operated the general technology principle is provided.The concrete exemplary materials of the following stated is the examples of materials that can be used for making fine-fibered material of the present invention, and following material has disclosed best pattern.Made these exemplary materials, use be following characteristic and operational condition.Use the electrostatic field of improving oneself to play the electrostatic force of pulling effect, the polymeric spray thing is pulled into very thin filament, obtain diameter less than 10 microns the static fiber that reels off raw silk from cocoons.Though in the static drawing process, can use polymer melt,, the most handy polymers soln makes the fiber that is narrower than 1 rice.When polymkeric substance constituted more minor diameter, the size of fiber was fallen and is helped reducing in solvent evaporation.Based on a variety of causes, choice of Solvent is very crucial.If solvent is done too soon, so fiber can flatten and diameter big.If solvent is done too slowly, solvent can lysigenous once more fiber.Therefore rate of drying and fibroplastic cooperation are very crucial.When high productivity, a large amount of exhausted airs can prevent inflammable gas and reduce the danger of catching fire.Non-flammable solvent is useful.In production environment, processing units needs purification frequently.The situation that the safety and low toxicity solvent can make the workman be exposed to hazardous chemical is reduced to minimum.Static reels off raw silk from cocoons and can operate under the flow velocity of 1.5 miles of every projector per minutes, 8 inches range, 88 kilovolts transmitter voltage, 200 rev/mins projector rotating speed and these conditions of relative humidity of 45%.
The selection of polymer system is very important concerning given purposes.For adopting pulse to purify, micrometer fibers layer as thin as a wafer helps the outside surface that can provide particle capture and release under the very little situation of the pressure-losses making.The preferred diameter that uses should be less than 0.3 micron fibre thin layer less than 2 microns.Good tack is very important between micrometer fibers or nanofiber and its deposition substrate.When the mixture that is made of substrate and micrometer fibers and nanofiber when strainer made, this mixture can be applicable to the good filtration medium of self-purification.Purify described surface by repetition pulse dorsad and just upgraded filtration medium.When applying big reactive force from the teeth outwards, the fine-fibered of poor adhesion delamination occurs owing to pulse dorsad in the substrate, described pulse dorsad from filter interior by the substrate micrometer fibers of flowing through.Therefore, good adhere to and the purposes of adhering to success that basilar fibers and static reel off raw silk from cocoons between the fiber is very important between the micrometer fibers.
The fiber that uses various polymer materialss to make can obtain to adapt to the product of above-mentioned requirements.Fine-fibered with good adherence performance can and contain various nylon such as the polymkeric substance of nylon 6, nylon 4,6, nylon 6,6, nylon 6,10 and multipolymer and their multipolymer make by for example polyvinylidene dichloride, polyvinyl alcohol.Can make fiber with excellent by PVDF, but making the enough little fiber of diameter needs chlorinated solvent.Nylon 6, nylon 66 and nylon 6,10 can carry out static and reel off raw silk from cocoons.But it is for example formic acid, m-cresols, trifluoroethanol, hexafluoroisopropanol equal solvent or very difficult operation, or very expensive.Because of its hypotoxicity, preferred solvent comprises water, ethanol, Virahol, acetone and N-Methyl pyrrolidone.Made extensive studies with this solvent systems compatible polymers.We have found that the fiber that is made by PVC, PVDC, polystyrene, polyacrylonitrile, PMMA, PVDF need obtain structure properties by extra adhesive bonding method.When we also found, ethanol water-soluble when polymkeric substance, Virahol, acetone, methyl alcohol and their mixture and successfully make fiber, they had good adhesion property to substrate, can make the good strainer that is suitable for self-purification thus.When strainer is used for very high dust concentration, by air back of the body pulse self-purification or stranded be useful.The fiber that is made by polymeric amide that dissolves in alcohol and polyvinyl alcohol successfully uses in this purposes.The polymeric amide example that dissolves in alcohol comprises the Macromelt6238,6239 and 6900 that buys from Henkle; The Elvamide 8061 that buys from duPont and 8063 and the SVP 637 and 651 that buys from Shakespear monofilament Company.Other one group of polymeric amide that dissolves in alcohol is 8 type nylon, alkoxyalkyl modification of nylon 66 (with reference to Nylon Plastichandbook, the 447th page, melvin Kohan etc., hanser Publisher, New York, 1995).The polyvinyl alcohol example comprises from Kuraray, the PVA-217 that Japan buys, 224 and the Vinol 540 that buys from Air Products andChemical Company.
Have been found that strainer can be under the extreme environmental conditions.Strainer in the Saudi Arabia desert may be in up to 150 or higher temperature.The strainer that is installed in Indonesia or U.S. Gulf Coast may be in greater than the high humidity of 90%RH and 100 temperature.These strainers also may be in the rain.We find, below the cover of the mobile equipment of car, truck, tractor and the strainer that uses in the building equipment may be in the condition of high temperature (+200), high humidity and other chemical substance.We have studied testing method and have estimated the prolonged property of micrometer fibers system under mal-condition.The filtration medium sample was immersed in the hot water (140) 5 minutes or is in high humidity, high-temperature and the airflow.
Experiment
Use following static drawing process condition to produce following material.
Use revolving expeller system or kapillary needle system to reel off raw silk from cocoons and make following material.These two kinds of systems all can produce essentially identical filamentary material.
Described flow velocity is 1.5 miles of every projector per minutes, and range is 8 inches, and transmitter voltage is 88 kilovolts, and relative humidity is 45%, and the rotating speed of revolving expeller is 35 rev/mins.
