CN102277644B - Polyacrylonitrile-based protofilaments modified by phenolic resin and preparation method thereof - Google Patents
Polyacrylonitrile-based protofilaments modified by phenolic resin and preparation method thereof Download PDFInfo
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- CN102277644B CN102277644B CN 201110182690 CN201110182690A CN102277644B CN 102277644 B CN102277644 B CN 102277644B CN 201110182690 CN201110182690 CN 201110182690 CN 201110182690 A CN201110182690 A CN 201110182690A CN 102277644 B CN102277644 B CN 102277644B
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Abstract
The invention relates to polyacrylonitrile-based protofilaments modified by phenolic resin and a preparation method thereof. The protofilaments comprise the components of polyacrylonitrile and the phenolic resin, wherein the weight percentage of the phenolic resin is 0.1-15%. The preparation method of the protofilaments comprises the steps of: (1) mixing the polyacrylonitrile and an organic solvent, then adding the dried phenolic resin, and stirring to obtain a spinning solution; and (2) extruding the spinning solution through a spinning nozzle, feeding the extruded spinning solution into a coagulating bath directly for forming in the coagulating bath, and then performing the processes of coagulating bath drawing, water bath and oil application on the formed spinning solution to obtain the protofilaments. The polyacrylonitrile-based protofilaments prepared by adopting the preparation method disclosed by the invention have more obviously enhanced fiber mechanical property after preoxidation treatment, thus, a new approach to development of novel polyacrylonitrile-based carbon fibers is provided. The preparation method disclosed by the invention has the advantages of simple steps, simplicity and convenience for operation, low cost, low requirements on equipment and suitability for scale production.
Description
Technical field
The invention belongs to textile fabric precursor and preparing technical field thereof, particularly relate to a kind of phenolic resin modified polyacrylonitrile-based precursor and preparation method.
Background technology
Carbon fiber has the performance of many excellences.On the mechanical property, its processability is good, and light weight is and high-strength, and proportion only is 1/4th of iron, and specific strength but is 10 times of iron, especially plateau modulus carbon fiber, large 68 times than steel of its tensile strength, large 1.8～2.6 times of modular ratio steel.In the high temperature inert environment more than 2000 ℃, material with carbon element is the material that unique intensity does not descend, and is that other primary structure materials (metal and alloy thereof) are incomparable.On the chemical property, extremely stable, high temperature resistant and low temperature and corrosion resistance height.From thermal property, it is low temperature resistant that it is high temperature resistant, and namely its property retention is constant under 600 ℃ of high temperature, still very pliable and tough under-180 ℃ of low temperature, but also not with adverse circumstances under acid, alkali, the reaction of salt corrosion.
At present, carbon fiber and composite thereof mainly have a wide range of applications and market in each large fields such as Aero-Space, sports, civil construction, automobile even health cares, such as aircraft wing, tennis racket, concrete, automobile buffer, heart valve prosthesis valve body etc.
Angle from raw material, carbon fiber mainly is divided into four large material systems of viscose glue base, alkyd resin based fiber, the basic fiber of polyacrylonitrile (PAN) and asphalt base carbon fiber, and wherein especially maximum with PAN base carbon fibre output, most widely used, be the main flow in carbon fiber market.
Polyacrylonitrile fiber is the presoma of carbon fiber, the performance quality key of carbon fiber is the quality of precursor, the internal flaw of precursor is almost completely constant being retained in the carbon fiber after carbonization, and polyacrylonitrile fibril not only affects the quality of carbon fiber, and affect its output and production cost.Former yarn quality has become one large " bottleneck " of China's carbon fiber development.
