CN101037809A - Continuously static spinning method of polyamide 6/66 copolymer filament yarn - Google Patents
Continuously static spinning method of polyamide 6/66 copolymer filament yarn Download PDFInfo
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- CN101037809A CN101037809A CN 200710020792 CN200710020792A CN101037809A CN 101037809 A CN101037809 A CN 101037809A CN 200710020792 CN200710020792 CN 200710020792 CN 200710020792 A CN200710020792 A CN 200710020792A CN 101037809 A CN101037809 A CN 101037809A
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Abstract
The invention discloses a continuous electrospinning method for polyamide 6/66 copolymer filament yarns. The polymer particles dissolve in formic acid to obtain 10-25% of spinning fluid by mass percent. The bath liquid is prepared by peregal O, using electrospinning method. Under high voltage electrostatic field, fibres of millimicron or submicron size are formed by unstable scourge action and multiple splitting. The fibres are accumulated in the surfactant bath liquid and the residual solvent diffuses in the liquid. After accumulating, the fibres are winded into initial yarns, and then through heating and succeeding stretch, the polyamide 6/66 copolymer filament yarns are obtained. The said polyamide 6/66 copolymer filament yarns formed by fibres with diameter of hundreds nanometer are prepared in the invention, and there in no broken thread during continuous spinning for above 12 hours. At the same time, the invention solves the problem that it is difficult to effectivle improve the structure and performance of fibre through suceeding stretch and heat setting processing by the general electrospinning method.
Description
Technical field
The present invention relates to a kind of spinning process of filament yarn, be specifically related to a kind of employing electrospinning process polyamide 6/66 copolymers are carried out the method for continuous spinning filament yarn yarn.
Background technology
Electrostatic spinning is a kind of simple spining technology, utilize this spinning process can prepare diameter from the number nanometers to the several microns fibers that do not wait, and its manufacturing nano-scale fiber ability, more make this technology in recent years, obtain fast development.At present, the product form that obtains by electrostatic spinning substantially all is the non-weaving cloth that fiber is the random alignment state, and product has potential using value at aspects such as filtering material, organizational project matrix, wound dressing and useful for drug delivery material, biomimetic material, fibre reinforced composites.The advantage of the non-weaving cloth flaky material that directly obtains by electrostatic spinning can directly be used, but exist that the mechanical property of fiber is relatively poor, fiber assembly structural disorder and secondary operations wayward, product defective such as be restricted, can only be used with single form.If the method that can adopt electrostatic spinning is the filament yarn that is made of Sub-micro Fibers of spinning continuously, then will have great importance at the structure of improving product by secondary operations and performance, the aspects such as Application Areas enriching the form of final products and enlarge product by weaving processing.
In order to obtain the static textile product that fiber is the state of being arranged in parallel, the researcher has also carried out a series of improvement aspect the method for electrostatic spinning, and topmost have the following aspects: the cylinder that 1. general plane electric conductivity receiving screen is changed into rotation; 2. with having the slim runner of sharp edges as receiving system; 3. on gathering-device, add auxiliary electrode or electric field; 4. use metal framework as receiving screen; 5. the framework that in stream range, vibrates ground connection; 6. positive and negative electrode is connected on two spinning heads staggered relatively, and collects fiber with the cylinder of rotation; 7. fiber is spun in the surface plate that fills deionized water or fill in the bath of coagulating bath, be wound on the cylinder after collecting fibre bundle; 8. with the gathering system of two electric conductivity collecting rings that are arranged in parallel as electrostatic spinning fiber; 9. will twist again behind the electrostatic spinning fiber boundling and reel.Above several for the improved fiber collecting method of static textile product that is arranged in parallel of preparation fiber in, some can spin and obtain the yarn that formed by the collection of filaments, as: method is 6., 7. and 9..Some can only obtain the plates that are made of the fiber that is arranged in parallel or the fibre bundle of limited length, as: method is 1., 3., 4. and 8..But these methods can't realize that all long-time (more than 10 hours) of yarn spin continuously, and basic in the spinning system do not have first spinning is not carried out the processing of online back with the structure of improving fiber, the uniformity of yarn and the mechanism of mechanical property yet.
