CN1641082A - Selly spun polyethylene/thermotropic liquid crystal composite fiber and its preparing method - Google Patents
Selly spun polyethylene/thermotropic liquid crystal composite fiber and its preparing method Download PDFInfo
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Abstract
The present invention discloses one kind of composite freeze spun polyethylene/thermal liquid crystal fiber and its preparation process. The composite fiber contains ultrahigh molecular weight polyethylene powder 100 weight portions, thermal liquid crystal 1-10 weight portions, antioxidant 0.1-5 weight portions and antioxidant assistant 0.01-2 weight powder, and the ultrahigh molecular weight polyethylene has molecular weight of 1E6-3E6. The thermal liquid crystal as modifier has excellent performance and few damage on the performance of ultrahigh molecular weight polyethylene, and the composite freeze spun polyethylene/thermal liquid crystal fiber has excellent performance, especially improved processing performance, heat resistance and creeping resistance. The composite freeze spun polyethylene/thermal liquid crystal fiber with improved performance may be produced in available production apparatus with slight improvement.
Description
Technical field
The present invention relates to a kind of Selly spun polyethylene/thermotropic liquid crystal composite fiber and preparation method thereof, particularly gel-spun ultra-high molecular weight polyethylene/thermotropic liquid crystal complex fiber.
Background technology
As everyone knows, ultra high molecular weight polyethylene (is called for short UHMWPE, down together) fiber is to be raw material with the ultra high molecular weight polyethylene, the special fibre of a kind of novelty that technical process such as process dissolution with solvents, gel fiber that quenching is spun, extraction, drying, the hot ultra-drawing of segmentation are made.This fiber has premium properties such as light weight, high-strength, Gao Mo, anti-ultraviolet, shock-resistant, seawater corrosion resistance, electric insulation, has a wide range of applications in fields such as military affairs, Aeronautics and Astronautics, navigation engineering and sports apparatus.Yet because the molecular weight of UHMWPE is bigger, up to more than 1,000,000; Strand is very long, very easily tangles, and is mobile relatively poor, is difficult to processing.And because the macromolecular structure of UHMWPE is a linear structure, form by the methylene group, no any polar group on the strand, so its heat resistance poor (serviceability temperature generally is lower than 100 ℃), and its comprehensive mechanical intensity is also relatively poor, creep is serious, has greatly limited the application of UHMWPE fiber.The processability, heat resistance and the creep resistance that how to change the UHMWPE fiber have become the important topic that further develops the UHMWPE fiber.
At present, the method for improving processability, heat resistance and the creep resistance of UHMWPE fiber mainly contains following several: add medium molecular weight polyvinyl, make the fiber self-crosslinking, to wherein adding inorganic filler and making method such as itself and other fiber hybrid.Though this several method can be to a certain extent processability, heat resistance and the creep resistance of UHMWPE fiber is increased, but the insufficient amplitude ideal that improves, and, this several method all can not improve its processability, heat resistance and creep resistance simultaneously, but when improving a kind of performance, damaged another kind of performance.
Wherein, add medium molecular weight polyvinyl (MMWPE) and comprise adding low density polyethylene (LDPE) (LDPE) and high density polyethylene (HDPE) (HDPE).Though the affiliation that adds of LDPE and HDPE makes moderate progress the flowability of UHMWPE, make the mechanical property of UHMWPE reduce a lot.
Make the method for UHMWPE fiber self-crosslinking have two kinds: chemical crosslinking and crosslinking with radiation.For chemical crosslinking, be exactly after UHMWPE adds suitable crosslinking agent, in melting process, take place crosslinked, because the molecular weight of UHMWPE is very big, is difficult for fusion, and nonpolarity group on the strand, so chemical crosslinking is difficult for carrying out, the effect of modification is not clearly, and also degradation reaction can take place in cross-linking process, and the performance of UHMWPE is reduced.So main now method that adopts crosslinking with radiation, utilize high-energy radiation to make between strand to produce laterally crosslinked, this can improve the heat resistance and the creep-resistant property of UHMWPE fiber to a certain extent, but in crosslinked process, also inevitably produce chain-scission degradation, along with the increase of dosage of radiation, palliating degradation degree also increases, and the TENSILE STRENGTH of fiber and extension at break are decreased, in addition, this technical process is comparatively complicated.
