CN100441753C - Prepn of hollow high-strength light-modulus polyethylene fiber - Google Patents
Prepn of hollow high-strength light-modulus polyethylene fiber Download PDFInfo
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- CN100441753C CN100441753C CNB2006100290315A CN200610029031A CN100441753C CN 100441753 C CN100441753 C CN 100441753C CN B2006100290315 A CNB2006100290315 A CN B2006100290315A CN 200610029031 A CN200610029031 A CN 200610029031A CN 100441753 C CN100441753 C CN 100441753C
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Abstract
The present invention discloses preparation process of hollow high-strength and high-modulus polyethylene fiber. The preparation process includes the following steps: high temperature swelling and dissolving to obtain spinning fluid of ultra high molecular weight polyethylene, gel spinning with inserted tubular spinning jet with high temperature compressed air introduced to inside, quenching to form gel fiber, extracting and super drawing to obtain the hollow high-strength and high-modulus polyethylene fiber. The present invention has shortened path for the solvent inside fiber to diffuse out, high extracting efficiency, simplified extracting process, homogenized structure and raised mechanical performance of fiber.
Description
Technical field
The present invention relates to a kind of preparation method of polyethylene fiber, particularly relate to the preparation method of a kind of hollow high-strength high-modulus polyethylene fiber (UHMWPE, weight average relative molecular weight are 100～5,000,000).
Background technology
The ultra high molecular weight polyethylene fiber is the third generation high-performance fiber that occurs after carbon fiber and aramid fiber, have other high-performance fiber incomparable mechanical property.In present synthetic fiber, the UHMWPE fiber has lower density, higher elongation at break, specific strength and specific modulus maximum have surpassed metal material, the more important thing is that it also has the excellent energy absorption characteristic, optimum absorbs the fragmentation impact energy of low speed, and ballistic performance is best, and does not have the secondary lethal effect, be a kind of desirable bullet resistant material, be widely used in security personnel and military aspect at present.The UHMWPE fiber is owing to have multiple excellent properties such as ultralight, high specific strength, high ratio modulus, shock-resistant, chemicals-resistant, UV resistant, low temperature resistant, electric insulation, be present best hawser material and high-tech armament material, also very desirable on space flight navigation purposes.Its reinforced composite has also obtained using widely because of having excellent characteristic.
The ultra high molecular weight polyethylene fiber normally adopts gel spinning-super drawing method to be prepared from.In CN99111581, reported a kind of production technology of high-strength high-modulus polyethylene fiber as Chen Chengsi, at first the super high molecular weight condensate is dissolved among the corresponding solvent, obtain the solution of low big molecular entanglement, become gel spun fiber through the spinning quenching, through technical process such as extraction, drying and multistage hot-stretchs, make the polyethylene fiber of high-strength and high-modulus then.The process of the preparation high-strength high-modulus polyethylene fiber that other have proposed is mostly similar, patent that just has such as CN90102855, CN97101010, whole gel spinning-ultra-drawn all technical process are described and claim as USP5342567, USP5443904, CN02115024 etc., what have then is described and claim limitation the technical process in a certain stage wherein, discloses the preparation method of extra high molecular polyethylene high-concentrated solution for spinning as CN01123600; CN02160744, CN200410096619, CN200510073249 then disclose extraction, the drying process method in the superhigh molecular weight polyethylene fibers preparation; USP5578374, USP5741451, USP5958582 have carried out detailed description and right qualification to the super drawing process of gel spinning gained fiber.
Above-mentioned the whole bag of tricks gained polyethylene fiber frozen glue is solid fiber.Owing to contain a large amount of solvents in the gel spun fiber of gel spinning-quenching gained, as described in the above-mentioned process like that, need to surpass a times hot-stretch more afterwards and obtain high-strength high-modulus fibre through the solvent that fiber is removed in extraction.Because the mechanism of extraction is based on interpenetrating and spread between fiber solvent and the extractant, then the speed that desolventizes of gel spun fiber depends on the size of the movement velocity of solvent and extractant molecules to a great extent.Outside the Pass the speed of solvent diffuse speed removed and to have with the extraction process condition, also the path of passing through with solvent diffuse was relevant.In the gel spun fiber extraction process, the solvent molecule of fibrous outer preferentially diffuses out in gel spun fiber, because the iris action of polyethylene macromolecular network, the solvent molecule of gel spun fiber core difficulty diffuses out, and can make the fibre section form skin-core structure.Though this skin-core structure is so obvious not as wet spun fibre, this structure irregular can influence the super drawing of fiber, and and then influence the mechanical property of finished fiber.
