CN1041190A - The halogenated hydrocarbon that is used for flash distillation weaving polymer brushes silk - Google Patents
The halogenated hydrocarbon that is used for flash distillation weaving polymer brushes silk Download PDFInfo
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- CN1041190A CN1041190A CN89107885A CN89107885A CN1041190A CN 1041190 A CN1041190 A CN 1041190A CN 89107885 A CN89107885 A CN 89107885A CN 89107885 A CN89107885 A CN 89107885A CN 1041190 A CN1041190 A CN 1041190A
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- chloro
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- halogenated hydrocarbon
- pressure
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/42—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/11—Flash-spinning
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
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- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The present invention discloses a kind of improved method, adopts this method can be spun to the plexifilamentary film fibril silk ribbon of fibrillated polyolefin with a little family halogenated hydrocarbon liquid flashes.This halogenated hydrocarbon liquid is discharged into the atmosphere, and compares at the industrial halogenated hydrocarbon that is used to make this plexifilamentary film fibril silk ribbon that generally uses, and can reduce the harmfulness to ozone-depleting widely, the halogenated hydrocarbon of used for this purpose the best is 1,1-two chloro-2,2, the 2-HFC-143a.
Description
The application is the application that continues of another application of awaiting the reply.The name of this application of awaiting the reply is called " halogenated hydrocarbon that is used to dodge spun polyethylene clump silk ", and its applying date is on August 30th, 1988, and application number is 07/238442.
The present invention relates to dodge spinning polymer film-fibril strands silk ribbon.Say that more specifically the present invention is the improvement on a kind of method, the method can be dodged to spin and be formed the fibril silk ribbon with liquid, and if this liquid be released in the atmosphere, also can not endanger the ozone layer of the earth.
Mine-laying (Blades) and White's (White) the patent No. now is 3,081,519 United States Patent (USP), has described a kind of sudden strain of a muscle spinning process method of producing plexifilamentary film fibril silk ribbon with fibre-forming polymer.With polymer dissolution in liquid, this liquid is when being equal to or less than its normal boiling point, to polymer is no solvent, when being higher than the temperature of this liquid normal boiling point, solution is clamp-oned a kind of low temperature under self-heating or higher pressure condition and normally in the medium of low pressure.Thereby this kind sudden strain of a muscle is spun and has been caused the liquid evaporation to make its extrudate cooling.This extrudate has formed polymer brushes silk film-fibril strands silk ribbon.Proper polymer comprises crystalline polymerizing hydrocarbon, as polyethylene and polypropylene.
According to mine-laying (Blades) and White's (White) method now, liquid is spun in suitable sudden strain of a muscle need have following feature: (a) boiling point need be lower than at least 25 ℃ of the molten points of polymer; (b) under extrusion temperature, do not react usually with polymer; (c) should be (to that is to say that extrusion temperature and pressure are respectively 165 ℃ to 225 ℃ and 545 pounds/inch in the temperature of present specification and the solvent of the polymer under the pressure
2To 1490 pounds/inch
2); (d) should be when being equal to or less than its normal boiling point, dissolving to polymer is less than 1%, and should form a kind of solution, this solution can carry out quick thing and be separated when being extruded, so that form a kind of polymer phase, a small amount of solvent that is contained in this polymer phase can not make this polymer plasticizing.For used specific polymer, following liquid is applicable to the sudden strain of a muscle spinning process: arene, and as benzene, toluene etc.; Aliphatic hydrocarbon, as butane, pentane, hexane, heptane, octane and their isomer and homologue; Alicyclic hydrocarbon type is as cyclohexane; Unsaturated hydro carbons; Halogenated hydrocarbons, as carrene, carbon tetrachloride, chloroform (chloroform), chloroethanes, chloromethane; Alcohols; The ester class; Ethers; Ketone; Nitrile; Acid amides; The fluorocarbon class; Sulfur dioxide; Carbon disulfide; Nitromethane; Water and above mixtures of liquids.This patent has also been set forth some with chart and has been helped to set up best spinning condition to obtain the principle of clump silk ribbon.Mine-laying (Blades) and White's (White) method explanation is now dodged the solution that spins usefulness and can also be contained a kind of soluble gas, as nitrogen, and carbon dioxide, helium, hydrogen, methane, propane, butane, ethene, propylene, butylene or the like.Relatively the gas of the fibrillation effect of Chang Yong raising organic matter fiber is some less dissolved gases, they be those under spinning condition, its concentration of ordinary dissolution in polymer solution is less than 7% gas.Common additives resembles antioxidant, ultra-violet stabilizer, and dyestuff, pigment and suchlike thing also can be added in the solution before extruding operation.
The patent No. of Anderson (Anderson) and Romano (Romano) is 3,227,794 United States Patent (USP), has disclosed one and has been similar to the mine-laying chart of (Blades) and White's (White) method now, the condition of clump silk ribbon that is used to select to weave.This graphical presentation the relation of spinning temperature and spinning pressure, 10(is heavy) %～16(is heavy) linear polyethylene of % is dissolved in and makes solutions employed in the Arcton 11.This patent also is described in detail in temperature and is about 185 ℃ and pressure and is about 1640 pounds/inch
2Under the condition of gauge pressure, that 14(is heavy) the high-density linear polyethylene dissolving of %, solution is discharged chamber from one and is extruded then, and operating temperature is 185 ℃, and pressure is 1050 pounds/inch
2Gauge pressure.Closely similar with it temperature, pressure and concentration have been used to the polyethylene sudden strain of a muscle is spun in the industrial production of plexifilamentary film fibril silk ribbon, and this silk ribbon is changed system into flaky texture then.
Though Arcton 11 is of great use as a kind of solvent for spinning plexifilamentary film fibril silk ribbon with the polyethylene sudden strain of a muscle, and be used for industrial production polyethylene clump silk ribbon, but this halogenated hydrocarbon is discharged into the chief-criminal who but is considered to consume earth ozone in the air.Now caused people's attention at large about ozone depletion problem.Be published in " chemistry and the Engineering News Record " (Chemical on February 8th, 1988; Engineering News) article of the PS Ze Er (PSZurer) on the 17-20 page or leaf " substitute of the halogenated hydrocarbons that consumes ozone is sought in reinforcement " is exactly an example.