Adopt fillers such as glass microballoon, mica, talcum powder, silica, alchlor, molybdenum bisuphide, carbon black to carry out filling-modified to UHMWPE, because UHMWPE is a kind of high tenacity material, the filler that adds forms the physical crosslinking point, limited the warm-up movement of molecule, can improve its heat resistance and creep resistance, but after adding these inorganic fillers, make the mobile variation of UHMWPE more to be difficult to processing.
UHMWPE fiber and carbon fiber, glass fibre and Kevlar is fiber blended, also can improve its heat resistance and creep resistance, but owing to do not have polar group and smooth surface on the UHMWPE strand, can not and use with and form compatible interface between fiber, can not form good active force between two components, and add the mobile variation that these fibers also can make UHMWPE, be difficult to processing.
The technical issues that need to address of the present invention are to disclose a kind of gel-spun ultra-high molecular weight polyethylene/thermotropic liquid crystal complex fiber and preparation method thereof, to overcome the above-mentioned defective that prior art exists.
Technical conceive of the present invention is such:
Liquid crystal is a kind of Thermodynamically stable phase between isotropic liquid and complete ordering crystal, and the flowability of its existing liquid has the optical anisotropy of crystal again, can be regarded as the position disordered crystal, also can be regarded as the ordered orientation fluid.The physical condition that forms by liquid crystal can be divided into lyotropic liquid crystal (LLCP) and thermotropic liquid crystal (TLCP) two big classes again, the LCP that uses as reinforced composite is TLCP, and it is a kind of high temperature resistant, the high performance engineering plastics with high strength and high-modulus of the exploitation of nearly more than ten years.The present invention selects thermotropic liquid crystal to have suitable advantage as the modifier of the processability of improving the UHMWPE fiber, heat resistance and creep resistance.Its reason is:
1. behind the thermotropic liquid crystal heating and melting liquid crystal state appears just, when the TLCP melt is in liquid crystal state, and good fluidity, viscosity is low, and big molecule parllel arrangement, does not have between macromolecular chain and twines, and is very responsive to shear rate.When the unordered liquid crystal microcell that is made of the big molecule of rigidity extended chain of TLC macroscopic view is subjected to the shearing field to do the time spent in molten condition, can in UHMWPE, form elongational flow field and streamwise generation macroscopic orientation, become fine, that is formed the liquid crystal fento of each diversity on the spot, it is lubricated melt, thereby reduced the viscosity of UHMWPE and TLCP co-mixing system, processability improves.
2. because the big numberator height orientations of TLCP is piled up closely between strand, the big intermolecular force of main chain is big, and macromolecular dyskinesia causes the heat distortion temperature height, and heat resistance and creep resistance are good.
Technical scheme of the present invention:
Gel-spun ultra-high molecular weight polyethylene/thermotropic liquid crystal complex fiber of the present invention is a kind of composition, by ultra high molecular weight polyethylene, thermotropic liquid crystal, antioxidant with help antioxidant to constitute,
Wherein:
100 parts in ultra high molecular weight polyethylene powder
1～10 part of thermotropic liquid crystal
0.1～5 part of antioxidant
Help 0.01～2 part of antioxidant
Molecular weight Mw=1 * 10 of said ultra high molecular weight polyethylene
6～3 * 10
6
Said thermotropic liquid crystal is selected from thermotropic liquid crystal polyamide, liquid crystalline polysiloxane or liquid crystal polyester, preferred liquid crystal polyester.
