聚丙烯腈熔融纺丝技术进展

叙述了聚丙烯腈的结构特征，丙烯腈聚合物的增塑，增塑和非增塑聚丙烯腈熔融纺丝工艺和纤维性质。熔纺制得的聚丙烯腈纤维，适用于纺织、地毯以及用作碳纤维原丝。增塑熔融纺丝技术已达到相当高的水平，熔纺纤维的形态与普通聚丙烯腈纤维类似，但存在皮芯结构，芯部有微孔。制得的聚丙烯腈基碳纤维原丝，拉伸强度达５．５～６．６ｃＮ／ｄｔｅｘ，用这种原丝生产的碳纤维的拉伸强度约为３．６×１０３ＭＰａ，模量约为２．３３×１０５ＭＰａ，伸长率约为１．５％，可制得性能优良的航空航天用复合材料。非增塑熔融纺丝，采用特定的丙烯腈聚合物和纺丝条件，不添加任何增塑剂，用普通熔融纺丝机在１０００ｍ／ｍｉｎ或２０００ｍ／ｍｉｎ以上的速度纺丝，经拉伸可得强度２．２～１１ｃＮ／ｄｔｅｘ、伸长率５％～３０％和模量５５～２２２ｃＮ／ｄｔｅｘ的纤维。     

Preparation and properties of polyimide fibers

Polyimides were synthesized from 4,4′-diamino diphenyl methane and pyromellitic dianhydride using low-temperature solution polycondensation. Solutions of these polyamic acids in dimethyl-formamide (DMF) were spun into fibers by the wet spinning technique using a mixture of DMF and water as coagulants. Various spinning parameters such as dope concentration, bath composition, and jet stretch were standardized to get polyimide fibers with optimum properties. It was observed that fibers spun at higher jet stretch did not cyclize satisfactorily. Higher dope concentrations gave fibers with better properties. Cyclodehydrated fibers were hot-drawn at 300°C. Fibers with a tenacity of 380 mN/tex, an extension at break of 10%, and initial modulus of 4060 mN/tex were obtained. Mechanical properties of fibers at elevated temperatures, i.e., 100 and 200°C were also measured. Heat aging at 100, 200, and 300°C was carried out for 10 hr. This resulted in an increase in the initial modulus of fibers. However, a 28% decrease in tenacity was observed when the fibers were heat-aged at 300°C. The dynamic thermogravimetry in air showed that fibers were stable up to 400°C. The activation energy of decomposition, calculated from these thermograms in the temperature range 540–610°C was 101 kJ/mole.     

Physical properties of poly(vinyl alcohol) fibers prepared from wet spinning/multi-step drawing

The preparation of poly(vinyl alcohol) (PVA) fibers by multi-step drawing was examined. The high draw ratio was attained when the drawing just before melting point was repeated. The influences of the draw ratio on mechanical and thermal properties of the fibers were studied. We utilized the wide angle x-ray diffraction (WAXD) as a medium to observe the erystallinity and the orientation of PVA fibers to study their effects on the physical properties of the fibers. With various coagulation bath concentration, both the tenacity and Young's modulus of fibers would increase as the draw ratios increased, the elongation would decrease at the same time. The tenacity was able to reach 41.0 cN/tex with the Young's modulus being 856.2 cN/tex; also, as the draw ratios increased, both crystallinity and orientation would increase. The crystallinity was about 67.2 % and the orientation was about 86.4%.     

Preparation and properties of keratin–poly(vinyl alcohol) blend fiber

Keratin–poly(vinyl alcohol) (PVA) blend fibers containing 13–46 wt % of –SSONa⁺ (S‐sulfo) keratin were prepared by the wet‐spinning technique. They were formed by dehydration of an aqueous solution of S‐sulfo keratin and PVA (spinning dope) in a coagulation bath of sodium sulfate–saturated solution and subsequently drawn. Keratin–PVA fibers showed higher tenacity than that of wool, presumably originating from the high mechanical strength of the PVA component. The heat treatment at about 200°C improved the waterproof characteristics such as shrinkage of keratin–PVA fibers more conspicuously than did PVA fibers. That is, after heat treatment at 195°C for 10 min, keratin–PVA blend fiber shrank 20% in water at 60°C, whereas PVA fiber shrank 56%. Differential thermal analysis suggested the crosslinking of disulfide bonds between keratin molecules during the heat treatment, whereas the additional crystallization of PVA component was not observed. Adsorption of heavy metal and toxic gas to keratin–PVA fibers was also investigated. Keratin–PVA fiber was found to adsorb Ag⁺ and formaldehyde gas more efficiently than PVA. Thus, blends of keratin and PVA were advantageous for both polymer fibers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 756–762, 2004     

