CN1210455C - Method for increasing heat-resistant, creep resisting and adhesive bonding properties of high strength polytene at same time - Google Patents
Method for increasing heat-resistant, creep resisting and adhesive bonding properties of high strength polytene at same time Download PDFInfo
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- CN1210455C CN1210455C CN 03115300 CN03115300A CN1210455C CN 1210455 C CN1210455 C CN 1210455C CN 03115300 CN03115300 CN 03115300 CN 03115300 A CN03115300 A CN 03115300A CN 1210455 C CN1210455 C CN 1210455C
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Abstract
The present invention relates to a method for improving heat resistant, creep resistant performance and surface adhesive performance of polytene fiber of which the ultrahigh molecular weight is from 10000000 to 500000000 at same time, which belongs to the technical field of UHMWPE fibre modification. The present invention is characterized in that UHMWPE fibre of which impurities on the surface are removed and washed by propanone is soaked in organic solution composed of photosensitizer and cross-linking agents; then, the fiber is irradiated by ultraviolet light for crosslinking; the photosensitizer is benzophenone and derivants thereof, and the concentration of the photosensitizer is from 0.3 to 1.5% (by quality) in soak solution; the cross-linking agents are a trifunctional group reagent or a bifunctional group reagent of acrylics; the concentration of cross-linking agents is from 5 to 50% (by quality) in the soak solution; the solvent of the photosensitizer and the cross-linking agents is one of propanone, dimethylbenzene or normal heptane; the soak time is from 0.1 to 5 hours; the crosslinking is carried out under highly pure nitrogen atmosphere; the ultraviolet irradiation strength is from 0.05 to 1.5 J/cm.
Description
Technical field
The present invention relates to a kind of raising superelevation average molecular weight northylen (UHMWPE, weight average relative molecular weight are 100～5,000,000) fiber heat resistance, creep resistance and surperficial close-burning method, belong to UHMWPE fibre modification field.
Background technology
The UHMWPE fiber is the third generation high-performance fiber that occurs after carbon fiber and aramid fiber, have other high-performance fiber incomparable mechanical property (seeing Table 1), in addition, it also has multiple excellent properties such as chemical resistance and weather resisteant, high-energy absorption, low temperature resistant and electric insulation, is applied in military affairs, space flight navigation engineering and fields such as high-performance, light composite material and sports apparatus widely.But UHMWPE fiber self inherent structure makes it have many weak points, as the fiber poor heat resistance, has limited the serviceability temperature of fiber; Be easy to generate creep under the stress effect, limited the application of fiber in high-strength rope field; The fiber surface adhesive property is relatively poor, has limited the application of fiber in field of compound material etc.
The performance of table 1 UHMWPE fiber and other high-performance fiber relatively
UHMWPE fiber aramid fiber carbon fiber
The high-strength nylon of performance glass
I II III I II I II
Density (g/em
3) 0.97 0.97 0.97 1.44 1.44 1.81 1.81 2.50 1.14
Intensity (cN/dtex) 27.8 33.0 40.2 19.2 19.2 17.6 12.3 18.4 7.9
Modulus (cN/dtex) 918 1,021 1,412 611 861 1,323 1,764 360 754
Percentage elongation (%) 3.5 3.7 3.7 3.6 2.5 1.2 0.6 5.4 5.4
Specific strength (10
5M) 2.87 3.40 4.14 1.33 1.33 0.97 0.68 0.74 0.69
Specific modulus (10
5M) 95 105 146 42 60 73 97 14 66
Improve the interfacial adhesion strength between UHMWPE fiber and resin matrix, can carry out modification to fiber by methods such as chemical reagent etch, Cement Composite Treated by Plasma modification, Corona discharge Treatment, photooxidation surface modification treatment, radiation grafting processing, make the activation of fiber inactive surfaces layer, introduce carboxyl, carbonyl, hydroxyl isopolarity group at nonpolar fiber surface, but these class methods can not be improved the heat resistance and the creep-resistant property of fiber.
