CN1246511C - Extracting and drying process for superhigh relative molecular weight polyvinyl gel fibre - Google Patents
Extracting and drying process for superhigh relative molecular weight polyvinyl gel fibre Download PDFInfo
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- CN1246511C CN1246511C CN 02160744 CN02160744A CN1246511C CN 1246511 C CN1246511 C CN 1246511C CN 02160744 CN02160744 CN 02160744 CN 02160744 A CN02160744 A CN 02160744A CN 1246511 C CN1246511 C CN 1246511C
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Abstract
The present invention relates to an extracting and drying process of super high relative molecular weight polyethylene gel fibers with weight average relative molecular weight of 100 thousand to 500 thousand, which is characterized in that gel fibers which uses mineral oil as solvent and is prepared by spanning and quenching gel is firstly stretched in advance in 2 to 10 times at room temperature; then, ultrasonic extraction is carried out by dichloromethane or xylene under the state of tension; drying is carried out under the temperature below 40 DEG C; subsequently, first-stage stretching, second-stage stretching, third-stage stretching, prestretching, extraction and drying are carried out; the first-stage stretching, the second-stage stretching and the third-stage stretching are continuously carried out. The strength of the prepared fibers is from 28.3 to 29.6 cN/tax, the modulus is from 1080 to 1120 cN/tax, and the breaking elongation is from 3.57 to 3.61%.
Description
Technical field
The present invention relates to superelevation average molecular weight northylen (UHMWPE, the weight average relative molecular weight is 1,000,000～5,000,000) the extraction drying process of gel spun fiber, or rather, relate to the formulation of selection of Extractant and extraction drying process, belong to the polyethylene fiber preparation field.
Background technology
The UHMWPE gel spun fiber that forms through gel spinning, owing to contain a large amount of solvents, network structure is extremely loose, the big intermolecular force of polyethylene is broken by solvent molecule and is become very little in the network, very easily produce big intermolecular slippage during stretching, thereby be difficult to carry out stable super multiplying power and effectively stretch, more can't reach high-strength and high-modulus.Therefore, before stretching, must extract dried to remove a large amount of solvent in the fiber.
" preparation method of high-strength high-modulus polyethylene fiber " (application number 90102855.X) by people such as Yang Nianci, Gu Bai proposition, be ultra-high molecular weight polyethylene to be dissolved in make half weak solution in the kerosene solvent, become gel spun fiber through the spinning quenching, the kerosene that is included in the gel spun fiber is limited the extraction and the drying of contraction with industrial naptha, carry out hot-stretch then and make high-strength high-modulus fibre.This method has solved in the past that solvent and extractant are separated from solvent, recovery and the difficult treatment that different solvents causes, has reduced product cost and three waste discharge simultaneously.Yet, flammable big because the kerosene boiling range is low, dangerous big during spinning, limited the raising of dissolving and spinning temperature, thereby prepared UHMWPE fibre property is not ideal enough.And the boiling range broad of industrial naptha easily is trapped in after the extraction in the fiber, and need could be removed clean under higher temperature, and easily further crystallization of fiber under the high temperature, thereby influences the super drawing performance of fiber.
Again, it is that extractant extracts the UHMWPE gel spun fiber and drying that JP86-231211,86-231212 and JP87-184112 have adopted trichorotrifluoroethane, the filament contraction rate will reach more than 10% in this process, and, in international Meng Teer meeting in 1987, determined its restriction is used because trichorotrifluoroethane can damage the ozone layer.
USP5342567 has reported a kind of production technology of high-strength high-modulus polyethylene fiber, selects cycloalkanes, cyclenes or its mixture solvent as dissolving super high molecular weight PE for use, selects for use volatile solvent such as cyclohexanone or its mixture as extractant.This technology can directly stretch after spinning, extraction and save middle winding portion.It is said the TENSILE STRENGTH of prepared fiber greater than 15g/d, and modulus is greater than 350g/d, and extension at break is less than 10%, and degree of crystallinity is greater than 60%.This technology solvent for use and extractant price are all comparatively expensive, and directly extract without being separated after this technology spinning, make extraction and subsequent separated from solvent pressure recovery become big, thereby cause the fiber production cost to improve.
In sum, in ultra-high molecular weight polyethylene (UHMWPE) production technology selection of Extractant and drying process determine it is very crucial, so far still among continuous research and development.
Summary of the invention
The object of the present invention is to provide the extractant that a kind of extraction drying process of superelevation average molecular weight polyethylene gel fiber uses and formulate its extraction drying process, improving the tensility of gel spun fiber, and a large amount of volatilizations of organic extractant and cause the raising and the problem of environmental pollution of fiber cost when solving the gel spun fiber extraction.
