CN111235665A - Ultra-high molecular weight polyethylene fiber and preparation method thereof - Google Patents
Ultra-high molecular weight polyethylene fiber and preparation method thereof Download PDFInfo
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- CN111235665A CN111235665A CN202010181796.0A CN202010181796A CN111235665A CN 111235665 A CN111235665 A CN 111235665A CN 202010181796 A CN202010181796 A CN 202010181796A CN 111235665 A CN111235665 A CN 111235665A
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- boron nitride
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- sized short
- weight polyethylene
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- 239000000835 fiber Substances 0.000 title claims abstract description 301
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 118
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 213
- 229910052582 BN Inorganic materials 0.000 claims abstract description 177
- 239000004698 Polyethylene Substances 0.000 claims abstract description 27
- -1 polyethylene Polymers 0.000 claims abstract description 27
- 229920000573 polyethylene Polymers 0.000 claims abstract description 27
- 239000011159 matrix material Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims description 54
- 239000002245 particle Substances 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 39
- 239000000843 powder Substances 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 28
- 239000007822 coupling agent Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 230000001112 coagulating effect Effects 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000009987 spinning Methods 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 229940078456 calcium stearate Drugs 0.000 claims description 3
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 229940057995 liquid paraffin Drugs 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 229940057977 zinc stearate Drugs 0.000 claims description 3
- 238000002715 modification method Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 230000006378 damage Effects 0.000 abstract description 6
- 238000004043 dyeing Methods 0.000 abstract description 3
- 239000012779 reinforcing material Substances 0.000 abstract description 3
- 229910021389 graphene Inorganic materials 0.000 abstract 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 16
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 16
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 238000007580 dry-mixing Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- PHVDOBHQKJEDJO-UHFFFAOYSA-N OB(O)OB(O)O.NC1=NC(N)=NC(N)=N1 Chemical compound OB(O)OB(O)O.NC1=NC(N)=NC(N)=N1 PHVDOBHQKJEDJO-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- 208000003251 Pruritus Diseases 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QJRVOJKLQNSNDB-UHFFFAOYSA-N 4-dodecan-3-ylbenzenesulfonic acid Chemical compound CCCCCCCCCC(CC)C1=CC=C(S(O)(=O)=O)C=C1 QJRVOJKLQNSNDB-UHFFFAOYSA-N 0.000 description 1
- PWTIWIZYPHOOGL-UHFFFAOYSA-N B(O)OBO.N1=C(N)N=C(N)N=C1N Chemical compound B(O)OBO.N1=C(N)N=C(N)N=C1N PWTIWIZYPHOOGL-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007803 itching Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012758 reinforcing additive Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Abstract
The invention relates to an ultrahigh molecular weight polyethylene fiber and a preparation method thereof, wherein the ultrahigh molecular weight polyethylene fiber comprises an ultrahigh molecular weight polyethylene matrix and boron nitride micron-sized short fibers dispersed in the ultrahigh molecular weight polyethylene matrix, and the content of the boron nitride micron-sized short fibers is 0.25-20 wt%. Compared with the existing polyethylene fiber filled with other inorganic high-hardness reinforcing materials, the ultrahigh molecular weight polyethylene fiber disclosed by the invention has high cutting resistance and easy dyeing property, and boron nitride has the lubricity similar to that of graphene, so that the ultrahigh molecular weight polyethylene fiber has no damage to fiber forming equipment. The invention also relates to a preparation method of the ultra-high molecular weight polyethylene fiber and a cutting-proof glove or cutting-proof clothes knitted by the ultra-high molecular weight polyethylene fiber. Tests prove that the gloves knitted by the ultra-high molecular weight polyethylene fibers have soft hand feeling, no pricked feeling and comfortable wearing, and the cut resistance grade is 4-5 grades through EN388-2003 tests.
Description
Technical Field
The invention relates to the technical field of artificial fibers, in particular to an ultrahigh molecular weight polyethylene fiber and a preparation method thereof.
Background
The ultra-high molecular weight polyethylene fiber is the fiber with the highest specific strength in the existing industrialized fiber materials, has excellent properties of high strength, high modulus, wear resistance, chemical corrosion resistance and the like, and is widely applied to the fields of national defense and military, maritime work mooring ropes, individual protection and the like. Along with the continuous deepening of military and civil integration, the application of the ultra-high molecular weight polyethylene fiber in the civil market is gradually increased, wherein the civil market mainly comprising the cut-proof gloves gradually takes a leading position. At present, the cutting grade of protective gloves made of commonly used 400D ultrahigh molecular weight polyethylene fibers is highest grade 3 of EN388-2003 standard, and the protective gloves are very unstable and are not more and more suitable for the requirements of protecting the injury from the cut in the actual working environment.
In order to improve the cutting-resistant grade of the gloves, the common method is to blend and weave materials such as glass fiber and steel wire with the ultra-high molecular weight polyethylene fiber, so as to achieve the purpose of improving the ultra-high cutting-resistant grade. Although the method can improve the cutting resistance of the gloves, the steel wires are hard (the steel wires are hard and are not easy to wear and the comfort is poor), the glass fibers are brittle and easy to break and expose, the hand feeling of the gloves is poor, the wearing comfort is low, the burrs of the glass fibers easily cause secondary damage such as itching, pricking and poking on the hands, and the compatibility of the protective performance and the comfort cannot be realized.
In addition, it is proposed in the industry to add inorganic high-hardness materials into the high-molecular polyethylene powder and mix them to prepare high-molecular polyethylene nascent fibers so as to enhance the cutting resistance of the ultra-high-molecular polyethylene fibers. Although the method can improve the cutting resistance of the ultra-high molecular weight polyethylene fiber to a certain extent, the method still has the problems that firstly, the inorganic high-hardness materials have higher hardness, seriously wear equipment and need to frequently replace consumable components of the equipment, thereby increasing the cost and reducing the efficiency; secondly, the reinforced material has low flexibility and is easy to puncture the matrix of the ultra-high molecular weight polyethylene fiber in the repeated use process, the fiber is damaged, and the high-strength cutting-resistant performance is ineffective; thirdly, the cutting resistance is to be further improved; fourth, although it is proposed to use carbon fibers with good flexibility as the reinforcing material, the natural color of the carbon fibers is black, so that the dyeability of the prepared high molecular weight polyethylene fibers is poor.