CN1035308A discloses a kind of method of the UHMWPE of raising fiber surface adhesive property, it is that the UHMWPE fiber surface is carried out Cement Composite Treated by Plasma, the method can effectively improve wettability and the surperficial adhesion strength of fiber to base-material commonly used, but the hot property and the croop property of fiber do not influenced.
USP5578374 and USP5958582 disclose a kind of employing and have stretched once more and improve the method for UHMWPE fiber heat resistance and creep-resistant property, under 135～160 ℃ the UHMWPE finished fiber repeatedly being stretched or earlier fiber being heat-treated again repeatedly stretches, and can effectively improve the heat resistance and the creep resistance of UHMWPE fiber.But this method can not be improved the surperficial adhesive property of UHMWPE fiber simultaneously, and adopts secondary or when stretching for three times, draft temperature is higher, and draw speed is very low, thereby causes fiber cost to increase substantially.
USP4870136 discloses the method for a kind of UHMWPE of raising fiber heat resistance, creep resistance and surperficial adhesive property.This method is earlier with a certain proportion of UHMWPE powder, radical initiator, silane compound and diluent melting mixing in screw rod, carry out the plasticising melt spinning, cause the silanization graft reaction of finishing UHMWPE by heat in the spinning stage, to spin to such an extent that fiber carries out hot-stretch in the medium of extractant and crosslinking agent, and then place boiling water to finish cross-linking reaction.This method gained fiber equilibrium melting point improves greatly, and fiber creep resistance and surperficial adhesive property also improve.But this method is owing to add a large amount of initators and graft compound and stretch after graft reaction is finished again in the UHMWPE spinning solution, thereby makes the tensile fiber multiple lower, and the mechanical property of last gained fiber is relatively poor.
Cross-linked structure is introduced the UHMWPE fiber, play the fixedly effect of macromolecular chain, can improve the heat resistance and the creep-resistant property of fiber simultaneously.
P.G.Klein is at " The effect of electron irradiation on the structure andmechanical property of high drawn polyethylene fibers " (Journal of polymerscience, 1987, propose to adopt 25:1359-1379) γ-or electron beam fiber is carried out high-energy radiation and causes crosslinked, can effectively improve the heat resistance and the creep-resistant property of fiber, but except that cross-linking reaction, high-energy ray also can cause the fiber backbone breaking, and the sharply acceleration with the increase of irradiation dose, the mechanical property of fiber is reduced greatly.
J.P.Penning etc. are at " Influence of chemical crosslinking on the creep behaviorof ultra-high molecular weight polyethylene fibers " (Colloid Polym.Sci., 272:664-676) the UHMWPE fiber was soaked in the organic solution of cumyl peroxide 120～135 hours, carried out ultraviolet irradiation then crosslinked 0～150 hour, can under the prerequisite that does not influence the good mechanical property of fiber, improve the creep-resistant property of fiber greatly, but the method is soaked and the ultraviolet irradiation time is all oversize, no industrialization possibility.
People such as Bengt Ranby are at " Photocrosslinking of polyethylene for production ofthin wall insulated wire " (Polym.Eng.Sci., 1995,35 (12): 1005-1014) with " Photocross-linking of low-density polyethylene " (J.Appl.Polym.Sci., 1993, it is crosslinked 48:701-709) polyvinyl resin of molten condition to be carried out ultraviolet irradiation, can improve the heat resistance and the creep-resistant property of polyethylene products greatly.Yet the method can not be used for the modification of UHMWPE fiber.And the ultraviolet irradiation that is used for the UHMWPE fiber of many bibliographical informations is cross-linking modified, and the adding of photosensitizer and crosslinking agent mainly is the dissolution phase at UHMWPE, to the ultraviolet irradiation of UHMWPE fiber in drawing process or stretch and carry out after finishing.But the existence of photosensitizer and crosslinking agent can influence the tensile property of UHMWPE gel spun fiber greatly, thereby can not obtain the UHMWPE fiber of high-strength and high-modulus.
