CN100564413C - The preparation method of polymer for polyacrylonitrile base carbon fiber precursors - Google Patents
The preparation method of polymer for polyacrylonitrile base carbon fiber precursors Download PDFInfo
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- CN100564413C CN100564413C CNB2007100563459A CN200710056345A CN100564413C CN 100564413 C CN100564413 C CN 100564413C CN B2007100563459 A CNB2007100563459 A CN B2007100563459A CN 200710056345 A CN200710056345 A CN 200710056345A CN 100564413 C CN100564413 C CN 100564413C
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 58
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 38
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002243 precursor Substances 0.000 title claims abstract description 30
- 229920000642 polymer Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title description 6
- 239000000178 monomer Substances 0.000 claims abstract description 45
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 34
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000009987 spinning Methods 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 10
- 239000008346 aqueous phase Substances 0.000 claims abstract description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004160 Ammonium persulphate Substances 0.000 claims abstract description 7
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000019395 ammonium persulphate Nutrition 0.000 claims abstract description 7
- 230000000977 initiatory effect Effects 0.000 claims abstract description 6
- 238000012360 testing method Methods 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 5
- 238000005829 trimerization reaction Methods 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 11
- 238000003763 carbonization Methods 0.000 description 11
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 239000000835 fiber Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- -1 methylene-succinic acid acid amides Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- OQTRPSFMBXCQIY-UHFFFAOYSA-N azane;2-methylidenebutanedioic acid Chemical compound N.OC(=O)CC(=C)C(O)=O OQTRPSFMBXCQIY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000004223 radioprotective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Inorganic Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
A kind of is the method for the aqueous-phase suspending copolymerization polymer for polyacrylonitrile base carbon fiber precursors of initiator system with ammonium persulphate-ammonium sulphite or ammonium bisulfite, stir down the first monomer vinyl cyanide, the second monomer vinylformic acid, methyl acrylate or acrylamide, the 3rd methylene-succinic acid, or with the first monomer vinylformic acid, second monomer methyl acrylate or the methylene-succinic acid, and the inorganic oxide-reduction initiating system ammonium persulphate of no any metal ion, ammonium sulphite or ammonium bisulfite, the acidifying deionized water adds in the polymeric kettle in proportion, the control certain temperature, stir reaction certain hour down, discharging is through removing residual monomer, washing, oven dry makes the polyacrylonitrile powder, its weight-average molecular weight 17.5～26.1 ten thousand, molecular weight distributing index 2.70～2.91; Through its polyacrylonitrile fibril intensity of spinning sample testing is 4.58～6.61CN/dtex; Carbon fiber strength is 3.61～5.06Gpa.
Description
Technical field
The present invention relates to the preparation method of polyacrylonitrile-based precursor powder, relate in particular to a kind of preparation method of polymer for polyacrylonitrile base carbon fiber precursors.
Technical background
Carbon fiber is the enhancement type and the functional type filamentary material of a kind of high strength ratio, high ratio modulus, is the high-tech product that develops rapidly in the sixties in 20th century.A series of over-all propertieies such as it has that density is low, heat-resisting, resistance to chemical attack, rub resistance, thermal shock resistance and conduction, heat conduction, radioprotective, good damping, damping, noise reduction, widespread use at present has been penetrated into a plurality of fields such as sports equipment, amusement and leisure, Tourist facilities, automobile component, train part, aircraft manufacturing, electric power, oil, chemical industry, navigation, biomedicine, building, strategic missile, bulletproof armour.
