CN108221075A - A kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance - Google Patents
A kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance Download PDFInfo
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- 238000009987 spinning Methods 0.000 title claims abstract description 35
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 34
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 26
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000007788 liquid Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 62
- 239000012530 fluid Substances 0.000 claims abstract description 53
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 18
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 17
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 17
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 vinyl compound Chemical class 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000005580 one pot reaction Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 238000005422 blasting Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000003999 initiator Substances 0.000 claims abstract 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 10
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 10
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 10
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Chemical group 0.000 claims description 2
- 229910052739 hydrogen Chemical group 0.000 claims description 2
- MZNSQRLUUXWLSB-UHFFFAOYSA-N 2-ethenyl-1h-pyrrole Chemical compound C=CC1=CC=CN1 MZNSQRLUUXWLSB-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 15
- 239000000835 fiber Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- LYIPVSJHMKXWFN-UHFFFAOYSA-N 2-ethenylpyridine pyrrolidin-2-one Chemical compound C(=C)C1=NC=CC=C1.N1C(CCC1)=O LYIPVSJHMKXWFN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- 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
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
-
- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to polymeric material field, specifically a kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance.Using dimethyl sulfoxide (DMSO) as solvent, azodiisobutyronitrile is initiator, using acrylonitrile, itaconic acid, bulky side chain vinyl compound as polymer monomer, acrylonitrile：Itaconic acid：The weight percent of bulky side chain vinyl compound is 98~99:0.5~1:0.5~1, a concentration of the 18%~22% of the polymer monomer, the dosage of azodiisobutyronitrile is the 0.3%~0.75% of polymer monomer weight；Each material is weighed, and in the reactor that material stirring is uniform by proportioning；By uniformly mixed material, polymerisation is carried out at 60~80 DEG C, the pH for blasting ammonia to polymer fluid in the backward reactor of 12~18h is 8.5, terminates polymerisation, finally obtains polymer fluid；De- single, deaeration carries out the polymer fluid after filtering by de- one-pot, deaeration kettle, to deviate from remaining monomer and bubble in polymer fluid, then polymer fluid is filtered, filters out the impurity more than 0.5 micron in polymer fluid, finally obtains spinning solution.
Description
Technical field
The present invention relates to polymeric material fields, and specifically one kind two is a kind of improves polyacrylonitrile carbon fiber drawdown
The spinning liquid and preparation method thereof of energy.
Background technology
It is well known that since carbon fiber has the excellent properties such as high intensity, low-density, high temperature resistant, corrosion-resistant, extensively
Applied to numerous areas such as aerospace, national defense and military and building automobiles.Wherein, most widely used carbon fiber is polyacrylonitrile
（PAN）Base carbon fibre.PAN precursor is the raw material for manufacturing carbon fiber.The performance of precursor can be largely fixed carbon fiber
Performance, to obtain function admirable carbon fiber, it is necessary to have the flawless PAN precursor of function admirable first.
The performance of PAN precursor, inherently considers, depends primarily on the structure of PAN molecules therein.Due to homopolymerization PAN
Macromolecular chain structure it is more regular, crystallinity is high, molecule inner injection can be big, cause fiber softening poor, be not suitable for being processed into carbon fibre
Dimension.Therefore it needs to introduce second comonomer, Third monomer and be copolymerized, regulate and control the regularity of macromolecular chain, reduce between macromolecular chain
Cohesive energy and suitably reduce crystallinity, assign its flexibility and machinability.But as comonomer dosage increases, fiber
Hot property decline, so its dosage should be controlled strictly.
The common comonomer of carbon fiber industry has unsaturated carboxylic acid and beta-unsaturated esters, and carboxylic acid can promote ring at high temperature
Change the progress of reaction, reduce the activation energy of cyclization and controlled cyclization；Beta-unsaturated esters be then using ester group or
The bulk effect of the larger side group of volume reduces the cohesive energy of polyacrylonitrile, improves the permeability of oxygen, so as to improve polymer can
The property spun.
Studies have reported that claiming, use（Methyl）Methyl acrylate,（Methyl）The vinyl compounds such as butyl acrylate are as altogether
Polycondensation monomer improves the drawdown of polyacrylonitrile, is more easy to be drafted in drafting process, can provide the precursor of high quality.But
Above two monomer and acrylonitrile polymerization, if addition is excessive, copolymer glass transition temperature is too low, to polyacrylonitrile fibre
Effect of Thermal Performance is very big, if addition is very few, effect unobvious, it is difficult to suitable addition be controlled to obtain high-performance fiber.
