CN113293452A - Ultra-high molecular weight polyethylene fiber cable, cable material and preparation method thereof - Google Patents
Ultra-high molecular weight polyethylene fiber cable, cable material and preparation method thereof Download PDFInfo
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- CN113293452A CN113293452A CN202110274682.5A CN202110274682A CN113293452A CN 113293452 A CN113293452 A CN 113293452A CN 202110274682 A CN202110274682 A CN 202110274682A CN 113293452 A CN113293452 A CN 113293452A
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- mixture
- molecular weight
- weight polyethylene
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- high molecular
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- 239000000463 material Substances 0.000 title claims abstract description 157
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 138
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 137
- 239000000835 fiber Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003607 modifier Substances 0.000 claims abstract description 44
- 230000008961 swelling Effects 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 36
- 238000001816 cooling Methods 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 238000004804 winding Methods 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000001125 extrusion Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 176
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 35
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- 239000002244 precipitate Substances 0.000 claims description 20
- 239000012188 paraffin wax Substances 0.000 claims description 19
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 18
- 229920000877 Melamine resin Polymers 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 17
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 230000001804 emulsifying effect Effects 0.000 claims description 16
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 239000003242 anti bacterial agent Substances 0.000 claims description 15
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 15
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 14
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 14
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000008098 formaldehyde solution Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000012745 toughening agent Substances 0.000 claims description 8
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 claims description 7
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 235000019198 oils Nutrition 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 4
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001427 strontium ion Inorganic materials 0.000 claims description 4
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000005662 Paraffin oil Substances 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- 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 claims description 3
- 206010042674 Swelling Diseases 0.000 description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 26
- 230000000844 anti-bacterial effect Effects 0.000 description 21
- 239000004408 titanium dioxide Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 9
- 230000003385 bacteriostatic effect Effects 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- -1 Polyethylene Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000003902 seawater pollution Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
- D01D5/0885—Cooling filaments, threads or the like, leaving the spinnerettes by means of a liquid
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
-
- 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
-
- 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
- D01F1/103—Agents inhibiting growth of microorganisms
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B1/00—Constructional features of ropes or cables
- D07B1/02—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics
- D07B1/025—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics comprising high modulus, or high tenacity, polymer filaments or fibres, e.g. liquid-crystal polymers
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2205/00—Rope or cable materials
- D07B2205/20—Organic high polymers
- D07B2205/201—Polyolefins
- D07B2205/2014—High performance polyolefins, e.g. Dyneema or Spectra
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Artificial Filaments (AREA)
Abstract
The invention provides an ultra-high molecular weight polyethylene fiber cable, a cable material and a preparation method thereof. The preparation method comprises the following steps: s11, preparing ultra-high molecular weight polyethylene: modifying agent: solvent (10-30): (4-6): 100, uniformly mixing raw materials comprising ultrahigh molecular weight polyethylene, a modifier and a solvent to obtain a first material; s12, swelling, melt extrusion and water bath cooling are carried out on the first material to obtain ultra-high molecular weight polyethylene precursor; and S13, extracting, drying, drafting and winding the ultra-high molecular weight polyethylene precursor to obtain the ultra-high molecular weight polyethylene fiber cable material. The ultra-high molecular weight polyethylene fiber cable material obtained by the invention has excellent performance, high toughness and high mechanical strength.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an ultra-high molecular weight polyethylene fiber cable, a cable material and a preparation method thereof.
Background
Ultra-High Molecular Weight Polyethylene Fiber (UHMWPEF) is also called High-strength High-modulus Polyethylene Fiber, and refers to Fiber spun from Polyethylene with Molecular Weight of 100-500 ten thousand. The method has wide application prospect in various fields such as aerospace, automobiles, ships, medical instruments, daily lives and the like.
The ultra-high molecular weight polyethylene fiber has the advantages of high strength and impact resistance, and is suitable for being used as a material for manufacturing the mooring rope. When the ultra-high molecular weight polyethylene fiber is used as a material for manufacturing the mooring rope, modification treatment of the ultra-high molecular weight polyethylene fiber is absolutely necessary in order to guarantee the service life of the mooring rope.
Disclosure of Invention
The present invention is directed to solving at least one of the above-mentioned problems to improve the properties of ultra-high molecular weight polyethylene fibers.
In order to achieve the first object of the present invention, an embodiment of the present invention provides a method for preparing an ultra-high molecular weight polyethylene fiber cable material, including:
s11, preparing ultra-high molecular weight polyethylene: modifying agent: solvent (10-30): (4-6): 100, uniformly mixing raw materials comprising ultrahigh molecular weight polyethylene, a modifier and a solvent to obtain a first material;
s12, swelling, melt extrusion and water bath cooling are carried out on the first material to obtain ultra-high molecular weight polyethylene precursor;
and S13, extracting, drying, drafting and winding the ultra-high molecular weight polyethylene precursor to obtain the ultra-high molecular weight polyethylene fiber cable material.
Further, the modifying agent comprises at least one of the following or a combination thereof: silver ion antibacterial agent, strontium ion antibacterial agent, and titanium ion antibacterial agent.
Further, the modifying agent comprises at least one of the following or a combination thereof: silicon nitride toughening agent and silicon carbide toughening agent.
Further, the solvent comprises at least one of the following or a combination thereof: white oil, mineral oil, vegetable oil, decalin, paraffin oil.
Further, swelling, melt-extruding and cooling in water bath are carried out on the first material to obtain the ultra-high molecular weight polyethylene precursor, which comprises the following steps:
s121, feeding the first material into a swelling kettle, and swelling for 0.5 to 1.5 hours at the temperature of 100 to 110 ℃ to obtain a second material, wherein the shear rate of the swelling kettle is 1200 seconds-1To 1500 seconds-1；
S122, feeding the second material into a double-screw extruder, and performing melt extrusion under the conditions of the temperature of 120-220 ℃ and the rotating speed of 200-400 rpm to obtain a third material;
and S123, cooling the third material in a water bath for 18 to 24 hours at the temperature of between 20 and 25 ℃ to obtain the ultra-high molecular weight polyethylene precursor.