Embodiment 1: the influence of fiber size
With end group volumetry (J.E.Walz and G.B.Taylor work " determining of nylon molecular weight ", chemistry annual report Vol.19, Number 7, the 448-450 pages (1947)) analyzes the molecular weight of b by the fine-fibered sample of nylon 6,66,610 nylon multipolymer resins (SVP-651) preparation.Number-average molecular weight is 21,500-24,800.The melt temperature phasor of yynw composition by three kinds of component nylon such as about 45% nylon 6, about 20% nylon 66 and about 25% NYLON610 (people's work " nylon plastics handbook " the 286th page such as Melvin Kohan, Hanser press, New York (1995)) estimate.The physical properties of SVP 651 resins of report is:
Character The ASTM method Unit Representative value
Proportion D-792 1.08
Water-absorbent (24 hours dippings) D-570 2.5
Hardness D-240 Shore D 65
Fusing point DSC ℃() 154(309)
Tensile strength @ surrender D-638 MPa(kpsi) 50(7.3)
Elongation at break D-638 350
Modulus in flexure D-790 MPa(kpsi) 180(26)
Volume resistivity D-257 Ω-cm 10 12
Be used for producing diameter and be 0.23 and 0.45 micron fiber.Sample is immersed in the water of room temperature, air-dry and measure its efficient.Thicker fiber needs long time degraded, and palliating degradation degree is lower, shown in the curve among Figure 12.Though do not wish to be subjected to the restriction of particular theory, look to have degrading of higher surface/volume than the easier influence of fine-fibered owing to environment., thicker fiber can not be used as effective filtration medium.
Embodiment 2: the crosslinked and resol and the Resins, epoxy of nylon fiber
In order to improve the chemical resistant properties of fiber, tested the chemically crosslinked of nylon fiber.Mix aforesaid copolyamide (nylon 6,66,610) and be pumped into fiber with the resol that is called Georgia Pacific5137.The melt temperature of their mixture when of nylon and resol is expressed as follows:
Form Melt temperature ()
Polymeric amide: resol=100:0 150
Polymeric amide: resol=80:20 110
Polymeric amide: resol=65:35 94
Polymeric amide: resol=50:50 65
We have produced comparable fiber from these mixtures.The mixture of 50:50 can not be next crosslinked by heating, because can destroy fibrous texture.Mixture at the 65:35 of heating below 90 ℃ improved the chemical resistant properties of gained fiber in 12 hours, suppressed its dissolving in alcohol.Can use the mixture of polymeric amide and Resins, epoxy, as derive from the Epon 828 of Shell and Epi-Rez 510.
Embodiment 3: use fluorochemical additive
Figure C200510116220D00211
The surface modification of water-resisting agent
Before reeling off raw silk from cocoons, in polymeric amide, added and derived from the pure solvable of 3M company
Figure C200510116220D00212
FC-430 and 431.Add-on is a solid 10%.The adding of Scotchgard does not hinder the formation of fiber.The high molecular water-resisting agent that the THC platform shows similar Scotchgard finally can not improve water-repellancy.Advise as manufacturing firm, the Scotchgard sample that adds has been heated 10 minutes 300.
Embodiment 4: with the modification of coupling agent
Polymeric film comes castable by polymeric amide together with the titanate coupling agent that derives from Kenrich Petrochemicals company limited.Titanate coupling agent comprises: sec.-propyl three isostearoyl titanic acid ester (KRTTS), neo-pentyl (hexadiene) oxidation three (dioctyl) titanium phosphate acid esters (LICA12), neo-pentyl (hexadiene) oxidation three (N-second diamino) ethyl zirconate (NZ44).The film of castable is immersed in the boiling water.Do not use the control sample of coupling agent to lose intensity immediately, and the sample that has added coupling agent was kept its profile until 10 minutes.These samples that add coupling agent have been pumped into fiber (0.2 micron fiber).
Embodiment 5: with the modification of low-molecular-weight p-tert-butylphenol polymkeric substance
Molecular weight is the EnzymolInternational company of the oligopolymer of 400-1100 p-tert-butylphenol available from Ohio state Columbus.These low-molecular-weight polymkeric substance may be dissolved in alcohol, in ethanol, Virahol and butanols.These polymkeric substance are added in the aforementioned copolyamide and static reels off raw silk from cocoons into 0.2 micron fiber, do not have disadvantageous consequence.Some polymkeric substance and additive can hinder the static drawing process.Different with the resol of the routine described in the embodiment 2, we find that this group polymkeric substance can not disturb the fiber-forming process.
We find that this group additive has prevented that fine-fibered is subjected to the influence of wet environment, shown in curve.Figure 13-16 shows oligopolymer extraordinary protection is provided under 140,100% humidity, but is not very good 160 o'clock performance.We have added this additive of the polymkeric substance 5-15% that uses.Find that they are exposed to high humidity following time to the protection fiber 140 is effectively same.We also find when fiber 150 ℃ stand a bit of time after, their performance increases.
The temperature and time that table 1 shows exposure is to the influence of the tynex that contains 10% additive.
The conservation rate of efficient after table 1.140 soaks
This is an astonishing result.We see that this class additive of use makes water-repellancy that very big improvement arranged.In order to understand how this group additive works, and we use the surface analysis technique that is called ESCA to analyze the fine-fibered mat.Be University of Minnesota with esca analysis 10% additive sample shown in the table 1, it the results are shown in table 2.
