CN104532395A - Preparation method of macromolecular hydrogen bond compound fiber - Google Patents
Preparation method of macromolecular hydrogen bond compound fiber Download PDFInfo
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- CN104532395A CN104532395A CN201410797962.4A CN201410797962A CN104532395A CN 104532395 A CN104532395 A CN 104532395A CN 201410797962 A CN201410797962 A CN 201410797962A CN 104532395 A CN104532395 A CN 104532395A
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Abstract
The invention relates to a preparation method of a macromolecular hydrogen bond compound fiber. The method comprises the following steps: respectively dissolving and mixing a macromolecular hydrogen bond donor and a macromolecular hydrogen bond acceptor, so as to obtain a uniform spinning solution; defoaming, filtering, standing and deforming the spinning solution, metering, entering a coagulating bath to coagulate and mold through a spinneret plate, so as to obtain a nascent fiber; and drying the nascent fiber, so as to obtain the macromolecular hydrogen bond compound fiber. Two high polymers which are difficult in fiber forming are successfully spun into a compound fiber on the basis of mutual action of hydrogen bonds, so that the spinning field and the application space of the high polymers are expanded; the high polymers also have novel properties, such as high elasticity and humidity sensitivity.
Description
Technical field
The invention belongs to the preparation field of complex fiber material, particularly a kind of preparation method of large molecule hydrogen bond compounding fiber.
Background technology
Along with the development of chemical fiber industry, the kind of chemical fibre gets more and more, but the spinning process of different chemical fibres and technique also also exist very large difference.Traditional spinning process comprises melt spinning and solution-polymerized SBR.For melt spinning, it typically is unitary system, only relate to the mass transfer between polymer melt strand and cooling medium, the change that spinning system does not form, is the simplest spinning process.But melt spinning is not suitable for can not melting or heat-labile high polymer.And wet spinning compensate for this defect of melt spinning to a certain extent.According to the difference of physical and chemical principle, wet spinning can be further divided into phase separation method, liquid crystal Method and frozen glue method (also claiming gel method).In actual production, wet spinning is implemented by phase separation method usually.Spinning solution enters coagulating bath through spinnerets, and by double diffusion, namely the solvent of spinning solution is to external diffusion, and precipitating agent spreads in spinning solution, thus causes phase transformation.In frozen glue method, due to the temperature in solution or change in concentration, polymer solution passes through the formation of intermolecular linkage in the solution and solidifies.For intermolecular interaction, hydrogen bond is the interaction that a class is relatively strong.Particularly when the hydrogen bond that intermolecular formation is a large amount of, reach supramolecular structure rank, enhance intermolecular interaction greatly.At present, a lot of scientific research person is carrying out the theoretical research of H-bonding self-assembly membrane material, as Zhang Xi professor has carried out the deep research of system in Supramolecular Assembling and thin polymer film.But, rarely have people to rely on hydrogen bond action by high polymer fibroblast.Therefore, based on interaction of hydrogen bond fibroblast, be very significant to the research range of expansion hydrogen bond.For one by hydrogen bond donor and the large molecular system of hydrogen bond receptor, under a higher ph condition, the quantity of hydrogen bond donor declines, thus reduces intermolecular interaction of hydrogen bond, and system becomes a thickness homogeneous phase solution.When this homogeneous phase solution enters in the lower acid solution of pH value, at H
+effect under, the quantity of hydrogen bond donor increases, and forms hydrogen bond, form water-fast compound with hydrogen bond receptor, thus from acid solution precipitation, coagulation forming.By the pH value of adjustment and control system, control large intermolecular interaction of hydrogen bond, successfully some high polymers self being difficult to fibroblast can not only be spun into fiber, expand the application space of spinning field and high polymer, also impart some new performance of high polymer, as high elasticity, moisture-sensitive etc.
