CN102277644A - 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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- CN102277644A CN102277644A CN 201110182690 CN201110182690A CN102277644A CN 102277644 A CN102277644 A CN 102277644A CN 201110182690 CN201110182690 CN 201110182690 CN 201110182690 A CN201110182690 A CN 201110182690A CN 102277644 A CN102277644 A CN 102277644A
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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, and its tensile strength is bigger 68 times than steel, and the modular ratio steel are big 1.8～2.6 times.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 promptly 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 generation corrosivity.
At present, carbon fiber and composite thereof mainly have a wide range of applications and market in each big fields such as Aero-Space, sports, civil construction, automobile even health cares, 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 big material systems of viscose glue base, alkyd resin based fiber, the basic fiber of polyacrylonitrile (PAN) and asphalt base carbon fiber, and wherein especially with PAN base carbon fibre output maximum, most widely used, be the main flow in carbon fiber market.
Polyacrylonitrile fiber is the presoma of carbon fiber, properties of carbon quality key 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 influences the quality of carbon fiber, and influence its output and production cost.Former yarn quality has become one big " 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 technology 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 the aqueous-phase suspending copolymerization polyacrylonitrile base carbon fiber precursors of initiator system 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.U.S. Pat 6054214 reported when acrylonitrile be 95%～98% with mass percent, 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, present domestic still do not have document or patent report.
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 more significantly 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, add dry phenolic resins then, 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, coagulating bath stretching, water-bath and the process that oils are passed through in moulding in coagulating bath then, promptly get to contain the precursor that percentage by weight is a 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 the 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 deionized water for 70 ℃ of temperature is bathed in first washing in the water-bath described in the step (2), and the second washing bath is 90 ℃ deionized water for temperature.
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 a dimethyl siloxane.
The present invention is matrix with the polyacrylonitrile, 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 at pre-oxidation temperature section (200-300 ℃) has more significantly 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 take place 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, thereby has effectively improved the mechanical property of fiber under the pre-oxidation temperature.
Beneficial effect
(1) the prepared polyacrylonitrile-based precursor of the present invention, the fibrous mechanical property after pre-oxidation treatment have more significantly 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 to the present invention is described and are not used in to 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 the application's appended claims equally and say restricted portion.
Embodiment 1
(1) polyacrylonitrile that drying is 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 powerful the stirring 2 hours after 3 hours thorough swellings; The dry phenolic resins powder of crossing of 3.2g is joined in the there-necked flask, continue powerful stir 1 hour even up to blend.
(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 powerful the stirring 1.5 hours after 2 hours the thorough swelling; The dry phenolic resins powder of crossing of 6.0g is joined in the there-necked flask, continue powerful stir 0.5 hour even up to blend.
(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 powerful the stirring 2.5 hours after 4 hours thorough swellings; The dry phenolic resins powder of crossing of 9.6g is joined in the there-necked flask, continue powerful stir 12 hours even up to blend.
(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 powerful the stirring 2 hours after 3 hours thorough swellings; The dry phenolic resins powder of crossing of 0.50g is joined in the there-necked flask, continue powerful stir 2 hours even up to blend.
(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, the powerful 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 handled 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 (10)
1. phenolic resin modified polyacrylonitrile-based precursor, the composition of this precursor is polyacrylonitrile and phenolic resins, wherein the percentage by weight of phenolic resins is 0.1-15%.
2. a kind of phenolic resin modified polyacrylonitrile-based precursor according to claim 1 is characterized in that: described polyacrylonitrile is that molecular weight is the polyacrylonitrile of 6-10 ten thousand; Phenolic resins is epoxide modified novolac resin.
3. a kind of phenolic resin modified polyacrylonitrile-based precursor according to claim 1 is characterized in that: 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.
4. 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, add dry phenolic resins then, 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, moulding in coagulating bath is then through coagulating bath stretching, water-bath and the process that oils, promptly.
5. the preparation method of a kind of phenolic resin modified polyacrylonitrile-based precursor according to claim 4, it is characterized in that: the phenolic resins described in the step (1) is epoxide modified novolac resin, and described organic solvent is a methyl-sulfoxide.
6. the preparation method of a kind of phenolic resin modified polyacrylonitrile-based precursor according to claim 4, 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.
7. the preparation method of a kind of phenolic resin modified polyacrylonitrile-based precursor according to claim 4, it is characterized in that: the coagulating bath described in the step (2) is that volume ratio is 50: 50 the pure water and the mixed solution of organic solvent, and temperature is 25 ℃.
8. the preparation method of a kind of phenolic resin modified polyacrylonitrile-based precursor according to claim 7, it is characterized in that: described organic solvent is a methyl-sulfoxide.
9. the preparation method of a kind of phenolic resin modified polyacrylonitrile-based precursor according to claim 4 is characterized in that: the draw ratio of the stretching described in the step (2) be 5.0-6.2 doubly.
10. the preparation method of a kind of phenolic resin modified polyacrylonitrile-based precursor according to claim 4, it is characterized in that: the deionized water for 70 ℃ of temperature is bathed in first washing in the water-bath described in the step (2), and the second washing bath is 90 ℃ deionized water for temperature.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN104726954A (en) * | 2015-03-07 | 2015-06-24 | 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 |
| CN105603543A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Fibre spinning method for polyacrylonitrile solution |
| CN107815742A (en) * | 2017-11-10 | 2018-03-20 | 中国科学院山西煤炭化学研究所 | A kind of clotting method of thermosetting phenolic resin precursor |
| CN109082731A (en) * | 2018-08-20 | 2018-12-25 | 天津工业大学 | A kind of cross-linked porous carbon nano-fiber 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 |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN105603543A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Fibre spinning method for polyacrylonitrile solution |
| 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 |
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| CN109082731A (en) * | 2018-08-20 | 2018-12-25 | 天津工业大学 | A kind of cross-linked porous carbon nano-fiber and preparation method thereof |
| 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 |
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