Both at home and abroad the method for improving former yarn quality and preparing high-performance carbon fibre technique is seen in report.Chinese patent such as CN101705523A have reported and have adopted gel spinning to prepare the method for polyacrylonitrile fibril, CN101092761A discloses the method for utilizing phenolic resin modified polypropylene to prepare carbon nano-fiber, it is that the aqueous-phase suspending copolymerization of initiator system prepares polyacrylonitrile base carbon fiber precursors that CN101161880 has mentioned with ammonium persulfate-ammonium sulfite or ammonium bisulfite, its mechanical property improved after CN101245500A utilized attapulgite nano-particle that polyacrylonitrile fibril is carried out modification, and TENSILE STRENGTH is brought up to 6～9cN/dtex.US Patent No. 6054214 reported when acrylonitrile take mass percent as 95%～98%, can catalysed promoted when the generating vinyl carboxylate monomer is enough to hold mol ratio and is 1%～4% ammonium ion or this class comonomer of amine intermolecular and intramolecular cyclization interlinkage and then make high-performance carbon fibre.
But utilize phenolic resins (PF) that polyacrylonitrile base carbon fiber precursors is carried out modification, at present domestic document or the patent report of there is no.
Summary of the invention
Technical problem to be solved by this invention provides a kind of phenolic resin modified polyacrylonitrile-based precursor and preparation method; the fibrous mechanical property of this polyacrylonitrile-based precursor after pre-oxidation treatment has obvious raising; this preparation method's step is simple; easy and simple to handle; cost is low; to equipment require lowly, be produced on a large scale.
A kind of phenolic resin modified polyacrylonitrile-based precursor of the present invention, its composition is polyacrylonitrile and phenolic resins, wherein the percentage by weight of phenolic resins is 0.1-15%.
Described polyacrylonitrile is that molecular weight is the polypropylene dedicated nitrile of carbon fiber of 6-10 ten thousand; Phenolic resins is epoxide modified novolac resin (commercially available).
Described phenolic resin modified polyacrylonitrile-based precursor, the fiber number after pre-oxidation are 6.72-8.09dtex, and TENSILE STRENGTH is 2.71-6.72cN/dtex.
The preparation method of a kind of phenolic resin modified polyacrylonitrile-based precursor of the present invention comprises:
(1) preparation of spinning solution:
Polyacrylonitrile and organic solvent are mixed, under 80-100 ℃, stirred 1-3 hour after swelling 2-4 hour, then add dry phenolic resins, stirred 0.5-2 hour, get spinning solution; Wherein phenolic resins accounts for the 0.1-15% of phenolic resins and polyacrylonitrile weight sum, and the weight sum of phenolic resins and polyacrylonitrile and the weight ratio of organic solvent are 2-3: 15.
(2) spinning:
Above-mentioned spinning solution directly enters coagulating bath after spinning head is extruded, then moulding in coagulating bath passes through coagulating bath stretching, water-bath and the process that oils, and namely gets to contain the precursor that percentage by weight is 0.1-15% phenolic resins.
Phenolic resins described in the step (1) is commercially available epoxide modified novolac resin, and described organic solvent is technical pure methyl-sulfoxide (DMSO).
Spinning condition described in the step (2) is: pump is 1.1-1.4g/min for amount, and the spray silk is the 30-60 hole.
Coagulating bath described in the step (2) is that volume ratio is 50: 50 pure water and the mixed solution of organic solvent, and temperature is 25 ℃, wherein the preferential DMSO of organic solvent.
The draw ratio of the stretching described in the step (2) is 5.0-6.2 times.
The first water washing bath is the deionized water of temperature 70 C in the water-bath described in the step (2), and the second water washing bath is that temperature is 90 ℃ deionized water.
Oil in the oiling described in the step (2) is that polyacrylonitrile-based carbon fibre is oil solution dedicated, and its Main Ingredients and Appearance is dimethyl siloxane.
The present invention is take polyacrylonitrile as matrix, phenolic resins is decentralized photo, and PF and PAN blend are obtained spinning solution, makes the PF/PAN blended fiber through wet spinning again, behind pre-oxidation treatment (200-300 ℃, air atmosphere) blended fiber crosslinking curing, obtain pre-oxygen silk again.The fiber number of this fiber is: 6.72-8.09dtex, TENSILE STRENGTH is 2.71-6.72cN/dtex.Compare with pure polyacrylonitrile fibril, the intensity of passing through phenolic resin modified fiber in Pre oxidation section (200-300 ℃) has obvious raising.
