CN101307509A - Ultra-high molecular weight polyethylene fiber spinning method - Google Patents
Ultra-high molecular weight polyethylene fiber spinning method Download PDFInfo
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- CN101307509A CN101307509A CNA2007100406782A CN200710040678A CN101307509A CN 101307509 A CN101307509 A CN 101307509A CN A2007100406782 A CNA2007100406782 A CN A2007100406782A CN 200710040678 A CN200710040678 A CN 200710040678A CN 101307509 A CN101307509 A CN 101307509A
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Abstract
The invention relates to a novel spinning method for ultrahigh molecular weight polyethylene fiber, which belongs to the polymer material preparation technical field. A certain amount of silicon oil or a derivative thereof is added during the spinning, the silicon oil or the derivative thereof, ultrahigh molecular weight polyethylene powder and solvent can be injected into an untwisting kettle according to the proportion, the high shear is performed in the solvent to ensure that giant molecules of ultrahigh molecular weight polyethylene are appropriately untwisted to form uniform mixed emulsion, then the mixed emulsion passes through a storage tank, is stirred and quantificationally fed into a screw extruder for extruding spinning at the same time, and a high strength and high modulus polyethylene fiber finished product is produced through cooling, solidification, extraction, drying and ultra-drawing. Or a certain amount of the silicon oil or the derivative thereof is added into coagulation bath, and extruded fiber is cooled, solidified, extracted, dried and ultra-drawn to produce the high strength and high modulus polyethylene fiber finished product. The silicon oil or the derivative thereof contained in the fiber accounts for 0.05 to 5 percent of the weight of the fiber, the fiber at least obtains more than 20 times of drawing, the strength of the fiber reaches 30cN/dtex, and the modulus is more than 1000 cN/dtex.
Description
The present invention relates to a kind of ultra-high molecular weight polyethylene fiber spinning method.
The super high molecular weight polyethylene gel spinning by ultra-drawing prepare high strength, high-modulus polyethylene fiber has entered suitability for industrialized production.Polyethylene gel spins relevant patent EP0205960A, and EP0213208A1 also has US4413110, WO01/73173A1, and EP1746187A1 etc. are many to be improved spining technology.The letter of super high molecular weight polyethylene gel spinning key step is chatted as follows: ultra-high molecular weight polyethylene is added in the suitable solvent stirring and dissolving make solution, solution is extruded by screw extruder, through the spinneret orifice moulding, cool off then, extraction, dry ultra-drawing, finally obtain finished fiber.Wherein obtaining dissolving uniform high polymeric solution is crucial with even ultra-drawing.Their uniformity is the prerequisite of finished fiber stable performance.Because the size of supra polymer is huge, exist mutually again between the big molecule and tangle, but the stretching ratio that helps improving fiber that tangles between the big molecule obtains high orientation, makes fiber reach high strength and modulus.But the various viscoplasticity effects that too much and strong big intermolecular entanglement causes in the high polymer make to stretch and become much complicated, are unfavorable for ultra-drawing again, and big intermolecular entanglement is discongested.By adding additive the entanglement state is changed, and be easy to carry out ultra-drawing.
The frozen glue undrawn yarn of making can have surprising high magnification to stretch λ max ∝ V～1/ て
λ max is the maximum tension multiplying power, and V is a draw speed, and て is the relaxation time of fiber.
Draw speed is subjected to industrial restriction, and the relaxation time of change fiber is drawn strand simultaneously effectively and can be reached ultra-drawing from crystallization, finally obtain high strength, high-modulus finished fiber.
New method of the present invention is: add a certain amount of silicone oil or derivatives thereof in the process of spinning, the silicone oil or derivatives thereof can be injected to separate with ultra-high molecular weight polyethylene powder and solvent in proportion and twine in the still, high shear makes between the big molecule of ultra-high molecular weight polyethylene appropriateness separate to twine in solvent, form the mixed liquid of homogeneous emulsion form, the mixed liquid of emulsion form passes through storage tank then, quantitatively feed the screw extruder extruding spinning while stirring, cool off, solidify, extraction, dry ultra-drawing get high strength and modulus finished product polyethylene fiber.Or a certain amount of silicone oil or derivatives thereof added in the coagulating bath, the fiber of extruding through cool off, solidify, extraction, dry ultra-drawing get high strength and modulus finished product polyethylene fiber.The silicone oil or derivatives thereof that contains in the fiber is the 0.05%-5% of fibre weight, and fiber obtains the stretching more than 20 times at least, and the intensity of fiber reaches 30cN/dtex, and modulus is more than 1000cN/dtex.