A kind of determine easily the solvent of giving whether be suitable for dodging spin known polymer method of testing by the U.S. Patent Publication of Wood that (Woodwell), its patent No. is 3,655,498.This method of testing is used for widely determining by the manufacturer of maximum in the world sudden strain of a muscle spun polyethylene product whether the substitute of the Arcton 11 solvent of preparation clump silk ribbon is suitable for.In test process, solvent with polymer and some, the amount of the solvent of this some is to calculate well, so that it is heavy to contain 10(in the solution that forms) polymer of %, mixture is sealed in the heavy-walled glass tubes (the shared volume of mixture be test tube volume 1/3 to 1/2), and mixture is heated under the pressure of self-heating, during test temperature range normally from about 100 ℃ to the critical-temperature that just is lower than fluid to be measured.You (Woodwell) point out Wood, if all do not have in test tube to form single-phase, a flowable solution (the perhaps decomposition temperature of polymer in any temperature that is lower than the solvent critical temperature Tc, get lower one), the dissolving power of solvent is just too low so.Another extremely then is, if a single phase soln forms in a certain temperature of subcritical temperature T c, but that solution (still be lower than Tc) under the higher temperature and can not be transformed into liquid being heated to biliquid phase, this dissolving power is just too high.Those dissolving powers own can not drop to the solvent between these limit, can suitably dilute with no dissolving power or the strong additive of dissolving power, to make it to be suitable for application.After choosing appropriate solvent or solvent mixture, the restrained condition of the single-phase and biliquid phase of solvent or solvent mixture just can be determined operating temperature and the pressure when different polymer concentration, is narrated as above-mentioned Anderson (Anderson) and Romano (Romano).
The objective of the invention is for the flash distillation weaving plexifilamentary film fibril silk ribbon that becomes fibrillated polyolefin class material provides a kind of method of having improved, make wherein solvent not have the harm of consumption to earth's ozone layer.
The present invention spins plexifilamentary film fibril silk ribbon for sudden strain of a muscle a kind of improved process is provided, wherein dodge and spin required polyethylene and be dissolved in a kind of halogenated hydrocarbon textile fluids, to constitute weaving solution, this solution contains the polyethylene of counting 10%-20% by solution weight, operating temperature range is 130 ℃～210 ℃, and pressure will be higher than 3000 pounds/inch
2Under this temperature and pressure, solution is flashed spinning and enters in fact temperature and all lower zone of pressure.This improvement comprises from by 1,1-two chloro-2,2, and 2-HFC-143a and 1,2-two chloro-1,2 are selected halogenated hydrocarbon in the family that the 2-HFC-143a is formed.
The present invention spins plexifilamentary film fibril silk ribbon for sudden strain of a muscle a kind of improved process is provided, wherein dodge and spin required polyethylene and be dissolved in a kind of halogenated hydrocarbon textile fluids to constitute weaving solution, this solution contains the polyethylene of counting 10%-20% by solution weight, operating temperature range is 130 ℃～210 ℃, and pressure will be higher than 1800 pounds/inch
2Solution is flashed spinning and enters in fact temperature and all lower zone of pressure under this temperature and pressure.This improvement comprises that halogenated hydrocarbon is to be selected from 1,1-two chloro-2,2-Difluoroethane and 1,2-two chloro-1,1-Difluoroethane.
The present invention spins plexifilamentary film fibril silk ribbon for sudden strain of a muscle a kind of improved process is provided, wherein dodge and spin required polyethylene and be dissolved in a kind of halogenated hydrocarbon textile fluids to constitute weaving solution, this solution contains the polyethylene of counting 10%-20% by solution weight, operating temperature range is 130 ℃～210 ℃, and pressure will be higher than 2000 pounds/inch
2Solution is flashed spinning and enters in fact temperature and all lower zone of pressure under this temperature and pressure.This improvement comprises that halogenated hydrocarbon is: 1, and 1-two chloro-1-fluoroethanes.
The present invention spins plexifilamentary film fibril silk ribbon for sudden strain of a muscle a kind of improved process is provided, wherein dodge and spin required polyethylene and be dissolved in a kind of halogenated hydrocarbon textile fluids, to constitute weaving solution, this solution contains the polyethylene of counting 10%-20% by solution weight, operating temperature is 130 ℃～210 ℃, and pressure will be higher than 1500 pounds/inch
2Solution is flashed spinning and enters in fact temperature and all lower zone of pressure under this temperature and pressure.This improvement comprises from by 1,1-two chloro-2,2, and 2-HFC-143a, 1,2-two chloro-1,2,2-HFC-143a, 1,1-two chloro-2,2-Difluoroethane, 1,2-two chloro-1,1-Difluoroethane and 1 is selected halogenated hydrocarbon in the family that 1-two chloro-1-one fluoroethane is formed.
The present invention spins plexifilamentary film fibril silk ribbon for sudden strain of a muscle a kind of improved method is provided.Wherein become fibrillated polyolefin 130 ℃ to 210 ℃ of temperature, pressure is higher than 1000 pounds/inch
2Condition under be dissolved in the halogenated hydrocarbon textile fluids, and this weaving liquid is when containing another kind of solvent, no matter this solvent accounts for the hydrocarbon of textile fluids total amount 2% to 25% or accounts for the carrene of textile fluids gross weight 5% to 50%, can constitute the weaving solution that contains the one-tenth fibrillated polyolefin of 10%-20% by solution weight, and then be flashed spinning and enter in fact a temperature and all lower zone of pressure.This improvement comprise from by
1,1-two chloro-2,2, the 2-HFC-143a,
1,2-two chloro-1,2, the 2-HFC-143a,
1,1-two chloro-2, the 2-Difluoroethane,
1,2-two chloro-1, the 1-Difluoroethane and
1, select halogenated hydrocarbon in the family that 1-two chloro-1-one fluoroethane is formed.