The present invention and different and phenolic aldehyde base carbon fiber protofilament, but remove modified polyacrylonitrile-based precursor with commercially available epoxide modified novolac resin, cause to reduce polyacrylonitrile-based precursor pre-oxidation to occur when the post processing mechanical property rapid drawdown may, and finally improve the mechanical property of fiber after the pre-oxidation.
Principle of the present invention is to utilize the method for blend, and the phenolic resins that drying is good joins in the organic solvent that contains polyacrylonitrile, by wet spinning, makes composite polypropylene itrile group precursor, thus Effective Raise the mechanical property of fiber under the Pre oxidation.
Beneficial effect
(1) the prepared polyacrylonitrile-based precursor of the present invention, the fibrous mechanical property after pre-oxidation treatment has obvious raising, and this provides a kind of new approach for the development of new polyacrylonitrile-based carbon fibre;
(2) preparation method's step of the present invention is simple, easy and simple to handle, and cost is low, to equipment require lowly, be produced on a large scale.
Specific embodiments
The invention will be further elaborated below in conjunction with specific embodiment, should be understood that these embodiment only are used for explanation the present invention and are not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalences fall within equally the application's appended claims and say restricted portion.
Embodiment 1
(1) polyacrylonitrile of drying being crossed and organic solvent DMSO put into there-necked flask according to the ratio of weight ratio 60.8g: 336g, and oil bath temperature is 90 ℃, through strong stirring after 3 hours thorough swellings 2 hours; The dry phenolic resins powder of crossing of 3.2g is joined in the there-necked flask, continue strong stirring 1 hour until blend is even.
(2) stoste makes the polyacrylonitrile-based precursor that contains 5% phenolic resins through wet spinning, and wherein the wet spinning coagulating bath is pure water and DMSO mixed solution, and the coagulating bath concentration ratio is 50: 50; Temperature is 25 ℃, and the spinneret orifice hole count is 50, and pump is 1.2g/min for amount, and draw ratio is 5.5 times, and the first deionized water washing temperature is 70 ℃, and the second deionized water washing temperature is 90 ℃, and oils.
The phenolic resins composite polypropylene itrile group precursor that makes, the fiber number of the fiber after the pre-oxidation in 10 minutes of 250 ℃ of oven is: 8.09dtex, TENSILE STRENGTH is: 2.71cN/dtex.
Embodiment 2
(1) the polyacrylonitrile waste silk and the organic solvent DMSO that drying are crossed put into there-necked flask according to the ratio of weight ratio 54.0g: 336g, and oil bath temperature is 80 ℃, through strong stirring after 2 hours the thorough swelling 1.5 hours; The dry phenolic resins powder of crossing of 6.0g is joined in the there-necked flask, continue strong stirring 0.5 hour until blend is even.
(2) stoste makes the polyacrylonitrile-based precursor that contains 10% phenolic resins through wet spinning, and wherein the wet spinning coagulating bath is pure water and DMSO mixed solution, and the coagulating bath concentration ratio is 50: 50; Temperature is 25 ℃, and the spinneret orifice hole count is 40, and pump is 1.1g/min for amount, and draw ratio is 5.5 times, and the first deionized water washing temperature is 70 ℃, and the second deionized water washing temperature is 90 ℃, and oils.
The phenolic resins composite polypropylene itrile group precursor that makes, the fiber number of the fiber after the pre-oxidation in 30 minutes of 220 ℃ of oven is: 6.72dtex, TENSILE STRENGTH is: 6.72cN/dtex.
Embodiment 3
(1) the polyacrylonitrile waste silk and the organic solvent DMSO that drying are crossed put into there-necked flask according to the ratio of weight ratio 54.4g: 427g, and oil bath temperature is 100 ℃, through strong stirring after 4 hours thorough swellings 2.5 hours; The dry phenolic resins powder of crossing of 9.6g is joined in the there-necked flask, continue strong stirring 12 hours until blend is even.