Example 1
Ultra-high molecular weight polyethylene (average molecular mass 4,500,000 relatively); dissolvant white oil (70#) is that 10% (weight) is injected to separate respectively and twined in the still with above-mentioned polyethylene and white oil by nominal concentration at room temperature; add 1% epoxide modified silicone oil simultaneously; nitrogen protection down cut 5 minutes, shear rate 3000 seconds
-1, obtain the mixed liquid input of homogeneous emulsion form storage tank and quantitatively feed double screw extruder while stirring.Extruder diameter 25mm, L/D=(24), temperature is controlled at 250 ℃, screw extruder rotating speed 30rpm. extrudate sprays from spinneret orifice after measuring pump is measured through the filter casing, go into water-bath then and extract dry ultra-drawing after treatment, the stretching general times is 40, and the fibre strength that obtains reaches 30cN/dtex, and modulus is more than 1000cN/dtex.
Example 2
Ultra-high molecular weight polyethylene (relatively average molecular mass 5,000,000), dissolvant white oil (90#) are that 12% (weight) is injected to separate respectively and twined in the still nitrogen protection down cut 10 minutes, shear rate 2000 seconds with above-mentioned polyethylene and white oil by nominal concentration at room temperature
-1, obtain the mixed liquid input of homogeneous emulsion form storage tank, quantitatively feed double screw extruder while stirring.Extruder diameter 25mm, L/D=(24), temperature is controlled at 250 ℃, screw extruder rotating speed 30rpm.Extrudate sprays from spinneret orifice after measuring pump is measured through the filter casing, gone into to add the water-bath of 1.5% epoxide modified silicone oil then, extraction after treatment, dry, ultra-drawing, the stretching general times is 40, the fibre strength that obtains reaches 35cN/dtex, and modulus is more than 1050cN/dtex.
Example 3
Ultra-high molecular weight polyethylene (average molecular mass 4,500,000 relatively); dissolvant white oil (90#); be that 10% (weight) is injected to separate and twined in the still by nominal concentration at room temperature with white oil; to be 10% weight by spiral propeller add to separate with 0.5kg/Min speed ultra-high molecular weight polyethylene twines in the still with nominal concentration; the following sheared edge of nitrogen protection adds shear rate 1000 seconds
-1, obtain the mixed liquid input of homogeneous emulsion form storage tank and quantitatively feed double screw extruder while stirring.Extruder diameter 25mm, L/D=(24), temperature is controlled at 250 ℃.Screw extruder rotating speed 30rpm.Extrudate sprays from spinneret orifice after measuring pump is measured through the filter casing.The water-bath of having gone into to add 2% polyethers-epoxide modified silicone oil then extracts after treatment, dry, ultra-drawing, and the stretching general times is 40, and the fibre strength that obtains reaches 30cN/dtex, and modulus is more than 1000cN/dtex.
Claims (10)
- A ultra-high molecular weight polyethylene fiber spinning method it comprise: in the process of spinning, add a certain amount of silicone oil or derivatives thereof, the silicone oil or derivatives thereof can be injected to separate with ultra-high molecular weight polyethylene powder and solvent in proportion and twine in the still, high shear makes between the big molecule of ultra-high molecular weight polyethylene appropriateness separate to twine in solvent, form the mixed liquid of homogeneous emulsion form, the mixed liquid of emulsion form passes through storage tank then, quantitatively feed the screw extruder extruding spinning while stirring, cooling, solidify, extraction, dry ultra-drawing gets high strength and modulus finished product polyethylene fiber.Also a certain amount of silicone oil or derivatives thereof can be added in the coagulating bath, the fiber of extruding through cool off, solidify, extraction, dry ultra-drawing get high strength and modulus finished product polyethylene fiber.The silicone oil or derivatives thereof that contains in the fiber is the 0.05%-5% of fibre weight, and fiber obtains the stretching more than 20 times at least, and the intensity of fiber reaches 30cN/dtex, and modulus is more than 1000cN/dtex.
- 2. according to the described method of claim 1: solvent is a liquid when room temperature, can be alkane, cycloalkane, aromatic hydrocarbon, or alkane cycloalkane the derivative of aromatic hydrocarbon, or any mixture in them.
- 3. according to the described method of claim 1: the nominal concentration of ultra-high molecular weight polyethylene and solvent is 1-50% (quality).
- 4. according to the described method of claim 1: separate and twine one or more auxiliary agents that can add simultaneously in the still in antioxidant, stabilizing agent, coloring agent, fire retardant, the silicone oil or derivatives thereof.
- 5. according to the described method of claim 1: the silicone oil or derivatives thereof can be injected to separate with ultra-high molecular weight polyethylene powder and solvent in proportion and twine in the still, also a certain amount of silicone oil or derivatives thereof can be added coagulating bath.
- 6. according to the described method of claim 1: the relative average molecular mass of ultra-high molecular weight polyethylene is at least 1,000,000, particularly more than 4,000,000.
- 7. according to the described method of claim 1: the silicone oil or derivatives thereof that contains in the fiber is the 0.05%-5% of fibre weight.