Further, extracting, drying, drafting and winding the ultra-high molecular weight polyethylene precursor to obtain the ultra-high molecular weight polyethylene fiber cable material, which comprises the following steps:
s131, feeding the ultra-high molecular weight polyethylene precursor into an extractor, and extracting at the temperature of 36-38 ℃ to obtain a fourth material;
s132, drying the fourth material at the temperature of 30-36 ℃ in a nitrogen environment to obtain a fifth material;
s133, performing primary stretching on the fifth material at a temperature of between 90 and 110 ℃, performing secondary stretching at a temperature of between 120 and 130 ℃, and performing tertiary stretching at a temperature of between 140 and 150 ℃ to obtain a sixth material, wherein the stretching multiple of the primary stretching is between 3 and 4, the stretching multiple of the secondary stretching is between 2 and 3, and the stretching multiple of the tertiary stretching is between 1.5 and 2;
and S134, feeding the sixth material into a winding machine for winding to obtain the ultra-high molecular weight polyethylene fiber cable material.
Further, the modifier is prepared by the following steps:
s21, mixing titanium tetrachloride, polyvinyl alcohol and ethanol to obtain a first mixture;
s22, mixing silicon nitride, vinyl trimethoxy silane and ethanol to obtain a second mixture;
s23, mixing the first mixture and the second mixture to obtain a third mixture, and dropwise adding a sodium hydroxide solution into the third mixture and synchronously stirring until the pH value of the third mixture is adjusted to 10-12;
s24, feeding the third mixture into a reaction kettle, reacting for 3 to 4 hours at the temperature of 180 to 200 ℃, and then cooling, filtering, washing and drying to obtain a precipitate;
s25, mixing paraffin, sodium dodecyl benzene sulfonate and water, and ultrasonically emulsifying to obtain a fourth mixture;
s26, mixing and ultrasonically emulsifying sodium hexametaphosphate, the precipitate and the fourth mixture to obtain a fifth mixture, and adjusting the pH value of the fifth mixture to 5-6;
s27, mixing melamine, a formaldehyde aqueous solution and water to obtain a sixth mixture, and adjusting the pH value of the sixth mixture to 8-9;
s28, dropwise adding the sixth mixture into the fifth mixture, synchronously stirring, standing after dropwise adding is finished, adjusting the pH value to 7-8 after standing is finished, and filtering, washing and drying after the pH value is adjusted to obtain the modifier.
Further, the modifier is prepared by the following steps:
s31, preparing titanium tetrachloride: polyvinyl alcohol: ethanol ═ (10-20): 15: mixing titanium tetrachloride, polyvinyl alcohol and ethanol according to a mass ratio of 100 to obtain a first mixture;
s32, according to the silicon nitride: vinyl trimethoxy silane: ethanol ═ (10-20): 15: mixing silicon nitride, vinyl trimethoxy silane and ethanol according to the mass ratio of 100 to obtain a second mixture;
s33, according to the first mixture: second mixture ═ (20-40): 100, mixing the first mixture and the second mixture to obtain a third mixture, and dropwise adding a sodium hydroxide solution into the third mixture at a rate of 6 ml/min to 10 ml/min and synchronously stirring until the pH value of the third mixture is adjusted to 10 to 12;
s34, feeding the third mixture into a reaction kettle, reacting for 3 to 4 hours at the temperature of between 180 and 200 ℃, and then cooling, filtering, washing and drying to obtain a precipitate;
s35, according to paraffin: sodium dodecylbenzenesulfonate: water ═ 10-20: (10-15): 100, mixing paraffin, sodium dodecyl benzene sulfonate and water at the temperature of 55-65 ℃, and ultrasonically emulsifying for 20-40 minutes to obtain a fourth mixture;
s36, mixing sodium hexametaphosphate: and (3) precipitation: fourth mixture ═ (0.5-1): (8-12): 100, mixing and ultrasonically emulsifying the sodium hexametaphosphate, the precipitate and the fourth mixture at the temperature of 80-85 ℃ for 20-40 minutes, cooling to room temperature to obtain a fifth mixture, and adjusting the pH value of the fifth mixture to 5-6;
s37, adding melamine: aqueous formaldehyde solution: water ═ 40-50: (50-80): mixing melamine, 35 wt% to 40 wt% aqueous formaldehyde solution and water to obtain a sixth mixture, and adjusting the pH value of the sixth mixture to 8 to 9, wherein the mass ratio of the melamine is 100;
s38, heating the fifth mixture to 55-65 ℃, dropwise adding the sixth mixture into the fifth mixture at a rate of 12-18 ml/min, synchronously stirring, stopping heating after dropwise adding, standing for 1-2 hours, adjusting the pH value to 7-8 after standing, and filtering, washing and drying after pH value adjustment to obtain the modifier, wherein the dropwise adding amount of the sixth mixture is 1.5-1.6 times of the adding mass of the paraffin.
To achieve the second object of the present invention, embodiments of the present invention provide an ultra-high molecular weight polyethylene fiber cable material, which is obtained by the preparation method according to any one of the embodiments of the present invention.
To achieve the third objective of the present invention, embodiments of the present invention provide an ultra-high molecular weight polyethylene fiber cable, wherein the cable is made of a material obtained by the preparation method according to any one of the embodiments of the present invention.
The beneficial effects of the invention are as follows. The invention adopts ultra-high molecular weight polyethylene as a main raw material, and prepares the ultra-high molecular weight polyethylene fiber cable material through the steps of swelling, melt extrusion, water bath cooling, extraction, drying, drafting, winding and the like. The modifier is added in the preparation process of the ultra-high molecular weight polyethylene fiber cable material, so that the performance of the ultra-high molecular weight polyethylene fiber cable material is improved, and the service life of the cable material is prolonged. Optionally, the modifier adopted by the invention comprises a toughening agent and an antibacterial agent, wherein the toughening agent can improve the strength of the high-ultrahigh molecular weight polyethylene fiber, and the antibacterial agent can improve the antibacterial and bacteriostatic properties of the high-ultrahigh molecular weight polyethylene fiber and reduce the influence of corrosion damage of a seawater environment on the ultrahigh molecular weight polyethylene fiber cable material.