The invention provides a kind of new solution, this solution in fact by for 10(heavy) %～20(is heavy) one-tenth fibrillated polyolefin and the 90(of % be heavy) %～80(is heavy) liquid that contains halogenated hydrocarbon of % forms.This halogenated hydrocarbon is from by 1,1-two chloro-2,2, and 2-HFC-143a, 1,2-two chloro-1,2,2-HFC-143a, 1,1-two chloro-2,2-Difluoroethane, 1,2-two chloro-1,1-Difluoroethane and 1 chooses in the family that 1-two chloro-1-one fluoroethane is formed.
The invention provides a kind of new solution, this solution in fact by for 10(heavy) %～20(is heavy) one-tenth fibrillated polyolefin and the 90(of % be heavy) %～80(is heavy) the halogenated hydrocarbon liquid of % forms.This halogenated hydrocarbon is from by 1,1-two chloro-2,2,2-HFC-143a, 1,2-two chloro-1,2,2-HFC-143a, 1,1-two chloro-2,2-Difluoroethane, 1,2-two chloro-1,1-Difluoroethane and 1 chooses in the family that 1-two chloro-1-one fluoroethane is formed.
Most preferred embodiment describes in detail
" polyolefin " here mentioned is meant any in the polymerizing hydrocarbon series of HI SA highly saturated open chain of a carbon containing and hydrogen.Typical polyolefin comprises (but being not limited only to these): polyethylene, polypropylene and polymethylpentene.For simplicity, polyethylene and polypropylene are by top-priority polyolefin in technology of the present invention.
Here used " polyethylene " not only comprises the homopolymers of ethene, comprises that also having 85% recurring unit at least is the copolymer of ethene unit.Polyethylene commonly used is a kind of linear polyethylene of homopolymerization, and the upper limit of this polyethylene melt temperature is 130 ℃～135 ℃, and density is 0.94 gram per centimeter
3～0.98 gram per centimeter
3, and melt index (definition sees ASTM D-1238-57T, condition E for details) is between 0.1 to 6.0.
Here used " polypropylene " not only comprises the homopolymers of propylene, comprises that also having 85% recurring unit at least is the copolymer of propylene unit.
Here said " plexifilamentary film fibril silk ribbon " is meant a kind of silk ribbon, it is the complete WEB with three-dimensional dimension, it is made up of the film-based fibre element of many very thin strips, these leement durations are uneven, average thickness is approximately less than 4 microns, and its major axis is that long axis direction along silk ribbon extends usually.Film shape fibre element links to each other with irregular gap periods ground with thick all places or separates at the length and width that spreads all over silk ribbon, to form three-dimensional netted thing.This silk ribbon mine-laying now (Blades) and White's (White) the patent No. to be 3,081,519 United States Patent (USP) and Anderson (Anderson) described in detail in 3,227,794 the United States Patent (USP) with the patent No. of Romano (Romano).
The present invention provides a kind of improvement to known method for the plexifilamentary film fibril silk ribbon that produces fibrillated polyolefin with halogenated hydrocarbon weaving solution, and it is heavy that this solution contains 10() % to 20(is heavy) the one-tenth fibrillated polyolefin of %.Become fibrillated polyolefin to be dissolved in the textile fluids that contains halogenated hydrocarbon, contain with formation and count 10%～20% linear polyethylene weaving solution by solution weight.Be that 130 ℃～210 ℃ and pressure are higher than under the condition of weaving liquid self-heating pressure this solution flash spinning is entered into pressure and the in fact all lower zone of temperature in temperature range then.
Key improvements of the present invention requires the halogenated hydrocarbon will be from by 1 exactly, 1-two chloro-2,2,2-HFC-143a (" HC-123 "), 1,2-two chloro-1,2,2-HFC-143a (" HC-123a), 1,1-two chloro-2; 2-Difluoroethane (" HC-132a "), 1; 2-two chloro-1,1-Difluoroethane (" HC-132b ") and 1 chooses in the family that 1-two chloro-1-one fluoroethane (" HC-141b) is formed.
Here used sign is the abbreviation of halogenated hydrocarbon chemical formula in the bracket.Following table has been listed the known boiling point under normal atmosphere (Tbp), critical-temperature (Tcr) and the critical pressure (Pcr) of selected halogenated hydrocarbon and prior art solvent for use.In the stringer of indicating " dissolubility ", also provided in the table temperature 130 ℃～225 ℃ and under self-heating pressure 10% poly solution can in halogenated hydrocarbon, form.
Boiling point ℃ critical-temperature ℃ critical pressure (pound/inch
2) dissolubility
HC-123 28.7 185 550 is insoluble
HC-123a 28 is insoluble
HC-132a 60 238 is insoluble
HC-132b 46.8 220 570 is insoluble
HC-141b 32 210 673 is insoluble
Arcton 11 23.8 198.0 639.5 is solvable
Carrene 39.9 237.0 894.7 is solvable
Hexane 68.9 234.4 436.5 is solvable
Cyclohexane 80.7 280.4 590.2 is solvable
Note, on show five kinds of listed suitable halogenated hydrocarbons just representative be applicable to a very special little family halogenated hydrocarbon of the present invention, also have various halogenated hydrocarbons available.The method of traditional examination liquid (just above-mentioned poly solubility test under self-heating pressure) is unconformable in the present invention, because compare with the solvent of above-mentioned prior art, the halogenated hydrocarbon that is applicable to invention is polyethylene dissolving not under self-heating pressure.The prior art solvent for use is selected does further research, because they are determined under self-heating pressure and can form solution with polyethylene.Furtherly, spin used liquid with the sudden strain of a muscle in past and compare, do not have in the selected halogenated hydrocarbon of the present invention a kind of desired concentration and temperature and at pressure less than 1500 pounds/inch
2Condition under, form single-phase solution with polyethylene.Certainly, these halogenated hydrocarbons also have known one-tenth fibrillated polyolefin really and dodge and spin some feature that liquid has.For example, these halogenated hydrocarbons extrusion temperature also not with polymer reaction.Under some certain conditions, these halogenated hydrocarbons also can be used as into the solvent of fibrillated polyolefin, and dissolving is less than 1% polymer when being equal to or less than the polyolefin normal boiling point, formation solution.When extruding, this solution is separated rapidly, forms polymer phase, and the solvent that contains in this polymer phase can not make this polymer plasticizing.