- 8. according to the described method of claim 1: gel spun fiber obtains the stretching more than 20 times at least.
- 9. according to the described method of claim 1: separate and twine still and can provide at least 1000 seconds -1Shear rate, can be any or their combination in agitator, colloid mill, homogenizer, the Venturi tube.
- 10. according to the described method of claim 1: the mixed liquid of emulsion form can directly feed screw extruder, also can be by the material-storage jar of band stirring, and material-storage jar can be one or more.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100406782A CN101307509A (en) | 2007-05-15 | 2007-05-15 | Ultra-high molecular weight polyethylene fiber spinning method |
| PCT/CN2007/002906 WO2008055405A1 (en) | 2006-11-08 | 2007-10-09 | A process for producing fiber of ultra high molecular weight polyethylene |
| EP07816520A EP2080824B1 (en) | 2006-11-08 | 2007-10-09 | A process for producing fiber of ultra high molecular weight polyethylene |
| DE602007008600T DE602007008600D1 (en) | 2006-11-08 | 2007-10-09 | METHOD FOR PRODUCING FIBERS FROM POLYETHYLENE WITH ULTRA-HIGH MOLECULAR WEIGHT |
| AT07816520T ATE478178T1 (en) | 2006-11-08 | 2007-10-09 | METHOD FOR PRODUCING ULTRA HIGH MOLECULAR WEIGHT POLYETHYLENE FIBERS |
| US12/299,205 US20100233480A1 (en) | 2006-11-08 | 2007-10-09 | Process for producing fiber of ultra high molecular weight polyethylene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100406782A CN101307509A (en) | 2007-05-15 | 2007-05-15 | Ultra-high molecular weight polyethylene fiber spinning method |
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| Publication Number | Publication Date |
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| CN101307509A true CN101307509A (en) | 2008-11-19 |
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| CNA2007100406782A Pending CN101307509A (en) | 2006-11-08 | 2007-05-15 | Ultra-high molecular weight polyethylene fiber spinning method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103320887A (en) * | 2013-06-21 | 2013-09-25 | 仲杰 | Production method of functional polyethylene monofilament |
| CN104073898A (en) * | 2013-03-27 | 2014-10-01 | 金云良 | Migrated bipolar functional group additive |
| CN104562267A (en) * | 2014-06-30 | 2015-04-29 | 巢湖市荷花渔网有限公司 | Fishing net thread |
| CN106400154A (en) * | 2016-09-28 | 2017-02-15 | 青岛信泰科技有限公司 | Full-dull super high molecular weight polyethylene fiber and preparation method thereof |
| CN106555245A (en) * | 2015-09-24 | 2017-04-05 | 北京同益中特种纤维技术开发有限公司 | A kind of cut resistant superhigh molecular weight polyethylene fibers and its preparation method and application |
| CN106591981A (en) * | 2017-02-21 | 2017-04-26 | 青岛信泰科技有限公司 | Production device of compound graphene high-strength high-mold polyethylene fiber and preparation method thereof |
| CN112941648A (en) * | 2021-01-26 | 2021-06-11 | 浙江金昊新材料有限公司 | Method for manufacturing high-strength and high-modulus polyethylene fiber |
-
2007
- 2007-05-15 CN CNA2007100406782A patent/CN101307509A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104073898A (en) * | 2013-03-27 | 2014-10-01 | 金云良 | Migrated bipolar functional group additive |
| CN103320887A (en) * | 2013-06-21 | 2013-09-25 | 仲杰 | Production method of functional polyethylene monofilament |
| CN103320887B (en) * | 2013-06-21 | 2016-03-02 | 仲杰 | A kind of production method of functional polyethylene monofilament |
| CN104562267A (en) * | 2014-06-30 | 2015-04-29 | 巢湖市荷花渔网有限公司 | Fishing net thread |
| CN106555245A (en) * | 2015-09-24 | 2017-04-05 | 北京同益中特种纤维技术开发有限公司 | A kind of cut resistant superhigh molecular weight polyethylene fibers and its preparation method and application |
| CN106555245B (en) * | 2015-09-24 | 2019-04-30 | 北京同益中特种纤维技术开发有限公司 | A kind of cut resistant ultra high molecular weight polyethylene fiber and its preparation method and application |
| CN106400154A (en) * | 2016-09-28 | 2017-02-15 | 青岛信泰科技有限公司 | Full-dull super high molecular weight polyethylene fiber and preparation method thereof |
| CN106591981A (en) * | 2017-02-21 | 2017-04-26 | 青岛信泰科技有限公司 | Production device of compound graphene high-strength high-mold polyethylene fiber and preparation method thereof |
| CN112941648A (en) * | 2021-01-26 | 2021-06-11 | 浙江金昊新材料有限公司 | Method for manufacturing high-strength and high-modulus polyethylene fiber |
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Open date: 20081119 |