Current China Man-made Fibre Industry development has entered firm developing stage, and chemical fibre output increases sharply, and has developed into the industry with great variety of goods such as terylene, polyamide fibre, acrylic fibers, polyvinyl, polypropylene fibre.But the fiber of the overwhelming majority is all made up of single high polymer.For most multicomponent fibre, be generally that parallel type, core-skin type (with core or core shift), sky are star-like, multi-core type or fabric of island-in-sea type etc., but not form uniform compounding fiber.This fibrid is that 3 D stereo is curling, high loft; The shortcomings such as have component uneven, structure is uneven simultaneously, and non-homogeneous expansion is even.Along with the development of science and technology, people are not exclusively satisfied with the warming effect that traditional fibre is brought, and more should pursue becoming more meticulous, health, quality.Therefore be necessary to develop and a kind ofly reach the blended composite fibre of molecule aspect, i.e. even structure, form uniform function and service fiber.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of large molecule hydrogen bond compounding fiber, and preparation method of the present invention is simple, and cost is low, low for equipment requirements, preparation technology's environmental protection.
The preparation method of a kind of large molecule hydrogen bond compounding fiber of the present invention, comprising:
(1), under 0-80 DEG C of condition, large molecule hydrogen bond donor, large molecule hydrogen bond receptor are dissolved respectively, add alkali, mixing, obtains homogeneous spinning solution;
(2) by above-mentioned spinning solution after filtration, deaeration, enters acid coagulating bath coagulation forming through spinnerets after metering, obtains as-spun fibre;
(3) by above-mentioned as-spun fibre drying, large molecule hydrogen bond compounding fiber is obtained.
In described step (1), the molecular weight of large molecule hydrogen bond donor is 50 ~ 4500kDa; The molecular weight of large molecule hydrogen bond receptor is 50 ~ 5000kDa.
In described step (1), large molecule hydrogen bond donor is polyacrylic acid, polymethylacrylic acid, poly-ethylacrylic acid, tannic acid, poly-contraposition vinyl phenol, phenol formaldehyde resin, polyaniline, one or more in fluorinated alohol polymer; Large molecule hydrogen bond receptor is poly(ethylene oxide), polyvinyl methyl ether, PVP, P4VP, polyacrylamide, Vinylcaprolactam homopolymer, poly-N-isopropyl acrylamide Ju oxazoline, polyvinyl alcohol, gathers one or more in polysaccharide; Alkali is NaOH.
In described step (1), large molecule hydrogen bond donor, large molecule hydrogen bond receptor are dissolved in water respectively, and mixing time is 3-12h; In spinning solution, the mass percent of large molecule hydrogen bond donor is 1 ~ 18%, and the mass percent of large molecule hydrogen bond receptor is 1 ~ 18%.
In described step (1), in compound spinning solution, the mass ratio of hydrogen bond donor and hydrogen bond receptor is 10:1 ~ 1:10.
By regulating ionic strength, adjust ph in described step (1), (2), regulating and controlling temperature or employing special solvent suppress or promote large intermolecular hydrogen bond action.
Special solvent is one or more in dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, tetramethylurea, DMA.
In described step (2), deaeration is vacuum defoamation, evacuation and centrifugal degassing or standing and defoaming; Be filtered into and adopt tank filter to filter, filter cloth is made up of terylene or polyamide fibre or polypropylene fibre, and the aperture of filtering material is between 200 ~ 1200 orders, and filter cylinder is made up of stainless steel, filter pressure 0.1 ~ 0.5MPa; Spinnerets is single hole spinnerets or porous spinnerets, and pore diameter range is 0.02 ~ 0.80mm; Acid coagulating bath is organic acid or inorganic acid aqueous solution; The pH value of acid coagulating bath is less than 3; The temperature of acid coagulating bath is 0-80 DEG C.
Described inorganic acid is one or more in hydrochloric acid, nitric acid, sulfuric acid; Organic acid is one or more in formic acid, acetic acid, ethanedioic acid.
The nascent spinning fibre obtained in described step (2) leaves standstill 5-30min in coagulating bath.
In described step (3), baking temperature is 10-30 DEG C; In large molecule hydrogen bond compounding fiber, hydrogen bond donor mass fraction is 10 ~ 90%, and all the other are hydrogen bond receptor.
The average filament diameter of large molecule hydrogen bond compounding fiber obtained in described step (3) is 70-145 μm, and percentage elongation is 500-2300%, and average filament strength is 1-15MPa.