Except that above-mentioned feature, be applicable to that the halogenated hydrocarbon of method of the present invention and solution is: (1) its boiling point is between 0 ℃～80 ℃; (2) fluoridized and/or chlorination by incomplete; (3) flammable low; (4) have enough heats of vaporization and dodge the organic matter fiber that spins formation with quick cooling; (5) has the required hydrolysis of sudden strain of a muscle spinning process and the stability of temperature; (6) when gaseous state, has very high electrostatic breakdown power, therefore can be used to traditional spunbond technology (for example to form clump silk thin slice, the United States Patent (USP) of Si Taiyoubai (Steuber), the patent No. 3,169, the decomposition excessively of halogenated hydrocarbon and (7) 899), and not appear under 130 ℃～225 ℃ temperature and be lower than 1500 pounds/inch
2The polyethylene that can not form 10% weight under any pressure of pressure is dissolved in the single phase soln in the liquid.Especially, as with HC-123 and HC-123a, only at pressure greater than 3000 pounds/inch
2Shi Caineng forms this polyethylene solution in halogenated hydrocarbon liquid; If, have only pressure greater than 1800 pounds/inch with HC-132a and HC-132b
2Shi Caineng forms this polyethylene solution in halogenated hydrocarbon liquid; If HC-141b arranged, only at pressure greater than 2000 pounds/inch
2Shi Caineng forms this polyethylene solution in halogenated hydrocarbon liquid.Has only pressure greater than 1500 pounds/inch
2, could in halogenated hydrocarbon weaving liquid of the present invention, form this polypropylene solution.
The solution of more gratifying polymer and halogenated hydrocarbon can be at pressure greater than 1000 pounds/inch
2Form, but this situation has only when having other high solvent solvent in the halogenated hydrocarbon weaving liquid and could take place.
The combination of having found the halogenated hydrocarbon characteristic is in fact only satisfied by five kinds of above-mentioned halogenated hydrocarbons.For play with these five kinds of halogenated hydrocarbons in arbitrary similar effect, another kind of halogenated hydrocarbon will satisfy equally and is actually all these characteristics, spins the clump silk ribbon that high-quality polyolefin constitutes so that be suitable for dodging.
Both made and be suitable for also should noting the unfavorable characteristic of avoiding some to occur between five kinds of halogenated hydrocarbons of the inventive method.For example, use HC-123a, HC-132a should avoid heat time heating time long so that the decomposition that dehydrohalogenation and hydrolysis owing to halogenated hydrocarbon are produced reduces to minimum when HC-132b and HC-141b.Also need pay special attention to when using HC-132b, because there are indications that these chemicals may be the regeneration toxin of buck.Consider that from stability and these problems of toxicity HC-123 is the halogenated hydrocarbon preferably that is used for technology of the present invention.
In the time will becoming fibrillated polyolefin to be dissolved in the halogenated hydrocarbon of the present invention preparation solution, must will become in the temperature range of the mixture heated to 130 ℃ of fibrillated polyolefin and halogenated hydrocarbon～210 ℃.If the polyolefin here is a polyethylene, and if halogenated hydrocarbon is HC-141b, the pressure of mixture just should be higher than 2000 pounds/inch
2If halogenated hydrocarbon is HC-123 or HC-123a, pressure just should be higher than 3000 pounds/inch
2If, HC-132a or HC-132b, pressure just should be higher than 1800 pounds/inch
2If the use polypropylene, no matter which kind of selected halogenated hydrocarbon is, pressure all will be higher than 1500 pounds/inch
2Said mixture should continue under required pressure conditions to be dissolved in solution in the liquid up to being formed into fibrillated polyolefin.In general, the pressure of optimal maximum should be less than 10000 pounds/inch
2After the one-tenth fibrillated polyolefin has dissolved, can reduce pressure, then mixture is extruded to form the structure of required high-quality clump silk ribbon.
Becoming the concentration of fibrillated polyolefin in weaving liquid with liquid and the total restatement that becomes fibrillated polyolefin, generally is between 10% to 20%.
Spinning solution preferably is made up of halogenated hydrocarbon liquid and one-tenth fibrillated polyolefin, if but the pressure that the preparation of solution and spinning need is lower, and spinning solution can contain second kind of liquid, and promptly the solvent of another kind of coexistence is to satisfy into the needs of fibrillated polyolefin.When the solvent of coexistence is a kind of solvent of hydrocarbon, article of cyclohexane, toluene, chlorobenzene, hexane, pentane, 3-methylpentane and the like for example, the concentration of cosolvent is generally 2(heavily in the mixture of halogenated hydrocarbon and cosolvent) %～25(weight) %, preferable selection is to be lower than 15(to weigh) %, so that potential flammability problem minimization.Certainly, when carrene during as cosolvent, in the mixture of halogenated hydrocarbon/cosolvent (not comprising into fibrillated polyolefin) concentration of carrene to be generally 5(heavy) %～50(is heavy) %.
Traditional sudden strain of a muscle is spun used additive and can be added in the spinning mixture with the method for prior art.These additives can be ultra-violet stabilizers, antioxidant, filler, the suchlike article of dye well.
Various characteristics and character in the example of above being discussed and hereinafter given are measured with following method.
Test method: the deliquescent test under self-heat condition of polyethylene and polypropylene is a kind of method that seals test tube test easily with your (Woodwell) invention of Wood, and it is in 3,655,498 the United States Patent (USP) that this method is disclosed in the patent No..It is set forth in the last paragraph of part in " the prior art description " of this paper.
Can do subjective assessment to the quality of the plexifilamentary film fibril silk ribbon made in the example.Grade " 5 " represents that this silk ribbon has the better fibrillation of spunbond film than the industrial products of producing with this sudden strain of a muscle spun polyethylene silk ribbon; Grade " 4 " represents that then this silk ribbon and industrial sudden strain of a muscle spinning band are good equally; Grade " 3 " represents that this silk ribbon and industrial sudden strain of a muscle spinning band are more or less the same; Grade " 2 " represents that then fibrillation is very poor, and silk ribbon is less; Grade " 1 " expression does not have silk ribbon to form.Grade " 3 " is the lowest limit that is used for method of the present invention satisfactorily.Industry silk ribbon product is to be used in the solution that accounts for about 12.5% linear polyethylene in the Arcton 11 to make.This method has been that 4,554,207 United States Patent (USP) has been done detailed explanation by Lee's (Lee) the patent No..Please refer to the 4th of this document arrange the 63rd walk to the 5th arrange the 10th the row, the present invention has quoted related content.