The table 2. surface composition ratio of additive (polymkeric substance with)
Figure C200510116220D00232
Just begin, the surface concn of having found additive is that what meaning as if the twice of bulk concentration do not have., we think that this can explain by the molecular weight of additive.Be about the polymkeric substance that the molecular weight of 600 additive forms much smaller than principal fiber.Because their size is less, they can move on the solvent molecule that is evaporating.Like this, we just can realize the high surfaces concentration of additive.Further handle the surface concn that has increased protective additive., exposing 10 minutes at 150 ℃ can not make concentration increase.So just can show,, can take place mixing of these two kinds of components of copolyamide and oligomer molecules because long chain polymer moves around if having time.What this analysis was told us is suitably to select the time of aftertreatment and temperature can improve performance, and handles the influence that the oversize time has reverse side.
We use the technology that is called Time of Flight (ToF) SIMS further to check the micrometer fibers that has added these additives.This technology is to use the electron-bombardment object, and observation has anything to come from the surface.The sample that does not contain additive shows has the organonitrogen material to come out with electron-bombardment the time.This shows that fracture has taken place polyamide materials.This result has also shown small amount of impurities, as the existence of sodium and silicon.The sample that contains additive but do not heat-treat (lip-deep additive concentration is 23%) shows section essential substance at the bottom of the tertiary butyl, and observes the little of polymeric amide and peak clearly.Also observe relative with the tert-butyl phenol high quality peak of 148amu that is of poor quality simultaneously.To the sample (learning that by esca analysis surface additive concentration is 50%) of having handled 10 minutes at 150 ℃, check.Section is occupied an leading position at the bottom of showing the tertiary butyl, and faint polymeric amide peak is arranged, and checks do not have to show and whole tert-butyl phenol and the relevant peak of polymkeric substance thereof if having really.Check and also show and C 2H 3The peak that the O fragment is relevant.
The ToF sims analysis shows that this can emit nitrogen fragment and the lip-deep pollutent that ruptures on the polymer chain of exposure tynex when being subjected to bombardment by ions.Added additive but do not heat-treated, then covered not exclusively, shown that additive does not cover on some part of surface.When this surface of ion beam strikes, complete molecule can be emitted together with section at the bottom of the unsettled tertiary butyl.If added additive and carried out thermal treatment, just impelled to show covering fully.In addition, molecule is closely aligned and makes that the unsettled fragment such as the tertiary butyl are only arranged, and may be that CH=CH-OH emits, and the whole molecule of tert-butyl phenol is not emitted.ESCA and ToF SIMS check at the different depths place on surface.The darker position that ESCA checks is until 100 dusts, and ToF SIMS only checks 10 angstroms depths.These analyze consistent.
Embodiment 6: the exploitation of surface coated multipolymer
The nylon of development types 8 is the solvable crosslinkable resin that is used to be coated with and adhere to purposes in order to prepare originally.This base polymer be under the condition that acid exists polyamide 66 and formaldehyde and alcohol react make (with reference to Cairns, T.L.; Foster, H.D.; Larcher, A.W.; Schneider, A.K.; Schreiber, R.S. work J.Am.Chem.Soc.1949,71,651).This base polymer can static reels off raw silk from cocoons and crosslinked., this polymer formation fiber is inferior to copolyamide, and crosslinked being difficult for carries out.
In order to prepare the nylon of type 8, reinforced in the high-pressure reactor of 10 gallons of following ratio fillings:
10 pounds of nylon 66 (duPont Zytel)
15.1 pounds of methyl alcohol
2.0 pounds in water
12.0 pounds in formaldehyde
Then, under pressure with this reactor of nitrogen wash and be heated at least 135 ℃.After reaching required temperature, add small amount of acid as catalyzer.Acid catalyst comprises: trifluoroacetic acid, formic acid, toluenesulphonic acids, toxilic acid, maleic anhydride, phthalic acid, Tetra hydro Phthalic anhydride, phosphoric acid, citric acid and their mixture.Also can use Polymkeric substance is as catalyzer.Add after the catalyzer, reaction was carried out 30 minutes.Formed viscosity homopolymer solution in this stage.After the reaction times of regulation, the material in the high pressure vessel transferred in the bath that contains methyl alcohol, water and alkali such as ammonium hydroxide or sodium hydroxide make the reaction short stopping.Behind the abundant quenching of solution, it is precipitated in deionized water, form soft particle.Then, with polymer beads centrifugation, vacuum-drying again.This polymkeric substance can dissolve in the mixture of methyl alcohol, ethanol, propyl alcohol, butanols and they and water different ratios, also may be dissolved in the mixtures of different alcohol.
The polymeric amide of the alkoxyalkyl modification type 8 that forms like this is dissolved in the mixture of ethanol/water.This polymers soln carries out static with the method that is described in Barris U.S. Patent No. 4,650,516 and reels off raw silk from cocoons.The viscosity of polymers soln increases in time.Usually known polymer viscosity has important effect to the decision fiber size.So just be difficult to control commercial size quantity-produced process.In addition, under identical condition, type 8 polymeric amide can not form micrometer fibers effectively as copolyamide.; when formulations prepared from solutions, added acid catalyst; as toluenesulphonic acids, maleic anhydride, trifluoromethayl sulfonic acid, citric acid, xitix etc., and after fiber-forming mat of fibers is carried out thermal treatment carefully, the fiber of gained has extraordinary chemical resistant properties (Figure 13).Must be careful at cross-linking stage, do not destroy fibrous texture.