In the present invention, compounding fiber relies on interaction of hydrogen bond fibroblast, for spinning solution, at higher ph values, reduces the quantity of hydrogen bond donor, destroys the formation of hydrogen bond, thus can obtain forming homogeneous spinning solution.When dynamic analysis of spinning enters acid coagulating bath, at H
+effect under, the quantity of hydrogen bond donor increases, and forms hydrogen bond, form water-fast compound with hydrogen bond receptor, thus from coagulating bath precipitation, coagulation forming.
For PEO/PAA in Fig. 1, under higher ph condition, between PEO and PAA, do not form hydrogen bond; And under lower ph condition, H
+with COO
-be combined into carboxyl, make between PEO and PAA, to form a large amount of hydrogen bonds, thus separate out, coagulation forming.
A preparation method for large molecule hydrogen bond compounding fiber, concrete principle is as follows:
(1) for spinning solution, need the interaction effectively suppressing hydrogen bond, thus ensure that spinning solution is flowable, homogeneous liquid; (2) for coagulating bath, need to impel in dynamic analysis of spinning effectively forming hydrogen bond, obtain insoluble compound, thus ensure that fibre deposition is shaping; (3) namely spinning is realized by the large intermolecular interaction of hydrogen bond of regulation and control.
The present invention is by controlling large intermolecular interaction of hydrogen bond, successfully some high polymers self being difficult to fibroblast can not only be spun into fiber, expand the application space of spinning field and high polymer, also imparted some new performance of high polymer, as high elasticity, moisture-sensitive etc.
beneficial effect
The present invention utilizes the interaction of hydrogen bond between high polymer, pass through wet spinning, the high polymer that two kinds self are difficult to fibroblast is spun into compounding fiber by success, this has expanded the field of spinning and the application space of high polymer to a certain extent, also impart some new performance of high polymer, as high elasticity, moisture-sensitive etc.; The invention has the advantages that the preparation method of this fiber is simple, cost is low, low for equipment requirements, preparation technology's environmental protection.
Accompanying drawing explanation
Fig. 1 is the change schematic diagram of PEO/PAA interaction of hydrogen bond under different pH condition;
Fig. 2 is PEO/PAA composite fibre strength of filament stretching figure, and wherein (a) initial clamp distance is the fiber of 1cm; B () stretching reaches fiber when 900%; (c) fiber for stretching when reaching 1450%.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
Raw material: PAA, relative molecular mass: 450KDa; PEO, relative molecular mass: 600kDa.
Added to respectively in water by PAA and PEO, under normal temperature, constant speed stirs 8 hours, is made into the aqueous solution that mass fraction is 8%, and mixes in the ratio of 1:1.Drip NaOH solution, be made into the spinning solution of stable homogeneous; Then filter (adopt tank filter to filter, filter cloth is made up of terylene, and the aperture of filtering material is at 200 orders, and filter cylinder is made up of stainless steel, filter pressure 0.1 ~ 0.5MPa), spinning solution is evacuation and centrifugal degassing 45min at 25 DEG C, rotating speed 4500r/min.Utilize wet spinning technology, adopt single hole spinnerets, spinneret hole diameter is 0.08mm, and spinning solution is extruded through measuring pump and spinnerets, enters the acid coagulating bath of 25 DEG C, and coagulating bath is the hydrochloric acid solution of pH=1, obtains as-spun fibre; As-spun fibre leaves standstill after 15 minutes in coagulating bath, takes out, and dry in 25 DEG C, namely obtaining average filament diameter is 145 μm, and percentage elongation is 1000%, and average filament strength is the large molecule hydrogen bond compounding fiber of 3.3MPa.
Embodiment 2
Raw material: PAA, relative molecular mass: 450kDa; PEO, relative molecular mass: 600kDa.