The main raw material of high-strength carbon fiber is polyacrylonitrile-radical (PAN) precursor, and the quality of polyacrylonitrile fibril is determining the quality of carbon fiber to a great extent.Acrylonitrile homopolymer is a high crystallinity polymer, and is poorly soluble, difficulty in spinning; During preoxidation, heat release is concentrated, and process is wayward, generally addresses this problem by adding second monomer or the 3rd monomer copolymerization.Usually the comonomer that adds has: vinylformic acid, methacrylic acid, methyl acrylate, acrylamide, methyl methacrylate, methylene-succinic acid, methylene-succinic acid ammonia, methylene-succinic acid acid amides etc.At present, the domestic production polyacrylonitrile fibril for carbon fiber mostly adopts single stage method, be about to vinyl cyanide and second, third copolymer and dimethyl formamide, dimethyl sulfoxide (DMSO), nitric acid or thiocyanic acid are received equal solvent and are joined in the reactor together and mix, under certain temperature and atmosphere, form the spinning solution of the polyacrylonitrile that contains certain molecular weight through the certain hour post polymerization, eyelet by spinning nozzle is directly injected to stoste and prepares polyacrylonitrile fibril in the coagulation bath then, and this method is the single stage method wet-spinning.Utilize this legal system to be equipped with polyacrylonitrile fibril and yield poorly, and polymerization process is restive, be prone to gel in the production process, and molecular weight distribution is wide, the molecular arrangement order is irregular, thereby causes the instability of precursor performance.
For the research of adopting two-step approach to prepare carbon fibre precursor, the China Patent No. ZL92113445.2 of Mitsubishi Li Yang Co., Ltd. has proposed a kind of purification process of polyacrylonitrile, its main purpose is to remove in the polyacrylonitrile of two-step approach inorganic oxide-reduction initiation aqueous suspension polymerization preparation the iron ion or the aluminum ion as impurity that may contain.Owing to increased whole processing step, this method can increase the production cost of carbon fiber greatly.
The China Patent No. ZL200610070589.8 of Shandong University has proposed the novel method that a kind of aqueous suspension polymerization is produced carbon fibre precursor, its polymerization technique has adopted single Ammonium Persulfate 98.5 as initiator, compare with oxidation-reduction trigger system, this initiator system efficient is lower.
Summary of the invention
The object of the present invention is to provide a kind of is the method for the aqueous-phase suspending copolymerization polymer for polyacrylonitrile base carbon fiber precursors of initiator system with ammonium persulphate-ammonium sulphite or ammonium bisulfite, when keeping higher efficiency of initiation, the purity of polymkeric substance is very high, need not remove impurity, reduce production costs greatly; The carbon fiber polyacrylonitrile fibril that makes has characteristics such as high strength, high elastic coefficient, high-compactness, high orientation intensity, the trickle value of monofilament are low.
A kind of is the method for the aqueous-phase suspending copolymerization polymer for polyacrylonitrile base carbon fiber precursors of initiator system with ammonium persulphate-ammonium sulphite or ammonium bisulfite, it is characterized in that: to react total material is that 100 weight parts are benchmark { i.e. (polymerization single polymerization monomer+ammonium persulphate+ammonium sulphite or ammonium bisulfite+acidifying deionized water)=100 weight parts }, stir down 10～50 parts of the first polymerization single polymerization monomer vinyl cyanide, the second polymerization single polymerization monomer vinylformic acid, methyl acrylate or acrylamide 1.0-7.0 part, trimerization monomer methylene-succinic acid 0.5-5.0 part, ammonium persulphate 0.1-1.0 part, ammonium sulphite or ammonium bisulfite 0.1-0.75 part, the acidifying deionized water adds in the polymeric kettle for 45～85 parts, intensification also remains on 60～65 ℃, stirring velocity is 100rpm, reacted 5～6 hours, discharging is through removing residual monomer, washing, oven dry makes the polyacrylonitrile powder, its weight-average molecular weight 17.5～21.8 ten thousand, molecular weight distributing index 2.70～2.91; Through its polyacrylonitrile fibril intensity of spinning sample testing is 6.01～6.61CN/dtex; Carbon fiber strength is 3.61～4.65Gpa.
A kind of is the method for the aqueous-phase suspending copolymerization polymer for polyacrylonitrile base carbon fiber precursors of initiator system with ammonium persulphate-ammonium sulphite or ammonium bisulfite, it is characterized in that: to react total material is that 100 weight parts are benchmark, stir down first polymerization single polymerization monomer vinyl cyanide 10-50 part, the second polymerization single polymerization monomer methyl acrylate or methylene-succinic acid 0.5-5 part, ammonium persulphate 0.1-1.0 part in inorganic oxide-reduction initiating system, ammonium sulphite 0.1-0.75 part, medium acidifying deionized water adds in the polymeric kettle for 58～68 parts, intensification also remains on 60～65 ℃, stirring velocity is 100rpm, reacted 5～6 hours, discharging is through removing residual monomer, washing, oven dry makes the polyacrylonitrile powder, its weight-average molecular weight 24.0～26.1 ten thousand, molecular weight distributing index 2.65～3.01; Through its polyacrylonitrile fibril intensity of spinning sample testing is 4.58～5.06CN/dtex; Carbon fiber strength is 4.85～5.06Gpa.