In sum, can carry out various processing to improve its heat resistance, creep resistance and surperficial caking property to fiber by existing technology, but all technology all can not make above-mentioned three kinds of performances of fiber that improvement is arranged simultaneously, and lose another kind of performance often when improving wherein a kind of performance.
Summary of the invention
The object of the present invention is to provide a kind of crosslinked method that does not influence the fiber excellent mechanical property with the heat resistance, creep resistance and the surperficial caking property that improve fiber of ultraviolet irradiation of the UHMWPE fiber being carried out particular form.
This method mainly is cross-linking modified at the ultraviolet irradiation of finished product UHMWPE, by the mode of soaking photosensitizer and crosslinking agent are introduced finished product UHMWPE fiber, then in that to carry out ultraviolet irradiation crosslinked, the control felicity condition, can not influence on the basis of UHMWPE fiber excellent mechanical property substantially, improve fiber heat resistance, creep-resistant property and and resin matrix between adhesive property.
The cross-linking radiation technology of UHMWPE provided by the invention (the weight average relative molecular weight is greater than 1,000,000) finished fiber is characterised in that: the UHMWPE fiber through removing surface impurity after the acetone carrying out washing treatment soaks certain hour in the organic solution of finite concentration photosensitizer and crosslinking agent, and then fiber is carried out ultraviolet light irradiation cross-linking; Described photosensitizer is benzophenone and derivative thereof, and concentration is 0.3～1.5% (quality) in soak, is preferably 0.5～1.0%; Described crosslinking agent is the trifunctional or the difunctional of esters of acrylic acid, and concentration is 5～50% (quality) in soak, is preferably 10～30%; The solvent of described photosensitizer and crosslinking agent preferably has the solvent of certain swelling ability to the UHMWPE fiber, as a kind of in acetone, dimethylbenzene, the normal heptane, be preferably acetone; Described UHMWPE fiber soak time in the solution of photosensitizer and crosslinking agent is 0.1～5 hour, is preferably 0.3～1 hour; The ultraviolet irradiation of described UHMWPE fiber is crosslinked to carry out in high pure nitrogen atmosphere, is preferably under the complete anaerobic state and carries out; Described average ultraviolet irradiation intensity to the UHMWPE fiber is 0.05～1.5Jcm
-2, be preferably 0.1～1.0Jcm
-2
Advantage of the present invention is to carry out the ultraviolet light irradiation cross-linking modification, not in drawing process or after drawing process finishes, carry out behind the solution certain hour of forming by crosslinking agent and photosensitizer but be immersed at fiber, so not only the fiber itself rerum natura there is not influence, modification when making its heat resistance, creep resistance, surperficial caking property all have in various degree on the contrary (seeing table 1-4 for details).
The specific embodiment
Embodiment 1
The UHMWPE fiber is washed in acetone repeatedly to remove the impurity of fiber surface, then with fiber in that to contain benzophenone and derivative thereof be 0.6wt%, contain in the acetone soln of trihydroxy propane triacrylate 20wt% and soaked 0.5 hour.Soaked fiber is put into the ultraviolet light cross-linking reactor, carry out ultraviolet irradiation cross-linking reaction (ultraviolet source and fibrous septum one deck glass are to prevent the raising of temperature in the cross-linking reaction device) under high pure nitrogen atmosphere, average irradiation intensity is 0.26Jcm
-2
Embodiment 2
The average ultraviolet irradiation intensity of UHMWPE is 0.8Jcm
-2, ultraviolet irradiation is to carry out the cross-linking radiation reaction under anaerobic state.All the other are with example 1.
Mechanical property, heat resistance, creep resistance and the surperficial adhesive property of crosslinked front and back UHMWPE fiber see Table 1～4.