The UHMWPE gel spun fiber that forms through gel spinning contains a large amount of solvent (70～90%), this part solvent is depended merely on the extraction removal can make extracting pressure bigger, the present invention carries out the predraft processing of certain multiple to gel spun fiber before extraction, can further reduce the solvent in the gel spun fiber, thereby reduce the extracting pressure of postorder.
With the character of solvent, generally select boiling point low according to the essence of purpose, the extraction of extraction and spinning, volatile and nonflammable reagent is as extractant, as: gasoline, carbon tetrachloride, dimethylbenzene, halogenated alkane etc.The extractant difference is to the extracting power of gel spun fiber also different (seeing Table 1).For being the UHMWPE gel spun fiber that solvent makes with mineral oil, the present invention selects for use carrene as extractant.
The various extractants of table 1 are to the extraction oil removal rate * of UHMWPE gel spun fiber
1(%)
| Extractant | Dichloroethanes | Carbon tetrachloride | Gasoline | Dimethylbenzene | Carrene |
| Leave standstill | 8.68 | 9.52 | 10.30 | 14.20 | 15.44 |
| Ultrasonic extraction | 11.95 | 13.10 | 14.20 | 17.31 | 18.62 |
*1:UHMWPE gel spun fiber solvent is a mineral oil, and the extraction oil removal rate is extraction weight of solvent of removing and the ratio that extracts preceding gel spun fiber weight, and the extraction time is 2 seconds.
Because the mechanism of extraction is based on interpenetrating and spread between fiber solvent and the extractant, then Cui Qu speed depends on the size of the movement velocity of solvent and extractant molecules to a great extent.Since the motion of ultrasonic wave energy acceleration molecular, therefore industrial common employing ultrasonic extraction.Extraction rate (seeing Table 1) has been accelerated in ultrasonic extraction greatly, but has also quickened the volatilization of extractant simultaneously, causes the raising of fiber cost, has also worsened environment.And when adopting carrene as extractant because carrene density is bigger than water, therefore can be on carrene front cover layer water, can significantly reduce the volatilization of carrene in the extraction process.
After extraction, tangible contraction can take place in gel spun fiber, and this is caused by two aspects.On the one hand, with the carrying out of extraction process, solvation effect progressively weakens between big molecule of the polyethylene in the gel spun fiber and former solvent molecule, and extractant molecules has replaced the solvent molecule in the gel spun fiber gradually, be present in the frozen glue network with free state, make fiber each take place to contraction; Because extractant has substituted the former solvent in the fiber, extractant is volatilization rapidly under the air dry state, makes the macroreticular system have a large amount of holes on the other hand, causes fiber to take place obviously to shrink.If leave filament contraction, the further crystallization of fiber meeting makes tensile fiber degradation (seeing Table 2) in the extraction dry run.
Table 2 extraction drying shrinkage is to the gel spun fiber crystallinity X
c*
2With fiber maximum tension multiple R
m*
3Influence
| Shrinkage factor (%) | 0 | 10 | 20 | 30 | 42 |
| X c(％) | 56.32 | 57.38 | 58.6 | 59.9 | 60.71 |
| R m | 24.8 | 23 | 21.1 | 19.3 | 17.7 |
*2: the mensuration of fibre crystallinity Xc: with daily output Rigaku D/MAX-RB type X-ray diffractometer, adopt powder method in 2 θ are 10～30 ° of scopes, to scan, after swarming is handled, get sample degree of crystallinity with weight method.
*3: fiber maximum tension multiple R
mMensuration: will extract dried gel spun fiber one end and fix, the other end with the constant stretch speed of 1m/min at 100 ℃ of following drawing of fibers until fracture, the maximum tension multiple R of fiber
mLength before length/fibre abstraction during=fibrous fracture.
The extraction drying process of superelevation average molecular weight northylen provided by the invention (molecular weight 100～5,000,000) gel spun fiber is characterised in that:
1, with mineral oil is the UHMWPE gel spun fiber that solvent forms through gel spinning, quenching, carry out certain predraft earlier, then with extractant to its extract, drying, to reduce the extracting pressure of fiber, and make fiber have draftability preferably, then carry out one, two, three stretching again, one, two, three draft temperatures are respectively 100 ℃, 110 ℃ and 120 ℃, and draw ratio (extensibility) is respectively 6-10 doubly; 1-2 doubly and 1-1.5 times and predraft, extraction, drying and dried one, two, three stretching carry out continuously.
2, the predraft temperature of UHMWPE gel spun fiber is a room temperature, and draw ratio is 2～10 times, is preferably 2～6 times.
3, the extractant of UHMWPE gel spun fiber is carrene or dimethylbenzene, and front cover layer water thereon.
Fiber was a tensioning state when 4, the UHMWPE gel spun fiber extracted, and carried out ultrasonic extraction.