The surface area of plexifilamentary film fibril silk ribbon is that the another kind of the quality of grade of dodging textile product and fibrillation is weighed, surface area can be used Bu Lunaer (S.Brunauer), Emmett (PHEmmete) and Taylor's (ETeller) BET nitrogen adsorption method (USA Magazine " chemical association " the 60th volume, the 309th～319 page (1938)) test, and with rice
2/ gram is represented.
The breaking strength of the silk ribbon that sudden strain of a muscle is spun is with Instron (Instron) stretching test machine determination.Silk ribbon is processed and test under the condition of 70 and 65% relative humidity.
The yarn denier of silk ribbon depends on the weight of the silk ribbon sample of 15 centimetre lengths.Then sample being twisted into per inch 10 circles tests in the jaw of Instron (Instron) testing machine.Adopt 1 inch the standard sample length and the percentage elongation of per minute 60%, note the breaking strength in its when fracture, and represent with gram/Denier (gpd).
The present invention illustrates with example.Example is to carry out Batch Process with the equipment of reduced size comparatively speaking.This Batch Process method can enlarge and be converted into the successive flash vaporization spinning technique of practical application in proportion, for example, at United States Patent (USP) the 3rd, 227, use on that kind equipment by Anderson (Anderson) and Romano (Romano) invention in No. 794, in example and chart, technology of the present invention is indicated by Arabic numerals.The technology of indicating with capitalization then is the outer contrast technology of the present invention.
For each example of example 1-25 and A and the B that is used for comparison, to be 0.76 high-density linear polyethylene be spun into gratifying plexifilamentary film fibril silk ribbon (except the example 7, selecting melt index for use because of it is 26 low density linear polyethylene) according to the present invention by sudden strain of a muscle to a kind of melt index.
The device of two kinds of forms is used to prepare halogenated hydrocarbon and the mixture that becomes fibrillated polyolefin, and is used to dodge and spins production.The device of indicating " I " is used for example 1,5 and 16, indicates that the device of " II " is used for all the other all examples and compares technology.
Device " I " is a kind of high-tension apparatus, and having a volume is 50cm
3Cylindrical container, and the trunk-piston that a material that is used in container is exerted pressure is housed at the one end.The other end of container is equipped with a spinneret assembly, and it has 0.030 inch of a diameter, long 0.060 inch the spinning nozzle and the snap-action device of a rapidly opened and closed spinning nozzle, the device that also has measuring vessel internal pressure and temperature.In practical operation, filled one-tenth fibrillated polyolefin and halogenated hydrocarbon in the container, apply high pressure (as 4500 pounds/inch to fill
2), and under required temperature (as 140 ℃), be heated about one hour, to produce solution, this solution is owing to checker pressure is " blended " for about 10 times then.Pressure is reduced to the spinning nozzle valve open of required pressure of spinning and spinneret then, even if with having obtained the sudden strain of a muscle textile product that generates.
Device " II " comprises a pair of high pressure cylindrical container, and each container all is equipped with a piston in order to exert pressure.Each container is all similar to device " I ", but each container does not all have spinneret assembly.These two containers are connected to each other by feed-line.One group of thin screen cloth is housed in the feed-line is used for the mixed packing thing, its method be force fill by feed-line from a container transport to another container.A spinneret assembly is connected on the carrier pipe, and this spinneret assembly has the spinning nozzle of 0.030 inch of a diameter and the snap-action device of rapidly opened and closed spinning nozzle is arranged.The device that also has measuring vessel internal temperature and pressure in operation, is filled into fibrillated polyolefin and halogenated hydrocarbon and fill and is carried out very high pressure in the container.Fill is heated about one and a half hours under desired temperature then.During this period, in two adjacent containers, apply alternately with each other and differ about 50 pounds/inch
2Different pressure, with force filler pass through carrier pipe alternately from a container transport to another container, fully mix, and make it to form solution.And then apply the required pressure of spinning and open the spinning nozzle of spinning head.Even if with having obtained the sudden strain of a muscle textile product that generates.
All examples and relatively all available similar form of technology finish, equipment therefor is looked in practical operation, the specific composition of mixture shown in actual conditions and the abridged table and deciding.These forms have also write down and have dodged some characteristics of spinning the silk ribbon that forms.
In the table I, example 1-7 shows the different halogenated hydrocarbon that is applicable to technology of the present invention and solution, and relatively technology A and B then represent to use same halogenated hydrocarbon, but can not generate gratifying silk ribbon product under some conditions.
The table I
Instance number 12 A 3 B
Device I II II II II
Polyethylene 14.4 12 12 12 12
Concentration (weight) %
Solvent: HC 123 123 123 132b 132b
Mix
Temperature (℃) 140 140 170 140 140
Pressure (pound/inch
2Gauge pressure) 4,500 5,700 2,900 2,000 1500
-3800
Sudden strain of a muscle is spun
Temperature (℃) 170 140 170 180 200
Pressure (pound/inch
2Gauge pressure) 2,500 3,200 2,900 2,000 1500
-4200
The bar carries product
Denier 776 1003 ns
*476 ns
Breaking strength (gram/Denier) 3.25 2.91 ns 3.03 ns
Quality 441 4.5 1
Table I (continuing)
Instance number 4567
Device II II II II
Polyethylene 12 11.4 12 12
Concentration (weight) %
Solvent: HC 141b 123a 132a 132a
Mix
Temperature (℃) 140 140 140 140
Pressure (pound/inch
2Gauge pressure) 2,500 4,200 2,500 2500
Sudden strain of a muscle is spun
Temperature (℃) 170 170 200 180
Pressure (pound/inch
2Gauge pressure) 2,500 2,500 2,500 2500
The bar carries product
Denier 598 nm
*Nm nm
Breaking strength (gram/Denier) 2.8 nm nm nm
Quality 4343
In the table II, embodiment 8-25 shows the various cosolvent that use with halogenated hydrocarbon.