Disclosure of Invention
Technical problem to be solved
In view of the above, the present inventors have desired to provide an ultra-high molecular weight polyethylene fiber and a method for preparing the same, which overcome the problems of the prior art. The ultra-high molecular weight polyethylene fiber can be woven into cutting-proof gloves or cutting-proof protective clothing and the like, high-strength protective performance and better wearing comfort are realized, the dyeing property of zero number is easy, meanwhile, abrasion and damage to production equipment can be avoided, the production cost is saved, and the performance timeliness of the cutting-proof gloves or the cutting-proof protective clothing is prolonged.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
in one aspect of the application, an ultra-high molecular weight polyethylene fiber is provided, which comprises an ultra-high molecular weight polyethylene matrix and boron nitride micron-sized short fibers dispersed in the matrix, wherein the content of the boron nitride micron-sized short fibers is 0.25-20 wt%
Typically, but not by way of limitation, the boron nitride micro-sized staple fibers are present in the ultra high molecular weight polyethylene-containing matrix in an amount of 0.25 wt%, 0.5 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 3.5 wt%, 4.0 wt%, 4.5 wt%, 5.0 wt%, 5.5 wt%, 6.0 wt%, 6.5 wt%, 7.0 wt%, 7.5 wt%, 8.0 wt%, 8.5 wt%, 9.0 wt%, 9.5 wt%, 10.0 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, or 20 wt%. Tests show that: generally, when the content of the boron nitride micron-sized short fibers is more than 7%, the cutting grade is more than 5; among them, 8-11% of the cut resistance can be very good, and 4-5.5% is on the cut-proof level 4. However, the higher the content of the boron nitride micron-sized short fibers is, the greater the production difficulty is, the poorer the spinnability of the prepared polyethylene fiber yarns is, and therefore, the preferred content of the boron nitride micron-sized short fibers is 5-12 wt%.
If the content of the boron nitride micron-sized short fibers is too high, the specific gravity of the polyethylene matrix is too low, the spinnability of the prepared ultra-high molecular weight polyethylene fiber is poor (the fiber is easy to break in the spinning process), and if the content of the boron nitride micron-sized short fibers is too low, the purpose of increasing the anti-cutting performance cannot be achieved.
The commonly prepared boron nitride is of a graphite type structure, commonly called white graphite, and the natural color of the boron nitride is white, so that the dyeing property of the ultrahigh molecular weight polyethylene fiber is not influenced. The cubic boron nitride is a novel high-temperature-resistant superhard material used for manufacturing drill bits, grinding tools and cutting tools, and can be converted into diamond-type boron nitride under the conditions of high temperature (1800 ℃) and high pressure (800Mpa), similar to the principle that graphite is converted into diamond. The boron nitride used in the invention mainly refers to stereo boron nitride, and some graphite type boron nitride (such as mass ratio of 6-8: 4-2) can be doped. The boron nitride has certain self-lubricating property, the friction coefficient of the hexagonal boron nitride is as low as 0.16, and the hexagonal boron nitride can be used as a lubricant in some occasions. Due to the self-lubricating property, the friction loss effect on preparation equipment can be reduced, and the service life of the equipment is prolonged.
The diameter of the boron nitride micron-sized short fiber is preferably 0.1-20 μm, and more preferably 5-12 μm; the length of the boron nitride micron-sized short fibers is preferably 1 to 180 μm, more preferably 50 to 100 μm; and the shape of the boron nitride micron-sized short fiber is long rod-shaped particles with the length larger than the diameter. Compared with powdery boron nitride, the fibrous boron nitride has better anti-cutting performance for the prepared ultra-high molecular weight polyethylene fiber. The inorganic micro powder mainly plays a role of a physical cross-linking point in the fiber, and the improvement of the cutting resistance of the fiber is realized by limiting the slippage between macromolecular chains of the polyethylene fiber, but the inorganic micro powder is more prone to be squeezed to one side by a blade edge instead of resisting the damage of the blade edge in the fiber cutting process of the blade, so the improvement degree of the cutting resistance is limited. The fibrous boron nitride has no problem of being squeezed to one side by a blade, and can play a better role in cutting resistance.
However, the boron nitride micron-sized short fibers are inorganic fillers, the affinity with the polyethylene matrix is poor, the pure boron nitride micron-sized short fibers cannot be well dispersed when being added into the polyethylene matrix, the dispersion uniformity and firmness of the boron nitride micron-sized short fibers in the matrix have great influence on the properties of finally prepared polyethylene fiber yarns, and the boron nitride micron-sized short fibers are not good in binding force with ultra-high molecular weight polyethylene fibers under the condition of poor affinity, are easy to fall off or pull out in the spinning and stretching processes, and influence on the cutting resistance.
Therefore, further, in order to improve the affinity and dispersibility between the boron nitride micron-sized short fibers and the polyethylene matrix, the invention adopts one or more of the following modes:
the first method is as follows: modifying the boron nitride micron-sized short fibers by using a coupling agent;
the second method comprises the following steps: coating modification, namely coating a high molecular polymer on the surface of the boron nitride micron-sized short fiber;
the third method comprises the following steps: mixing the boron nitride micron-sized short fibers and boron nitride particles for use, wherein the crossed positions or gaps of the short fibers are supplemented by the boron nitride particles;
the method is as follows: the EVA (ethylene-vinyl acetate copolymer) is doped into the ultra-high molecular weight polyethylene, and the dispersibility of the boron nitride micron-sized short fibers in the matrix material can be obviously improved by doping the EVA;
the fifth mode is as follows: a plurality of tiny micropores (mostly nano micropores) can be formed on the surface of the short fiber, so that on one hand, the specific surface area of the boron nitride micron-sized short fiber can be increased, and the bonding tightness between the boron nitride micron-sized short fiber and the ultrahigh molecular weight polyethylene is improved; on the other hand, compared with the boron nitride micron-sized short fiber without micropores, the boron nitride micron-sized short fiber has better flexibility which is comparable with that of carbon fiber, and is beneficial to improving the spinnability of the finally prepared anti-cutting ultrahigh molecular weight polyethylene fiber and the softness, the fitting property and the wearability of a woven glove; the boron nitride fiber with better flexibility is not easy to puncture the polyethylene substrate along with the repeated bending use of the polyethylene fiber wire to cause the pulling-out of the polyethylene substrate, and has less damage to equipment.
The specific method of the first mode can be as follows: dissolving the boron nitride micron-sized short fibers in 1-5mol/L sodium hydroxide solution, stirring for 10-20h at 110-120 ℃, performing suction filtration, washing with deionized water, and drying to obtain activated boron nitride micron-sized short fibers with hydroxylated surfaces; preparing acetone and dilute hydrochloric acid with the pH value of 2-4 into a solution according to the volume ratio of 6-10:1, adding a coupling agent into the solution, hydrolyzing at 40-60 ℃ for 0.5-1h, adding activated boron nitride micron-sized short fibers into the solution, continuously stirring for 2-5h, and drying to obtain the modified boron nitride micron-sized short fibers. Wherein the coupling agent is KH570 or CAI, and the coupling agent accounts for 1-10% of the raw material of the boron nitride micron-sized short fiber.