When type 8 polymeric amide (polymeric amide B) mixed with pure solvable copolyamide, we had found an astonishing result.Substitute the polyamide 66 of the alkoxyalkyl modification of 30 weight % with the solvable copolyamide of alcohol such as SVP 637 or 651 (polymeric amide A), Elvamide 8061, found synergistic effect.The fiber-forming of mixture is more effective than any independent component.Be immersed in the ethanol and measure filtration efficiency shown filtration efficiency conservation rate greater than 98%, THC bench teat test show with independent type 8 polyamide-based like the result.Such mixture shows, we can obtain the advantage of the effective fiber-forming and the fabulous filtering feature of copolyamide, and the fabulous chemical-resistant advantage of crosslinked type 8 polymeric amide.It is crosslinked that alcohol immersion test has shown that consumingly non-crosslinked copolyamide has participated in, and kept 98% filtration efficiency.
In the mixture heating up to 250 ℃ (full cross-linked) of polymer A and B afterwards, their DSC (referring to Figure 17-20) becomes and is difficult to and independent polymer A is distinguished, and does not have diacritic melt temperature.This has shown that consumingly the mixture of polymer A and B is the complete polymkeric substance that is cross-linked to form by polymer B and polymer A at this moment.
Similarly, the molten mixture of polyethylene terephthalate and polybutylene terephthalate has similar character.Under temperature is higher than the melt temperature of each component, carry out in the process of melting operation, the ether group exchange takes place and form the multipolymer of PET and PBT.And our crosslinking temperature is lower than arbitrary independent component.Can not expect that this group exchange takes place at low temperatures.Therefore, the solution of polyamides by type A and type B is mixed and is crosslinked when temperature is lower than the fusing point of each component, and we have be sure of to find the new polymeric amide of a class.
When we added the tert-butyl phenol oligopolymer (additive 7) of 10 weight % and carry out heat treated under crosslinked required temperature, we had found better result.We think that the hydroxy functional group of tert-butyl phenol oligopolymer has participated in the reaction with the functional group of the nylon of type 8.We find that this component system provides fiber-forming preferably, have improved to the prolonged property of high temperature and high humidity and to the hydrophobicity on fine fiber layer surface.
We have prepared the mixture sample (sample 6A) of polymer A and polymer B and the mixture sample (sample 6B) of another polymer A, polymer B and additive 7.Then, we have formed fiber with the static method of reeling off raw silk from cocoons, and 300 mat of fibers are exposed 10 minutes and have measured surface composition with the ESCA surface analysis.
Table 3: the esca analysis of sample 6A and 6b
Figure C200510116220D00261
Except hydrogen concentration can not provide, ESCA can provide the information of relevant surface composition.It can provide the information of carbon, nitrogen and oxygen.Because additive 7 is nonnitrogenous, we can estimate the ratio of nitrogenous polymeric amide and unazotized additive by the concentration that compares nitrogen.Other qualitative information can obtain by the O1s power spectrum that detects bound energy between 535-527eV.The bound energy of C=O key is about 531eV, and the bound energy of C-O key is 533eV.By the peak height at these two peaks relatively, can estimate with the polymeric amide of main C=O and only with the relative concentration of the additive of C-O group.Polymer B has the C-O key because of modification, and the concentration of C-O key will descend when crosslinked.ESCA confirms that this reaction has positively taken place, because demonstrate the relative minimizing (Fig. 4 is the polymer A of not heat-treating and the mixture of fibers of polymer B, and Fig. 5 is the mixture of fibers of having carried out heat treated polymer A and polymer B) of C-O key.The branch period of the day from 11 p.m. to 1 a.m that has additive 7 on the surface can expect to have more C-O key.Situation is like this really, by Fig. 6 and 7 visible (Fig. 6 is the mixture of fibers that polymer A, polymer B and additive 7 are pumped into, and Fig. 7 is that polymer A, polymer B and additive 7 have carried out heat treated mixture of fibers).The concentration that Fig. 6 shows embodiment 7C-O key has raising.This result is consistent with the surface concn of composing based on the XPS multichannel of Fig. 8-11.
Tertiary butyl oligomer molecules is shifted to the surface of fine-fibered and is formed approximately Hydrophobic coating.The nylon of type 8 has functional group as-CH 2OH and-CH 2OCH 3, we expect their can with tert-butyl phenol-the OH functional group reactions.Like this, just can be desirably in and see less oligomer molecules on the fiber surface.The hypothesis that found that us is incorrect, and the surface of multipolymer has a thin coating.
Sample 6A, 6B and be described in the 5th the joint repeat sample be exposed under the 100%RH condition on the 160 THC platforms.In prosthomere, sample be exposed to 140 and 100%RH under.Under these conditions, tert-butyl phenol has prevented the degraded of trimer copolyamide., if temperature is elevated to 160 and 100%RH, then the ability of the trimer copolyamide below the protection of tert-butyl phenol oligopolymer is not good.We 160 and 100%RH compared these samples.
Table 4: be exposed to 160 and 100%R down after the conservation rate of fine-fibered efficient
Sample After 1 hour After 2 hours After 3 hours
Sample 6A 82.6 82.6 85.9
Sample 6B 82.4 88.4 91.6
Sample 5 10.1
This table shows that sample 6B helps to prevent the influence of high temperature and high humidity.
When we are exposed to water droplet on mat of fibers, can show more surprising difference.When we placed the DI water droplet on the surface of sample 6A, water droplet was sprawled on mat of fibers and wet substrates paper immediately.And when water droplet being placed on the surface of sample 6B, this water droplet forms globule and does not sprawl on mat surface.By adding the oligopolymer of p-tert-butylphenol, we are hydrophobicity with the surface modification of sample 16.This series products can be used as the water smoke eliminator, because water droplet can be by the fine-fibered upper layer of sample 6B.
Place temperature to be set at 310 stove the repeat sample of sample 6A, 6B and the 5th band.Following table shows that sample 6A and 6b are kept perfectly, and the sample of the 5th joint seriously damages.
