CN1247838C - Preparation method of polyacrylonitrile carbon raw yarn - Google Patents
Preparation method of polyacrylonitrile carbon raw yarn Download PDFInfo
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- CN1247838C CN1247838C CN 03109141 CN03109141A CN1247838C CN 1247838 C CN1247838 C CN 1247838C CN 03109141 CN03109141 CN 03109141 CN 03109141 A CN03109141 A CN 03109141A CN 1247838 C CN1247838 C CN 1247838C
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- polyacrylonitrile
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Abstract
The present invention relates to a method for preparing a polyacrylonitrile carbon precursor. The method comprises the steps: acrylonitrile, small quantity of methyl acrylate and itaconic acid are dissolved in a 49 to 54% sodium thiocyanate solution for homogeneous polymerization; a formed polymer is reserved in the sodium thiocyanate solution to form a homogeneous phase high-molecular solution, namely a spinning solution; the spinning solution is spun after multi-stage precision filtering, defoaming and temperature regulating, and the spinning operation is carried out via a combined spinneret; the spinning solution flows into a long slot for solidification and formation via impregnating bath; the polyacrylonitrile carbon precursor with excellent property is prepared via washing, two-stage water bath drafting, oil adding and hot roller drying. The method has the advantages of short production process and simple technology; because the present invention uses the technology of preceding washing and back drafting to produce the precursor with uniform breaking elongation by regulating the drafting times and drafting bath length, and the non-uniform rate of the breaking elongation of the precursor is controlled within 10%. The polyacrylonitrile carbon precursor is the raw material for manufacturing a polyacrylonitrile-based preoxidizing fibre with excellent fire-retardant property, and a polyacrylonitrile-based carbon fibre with high strength and high modulus.
Description
Technical field
The present invention relates to a kind of preparation method of polyacrylonitrile carbon precursor, particularly is the preparation method of the polyacrylonitrile carbon precursor of solvent with the sodium sulfocyanate.
Background technology
Polyacrylonitrile carbon precursor is the raw material of preparation polyacrylonitrile-based carbon fibre.Polyacrylonitrile carbon precursor is after pre-oxygen, carbonization, and the polyacrylonitrile-based carbon fibre that makes has multifrequency natures such as high strength, high-modulus, is one of current the most valued high performance material.As everyone knows, what former sodium sulfocyanate legal system was equipped with the employing of carbon precursor is the process route of first drawing-off, after washing, its production process is as follows: the stoste thread is an as-spun fibre through coagulation forming, as-spun fibre is behind preliminary draft, again through 5～8 times water-bath drawing-off or steam drafting, wash then, oil, dry and promptly get polyacrylonitrile carbon precursor.No matter be water-bath drawing-off or steam drafting, the extension at break irregularity of the carbon precursor that makes is higher, generally greater than 10%.
Summary of the invention
The object of the present invention is to provide a kind of method that is different from original sodium sulfocyanate one-step method system polyacrylonitrile carbon precursor, emphasis solves the higher problem of carbon precursor extension at break irregularity that makes.
For achieving the above object, the technical scheme taked of the present invention is: polyacrylonitrile carbon precursor of the present invention is the copolymer of acrylonitrile, methyl acrylate, itaconic acid.Preferred carbon precursor contains acrylonitrile 90～94%, methyl acrylate 5～8%, itaconicacid 1～2%, in 49～54% sodium thiocyanate solution, aggregate into stoste, stoste sprays through composite spinning head, moulding in coagulating bath, again through washing, two sections water-bath drawing-offs oil, and oven dry promptly gets polyacrylonitrile carbon precursor.
1. stoste preparation: reactant is a monomer with 90～94% acrylonitrile, 5～8% methyl acrylates and 1～2% itaconic acid, the employing azodiisobutyronitrile is an initator, and thiourea dioxide is a light-colored agent, and isopropyl alcohol is made molecular weight regulator, with 49～54% sodium thiocyanate solutions is solvent, enters polymeric kettle.Under 60～80 ℃ temperature, reacted 2～4 hours, and, unreacted monomer in the polymer is deviate from reuse, and condensate was stayed in the sodium thiocyanate solution, becomes homogeneous phase Polymer Solution---spinning solution by taking off Dan Ta continuously.
2. spin preceding preparation: for removing impurity, the bubble in the polymerization stoste, will filter stoste before the spinning, deaeration, temperature adjustment etc. spin preceding preparation.Polymerization stoste is at first after flame filter press filters, enter vacuum again and be deaeration in the deaeration tower of 0.075～0.085Mpa, through stoste thermosistor temperature adjustment to 25～35 ℃, filter and the measuring pump metering then, enter spinneret assembly spray thread by large and small filter.