Invention content
The purpose of the present invention is exactly to overcome the deficiencies of the prior art and provide a kind of improvement polyacrylonitrile carbon fiber drawing-off
The spinning liquid and preparation method thereof of performance, solve existing polyacryl-nitrile spinning fluid intolerant to drawing-off, flexibility is poor, hot property reduces
The problems such as amplitude is big.
The present invention solve above-mentioned technical problem the technical solution adopted is that：A kind of improvement polyacrylonitrile carbon fiber drawing-off performance
Spinning liquid and preparation method thereof, it is characterised in that：Its step are as follows, and using dimethyl sulfoxide (DMSO) as solvent, azodiisobutyronitrile is causes
Agent, using acrylonitrile, itaconic acid, bulky side chain vinyl compound as polymer monomer, acrylonitrile：Itaconic acid：Bulky side chain alkenes chemical combination
The weight percent of object is 98~99:0.5~1:0.5~1, a concentration of the 18%~22% of the polymer monomer, azo two is different
The dosage of butyronitrile is the 0.3%~0.75% of polymer monomer weight；Each material is weighed, and in the reactor stir material by proportioning
It mixes uniformly；By uniformly mixed material, polymerisation is carried out at 60~80 DEG C, ammonia is blasted in the backward reactor of 12~18h
The pH of gas to polymer fluid is 8.5, terminates polymerisation, finally obtains polymer fluid；After taking off one-pot, deaeration kettle to filtering
Polymer fluid carries out de- single, deaeration, to deviate from remaining monomer and bubble in polymer fluid, then polymer fluid is filtered, filters out poly-
The impurity more than 0.5 micron in liquid is closed, finally obtains spinning solution.
The bulky side chain vinyl compound is contains isobornyl acrylate, isobornyl methacrylate, vinyl
Pyrrolidones one or more therein.
The isobornyl methacrylate or isobornyl acrylate have following shown structural formula：
R is methyl or hydrogen in formula.
The vinyl pyrrolidone has following shown structural formula：
The invention has the advantages that additive amount is small, reaction speed is fast, utilizes（Methyl）Isobornyl acrylate, vinylpyridine
Pyrrolidone has the bulk effect of larger side group, can reduce the cohesive energy of PAN, improves the permeability of oxygen, and it is molten to improve polymer
Liquid spinnability improves the resistance to drawdown of precursor.And（Methyl）Isobornyl acrylate, the side chain of vinyl pyrrolidone are hard,
Glass transition temperature is reduced little, the hot property of polyacrylonitrile fibre will not be destroyed, therefore can obtain that lousiness is few, compact structure
The high high-performance carbon fibre of change degree.
Specific embodiment
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1, a kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance, its step are as follows：
Acrylonitrile, itaconic acid, isobornyl acrylate, dimethyl sulfoxide (DMSO), azodiisobutyronitrile are mixed, ratio is propylene
Nitrile：Itaconic acid：The weight ratio of isobornyl acrylate is 99:0.5:0.5, a concentration of the 20% of polymerized monomer, azodiisobutyronitrile
Dosage be the 0.6% of monomer weight, weigh each material, and in the reactor that material stirring is uniform by proportioning.It will be uniformly mixed
Material, polymerisation is carried out at 70 DEG C, ammonia is blasted in the backward reactor of 13h to the pH of polymer fluid as 8.5, is terminated poly-
Reaction is closed, finally obtains polymer fluid.De- single, deaeration carries out the polymer fluid after filtering by de- one-pot, deaeration kettle, with abjection
Remaining monomer and bubble in polymer fluid, then polymer fluid is filtered, the impurity more than 0.5 micron in polymer fluid is filtered out, most
Spinning solution is obtained eventually.
Embodiment 2, a kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance, its step are as follows：
Acrylonitrile, itaconic acid, isobornyl methacrylate, dimethyl sulfoxide (DMSO), azodiisobutyronitrile are mixed, ratio is
Acrylonitrile：Itaconic acid：The weight ratio of isobornyl methacrylate is 99:0.5:0.5, a concentration of the 20% of polymerized monomer, azo
The dosage of bis-isobutyronitrile is the 0.6% of monomer weight, and each material is weighed, and in the reactor that material stirring is uniform by proportioning.It will
Uniformly mixed material, carries out polymerisation at 70 DEG C, and the pH for blasting ammonia to polymer fluid in the backward reactor of 14h is
8.5, polymerisation is terminated, finally obtains polymer fluid.By de- one-pot, deaeration kettle the polymer fluid after filtering is carried out it is de- it is single,
Deaeration to deviate from remaining monomer and bubble in polymer fluid, then polymer fluid is filtered, filters out micro- more than 0.5 in polymer fluid
The impurity of rice, finally obtains spinning solution.