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be described in further detail with reference to specific embodiments. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and thus the scope of the present invention is not limited by the specific embodiments disclosed below.
The embodiment provides a preparation method of an ultra-high molecular weight polyethylene fiber cable material, which comprises the following steps:
s11, preparing ultra-high molecular weight polyethylene: modifying agent: solvent (10-30): (4-6): 100, uniformly mixing raw materials comprising ultrahigh molecular weight polyethylene, a modifier and a solvent to obtain a first material;
s12, swelling, melt extrusion and water bath cooling are carried out on the first material to obtain ultra-high molecular weight polyethylene precursor;
and S13, extracting, drying, drafting and winding the ultra-high molecular weight polyethylene precursor to obtain the ultra-high molecular weight polyethylene fiber cable material.
It should be noted that the first material in the above step is a mixture of ultra-high molecular weight polyethylene, modifier and solvent. The ultra-high molecular weight polyethylene precursor obtained in the above steps is also called as gel precursor.
Optionally, in the above embodiment, the modifier comprises at least one of the following or a combination thereof: silver ion antibacterial agent, strontium ion antibacterial agent, and titanium ion antibacterial agent.
Alternatively, in the above embodiment, the silver ion antibacterial agent, the strontium ion antibacterial agent, and the titanium ion antibacterial agent are added in the form of oxides.
Optionally, in the above embodiment, the modifier comprises at least one of the following or a combination thereof: silicon nitride toughening agent and silicon carbide toughening agent.
Optionally, in the above embodiment, the solvent includes at least one of the following or a combination thereof: white oil, mineral oil, vegetable oil, decalin, paraffin oil.
Alternatively, in the above embodiments, the ultra-high molecular weight polyethylene refers to fibers spun from polyethylene having a molecular weight of 100 to 500 ten thousand. Optionally, the molecular weight of the ultra-high molecular weight polyethylene used in the above step is 400 to 500 ten thousand. Optionally, the ultra-high molecular weight polyethylene used in the above step is powder with an average particle size range of 200 to 800 microns.
Optionally, in the above embodiment, the crystallinity of the ultrahigh molecular weight polyethylene used in the above step is greater than or equal to 55%. Optionally, the melting point of the ultra-high molecular weight polyethylene used in the above step is greater than or equal to 145 ℃. Optionally, the bulk density of the ultra-high molecular weight polyethylene used in the above step is less than or equal to 0.34 g/cc.
Optionally, in the above embodiment, the kinematic viscosity of the solvent used in the above step is greater than or equal to 64 mm/s.
Alternatively, in the above embodiment, the swelling step may be performed by using a swelling kettle, the melt extrusion step may be performed by using a twin-screw extruder, the water bath cooling may be performed by using a water bath device, the extraction step may be performed by using an extractor, the drying step may be performed by using an air-blowing drying device or an infrared drying device, and the drawing and winding may be performed by using a drawing machine and a winding machine.
Optionally, in the above embodiment, the temperature range of the swelling step in the above step is 100 to 140 degrees celsius. Optionally, the treatment time of the swelling step in the above step is 0.5 to 2.5 hours. Optionally, the shear rate of the swelling step in the above step is 1000 seconds-1To 2000 seconds-1。
Alternatively, in the above embodiment, the swelling step in the above step may be performed in two or more stages. For example, in the first stage, the swelling temperature is controlled to be 100 ℃ to 105 ℃, and the swelling time is controlled to be 20 minutes to 30 minutes; in the second stage, the swelling temperature is controlled to be 105 ℃ to 110 ℃, and the swelling time is controlled to be 30 minutes to 40 minutes.
Optionally, in the above embodiment, the temperature range of the melt extrusion step in the above step is 100 to 240 ℃. Optionally, the processing time of the melt extrusion step in the above steps is 0.5 hour to 1 hour. The screw rotation speed of the melt extrusion step in the above step is 100 to 400 revolutions per minute.
Optionally, in the above embodiment, the processing temperature of the melt extrusion step in the above step is stepped. For example, the inlet temperature of the twin-screw extruder is 100 to 110 ℃, the temperature of the intermediate extrusion dissolution is 140 to 170 ℃, and the outlet temperature is 160 to 200 ℃.
Alternatively, in the above examples, the raw material may be passed through the dissolution tank and the feeding tank in the above steps between the feeding of the raw material from the swelling tank to the twin-screw extruder.
Optionally, in the above embodiment, the temperature range of the water bath cooling in the above step is 15 to 30 ℃. The treatment time of the water bath cooling step in the above steps is 10 to 36 hours.
Optionally, in the above embodiment, the temperature range of the extraction step in the above step is 36 to 38 ℃. The treatment time in the extraction step in the above step is 0.5 to 1.5 hours. The extracting agent in the extracting step in the step is one or more of dichloromethane, hydrocarbon extracting agent, gasoline, carbon tetrachloride, toluene or toluene.
Optionally, in the above embodiment, the temperature range of the drying step in the above step is 30 to 45 ℃. Optionally, nitrogen or carbon dioxide or the like may be used to form a protective atmosphere in the drying step.
Optionally, in the above embodiment, in the above step, the raw material may be subjected to multi-stage stretching in the stretching step, the stretching temperature ranges from 90 degrees celsius to 160 degrees celsius, and the total stretching multiple is 6 times to 80 times.
Optionally, in the above embodiment, other additives such as an antioxidant, a coupling agent, a colorant, and a dispersant may also be added to the raw materials for obtaining the first material in the above step.