聚丙烯高速纺丝工艺的研究——卷绕丝超分子结构与后加工性能的工艺控制

利用X射线衍射、DSC、双折射、密度梯度等方法探讨了在3km/min高纺速下,纺丝温度对丙纶POY的超分子结构与后加工性能的影响,对冷却条件的影响也进行了讨论。指出在280℃以下范围提高纺丝温度可以降低聚丙烯高速纺程上的流变张力,使卷绕丝的结晶度降低,结晶成分中次晶含量增加,非晶区取向度提高。采用缓慢冷却有和于提高POY的非晶区预取向。采用MI=35的聚丙烯树脂,在纺丝温度270℃和缓冷条件下可得具有优良后加工性能的丙纶POY,在414m/min速度下经加弹所得DTY的强度为41.1cN/t(?)x,伸长为34.1%,卷曲率为20%,卷曲稳定性为92%。     

Melt spinning and drawing of 2‐methyl‐1,3‐propanediol‐substituted poly(ethylene terephthalate)

The structure and properties of fibers prepared from copolymers of poly(ethylene terephthalate) (PET) in which 2‐methyl‐1,3‐propanediol (MPDiol® Glycol is a registered trademark of Lyondell Chemical Company) at 4, 7, 10, and 25 mol% was substituted for ethylene glycol were studied and compared with those of PET homopolymer. Filaments were melt spun over a range of spinning conditions, and some filaments that were spun at relatively low spinning speeds were subjected to hot drawing. The filaments were characterized by measurements of birefringence, differential scanning calorimetry (DSC) crystallinity, melting point, glass transition temperature, wide‐angle X‐ray diffraction patterns, boiling water shrinkage, tenacity, and elongation to break. Filaments containing 25 mol% MPDiol did not crystallize in the spinline at any spinning speed investigated, whereas the other resins did crystallize in the spinline at high spinning speeds. However, compared with PET homopolymer, increasing substitution of MPDiol reduced the rate at which the crystallinity of the melt spun filaments increased with spinning speed and reduced the ultimate crystallinity that could be achieved by high‐speed spinning. The rate of development of molecular orientation, as measured by birefringence, also decreased somewhat with increasing MPDiol content. Shrinkage in boiling water decreased at high spinning speeds as the amount of crystallinity increased; however, the shrinkage decreased more slowly with increase in spinning speed as MPDiol content increased. Tenacity also decreased slightly at any given spinning speed as MPDiol content increased, but there was no significant effect on elongation to break. The addition of MPDiol in amounts up to 7 mol% increased the maximum take‐up velocity that could be achieved at a given mass throughput. This result indicates that the use of higher spinning speeds could potentially increase the productivity of melt spun yarns. Copolymer filaments spun at low speeds were readily drawn to produce highly oriented fibers with slightly less birefringence, crystallinity, and tenacity than similarly processed PET homopolymer. Preliminary dyeing experiments showed that the incorporation of MPDiol improved the dyeability of the filaments. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2598–2606, 2003     

Surface hydrolysis of filaments based on poly(trimethylene terephthalate) spun at high spinning speeds

The surface alkaline hydrolysis of fibers made from poly(trimethylene terephthalate) (PTT) was studied after extruding the polymer at high spinning speeds from 2000 to 6000 m/min and heat setting in the range of temperatures from 100 to 180°C. Fiber weight loss increased with an increasing heat‐setting temperature but it was also dependent on the spinning speed. Some of the partially hydrolyzed fibers had a well‐developed, hydrophilic surface, and pore size in the range of 0.69 to 1.20 μm. The optimum reaction and morphological conditions for increasing porosity in PTT fibers depends on spinning speed and heat‐setting temperature. A temperature of 180°C is the upper limit for heat‐setting PTT filaments but seems to be the most effective for making porous fibers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1724–1730, 2004     

Fiber formation and physical properties of chitosan fiber crosslinked by epichlorohydrin in a wet spinning system: The effect of the concentration of the crosslinking agent epichlorohydrin