The chemical structural formula of liquid crystal polyamide is:
Wherein: n=4～12, x=8～12, y=12～14;
When n=4～12, show thermotropic liquid crystal and excellent melt processability, and performances such as high-strength and high-modulus, heat-resisting, anti-solvent;
The chemical structural formula of liquid crystalline polysiloxane is:
Wherein: m=1～4, n1=1～5;
The chemical structural formula of liquid crystal polyester is:
This liquid crystal is the copolyesters [HBA/HQ/SA] of P-hydroxybenzoic acid, hydroquinones and decanedioic acid,
Wherein: x1=8～12, y1=12～14, z1=3～6, f=4～6
This copolyesters becomes the nematic liquid crystal fully between 175～185 ℃;
Said antioxidant is this area antioxidant commonly used, 2, and 6-two-examination yellow acid-butyl-4-methylphenol, N-b Phenyl beta naphthylamine; Preferred 2,6-two-examination yellow acid-butyl-4-methylphenol, model is Irganox 245, Irganox 1010 or Irganox 1076.
Said help antioxidant be this area commonly used help antioxidant, preferred diphosphorous acid pentaerythrite two hard ester alcohol esters, model is Irgafos 168P-EPQ, Irganox PS802FL or IrganoxPS800.In order on the basis of not damaging the original excellent properties of ultra high molecular weight polyethylene fiber, to improve processability, heat resistance and the creep resistance of UHMWPE fiber better, its preparation method is very crucial, the invention provides a kind of ultra high molecular weight polyethylene/thermotropic liquid crystal complex fiber and preparation method thereof, this method comprises the steps:
(1) drying of ultra high molecular weight polyethylene powder and thermotropic liquid crystal is with ultra-high molecular weight polyethylene and thermotropic liquid crystal, antioxidant with help antioxidant to mix;
(2) above-mentioned gained gel-spun ultra-high molecular weight polyethylene/thermotropic liquid crystal complex fiber prepared using ultrasonic wave is evenly dispersed in the paraffin oil; under the nitrogen protection effect; slowly be warming up to 170～200 ℃; programming rate is controlled at 0.5～5 ℃/min; be incubated 1～4 hour, obtain spinning solution.The present invention preferably slowly heats up according to table 1 heating step:
Table 1
| Between heating zone (℃) | ??0～100 | ??100～110 | ??110～120 | ??120～130 | ??130～190 |
| Temperature retention time (min) | ??5～15 | ??5～15 | ??5～15 | ??10～20 | ??20～30 |
(3) gel spinning: to fully the UHMWPE/TLCP composite solution of dissolving adopt conventional gel spinning method to carry out spinning, can obtain fiber of the present invention.
The spinning temperature of said gel spinning method is 170～190 ℃, and the gelatine silk of preparation obtains fiber of the present invention through extraction, three hot drawing-offs etc.
Fiber of the present invention can overcome the shortcoming that prior art exists to a great extent, obtains the UHMWPE fiber of high comprehensive performance, can expand it in many-sided application.Because thermotropic liquid crystal itself can be regarded as a kind of self-reinforced material, in to the process of UHMWPE tensile fiber, form certain orientation, the performance of composite fibre is further enhanced.Because thermotropic liquid crystal has a lot of premium properties, it has good processability, heat resistance and creep resistant shape, according to the compatibility principle of composite, can reach the purpose of the processability, heat resistance and the creep resistance that improve the UHMWPE fiber theoretically.
(1) modifier thermotropic liquid crystal itself has excellent performance, reveal more performance than other modifier (as inorganic filler and fiber) and UHMWPE composite table, especially aspect processability, heat resistance and creep resistance, and very little to the damage of the original excellent properties of UHMWPE fiber.
(2) ratio adds the intensity height that medium molecular weight polyvinyl obtains fiber, implementation method than high-energy radiation method of modifying is simple, can improve processability, heat resistance and the creep resistance of fiber simultaneously, and the equipment that requires is simple, can improve a little on the production equipment of original UHMWPE fiber and directly produce.
