CN1752302A - Wet spinning method for polyacryl-nitrile fibre - Google Patents
Wet spinning method for polyacryl-nitrile fibre Download PDFInfo
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- CN1752302A CN1752302A CN200410066607.6A CN200410066607A CN1752302A CN 1752302 A CN1752302 A CN 1752302A CN 200410066607 A CN200410066607 A CN 200410066607A CN 1752302 A CN1752302 A CN 1752302A
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Abstract
The wet spinning method of polyacrylonitrile fibre includes the following steps: dissolving fibre-grade polyacrylonitrile resin in the solvent to obtain spinning solution, making the spinning solution the passed through spinneret component to form primary fibre, then making the primary fibre be passed through a coagulating bath and coagulated to form the invented fibre. Said invention also provides the chemical structure formula of said solvent, and the polyacrylonitrile resin content in the spinning solution is 10-35 wt%.
Description
Technical field
The present invention relates to a kind of wet spinning process of polyacrylonitrile fibre, particularly adopting ionic liquid is the wet spinning process of the polyacrylonitrile fibre of solvent.
Background technology
The polyacrylonitrile fibre performance exactly likes wool, occupies very big proportion in the synthetic fiber production.
But the raw material polyacrylonitrile resin of making polyacrylonitrile fibre has a defective, be that its fusing point (theoretical value is 319 ℃) is higher than decomposition temperature (being generally 250 ℃), therefore it can't be processed with the method for fusion, usually can only use the method manufacturing of solvent spinning, soon polyacrylonitrile resin is dissolved in and forms spinning solution in the solvent, and the solvent in the as-spun fibre overflows after coagulation and is configured as fiber.In the prior art, solvent mainly is divided into volatilizable organic solvent and is the aqueous solution solvent two big classes of coagulating agent with water, and corresponding spinning technique also is divided into dry spinning and wet spinning two classes.The advantage of dry spinning is that technology and equipment are all fairly simple, but shortcoming is a difficult solvent recovery, cost is higher, and because the volatile characteristic of solvent has caused the production environment air pollution serious, so wet spinning is still the more adopted technology of industrialization manufacturing polyacrylonitrile fibre at present.The solvent that traditional wet spinning adopts is mainly sodium thiocyanate water solution, the advantage of this process route is that the operation operating cost of producing is relatively low, constant product quality, but its shortcoming is a sodium sulfocyanate has very strong corrosivity, therefore production equipment corrosion-resistant required highly, the environment of production operation is also relatively poor.
And we know that ionic liquid at room temperature is a kind of green solvent that comes out recently, it can exist with liquid state in wider temperature range, have advantages such as boiling point height, not volatile, Heat stability is good, the combination that ionic liquid also can be by the yin, yang ion selecting to suit is to change its physicochemical properties.Ionic liquid is used as the good solvent of many organic matters, inorganic matter and macromolecular material morely at present, and as U.S. Pat 5,304,615 disclose a kind of method for preparing the high molecular polyisoolefines in ionic liquid.
Summary of the invention
The invention provides a kind of wet spinning process of polyacrylonitrile fibre, it has selected the solvent of a kind of desirable ionic liquid as spinning solution, and it can solve high this technical problem of solvent corrosion that traditional wet spinning adopts well.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of wet spinning process of polyacrylonitrile fibre, this method comprise makes spinning solution with fibrous polypropylene nitrile resin dissolves in solvent, spinning solution forms as-spun fibre by spinneret component, and as-spun fibre is a fiber by the coagulating bath solidification forming immediately.Solvent in the spinning solution is the ionic liquid with structural formula A:
R1, R2, R3 and the R4 alkyl of H or C1～C8 of respectively doing for oneself wherein, X
-Take from Cl
-, BF
4 -, PF
6 -, CF
3SO
3 -, CF
3COO
-, (CF
3SO
2)
2N
-Or (CF
3SO
2)
2C
-In a kind of, the content of polyacrylonitrile resin is 10～35wt% in the spinning solution, coagulating bath is to have the solution that the ionic liquid of structural formula A and water form, wherein ion liquid content is 20～35wt%.