The mechanical property of the crosslinked front and back of table 1 UHMWPE fiber
* 1
| Sample | Fracture strength (cN/dtex) | Young modulus (cN/dtex) | Extension at break (%) |
| Uncrosslinked fiber | 23.7 | 1020 | 3.82 |
| Example 1 fiber | 23.85 | 1032 | 3.54 |
| Example 2 fibers | 22.73 | 1015 | 3.52 |
*1: the mechanical property of fiber adopts AGS-500ND type strength tester to measure, and folder is apart from being 200mm, and draw speed is 250mm/min, tries to achieve the ultimate strength and the extension at break of fiber, and is tried to achieve the young modulus of fiber by the slope of the initial straight line portion of S-S curve.
The thermomechanical property of the crosslinked front and back of table 2 UHMWPE fiber
* 2
| Sample | Rapid shrinkage temperature (℃) | Fusing-off temperature (℃) | Maximum collapse (%) |
| Uncrosslinked fiber | 137.5 | 175.5 | 83.5 |
| Example 1 fiber | 140.3 | 180.3 | 75.2 |
| Example 2 fibers | 144.5 | 184 | 69.8 |
The heat shock creep (%) of the crosslinked front and back of table 3 UHMWPE fiber
* 2
| Sample | 80℃ | 100℃ | 120℃ | 130℃ | 140℃ | 145℃ |
| Uncrosslinked fiber | 0.65 | 0.84 | 1.06 | 2.04 | 3.83 | 8.35 |
| Example 1 fiber | 0.28 | 0.59 | 0.75 | 1.28 | 2.31 | 4.93 |
| Example 2 fibers | 0.21 | 0.48 | 0.62 | 1.04 | 1.98 | 4.06 |
*2: fiber thermomechanical property under the condition of high temperature and heat shock croop property thereof are tested by ZDFd-100 fiber type thermomechanical property testing instrument.The rate of heat addition is 10 ℃/min, and it is 0.05cN/dtex that the thermal contraction test adds tension force, and it is 5.57cN/dtex that heat shock creep test adds tension force.
The surperficial adhesive property of the crosslinked front and back of table 4 UHMWPE fiber
* 3
| Sample | Uncrosslinked fiber | Example 1 fiber | Example 2 fibers |
| Maximum pull-out strength (Mpa) | 0.57 | 0.89 | 0.97 |
*3: for surveying the surperficial adhesive property of fiber, 100 parts of epoxy resin (trade mark E-51) and curing agent (trade mark 593) are placed in the high disk of 3mm for 26 parts, allow fiber vertical hanging to be measured pass disc centre and also at room temperature solidified 8 hours.Solidify the back and carry out the filament pull on tensometer, draw speed is 1mm/min.
The adhesive property of representing fiber and epoxy resin with maximum withdrawal force.Maximum pull-out strength may be defined as:
Maximum pull-out strength=maximum withdrawal force/interfacial area=maximum withdrawal force/π NDL
The N-number of fiber; The D-fibre diameter; L-epoxy thickness (soak and bury length).
Claims (9)
1. method that makes superhigh molecular weight polyethylene fibers heat resistance, creep resistance and the modification simultaneously of surperficial caking property is characterized in that:
(1) the UHMWPE fiber of removal surface impurity after the acetone carrying out washing treatment is immersed in the organic solution of photosensitizer and crosslinking agent composition; Then the fiber that soaks is carried out ultraviolet light irradiation cross-linking;
(2) described photosensitizer is benzophenone and derivative thereof, and mass concentration is 0.3～1.5% in soak;
(3) described crosslinking agent is the trifunctional or the difunctional of esters of acrylic acid, and the mass concentration in soak is 5～50%;
(4) described ultraviolet irradiation intensity is 0.05～1.5Jcm
-2
2. by the described a kind of method that makes the modification simultaneously of superhigh molecular weight polyethylene fibers heat resistance, creep resistance and surperficial caking property of claim 1, it is characterized in that: the photosensitizer mass concentration is 0.5～1.0% in the described soak.