Polyamide, be commonly called as nylon, be contain on the molecular backbone recurring amide radical group-[NHCO]-the general name of thermoplastic resin, du pont company is developed at first, realize industrialization in nineteen thirty-nine, obtained using widely owing to it has good comprehensive performances and is easy to processing.Principal item wherein is polyamide 6 and polyamide 66, also has polyamide 11,12 etc. and multiple copolymer in addition.Polyamide 6/66 copolymers receive publicity because of its high strength and high elasticity.
Summary of the invention
The object of the invention provides a kind of employing electrostatic spinning technique polyamide 6/66 copolymers is carried out the method for continuous spinning, with the filament yarn that obtains to be made of Sub-micro Fibers.
For achieving the above object, the technical solution used in the present invention is: the continuously static spinning method of a kind of polyamide 6/66 copolymer filament yarns, comprise the following steps: polyamide 6/66 copolymer particles are dissolved in the formic acid, make the spinning solution of mass percent 10～25%, paregal O is dissolved in the body lotion that makes mass percent 0.4～1.2% in the deionized water, adopt electrospinning process, spinning solution is poured in the spin duct, the positive pole that connects high pressure generator, body lotion places in the bath, the negative pole that connects high pressure generator, body lotion, form fibre bundle from the spinning solution of spin duct ejection, fiber behind the boundling obtains spinning just through winding shaping, again through the hot-stretch typing, promptly obtains to have polyamide 6/66 copolymer filament yarns of excellent mechanical performances.
In the technique scheme, during described electrostatic spinning, voltage is 8～20 kilovolts, and spinning head is 3～13 centimetres to the difference in height of bath surface, and winding speed is not more than 7 meters/minute.
The heating-up temperature that described spinning is just stretched is 90～120 ℃, and draw ratio is 0.5～3.0, and drawing process can carry out once or twice as required.
Operation principle of the present invention is: at normal temperatures, be dissolved in polyamide 6/66 copolymer spinning fluid jets in the formic acid under the effect of high-pressure electrostatic field force, moving and the multistage division through the unstability whip and form nanoscale or Sub-micro Fibers, make the collection of filaments in the surfactant body lotion, residual solvent in the fiber spreads therein, the lubricity on surface increased when fiber further solidified, easy fracture not in after-drawing and winding process.Fiber behind the boundling is wound on the bobbin by the form of winding shaping mechanism with filament yarn, and what obtain thus spins for first.Install heater additional between boundling place and winding shaping mechanism, make behind the strand boundling by the thermal treatment zone and shaping area, be wound into tube again, then can make spun yarn obtain to a certain degree stretching by improving winding speed, this is called " one-off drawing yarn "; After this yarn carried out secondary hot-stretch typing, the structure of yarn and performance are further improved, are referred to as " succeeding stretch yarn ".Use that this electrostatic spinning system obtains that polyamide 6/66 copolymer filament yarns have continuity is good, characteristics such as line density is even.The yarn that just spins has certain intensity and bigger elongation, and after the hot-stretch typing, the fracture strength of yarn is significantly improved, and elongation at break obviously reduces, and meets the instructions for use of weaving processing technology to yarn.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. the present invention transforms fiber collecting method and gathering-device in the common electrospinning process, utilize the surfactant body lotion to collect fiber, and the boundling fiber reeled, thereby having prepared by diameter is polyamide 6/66 copolymer filament yarns that the fiber of hundreds of nanometers constitutes, and can reach the continuous broken end that do not have more than 12 hours in the spinning process.
2. the present invention has increased secondary hot-stretch typing and secondary coiling on the basis of common electrostatic spinning, by hot-stretch typing and the further improvement of adjustment of winding speed and the structure and the performance of controlling fiber to yarn, formed a kind of continuous electro-spinning technology and method of novel submicron order synthetic fiber filament yarn, changed the single product form of existing electrostatic spinning product, and solved general electrospinning process and be difficult to improve the structure of fiber and the problem of performance effectively by the secondary operations of material based on non-weaving cloth.