(2) stoste makes the polyacrylonitrile-based precursor that contains 15% phenolic resins through wet spinning, and wherein the wet spinning coagulating bath is pure water and DMSO mixed solution, and the coagulating bath concentration ratio is 50: 50; Temperature is 25 ℃, and the spinneret orifice hole count is 60, and pump is 1.3g/min for amount, and draw ratio is 6.0 times, and the first deionized water washing temperature is 70 ℃, and the second deionized water washing temperature is 90 ℃, and oils.
The phenolic resins composite polypropylene itrile group precursor that makes, the fiber number of the fiber after the pre-oxidation in 10 minutes of 250 ℃ of oven is: 6.72dtex, TENSILE STRENGTH is: 5.86cN/dtex.
Embodiment 4
(1) the polyacrylonitrile waste silk and the organic solvent DMSO that drying are crossed put into there-necked flask according to the ratio of weight ratio 49.5g: 238g, and oil bath temperature is 90 ℃, through strong stirring after 3 hours thorough swellings 2 hours; The dry phenolic resins powder of crossing of 0.50g is joined in the there-necked flask, continue strong stirring 2 hours until blend is even.
(2) stoste makes the polyacrylonitrile-based precursor that contains 1.0% phenolic resins through wet spinning, and wherein the wet spinning coagulating bath is pure water and DMSO mixed solution, and the coagulating bath concentration ratio is 50: 50; Temperature is 25 ℃, and the spinneret orifice hole count is 50, and pump is 1.4g/min for amount, and draw ratio is 5.0 times, and the first deionized water washing temperature is 70 ℃, and the second deionized water washing temperature is 90 ℃, and oils.
The phenolic resins composite polypropylene itrile group precursor that makes, the fiber number of the fiber after the pre-oxidation in 10 minutes of 280 ℃ of oven is: 6.72dtex, TENSILE STRENGTH is: 1.02cN/dtex.
Comparative example 1
(1) the polyacrylonitrile waste silk and the organic solvent DMSO that drying are crossed put into there-necked flask according to the ratio of weight ratio 64g: 336g, and oil bath temperature is 90 ℃, through thorough swelling after 3 hours the immersion, strong stirring 3 hours.
(2) stoste makes the polyacrylonitrile-based precursor that does not contain phenolic resins through wet spinning, and wherein the wet spinning coagulating bath is pure water and DMSO mixed solution, and the coagulating bath concentration ratio is 50: 50; Temperature is 25 ℃, and the spinneret orifice hole count is 50, and pump is 1.2g/min for amount, and draw ratio is 5.0 times, and the first deionized water washing temperature is 70 ℃, and the second deionized water washing temperature is 90 ℃, and oils.
The polyacrylonitrile-based precursor that does not contain phenolic resins that makes, through 220 ℃, 250 ℃ and 280 ℃ of baking ovens were processed respectively 10 minutes, and the fiber number of fiber is after the pre-oxidation: 7.99dtex, TENSILE STRENGTH is respectively: 2.48cN/dtex, 1.92cN/dtex and 0.98cN/dtex.
Claims (7)
1. the preparation method of a phenolic resin modified polyacrylonitrile-based precursor comprises:
(1) polyacrylonitrile and organic solvent are mixed, under 80-100 ℃, stirred 1-3 hour after swelling 2-4 hour, then add dry phenolic resins, stirred 0.5-2 hour, get spinning solution; Wherein phenolic resins accounts for the 0.1-15% of phenolic resins and polyacrylonitrile weight sum, and the weight sum of phenolic resins and polyacrylonitrile and the weight ratio of organic solvent are 2-3:15,
(2) above-mentioned spinning solution directly enters coagulating bath after spinning head is extruded, and moulding in coagulating bath then through coagulating bath stretching, water-bath and the process that oils, and get final product.
2. the preparation method of a kind of phenolic resin modified polyacrylonitrile-based precursor according to claim 1, it is characterized in that: the phenolic resins described in the step (1) is epoxide modified novolac resin, and described organic solvent is methyl-sulfoxide.