Optionally, in the above embodiment, swelling, melt-extruding, and cooling in a water bath are performed on the first material to obtain the ultra-high molecular weight polyethylene filament, including:
s121, feeding the first material into a swelling kettle, and swelling for 0.5 to 1.5 hours at the temperature of 100 to 110 ℃ to obtain a second material, wherein the shear rate of the swelling kettle is 1200 seconds-1To 1500 seconds-1；
S122, feeding the second material into a double-screw extruder, and performing melt extrusion under the conditions of the temperature of 120-220 ℃ and the rotating speed of 200-400 rpm to obtain a third material;
and S123, cooling the third material in a water bath for 18 to 24 hours at the temperature of between 20 and 25 ℃ to obtain the ultra-high molecular weight polyethylene precursor.
Optionally, in the above embodiment, the second material refers to a first material subjected to swelling treatment, and after the first material is subjected to swelling treatment, the physical property and/or chemical property of the first material changes, so this embodiment distinguishes the swollen raw material by the second material and the first material.
Optionally, in the above embodiment, the third material refers to a melt-extruded second material, and after the melt-extruded second material is melt-extruded, the physical property and/or the chemical property of the second material are changed, so that the melt-extruded raw materials are distinguished by the third material and the second material in this embodiment.
Optionally, in this embodiment, extracting, drying, drafting, and winding the ultra-high molecular weight polyethylene precursor to obtain the ultra-high molecular weight polyethylene fiber cable material, includes:
s131, feeding the ultra-high molecular weight polyethylene precursor into an extractor, and extracting at the temperature of 36-38 ℃ to obtain a fourth material;
s132, drying the fourth material at the temperature of 30-36 ℃ in a nitrogen environment to obtain a fifth material;
s133, performing primary stretching on the fifth material at the temperature of 90-110 ℃, performing secondary stretching at the temperature of 120-130 ℃, and performing tertiary stretching at the temperature of 140-150 ℃ to obtain a sixth material;
and S134, feeding the sixth material into a winding machine for winding to obtain the ultra-high molecular weight polyethylene fiber cable material.
Optionally, in the above embodiment, the fourth material is extracted ultrahigh molecular weight polyethylene precursor, and after the ultrahigh molecular weight polyethylene precursor is subjected to extraction treatment, physical properties and/or chemical properties of the ultrahigh molecular weight polyethylene precursor change, so that the ultrahigh molecular weight polyethylene precursor before and after the extraction treatment is distinguished by the fourth material in this embodiment.
Optionally, in the foregoing embodiment, the fifth material refers to a dried fourth material, and after the fourth material is dried, the physical property and/or the chemical property of the fourth material including the moisture content changes, so that the fourth material and the fifth material are used to distinguish the raw materials before and after the drying process.
Optionally, in the above embodiment, the sixth material is a stretched fifth material, and after the fifth material is subjected to stretching treatment, the physical properties and/or chemical properties of the fifth material, including the length and the diameter, are changed, so that in this embodiment, the sixth material and the fifth material are used to distinguish between the raw materials before and after the stretching treatment.
Alternatively, in the above embodiment, the ultra-high molecular weight polyethylene fiber cable material refers to a sixth material which is wound.
Alternatively, in the above examples, the stretching ratio of the primary stretching is 3 times to 4 times, the stretching ratio of the secondary stretching is 2 times to 3 times, and the stretching ratio of the tertiary stretching is 1.5 times to 2 times.
In the above embodiment, the addition of the modifier can improve the performance of the ultra-high molecular weight polyethylene fiber cable material, so as to improve the service life of the ultra-high molecular weight polyethylene fiber cable material.
Alternatively, in the above examples, the modifier was prepared by the following steps:
s21, mixing titanium tetrachloride, polyvinyl alcohol and ethanol to obtain a first mixture;
s22, mixing silicon nitride, vinyl trimethoxy silane and ethanol to obtain a second mixture;
s23, mixing the first mixture and the second mixture to obtain a third mixture, and dropwise adding a sodium hydroxide solution into the third mixture and synchronously stirring until the pH value of the third mixture is adjusted to 10-12;
s24, feeding the third mixture into a reaction kettle, reacting for 3 to 4 hours at the temperature of 180 to 200 ℃, and then cooling, filtering, washing and drying to obtain a precipitate;
s25, mixing paraffin, sodium dodecyl benzene sulfonate and water, and ultrasonically emulsifying to obtain a fourth mixture;
s26, mixing and ultrasonically emulsifying sodium hexametaphosphate, the precipitate and the fourth mixture to obtain a fifth mixture, and adjusting the pH value of the fifth mixture to 5-6;
s27, mixing melamine, a formaldehyde aqueous solution and water to obtain a sixth mixture, and adjusting the pH value of the sixth mixture to 8-9;
s28, dropwise adding the sixth mixture into the fifth mixture, synchronously stirring, standing after dropwise adding is finished, adjusting the pH value to 7-8 after standing is finished, and filtering, washing and drying after the pH value is adjusted to obtain the modifier.