Table 5: the retention rate that is exposed to 310 back fine-fibered efficient
Sample After 6 hours After 77 hours
Sample 6A
100% 100
Sample 6B
100% 100
Sample
5 34% 33%
Though add the high thermal resistance that the oligopolymer of polymer A has improved fine fiber layer separately, and the adding of additive 7 does not have any effect to being exposed to high temperature.
We clearly illustrate that; the nylon 66 of trimer copolyamide, alkoxyalkyl modification and the mixture of tert-butyl phenol oligopolymer can be provided at the quality products of protection fine-fibered under the rugged environment, and the while can be improved productive rate when the mixture of the nylon 66 of the mixture of making trimer copolyamide and tert-butyl phenol oligopolymer or trimer copolyamide and alkoxyalkyl modification.The mixture of these two kinds of components also has improvement than single-component system.
Embodiment 7: the compatible blend of polymeric amide and polymer with bis phenol A compound
The polymkeric substance that one class is new can prepare (Pecora, A by the oxidative coupling of phenol ring; Cyrus, the United States Patent (USP) 4,900 of W., 671 (1990) and Peroca, A; Cyrus, W.; Johnson, the United States Patent (USP) 5,153 of M., 298 (1992)).Wherein, the attractive especially polymkeric substance that makes by dihydroxyphenyl propane available from Enzymol company.The catalytic oxidation of the soybean peroxidase of dihydroxyphenyl propane can begin by the either side of two-OH group from dihydroxyphenyl propane.With the dihydroxyphenyl propane of linearity is that polycarbonate is different, such dihydroxyphenyl propane polymer formation over-expense polymkeric substance.Because the over-expense character of this base polymer, they can reduce the viscosity of polymeric blends.
We find that such polymer with bis phenol A compound can mix with polyamide solution.Hansen ' s the solubility parameter of the nylon of report is 18.6 (the CRC press of Florida state Boca Raton published in 1985 for " solubility parameter and poly-parameter handbook in other " the 317th page, people such as A.Barton work).If calculate solubility parameter (" solubility parameter handbook " the 61st page), then the solubility parameter value of Ji Suaning is 28.0.Because these solubility of substances parameters have nothing in common with each other, and expect that they can not mix mutually., we find that they are very easy to mix and provide unexpected performance.
In ethanolic soln, make the bisphenol a resin of molecular weight 3,000 of 50:50 and the mixture of copolyamide.Total concn in ethanolic soln is 10%.Can produce the fiber of 0.2 micron of diameter separately with copolyamide.And this mixture forms the soft layer of about 1 micron fiber.The dihydroxyphenyl propane of molecular weight 7,000 and copolyamide instability together time the, precipitation easily.
Do not see melt temperature on the DSC of 50: 50 mixtures.The melt temperature of copolyamide is about 150 ℃, and bisphenol a resin is the glassiness polymkeric substance of Tg about 100.And this mixture of these two kinds of materials does not have tangible melting phenomenon.When fiber mat was exposed to 100 ℃, this fiber mat disappeared.This mixture can be made into fabulous filtration medium, and the last use temperature of this filtration medium is not very high, but needs low pressure drop.This polymer system can not carry out crosslinked with reasonable manner.
Embodiment 8: dihydroxyphenyl propane is as solvent in the mixture and solid dual function
An astonishing feature of dihydroxyphenyl propane mixture of polymers is that the polymer with bis phenol A compound that is the solution form plays similar solvent, and the polymkeric substance that is solid form then plays the solid effect.We find that this dual function of dihydroxyphenyl propane is real unique.
Make following prescription:
The PA66 of alkoxyalkyl modification: polymer B 180g
Bisphenol a resin (molecular weight 3,000): polymkeric substance C 108g
190 rank ethanol 827g
Acetone 218g
DI water 167g
Catalyzer 9.3g
The viscosity that the Brookfield viscometer records this mixture is 32.6 centipoises.Total polymer concentration is 19.2%.The solution that contains the mixture of 19.2% polymer B, its viscosity surpasses 200 centipoises.The viscosity that 12% polymer B is singly arranged in similar solvent is about 60 centipoises.This is the obvious example that bisphenol a resin plays similar solvent action, because the viscosity of total solution is lower than the value of expection.The Fibre diameter of gained is 0.157 micron.If polymer B participates in fiber-forming separately, then Yu Qi fiber size should be less than 0.1 micron.In other words, polymkeric substance C also participates in fiber-forming.We do not know that a component has any other example of unique dual function like this.After sample immerses in the ethanol, measure filtration efficiency and fiber size.After alcohol soaked, it was constant to have kept 85.6% filtration efficiency and fiber size.It is crosslinked that this shows that polymkeric substance C has participated in, and plays the effect of similar polymer solids.
Another polymers soln is pressed following formulation:
The PA66 of alkoxyalkyl modification: polymer B 225g
Bisphenol a resin (molecular weight 3,000): polymkeric substance C 135g
190 ° of rank ethanol 778g
Acetone 205g
DI water 15.7g
Catalyzer 11.6g
The viscosity of this mixture is 90.2 centipoises.Solid for 24%, this is a low-down viscosity number.Moreover this shows that polymkeric substance C plays similar solvent in solution., after this solution static reeled off raw silk from cocoons into fiber, Fibre diameter was 0.438 micron.Singly there is 15% solution of polymer B should produce about 0.2 micron fiber.When final state, polymkeric substance C plays the effect that enlarges fiber size.Moreover this enforcement shows that such branched polymer is used as solvent in solution, and is used as solid in final state.After immersing ethanolic soln, the filtration efficiency and the fiber size of reservation 77.9% are constant.