The wet spinning of chitosan fibers was studied with 2% acetic acid as the solvent, 10% aqueous sodium hydroxide as the nonsolvent, and a 4% chitosan solution as the polymer. This article describes the crosslinking of the chitosan fibers. Epichlorohydrin (ECH) was selected as a convenient base‐catalyzed crosslinking agent. The coagulation and crosslinking of the chitosan fibers occurred simultaneously in the coagulation bath. In this study, we investigated the effect of the concentration of the crosslinking agent, ECH, in the spinning dope on the structural, thermal, morphological, and mechanical properties (e.g., the tenacity, elongation, and work of rupture) of chitosan fibers. The tenacity of the chitosan fibers, especially the wet tenacity, was improved by crosslinking. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2054–2062, 2004     

Influence of drawing speed on some properties of acrylic fibers

The effect of drawing speed on several properties of acrylic fibers has been examined. The acrylic fibers were prepared by the wet-spinning process. The coagulation bath contained 30–70% DMF and was held at a temperature varying from 10–45°C. From x-ray diffraction measurement, the orientation of finished fibers increased with an increase in drawing speed, and became constant when the drawing speed exceeded 40–50 m/min. The tenacity and stability to repetitive deformation also increased to a drawing speed of 40–50 m/min, but then decreased. The spinning conditions (spin-bath composition and temperature) influenced the most attainable properties of the finished fibers. The results are discussed from the point of view of structural changes in fibers during drawing.     

Preparation and characterization of chitosan/poly(vinyl alcohol) blend fibers

Chitosan and poly(vinyl alcohol) blend fibers were prepared by spinning their solution through a viscose‐type spinneret at 25°C into a coagulating bath containing aqueous NaOH and ethanol. The influence of coagulation solution composition on the spinning performance was discussed, and the intermolecular interactions of blend fibers were studied by infrared analysis (IR), X‐ray diffraction (XRD), and scanning electron micrograph (SEM) and by measurements of mechanical properties and water‐retention properties. The results demonstrated that the water‐retention properties and mechanical properties of the blend fibers increase due to the presence of PVA in the chitosan substract, and the mechanical strength of the blends is also related to PVA content and the degree of deacetylation of chitosan. The best mechanical strength values of the blend fibers, 1.82 cN/d (dry state) and 0.81 cN/d (wet state), were obtained when PVA content was 20 wt % and the degree of deacetylation of chitosan was 90.2%. The strength of the blend fibers, especially wet tenacity could be improved further by crosslinking with glutaraldehyde. The water‐retention values (WRV) of the blend fibers were between 170 and 241%, obviously higher than pure chitosan fiber (120%). The structure analysis indicated that there are strong interaction and good miscibility between chitosan and poly(vinyl alcohol) molecular resulted from intermolecular hydrogen bonds. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2558–2565, 2001     

Influence of process parameters on the structure formation of man‐made cellulosic fibers from ionic liquid solution

The influence of dry‐jet wet spinning parameters on the production of man‐made cellulosic fibers from 13 wt % cellulose/1,5‐diazabicyclo[4.3.0]non‐5‐ene acetate solutions was investigated. The spinneret nozzle diameter, extrusion velocity, draw ratio, and coagulation bath temperature were the studied parameters. The production of highly oriented fibers was favored by selecting higher extrusion velocity and lower spinneret diameter. A spinneret size of 100 µm and a draw ratio of 6 were sufficient to highly orient the cellulose macromolecules and achieve tenacities above 40 cN/tex (600 MPa). Total orientation assessed via birefringence measurement, tenacity, and Young's modulus values reached a plateau at a draw of 6 and no further development in properties was observed. A temperature of the aqueous coagulation bath of 15 °C slightly promoted greater orientation of the fibers by hampering structural changes of the cellulose macromolecules in the nascent solid fibers. Furthermore, the determination of the elongational viscosity of the liquid thread via the measurement of radial force tensor was tested and showed promising results. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43718.     