For the hollow polyethylene fiber, the method that has proposed at present all concentrates on produces on the doughnut filter membrane.Disclose the method for preparing polyethylene hollow fiber as USP4115492, USP5294338, USP6436319, ZL200510049263 etc., used polyethylene is high density polyethylene (HDPE), employing be melt spinning method.And USP5695702 and ZL95193838 disclose thermoplasticity hollow fiber film assembly and manufacture method thereof, wherein mentioned the doughnut that ultrahigh molecular weight polyethylene forms fully, but this fiber only limits to filter the hollow-fibre membrane of usefulness, high-strength and high-modulus far from.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of hollow high-strength high-modulus polyethylene fiber, to remedy the deficiencies in the prior art or defective, meets the demands of production and living.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of preparation method of hollow high-strength high-modulus polyethylene fiber comprises the steps:
(1) with the weight average relative molecular weight be 100～5,000,000 polyethylene powders and mineral oil by weight proportion 1-12: 88-99 be made into and poise liquid, ratio in polyethylene and antioxidant weight is 100: the ratio of 0.1-1.0 adds antioxidant, under stirring, be warming up to 105-130 ℃ of swelling 0.5-2 hour, and then be warming up to 160-200 ℃ of dissolving and made spinning solution in 0.5-2 hour, wherein ultra high molecular weight polyethylene contains 1～12%;
(2) adopting slit width is 0.3-0.8mm, bore is the insertion tubular type spinning head of 0.3-0.6mm, spinning solution is sprayed via the slit that inserts the tubular type spinning head, spinning temperature is 140～180 ℃, and spinning pressure is 2～4 times of the feeding compressed air pressure, and inserting the inner compressed air temperature that feeds of pipe is 130～150 ℃, after the ejection of spinning solution stream, through the air layer of 2-10mm, directly enter in-1 ℃-25 ℃ the cold bath, quenching becomes the hollow gel spun fiber;
(3) gained hollow gel spun fiber directly enters and carries out ultrasonic tensioning extraction in the carrene, enter air dry oven and carry out room temperature tensioning drying, the one-level of carrying out 15～30 times then under 60-100 ℃ stretches, under 90-118 ℃, carry out 1.3～3 times of secondary drawing, under 120-150 ℃, carry out 1.1～1.9 times of three grades of stretchings, gained finished product polyethylene fiber.
As optimized technical scheme: described mineral oil is the white oil of commercially available 70#-120#, paraffin oil, one or more in the atoleine.
Described antioxidant is commercial antioxidant 1010,1076,168, B215, B225, B561, B900,3114,1098,1024,1035,1135,245,300, BHT, DSTP, DLTP, TPP, TNPP, one or more in the CA series.
The invention has the beneficial effects as follows: the present invention has shortened the path that the fiber internal solvent diffuses out the gel spun fiber process, improves extraction efficiency, simplied extraction process, and it is irregular to eliminate structure, further improves the mechanical property of fiber.
Description of drawings
The high-strength polyethylene doughnut cross section microscope figure that Fig. 1 the present invention makes
The vertical microscope figure of the high-strength polyethylene doughnut that Fig. 2 the present invention makes
The specific embodiment
Below in conjunction with specific embodiment the present invention is further elaborated.