3. the preparation method of a kind of phenolic resin modified polyacrylonitrile-based precursor according to claim 1, it is characterized in that: the spinning condition described in the step (2) is: pump is 1.1-1.4g/min for amount, the spray silk is the 30-60 hole.
4. the preparation method of a kind of phenolic resin modified polyacrylonitrile-based precursor according to claim 1, it is characterized in that: the coagulating bath described in the step (2) is that volume ratio is the pure water of 50:50 and the mixed solution of organic solvent, and temperature is 25 ℃.
5. the preparation method of a kind of phenolic resin modified polyacrylonitrile-based precursor according to claim 4, it is characterized in that: described organic solvent is methyl-sulfoxide.
6. the preparation method of a kind of phenolic resin modified polyacrylonitrile-based precursor according to claim 1 is characterized in that: the draw ratio of the stretching described in the step (2) be 5.0-6.2 doubly.
7. the preparation method of a kind of phenolic resin modified polyacrylonitrile-based precursor according to claim 1, it is characterized in that: the first water washing bath is the deionized water of temperature 70 C in the water-bath described in the step (2), and the second water washing bath is that temperature is 90 ℃ deionized water.
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| CN103710792A (en) * | 2012-10-08 | 2014-04-09 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile-based carbon fiber |
| CN105603543B (en) * | 2014-11-20 | 2018-06-08 | 中国石油化工股份有限公司 | The silk spraying method of polyacrylonitrile solution |
| CN104726954B (en) * | 2015-03-07 | 2017-04-19 | 盐城工业职业技术学院 | Alizarin red pH response color-changing fibers and preparation method thereof |
| CN104878616A (en) * | 2015-06-08 | 2015-09-02 | 江苏同康特种活性炭纤维面料有限公司 | Long-service-life high-strength viscose-based active carbon fiber fabric |
| CN107815742B (en) * | 2017-11-10 | 2020-05-01 | 中国科学院山西煤炭化学研究所 | Solidification method of thermosetting phenolic resin protofilament |
| CN109082731B (en) * | 2018-08-20 | 2020-01-10 | 天津工业大学 | Crosslinked porous carbon nanofiber and preparation method thereof |
| CN109322010A (en) * | 2018-10-17 | 2019-02-12 | 北京化工大学 | Utilize the polyacrylonitrile carbon fiber and preparation method thereof of waste polypropylene nitrile fiber preparation |
| CN113046864A (en) * | 2021-03-18 | 2021-06-29 | 湖南蓝凯新材料科技有限公司 | Phenolic resin improved lignin carbon fiber and preparation method thereof |
| CN114687011A (en) * | 2022-05-06 | 2022-07-01 | 广州碳加科技有限公司 | Preparation method of low-cost carbon fiber precursor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002069758A (en) * | 2000-08-25 | 2002-03-08 | Toray Ind Inc | Method for manufacturing graphite fiber |
| CN101250770A (en) * | 2008-03-11 | 2008-08-27 | 东华大学 | Method for manufacturing polyacrylonitrile-based carbon fiber with enganced carbon nano-tube |
| TW200846514A (en) * | 2007-05-16 | 2008-12-01 | Ind Tech Res Inst | Activated carbon fibers and precursor material thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0735614B2 (en) * | 1988-10-03 | 1995-04-19 | 新王子製紙株式会社 | Method for producing highly graphitized carbon fiber |
| JPH05195324A (en) * | 1992-01-21 | 1993-08-03 | Toray Ind Inc | Precursor for carbon fiber production and method for producing the precursor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002069758A (en) * | 2000-08-25 | 2002-03-08 | Toray Ind Inc | Method for manufacturing graphite fiber |
| TW200846514A (en) * | 2007-05-16 | 2008-12-01 | Ind Tech Res Inst | Activated carbon fibers and precursor material thereof |
| CN101250770A (en) * | 2008-03-11 | 2008-08-27 | 东华大学 | Method for manufacturing polyacrylonitrile-based carbon fiber with enganced carbon nano-tube |
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