Alternatively, in the above examples, the modifier was prepared by the following steps:
s31, preparing titanium tetrachloride: polyvinyl alcohol: ethanol ═ (10-20): 15: mixing titanium tetrachloride, polyvinyl alcohol and ethanol according to a mass ratio of 100 to obtain a first mixture;
s32, according to the silicon nitride: vinyl trimethoxy silane: ethanol ═ (10-20): 15: mixing silicon nitride, vinyl trimethoxy silane and ethanol according to the mass ratio of 100 to obtain a second mixture;
s33, according to the first mixture: second mixture ═ (20-40): 100, mixing the first mixture and the second mixture to obtain a third mixture, and dropwise adding a sodium hydroxide solution into the third mixture at a rate of 6 ml/min to 10 ml/min and synchronously stirring until the pH value of the third mixture is adjusted to 10 to 12;
s34, feeding the third mixture into a reaction kettle, reacting for 3 to 4 hours at the temperature of between 180 and 200 ℃, and then cooling, filtering, washing and drying to obtain a precipitate;
s35, according to paraffin: sodium dodecylbenzenesulfonate: water ═ 10-20: (10-15): 100, mixing paraffin, sodium dodecyl benzene sulfonate and water at the temperature of 55-65 ℃, and ultrasonically emulsifying for 20-40 minutes to obtain a fourth mixture;
s36, mixing sodium hexametaphosphate: and (3) precipitation: fourth mixture ═ (0.5-1): (8-12): 100, mixing and ultrasonically emulsifying the sodium hexametaphosphate, the precipitate and the fourth mixture at the temperature of 80-85 ℃ for 20-40 minutes, cooling to room temperature to obtain a fifth mixture, and adjusting the pH value of the fifth mixture to 5-6;
s37, adding melamine: aqueous formaldehyde solution: water ═ 40-50: (50-80): mixing melamine, 35 wt% to 40 wt% aqueous formaldehyde solution and water to obtain a sixth mixture, and adjusting the pH value of the sixth mixture to 8 to 9, wherein the mass ratio of the melamine is 100;
s38, heating the fifth mixture to 55-65 ℃, dropwise adding the sixth mixture into the fifth mixture at a rate of 12-18 ml/min, synchronously stirring, stopping heating after dropwise adding, standing for 1-2 hours, adjusting the pH value to 7-8 after standing, and filtering, washing and drying after pH value adjustment to obtain the modifier, wherein the dropwise adding amount of the sixth mixture is 1.5-1.6 times of the adding mass of the paraffin.
In the related art, the modification treatment of the high ultra high molecular weight polyethylene fiber includes the following two. One of the methods is to improve the mechanical strength and toughness of the ultra-high molecular weight polyethylene fiber by adding a toughening modifier. For example, inorganic substances such as silicon carbide powder, silicon nitride powder, graphite powder, glass fiber, etc. may be added to the high ultra-high molecular weight polyethylene raw material for preparing the high ultra-high molecular weight polyethylene fiber, thereby improving the mechanical strength and toughness of the ultra-high molecular weight polyethylene fiber. The other method is to add an antibacterial modifier to improve the antibacterial and bacteriostatic performance of the ultra-high molecular weight polyethylene fiber. For example, antibacterial agents such as titanium dioxide powder, silver oxide, zinc oxide, strontium oxide, etc. may be added to the high ultra high molecular weight polyethylene raw material for preparing the high ultra high molecular weight polyethylene fiber, thereby improving the antibacterial and bacteriostatic properties of the ultra high molecular weight polyethylene fiber. However, one of the problems in the related art is that the above toughening modifiers and antibacterial modifiers are generally inorganic substances, which are in the form of particles or powders, and have high surface energy. Therefore, the dispersion performance of the toughening modifier and the antibacterial modifier in the high molecular polymer is not ideal. In particular, for high ultra-high molecular weight polyethylene, it not only has a low surface energy and surface tension, but also a high crystallinity, and its surface is smooth. Therefore, it is difficult to effectively combine the high ultra high molecular weight polyethylene with the inorganic modifier. In other words, the inorganic modifier is difficult to uniformly disperse in the high ultrahigh molecular weight polyethylene. The problem results in that the modification effect of the inorganic modifier on the high and ultrahigh molecular weight polyethylene is not ideal enough, and the uniformity of the material of the high and ultrahigh molecular weight polyethylene added with the inorganic modifier needs to be improved. To this end, the above-described embodiments of the present invention produce a modifier that is particularly suitable for addition to high ultra-high molecular weight polyethylene. The modifier includes silicon nitride and titanium dioxide. The silicon nitride can improve the strength and toughness of the high-ultrahigh molecular weight polyethylene fiber. The titanium dioxide improves the antibacterial and bacteriostatic effects of the high-ultrahigh molecular weight polyethylene fibers. In addition, the modifier not only has lower surface energy, but also is easy to be uniformly dispersed in the polyethylene with high ultrahigh molecular weight. Therefore, the ultrahigh molecular weight polyethylene fiber adopting the modifier prepared in the embodiment of the invention has excellent mechanical strength and antibacterial and bacteriostatic properties. The mooring rope made of the ultra-high molecular weight polyethylene fiber prepared by the embodiment of the invention is not easy to break and damage, and can resist the corrosion action of organic organisms or substances such as bacteria, fungi, seawater pollution and the like in seawater. Specifically, the embodiment of the present invention mixes titanium tetrachloride, polyvinyl alcohol, and ethanol through step S21 or S31 to obtain a first mixture. Titanium tetrachloride, which is liquid at room temperature, is used as a titanium source. Polyvinyl alcohol and ethanol are used as solvents for dissolving titanium tetrachloride. Thus, the first mixture is a mixture comprising a titanium source. Further, the embodiment of the present invention mixes silicon nitride, vinyltrimethoxysilane and ethanol through steps S22 or S32. The silicon nitride is introduced in the form of a powder. The silicon nitride has excellent hardness and impact resistance, and can improve the mechanical strength of the ultra-high molecular weight polyethylene fiber. Vinyl trimethoxy silane is used as a coupling agent, and can reduce the surface energy of silicon nitride to a certain extent. In step S22 or S32, ethanol is used as a solvent. The silicon nitride was suspended in ethanol by the coupling of vinyltrimethoxysilane to form a second mixture in the form of a suspension. Thereafter, the embodiment of the present invention mixes the first mixture and the second mixture through step S23 or S33 to obtain a third mixture. The third mixture includes silicon nitride and titanium tetrachloride. Subsequently, the embodiment of the present invention feeds the third mixture to the reaction kettle for reaction through step S24 or S34, and performs cooling, filtering, washing and drying after the reaction is completed to obtain a precipitate. The pH value of the third mixture can be increased by adding sodium hydroxide solution dropwise into the third mixture and stirring synchronously, so that titanium tetrachloride forms titanium dioxide under the action of hydroxide radical and deposits and coats the surface of the granular or powdery silicon