The table II
Instance number 89 10 11
Device II II II II
Polyethylene
Concentration (weight) % 12 12 12 12
Solvent: HC 123 123 123 132b
Cosolvent: CH
2Cl
2CH
2Cl
2CH
2Cl
2The 3-methylpentane
(weight) % 25 33 50 7
Mix
Temperature (℃) 140 140 140 140
Pressure (pound/inch
2Gauge pressure) 2,500 1,800 2,500 2500
Sudden strain of a muscle is spun
Temperature (℃) 170 160 170 200
Pressure (pound/inch
2Gauge pressure) 2,500 1,800 2,500 2500
The bar carries product
Denier 577 566 686 nm
Breaking strength (gram/Denier) 2.74 2.58 2.43 nm
Surface area (rice/gram) 3.78 49.6 63.1 nm
Quality 4.5 4.5 4 4.5
Table II (continuing)
Instance number 12 13 14 15
Device II II II II
Polyethylene
Concentration (weight) % 12 12 12 12
Solvent: HC 123 123 123 123
Cosolvent: C
6H
12C
6H
12Toluene toluene
(weight) % 13.3 16.7 6.7 13.3
Mix
Temperature (℃) 140 140 140 140
Pressure (pound/inch
2Gauge pressure) 2,800 2,500 2,600 2000
Sudden strain of a muscle is spun
Temperature (℃) 170 170 170 160
Pressure (pound/inch
2Gauge pressure) 2,900 2,500 2,900 2000
The bar carries product
Denier 564 612 642 877
Breaking strength (gram/Denier) 2.3 1.96 2.41 1.70
Surface area (rice
2/ gram) 34.9 28.0 15.9 25.6
Quality 55 4.5 4.5
Table II (continuing)
Instance number 16 17 18
Device I II II
Polyethylene
Concentration (weight) % 11.4 12 12
Solvent: HC 123 123 123
Cosolvent pentane hexane chlorobenzene
(weight) % 13.1 20 6.7
Mix
Temperature (℃) 140 140 140
Pressure (pound/inch
2Gauge pressure) 4200～3,700 2,700 2600
Sudden strain of a muscle is spun
Temperature (℃) 170 170 170
Pressure (pound/inch
2Gauge pressure) 3,000 2,900 2800
The bar carries product
Quality 454
Table II (continuing)
Instance number 19 20 21
Device II II II
Polyethylene
Concentration (weight) % 12 12 15
Solvent: HC 123 123 123
Cosolvent CH
2Cl
2CH
2Cl
2CH
2Cl
2
(weight) % 5 10 10
Mix
Temperature (℃) 140 140 140
Pressure (pound/inch
2Gauge pressure) 5,500 5,500 5500
Sudden strain of a muscle is spun
Temperature (℃) 170 160 170
Pressure (pound/inch
2Gauge pressure)～4700～4700～4000
The bar carries product
Denier 527 374 596
Breaking strength (gram/Denier) 4.61 2.93 4.22
Surface area (rice
2/ gram) 34.2 36.4 52.9
Quality 454
Table II (continuing)
Instance number 22 23 24 25
Device II II II II
Polyethylene
Concentration (weight) % 12 12 12 12
Solvent: HC 123 123 123 123
Cosolvent CH
2Cl
2CH
2Cl
2C
6H
12Toluene
(weight) % 32.5 40 55
Mix
Temperature (℃) 140 140 140 140
Pressure (pound/inch
2Gauge pressure) 1,800 1800～5,000 4000
Sudden strain of a muscle is spun
Temperature (℃) 170 200 170 170
Pressure (pound/inch
2Gauge pressure) 1,575 1575～5000～3650
The bar carries product
Denier 486.8 399.2 707 549
Breaking strength (gram/Denier) 2.67 2.43 1.79 2.94
Surface area (rice
2/ gram) 29.7 36.2 34.9 30.5
Quality 5 4.5 44
Annotate: " ns " expression does not have band to produce.
" nm " expression is not tested.
+ C
6H
12It is cyclohexane.
The example 26 of table III demonstrates, and adopts method of the present invention, also can obtain to have the clump silk ribbon of good fiber characteristic with other polyolefin.Device of using in this example and method of operating thereof are identical with the table II, just the used polyethylene of this example is 0.4 isotactic polypropylene replacement with the melt-flow rate, it is by (the Hercules of He Ka Laeis GmbH of Wilmington, the Delaware State (Wilmington), Inc) titled with the trade name of " Profax "-6823, can on market, buy.In addition, temperature that need be higher during mixing is so that be consistent with higher melting point polymer.The character of used condition and fiber product is concluded out in the table III, contain 3.6%(by polymer weight in this mixture of polymers) the trade mark of Irganox 1010(Ciba-Geigy company, a kind of steric hindrance polyphenol of high molecular) as antioxidant.
The table III
Instance number 26
The device II
Polypropylene
Concentration (weight) % 16
Solvent: HC 123
Mix
Temperature (℃) 180
Pressure (pound/inch
2) 1800
Sudden strain of a muscle is spun
Temperature (℃) 180
Pressure (pound/inch
2) 1800
The bar carries product
Denier 483
Breaking strength (gram/Denier) 1.23
Quality 4
Claims (18)
1, improving one's methods of plexifilamentary film fibril silk ribbon spun in a kind of sudden strain of a muscle, wherein, is 130 ℃ to 210 ℃ in temperature range, and pressure is higher than 3000 pounds/inch
2Condition under, polyethylene is dissolved in the halogenated hydrocarbon textile fluids, form weaving solution, polyethylene accounts for 10% to 20% of solution weight, this solution flash spinning is entered in fact a temperature and all lower zone of pressure, it is characterized in that, used halogenated hydrocarbon be from by
1,1 one dichloro 1,2,2 one HFC-143as and
1,2 one dichloro 1,2,2 one HFC-143as
Select in the family that forms.