Preparation of alginate/soy protein isolate blend fibers through a novel coagulating bath

Alginate and soy protein isolate blend fibers were prepared by spinning their solution through a viscose‐type spinneret into a novel coagulating bath containing aqueous CaCl₂, HCl, and ethanol. The structures and properties of the fibers were studied with the aids of infrared spectra (IR), X‐ray diffraction (XRD), and scanning electron micrograph (SEM). Mechanical properties and water‐retention properties were measured. And with the sample of AS1 fiber (soy protein isolate weight content was 10%), the effects of the composition of the novel coagulating bath were also studied. The best values of the tensile strength of AS1 were 14.1 cN/tex in the dry state and 3.46 cN/tex in the wet state, respectively. Both the dry state and wet state breaking elongation were also having the best value 20.71% and 56.7% with AS1. Mechanical properties of the AS1 enhanced with the CaCl₂ content increased in the coagulating bath. When the HCl content was 1%, the mechanical property of the fiber was best. Ethanol in the coagulating bath increased the wet mechanical properties of the fiber by 41.2% (tensile strength) and 45.1% (breaking elongation) when the ethanol weight content in the coagulating bath was 50%; but it had little effect on the dry mechanical properties. And the water‐retention value (WRV) of blend fibers decreased as the amount of soy protein isolate was raised. The structure analysis indicated that there were strong interaction and a certain level of miscibility between alginate and soy protein isolate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 425–431, 2006     

120 dtex/144 f涤纶直纺预取向丝生产工艺探讨

通过对熔体质量和工艺条件的选择,采用喷丝板孔径0.13mm,纺丝温度296℃,侧吹风风速0.35m/s,集束点位置600～700mm,纺丝速度2750m/min,以及适当控制其它工艺条件,纺得涤纶POY微细旦丝的断裂强度2.48cN/dtex,断裂伸长率127.6%,可满足后加工要求。     

Structure development during dry–jet–wet spinning of acrylonitrile/vinyl acids and acrylonitrile/methyl acrylate copolymers

Dry–jet–wet spinning of three copolymers, poly(acrylonitrile/methyl acrylate), poly(acrylonitrile/methacrylic acid), and poly(acrylonitrile/itaconic acid), was performed with a dimethylformamide/water (60:40 v/v) coagulation bath at different temperatures (10–40°C). The fibers were stretched to different levels (1.1–6×) in boiling water, collapsed, and annealed over a heater plate at 130°C. The effects of the polymer composition, coagulation bath temperature, and draw ratio on the cross‐sectional morphology, structure, and tensile properties are reported. The cross‐sectional shape of the gel fibers underwent a transition from a kidney shape to an oval shape, and macrovoids began to appear at higher temperatures. However, F(AN/IA) gel fibers changed from a kidney shape to an irregular shoe type with a gel network of interconnected polymer fibrils. For F(AN/MAA) gel fibers, the diameter increased from 45 to 67 μm when the coagulation bath temperature was increased from 10 to 40°C, and the denier value decreased from 17.5 to 14.3 den/filament. The strength, modulus, and elongation at break decreased with an increase in the coagulation bath temperature. For F(AN/MAA) fibers coagulated at 10°C in a spin bath, the strength increased from 0.43 to 2.213 g/den, the modulus increased from 27 to 76 g/den, and the density increased from 1.177 to 1.196 g cm^?3 when the gel fibers were drawn to 6×. However, 6× drawn F(AN/MA) fibers had a higher strength (3.1 g/den) and elongation (14.6%) in a 40°C coagulation bath. F(AN/IA) fibers could be drawn only to a draw ratio of 4× instead of the 6× draw ratio for F(AN/MAA) and F(AN/MA) fibers. Therefore, the final F(AN/IA) fibers exhibited poor mechanical properties (tenacity = 0.81 g/den, modulus = 22 g/den, and elongation at break = 8%). The crystallinity did not change significantly (χ_c = 61–63%) with the draw ratio, but the crystal size increased from 22.9 to 43.4 Å and orientation factor from 0.41 to 0.78. The dichroic ratio, measured with Fourier transform infrared, decreased with an increase in the draw ratio, but the sonic modulus and crystalline orientation values increased with an increase in the draw ratio. Thermomechanical data show a maximum physical shrinkage of 51.7% for 6× drawn F(AN/MA) and a minimum physical shrinkage of 30.5% for 4× drawn F(AN/IA) fibers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 773–787, 2002     

278dtex/48f特种工业用锦纶生产工艺探讨

阐述了用技术改造后的 VC404纺丝机研制高强力低延伸的特种工业用锦纶的过程,探讨了低熔体温度纺丝新工艺.要求熔体温度为254—258℃;丝室温度为34—38℃;卷绕丝含水3.5%—4.5%。该项新产品线密度275.8—283.4dtex/48f;CV%为1.60—1.76;相对强度6.0—6.2cN/dtex;伸长率19.2%—20.4%;捻度114—117捻/m;沸水收缩率4.4%—4.8%.     