nitride. Thus, the precipitation may include deposition of silicon nitride coated with titanium dioxide. The deposited silicon nitride coated with titanium dioxide can not only improve the mechanical strength of the ultrahigh molecular weight polyethylene fiber, but also utilize the photocatalysis performance of the titanium dioxide to endow the ultrahigh molecular weight polyethylene fiber with excellent antibacterial and bacteriostatic effects. In addition, because the titanium dioxide is deposited on the silicon nitride surface in a wet coating mode, compared with the technical scheme that the antibacterial modifying agent is directly added into the ultra-high molecular weight polyethylene in a titanium dioxide powder form in the related art, the titanium dioxide in the embodiment of the invention has smaller particle size and larger contact area with organic microorganisms or organic substances such as bacteria and fungi, and therefore, the modifying agent in the embodiment of the invention has higher photocatalytic activity and better antibacterial and bacteriostatic properties. In order to improve the dispersibility of the precipitate including silicon nitride coated with titanium dioxide in ultra-high molecular weight polyethylene, the embodiment of the present invention treats the precipitate. Specifically, the inventive example mixed and ultrasonically emulsified paraffin, sodium dodecylbenzenesulfonate and water through steps S25 or S35 to obtain a fourth mixture. Among them, sodium dodecylbenzenesulfonate was used as an emulsifier. The fourth mixture is a milky mixture. Further, the embodiment of the present invention mixes and sonicates sodium hexametaphosphate, the precipitate, and the fourth mixture by steps S26 or S36 to obtain a fifth mixture, and adjusts the fifth mixture to be weakly acidic. Wherein the pH of the fifth mixture can be adjusted using citric acid or acetic acid. Thereafter, in the embodiment of the present invention, the melamine and the aqueous solution of formaldehyde are mixed in water in steps S27 or S37 to obtain a sixth mixture, and the pH of the sixth mixture is adjusted to be weakly alkaline, so that the melamine and the formaldehyde react to form a prepolymer. Wherein the pH of the sixth mixture can be adjusted with aqueous ammonia or aqueous sodium hydroxide. Finally, the present embodiment adds the sixth mixture dropwise to the fifth mixture through steps S28 or S38. The sixth mixture comprises a prepolymer which is adsorbed and precipitated on the surfaces of the tiny silicon nitride particles coated with titanium dioxide and polymerized into a film, and the prepolymer is used as a wall material coated outside the core material of the silicon nitride particles, so that the surface energy and the surface tension of the silicon nitride particles coated with titanium dioxide are reduced. In conclusion, the modifier provided by the embodiment of the invention not only has lower surface energy, but also is easy to be uniformly dispersed in the polyethylene with high ultrahigh molecular weight. Therefore, the ultrahigh molecular weight polyethylene fiber adopting the modifier prepared by the embodiment of the invention has excellent mechanical strength and antibacterial and bacteriostatic properties.
Example 1
The embodiment provides a preparation method of an ultra-high molecular weight polyethylene fiber cable material, which comprises the following steps.
S401, according to titanium tetrachloride: polyvinyl alcohol: ethanol ═ 10: 15: mixing titanium tetrachloride, polyvinyl alcohol and ethanol according to a mass ratio of 100 to obtain a first mixture;
s402, according to the silicon nitride: vinyl trimethoxy silane: ethanol ═ 10: 15: mixing silicon nitride, vinyl trimethoxy silane and ethanol according to the mass ratio of 100 to obtain a second mixture;
s403, according to the first mixture: second mixture 20: 100 by mass, mixing the first mixture obtained in S401 and the second mixture obtained in S402 to obtain a third mixture, and adding a sodium hydroxide solution dropwise to the third mixture at a rate of 6 ml/min while stirring until the pH of the third mixture is adjusted to 10;
s404, feeding the third mixture obtained in the step S403 into a reaction kettle, reacting for 3 hours at the temperature of 180 ℃, and then cooling, filtering, washing and drying to obtain a precipitate;
s405, according to paraffin: sodium dodecylbenzenesulfonate: water 10: 10: 100, mixing and ultrasonically emulsifying the paraffin obtained in the step S404, sodium dodecyl benzene sulfonate and water at the temperature of 55 ℃ for 20 minutes to obtain a fourth mixture;
s406, mixing sodium hexametaphosphate: and (3) precipitation: fourth mixture ═ 0.5: 8: 100, mixing and ultrasonically emulsifying sodium hexametaphosphate, the precipitate obtained in the step S404 and the fourth mixture obtained in the step S405 at the temperature of 80 ℃ for 20 minutes, cooling to room temperature to obtain a fifth mixture, and adjusting the pH value of the fifth mixture to 5;
s407, adding melamine: aqueous formaldehyde solution: water-40: 50: mixing melamine, 35 wt% formaldehyde aqueous solution and water according to the mass ratio of 100 to obtain a sixth mixture, and adjusting the pH value of the sixth mixture to 8;
s408, heating the fifth mixture obtained in the step S406 to 55 ℃, dropwise adding the sixth mixture obtained in the step S407 into the fifth mixture at a rate of 12 ml/min, synchronously stirring, stopping heating after dropwise adding, standing for 1 hour, adjusting the pH value to 7 after standing, and filtering, washing and drying after pH value adjustment to obtain the modifier, wherein the dropwise adding amount of the sixth mixture is 1.5 times of the adding mass of the paraffin;
s410, preparing the following components by using ultra-high molecular weight polyethylene: modifying agent: solvent 10: 4: 100, uniformly mixing raw materials comprising ultrahigh molecular weight polyethylene, the modifier obtained in the step S408 and a solvent to obtain a first material, wherein the solvent is white oil;
s411, feeding the first material obtained in the step S410 into a swelling kettle, and swelling at the temperature of 100 ℃ for 0.5 hour to obtain a second material, wherein the shear rate of the swelling kettle is 1200 seconds-1；
S412, feeding the second material obtained in the step S411 into a double-screw extruder, and performing melt extrusion under the conditions of the temperature of 180 ℃ and the rotating speed of 200 revolutions per minute to obtain a third material;
s413, cooling the third material obtained in the step S412 in a water bath at the temperature of 20 ℃ for 18 hours to obtain ultrahigh molecular weight polyethylene precursor;
s414, sending the ultra-high molecular weight polyethylene precursor obtained in the step S413 into an extractor, and extracting at the temperature of 36 ℃ to obtain a fourth material;
s415, drying the fourth material obtained in the step S414 at the temperature of 30 ℃ in a nitrogen environment to obtain a fifth material;
s416, performing primary stretching on the fifth material obtained in the step S415 at the temperature of 90 ℃, performing secondary stretching at the temperature of 120 ℃, and performing tertiary stretching at the temperature of 140 ℃ to obtain a sixth material, wherein the stretching multiple of the primary stretching is 3-4 times, the stretching multiple of the secondary stretching is 2-3 times, and the stretching multiple of the tertiary stretching is 1.5-2 times;
and S417, feeding the sixth material obtained in the step S416 into a winding machine for winding to obtain the ultra-high molecular weight polyethylene fiber cable material.