2, improving one's methods of plexifilamentary film fibrillation band spun in a kind of sudden strain of a muscle, wherein, is 130 ℃ to 210 ℃ in temperature range, and pressure is higher than 1800 pounds/inch
2Condition under, polyethylene is dissolved in the halogenated hydrocarbon textile fluids, form weaving solution, polyethylene accounts for 10% to 20% of solution weight, this solution flash spinning is entered in fact a temperature and all lower zone of pressure, it is characterized in that, used halogenated hydrocarbon be from by
1,1-two chloro-2, the 2-Difluoroethane and
1,2-two chloro-1,1-Difluoroethane
Select in the family that forms.
3, improving one's methods of plexifilamentary film fibril silk ribbon spun in a kind of sudden strain of a muscle, wherein, is 130 ℃ to 210 ℃ in temperature range, and pressure is higher than 2000 pounds/inch
2Condition under, polyethylene is dissolved in the halogenated hydrocarbon textile fluids, form weaving solution, polyethylene accounts for 10% to 20% of solution weight, and this solution flash spinning is entered in fact a temperature and all lower zone of pressure, it is characterized in that used halogenated hydrocarbon is
1,1-two chloro-1-one fluoroethane.
4, improving one's methods of plexifilamentary film fibril silk ribbon spun in a kind of sudden strain of a muscle, wherein, is 130 ℃ to 210 ℃ in temperature range, and pressure is higher than 1500 pounds/inch
2Condition under, polyethylene is dissolved in the halogenated hydrocarbon textile fluids, form weaving solution, polyethylene accounts for 10% to 20% of solution weight, and this solution flash spinning is entered in fact a temperature and all lower zone of pressure,
It is characterized in that, used halogenated hydrocarbon be from by
1,1-two chloro-2,2, the 2-HFC-143a,
1,2-two chloro-1,2, the 2-HFC-143a,
1,1-two chloro-2,2-Difluoroethane
1,2-two chloro-1, the 1-Difluoroethane and
1,1-two chloro-1-one fluoroethane
Select in the family that forms.
5, improving one's methods of plexifilamentary film fibril silk ribbon spun in a kind of sudden strain of a muscle, wherein, is 130 ℃ to 210 ℃ in temperature range, and pressure is greater than 1000 pounds/inch
2Condition under, to become fibrillated polyolefin to be dissolved in the halogenated hydrocarbon textile fluids, contain 2% to 25% the hydrocarbon cosolvent that accounts for its gross weight in this textile fluids, so that generate a kind of weight with this weaving solution serves as that base calculates, the weaving solution that contains 10% to 20% one-tenth fibrillated polyolefin, this weaving solution flash spinning is entered in fact a temperature and all lower zone of pressure, it is characterized in that, used halogenated hydrocarbon be from by
1,1-two chloro-2,2, the 2-HFC-143a,
1,2-two chloro-1,2, the 2-HFC-143a,
1,1-two chloro-2, the 2-Difluoroethane,
1,2-two chloro-1, the 1-Difluoroethane and
1,1-two chloro-1-one fluoroethane
Select in the family that forms.
According to the method for claim 5, it is characterized in that 6, described cosolvent is from by the 3-methylpentane, cyclohexane, toluene, pentane, select in the family that hexane and chlorobenzene are formed.
According to the method for claim 6, it is characterized in that 7, the amount of described cosolvent should not surpass 15% of textile fluids gross weight.
8, improving one's methods of plexifilamentary film fibril silk ribbon spun in a kind of sudden strain of a muscle, wherein, is 130 ℃ to 210 ℃ in temperature range, and pressure is higher than 1000 pounds/inch
2Condition under, to become fibrillated polyolefin to be dissolved in the halogenated hydrocarbon textile fluids, contain in this textile fluids account for its gross weight 5% to 50% carrene as cosolvent, so that generate a kind of weight with this weaving solution serves as that base calculates, the weaving solution that contains 10% to 20% one-tenth fibrillated polyolefin, this weaving solution flash spinning is entered in fact a temperature and all lower zone of pressure, it is characterized in that, used halogenated hydrocarbon be from by
1,1-two chloro-2,2,2-HFC-143a
1,2-two chloro-1,2,2-HFC-143a
1,1-two chloro-2, the 2-Difluoroethane,
1,2-two chloro-1, the 1-Difluoroethane and
1,1-two chloro-1-one fluoroethane
Select in the family that forms.
9, according to claim 1,4,5,6,7 or 8 method, it is characterized in that described halogenated hydrocarbon is
1,1-two chloro-2,2,2-HFC-143a.
10, according to claim 5,6,7,8 or 9 method, it is characterized in that described polyolefin is a polyethylene.
11, according to claim 5,6,7,8 or 9 method, it is characterized in that described polyolefin is a polypropylene.
12, a kind of solution, this solution are heavy by 10(in fact) % to 20(is heavy) one-tenth fibrillated polyolefin and the 90(of % be heavy) % to 80(is heavy) liquid of % forms, this liquid contains a kind of halogenated hydrocarbon, this halogenated hydrocarbon be from by
1,1-two chloro-2,2, the 2-HFC-143a,
1,2-two chloro-1,2, the 2-HFC-143a,
1,1-two chloro-2, the 2-Difluoroethane,
1,2-two chloro-1, the 1-Difluoroethane and
1,1-two chloro-1-one fluoroethane
Select in the family that forms.
13, a kind of solution, this solution are heavy by 10(in fact) % to 20(is heavy) one-tenth fibrillated polyolefin and the 90(of % be heavy) % to 80(is heavy) a kind of halogenated hydrocarbon liquid of % forms, this halogenated hydrocarbon liquid be from by
1,1-two chloro-2,2,2-HFC-143a
1,2-two chloro-1,2, the 2-HFC-143a,
1,1-two chloro-2, the 2-Difluoroethane,
1,2-two chloro-1, the 1-Difluoroethane and
1,1-two chloro-1-one fluoroethane
Select in the family that forms.
14, according to the solution of claim 12, it is characterized in that, contain 2% to 25% the hydrocarbon cosolvent that accounts for halogenated hydrocarbon and cosolvent gross weight in the described liquid.
15, according to the solution of claim 12, it is characterized in that, contain in the described liquid account for halogenated hydrocarbon and carrene gross weight 5% to 50% carrene as cosolvent.
