CN102021665B - Preparation method of ultrahigh molecular weight polyamide 6 fiber - Google Patents
Preparation method of ultrahigh molecular weight polyamide 6 fiber Download PDFInfo
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- CN102021665B CN102021665B CN 200910092063 CN200910092063A CN102021665B CN 102021665 B CN102021665 B CN 102021665B CN 200910092063 CN200910092063 CN 200910092063 CN 200910092063 A CN200910092063 A CN 200910092063A CN 102021665 B CN102021665 B CN 102021665B
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Abstract
The invention belongs to the field of the preparation of polyamide fibers. In the technical scheme, the invention comprises the following steps of: extruding an ultrahigh molecular weight polyamide 6 spinning solution which contains calcium chloride serving as a complexing agent from a spinning pack, introducing the spinning solution into a coagulating bath composed of tetrachloroethane and trichloromethane for quenching into a primary gelatin silk, stretching the primary gelatin silk at room temperature, decomplexing in a mixed solution of ethanol and water, then heat stretching, and finally heat setting to obtain an ultrahigh molecular weight polyamide 6 fiber. In the invention, the stretching of the polyamide 6 fiber can be over eight times, the fiber maximum strength can reach 70.3GPa, and the breaking strength is over 0.4Gpa.
Description
Technical field
The invention belongs to the preparation field of polyamide fiber, particularly a kind of gel spinning method of super high molecular weight daiamid-6 fiber.
Background technology
The polyamide 6 molecule contain the polarity amide groups (CO-NH-), wherein-NH-forms intermolecular hydrogen bonding with-C=O, causes polyamide 6 to have higher degree of crystallinity, makes the fusing point of polyamide 6 up to 220 ℃, is higher than polyethylene fiber.And wear-resisting, corrosion-resistant, advantages such as adhesiveness is good, easy dyeing that daiamid-6 fiber has are the good raw materials of industry cloth, building, high-performance hawser.The method for preparing daiamid-6 fiber up to now both at home and abroad has gel spinning of plasticising melt spinning, dry spinning, polyamide 6/benzyl alcohol solution etc.; Wherein the performance of dry spinning gained daiamid-6 fiber is best; The fiber maximum intensity is 0.8GPa; High-modulus is 19GPa, but differs greatly with the theoretical strength 28GPa and the theoretical modulus 263GPa of daiamid-6 fiber.The reason that causes this situation is many-sided, concludes and gets up to mainly contain following two aspects:
(1) degree of polymerization of polyamide 6 and the stereoregularity of self.The relative molecular mass of the polyamide 6 of mentioning in commercialization at present or the document is often less, and limited macromolecular chain length makes that molecular end increases in the fiber, so the tiny flaw on the fibre structure must increase;
(2) super drawing of daiamid-6 fiber.The key for preparing high-intensity fiber from the flexible chain macromolecule is that folding macromolecular chain is stretched and orientation along fiber axis direction height; For polyamide 6; Because the amide groups on the strand forms intermolecular hydrogen bonding each other easily, and it is suitable with destroying a C-C covalent bond to destroy the energy that 5 hydrogen bonds need.Stretch in the process in molecules align, the effect of strong hydrogen bonding makes the draw ratio of polyamide 6 have only about 6, if further stretch, will destroy the C-C covalent bond, causes forming high orientation.
Therefore, the high key of strengthening of daiamid-6 fiber is: adopt suitable polymerization technique, prepare the polyamide 6 polymer of high molecular weight, obtain the good spun filament of tensile property with suitable spinning process.Effect through reduction intermolecular hydrogen bonding before stretching reaches high draw ratio, then manages to increase the effect of intermolecular hydrogen bonding, promptly increases the physical crosslinking point between the molecule, thereby makes the daiamid-6 fiber of high draw ratio obtain corresponding high intensity and modulus.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of super high molecular weight daiamid-6 fiber,, satisfy the needs of association area development to overcome the defective that prior art exists.