Example 2
The embodiment provides a preparation method of an ultra-high molecular weight polyethylene fiber cable material, which comprises the following steps.
S501, preparing titanium tetrachloride: polyvinyl alcohol: ethanol ═ 20: 15: mixing titanium tetrachloride, polyvinyl alcohol and ethanol according to a mass ratio of 100 to obtain a first mixture;
s502, according to the silicon nitride: vinyl trimethoxy silane: ethanol ═ 20: 15: mixing silicon nitride, vinyl trimethoxy silane and ethanol according to the mass ratio of 100 to obtain a second mixture;
s503, according to the first mixture: second mixture 40: 100 by mass, mixing the first mixture obtained in S501 and the second mixture obtained in S502 to obtain a third mixture, and adding a sodium hydroxide solution dropwise to the third mixture at a rate of 10 ml/min while stirring until the pH of the third mixture is adjusted to 12;
s504, feeding the third mixture obtained in the step S503 into a reaction kettle, reacting for 4 hours at the temperature of 200 ℃, and then cooling, filtering, washing and drying to obtain a precipitate;
s505, according to paraffin: sodium dodecylbenzenesulfonate: 20 parts of water: 15: 100, mixing and ultrasonically emulsifying the paraffin obtained in the step S504, sodium dodecyl benzene sulfonate and water at the temperature of 65 ℃ for 40 minutes to obtain a fourth mixture;
s506, mixing sodium hexametaphosphate: and (3) precipitation: fourth mixture ═ 1: 12: 100, mixing and ultrasonically emulsifying sodium hexametaphosphate, the precipitate obtained in the step S504 and the fourth mixture obtained in the step S505 at the temperature of 85 ℃ for 40 minutes, cooling to room temperature to obtain a fifth mixture, and adjusting the pH value of the fifth mixture to 6;
s507, adding melamine: aqueous formaldehyde solution: 50 parts of water: 80: mixing melamine, 40 wt% aqueous formaldehyde solution and water according to a mass ratio of 100 to obtain a sixth mixture, and adjusting the pH value of the sixth mixture to 9;
s508, heating the fifth mixture obtained in the step S506 to 65 ℃, dropwise adding the sixth mixture obtained in the step S507 into the fifth mixture at a rate of 18 ml/min, synchronously stirring, stopping heating after dropwise adding, standing for 2 hours, adjusting the pH value to 8 after standing, filtering, washing and drying after pH value adjustment to obtain the modifier, wherein the dropwise adding amount of the sixth mixture is 1.6 times of the adding mass of the paraffin;
s510, mixing the following components in parts by weight: modifying agent: solvent 30: 6: 100, uniformly mixing raw materials comprising the ultra-high molecular weight polyethylene, the modifier obtained in the step S508 and the solvent to obtain a first material, wherein the solvent is white oil;
s511, feeding the first material obtained in the step S510 into a swelling kettle, and swelling at the temperature of 110 ℃ for 1.5 hours to obtain a second material, wherein the shear rate of the swelling kettle is 1500 seconds-1；
S512, feeding the second material obtained in the step S511 into a double-screw extruder, and performing melt extrusion at the temperature of 220 ℃ and the rotating speed of 400 revolutions per minute to obtain a third material;
s513, cooling the third material obtained in the step S512 in a water bath at the temperature of 25 ℃ for 24 hours to obtain an ultrahigh molecular weight polyethylene precursor;
s514, feeding the ultra-high molecular weight polyethylene precursor obtained in the step S513 into an extractor, and extracting at 38 ℃ to obtain a fourth material;
s515, drying the fourth material obtained in the step S514 at the temperature of 36 ℃ in a nitrogen environment to obtain a fifth material;
s516, performing primary stretching on the fifth material obtained in the step S515 at the temperature of 110 ℃, performing secondary stretching at the temperature of 130 ℃, and performing tertiary stretching at the temperature of 150 ℃ to obtain a sixth material, wherein the stretching multiple of the primary stretching is 3-4 times, the stretching multiple of the secondary stretching is 2-3 times, and the stretching multiple of the tertiary stretching is 1.5-2 times;
and S517, feeding the sixth material obtained in the step S516 into a winding machine for winding to obtain the ultra-high molecular weight polyethylene fiber cable material.