Embodiment 9: the exploitation of crosslinked polyamide/dihydroxyphenyl propane mixture of polymers
Resin, alcohol and water are mixed, prepared different samples in 2 hours 60 ℃ of stirrings.Solution is cooled to room temperature and to wherein adding catalyzer, this mixture of restir 15 minutes.Subsequently, measure the viscosity of solution and it is pumped into fiber.
Following table shows following sample:
Prescription (g) Sample 9A Sample 9B Sample 9C
Polymer B 8.4 12.6 14.7
Polymer A 3.6 5.4 6.3
Polymkeric substance C 7.2 10.8 12.6
190 rank ethanol 89.3 82.7 79.5
Virahol 23.5 21.8 21.0
DI water 18.0 16.7 15.9
Catalyzer 0.45 0.58 0.79
Viscosity (cP) 22.5 73.5 134.2
Fiber size (micron) 0.14 0.258 0.496
We find that this mixture can produce fiber effectively, compare with the prescription of polymer A, and the fiber quality of generation is more than 50%.In addition, the polymer microfibers of gained chemical resistant properties more.After soaking in alcohol, even intrinsic crosslinked polymkeric substance only be 44% of a solids composition, the strainer maintenance that is made by these fibers is greater than 90% filtration efficiency and keep Fibre diameter constant.The nylon 66 of this copolyamide, alkoxyalkyl modification and the terpolymer composition of dihydroxyphenyl propane have generated the fiber-forming performance the chemical-resistant material again.
Embodiment 10: the multipolymer of the alkoxyalkyl modification of nylon 66 and nylon 46
In one 10 gallons high-pressure reactor, carry out following reaction, and analyze the polymkeric substance of gained.After reaching temperature of reaction, the adding catalyzer also reacted 15 minutes.Subsequently, with polymers soln quenching, precipitation, cleaning and dry.
Figure C200510116220D00311
The DSC of the polymkeric substance that makes with nylon 46 and nylon 66 has shown wide single melt temperature, and it is lower than the melt temperature of the nylon 66 (210 ℃) of the nylon 46 (241 ℃) of modification or modification.This shows that in reaction process two kinds of components can distribute randomly along polymer chain.Like this, we think and have obtained with the nylon 46 of alkoxyalkyl modification and the random copolymers of nylon 66.These polymkeric substance may be dissolved in the mixture of pure and mild alcohol and water.
Character ASTM Nylon 6.6 Nylon 4.6
T m 265℃ 295℃
Tensile strength D638 13.700 8.500
Elongation at break D638 15-80 60
Tensile yield strength D638 8000-12,000
Flexural strength D790 17,8000 11,500
Tensile modulus * 10 3psi D638 230-550 250
Izod ft-1b/ inch recess D256A 0.55-1.0 17
Deflection temperature under bending load 264psi D648 158 194
These two kinds of nylon all are high crystalline and are insoluble in the common alcohol.
Source: contemporary plastics encyclopedia 1998
Embodiment 11: the exploitation of the interpolymer of copolyamide and alkoxy-modified nylon 46/66 multipolymers and quiet The reel off raw silk from cocoons formation of fiber of electricity
Use aforesaid method that the sample of polymkeric substance 10B and 10D (seeing the following form) is made fiber.Successfully having carried out static with nylon 46/66 (polymkeric substance D) of alkoxyalkyl modification separately reels off raw silk from cocoons.Polymkeric substance D can produce following extra benefit with mixing of polymer A: more effective fiber-forming and make robust fibre more and do not contain the bridging property of sacrificial polymer D, as shown in the table:
Figure C200510116220D00321
Quality of fiber multiply by sectional area than the total length by fiber and calculates.The conservation rate of filtration efficiency is measured by fiber samples is immersed in the ethanol.It is constant to soak the back fiber size in the alcohol.
Embodiment 12: the static of crosslinked PVA reels off raw silk from cocoons
The PVA powder is available from Aldrich Chemicals company.This powder dissolution is in 50/50 mixture of water or first alcohol and water.Before static reels off raw silk from cocoons, make itself and linking agent and toluenesulphonic acids catalyst mix.Before being exposed to the THC platform, the fiber mat of gained placed 150 ℃ crosslinked 10 minutes of stove.
Sample 12A Sample 12B Sample 12C Sample 12D
The PVA degree of hydrolysis 98-99 87-89 87-89 87-89
Molecular weight 31,500-50,000 31,500-50,000 31,500-50,000 31,500-50,000
PVA concentration (%) 10 10 10 10
Solvent Water Mixture Mixture (c) Mixture (d)
Other polymkeric substance Do not have Do not have Vinylformic acid Cymel 385
Other polymkeric substance/PVA (%) 0 0 30 30
The retention rate of fiber (%) on the THC platform after 1 hour 0(a) 0(a,b) 95(b) 20(b)
The retention rate of fiber (%) on the THC platform after 3 hours 90(a)
(a): temperature 160, humidity 100%
(b): temperature 140, humidity 100%
(c): molecular weight 2000
(d): the melamine formaldehyde resin that derives from Cytec company
Embodiment 13
Use conventional Mierocrystalline cellulose air filtration media as substrate.The basic weight of this substrate is 67 pounds/3000 square feet, and the Frazier rate of permeation of falling at 0.5 inch hydraulic pressure is 16 feet per minute clocks, and thickness is 0.012 inch, and LEFS efficient is 41.6%.Using described method is that 0.2 micron fine fiber layer is added on the substrate surface with the nominal Fibre diameter of embodiment 1.The LEFS efficient of gained mixture is 63.7%, and the air that is exposed to 140F at the sample that under 100% relative humidity will be substrate is after 1 hour, allows sample cooling and dry, and its LEFS efficient is 36.5%.After 1 hour, allow sample cool off and drying at the air that under 100% relative humidity mixture is exposed to 140F, then its LEFS efficient is 39.7%.Use described mathematical formula to calculate, the efficient that obtains exposing the fine fiber layer that keeps after 1 hour is 13%, and the effective fine-fibered number of reservation is 11%.