Embodiment 3, a kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance, its step are as follows：
Acrylonitrile, itaconic acid, isobornyl methacrylate, dimethyl sulfoxide (DMSO), azodiisobutyronitrile are mixed, ratio is
Acrylonitrile：Itaconic acid：The weight ratio of vinyl pyrrolidone is 99:0.5:0.5, a concentration of the 20% of polymerized monomer, azo two is different
The dosage of butyronitrile is the 0.6% of monomer weight, and each material is weighed, and in the reactor that material stirring is uniform by proportioning.It will mixing
Uniform material carries out polymerisation at 70 DEG C, and the pH for blasting ammonia to polymer fluid in the backward reactor of 12h is 8.5, eventually
Only polymerisation finally obtains polymer fluid.De- single, deaeration carries out the polymer fluid after filtering by de- one-pot, deaeration kettle, with
Deviate from remaining monomer and bubble in polymer fluid, then polymer fluid is filtered, filter out miscellaneous more than 0.5 micron in polymer fluid
Matter finally obtains spinning solution.
Embodiment 4, a kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance, its step are as follows：
Acrylonitrile, itaconic acid, isobornyl acrylate, dimethyl sulfoxide (DMSO), azodiisobutyronitrile are mixed, ratio is propylene
Nitrile：Itaconic acid：The weight ratio of isobornyl acrylate is 98:1:1, a concentration of the 20% of polymerized monomer, the use of azodiisobutyronitrile
0.6% for monomer weight is measured, each material is weighed, and in the reactor that material stirring is uniform by proportioning.By uniformly mixed object
Material, carries out polymerisation at 70 DEG C, and the pH for blasting ammonia to polymer fluid in the backward reactor of 14h is 8.5, and it is anti-to terminate polymerization
Should, finally obtain polymer fluid.De- single, deaeration carries out the polymer fluid after filtering by de- one-pot, deaeration kettle, to deviate from polymerization
Remaining monomer and bubble in liquid, then polymer fluid is filtered, the impurity more than 0.5 micron in polymer fluid is filtered out, it is final to obtain
To spinning solution.
Embodiment 5, a kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance, its step are as follows：
Acrylonitrile, itaconic acid, isobornyl methacrylate, dimethyl sulfoxide (DMSO), azodiisobutyronitrile are mixed, ratio is
Acrylonitrile：Itaconic acid：The weight ratio of isobornyl methacrylate is 98:1:1, a concentration of the 20% of polymerized monomer, azo two is different
The dosage of butyronitrile is the 0.6% of monomer weight, and each material is weighed, and in the reactor that material stirring is uniform by proportioning.It will mixing
Uniform material carries out polymerisation at 70 DEG C, and the pH for blasting ammonia to polymer fluid in the backward reactor of 15h is 8.5, eventually
Only polymerisation finally obtains polymer fluid.De- single, deaeration carries out the polymer fluid after filtering by de- one-pot, deaeration kettle, with
Deviate from remaining monomer and bubble in polymer fluid, then polymer fluid is filtered, filter out miscellaneous more than 0.5 micron in polymer fluid
Matter finally obtains spinning solution.
Embodiment 6, a kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance, its step are as follows：
Acrylonitrile, itaconic acid, isobornyl methacrylate, dimethyl sulfoxide (DMSO), azodiisobutyronitrile are mixed, ratio is
Acrylonitrile：Itaconic acid：The weight ratio of vinyl pyrrolidone is 98:1:1, a concentration of the 20% of polymerized monomer, azodiisobutyronitrile
Dosage be the 0.6% of monomer weight, weigh each material, and in the reactor that material stirring is uniform by proportioning.It will be uniformly mixed
Material, polymerisation is carried out at 70 DEG C, ammonia is blasted in the backward reactor of 13h to the pH of polymer fluid as 8.5, is terminated poly-
Reaction is closed, finally obtains polymer fluid.De- single, deaeration carries out the polymer fluid after filtering by de- one-pot, deaeration kettle, with abjection
Remaining monomer and bubble in polymer fluid, then polymer fluid is filtered, the impurity more than 0.5 micron in polymer fluid is filtered out, most
Spinning solution is obtained eventually.
Spinning solution by same process through wet spinning, solidification forming, coagulating bath drawing-off, washing, water-bath drawing-off, oil,
Compacting by drying receives silk, and polyacrylonitrile fibril is made.
Lousiness value test method：100m polyacrylonitrile fibril beams are taken, the hair of polyacrylonitrile fibril is measured with filoplume tester
Plumage number.