With the weight average relative molecular weight is that 4,500,000 polyethylene (UHMWPE) powder and 90# white oil were made into by weight 10: 90 and poise liquid, in the ratio of polyethylene (UHMWPE) and antioxidant 1010 weight is that 100: 0.6 ratio adds antioxidant, under stirring, be warming up to 130 ℃ of swellings 1 hour, and then be warming up to 180 ℃ of dissolvings and made spinning solution in 1 hour, wherein ultra high molecular weight polyethylene contains 10%;
The employing slit width is 0.5mm, bore is the insertion tubular type spinning head of 0.5mm, with spinning solution slit ejection via insertion tubular type spinning head under 180 ℃, insert the compressed air of 140 ℃ of the inner feedings of pipe, the control spinning pressure is 2 times of compressed air pressure.After the spinning solution stream ejection, the air layer through 5mm directly enters ice-water bath, and quenching becomes the hollow gel spun fiber, the cross section of gained hollow gel spun fiber and vertically microscope figure as shown in Figure 1, degree of hollowness is 20%.Gained hollow gel spun fiber directly enters and carries out ultrasonic tensioning extraction in the carrene, enter air dry oven and carry out room temperature tensioning drying, the one-level of carrying out 20 times then under 90 ℃ stretches, under 100 ℃, carry out 2 times of secondary drawing, under 120 ℃, carry out 1.3 times of three grades of stretchings, the fracture strength of gained finished product UHMWPE fiber is 32.6cN/dtex, and modulus is 1250cN/dtex, extension at break 2.8%.
Embodiment 2
With the weight average relative molecular weight is that 1,000,000 polyethylene (UHMWPE) powder and 80# white oil were made into by weight 1: 99 and poise liquid, in polyethylene (UHMWPE) and antioxidant 1076 weight ratio is that 100: 0.1 ratio adds antioxidant, under stirring, be warming up to 105 ℃ of swellings 2 hours, and then be warming up to 160 ℃ of dissolvings and made spinning solution in 2 hours, wherein ultra high molecular weight polyethylene contains 1%;
The employing slit width is 0.3mm, bore is the insertion tubular type spinning head of 0.6mm, with spinning solution slit ejection via insertion tubular type spinning head under 170 ℃, insert the compressed air of 160 ℃ of the inner feedings of pipe, the control spinning pressure is 3 times of compressed air pressure.After the ejection of spinning solution stream, air layer through 2mm, directly enter ice-water bath, quenching becomes the hollow gel spun fiber, and gained hollow gel spun fiber directly enters and carries out ultrasonic tensioning extraction in the carrene, enters air dry oven and carries out room temperature tensioning drying, the one-level of carrying out 30 times then under 60 ℃ stretches, under 90 ℃, carry out 3 times of secondary drawing, under 150 ℃, carry out 1.1 times of three grades of stretchings, make finished product UHMWPE fiber.
Embodiment 3
With the weight average relative molecular weight is that 5,000,000 polyethylene (UHMWPE) powder and paraffin oil were made into by weight 12: 88 and poise liquid, in polyethylene (UHMWPE) and antioxidant 168 weight ratios is that 100: 1.0 ratio adds antioxidant, under stirring, be warming up to 110 ℃ of swellings 0.5 hour, and then be warming up to 200 ℃ of dissolvings and made spinning solution in 0.5 hour, wherein ultra high molecular weight polyethylene contains 12%;
The employing slit width is 0.8mm, bore is the insertion tubular type spinning head of 0.3mm, with spinning solution slit ejection via insertion tubular type spinning head under 140 ℃, insert the compressed air of 180 ℃ of the inner feedings of pipe, the control spinning pressure is 4 times of compressed air pressure.After the ejection of spinning solution stream, air layer through 10mm, directly enter ice-water bath, quenching becomes the hollow gel spun fiber, and gained hollow gel spun fiber directly enters and carries out ultrasonic tensioning extraction in the carrene, enters air dry oven and carries out room temperature tensioning drying, the one-level of carrying out 15 times then under 100 ℃ stretches, under 118 ℃, carry out 2.8 times of secondary drawing, under 130 ℃, carry out 1.7 times of three grades of stretchings, make finished product UHMWPE fiber.
Comparative example:
Is that spinning head ejection, the quenching of 0.85mm becomes solid UHMWPE gel spun fiber with prepared spinning solution among the embodiment 1 via the aperture, adopt and same extraction, the drawing process of embodiment then, the intensity of prepared UHMWPE fiber is 24.8cN/dtex, modulus is 830cN/dtex, and extension at break is 2.92%.