Effect of hot drawing on properties of wet‐spun poly(L,D‐lactide) copolymer multifilament fibers

Polylactide stereocopolymer multifilament fibers were prepared by wet spinning and subsequent hot drawing. The stereocopolymers were poly‐(L,D ‐lactide) [P(L,D )LA], L/D ratio 96/4, and poly‐(L,DL ‐lactide) [P(L,DL )LA], L/DL ratio 70/30. They were dissolved in dichloromethane and coagulated in a spin bath containing ethanol. The hot‐drawing temperature was 65°C. The draw ratios (DR) were upto 4.5 to the P(L,D )LA 96/4 filaments and upto 3 to the P(L,DL )LA 70/30 filaments. Wet spinning decreased crystallinities of both copolymers. Hot drawing increased the crystallinity of the P(L,D )LA 96/4 filament but not to the level of the original copolymer, whereas the as‐spun and the hot‐drawn P(L,DL )LA 70/30 filaments were amorphous. The filament diameter, tenacity, Young's modulus, and elongation at break were dependent on the DR. The maximum tenacity (285 MPa) and Young's modulus (2.0 GPa) were achieved with the P(L,D )LA 96/4 filament at the DR of 4.5. Respectively, the maximum tenacity of the hot‐drawn P(L,DL )LA 70/30 filament was 175 MPa and Young's modulus 1.3 GPa at the DR of 3. Hot drawing slowed down in vitro degradation rate of both stereocopolymer filaments. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Comparative analysis of the structural parameters and strength properties of polyacrylonitrile fibers containing ceramic nanoadditives

The structural parameters and strength properties of three types of new‐generation precursor polyacrylonitrile fibers are comparatively analyzed. These fibers, after the carbonization process, can be used as implants supporting the process of bone reconstruction. They are characterized by a high tenacity ranging from 21 to 41 cN/tex. Tests and measurements have shown that the presence of nanoadditives causes a clear increase in the degree of fiber crystallinity. Moreover, the tenacity of the fibers can be considerably increased by the grinding of nanoadditive agglomerates with ultrasound. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

The influence of processing parameters on the properties of melt‐spun polypropylene hollow fibers

Isotactic polypropylene hollow fibers were produced by melt spinning. Spinning speeds up to 1880 m/min were used, and sample hollowness (percentage void in cross section) ranged from 0 to 69%. The fiber samples were characterized using dynamic mechanical analysis, birefringence, tensile testing, and differential scanning calorimetry. The hollow fibers were found to have higher crystallinity, orientation, and strength than the analogous solid fibers. In general, the polymer orientation in a hollow fiber was larger than the orientation in a solid fiber, even when the spinning speed for the latter was much larger. For a fixed outer diameter, increasing the hollowness improved fiber properties. However, as hollowness was further increased, fiber properties declined slightly. At a given percentage hollowness, increased spinning speed increased modulus and tenacity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1759–1772, 2002     

High‐speed melt spinning of various grades of polylactides

Five kinds of polylactides (PLAs), with different D ‐lactide contents and tacticities, were subjected to high‐speed melt‐spinning experiments. In addition to stereochemical purity, the PLA types differed in molecular mass and molecular mass distribution. The properties of the different PLA materials were characterized by thermogravimetry, differential scanning calorimetry, dynamic mechanical analysis, size exclusion chromatography, and ¹H‐NMR and ¹³C‐NMR spectroscopy. The material was spun with a high‐speed spinning process within the range 2000–5000 m/min. The physical and tensile properties of the fibers were determined. The maximum tensile properties of the fibers were a 300 MPa tenacity at an elongation at break of 30% and a tensile modulus of 6.8 GPa. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 800–806, 2004     

锦纶BCF的试制

介绍了锦纶BCF的生产技术。在从意大利引进的BCF纺丝机上,采用高粘度锦纶切片,设计合理的纺丝、拉伸、变形和卷绕工艺,可生产出适合于锦纶簇绒地毯的产品.线密度为180—195tex;相对强力23.9cN/tex,热卷曲伸长率17.7%,伸长率75.7%。