Fiber kept tensioning state when 5, extraction back gel spun fiber was dry, and baking temperature is preferably 10～30 ℃ less than 40 ℃.
Advantage of the present invention is conspicuous:
(1) is applicable to the extraction drying of the gel spun fiber of molecular weight 100～5,000,000.
(2) predraft, extraction is dry and dried one, two, three stretching is carried out continuously.
(3) fibre strength of gained, modulus are improved, and the rate of recovery of dimethylbenzene, carrene helps environmental protection up to 88%-92%.
The specific embodiment
Embodiment 1
With the weight average relative molecular weight is that 4,000,000 UHMWPE powder and various additives are carried out swelling, dissolving (the UHMWPE percetage by weight is 8%) in solvent mineral oil, make nascent gel spun fiber through twin-screw spinning (The hole diameter of spinneret is 0.8mm) then, put into fiber barrel and place a period of time and be separated fully.
Through the UHMWPE gel spun fiber after being separated, feeding speed with 60cm/min enters pre-stretching device, at room temperature carry out 3 times of predrafts, enter then and carry out ultrasonic tensioning extraction in the extraction bath carrene (going up front cover layer water), enter air dry oven and carry out room temperature tensioning drying, the one-level of UHMWPE dry freeze glue fiber being carried out 8 times under 100 ℃ stretches, under 110 ℃, carry out 1.4 times of secondary drawing, under 120 ℃, carry out 1.1 times of three grades of stretchings, predraft-extraction-the drying-one of fiber, two, three grades of stretchings are continuously to be carried out, the intensity of gained UHMWPE fiber is 29.6cN/dtex, and modulus is 1120cN/dtex, and extension at break is 3.61%.This technology in extraction, drying stage all establishes the extractant retracting device, but still some carrene evaporate in the atmosphere, the carrene rate of recovery is 92%, on average makes the 1kgUHMWPE fiber and approximately loses the 0.7kg carrene.
Comparative example 1:
The preparation of UHMWPE gel spun fiber and predraft-extraction-drying-drawing process subsequently are identical with example, and extractant changes dimethylbenzene into.The intensity that makes the UHMWPE fiber is 28.3cN/dtex, and modulus is 1080cN/dtex, and extension at break is 3.57%, and the dimethylbenzene rate of recovery is 88%, on average makes the 1kgUHMWPE fiber and approximately loses 1.2kg dimethylbenzene.
Claims (6)
1, a kind of extraction, drying process of superelevation average molecular weight polyethylene gel fiber, comprise with mineral oil being that solvent forms gel spun fiber through gel spinning, quenching, it is characterized in that carrying out earlier draw ratio is 2-10 predraft doubly, then with extractant extract, drying, then carry out one, two, three stretching again; And these three processes are carried out continuously; Described extractant is carrene or dimethylbenzene.
2, by extraction, the drying process of the described superelevation average molecular of claim 1 weight polyethylene gel fiber, it is characterized in that the predraft number is 2～6 times.
3, by extraction, the drying process of the described superelevation average molecular of claim 1 weight polyethylene gel fiber, it is characterized in that extractant is a carrene, fiber is a tensioning state during extraction, front cover layer water on carrene.
4, by extraction, the drying process of the described superelevation average molecular of claim 1 weight polyethylene gel fiber, it is characterized in that described baking temperature less than 40 ℃, fiber keeps tensioning state.
5, by extraction, the drying process of claim 1 or 3 described superelevation average molecular weight polyethylene gel fibers, it is characterized in that described baking temperature is 10～30 ℃.
6, press extraction, the drying process of the described superelevation average molecular of claim 1 weight polyethylene gel fiber, it is characterized in that one, two, three draft temperature of described dry back is respectively 100 ℃, 110 ℃ and 120 ℃, draw ratio is respectively 6-10, and 1-2 and 1-1.5 are doubly.
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| CN100427653C (en) * | 2006-11-24 | 2008-10-22 | 东华大学 | Prepn and application of jelly fiber of polyethylene in ultrahigh molecular weight |
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| CN100519847C (en) * | 2007-02-12 | 2009-07-29 | 北京特斯顿新材料技术发展有限公司 | Method for drying extractant during production of superhigh-molecular weight polyvinyl fibre |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100427653C (en) * | 2006-11-24 | 2008-10-22 | 东华大学 | Prepn and application of jelly fiber of polyethylene in ultrahigh molecular weight |
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Assignee: Changshu Super Fibers Co., Ltd. Assignor: Donghua University Contract fulfillment period: 2008.1.1 to 2012.12.31 contract change Contract record no.: 2009320000312 Denomination of invention: Extracting and drying process for superhigh relative molecular weight polyvinyl gel fibre Granted publication date: 20060322 License type: Exclusive license Record date: 2009.3.10 |
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