The present invention is a kind of to be the method for the aqueous-phase suspending copolymerization polymer for polyacrylonitrile base carbon fiber precursors of initiator system with ammonium persulphate-ammonium sulphite or ammonium bisulfite, has adopted a kind of not iron content ionic inorganic oxide-reduction initiating system.The available oxygenant has ammonium persulphate, Potassium Persulphate, Sodium Persulfate, and reductive agent has ammonium sulphite, ammonium bisulfite, S-WAT, sodium bisulfite, potassium sulfite, Potassium hydrogen sulfite, calcium sulfite Sulfothiorine, thiosulfuric acid amine, formaldehyde sodium sulfoxylate, L-xitix, glucose.Wherein, best initiator system can adopt Ammonium Persulfate 98.5-ammonium sulfite system.This initiator system biggest advantage is that polymkeric substance does not contain any metal ion, can be used to prepare high performance polyacrylonitrile fibril for carbon fiber.Whole polymerization system is by containing the first polymerization single polymerization monomer vinyl cyanide 10-50% (Wt%), second polymerization single polymerization monomer accounts for 1-7% (Wt%), second polymerization single polymerization monomer can be a kind of in vinylformic acid, methacrylic acid, methyl acrylate, acrylamide, the methyl methacrylate, and the trimerization monomer accounts for 0.5-5% (Wt%).The trimerization monomer can be a kind of in methylene-succinic acid, methylene-succinic acid ammonia, the methylene-succinic acid acid amides, also can select only to add a kind of in second polymerization single polymerization monomer, the trimerization monomer, and not add another monomer.Oxygenant 0.1-1.0% (Wt%), reductive agent 0.1-0.75% (Wt%), and the deionized water 45-85% (Wt%) of sulfuric acid acidation forms polymerization system.Feed polymeric kettle continuously and carry out polymerization, the polymeric kettle temperature is 30-80 ℃, polymerization time 60-600 minute, obtain polymer slurries, slurry makes this polymer powders of polyacrylonitrile powder and has the molecular weight characteristics viscosity between 0.250-0.254 after taking off list, washing, oven dry, narrow molecular weight distribution, the characteristics that the molecular arrangement order is neat.
The present invention compared with prior art has outstanding substantive distinguishing features, obvious improvement and positively effect:
(1) with ammonium persulphate-ammonium sulphite or ammonium bisulfite is the method for the aqueous-phase suspending copolymerization polymer for polyacrylonitrile base carbon fiber precursors of initiator system, do not contain any metal ion, adopt binary or termonomer, the polymer powders that makes has the molecular weight characteristics viscosity between 0.250-0.254, its weight-average molecular weight 17.6～26.1 ten thousand, molecular weight distributing index 2.65～3.04; Son amount narrowly distributing, the characteristics that the molecular arrangement order is neat.
(2) purity of polymkeric substance is very high, need not remove impurity, reduces production costs greatly, is used to prepare the polyacrylonitrile fibril of carbon fiber, has characteristics such as high strength, high elastic coefficient, high-compactness, high orientation intensity, the trickle value of monofilament are low.Through its polyacrylonitrile fibril intensity of spinning sample testing 4.58～6.61CN/dtex.Through its carbon fiber strength of carbonization is 3.61～5.06GPa.