The specific embodiment
Embodiment 1
Take by weighing 2g molecular weight Mw=1.5 * 10
6UHMWPE and 01.g_TLCP (copolyesters of hydroxybenzoic acid, hydroquinones and decanedioic acid [HBA/HQ/SA]), both are placed in the vacuum drying oven baking 48 hours simultaneously; Help antioxidant to mix the UHMWPE of drying and TLCP and 0.01g antioxidant, 0.002g;
With the above-mentioned gel-spun ultra-high molecular weight polyethylene/thermotropic liquid crystal complex fiber raw material that mixes, utilize ultrasonic wave to be evenly dispersed in the 98g paraffin oil, progressively slowly be warming up to 180 ℃ according to the following table temperature, programming rate is controlled at 1 ℃/min, be incubated 2.5 hours, obtain solution;
| Between heating zone (℃) | 0～100 | ?100～110 | ?110～120 | ?120～130 | ?130～190 |
| Temperature retention time (min) | 10 | ?30 | ?30 | ?30～60 | ?150 |
(3) gel spinning: to fully the UHMWPE/TLCP composite solution of dissolving adopt conventional gel spinning method to carry out spinning, can obtain fiber of the present invention.
The spinning temperature of said gel spinning method is 180 ℃, and the gelatine silk of preparation obtains fiber of the present invention through extraction, three hot drawing-offs etc.The performance test results such as table 2.
Comparative example 1
Except not adding any thermotropic liquid crystal, all by aforesaid preparation process, the preparation gel spun fiber.The performance test results such as table 2.
Comparative example 2
Except thermotropic liquid crystal is changed into the imvite, all prepare gel spun fiber by aforesaid preparation process.The performance test results such as table 2.
Table 2
| Test event | Young's modulus/GPa | Intensity/GPa | Shear viscosity during processability/170 ℃ | Creep properties/80,500MPa | Thermal degradation during heat resistance/390 ℃ | Spinnability | ||
| 10s -1 | ?50s -1 | 10 1s | ?10 4s | |||||
| Embodiment 1 | ?108 | ?2.2 | 8.7 | ?3.1 | 3.2 | ?3.7 | ?12 | Good |
| Comparative example 2 | ?91 | ?1.4 | ?11.1 | ?5.8 | ?3.6 | ?4.6 | ?14.6 | Difference |
| Comparative example 1 | ?78 | ?2.1 | ?10.3 | ?5.5 | ?4.1 | ?6.5 | ?19.4 | Good |
By table 2 as seen, the frozen glue that comparative example 2 adds imvites spins the PE fiber, although the common frozen glue of modular ratio spins the high about 17% of PE fiber, creep also has improvement, and loss of strength is bigger, and spinnability is very poor, frequent fracture of wire during stretching.Because the intercalation imvite is a 1-dimention nano synusia shape, two-dimensional can reach 10～80% of fibre diameter in addition, is disadvantageous to spinning fibre therefore.Spin the UHMWPE fiber and add thermotropic liquid crystal frozen glue, then because though TLCP is the very strong macromolecular material of rigidity, but at high temperature can present low melting viscosity and anisotropy, deformation and orientation can take place in work in-process, thereby the TLCP fento " is fixed " in composite.The morphosis of this composite and various performance are similar to traditional glass fibre filled composite in many aspects.Yet, because enhancing is to be obtained by the fiber that original position under the viscosity flow state forms, thereby avoided the fracture of fiber, and fiber modulus improves 40%, heat resistance raising about 50%.
Claims (10)
1. a Selly spun polyethylene/thermotropic liquid crystal composite fiber is characterized in that, by ultra high molecular weight polyethylene, thermotropic liquid crystal, antioxidant with help antioxidant to constitute, wherein:
100 parts in ultra high molecular weight polyethylene powder
1～10 part of thermotropic liquid crystal
0.1～5 part of antioxidant
Help 0.01～2 part of antioxidant.
2. Selly spun polyethylene/thermotropic liquid crystal composite fiber according to claim 1 is characterized in that, the molecular weight M of said ultra high molecular weight polyethylene
w=1 * 10
6～3 * 10
6
3. Selly spun polyethylene/thermotropic liquid crystal composite fiber according to claim 1 is characterized in that said thermotropic liquid crystal is selected from thermotropic liquid crystal polyamide, liquid crystalline polysiloxane or liquid crystal polyester.