The specific method of the second mode can be as follows: heating the boron nitride micron-sized short fiber raw material to 250-350 ℃, adding mixed resin and stirring to form a mixture, adding a dispersing agent and stirring before the mixture starts to agglomerate, and adding a curing agent and an accelerant and stirring; cooling the materials to 40-90 ℃, transferring the materials to a crusher for crushing, and finally sieving the materials for 200 meshes and 1000 meshes to obtain the modified boron nitride micron-sized short fibers coated with the high molecular polymer; the dispersing agent is one or more of polyethylene wax, stearic acid amide, ethylene bis-stearamide, calcium stearate, zinc stearate, liquid paraffin and silicone oil; the accelerant is mica powder, DDM, DMP-30, CaO and TiO2One or more of; the curing agent is one or more of imidazole, acid anhydride, Lewis acid, hexamethylenetetramine and ethyl orthosilicate compounds; the high molecular polymer can be phenolic resin, polyurethane resin, EVA and the like. Wherein the dosage of the dispersant is 0.02-0.05% of the mass of the boron nitride micron-sized short fiber raw material; the dosage of the curing agent is 0.1-0.5% of the mass of the boron nitride micron-sized short fiber raw material; the dosage of the accelerant is 0.1-1% of the mass of the boron nitride micron-sized short fiber raw material.
The third method can be as follows: the median particle size of the boron nitride particles is 0.1-12 mu m, and the mass ratio of the boron nitride micron-sized short fibers to the boron nitride particles is 5-20: 1. Before mixing with the ultrahigh molecular weight polyethylene master batch, the boron nitride micron-sized short fibers and the boron nitride particles can be premixed in a dry state, the boron nitride particles are adsorbed on the surfaces of the boron nitride micron-sized short fibers, the surface roughness of the boron nitride micron-sized short fibers is effectively improved, the surface potential is increased, the bonding force with the ultrahigh molecular weight polyethylene fiber interface is enhanced, and the cutting resistance of the fiber is improved. The method has the advantages that boron nitride particles are introduced on the basis of the boron nitride micron-sized short fibers, so that the effect of obvious reinforcement and toughening is achieved, firstly, in the stretching process of the ultra-high molecular weight polyethylene fibers, the boron nitride particles generate a stress concentration effect to excite surrounding matrixes to generate silver lines, and meanwhile, the matrixes among the particles generate yield to absorb certain deformation work, so that the toughening effect is achieved; secondly, the existence of the boron nitride particles can resist and passivate the crack propagation of the ultra-high molecular weight polyethylene fiber matrix, play a role of a physical cross-linking point and show fiber reinforcement; thirdly, the existence of the micro-nano particles enables the average size of crystal grains of the ultra-high molecular weight polyethylene fiber to be obviously reduced, thereby being beneficial to improving the modulus. The ultra-high molecular weight polyethylene fiber finally shows enhanced mechanical property, and can improve the cutting resistance.
The fourth way can be: the boron nitride is more inclined to be dispersed in the EVA, and the EVA has good affinity with the ultra-high molecular weight polyethylene and can be well mixed and mutually dissolved, so that the dispersibility of the boron nitride micron-sized short fibers in the ultra-high molecular weight polyethylene fibers can be enhanced by adding a certain proportion of the EVA. Preferably, the mass ratio of the EVA to the ultra-high molecular weight polyethylene is 1:20-30, and the EVA becomes a solid dispersant of the boron nitride.
The implementation of the fifth mode can be as follows: using boric acid and melamine as raw materials, carrying out hydrothermal synthesis on melamine diboric acid precursor powder, then adopting a freeze-drying method to rapidly cool a hot water solution of the melamine diboric acid precursor by using liquid nitrogen, and then drying to synthesize melamine diboric acid fibers; and then thermally cracking the melamine diboronic acid fiber at high temperature under a protective atmosphere to obtain the porous boron nitride fiber. Or taking nitrogen compound, boron compound and pore-forming agent as raw materials, dissolving and mixing the raw materials by water, heating the raw materials in water bath under violent stirring to form a mixture of boride and nitride, dehydrating and drying the mixture to obtain a boron nitride fiber precursor, then loading the precursor into a corundum fire boat, putting the corundum fire boat into a vacuum tube furnace, carrying out pyrolysis at a certain temperature for a certain time in a flowing nitrogen atmosphere, heating and carrying out heat treatment on the pyrolysis product in a muffle furnace at a certain temperature for a certain time to remove possible free carbon and the like, thus obtaining the boron nitride fiber with micropores, wherein the specific surface of the prepared porous boron nitride fiber can reach 450m2g-1The above.
Preferably, the first mode and the fourth mode can be jointly adopted, or the first mode and the third mode can be jointly adopted; the second mode can be used alone, and the fourth mode can be used alone. The combined use of the third mode and the fourth mode can also have good effect, and the process is simpler, the production cost is higher, and the process period is shorter.
Based on the above, the invention also relates to a preparation method of the ultra-high molecular weight polyethylene fiber, which comprises the following steps:
s1, mixing the boron nitride micron-sized short fibers with ultra-high molecular weight polyethylene powder with the molecular weight of 20-600 ten thousand, and then heating and swelling the mixture in a spinning solvent to obtain a mixed material; or:
dispersing boron nitride in a spinning solvent in advance, adding a surfactant, mixing to prepare an emulsified material, then dispersing ultra-high molecular weight polyethylene powder with the molecular weight of 20-600 ten thousand in the spinning solvent, stirring, adding the emulsified material, stirring again, heating and swelling to obtain a mixed material;
s2, blending and extruding the mixture through an extruder, cooling and forming through a coagulating bath to obtain nascent fibers, and extracting, drying and carrying out multistage hot drawing on the nascent fibers to obtain ultrahigh molecular weight polyethylene fibers; wherein the content of the boron nitride micron-sized short fibers is 0.25-20 wt%.
According to the preparation method, the diameter of the boron nitride micron-sized short fiber is 0.1-20 μm, the length of the boron nitride micron-sized short fiber is 1-180 μm, and the shape of the boron nitride micron-sized short fiber is long rod-shaped particles with the length larger than the diameter. More preferably, the boron nitride micro-sized short fibers preferably have a diameter of 5 to 12 μm and a length of 50 to 100 μm. For example, the boron nitride micro-sized staple fibers may have a diameter of 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm; the length can be 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm.