The preparation method of a kind of super high molecular weight daiamid-6 fiber provided by the present invention may further comprise the steps:
1) be 18～24 polyamide 6 according to the mol ratio of complexing agent and polyamide 6 unit's chain link with complexing agent calcium chloride and relative viscosity be 0.1～0.2 to be dissolved in the formic acid, the concentration that obtains polyamide 6 is the spinning solution of 14～20wt%, and deaeration under nitrogen protection;
2) spinning solution being extruded into continuous filament yarn through filament spinning component, to get into temperature be that quenching is solidified in 10～20 ℃ the coagulating bath, obtains nascent gel fiber through reeling; The spinning pressure of described spinning pack is 0.3～0.8MPa, and temperature is 30～50 ℃; Described coagulating bath is that tetrachloroethanes and chloroform are 3: 1 mixed liquor by volume;
3) gel fiber of will coming into being at room temperature stretches after 6～8 times, is soaked in separating that the second alcohol and water mixed in 1: 1 by volume and separates complexing 2～6h in the complexing agent;
4) will separate strand after the complexing 1.2～2 times of 180～200 ℃ of stretched, again in 120～140 ℃ of HEAT SETTING 10-20min.
Wherein, in the step 1) spinning solution is left standstill deaeration in 24～36 hours under nitrogen protection; Or with spinning solution centrifugal 30-40min deaeration under nitrogen protection.The diameter of the spinneret orifice of the spinning pack step 2) is 0.25～0.5mm, and draw ratio is 1: 10～1: 30.The preferred spinning pressure of spinning pack is 0.3～0.4MPa.
Daiamid-6 fiber can obtain the stretching more than 8 times among the present invention, and the intensity maximum of fiber can reach 70.3GPa, and fracture strength is more than 0.4GPa.
Below in conjunction with the specific embodiment the present invention is described further.
The specific embodiment
Embodiment 1
With complexing agent calcium chloride and relative viscosity is that 18 polyamide 6 is dissolved in the formic acid, and the mass fraction that obtains polyamide 6 is 20% spinning solution, and wherein the mol ratio of complexing agent and polyamide 6 unit chain link is 0.1.Under the room temperature, with spinning solution evacuation and centrifugal degassing 30min.Spinning solution is controlled to be 30 ℃ through temperature; Pressure control is 0.3MPa, and draw ratio is 1: 10, and orifice diameter is that the filament spinning component of 0.25mm extrudes that to get into temperature be in 10 ℃ the coagulating bath; It is 3: 1 tetrachloroethanes and chloroform that this coagulating bath contains volume ratio; Immersion length is 0.5m, and the speed that fiber goes out coagulating bath is 0.5m/min, reels to obtain nascent gel fiber.Adopt stretcher that the nascent gel fiber of polyamide 6 is at room temperature stretched after 6 times, under room temperature, be soaked in to separate and handle 2h in the complexing agent, this separates complexing agent, and to contain volume ratio be 1: 1 second alcohol and water.With separating strand after the complexing 1.2 times of 180 ℃ of stretched, then at 140 ℃ of following HEAT SETTING 10min.The total drawing ratio of resulting daiamid-6 fiber is 7.2 times, and modulus is 11.2GPa, and fracture strength is 0.26GPa, and elongation at break is 30%.
Embodiment 2
With complexing agent calcium chloride and relative viscosity is that 24 polyamide 6 is dissolved in the formic acid, and the mass fraction that obtains polyamide 6 is 14% spinning solution, and wherein the mol ratio of complexing agent and polyamide 6 unit chain link is 0.2.Under the room temperature, with spinning solution standing and defoaming 24h.Spinning solution is controlled to be 50 ℃ through temperature; Pressure control is 0.8MPa, and draw ratio is 1: 10, and orifice diameter is that the filament spinning component of 0.5mm extrudes that to get into temperature be in 20 ℃ the coagulating bath; It is 3: 1 tetrachloroethanes and chloroform that this coagulating bath contains volume ratio; Immersion length is 0.5m, and the speed that fiber goes out coagulating bath is 0.5m/min, reels to obtain nascent gel fiber.Adopt stretcher that the nascent gel fiber of polyamide 6 is at room temperature stretched after 7 times, under room temperature, be soaked in to separate and handle 6h in the complexing agent, this separates complexing agent, and to contain volume ratio be 1: 1 second alcohol and water.With separating strand after the complexing 1.4 times of 200 ℃ of stretched, then at 140 ℃ of following HEAT SETTING 20min.The total drawing ratio of resulting daiamid-6 fiber is 9.8 times, and modulus is 28.7GPa, and fracture strength is 0.34GPa, and elongation at break is 24%.