3. spinning and post processing: the spinneret assembly that spinning adopts specialized designs to make, the stoste thread of ejection is 6-15 ℃ in temperature, density is 1.050-1.090g/cm
3Sodium thiocyanate solution in coagulation forming be as-spun fibre, be 25-55 ℃, density 1.040-1.10g/cm in temperature again
3Preliminary draft bathe in 1-2 preliminary draft doubly in addition, turn to then in the desalted water that enters 50-70 ℃ of elongated slot adverse current and wash, adopt five roller drawing machines subsequently, finish drafting process through the drawing-off of major and minor twice boiling water, wherein dominant draft is 4～8 times, 1～2 times of secondary drawing-off, 90～100 ℃ of bath temperatures, 6～9 meters of length overalls are bathed in drawing-off.Oil with oil solution dedicated subsequently, and be that 110～140 ℃ steam hot-rolling oven dry back rolling promptly gets polyacrylonitrile fibril by temperature.
The method that the present invention prepares polyacrylonitrile carbon precursor be a kind of be solvent with the sodium sulfocyanate, the moulding of one-step method wet spinning prepares the new method of polyacrylonitrile carbon precursor, it is the new technology in special fibre field.It adopts the technology of washing first break draft earlier, utilize the more complete characteristics of washing back fibrous molecular structure, make the uniform precursor of extension at break by adjusting drafting multiple and drawing-off bath length, thereby the extension at break irregularity of polyacrylonitrile carbon precursor product is controlled in 10%.The polyacrylonitrile carbon precursor of excellent performance is the polyacrylonitrile base preoxidized fiber of preparation fire resistance excellence and the raw material of high-strength and high-modulus polyacrylonitrile-based carbon fibre.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
The specific embodiment
Embodiment 1: with 92% acrylonitrile, 6.5% methyl acrylate and 1.5% itaconic acid is monomer, the employing azodiisobutyronitrile is an initator, and thiourea dioxide is a light-colored agent, and isopropyl alcohol is made molecular weight regulator, with 52% sodium thiocyanate solution is solvent, enters polymeric kettle.Reactant reacted 2.2 hours under 78 ℃ temperature, by taking off Dan Ta continuously, unreacted monomer in the polymer was deviate from reuse.Polymerization stoste enters vacuum and is deaeration in the deaeration tower of 0.082Mpa at first after flame filter press filters again, and stoste thermosistor temperature adjustment to 33 ℃ is filtered and the measuring pump metering by large and small filter, enters spinneret assembly spray thread.Polymerization stoste is sprayed by composite spinning head, and entering temperature and be 6 ℃, density is 1.050g/cm
3Behind the coagulation forming, entering temperature is 30 ℃ in the following current coagulating bath, and density is 1.10g/cm
3Preliminary draft bathe in 1.5 times preliminary draft in addition, again through 60 ℃ of desalted waters washings, two sections water-bath drawing-offs, 8 times of dominant drafts, dominant draft is bathed long 4 meters, and 1.1 times of secondary drawing-offs, secondary drawing-off are bathed long 3 meters, 95 ℃ of drawing-off bath temperatures oil then, and 110 ℃ of hot-rolling oven dry promptly get the carbon precursor.Recording the extension at break irregularity with the YG-003 mono-fiber strong force instrument is 8.9%.
Embodiment 2: with 93% acrylonitrile, 5.5% methyl acrylate and 1.5% itaconic acid is monomer, the employing azodiisobutyronitrile is an initator, and thiourea dioxide is a light-colored agent, and isopropyl alcohol is made molecular weight regulator, with 52% sodium thiocyanate solution is solvent, enters polymeric kettle.Reactant reacted 2.1 hours under 78.5 ℃ temperature, by taking off Dan Ta continuously, unreacted monomer in the polymer was deviate from reuse.Polymerization stoste enters vacuum and is deaeration in the deaeration tower of 0.082Mpa at first after flame filter press filters again, and stoste thermosistor temperature adjustment to 33 ℃ is filtered and the measuring pump metering by large and small filter, enters spinneret assembly spray thread.Polymerization stoste is sprayed by composite spinning head, and entering temperature and be 8 ℃, density is 1.060g/cm
3Behind the coagulation forming, entering temperature is 35 ℃ in the following current coagulating bath, and density is 1.020g/cm
3Preliminary draft bathe in 1.2 times preliminary draft in addition, again through 60 ℃ of desalted waters washings, two sections water-bath drawing-offs, 7 times of dominant drafts, dominant draft is bathed long 3.5 meters, and 1.3 times of secondary drawing-offs, secondary drawing-off are bathed long 3 meters, 93 ℃ of drawing-off bath temperatures oil then, and 110 ℃ of hot-rolling oven dry promptly get the carbon precursor.Recording the extension at break irregularity with the YG-003 mono-fiber strong force instrument is 8.7%.