According to the preparation method of the invention, in step S1, the boron nitride micron-sized short fibers and boron nitride particles are dry-mixed in advance and then mixed with ultra-high molecular weight polyethylene powder; the boron nitride particles are boron nitride particles with the median particle size of 0.1-12 mu m, and the mass ratio of the boron nitride micron-sized short fibers to the boron nitride particles is 5-20: 1.
According to the preparation method, the boron nitride micron-sized short fiber is a modified boron nitride micron-sized short fiber with the surface coated with a high molecular polymer, or is activated by hydroxyl and then connected with a coupling agent; or the boron nitride micron-sized short fiber is a boron nitride short fiber with micropores formed on the surface in the preparation process.
According to the preparation method, the boron nitride micron-sized short fiber is a modified boron nitride micron-sized short fiber with the surface coated with a high molecular polymer, and the modification method comprises the following steps:
heating the boron nitride micron-sized short fiber raw material to 250-350 ℃, adding mixed resin and stirring to form a mixture, adding a dispersing agent and stirring before the mixture starts to agglomerate, and adding a curing agent and an accelerant and stirring; cooling the materials to 40-90 ℃, transferring the materials to a crusher for crushing, and finally sieving the materials for 200 meshes and 1000 meshes to obtain the modified boron nitride micron-sized short fibers coated with the high molecular polymer; the dispersing agent is one or more of polyethylene wax, stearic acid amide, ethylene bis-stearamide, calcium stearate, zinc stearate, liquid paraffin and silicone oil; the accelerant is mica powder, DDM, DMP-30, CaO and TiO2One or more of; the curing agent is one or more of imidazole, acid anhydride, Lewis acid, hexamethylenetetramine and ethyl orthosilicate compounds;
or the boron nitride micron-sized short fiber is modified boron nitride micron-sized short fiber which is activated by hydroxyl and then connected with a coupling agent, and the specific method comprises the following steps:
dissolving the boron nitride micron-sized short fibers in 1-5mol/L sodium hydroxide solution, stirring for 10-20h at 110-120 ℃, performing suction filtration, washing with deionized water, and drying to obtain activated boron nitride micron-sized short fibers with hydroxylated surfaces; preparing acetone and dilute hydrochloric acid with the pH value of 2-4 into a solution according to the volume ratio of 6-10:1, adding a coupling agent into the solution, hydrolyzing at 40-60 ℃ for 0.5-1h, adding activated boron nitride micron-sized short fibers into the solution, continuously stirring for 2-5h, and drying to obtain the modified boron nitride micron-sized short fibers.
According to the preparation method, the dosage of the dispersant is 0.02-0.05% of the mass of the boron nitride micron-sized short fiber raw material; the dosage of the curing agent is 0.1-0.5% of the mass of the boron nitride micron-sized short fiber raw material; the dosage of the accelerant is 0.1-1% of the mass of the boron nitride micron-sized short fiber raw material.
According to the preparation method, the coupling agent is KH570 or CAI, and the coupling agent accounts for 1-10% of the raw material of the boron nitride micron-sized short fiber.
According to the preparation method of the invention, in the step S1, EVA powder is further included, and the ratio of the EVA powder to the ultra-high molecular weight polyethylene powder is 1: 20-30.
Typically, but not by way of limitation, the ultra-high molecular weight polyethylene has a molecular weight of 20, 40, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, 500, 520, 540, 560, 580 or 600 ten thousand.
In a preferred embodiment of the present invention, the particles of the boron nitride micro-sized short fibers have a diameter of 0.1 to 20 μm and a length of 1 to 180 μm. Further, the shape of the particles of the boron nitride micron-sized short fibers is long rod-shaped particles with the length larger than the diameter; more preferably 20-60 μm in length. Typically, but not by way of limitation, the boron nitride micro-sized staple fibers have a particle length of 20-30 μm, 30-40 μm, 40-50 μm, 50-60 μm, 60-80 μm, or 80-100 μm.
Preferably, the spinning solvent is one or more selected from white oil, mineral oil, vegetable oil, paraffin oil and decalin.
In a preferred embodiment of the present invention, the molecular weight of the ultra-high molecular weight polyethylene is 200-500 ten thousand. The larger the molecular weight of the ultra-high molecular weight polyethylene is, the better the anti-cutting effect is, but the larger the preparation difficulty is, the spinnability of the polyethylene fiber yarn and the wearability after the polyethylene fiber yarn is prepared into the glove can be influenced.
The higher the molecular weight of the ultra-high molecular weight polyethylene is, the higher the anti-cutting performance and the mechanical strength are, but if the molecular weight is too large, the viscosity is too large, the difficulty is high when extruding and manufacturing the fiber yarn, the fiber yarn is not easy to form, the requirement on equipment is high in the preparation process, and the equipment loss is large. Through repeated tests, the performance of the ultra-high molecular weight polyethylene fiber yarn obtained when the molecular weight is 200-500 ten thousand is optimal in all aspects, and the loss to equipment is low.
In a preferred embodiment of the present invention, the extruder is a twin-screw extruder, and the temperature of each zone of the twin-screw extruder is controlled between 100 ℃ and 300 ℃.
The present invention relates to an ultrahigh molecular weight polyethylene fiber produced by the production method described in any one of the above examples.
The invention also relates to a cutting-proof glove or cutting-proof clothes, which comprises a braided fabric formed by braiding the ultra-high molecular weight polyethylene fiber prepared by any one of the embodiments or the preparation methods.
(III) advantageous effects
The invention has the beneficial effects that:
(1) according to the invention, the boron nitride micron-sized short fibers are used as reinforcing materials and dispersed in the ultrahigh molecular weight polyethylene fiber matrix material, so that the ultrahigh molecular weight polyethylene fiber with the cutting resistance is obtained. Compared with the method for blending and weaving the glass fiber, the steel wire and other materials with the ultra-high molecular weight polyethylene fiber in the prior art, the gloves or glove blanks woven by the ultra-high molecular weight polyethylene fiber with the ultra-high cutting resistance have better wearing comfort, such as softness, better touch feeling, no burr, pruritus, poking and scratching and other problems, and are easy to wear.
(2) Compared with a carbon fiber material (with black primary color) as a reinforcing additive, the boron nitride micron-sized short fiber used in the invention is white, so that the prepared ultra-high molecular weight polyethylene fiber can be dyed as required in the later period, and the polyethylene fiber or fabrics such as gloves woven in the later period can be dyed as required.
(3) The invention uses the boron nitride micron-sized short fiber instead of the boron nitride particle powder, thereby having better cutting resistance.