Added to respectively by PAA and PEO in anhydrating, under normal temperature, constant speed stirs 8 hours, is made into the aqueous solution that mass fraction is 8%, and mixes in the ratio of 1:3.Drip NaOH solution, be made into the spinning solution of stable homogeneous; Then filter (filtration of employing tank filter, filter cloth is made up of polyamide fibre, and the aperture of filtering material is between 1200 orders, filter cylinder is made up of stainless steel, filter pressure 0.1 ~ 0.5MPa), spinning solution is evacuation and centrifugal degassing 45min at 25 DEG C, rotating speed 4500r/min.Utilize wet spinning technology, adopt single hole spinnerets, spinneret hole diameter is 0.08mm, and spinning solution is extruded through measuring pump and spinnerets, enters the acid coagulating bath of 25 DEG C, and coagulating bath is the hydrochloric acid solution of pH=1, obtains as-spun fibre; As-spun fibre leaves standstill after 15 minutes in coagulating bath, takes out, and dry in 25 DEG C, namely obtaining average filament diameter is 110 μm, and percentage elongation is 1500%, and average filament strength is the large molecule hydrogen bond compounding fiber of 2MPa.Fig. 2 is the instance graph be stretched in extension test process in various degree.
Embodiment 3
Raw material: PAA, relative molecular mass: 450kDa; PEO, relative molecular mass: 600kDa.
Added to respectively in water by PAA and PEO, under normal temperature, constant speed stirs 8 hours, is made into the aqueous solution that mass fraction is 8%, and mixes in the ratio of 5:1.Drip NaOH solution, be made into the spinning solution of stable homogeneous; Then filter (filtration of employing tank filter, filter cloth is made up of polypropylene fibre, and the aperture of filtering material is between 500 orders, filter cylinder is made up of stainless steel, filter pressure 0.1 ~ 0.5MPa), spinning solution is evacuation and centrifugal degassing 45min at 25 DEG C, rotating speed 4500r/min.Utilize wet spinning technology, adopt single hole spinnerets, spinneret hole diameter is 0.08mm, and spinning solution is extruded through measuring pump and spinnerets, enters the acid coagulating bath of 40 DEG C, and coagulating bath is the sulfuric acid solution of pH=1.5, obtains as-spun fibre; As-spun fibre leaves standstill after 15 minutes in coagulating bath, takes out, and dry in 25 DEG C, namely obtaining average filament diameter is 130 μm, and percentage elongation is 650%, and average filament strength is the large molecule hydrogen bond compounding fiber of 12.1MPa.
Claims (11)
1. a preparation method for large molecule hydrogen bond compounding fiber, comprising:
(1), under 0-80 DEG C of condition, large molecule hydrogen bond donor, large molecule hydrogen bond receptor are dissolved respectively, adds alkali mixing, obtain homogeneous spinning solution;
(2) by above-mentioned spinning solution after filtration, deaeration, enter acid coagulating bath coagulation forming through spinnerets after metering, obtain as-spun fibre;
(3) by above-mentioned as-spun fibre drying, large molecule hydrogen bond compounding fiber is obtained.
2. the preparation method of a kind of large molecule hydrogen bond compounding fiber according to claim 1, is characterized in that: in described step (1), the molecular weight of large molecule hydrogen bond donor is 50 ~ 4500kDa; The molecular weight of large molecule hydrogen bond receptor is 50 ~ 5000kDa.
3. the preparation method of a kind of large molecule hydrogen bond compounding fiber according to claim 1, it is characterized in that: in described step (1), large molecule hydrogen bond donor is polyacrylic acid, polymethylacrylic acid, poly-ethylacrylic acid, tannic acid, poly-contraposition vinyl phenol, phenol formaldehyde resin, polyaniline, one or more in fluorinated alohol polymer; Large molecule hydrogen bond receptor is poly(ethylene oxide), polyvinyl methyl ether, PVP, P4VP, polyacrylamide, Vinylcaprolactam homopolymer, poly-N-isopropyl acrylamide Ju oxazoline, polyvinyl alcohol, gathers one or more in polysaccharide; Alkali is NaOH.
4. the preparation method of a kind of large molecule hydrogen bond compounding fiber according to claim 1, is characterized in that: in described step (1), large molecule hydrogen bond donor, large molecule hydrogen bond receptor are dissolved in water respectively, and mixing time is 3-12h; In spinning solution, the mass percent of large molecule hydrogen bond donor is 1 ~ 18%, and the mass percent of large molecule hydrogen bond receptor is 1 ~ 18%.