16, according to claim 12,13,14 or 15 solution, it is characterized in that described halogenated hydrocarbon is
1,1-two chloro-2,2,2-HFC-143a
17, according to claim 12,13,14,15 or 16 solution, it is characterized in that described one-tenth fibrillated polyolefin is a polyethylene.
18, according to claim 12,13,14,15 or 16 solution, it is characterized in that described one-tenth fibrillated polyolefin is a polypropylene.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US23844288A | 1988-08-30 | 1988-08-30 | |
| US238,442 | 1988-08-30 | ||
| US37929189A | 1989-07-18 | 1989-07-18 | |
| US379,291 | 1989-07-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1041190A true CN1041190A (en) | 1990-04-11 |
Family
ID=26931678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89107885A Pending CN1041190A (en) | 1988-08-30 | 1989-08-30 | The halogenated hydrocarbon that is used for flash distillation weaving polymer brushes silk |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0361684B1 (en) |
| JP (1) | JP2756489B2 (en) |
| KR (1) | KR0136110B1 (en) |
| CN (1) | CN1041190A (en) |
| AU (1) | AU627488B2 (en) |
| CA (1) | CA1338407C (en) |
| DE (1) | DE68909880T2 (en) |
| MX (1) | MX171962B (en) |
| RU (1) | RU2002861C1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107849740A (en) * | 2015-06-11 | 2018-03-27 | 纳幕尔杜邦公司 | Flash spinning processes |
| CN111286790A (en) * | 2020-03-05 | 2020-06-16 | 上海青昀新材料科技有限公司 | Safe solution spinning method |
| CN112609334A (en) * | 2020-11-30 | 2021-04-06 | 浙江青昀新材料科技有限公司 | Flash evaporation non-woven fabric and preparation method thereof |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU643386B2 (en) * | 1988-08-30 | 1993-11-11 | E.I. Du Pont De Nemours And Company | Non-ozone depleting halocarbons for flash-spinning polymeric plexifilaments |
| US5032326A (en) * | 1988-08-31 | 1991-07-16 | E. I. Du Pont De Nemours And Company | Flash-spinning of polymeric plexifilaments |
| TW204377B (en) * | 1989-07-12 | 1993-04-21 | Asahi Chemical Ind | |
| DE69030626T2 (en) * | 1990-02-26 | 1997-12-18 | Du Pont | Chlorofluorocarbons for the flash spinning of polyethylene fibers |
| US5459188A (en) * | 1991-04-11 | 1995-10-17 | Peach State Labs, Inc. | Soil resistant fibers |
| EP0527019B1 (en) * | 1991-08-03 | 1999-04-21 | Asahi Kasei Kogyo Kabushiki Kaisha | Halogen group solvent and solution using said solvent and process for producing three-dimensional fiber |
| US5279776A (en) * | 1991-09-17 | 1994-01-18 | E. I. Du Pont De Nemours And Company | Method for making strong discrete fibers |
| US5977237A (en) * | 1996-03-08 | 1999-11-02 | E. I. Du Pont De Nemours And Company | Flash-spinning solution |
| US5672307A (en) * | 1996-03-08 | 1997-09-30 | E. I. Du Pont De Nemours And Company | Flash spinning process |
| US5874036A (en) * | 1996-03-08 | 1999-02-23 | E. I. Du Pont De Nemours And Company | Flash-spinning process |
| US5985196A (en) * | 1998-01-20 | 1999-11-16 | E. I. Du Pont De Nemours And Company | Flash spinning process and flash spinning solution |
| US6524492B2 (en) | 2000-12-28 | 2003-02-25 | Peach State Labs, Inc. | Composition and method for increasing water and oil repellency of textiles and carpet |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3018519A (en) | 1958-03-06 | 1962-01-30 | Coats & Clark | Apparatus for molding plastic insert in threaded lock nut blanks |
| US3081519A (en) * | 1962-01-31 | 1963-03-19 | Fibrillated strand | |
| NL300881A (en) * | 1962-11-23 | |||
| US4528300A (en) * | 1984-01-31 | 1985-07-09 | The Dow Chemical Company | Process for producing dimensionally stable polyolefin foams using environmentally acceptable blowing agent systems |
-
1989
- 1989-08-29 AU AU40853/89A patent/AU627488B2/en not_active Ceased
- 1989-08-29 DE DE89308701T patent/DE68909880T2/en not_active Expired - Fee Related
- 1989-08-29 RU SU894614935A patent/RU2002861C1/en active
- 1989-08-29 MX MX017337A patent/MX171962B/en unknown
- 1989-08-29 EP EP89308701A patent/EP0361684B1/en not_active Expired - Lifetime
- 1989-08-30 JP JP1221847A patent/JP2756489B2/en not_active Expired - Fee Related
- 1989-08-30 CN CN89107885A patent/CN1041190A/en active Pending
- 1989-08-30 KR KR1019890012661A patent/KR0136110B1/en not_active IP Right Cessation
- 1989-08-30 CA CA000609848A patent/CA1338407C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107849740A (en) * | 2015-06-11 | 2018-03-27 | 纳幕尔杜邦公司 | Flash spinning processes |
| CN113046850A (en) * | 2015-06-11 | 2021-06-29 | 纳幕尔杜邦公司 | Flash spinning method |
| CN111286790A (en) * | 2020-03-05 | 2020-06-16 | 上海青昀新材料科技有限公司 | Safe solution spinning method |
| CN112609334A (en) * | 2020-11-30 | 2021-04-06 | 浙江青昀新材料科技有限公司 | Flash evaporation non-woven fabric and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE68909880T2 (en) | 1994-05-05 |
| KR900003435A (en) | 1990-03-26 |
| EP0361684A1 (en) | 1990-04-04 |
| JPH02160909A (en) | 1990-06-20 |
| KR0136110B1 (en) | 1998-04-28 |
| JP2756489B2 (en) | 1998-05-25 |
| CA1338407C (en) | 1996-06-18 |
| MX171962B (en) | 1993-11-25 |
| EP0361684B1 (en) | 1993-10-13 |
| DE68909880D1 (en) | 1993-11-18 |
| AU4085389A (en) | 1990-03-08 |
| RU2002861C1 (en) | 1993-11-15 |
| AU627488B2 (en) | 1992-08-27 |
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