Table 1 is the obtained spinning solution for improving polyacrylonitrile carbon fiber drawdown of Examples 1 to 6 and comparative run common poly- third
The detection data of alkene nitrile carbon fiber spinning solution
By improving the spinning solution of polyacrylonitrile carbon fiber drawdown and comparative run plain polypropylene nitrile obtained by Examples 1 to 6
The detection data of fibrous carbon spinning solution carries out comparison as can be seen that the obtained spinning solution for improving polyacrylonitrile carbon fiber drawdown
For viscosity for 32 Pas or so, modest viscosity is conducive to spinning, and conversion ratio is 98% or so, and residual monomer is few, lousiness number for 15/
100m or so less than the lousiness number of comparative run, due to the resistance to drawing-off of fiber that spinning solution of the present invention makes, is not easy in spinning process
Fracture, so greatly reducing the lousiness number of fiber.
Claims (4)
1. a kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance, it is characterised in that：Its step are as follows,
Using dimethyl sulfoxide (DMSO) as solvent, azodiisobutyronitrile is initiator, is poly- using acrylonitrile, itaconic acid, bulky side chain vinyl compound
Monomer adduct, acrylonitrile：Itaconic acid：The weight percent of bulky side chain vinyl compound is 98~99:0.5~1:0.5~1, institute
A concentration of the 18%~22% of polymer monomer is stated, the dosage of azodiisobutyronitrile is the 0.3%~0.75% of polymer monomer weight；
Each material is weighed, and in the reactor that material stirring is uniform by proportioning；By uniformly mixed material, carried out at 60~80 DEG C
Polymerisation, the pH for blasting ammonia to polymer fluid in the backward reactor of 12~18h are 8.5, terminate polymerisation, finally obtain
Polymer fluid；De- single, deaeration carries out the polymer fluid after filtering by de- one-pot, deaeration kettle, it is remaining in polymer fluid to deviate from
Monomer and bubble, then polymer fluid is filtered, the impurity more than 0.5 micron in polymer fluid is filtered out, finally obtains spinning solution.
2. a kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance according to claim 1, feature
It is containing isobornyl acrylate, isobornyl methacrylate, vinyl pyrrole to be the bulky side chain vinyl compound
Alkanone one or more therein.
3. a kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance according to claim 2, feature
It is that the isobornyl methacrylate or isobornyl acrylate have following shown structural formula：
R is methyl or hydrogen in formula.
4. a kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance according to claim 2, feature
It is that the vinyl pyrrolidone has following shown structural formula
。
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| CN201810115809.7A CN108221075A (en) | 2018-02-06 | 2018-02-06 | A kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance |
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| CN201810115809.7A Pending CN108221075A (en) | 2018-02-06 | 2018-02-06 | A kind of spinning liquid and preparation method thereof for improving polyacrylonitrile carbon fiber drawing-off performance |
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Cited By (2)
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| CN109321994A (en) * | 2018-09-30 | 2019-02-12 | 中国科学院山西煤炭化学研究所 | A kind of polyacrylonitrile-based carbon fiber dry and wet spinning dope and preparation method thereof |
| CN112030256A (en) * | 2020-09-07 | 2020-12-04 | 吉祥三宝高科纺织有限公司 | Preparation method of carbon nano tube reinforced polyacrylonitrile composite material |
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| CN104651979A (en) * | 2015-03-17 | 2015-05-27 | 威海拓展纤维有限公司 | Preparation method of high-strength medium-model carbon fiber |
| CN105037619A (en) * | 2015-08-12 | 2015-11-11 | 广州金发碳纤维新材料发展有限公司 | Demonomerisation method of polyacrylonitrile spinning solution |
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| CN1401835A (en) * | 2002-08-13 | 2003-03-12 | 中国科学院山西煤炭化学研究所 | Method for preparing carbon fiber spinning solution |
| CN101148489A (en) * | 2007-09-18 | 2008-03-26 | 中国科学院长春应用化学研究所 | Highly hydrophilic spinning solution and preparation method of high-performance polyacrylonitrile-based carbon fiber |
| CN104651979A (en) * | 2015-03-17 | 2015-05-27 | 威海拓展纤维有限公司 | Preparation method of high-strength medium-model carbon fiber |
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| CN109321994B (en) * | 2018-09-30 | 2021-03-19 | 中国科学院山西煤炭化学研究所 | A kind of polyacrylonitrile-based carbon fiber dry and wet spinning dope and preparation method thereof |
| CN112030256A (en) * | 2020-09-07 | 2020-12-04 | 吉祥三宝高科纺织有限公司 | Preparation method of carbon nano tube reinforced polyacrylonitrile composite material |
| CN112030256B (en) * | 2020-09-07 | 2022-06-17 | 吉祥三宝高科纺织有限公司 | A kind of preparation method of carbon nanotube reinforced polyacrylonitrile composite material |
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Application publication date: 20180629 |