Specific embodiments
Now the present invention is further described as follows by embodiment:
One, a kind of is the method for the aqueous-phase suspending copolymerization polymer for polyacrylonitrile base carbon fiber precursors of initiator system with ammonium persulphate-ammonium sulphite or ammonium bisulfite,
Embodiment 1
With acrylonitrile monemer solution by the ratio of volume pump according to 10% (Wt%), the second monomer acrylamide 3% (Wt%), the 3rd monomer methylene-succinic acid 1.5% (Wt%) adds polymeric kettle, ammonium persulfate and sulfurous acid ammonia are added in the polymeric kettle according to ratio and the acidifying deionized water 84.65% (Wt%) of 0.10% (Wt%) and 0.75% (Wt%) respectively, temperature keeps 6 ℃, 6 hours reaction times, stir speed (S.S.) 100rpm.The slurry that contains the polyacrylonitrile powder is discharged polymeric kettle continuously, makes the polyacrylonitrile powder after taking off list, washing, oven dry.Multipolymer to get weight-average molecular weight be 18.9 ten thousand, molecular weight distributing index is 2.86.Spinning under standard conditions gets precursor intensity 6.21g/d, carbonization under standard conditions, and carbon fiber strength is 3.82GPa.
Embodiment 2
With acrylonitrile monemer solution by the ratio of volume pump according to 50% (Wt%), the second monomer acrylamide 2% (Wt%), the 3rd monomer methylene-succinic acid 1.5% (Wt%) adds polymeric kettle, with ammonium persulfate and sulfurous acid ammonia respectively according to adding in the polymeric kettle in the ratio of 1.0% (Wt%) and 0.1% (Wt%) and acidifying deionized water 45.4% (Wt%) polymeric kettle, temperature keeps 6 ℃, 6 hours reaction times, stir speed (S.S.) 100rpm.The slurry that contains the polyacrylonitrile powder is discharged polymeric kettle continuously, makes the polyacrylonitrile powder after taking off list, washing, oven dry.Multipolymer to get weight-average molecular weight be 17.5 ten thousand, molecular weight distributing index is 2.70.Spinning under standard conditions, precursor intensity 6.01CN/dtex, carbonization under standard conditions, carbon fiber strength is 3.61GPa.
Embodiment 3
With acrylonitrile monemer solution by the ratio of volume pump according to 30% (Wt%), the second monomer vinylformic acid formicester 1% (Wt%), the 3rd monomer methylene-succinic acid 0.5% (Wt%) adds polymeric kettle, with ammonium persulfate and sulfurous acid ammonia respectively according to adding in the polymeric kettle in the ratio of 0.15% (Wt%) and 0.75% (Wt%) and acidifying deionized water 67.6% (Wt%) polymeric kettle, temperature keeps 60 ℃, 5 hours reaction times, stir speed (S.S.) 100rpm.The slurry that contains the polyacrylonitrile powder is discharged polymeric kettle continuously, makes the polyacrylonitrile powder after taking off list, washing, oven dry.Multipolymer to get weight-average molecular weight be 20.5 ten thousand, molecular weight distributing index is 2.85.Spinning under standard conditions gets precursor intensity 6.41CN/dtex, carbonization under standard conditions, and carbon fiber strength is 4.45GPa.
Embodiment 4
With acrylonitrile monemer solution by the ratio of volume pump according to 35% (Wt%), the second monomer vinylformic acid formicester 7% (Wt%), the 3rd monomer methylene-succinic acid 1% (Wt%) adds polymeric kettle, with ammonium persulfate and sulfurous acid ammonia respectively according to adding in the polymeric kettle in the ratio of 0.20% (Wt%) and 0.15% (Wt%) and acidifying deionized water 56.65% (Wt%) polymeric kettle, temperature keeps 60 ℃, 5 hours reaction times, stir speed (S.S.) 100rpm.The slurry that contains the polyacrylonitrile powder is discharged polymeric kettle continuously, makes the polyacrylonitrile powder after taking off list, washing, oven dry.Multipolymer to get weight-average molecular weight be 18.6 ten thousand, molecular weight distributing index is 2.91.Spinning under standard conditions gets precursor intensity 6.20CN/dtex, carbonization under standard conditions, and carbon fiber strength is 3.81GPa.