(4) The boron nitride has self-lubricating property, so that the wear to equipment is small in the production process, the equipment and production cost is reduced, and the production efficiency is not negatively influenced.
(5) The affinity and the dispersibility of the boron nitride micron-sized short fibers and the ultrahigh molecular weight polyethylene fiber matrix are further improved in various modes, the holding force of the polyethylene fiber matrix on the boron nitride micron-sized short fibers is improved, the boron nitride micron-sized short fibers are not easy to shift/separate from the surface of the matrix, and therefore the boron nitride micron-sized short fibers can be kept in the ultrahigh molecular weight polyethylene fiber matrix more durably, and the cutting resistance, the aging resistance and the like of finally prepared polyethylene fibers are improved.
In conclusion, the ultra-high molecular weight polyethylene fiber greatly improves the cutting resistance of the ultra-high molecular weight polyethylene fiber, and the cutting resistance grade of woven fabrics such as gloves can stably reach the 5 grade of European standard 388-2003 standard. The ultrahigh-cutting-resistant ultrahigh-molecular-weight polyethylene fiber produced according to the invention does not need to be blended and reinforced with materials such as steel wires and glass fibers, and the produced protective gloves are soft in texture, light, handy and sensitive, are not easy to fatigue after being worn for a long time, realize the consideration of ultrahigh cutting-resistant and wearing comfort, are easy to dye, and have good protection effect on equipment.
Detailed Description
In order that the invention may be better understood, it is described in detail below with reference to specific examples.
Example 1
The embodiment provides a preparation method of an ultrahigh molecular weight polyethylene fiber, which comprises the following steps:
(1) 1200g of boron nitride micron-sized short fibers with the length of 10-20 microns are taken and dispersed in 5Kg of white oil, 300g of linear alkyl benzene sodium sulfonate (LAS) serving as a surfactant is added, and the mixture is uniformly stirred at a high speed and emulsified to obtain an emulsified material.
(2) And (2) putting the emulsified material and 15Kg of ultra-high molecular weight polyethylene powder with the molecular weight of 200 ten thousand and the average particle size of 100 mu m into 95Kg of white oil, stirring and mixing at a high speed for 0.5h, heating to 70 ℃, preserving heat for 2h, stirring and mixing for 0.5h, and repeating until complete swelling to obtain a mixture.
(3) And (2) blending and extruding the mixture by a double-screw extruder, cooling and forming by a coagulating bath to obtain nascent fibers, extracting, drying and carrying out multi-stage hot drawing on the obtained nascent fibers to prepare white ultrahigh molecular weight polyethylene ultrahigh cutting-resistant fibers, wherein the dispersion concentration of the boron nitride micron-sized short fibers in the ultrahigh molecular weight polyethylene is 7.4%. Wherein, the temperature of each area of the double screw is controlled to be 180-260 ℃, and the drawing ratio is 15.
The fiber has good dyeability, no prickling feeling and comfortable wearing, and the cut-resistant grade is 5 grade by EN388-2003 test.
Example 2
The embodiment provides a preparation method of an ultrahigh molecular weight polyethylene fiber, which comprises the following steps:
(1) 1200g of boron nitride micron-sized short fibers with the length of 20-40um and a plurality of micropores on the surface are taken and dispersed in 5Kg of white oil, 300g of linear alkyl benzene sulfonic acid (LAS) serving as a surfactant is added, and the mixture is uniformly stirred at a high speed and emulsified to obtain an emulsified material.
(2) And (2) putting the emulsified material and 15Kg of ultra-high molecular weight polyethylene powder with the molecular weight of 200 ten thousand and the average particle size of 100 mu m into 95Kg of white oil, stirring and mixing at a high speed for 0.5h, heating to 70 ℃, preserving heat for 2h, stirring and mixing for 0.5h, and repeating until complete swelling to obtain a mixture.
(3) And (2) blending and extruding the mixture by a double-screw extruder, cooling and forming by a coagulating bath to obtain nascent fibers, extracting, drying and carrying out multi-stage hot drawing on the obtained nascent fibers to prepare white ultrahigh molecular weight polyethylene ultrahigh cutting-resistant fibers, wherein the dispersion concentration of the boron nitride micron-sized short fibers in the ultrahigh molecular weight polyethylene is 7.4%. Wherein, the temperature of each area of the double screw is controlled to be 180-260 ℃, and the drawing ratio is 15.
The fiber has the advantages of good dyeability, soft hand feeling, no prickling feeling and comfortable wearing, and the cut-resistant grade is 5 grade according to the EN388-2003 test.
Example 3
The embodiment provides a preparation method of an ultrahigh molecular weight polyethylene fiber, which comprises the following steps:
(1) and (2) dissolving 1000g of boron nitride micron-sized short fibers with the length of 20-30 microns in 1L of 5mol/L sodium hydroxide solution, stirring for 12 hours at 120 ℃, washing for 3 times by using deionized water after suction filtration, and drying at 60 ℃ to obtain the surface hydroxylated boron nitride micron-sized short fibers.
(2) Preparing acetone and dilute hydrochloric acid with the pH value of 3 into a solution according to the volume ratio of 9:1, adding 50g of a coupling agent KH570, hydrolyzing at 60 ℃ for 1h, then adding the surface hydroxylated boron nitride micron-sized short fiber obtained in the step (1) into the solution, mixing with the hydrolyzed coupling agent, stirring at 50 ℃ for 3h, carrying out suction filtration, washing with deionized water for 3 times, and drying to obtain the surface coupling agent modified boron nitride micron-sized short fiber.
(3) And (2) performing ball milling dry mixing on the surface coupling agent modified boron nitride micron-sized short fibers and 20Kg of ultra-high molecular weight polyethylene powder with the molecular weight of 300 ten thousand and the average particle size of 100 mu m for 20min, putting the mixture into 100Kg of white oil, stirring and mixing for 2h, heating to 65 ℃, stirring and mixing for 2h until the mixture is completely swelled, and thus obtaining a mixture.
(4) And (2) blending and extruding the mixed mixture by a double-screw extruder, cooling and forming by a coagulating bath to obtain nascent fibers, extracting, drying and carrying out multi-stage hot drawing on the nascent fibers to obtain white ultrahigh molecular weight polyethylene ultrahigh cutting-resistant fibers, wherein the dispersion concentration of the boron nitride fibers in the ultrahigh molecular weight polyethylene is 4.76%. Wherein the temperature of each area of the twin-screw is controlled at 170-220 ℃, and the drawing ratio is 20.
The fiber has good dyeability, no prickling feeling and comfortable wearing, and the anti-cutting grade is 4 grade according to the EN388-2003 test.