Above-mentioned polyacrylonitrile resin can be for comprising the copolymer of first monomer, second monomer and the 3rd monomer, and wherein the content of second monomer is that the content of 5～18wt%, the 3rd monomer is 0～1.0wt%.First monomer is an acrylonitrile; Second monomer is taken from a kind of in methyl acrylate, methyl methacrylate, methacrylonitrile, vinylacetate or the acrylamide, and the effect of second monomer is a flexibility of improving fiber; The 3rd monomer is taken from a kind of in the amino ethyl ester of itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, metering system benzene sulfonic acid sodium salt, vinylpyridine, 2-methyl-5-vinylpyridine or dimethylaminoethyl acrylate methyl, and the effect of the 3rd monomer is a dyeability of improving fiber.
The preparation process of described spinning solution can be: polyacrylonitrile resin swelling 0～90 minute in above-mentioned solvent, swelling temperature is 10～40 ℃, is dissolved to resin then under 50～150 ℃ temperature and dissolves fully.
The spinning solution temperature generally is controlled at 100～150 ℃ when spinning, is preferably 110～120 ℃; Coagulation bath temperature generally is controlled to be 30～60 ℃, is preferably 35～50 ℃.
X among the said structure formula A
-Preferably take from Cl
-, BF
4 -, PF
4 -Or CF
3SO
3 -In a kind of.
And second monomer is preferably taken from methyl acrylate or methyl methacrylate in the polyacrylonitrile copolymer; The 3rd monomer is preferably taken from a kind of in sodium allylsulfonate, methylpropene sodium sulfonate or the metering system benzene sulfonic acid sodium salt.
Key problem in technology of the present invention is to have adopted the spin solvent of ionic liquid as polyacrylonitrile fibre, and has searched out the spinning process condition that is fit to this solvent.This solvent is nontoxic, non-volatility, and can water be coagulating agent, and the recovery of solvent is also very convenient, so whole process of production is very beneficial for environmental protection, and can reduce production costs and help the saving of resource.The liquid temperature scope of solvent is very wide, helps the control of spinning temperature.In addition.Solvent is very strong to the solvability of polyacrylonitrile resin, and solubility is big, is applicable to the spinning of the acrylonitrile compolymer body of different compositions, different molecular weight, the adjustable range broadness of product.
Compared with prior art, the present invention has overcome the defective that existing polyacrylonitrile fibre spin solvent exists well, the solvent that is adopted does not only have volatilization, and basic non-corrosiveness, also have above-described plurality of advantages simultaneously, and these advantages do not possess mostly for existing polyacrylonitrile fibre spin solvent.
Below will the invention will be further described by specific embodiment.Because the composition of adoptable polyacrylonitrile resin copolymer, the technology of spinning pre-treatment and spinning later process of spinning solution etc. are essentially identical with prior art, these all are well known to those of ordinary skill in the art, so embodiment will give an example to solvent and the spinning technology partly selected for use emphatically.
In an embodiment, the copolymer of the polyacrylonitrile resin of employing for being polymerized by acrylonitrile, methyl acrylate and methylpropene sodium sulfonate, three's content is respectively 91.2wt%, 8.0wt% and 0.8wt% in the copolymer.
The physical index that makes fiber is tested in order to following method:
Fracture strength: GB (GB/T14337-93)
Extension at break: GB (GB/T14337-93)
The specific embodiment
[embodiment 1]
Polyacrylonitrile resin and ionic liquid are uniformly mixed to form slurries, and the content of polyacrylonitrile resin is 23wt% in the slurries.Swelling 10min under 40 ℃ temperature is warming up to 150 ℃ of dissolvings then and formed uniform solution in 2 hours and make spinning solution.Carry out spinning after the filtration of spinning solution process, the deaeration, former liquid temp is 150 ℃.Coagulating bath is an ionic liquid aqueous solution, and wherein ion liquid content is 20wt%, and coagulation bath temperature is 50 ℃.
The ionic liquid that adopts has following structural formula:
Spinning speed is 6m/min, the fiber of solidification forming through washing, stretching, dryness finalization, curl and the processing of later process such as cut-out, make the Orlon that specification is 2.5dtex * 65mm.Recording fracture strength is 3.5cN/dtex, and extension at break is 26%.