Embodiment 3: with 92.5% acrylonitrile, 6% methyl acrylate and 1.5% itaconic acid is monomer, the employing azodiisobutyronitrile is an initator, and thiourea dioxide is a light-colored agent, and isopropyl alcohol is made molecular weight regulator, with 52% sodium thiocyanate solution is solvent, enters polymeric kettle.Reactant reacted 2.3 hours under 77.5 ℃ temperature, by taking off Dan Ta continuously, unreacted monomer in the polymer was deviate from reuse.Polymerization stoste enters vacuum and is deaeration in the deaeration tower of 0.082Mpa at first after flame filter press filters again, and stoste thermosistor temperature adjustment to 32 ℃ is filtered and the measuring pump metering by large and small filter, enters spinneret assembly spray thread.Polymerization stoste is sprayed by composite spinning head, and entering temperature and be 10 ℃, density is 1.070g/cm
3Behind the coagulation forming, entering temperature is 50 ℃ in the following current coagulating bath, and density is 1.020g/cm
3Preliminary draft bathe in 1.5 times preliminary draft in addition, again through 65 ℃ of desalted waters washings, two sections water-bath drawing-offs, 6 times of dominant drafts, dominant draft is bathed long 3.3 meters, and 1.5 times of secondary drawing-offs, secondary drawing-off are bathed long 3 meters, 92 ℃ of drawing-off bath temperatures oil then, and 120 ℃ of hot-rolling oven dry promptly get the carbon precursor.Recording the extension at break irregularity with the YG-003 mono-fiber strong force instrument is 9.1%.
Embodiment 4: with 92.5% acrylonitrile, 6% methyl acrylate and 1.5% itaconic acid is monomer, the employing azodiisobutyronitrile is an initator, and thiourea dioxide is a light-colored agent, and isopropyl alcohol is made molecular weight regulator, with 52% sodium thiocyanate solution is solvent, enters polymeric kettle.Reactant reacted 2.3 hours under 77.5 ℃ temperature, by taking off Dan Ta continuously, unreacted monomer in the polymer was deviate from reuse.Polymerization stoste enters vacuum and is deaeration in the deaeration tower of 0.082Mpa at first after flame filter press filters again, and stoste thermosistor temperature adjustment to 32 ℃ is filtered and the measuring pump metering by large and small filter, enters spinneret assembly spray thread.Polymerization stoste is sprayed by composite spinning head, and entering temperature is 10 ℃, and density is 1.070g/cm
3Behind the coagulation forming, entering temperature is 50 ℃ in the following current coagulating bath, and density is 1.020g/cm
3Preliminary draft bathe in 1.5 times preliminary draft in addition, 9 times of drawing-offs in 94 ℃ boiling water then again through 65 ℃ of desalted waters washings, oil then, 120 ℃ of hot-rollings oven dry promptly get the carbon precursor.Recording the extension at break irregularity with the YG-003 mono-fiber strong force instrument is 11.6%.
Claims (1)
1. the preparation method of a polyacrylonitrile carbon precursor is characterized in that polyacrylonitrile carbon precursor is the copolymer of acrylonitrile, methyl acrylate, itaconic acid, and its production stage comprises:
1. stoste preparation: reactant is a monomer with 90～92% acrylonitrile, 5～8% methyl acrylates and 1～2% itaconic acid, the employing azodiisobutyronitrile is an initator, thiourea dioxide is a light-colored agent, isopropyl alcohol is made molecular weight regulator, with 49～54% sodium thiocyanate solutions is solvent, enter polymeric kettle, under 60～80 ℃ temperature, reacted 2～4 hours, by taking off Dan Ta continuously, unreacted monomer in the polymer is deviate from reuse, and condensate is stayed in the sodium thiocyanate solution, becomes homogeneous phase Polymer Solution---spinning solution;
2. spin preceding preparation: polymerization stoste is at first after flame filter press filters, enter vacuum again and be deaeration in the deaeration tower of 0.075～0.085Mpa, through stoste thermosistor temperature adjustment to 25～35 ℃, filter and the measuring pump metering then, enter spinneret assembly spray thread by large and small filter;
3. spinning and post processing: the spinneret assembly that spinning adopts specialized designs to make, the stoste thread of ejection are that 6-15 ℃, density are 1.050-1.090g/cm in temperature
3Sodium thiocyanate solution in coagulation forming be as-spun fibre, be 25-55 ℃ in temperature again, density 1.040-1.10g/cm
3Preliminary draft bathe in 1-2 preliminary draft doubly in addition, turn to then in the desalted water that enters 50-70 ℃ of elongated slot adverse current and wash, adopt five roller drawing machines subsequently, finish drafting process, wherein: 4～8 times of dominant drafts through the drawing-off of major and minor twice boiling water, 1～2 times of secondary drawing-off, 90～100 ℃ of bath temperatures, 6～9 meters of length overalls are bathed in drawing-off, oil with oil solution dedicated subsequently, and be 110～140 ℃ steam hot-rolling oven dry back rolling by temperature, promptly get polyacrylonitrile fibril.
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| CN101768791A (en) * | 2010-02-10 | 2010-07-07 | 北京化工大学 | Polyacrylonitrile-based hollow carbon fiber precursor and preparation method thereof |
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2003
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768791A (en) * | 2010-02-10 | 2010-07-07 | 北京化工大学 | Polyacrylonitrile-based hollow carbon fiber precursor and preparation method thereof |
| US10590258B2 (en) | 2017-11-22 | 2020-03-17 | Industrial Technology Research Institute | Carbon fiber precursor composition and method for preparing carbon fiber precursor |
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