Embodiment 14
Use conventional Mierocrystalline cellulose air filtration media as substrate.The basic weight of this substrate is 67 pounds/3000 square feet, and the Frazier rate of permeation of falling the place at 0.5 inch hydraulic pressure is 16 feet per minute clocks, and thickness is 0.012 inch, and LEFS efficient is 41.6%.Using described method is that 0.2 micron fine fiber layer is added on the surface with the nominal Fibre diameter of embodiment 5.The LEFS efficient of gained mixture is 96.0%.To be that the sample of substrate was exposed in the air of 160F after 3 hours under 100% relative humidity, and allow sample cooling and dry, its LEFS efficient be 35.3%.After 3 hours, allow sample cool off and drying at the air that under 100% relative humidity mixture is exposed to 160F, then its LEFS efficient is 68.0%.Use described mathematical formula to calculate, the efficient that obtains exposing the fine fiber layer that keeps after 3 hours is 58%, and the effective fine-fibered number of reservation is 29%.
Embodiment 15
Use conventional Mierocrystalline cellulose air filtration media as substrate.The basic weight of this substrate is 67 pounds/3000 square feet, and the Frazier rate of permeation of falling at 0.5 inch hydraulic pressure is 16 feet per minute clocks, and thickness is 0.012 inch, and LEFS efficient is 41.6%.Using described method is that the fine fiber layer of the mixture of 0.2 micron polymer A and polymer B is added on the surface with embodiment 6 described nominal Fibre diameters.The LEFS efficient of gained mixture is 92.9%.To be that the sample of substrate was exposed in the air of 160F after 3 hours under 100% relative humidity, and allow sample cooling and dry, its LEFS efficient be 35.3%.Under 100% relative humidity mixture is exposed in the air of 160F after 3 hours, allows sample cooling and dry, then its LEFS efficient is 86.0%.Use described mathematical formula to calculate, the efficient that obtains exposing the fine fiber layer that keeps after 3 hours is 96%, and the effective fine-fibered number of reservation is 89%.
Embodiment 16
Use conventional Mierocrystalline cellulose air filtration media as substrate.The basic weight of this substrate is 67 pounds/3000 square feet, and the Frazier rate of permeation of falling at 0.5 inch hydraulic pressure is 16 feet per minute clocks, and thickness is 0.012 inch, and LEFS efficient is 41.6%.Using described method is that the fine fiber layer of mixture of 0.2 micron polymer A, polymer B and tert-butyl phenol oligopolymer is added on the surface with embodiment 6 described nominal Fibre diameters.The LEFS efficient of the mixture of gained is 90.4%.To be that the sample of substrate was exposed in the air of 160F after 3 hours under 100% relative humidity, and allow sample cooling and dry, its LEFS efficient be 35.3%.Under 100% relative humidity mixture is exposed in the air of 160F after 3 hours, allows sample cooling and dry, then its LEFS efficient is 87.3%.Use described mathematical formula to calculate, the efficient that obtains exposing the fine fiber layer that keeps after 3 hours is 97%, and the effective fine-fibered number of reservation is 92%.
Embodiment 17
Use conventional Mierocrystalline cellulose air filtration media as substrate.The basic weight of this substrate is 67 pounds/3000 square feet, and the Frazier rate of permeation of falling at 0.5 inch hydraulic pressure is 16 feet per minute clocks, and thickness is 0.012 inch, and LEFS efficient is 41.6%.Using described method is that 0.2 micron the fine fiber layer with polyacrylic crosslinked PVA is added on the surface with the nominal Fibre diameter of embodiment 12.The LEFS efficient of the mixture of gained is 92.9%.To be that the sample of substrate was exposed in the air of 160F after 2 hours under 100% relative humidity, and allow sample cooling and dry, its LEFS efficient be 35.3%.Under 100% relative humidity mixture is exposed in the air of 160F after 2 hours, allows sample cooling and dry, then its LEFS efficient is 83.1%.Use described mathematical formula to calculate, the efficient that obtains exposing the fine fiber layer that keeps after 3 hours is 89%, and the effective fine-fibered number of reservation is 76%.
Embodiment 18
Make following filtration medium with embodiment 1-17 described methods.
Test method
The hot-water soak test
Use filtration efficiency as the measurement that reaches the fine-fibered number that is retained on the function in the structure effectively, this has some advantages than other feasible method such as SEM detection.
It is that several square inches medium is made an appraisal that one filtration is measured, and this can only observe zonule (usually less than 0.0001 square inch) than SEM microphotograph can draw better mean value.
One filters mensuration can determine to keep filteration in structure fibre number.Though those keep, but in groups in conjunction with or the fiber that otherwise in the structure that changes, exists just be presented in the efficient and function that records.
However, in the fibrous texture that filtration efficiency is difficult for recording, the fiber percentage ratio that still can use other method to measure reservation is estimated with respect to 50% retention criteria.
Illustrate:
This test is the accelerated test of expression filtration medium water resisting property.This test uses the LEFS testing table to measure the performance variation of water-immersed filtration medium.Water temperature is conclusive parameter, and the weather resistance experience result of the medium that gets according to institute reduces to the ability that minimum needs and test distinguish media type with test period and selects water temperature.General water temperature is 70,140 or 160.