5. the preparation method of a kind of large molecule hydrogen bond compounding fiber according to claim 1, is characterized in that: by adopting special solvent suppress or promote large intermolecular hydrogen bond action in described step (1), (2).
6. the preparation method of a kind of large molecule hydrogen bond compounding fiber according to claim 5, is characterized in that: described special solvent is one or more in dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, tetramethylurea, DMA.
7. the preparation method of a kind of large molecule hydrogen bond compounding fiber according to claim 1, is characterized in that: in described step (2), deaeration is vacuum defoamation, evacuation and centrifugal degassing or standing and defoaming; Be filtered into and adopt tank filter to filter, filter cloth is made up of terylene or polyamide fibre or polypropylene fibre, and the aperture of filtering material is between 200 ~ 1200 orders, and filter cylinder is made up of stainless steel, filter pressure 0.1 ~ 0.5MPa; Spinnerets is single hole spinnerets or porous spinnerets, and pore diameter range is 0.02 ~ 0.80mm; Acid coagulating bath is organic acid or inorganic acid aqueous solution; The pH value of acid coagulating bath is less than 3; The temperature of acid coagulating bath is 0-80 DEG C.
8. the preparation method of a kind of large molecule hydrogen bond compounding fiber according to claim 7, is characterized in that: described inorganic acid is one or more in hydrochloric acid, nitric acid, sulfuric acid; Organic acid is one or more in formic acid, acetic acid, ethanedioic acid.
9. the preparation method of a kind of large molecule hydrogen bond compounding fiber according to claim 1, is characterized in that: the nascent spinning fibre obtained in described step (2) leaves standstill 5-30min in coagulating bath.
10. the preparation method of a kind of large molecule hydrogen bond compounding fiber according to claim 1, is characterized in that: in described step (3), baking temperature is 10-30 DEG C; In large molecule hydrogen bond compounding fiber, hydrogen bond donor mass fraction is 10 ~ 90%, and all the other are hydrogen bond receptor.
The preparation method of 11. a kind of large molecule hydrogen bond compounding fibers according to claim 1, it is characterized in that: the average filament diameter of large molecule hydrogen bond compounding fiber obtained in described step (3) is 70-145 μm, percentage elongation is 500-2300%, and average filament strength is 1-15MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358099A (en) * | 2019-06-28 | 2019-10-22 | 吉林大学 | PVA based composites and its presoma, remodeling product, composite hydrogel, laminated film and preparation and application |
| CN110860212A (en) * | 2018-08-28 | 2020-03-06 | 浙江工业大学 | Preparation method of intelligent switch membrane with self-cleaning performance |
| CN111058103A (en) * | 2019-12-26 | 2020-04-24 | 东华大学 | Preparation method of crosslinked macromolecular hydrogen bond composite fiber |
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| CN1143125A (en) * | 1995-08-17 | 1997-02-19 | 四川联合大学 | Poly(acrylic nitrile-acrylamide-acrylic acid)/polyvinyl alcohol composite fibre |
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2014
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143125A (en) * | 1995-08-17 | 1997-02-19 | 四川联合大学 | Poly(acrylic nitrile-acrylamide-acrylic acid)/polyvinyl alcohol composite fibre |
Non-Patent Citations (2)
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| 李飞 等: "高分子共混物中氢键的作用Ⅱ.氢键对高分子共混物", 《高分子通报》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110860212A (en) * | 2018-08-28 | 2020-03-06 | 浙江工业大学 | Preparation method of intelligent switch membrane with self-cleaning performance |
| CN110860212B (en) * | 2018-08-28 | 2022-07-22 | 浙江工业大学 | Preparation method of intelligent switch membrane with self-cleaning performance |
| CN110358099A (en) * | 2019-06-28 | 2019-10-22 | 吉林大学 | PVA based composites and its presoma, remodeling product, composite hydrogel, laminated film and preparation and application |
| CN111058103A (en) * | 2019-12-26 | 2020-04-24 | 东华大学 | Preparation method of crosslinked macromolecular hydrogen bond composite fiber |
| CN111058103B (en) * | 2019-12-26 | 2023-10-10 | 东华大学 | Preparation method of crosslinked macromolecular hydrogen bond compound fiber |
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