Claims (3)
1, a kind of preparation method of hollow high-strength high-modulus polyethylene fiber is characterized in that, comprises the steps:
(1) with the weight average relative molecular weight be 100～5,000,000 polyethylene powders and mineral oil by weight proportion 1-12: 88-99 be made into and poise liquid, ratio in polyethylene and antioxidant weight is 100: the ratio of 0.1-1.0 adds antioxidant, under stirring, be warming up to 105-130 ℃ of swelling 0.5-2 hour, and then be warming up to 160-200 ℃ of dissolving and made spinning solution in 0.5-2 hour, wherein ultra high molecular weight polyethylene contains 1～12%;
(2) adopting slit width is 0.3-0.8mm, bore is the insertion tubular type spinning head of 0.3-0.6mm, spinning solution is sprayed via the slit that inserts the tubular type spinning head, spinning temperature is 140～180 ℃, and spinning pressure is 2～4 times of the feeding compressed air pressure, and inserting the inner compressed air temperature that feeds of pipe is 130～150 ℃, after the ejection of spinning solution stream, through the air layer of 2-10mm, directly enter in-1 ℃-25 ℃ the cold bath, quenching becomes the hollow gel spun fiber;
(3) gained hollow gel spun fiber directly enters and carries out ultrasonic tensioning extraction in the carrene, enter air dry oven and carry out room temperature tensioning drying, the one-level of carrying out 15～30 times then under 60-100 ℃ stretches, under 90-118 ℃, carry out 1.3～3 times of secondary drawing, under 120-150 ℃, carry out 1.1～1.9 times of three grades of stretchings, gained finished product polyethylene fiber.
2, preparation method according to claim 1 is characterized in that, described mineral oil is one or more in the white oil of 70#-120#.
3, preparation method according to claim 1 is characterized in that, described antioxidant is commercial antioxidant 1010,1076,168, B215, B225, B561, B900,3114,1098,1024,1035,1135,245,300, BHT, DSTP, DLTP, TPP, TNPP, one or more in the CA series.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN101230499B (en) * | 2008-02-26 | 2010-10-06 | 山东爱地高分子材料有限公司 | Coloured high-strength polyethylene fibre and method for manufacturing same |
| CN101575742B (en) * | 2008-05-05 | 2011-01-26 | 宁波荣溢化纤科技有限公司 | Preparation method of ultra-high molecular weight polyethylene fiber |
| CN101575756B (en) * | 2008-05-05 | 2011-01-26 | 宁波荣溢化纤科技有限公司 | Stretching method of ultra-high molecular weight polyethylene precursor fiber |
| CN101591813B (en) * | 2008-05-27 | 2011-02-09 | 宁波荣溢化纤科技有限公司 | Method for manufacturing super high molecular polyethylene fiber precursor |
| CN101629331B (en) * | 2008-07-17 | 2011-01-26 | 宁波荣溢化纤科技有限公司 | Method for drawing ultra-high molecular weight polyethylene fiber |
| CN101775666B (en) * | 2010-01-22 | 2011-07-27 | 东华大学 | Preparation method of high-strength high-modulus polyethylene fiber |
| CN101886298B (en) * | 2010-06-23 | 2013-05-08 | 东华大学 | Preparation method of ultra-high molecular weight polyethylene monofilaments |
| CN101962819B (en) * | 2010-09-13 | 2012-07-18 | 杭州翔盛高强纤维材料股份有限公司 | Ultrawhite ultrahigh-molecular weight ultrahigh-modulus polyethylene fibers and preparation process thereof |
| CN102154749B (en) * | 2011-04-20 | 2013-01-02 | 东华大学 | Preparation method of coarse denier ultrahigh molecular weight polyethylene (UHMWPE) fiber yarn |
| CN114481343A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Fiber spinning method and polyethylene spinning fiber |
| CN116351097B (en) * | 2023-04-12 | 2024-01-23 | 浙江蓝德能源科技发展有限公司 | Extractant for ultra-high molecular weight PE fibers and diaphragms and preparation and application methods thereof |
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