Embodiment 3
With complexing agent calcium chloride and relative viscosity is that 19.44 polyamide 6 is dissolved in the formic acid, and the mass fraction that obtains polyamide 6 is 16% spinning solution, and wherein the mol ratio of complexing agent and polyamide 6 unit chain link is 0.15.Under the room temperature, with spinning solution standing and defoaming 36h.Spinning solution is controlled to be 40 ℃ through temperature; Pressure control is 0.4MPa, and draw ratio is 1: 30, and orifice diameter is that the filament spinning component of 0.25mm extrudes that to get into temperature be in 10 ℃ the coagulating bath; It is 3: 1 tetrachloroethanes and chloroform that this coagulating bath contains volume ratio; Immersion length is 0.5m, and the speed that fiber goes out coagulating bath is 0.5m/min, reels to obtain nascent gel fiber.Adopt stretcher that the nascent gel fiber of polyamide 6 is at room temperature stretched after 8 times, under room temperature, be soaked in to separate and handle 6h in the complexing agent, this separates complexing agent, and to contain volume ratio be 1: 1 second alcohol and water.With separating strand after the complexing 1.3 times of 200 ℃ of stretched, then at 140 ℃ of following HEAT SETTING 10min.The total drawing ratio of resulting daiamid-6 fiber is 10.4 times, and modulus is 70.3GPa, and fracture strength is 0.41GPa, and elongation at break is 28%.
Although the present invention has been done detailed explanation and has quoted some instantiations as proof, for a person skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (4)
1. the preparation method of a super high molecular weight daiamid-6 fiber is characterized in that, may further comprise the steps:
1) be 18～24 polyamide 6 according to the mol ratio of complexing agent and polyamide 6 unit's chain link with complexing agent calcium chloride and relative viscosity be 0.1～0.2 to be dissolved in the formic acid, the concentration that obtains polyamide 6 is the spinning solution of 14～20wt%, and deaeration under nitrogen protection;
2) spinning solution being extruded into continuous filament yarn through filament spinning component, to get into temperature be that quenching is solidified in 10～20 ℃ the coagulating bath, obtains nascent gel fiber through reeling; The spinning pressure of described spinning pack is 0.3～0.8MPa, and temperature is 30～50 ℃; Described coagulating bath is that tetrachloroethanes and chloroform are 3: 1 mixed liquor by volume;
3) gel fiber of will coming into being at room temperature stretches after 6～8 times, is soaked in separating that the second alcohol and water mixed in 1: 1 by volume and separates complexing 2～6h in the complexing agent;
4) will separate strand after the complexing 1.2～2 times of 180～200 ℃ of stretched, again in 120～140 ℃ of HEAT SETTING 10-20min.
2. method according to claim 1 is characterized in that, in the step 1) spinning solution is left standstill deaeration in 24～36 hours under nitrogen protection; Or with spinning solution centrifugal 30-40min deaeration under nitrogen protection.
3. method according to claim 1 is characterized in that step 2) described in the diameter of spinneret orifice of spinning pack be 0.25～0.5mm, draw ratio is 1: 10～1: 30.
4. method according to claim 1 is characterized in that, the spinning pressure of described spinning pack is 0.3～0.4MPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910092063 CN102021665B (en) | 2009-09-21 | 2009-09-21 | Preparation method of ultrahigh molecular weight polyamide 6 fiber |
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| CN 200910092063 CN102021665B (en) | 2009-09-21 | 2009-09-21 | Preparation method of ultrahigh molecular weight polyamide 6 fiber |
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| CN102021665A CN102021665A (en) | 2011-04-20 |
| CN102021665B true CN102021665B (en) | 2012-07-11 |
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| CN103422179B (en) * | 2012-05-16 | 2016-04-13 | 中国石油化工股份有限公司 | The defoaming method of carbon fiber spinning primary fluid |
| CN110952162B (en) * | 2019-12-13 | 2022-06-24 | 招金矿业股份有限公司蚕庄金矿 | Method for preparing low-crystallinity high-elasticity nylon 66 by using gold extraction waste liquid |
| CN112501812B (en) * | 2020-11-05 | 2022-07-05 | 江苏文明人造草坪有限公司 | Artificial turf with high single-cluster pull-out force and preparation process thereof |
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