Description of drawings
Accompanying drawing 1 is the electrostatic spinning system structural representation that adopts in the embodiment of the invention one.
Wherein: 1, spin duct; 2, high voltage source; 3, capillary; 4, thread; 5, bath; 6, godet roller; 7, heater; 8, tension force guider; 9, coiler device.
The specific embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one: the continuously static spinning method of a kind of polyamide 6/66 copolymer filament yarns, and it is in 88% the formic acid that polyamide 6/66 copolymer particles are dissolved in concentration, makes the spinning solution of mass percent 10～25%; Paregal O is dissolved in the body lotion that makes mass percent 0.4～1.2% in the deionized water.
The method that adopts electrostatic spinning is spun surface at body lotion with above-mentioned spinning solution under certain process conditions, from body lotion with after the collection of filaments of basic solidification forming on winding drum around 2～3 circles, can carry out the continuous spinning of polyamide 6/66 copolymer filament yarns then.
Described spinning process condition:
Room temperature condition, relative humidity are 50～70%
Voltage 8-20kv
Spinning head is to the height 3～13cm of body lotion
Distance 10～the 50cm that reels
Winding speed is 0～7m/min
The temperature of heater is 90～120 ℃
Under above-mentioned process conditions, the time of continuous spinning (not having broken end), the line density of the first yarn that obtains was 0.6～2.85dtex more than 12h, and the average diameter of fiber is between 150～500nm, the fracture strength of yarn is 0.55～1.4cN/dtex, and elongation at break is 70%～180%.
Because just the extension at break of yarn is bigger, fracture strength is lower, and therefore the first yarn that will obtain carries out the succeeding stretch typing.The stretching of yarn is to utilize the linear differential of two cylinders to realize.Concrete technology is: yarn is moved back from a cylinder separate, by being wound up on another swing roller behind the thermal treatment zone and the shaping area.Heating-up temperature is 90～120 ℃, and draw ratio is 0.5～3.0.
Yarn breakage elongation through above-mentioned processing has reduced 20-120%, and fracture strength has improved 20-90%, has reached 1.08-2.05cN/dtex.
The spinning system that realizes said method mainly comprises several sections such as high voltage source 2, electrostatic spinning device, bath 5, godet roller 6, heater 7, tension force guider 8, coiler device 9, temperature speed control cabinet.Accompanying drawing 1 is the schematic diagram of spinning system.Wherein the temperature range of heater is 0～150 ℃, and the velocity interval of coiler device is 0～150m/min, and spinning at room temperature can be carried out.
The formic acid solution of polyamide 6/66 copolymers is poured in the spin duct 1, adjust spinning head to the distance between the interior bath surface of bath 5 and the voltage of high pressure generator, negative pole is through surfactant body lotion ground connection, high pressure generator makes spinning solution charged, and makes between taylor cone and the bath and produce high voltage electric field.The flow of regulating the spinning solution in the capillary 3 is sagging naturally to spinning mouth place dripless, make spinning solution form stable thread 4, thread accelerated motion and split into thread bunch under the effect of electrostatic force, surface at bath can be split into the fibre bundle that diameter reaches nanoscale or submicron order, with glass bar with fibre bundle slowly drawing-off go out bath and successively by godet roller 6, heater 7, tension force guider 8 etc., finally be wound up on the swing roller, can carry out the continuous spinning of filament yarn subsequently.
Embodiment two:
2g polyamide 6/66 copolymer particles are dissolved in the formic acid of 11.3g, after fully stirring, make the spinning solution of mass percent 15%.The paregal O of 4g is dissolved in the paregal O solution that forms mass percent 0.4% in the deionized water of 996g.In temperature about 25 ℃, about relative humidity 65%, voltage 11kv, setting temperature is 95 ℃, and winding speed 2m/min, spinning head are the average linear density 1.05dtex of the first yarn that obtains under the condition of 4.5cm to the height of liquid level, the average diameter of fiber is 187nm, the elongation at break of yarn is 87%, and fracture strength is 0.74cN/dtex, and the continuous spinning time is 12.5h.The yarn that spins carried out 50% heat (95 ℃) drawing and setting under similarity condition, the elongation at break of yarn drops to 57%, and fracture strength is brought up to 1.12cN/dtex, compares with first yarn, elongation at break has reduced by 34.5%, and fracture strength has improved 51.4%.