3. by the described a kind of method that makes the modification simultaneously of superhigh molecular weight polyethylene fibers heat resistance, creep resistance and surperficial caking property of claim 1, it is characterized in that: the crosslinking agent mass concentration is 10～30% in the described soak.
4. by the described a kind of method that makes superhigh molecular weight polyethylene fibers heat resistance, creep resistance and the modification simultaneously of surperficial caking property of claim 1, it is characterized in that: the solvent of the described solution of being made up of photosensitizer and crosslinking agent is a kind of in acetone, dimethylbenzene or the normal heptane.
5. by claim 1 or 4 described a kind of methods that make superhigh molecular weight polyethylene fibers heat resistance, creep resistance and the modification simultaneously of surperficial caking property, it is characterized in that: the solvent of the described solution of being made up of photosensitizer and crosslinking agent is an acetone.
6. by the described a kind of method that makes the modification simultaneously of superhigh molecular weight polyethylene fibers heat resistance, creep resistance and surperficial caking property of claim 1, it is characterized in that: superhigh molecular weight polyethylene fibers is 0.1～5 hour in the solution kind soak time of photosensitizer and crosslinking agent composition.
7. by the described a kind of method that makes the modification simultaneously of superhigh molecular weight polyethylene fibers heat resistance, creep resistance and surperficial caking property of claim 6, it is characterized in that: the time that superhigh molecular weight polyethylene fibers soaks in the solution of photosensitizer and crosslinking agent composition is 0.3～1 hour.
8. by the described method that makes the modification simultaneously of ultra high molecular polyethylene fiber heat resistance, creep resistance and surperficial caking property of claim 1, it is characterized in that: the ultraviolet irradiation of described superhigh molecular weight polyethylene fibers is crosslinked to carry out under high pure nitrogen atmosphere.
9. by the described a kind of method that makes the modification simultaneously of superhigh molecular weight polyethylene fibers heat resistance, creep resistance and surperficial caking property of claim 1, it is characterized in that: described ultraviolet irradiation intensity is 0 1～1.0Jcm
-2
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831802B (en) * | 2010-05-10 | 2012-06-27 | 上海化工研究院 | Ultraviolet radiation two-step grafting method on surface of polyethylene fiber with ultrahigh molecular weight |
| CN102400375A (en) * | 2010-09-14 | 2012-04-04 | 公安部第一研究所 | Method for producing modified ultrahigh molecular weight polyethylene fiber by using mutual radiation grafting technology |
| CN102493168B (en) * | 2011-12-22 | 2014-07-30 | 北京服装学院 | Method for improving creep resistant performance of ultra-high molecular weight polyethylene fiber |
| CN104695039A (en) * | 2015-03-04 | 2015-06-10 | 江苏神鹤科技发展有限公司 | Thermal-resistant anti-cutting ultra-high molecular weight polyethylene fiber and preparation method thereof |
| CN104846446B (en) * | 2015-05-22 | 2018-10-02 | 江苏神鹤科技发展有限公司 | Crosslinked superhigh molecular weight polyethylene fibers and its dry type preparation method |
| CN104818541A (en) * | 2015-05-22 | 2015-08-05 | 江苏神鹤科技发展有限公司 | Crosslinked ultrahigh molecular weight polyethylene fiber and wet preparation method thereof |
| CN109234850B (en) * | 2018-08-06 | 2020-01-17 | 东华大学 | Cross-linked modified ultra-high molecular weight polyethylene fiber and preparation method thereof |
| CN109914001B (en) * | 2019-03-28 | 2022-01-14 | 浙江千禧龙纤特种纤维股份有限公司 | Method for preparing high-toughness and high-strength polyethylene fiber |
| CN114855295B (en) * | 2021-01-20 | 2024-04-05 | 东华大学 | Spinning solution, heat-resistant creep-resistant fiber and preparation method thereof |
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