[embodiment 2]
Polyacrylonitrile resin and ionic liquid are uniformly mixed to form slurries, and the content of polyacrylonitrile resin is 10wt% in the slurries.Swelling 55min under 18 ℃ temperature is warming up to 60 ℃ of dissolvings then and formed uniform solution in 4.5 hours and make spinning solution.Carry out spinning after the filtration of spinning solution process, the deaeration, former liquid temp is 100 ℃.Coagulating bath is an ionic liquid aqueous solution, and wherein ion liquid content is 20wt%, and coagulation bath temperature is 35 ℃.
The ionic liquid that adopts has following structural formula:
Spinning speed is 9m/min, the fiber of solidification forming through washing, stretching, dryness finalization, curl and the processing of later process such as cut-out, make the Orlon that specification is 3.8dtex * 75mm.Recording fracture strength is 2.4cN/dtex, and extension at break is 39%.
[embodiment 3]
Polyacrylonitrile resin and ionic liquid are uniformly mixed to form slurries, and the content of polyacrylonitrile resin is 12wt% in the slurries.Swelling 40min under 20 ℃ temperature is warming up to 100 ℃ of dissolvings then and formed uniform solution in 3.5 hours and make spinning solution.Carry out spinning after the filtration of spinning solution process, the deaeration, former liquid temp is 110 ℃.Coagulating bath is an ionic liquid aqueous solution, and wherein ion liquid content is 27wt%, and coagulation bath temperature is 40 ℃.
The ionic liquid that adopts has following structural formula:
Spinning speed is 6m/min, the fiber of solidification forming through washing, stretching, dryness finalization, curl and the processing of later process such as cut-out, make the Orlon that specification is 3.3dtex * 65mm.Recording fracture strength is 2.7cN/dtex, and extension at break is 39%.
[embodiment 4]
Polyacrylonitrile resin and ionic liquid are uniformly mixed to form slurries, and the content of polyacrylonitrile resin is 16wt% in the slurries.Form uniform solution in 4.5 hours 95 ℃ of dissolvings and make spinning solution.Carry out spinning after the filtration of spinning solution process, the deaeration, former liquid temp is 110 ℃.Coagulating bath is an ionic liquid aqueous solution, and wherein ion liquid content is 26wt%, and coagulation bath temperature is 40 ℃.
The ionic liquid that adopts has following structural formula:
Spinning speed is 8m/min, the fiber of solidification forming through washing, stretching, dryness finalization, curl and the processing of later process such as cut-out, make the Orlon that specification is 2.8dtex * 55mm.Recording fracture strength is 3.1cN/dtex, and extension at break is 30%.
[embodiment 5]
Polyacrylonitrile resin and ionic liquid are uniformly mixed to form slurries, and the content of polyacrylonitrile resin is 30wt% in the slurries.Swelling 45min under 32 ℃ temperature is warming up to 105 ℃ of dissolvings then and formed uniform solution in 3.5 hours and make spinning solution.Carry out spinning after the filtration of spinning solution process, the deaeration, former liquid temp is 120 ℃.Coagulating bath is an ionic liquid aqueous solution, and wherein ion liquid content is 35wt%, and coagulation bath temperature is 60 ℃.
The ionic liquid that adopts has following structural formula:
Spinning speed is 8m/min, the fiber of solidification forming through washing, stretching, dryness finalization, curl and the processing of later process such as cut-out, make the Orlon that specification is 2.3dtex * 38mm.Recording fracture strength is 3.3cN/dtex, and extension at break is 24%.
[embodiment 6]
Polyacrylonitrile resin and ionic liquid are uniformly mixed to form slurries, and the content of polyacrylonitrile resin is 35wt% in the slurries.Swelling 90min under 10 ℃ temperature is warming up to 95 ℃ of dissolvings then and formed uniform solution in 4.5 hours and make spinning solution.Carry out spinning after the filtration of spinning solution process, the deaeration, former liquid temp is 125 ℃.Coagulating bath is an ionic liquid aqueous solution, and wherein ion liquid content is 20wt%, and coagulation bath temperature is 30 ℃.
The ionic liquid that adopts has following structural formula:
Spinning speed is 7m/min, the fiber of solidification forming through washing, stretching, dryness finalization, curl and the processing of later process such as cut-out, make the Orlon that specification is 2.7dtex * 65mm.Recording fracture strength is 3.0cN/dtex, and extension at break is 30%.