4. Selly spun polyethylene/thermotropic liquid crystal composite fiber according to claim 1 is characterized in that said antioxidant is selected from 2,6-two-examination yellow acid-butyl-4-methylphenol, N-b Phenyl beta naphthylamine.
5. Selly spun polyethylene/thermotropic liquid crystal composite fiber according to claim 1 is characterized in that, the said antioxidant that helps is diphosphorous acid pentaerythrite two hard ester alcohol esters.
6. prepare the method for each described ultra high molecular weight polyethylene/thermotropic liquid crystal complex fiber of claim 1～5, it is characterized in that, this method comprises the steps:
(1) with ultra-high molecular weight polyethylene and thermotropic liquid crystal, antioxidant with help antioxidant to mix;
(2) above-mentioned gained gel-spun ultra-high molecular weight polyethylene/thermotropic liquid crystal complex fiber raw material is dispersed in paraffin oil or the decahydronaphthalene, under the nitrogen protection effect, be warming up to 170～200 ℃, programming rate is controlled at 0.5～5 ℃/min, be incubated 1～4 hour, obtain spinning solution;
(3) gel spinning: to fully the UHMWPE/TLCP composite solution of dissolving adopt conventional gel spinning method to carry out spinning, can obtain fiber of the present invention.
7. method according to claim 6 is characterized in that, ultra high molecular weight polyethylene powder and thermotropic liquid crystal carry out drying earlier.
8. method according to claim 6 is characterized in that, the spinning temperature of gel spinning method is 170～190 ℃, and the gelatine silk of preparation is through extraction, repeatedly hot drawing-off.
9. method according to claim 6 is characterized in that, gained gel-spun ultra-high molecular weight polyethylene/thermotropic liquid crystal complex fiber prepared using ultrasonic wave is evenly dispersed in the paraffin oil, obtains spinning solution.
10. method according to claim 6 is characterized in that, slowly heats up according to table 1 heating step:
Table 1
Between heating zone (℃) ??0～100 ??100～110 ??110～120 ??120～130 ??130～190
Temperature retention time (min) ??5～15 ??5～15 ??5～15 ??10～20 ??20～30
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322183C (en) * | 2005-10-11 | 2007-06-20 | 东华大学 | Jelly spinning polyethylene/epoxy resin composite fiber and its preparing method |
| CN104987564A (en) * | 2015-06-08 | 2015-10-21 | 深圳市星源材质科技股份有限公司 | Composite microporous membrane and preparation method thereof |
| CN106633860A (en) * | 2016-12-29 | 2017-05-10 | 江苏沃特特种材料制造有限公司 | Liquid crystal polyester resin complex with low dielectric constant and preparation method of liquid crystal polyester resin complex |
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2004
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322183C (en) * | 2005-10-11 | 2007-06-20 | 东华大学 | Jelly spinning polyethylene/epoxy resin composite fiber and its preparing method |
| CN104987564A (en) * | 2015-06-08 | 2015-10-21 | 深圳市星源材质科技股份有限公司 | Composite microporous membrane and preparation method thereof |
| CN106633860A (en) * | 2016-12-29 | 2017-05-10 | 江苏沃特特种材料制造有限公司 | Liquid crystal polyester resin complex with low dielectric constant and preparation method of liquid crystal polyester resin complex |
| CN106633860B (en) * | 2016-12-29 | 2019-04-12 | 江苏沃特特种材料制造有限公司 | Low-k liquid-crystal polyester resin compound and preparation method thereof |
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Assignee: Jiangsu Shentai Science & Technology Development Co., Ltd. Assignor: Donghua University Contract fulfillment period: 2009.1.28 to 2017.1.28 contract change Contract record no.: 2009320000265 Denomination of invention: Selly spun polyethylene/thermotropic liquid crystal composite fiber and its preparing method Granted publication date: 20060830 License type: Exclusive license Record date: 2009.3.10 |
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