Program:
Cut the next 4 " samples of diameter from medium.The latex balloon that uses 0.8 μ m calculates the particle capture efficient of sample as the test pollutent in the LEFS that operates (about the description of LEFS test, referring to the ASTM standard F1215-89) platform under the 20FPM condition.Then, sample is immersed in (generally being 140) distilled water 5 minutes.Place oven dry to be allowed to condition at dry (generally spending the night) under the room temperature on the frame on sample.After samples dried, use the condition identical testing efficiency again on the LEFS platform with initial calculation.The substrate (but not having fine-fibered in the above) of fine-fibered being supported usefulness repeats previous step.
The final loss in efficiency that only can calculate the efficient composition that causes owing to fine-fibered and cause owing to the destruction of water by The above results.Behind the loss in efficiency of having determined to cause, can calculate the amount of the efficient of reservation owing to fine-fibered.
Calculate:
Fine fiber layer efficient: E i=initial mixture efficient;
E s=initial substrate efficient;
F e=fine fiber layer
F e=1—EXP(Ln(1—E i)—Ln(1—E x))
The efficient that fine fiber layer keeps: F i=initial fine fiber layer efficient;
F x=fine fiber layer efficient after soaking;
F rThe fine-fibered of=reservation
F r=F x/F i
Percentage ratio with reservation fine-fibered of effective efficiency also can be calculated by following formula:
%=log(1-F x)/log(1-F i)
Qualified/defective standard: the reservation percentage ratio of efficient〉50%
In the purposes of most of industrial pulse polishing filters, if fine-fibered efficient has kept at least 50%, then this strainer is enough to work.
THC platform (temperature, humidity)
Illustrate:
The purpose of this testing table is to estimate the effect to the temperature that raises and higher humidity of under hydrodynamic condition fine fiber media.This test objective is to simulate any ultimate operational condition in industrial filtration applications, gas turbine air inlet purposes or the heavy engine air admittance environment.With sample take out, dry and carry out the LEFS test at set intervals.This system is mainly used in the simulation wet heat condition, but also can be used for simulating hot/cold and dried condition.
Temperature-31 is to 390
(top temperature under the 100%RH is 160 to humidity 0-100%RH, at this
Be 16 hours the longest continuous time under the condition)
Flow velocity 1-35FPM
Program:
Cut off the one 4 " sample of diameter from medium.
Use 0.8 μ m latex balloon as the test pollutent in the LEFS platform of under the 20FPM condition, operating, be used for the particle capture efficient of test sample.Then, sample is inserted in the THC medium chuck.
Test period can be decided according to test conditions from several minutes by several days.
Sample is placed on the oven dry frame at room temperature dry (generally spending the night).After samples dried, use the condition identical testing efficiency again on the LEFS platform with initial trial.
Fine-fibered support base (above do not have fine-fibered) is repeated previous step tests.
Efficient composition that only causes owing to fine-fibered by above-mentioned test result calculations and the final loss in efficiency that causes owing to the destruction of soaking alcohol.
Determine the loss in efficiency of fine-fibered, can calculate the amount of the efficient of reservation.
Qualified/defective standard: the reservation percentage ratio of efficient〉50%.
In the purposes of most of industrial pulse polishing filters, if fine-fibered efficient has kept at least 50%, then this strainer is enough to work.
Alcohol (ethanol) soak test
Illustrate:
This test uses the LEFS testing table to measure the variation of the filtering medium property in the ethanol that is immersed in room temperature.
Program:
Cut off the one 4 " sample of diameter from medium.The latex balloon that uses 0.8 μ m is as the test pollutent in the LEFS platform of operating under the 20FPM condition, the particle capture efficient of test sample.Then, sample is immersed in the alcohol 1 minute.
Sample is placed on the oven dry frame at room temperature dry (generally spending the night).After samples dried, use the condition identical testing efficiency again on the LEFS platform with initial trial.Fine-fibered support base (above do not have fine-fibered) is repeated previous step tests.The final loss in efficiency that only can calculate the efficient composition that causes owing to fine-fibered and cause owing to the destruction of soaking alcohol by above-mentioned test result.Determine the loss in efficiency of fine-fibered, can calculate the amount of the efficient of reservation.
Qualified/defective standard: the reservation percentage ratio of efficient〉50%.
Above-mentioned explanation, embodiment and data are set forth the present invention.But, can make many variations and embodiment to described the present invention.The present invention is embodied in this paper accompanying Claim book.

Claims (6)

1. fine-fibered composition, described composition comprises polyvinyl alcohol polymer and linking agent, the Fibre diameter of described fine-fibered is the 0.01-2 micron.
2. fine-fibered composition as claimed in claim 1 is characterized in that polyvinyl alcohol is that linking agent with 1-40 weight % carries out crosslinked.
3. fine-fibered composition as claimed in claim 1 is characterized in that linking agent is the polymkeric substance that contains the vinylformic acid repeating unit, and described polymericular weight is 1000-5000.
4. fine-fibered composition as claimed in claim 3 is characterized in that described polymkeric substance is that molecular weight is the acrylic copolymer of 1000-5000.
5. fine-fibered composition as claimed in claim 3 is characterized in that described polymkeric substance is that molecular weight is the acrylate homopolymer of 1000-5000.
6. fine-fibered composition as claimed in claim 1 is characterized in that polyvinyl alcohol is is that the melamine-formaldehyde resin of 1000-3000 comes crosslinked with molecular weight.
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