Embodiment 5
With acrylonitrile monemer solution by the ratio of volume pump according to 30% (Wt%), the second monomer vinylformic acid 1% (Wt%), the 3rd monomer methylene-succinic acid 5% (Wt%) adds polymeric kettle, with ammonium persulfate and bisulfite ammonia respectively according to adding in the polymeric kettle in the ratio of 0.30% (Wt%) and 0.35% (Wt%) and acidifying deionized water 63.35% (Wt%) polymeric kettle, temperature keeps 60 ℃, 5 hours reaction times, stir speed (S.S.) 100rpm.The slurry that contains the polyacrylonitrile powder is discharged polymeric kettle continuously, makes the polyacrylonitrile powder after taking off list, washing, oven dry.Multipolymer to get weight-average molecular weight be 21.8 ten thousand, molecular weight distributing index is 2.75.Spinning under standard conditions gets precursor intensity 6.61CN/dtex, carbonization under standard conditions, and carbon fiber strength is 4.65GPa.
Embodiment 6
With acrylonitrile monemer solution by the ratio of volume pump according to 30% (Wt%), the second monomer vinylformic acid formicester 2% (Wt%), the 3rd monomer methylene-succinic acid 1.5% (Wt%) adds polymeric kettle, with ammonium persulfate and bisulfite ammonia respectively according to adding in the polymeric kettle in the ratio of 0.45% (Wt%) and 0.30% (Wt%) and acidifying deionized water 65.75% (Wt%) polymeric kettle, temperature keeps 6 ℃, 6 hours reaction times, stir speed (S.S.) 100rpm.The slurry that contains the polyacrylonitrile powder is discharged polymeric kettle continuously, makes the polyacrylonitrile powder after taking off list, washing, oven dry.Multipolymer to get weight-average molecular weight be 20.5 ten thousand, molecular weight distributing index is 2.85.Spinning under standard conditions gets precursor intensity 6.41CN/dtex, carbonization under standard conditions, and carbon fiber strength is 4.45GPa.
Embodiment 7
With acrylonitrile monemer solution by the ratio of volume pump according to 30% (Wt%), the second monomer methylene-succinic acid 2% (Wt%) adds polymeric kettle, with ammonium persulfate and sulfurous acid ammonia respectively according to adding in the polymeric kettle in the ratio of 0.20% (Wt%) and 0.15% (Wt%) and acidifying deionized water 67.65% (Wt%) polymeric kettle, temperature keeps 60 ℃, 6 hours reaction times, stir speed (S.S.) 100rpm.The slurry that contains the polyacrylonitrile powder is discharged polymeric kettle continuously, makes the polyacrylonitrile powder after taking off list, washing, oven dry.Multipolymer to get weight-average molecular weight be 24.0 ten thousand, molecular weight distributing index is 2.65.Spinning under standard conditions gets precursor intensity 6.85CN/dtex, carbonization under standard conditions, and carbon fiber strength is 4.85GPa.
Embodiment 8
With acrylonitrile monemer solution by the ratio of volume pump according to 40% (Wt%), the second monomer vinylformic acid formicester 2% (Wt%) adds polymeric kettle, with ammonium persulfate and sulfurous acid ammonia respectively according to adding in the polymeric kettle in the ratio of 0.15% (Wt%) and 0.12% (Wt%) and acidifying deionized water 57.73% (Wt%) polymeric kettle, temperature keeps 6 ℃, 6 hours reaction times, stir speed (S.S.) 100rpm.The slurry that contains the polyacrylonitrile powder is discharged polymeric kettle continuously, makes the polyacrylonitrile powder after taking off list, washing, oven dry.Multipolymer to get weight-average molecular weight be 23.1 ten thousand, molecular weight distributing index is 3.01.Spinning under standard conditions gets precursor intensity 6.52CN/dtex, carbonization under standard conditions, and carbon fiber strength is 4.58GPa.
Embodiment 9
With acrylonitrile monemer solution by the ratio of volume pump according to 30% (Wt%), the second monomer methylene-succinic acid 2.0% (Wt%) adds polymeric kettle, with ammonium persulfate and bisulfite ammonia respectively according to adding in the polymeric kettle in the ratio of 0.15% (Wt%) and 0.20% (Wt%) and acidifying deionized water 67.65% (Wt%) polymeric kettle, temperature keeps 60 ℃, 6 hours reaction times, stir speed (S.S.) 100rpm.The slurry that contains the polyacrylonitrile powder is discharged polymeric kettle continuously, makes the polyacrylonitrile powder after taking off list, washing, oven dry.Multipolymer to get weight-average molecular weight be 26.1 ten thousand, molecular weight distributing index is 2.72.Spinning under standard conditions gets precursor intensity 7.24CN/dtex, carbonization under standard conditions, and carbon fiber strength is 5.06GPa.