Embodiment three: 2g polyamide 6/66 copolymer particles are dissolved in the formic acid of 8g, make the spinning solution of mass percent 20% after fully stirring.The paregal O of 6g is dissolved in the paregal O solution that forms mass percent 0.6% in the deionized water of 994g.In temperature about 25 ℃, about relative humidity 65%, voltage 13kv, setting temperature is 95 ℃, and winding speed 5m/min, spinning head are the average linear density 1.25dtex of the first yarn that obtains under the condition of 5.5cm to the height of liquid level, the average diameter of fiber is 292nm, the elongation at break of yarn is 108%, and fracture strength is 0.81cN/dtex, and the continuous spinning time is 13h.The yarn that spins carried out 70% heat (95 ℃) drawing and setting under similarity condition, the elongation at break of yarn drops to 53%, and fracture strength is brought up to 1.35cN/dtex, compares with first yarn, elongation at break has reduced by 50.9%, and fracture strength has improved 66.7%.
Embodiment four: 2g polyamide 6/66 copolymer particles are dissolved in the formic acid of 6g, make the spinning solution of mass percent 25% after fully stirring.The paregal O of 8g is dissolved in the paregal O solution that forms mass percent 0.8% in the deionized water of 992g.In temperature about 25 ℃, about relative humidity 65%, voltage 15kv, setting temperature is 95 ℃, and winding speed 3m/min, spinning head are the average linear density 1.62dtex of the first yarn that obtains under the condition of 6.5cm to the height of liquid level, the average diameter of fiber is 224nm, the elongation at break of yarn is 133.4%, and fracture strength is 0.88cN/dtex, and the continuous spinning time is 13.6h.The yarn that spins carried out 80% heat (95 ℃) drawing and setting under similarity condition, the elongation at break of yarn drops to 43.2%, and fracture strength is brought up to 1.64cN/dtex, compares with first yarn, elongation at break has reduced by 67.6%, and fracture strength has improved 86.4%.
Claims (3)
1. the continuously static spinning method of polyamide 6/66 copolymer filament yarns, it is characterized in that, comprise the following steps: polyamide 6/66 copolymer particles are dissolved in the formic acid, make the spinning solution of mass percent 10～25%, paregal O is dissolved in the body lotion that makes mass percent 0.4～1.2% in the deionized water, adopt electrospinning process, spinning solution is poured in the spin duct, the positive pole that connects high pressure generator, body lotion places in the bath, the negative pole that connects high pressure generator, body lotion, form fibre bundle from the spinning solution of spin duct ejection, fiber behind the boundling obtains spinning just through winding shaping, through the hot-stretch typing, promptly obtains polyamide 6/66 copolymer filament yarns again.
2. the continuously static spinning method of filament yarn according to claim 1 is characterized in that: during described electrostatic spinning, voltage is 8～20 kilovolts, and spinning head is 3～13 centimetres to the difference in height of bath surface, and winding speed is not more than 7 meters/minute.