Example 4
The embodiment provides a preparation method of an ultrahigh molecular weight polyethylene fiber, which comprises the following steps:
(1) 1600g of boron nitride micron-sized short fibers with the length of 30-60um and 200g of boron nitride powder with the median particle size of 10um are taken to be dry-mixed in a ball mill for 20min in advance to obtain dry-mixed material of the boron nitride fibers and the boron nitride powder.
(2) And mechanically mixing the dry mixture and 20kg of ultra-high molecular weight polyethylene powder with the molecular weight of 260 ten thousand and the average particle size of 100um for 20min, adding the mixture into 100kg of white oil, heating to 65 ℃, stirring and mixing for 2h until the mixture is completely swelled to obtain the mixture.
(3) And (2) blending and extruding the mixed mixture by a double-screw extruder, cooling and forming by a coagulating bath to obtain nascent fiber, extracting, drying and carrying out multi-stage hot drawing on the obtained nascent fiber to prepare white ultrahigh molecular weight polyethylene ultrahigh cutting-resistant fiber, wherein the dispersion concentration of boron nitride in the ultrahigh molecular weight polyethylene is 8.26%. Wherein, the temperature of each area of the double screw is controlled at 220 ℃ below 180 ℃, and the drawing ratio is 8.
The fiber has good dyeability, no prickling feeling and comfortable wearing, and the cut-resistant grade is 5 grade by EN388-2003 test.
Example 5
The embodiment provides a preparation method of an ultrahigh molecular weight polyethylene fiber, which comprises the following steps:
(1) adding 800g of boron nitride micron-sized short fiber with the length of 20-30um to 260 ℃, then adding 100g of polyurethane resin (a mixture of hydroxyl-terminated dihydric alcohol and 1, 4-cyclohexane diisocyanate), stirring to form a mixture, and adding 0.35g of calcium stearate, 0.75g of imidazole curing agent and 0.75g of TiO before the beginning of caking2Then rapidly stirring. Stopping heating, cooling to 50 ℃, transferring to a crusher for crushing, sieving for 500 meshes and reserving 300 meshes, returning to the crusher for crushing again and sieving treatment when the materials can not be sieved. Finally, the modified boron nitride micron-sized short fiber coated with the high molecular polymer is prepared.
(2) And (2) mixing the modified boron nitride micron-sized short fibers and 20kg of ultra-high molecular weight polyethylene powder with the molecular weight of 360 ten thousand and the average particle size of 100 mu m in a ball mill for 15min, adding the mixture into 100kg of white oil, heating the mixture to 50 ℃, and stirring for 2h until the ultra-high molecular weight polyethylene is completely swelled to obtain a mixture.
(3) And (2) blending and extruding the mixed mixture by a double-screw extruder, cooling and forming by a coagulating bath to obtain nascent fibers, extracting, drying and carrying out multi-stage hot drawing on the obtained nascent fibers to obtain white ultrahigh molecular weight polyethylene ultrahigh cutting-resistant fibers, wherein the dispersion concentration of the boron nitride fibers in the ultrahigh molecular weight polyethylene is 3.84%. Wherein, the temperature of each area of the twin-screw is controlled to be 180-220 ℃, and the drawing ratio is 16.
The fiber has good dyeability, no prickling feeling and comfortable wearing, and the anti-cutting grade is 4 grade according to the EN388-2003 test.
Example 6
The embodiment provides a preparation method of an ultrahigh molecular weight polyethylene fiber, which comprises the following steps:
(1) 2.0kg of boron nitride micron-sized short fiber with the length of 40-60um is taken.
(2) The boron nitride micron-sized short fibers, 18kg of ultra-high molecular weight polyethylene powder with the molecular weight of 40 ten thousand and the average particle size of 100um and 1.0kg of master batch of EVA with the relative molecular weight of 2000 are mixed together in a ball mill for 30 min. Then, the mixture was added to 100kg of paraffin oil, heated to 75 ℃ and stirred until the mixture completely swelled.
(3) And (2) blending and extruding the mixed mixture by a double-screw extruder, cooling and forming by a coagulating bath to obtain nascent fibers, extracting, drying and carrying out multi-stage hot drawing on the nascent fibers to obtain white ultrahigh molecular weight polyethylene ultrahigh cutting-resistant fibers, wherein the dispersion concentration of the boron nitride fibers in the ultrahigh molecular weight polyethylene is 9.5%. Wherein, the temperature of each area of the twin-screw is controlled at 190 ℃ and 230 ℃, and the drawing magnification is 12.
The fiber has good dyeability, no prickling feeling and comfortable wearing, and the cut-resistant grade is 5 grade by an EN388-2003 test.
Example 7
The embodiment provides a preparation method of an ultrahigh molecular weight polyethylene fiber, which comprises the following steps:
(1) 1600g of boron nitride micron-sized short fiber with the length of 20-30um is taken, dissolved in 2L of 5mol/L sodium hydroxide solution, stirred for 12 hours at 120 ℃, washed by deionized water for 3 times after suction filtration, and dried at 60 ℃ to obtain the surface hydroxylated boron nitride micron-sized short fiber.
(2) Preparing acetone and dilute hydrochloric acid with the pH value of 3 into a solution according to the volume ratio of 9:1, adding 100g of a coupling agent KH570, hydrolyzing at 60 ℃ for 1.5h, then adding the surface-hydroxylated boron nitride micron-sized short fiber obtained in the step (1) into the solution, mixing with the hydrolyzed coupling agent, stirring at 50 ℃ for 3h, carrying out suction filtration, washing with deionized water for 3 times, and drying to obtain the surface-coupling-agent-modified boron nitride micron-sized short fiber.
(3) And (2) performing ball milling dry mixing on the surface coupling agent modified boron nitride micron-sized short fibers, 20Kg of ultrahigh molecular weight polyethylene powder with the molecular weight of 300 ten thousand and the average particle size of 100 mu m and 1.0Kg of master batch of EVA with the relative molecular weight of 2000 for 20min, putting the mixture into 100Kg of white oil, stirring and mixing for 2h, heating to 75 ℃, stirring and mixing for 2h until the mixture is completely swelled, and obtaining a mixture.
(4) And (2) blending and extruding the mixed mixture by a double-screw extruder, cooling and forming by a coagulating bath to obtain nascent fibers, extracting, drying and carrying out multi-stage hot drawing on the nascent fibers to obtain white ultrahigh molecular weight polyethylene ultrahigh cutting-resistant fibers, wherein the dispersion concentration of the boron nitride fibers in the ultrahigh molecular weight polyethylene is 7.07%. Wherein, the temperature of each area of the twin-screw is controlled at 160-190 ℃, and the drawing ratio is 10.