Two, the preparation of carbon fiber PAN based precursor:
Embodiment 10
With a kind of be the aqueous-phase suspending copolymerization polymer for polyacrylonitrile base carbon fiber precursors of initiator system with ammonium persulphate-ammonium sulphite or ammonium bisulfite, at-18 ℃ of slurry that are hybridly prepared into the 16wt% solid content down with N,N-DIMETHYLACETAMIDE, and be evacuated to 40Kpa, when being heated to 45 ℃, after dissolving in 1 hour, obtain the spinning solution (this solution can be preserved 24 hours) of 16% solid content, spinning solution is heated to 70 ℃ then, be transported to spinning pump, entering its concentration through 3000 hole spinning nozzle extruding is 50wt%, temperature is in 50 ℃ of spin ducts in the precipitation bath, the wet-spinning moulding is carried out in negative drawing-off 0.2%.
Nascent fibre is through flushing in 80～100 ℃ of hot water and except that after desolvating, it is stretched simultaneously with 6.98 stretch ratio, with fiber impregnation in containing the body lotion of silicone oil, and on the hot-rolling of 150 ℃ of temperature, move 4～5 minutes, stretch simultaneously with 1.75 stretch ratio, carry out compacting by drying, and on wire drawing device the rolling fiber, obtain the PAN based precursor.Gained fiber sweat is not higher than 0.1%, and total stretch ratio is 12.2, in this spinning step, does not almost observe the fracture of monofilament and the generation of burr, and apparent have a good stability of spinning process, detects rerum natura technical indicators such as its tensile strength.After the precursor that obtains carries out carbonization, record parameters such as its carbon fiber strength.
Claims (2)
1, a kind of is the method for the aqueous-phase suspending copolymerization polymer for polyacrylonitrile base carbon fiber precursors of initiator system with ammonium persulphate-ammonium sulphite or ammonium bisulfite, it is characterized in that: to react total material is that 100 weight parts are benchmark, stir down 10～50 parts of the first polymerization single polymerization monomer vinyl cyanide, the second polymerization single polymerization monomer vinylformic acid, methyl acrylate or acrylamide 1.0-7.0 part, trimerization monomer methylene-succinic acid 0.5-5.0 part, ammonium persulphate 0.1-1.0 part, ammonium sulphite or ammonium bisulfite 0.1-0.75 part, the acidifying deionized water adds in the polymeric kettle for 45～85 parts, intensification also remains on 60～65 ℃, stirring velocity is 100rpm, reacted 5～6 hours, discharging is through removing residual monomer, washing, oven dry makes the polyacrylonitrile powder, its weight-average molecular weight 17.5～21.8 ten thousand, molecular weight distributing index 2.70～2.91; Through its polyacrylonitrile fibril intensity of spinning sample testing is 6.01～6.61CN/dtex; Carbon fiber strength is 3.61～4.65GPa.
2, a kind of is the method for the aqueous-phase suspending copolymerization polymer for polyacrylonitrile base carbon fiber precursors of initiator system with ammonium persulphate-ammonium sulphite or ammonium bisulfite, it is characterized in that: to react total material is that 100 weight parts are benchmark, stir down first polymerization single polymerization monomer vinyl cyanide 10-50 part, the second polymerization single polymerization monomer methyl acrylate or methylene-succinic acid 0.5-5 part, ammonium persulphate 0.1-1.0 part in inorganic oxide-reduction initiating system, ammonium sulphite or ammonium bisulfite 0.1-0.75 part, medium acidifying deionized water adds in the polymeric kettle for 58～68 parts, intensification also remains on 60～65 ℃, stirring velocity is 100rpm, reacted 5～6 hours, discharging is through removing residual monomer, washing, oven dry makes the polyacrylonitrile powder, its weight-average molecular weight 24.0～26.1 ten thousand, molecular weight distributing index 2.65～3.01; Through its polyacrylonitrile fibril intensity of spinning sample testing is 4.58～5.06CN/dtex; Carbon fiber strength is 4.85～5.06GPa.
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