3. the continuously static spinning method of filament yarn according to claim 1 is characterized in that: the heating-up temperature that described spinning is just stretched is 90～120 ℃, and the multiple of stretching is 0.5～3.0.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845680A (en) * | 2010-04-08 | 2010-09-29 | 苏州大学 | Carbon nano tube/polyamide 6 composite nano fiber filament yarn and preparation method thereof |
| CN101845675A (en) * | 2010-05-10 | 2010-09-29 | 北京化工大学 | Electrostatic spinning method and device for preparing nano long fibers arranged in single direction along fiber axis |
| CN103760835A (en) * | 2013-09-27 | 2014-04-30 | 广东工业大学 | Control system and method for continuous-nanometer-fiber medical yarn device |
| CN103993376A (en) * | 2014-04-30 | 2014-08-20 | 苏州大学 | Electrostatic spinning device for manufacturing nanometer fiber bundles |
| CN104053829A (en) * | 2011-10-11 | 2014-09-17 | 奥斯瓦道·克鲁兹基金会 | Process for producing polymeric structures that have activated surfaces and activated polymeric structures |
| CN104480546A (en) * | 2015-01-19 | 2015-04-01 | 上海理工大学 | Electrospinning paralleling shaft spinning head with angle correlation and application |
| CN104775170A (en) * | 2015-04-30 | 2015-07-15 | 广西师范学院 | Electrostatic spinning continuous collection device |
| CN106319647A (en) * | 2016-10-21 | 2017-01-11 | 上海工程技术大学 | Method for preparing nanofiber aggregate and pretreatment device |
| CN107326454A (en) * | 2017-06-09 | 2017-11-07 | 东华大学 | A kind of method that electrostatic spinning prepares auxetic nano-fibre yams |
| CN113122947A (en) * | 2021-04-25 | 2021-07-16 | 江苏新视界先进功能纤维创新中心有限公司 | Multi-base color-changing luminescent fiber with antibacterial property and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845680A (en) * | 2010-04-08 | 2010-09-29 | 苏州大学 | Carbon nano tube/polyamide 6 composite nano fiber filament yarn and preparation method thereof |
| CN101845675A (en) * | 2010-05-10 | 2010-09-29 | 北京化工大学 | Electrostatic spinning method and device for preparing nano long fibers arranged in single direction along fiber axis |
| EP2767623A4 (en) * | 2011-10-11 | 2015-07-08 | Fundaç O Oswaldo Cruz | Process for producing polymeric structures that have activated surfaces and activated polymeric structures |
| CN104053829A (en) * | 2011-10-11 | 2014-09-17 | 奥斯瓦道·克鲁兹基金会 | Process for producing polymeric structures that have activated surfaces and activated polymeric structures |
| CN103760835A (en) * | 2013-09-27 | 2014-04-30 | 广东工业大学 | Control system and method for continuous-nanometer-fiber medical yarn device |
| CN103993376A (en) * | 2014-04-30 | 2014-08-20 | 苏州大学 | Electrostatic spinning device for manufacturing nanometer fiber bundles |
| CN103993376B (en) * | 2014-04-30 | 2017-06-06 | 苏州大学 | A kind of electrostatic spinning apparatus for preparing bundles of nanofibers |
| CN104480546A (en) * | 2015-01-19 | 2015-04-01 | 上海理工大学 | Electrospinning paralleling shaft spinning head with angle correlation and application |
| CN104775170A (en) * | 2015-04-30 | 2015-07-15 | 广西师范学院 | Electrostatic spinning continuous collection device |
| CN104775170B (en) * | 2015-04-30 | 2017-11-24 | 广西师范学院 | A kind of continuously trapping system of electrostatic spinning |
| CN106319647A (en) * | 2016-10-21 | 2017-01-11 | 上海工程技术大学 | Method for preparing nanofiber aggregate and pretreatment device |
| CN107326454A (en) * | 2017-06-09 | 2017-11-07 | 东华大学 | A kind of method that electrostatic spinning prepares auxetic nano-fibre yams |
| CN107326454B (en) * | 2017-06-09 | 2019-11-08 | 东华大学 | A kind of method of electrostatic spinning preparation auxetic nano-fibre yams |
| CN113122947A (en) * | 2021-04-25 | 2021-07-16 | 江苏新视界先进功能纤维创新中心有限公司 | Multi-base color-changing luminescent fiber with antibacterial property and preparation method thereof |
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| CN100575572C (en) | 2009-12-30 |
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Application publication date: 20070919 Assignee: Zhejiang Mesbon Chemical Fibre Limited Assignor: Soochow University Contract record no.: 2010330000393 Denomination of invention: Continuous electrostatic spinning method of polyamide 6/66 copolymer filament yarn Granted publication date: 20091230 License type: Exclusive License Record date: 20100402 |
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Address after: Suzhou City, Jiangsu province 215137 Xiangcheng District Ji Road No. 8 Patentee after: Soochow University Address before: 215123 Suzhou City, Suzhou Province Industrial Park, No. love road, No. 199 Patentee before: Soochow University |
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