The fiber has good dyeability, no prickling feeling and comfortable wearing, and the cut-resistant grade is 5 grade by an EN388-2003 test.
Example 8
The embodiment provides a preparation method of an ultrahigh molecular weight polyethylene fiber, which comprises the following steps:
(1) and (3) dissolving 850g of boron nitride micron-sized short fibers with the length of 30-60 microns in 2L of 5mol/L sodium hydroxide solution, stirring for 12 hours at 120 ℃, washing for 3 times by using deionized water after suction filtration, and drying at 60 ℃ to obtain the surface hydroxylated boron nitride micron-sized short fibers.
(2) Preparing acetone and dilute hydrochloric acid with the pH value of 3 into a solution according to the volume ratio of 9:1, adding 55g of a coupling agent KH570, hydrolyzing at 60 ℃ for 1.5h, then adding the surface-hydroxylated boron nitride micron-sized short fiber obtained in the step (1) into the solution, mixing with the hydrolyzed coupling agent, stirring at 50 ℃ for 3h, carrying out suction filtration, washing with deionized water for 3 times, and drying to obtain the surface-coupling-agent-modified boron nitride micron-sized short fiber.
(3) And (3) carrying out dry mixing on the surface coupling agent modified boron nitride micron-sized short fibers and 100g of boron nitride particle powder with the median particle size of 8 mu m in a ball mill for 20min in advance to obtain a dry mixture of boron nitride fibers and boron nitride powder.
(4) And (3) carrying out ball milling dry mixing on the dry mixture and 20Kg of ultra-high molecular weight polyethylene powder with the molecular weight of 300 ten thousand and the average particle size of 100um for 20min, putting the dry mixture and the ultra-high molecular weight polyethylene powder into 100Kg of white oil, stirring and mixing the mixture for 2h, heating the mixture to 75 ℃, and stirring and mixing the mixture for 2h until the mixture is completely swelled to obtain a mixture.
(5) And (2) blending and extruding the mixed mixture by a double-screw extruder, cooling and forming by a coagulating bath to obtain nascent fibers, extracting, drying and carrying out multi-stage hot drawing on the nascent fibers to obtain white ultrahigh molecular weight polyethylene ultrahigh cutting-resistant fibers, wherein the dispersion concentration of the boron nitride fibers in the ultrahigh molecular weight polyethylene is 4.5%. Wherein, the temperature of each area of the twin-screw is controlled at 200-230 ℃, and the drawing magnification is 12.
The fiber has good dyeability, no prickling feeling and comfortable wearing, and the anti-cutting grade is 4 grade according to the EN388-2003 test.
Example 9
The embodiment provides a preparation method of an ultrahigh molecular weight polyethylene fiber, which comprises the following steps:
(1) 1800g of boron nitride micron-sized short fibers with the length of 20-60um and 200g of boron nitride particles with the median particle size of 6-10um are mixed in advance in a mixer to obtain the boron nitride dry powder.
(2) The boron nitride dry mixture and 1.0Kg of EVA with the molecular weight of 18Kg of ultra-high molecular weight polyethylene powder with the molecular weight of 300 ten thousand and the average particle size of 100um and the molecular weight of about 2000 are ball-milled and dry-mixed for 20min, then are put into 100Kg of white oil together, stirred and mixed for 2h, heated to 75 ℃, stirred and mixed for 2h until the mixture is completely swelled, and stirred to obtain the mixture.
(3) And (2) blending and extruding the mixture by a double-screw extruder, cooling and forming by a coagulating bath to obtain nascent fibers, extracting, drying and carrying out multi-stage hot drawing on the obtained nascent fibers to prepare white ultrahigh molecular weight polyethylene ultrahigh cutting-resistant fibers, wherein the dispersion concentration of the boron nitride fibers in the ultrahigh molecular weight polyethylene is 9.5%. Wherein, the temperature of each area of the twin-screw is controlled at 210-240 ℃, and the drawing ratio is 10.
The fiber has good dyeability, no prickling feeling and comfortable wearing, and the cut-resistant grade is 5 grade by an EN388-2003 test.
Comparative example 1
The boron nitride micro-sized short fibers in example 1 were replaced with 1200g of boron nitride particle powder having a median particle size of 12 microns. Other conditions and treatment procedures referring to example 1, ultra-high molecular weight polyethylene ultra-high cut resistant fibers were prepared with a boron nitride dispersion concentration of 7.4% in the ultra-high molecular weight polyethylene. The cut-resistant rating was 4 as tested by EN 388-2003. The prepared fiber yarn has poor cutting resistance and high aging speed.
The ultra-high molecular weight polyethylene fibers prepared in examples 1 to 8 and comparative example 1 were woven into 13-pin protective gloves, and after being worn and used for 1 day (1d) and 20 days (20d) by workers operating in the same place, the performance of the gloves was respectively tested, and the test results were as follows:
the test results show that the anti-cutting grade of fabrics such as gloves woven by the ultra-high molecular weight polyethylene fiber can reliably and stably reach EN388-2003 standard grade 4-5. More importantly, the ultra-high molecular weight polyethylene fiber produced according to the invention is white without adding pigment, and the fiber yarn and the textile are easy to color.
Furthermore, as can be seen from the comparison between examples 2-8 and example 1, the cut resistance of example 1 decays rapidly, mainly due to the poor affinity, poor dispersibility and precipitation of boron nitride fibers in the ultra-high molecular weight polyethylene matrix. Example 2 and example 1 at the same content of boron nitride fiber, the cut resistance data of example 2 is substantially the same as that of example 1, but the decay rate of the cut resistance is obviously slower, and the prepared fiber filament is softer and has better spinnability than that of example 1, and the content concentration can be about 14%.
Comparative example 1 although the boron nitride content also reached 7.4%, the cut resistance was 1 rank weaker than that of the polyethylene fiber yarn reinforced with the same content of boron nitride micro-sized short fibers (example 1). Therefore, the cutting resistance of the ultra-high molecular weight polyethylene fiber obtained by replacing the boron nitride particle powder with the boron nitride micron-sized short fiber is greatly enhanced. In addition, the polyethylene fibers of example 1 and comparative example 1 both exhibited a certain degree of burring after 20 days of use, indicating that some boron nitride short fibers or granular powder was exuded.