[embodiment 7]
Polyacrylonitrile resin and ionic liquid are uniformly mixed to form slurries, and the content of polyacrylonitrile resin is 25wt% in the slurries.Swelling 60min under 20 ℃ temperature is warming up to 50 ℃ of dissolvings then and formed uniform solution in 5 hours and make spinning solution.Carry out spinning after the filtration of spinning solution process, the deaeration, former liquid temp is 105 ℃.Coagulating bath is an ionic liquid aqueous solution, and wherein ion liquid content is 35wt%, and coagulation bath temperature is 40 ℃.
The ionic liquid that adopts has following structural formula:
Spinning speed is 10m/min, the fiber of solidification forming through washing, stretching, dryness finalization, curl and the processing of later process such as cut-out, making specification is the polyacrylonitrile tow of 3.0dtex.Recording fracture strength is 5.2cN/dtex, and extension at break is 15%.
Claims (9)
1, a kind of wet spinning process of polyacrylonitrile fibre, this method comprises makes spinning solution with fibrous polypropylene nitrile resin dissolves in solvent, spinning solution forms as-spun fibre by spinneret component, as-spun fibre is a fiber by the coagulating bath solidification forming immediately, and the solvent in the spinning solution is the ionic liquid with structural formula A:
R1, R2, R3 and the R4 alkyl of H or C1～C8 of respectively doing for oneself wherein, X
-Take from Cl
-, BF
4 -, PF
4 -, CF
3SO
3 -, CF
3COO
-, (CF
3SO
2)
2N
-Or (CF
3SO
2)
2C
-In a kind of, the content of polyacrylonitrile resin is 10～35wt% in the spinning solution, coagulating bath is to have the solution that the ionic liquid of structural formula A and water form, wherein ion liquid content is 20～35wt%.
2, the wet spinning process of polyacrylonitrile fibre according to claim 1, it is characterized in that described polyacrylonitrile resin is for comprising first monomer, the copolymer of second monomer and the 3rd monomer, wherein the content of second monomer is 5～18wt%, the content of the 3rd monomer is 0～1.0wt%, first monomer is an acrylonitrile, second monomer is taken from methyl acrylate, methyl methacrylate, methacrylonitrile, a kind of in vinylacetate or the acrylamide, the 3rd monomer is taken from itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, the metering system benzene sulfonic acid sodium salt, vinylpyridine, a kind of in the amino ethyl ester of 2-methyl-5-vinylpyridine or dimethylaminoethyl acrylate methyl.
3, the wet spinning process of polyacrylonitrile fibre according to claim 1, the preparation process that it is characterized in that described spinning solution comprises: polyacrylonitrile resin swelling 0～90 minute in above-mentioned solvent, swelling temperature is 10～40 ℃, is dissolved to resin then under 50～150 ℃ temperature and dissolves fully.
4, the wet spinning process of polyacrylonitrile fibre according to claim 1 is characterized in that when spinning the spinning solution temperature is controlled to be 100～150 ℃, and coagulation bath temperature is controlled to be 30～60 ℃.
5, the wet spinning process of polyacrylonitrile fibre according to claim 4 is characterized in that described spinning solution temperature is controlled at 110～120 ℃.
6, the wet spinning process of polyacrylonitrile fibre according to claim 4 is characterized in that described coagulation bath temperature is controlled to be 35～50 ℃.
7, the wet spinning process of polyacrylonitrile fibre according to claim 1 is characterized in that X among the described structural formula A
-Take from Cl
-, BF
4 -, PF
4 -Or CF
3SO
3 -In a kind of.
8, the wet spinning process of polyacrylonitrile fibre according to claim 2 is characterized in that described second monomer takes from methyl acrylate or methyl methacrylate.
9,, it is characterized in that described the 3rd monomer takes from a kind of in sodium allylsulfonate, methylpropene sodium sulfonate or the metering system benzene sulfonic acid sodium salt according to the wet spinning process of claim 2 or 8 described polyacrylonitrile fibres.
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| CN102260919A (en) * | 2011-06-29 | 2011-11-30 | 中国科学院宁波材料技术与工程研究所 | Method for homogenizing, solidifying and forming polyacrylonitrile precursor |
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