In examples 6 and 8, the content of the boron nitride micron-sized short fiber is the highest, and the cutting resistance is the best, but if the content is too high, the spinnability of the fiber yarn is deteriorated, so that the content of the boron nitride is not too high, and the content is optimally 9 to 9.5 percent. In example 7, after the boron nitride micron-sized short fibers are modified by the coupling agent, the boron nitride particle powder or the EVA matrix doped with a certain proportion is introduced, so that the bonding stability of the boron nitride micron-sized short fibers in the polyethylene fibers can be significantly increased, and as can be seen from the use of 20d data, the cutting resistance and aging are not significant, and compared with example 1, the cutting resistance of the polyethylene fiber yarn in example 7 is slowly attenuated. Examples 3, 4, and 5 are methods of modifying, coating, or doping a certain proportion of EVA with a coupling agent, respectively, all of which can improve the dispersibility of boron nitride fibers in a polyethylene fiber matrix and improve the aging resistance of the cut resistance.
In addition, according to long-term observation and research, the abrasion of the mixing equipment and the extrusion molding equipment in the preparation process is not obvious in examples 1 to 8 and comparative example 1, which are mainly caused by the self-lubricating property of the boron nitride, so that the equipment loss speed is reduced.
Claims (10)
1. The ultra-high molecular weight polyethylene fiber is characterized by comprising an ultra-high molecular weight polyethylene matrix and boron nitride micron-sized short fibers dispersed in the matrix, wherein the content of the boron nitride micron-sized short fibers is 0.25-20 wt%.
2. The ultra-high molecular weight polyethylene fiber according to claim 1, wherein the boron nitride micro-sized short fibers have a diameter of 0.1 to 20 μm and a length of 1 to 180 μm, and are in the form of long rod-like particles having a length greater than the diameter.
3. The ultra-high molecular weight polyethylene fiber according to claim 1, wherein boron nitride particles with a median particle size of 0.1-12 μm are further dispersed in the ultra-high molecular weight polyethylene matrix, and the mass ratio of the boron nitride micro-sized short fibers to the boron nitride particles is 5-20: 1;
or the boron nitride micron-sized short fiber is a modified boron nitride micron-sized short fiber with the surface coated with a high molecular polymer;
or the boron nitride micron-sized short fiber is a modified boron nitride micron-sized short fiber which is activated by hydroxyl and then connected with a coupling agent;
or the boron nitride micron-sized short fiber is a short fiber with micropores on the surface.
4. A method for preparing ultra-high molecular weight polyethylene fibers is characterized by comprising the following steps:
s1, mixing the boron nitride micron-sized short fibers with ultra-high molecular weight polyethylene powder with the molecular weight of 20-600 ten thousand, and then heating and swelling the mixture in a spinning solvent to obtain a mixed material; or:
dispersing boron nitride in a spinning solvent in advance, adding a surfactant, mixing to prepare an emulsified material, then dispersing ultra-high molecular weight polyethylene powder with the molecular weight of 20-600 ten thousand in the spinning solvent, stirring, adding the emulsified material, stirring again, heating and swelling to obtain a mixed material;
s2, blending and extruding the mixture through an extruder, cooling and forming through a coagulating bath to obtain nascent fibers, and extracting, drying and carrying out multistage hot drawing on the nascent fibers to obtain ultrahigh molecular weight polyethylene fibers; wherein the content of the boron nitride micron-sized short fibers is 0.25-20 wt%.
5. The method of claim 4, wherein the boron nitride micro-sized short fibers have a diameter of 0.1 to 20 μm and a length of 1 to 180 μm, and are in the form of long rod-shaped particles having a length greater than the diameter.
6. The method of claim 5, wherein in step S1, the boron nitride micron-sized short fibers and boron nitride particles are dry-blended in advance and then mixed with the ultra-high molecular weight polyethylene powder; the boron nitride particles are boron nitride particles with the median particle size of 0.1-12 mu m, and the mass ratio of the boron nitride micron-sized short fibers to the boron nitride particles is 5-20: 1.
7. The preparation method according to claim 4 or 5, wherein the boron nitride micro-sized short fiber is a modified boron nitride micro-sized short fiber with a surface coated with a high molecular polymer, or a modified boron nitride micro-sized short fiber which is activated by hydroxyl and then connected with a coupling agent.
8. The preparation method according to claim 7, wherein the boron nitride micron-sized short fiber is a modified boron nitride micron-sized short fiber coated with a high molecular polymer on the surface, and the modification method comprises the following steps:
heating the boron nitride micron-sized short fiber raw material to 250-350 ℃, adding mixed resin and stirring to form a mixture, adding a dispersing agent and stirring before the mixture starts to agglomerate, and adding a curing agent and an accelerant and stirring; cooling the materials to 40-90 ℃, transferring the materials to a crusher for crushing, and finally sieving the materials for 200 meshes and 1000 meshes to obtain the modified boron nitride micron-sized short fibers coated with the high molecular polymer; the dispersing agent is one or more of polyethylene wax, stearic acid amide, ethylene bis-stearamide, calcium stearate, zinc stearate, liquid paraffin and silicone oil; the accelerant is mica powder, DDM, DMP-30, CaO and TiO2One or more of; the curing agent is one or more of imidazole, acid anhydride, Lewis acid, hexamethylenetetramine and ethyl orthosilicate compounds;
or the boron nitride micron-sized short fiber is modified boron nitride micron-sized short fiber which is activated by hydroxyl and then connected with a coupling agent, and the specific method comprises the following steps:
dissolving the boron nitride micron-sized short fibers in 1-5mol/L sodium hydroxide solution, stirring for 10-20h at 110-120 ℃, performing suction filtration, washing with deionized water, and drying to obtain activated boron nitride micron-sized short fibers with hydroxylated surfaces; preparing acetone and dilute hydrochloric acid with the pH value of 2-4 into a solution according to the volume ratio of 6-10:1, adding a coupling agent into the solution, hydrolyzing at 40-60 ℃ for 0.5-1h, adding activated boron nitride micron-sized short fibers into the solution, continuously stirring for 2-5h, and drying to obtain the modified boron nitride micron-sized short fibers.
9. The preparation method of claim 8, wherein the amount of the dispersant is 0.02-0.05% of the mass of the boron nitride micron-sized short fiber raw material; the dosage of the curing agent is 0.1-0.5% of the mass of the boron nitride micron-sized short fiber raw material; the amount of the accelerant is 0.1-1% of the mass of the boron nitride micron-sized short fiber raw material;
the coupling agent is KH570 or CAI, and accounts for 1-10% of the raw material of the boron nitride micron-sized short fiber.
10. The method of claim 5, wherein step S1 further comprises EVA powdering, and the ratio of EVA powdering to ultra-high molecular weight polyethylene powder is 1: 20-30.
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