Comparative example
S610, mixing the following components in parts by weight: silicon nitride: solvent 30: 6: 100, uniformly mixing raw materials comprising ultra-high molecular weight polyethylene, silicon nitride and a solvent to obtain a first material, wherein the solvent is white oil;
s611, feeding the first material obtained in the step S610 into a swelling kettle, and swelling at the temperature of 110 ℃ for 1.5 hours to obtain a second material, wherein the shear rate of the swelling kettle is 1500 seconds-1；
S612, feeding the second material obtained in the step S611 into a double-screw extruder, and performing melt extrusion at the temperature of 220 ℃ and the rotating speed of 400 revolutions per minute to obtain a third material;
s613, cooling the third material obtained in the step S612 in a water bath at the temperature of 25 ℃ for 24 hours to obtain ultra-high molecular weight polyethylene precursor;
s614, feeding the ultra-high molecular weight polyethylene precursor obtained in the step S613 into an extractor, and extracting at 38 ℃ to obtain a fourth material;
s615, drying the fourth material obtained in the step S614 at the temperature of 36 ℃ in a nitrogen environment to obtain a fifth material;
s616, performing primary stretching on the fifth material obtained in the step S615 at the temperature of 110 ℃, performing secondary stretching at the temperature of 130 ℃, and performing tertiary stretching at the temperature of 150 ℃ to obtain a sixth material, wherein the stretching multiple of the primary stretching is 3-4 times, the stretching multiple of the secondary stretching is 2-3 times, and the stretching multiple of the tertiary stretching is 1.5-2 times;
s617, feeding the sixth material obtained in the step S616 into a winding machine for winding to obtain the ultra-high molecular weight polyethylene fiber cable material.
Performance testing
The mechanical property test was performed on the ultra-high molecular weight polyethylene fibers obtained in example 1, example 2, and comparative example, respectively. The strength of the ultra-high molecular weight polyethylene fiber of example 1 was 38.2CN/dtex, the strength of the ultra-high molecular weight polyethylene fiber of example 2 was 38.9CN/dtex, and the strength of the ultra-high molecular weight polyethylene fiber of the comparative example was 37.1 CN/dtex.
AATCC 100-: evaluation method of Antibacterial textiles (Antibacterial fabrics on Textile Materials: Association of fusion Information), Antibacterial performance test was conducted on the ultrahigh molecular weight polyethylene fibers obtained in example 1 and example 2. Wherein, the calculation formula of the antibacterial performance of the ultra-high molecular weight polyethylene fiber obtained in the embodiment 1 is as follows: r1 (%) - (a1-B1)/a1 × 100%. R1 is the antibacterial ratio, a1 is the average number of recovered bacteria of the ultra-high molecular weight polyethylene fiber of the comparative example, and B1 is the average number of recovered bacteria of the ultra-high molecular weight polyethylene fiber of example 1. The ultrahigh-molecular-weight polyethylene fiber of example 1 had an antibacterial ratio R1 of 68.3%. The antibacterial performance calculation formula of the ultra-high molecular weight polyethylene fiber obtained in example 2 is as follows: r2 (%) - (a2-B2)/a2 × 100%. R2 is the antibacterial ratio, a2 is the average number of recovered bacteria of the ultra-high molecular weight polyethylene fiber of the comparative example, and B2 is the average number of recovered bacteria of the ultra-high molecular weight polyethylene fiber of example 2. The antibacterial ratio R of the ultra-high molecular weight polyethylene fiber of example 2 was 67.5%.
In the present disclosure, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; the term "plurality" means two or more unless expressly limited otherwise. The terms "mounted," "connected," "fixed," and the like are to be construed broadly, and for example, "connected" may be a fixed connection, a removable connection, or an integral connection; "coupled" may be direct or indirect through an intermediary. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the description herein, the description of the terms "one embodiment," "some embodiments," "specific embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of an ultra-high molecular weight polyethylene fiber cable material is characterized by comprising the following steps:
s11, preparing ultra-high molecular weight polyethylene: modifying agent: solvent (10-30): (4-6): 100, uniformly mixing the raw materials comprising the ultrahigh molecular weight polyethylene, the modifier and the solvent to obtain a first material;
s12, swelling, melt extrusion and water bath cooling are carried out on the first material to obtain ultra-high molecular weight polyethylene precursor;
and S13, extracting, drying, drafting and winding the ultra-high molecular weight polyethylene precursor fiber to obtain the ultra-high molecular weight polyethylene fiber cable material.
2. The method of making an ultra high molecular weight polyethylene fiber rope material as claimed in claim 1, wherein said modifier comprises at least one or a combination of: silver ion antibacterial agent, strontium ion antibacterial agent, and titanium ion antibacterial agent.
3. The method of making an ultra high molecular weight polyethylene fiber rope material as claimed in claim 1, wherein said modifier comprises at least one or a combination of: silicon nitride toughening agent and silicon carbide toughening agent.
4. The method of making an ultra high molecular weight polyethylene fiber rope material as claimed in claim 1, wherein said solvent comprises at least one or a combination of: white oil, mineral oil, vegetable oil, decalin, paraffin oil.
5. The method for preparing an ultra-high molecular weight polyethylene fiber cable material as claimed in any one of claims 1 to 4, wherein said swelling, melt-extruding, cooling in water bath, said first material to obtain ultra-high molecular weight polyethylene strands comprises:
s121, feeding the first material into a swelling kettle, and swelling for 0.5 to 1.5 hours at the temperature of between 100 and 110 ℃ to obtain a second materialIn (2), the shear rate of the swelling kettle is 1200 seconds-1To 1500 seconds-1；
S122, feeding the second material into a double-screw extruder, and performing melt extrusion under the conditions of the temperature of 120-220 ℃ and the rotating speed of 200-400 rpm to obtain a third material;
s123, cooling the third material in the water bath for 18 to 24 hours at the temperature of 20 to 25 ℃ to obtain the ultra-high molecular weight polyethylene precursor.
6. The method for preparing an ultra-high molecular weight polyethylene fiber cable material as claimed in any one of claims 1 to 4, wherein said extracting, drying, drawing and winding of said ultra-high molecular weight polyethylene filaments to obtain said ultra-high molecular weight polyethylene fiber cable material comprises:
s131, sending the ultra-high molecular weight polyethylene precursor into an extractor, and extracting at the temperature of 36-38 ℃ to obtain a fourth material;
s132, drying the fourth material at the temperature of 30-36 ℃ in a nitrogen environment to obtain a fifth material;
s133, performing primary stretching on the fifth material at a temperature of 90-110 ℃, performing secondary stretching at a temperature of 120-130 ℃, and performing tertiary stretching at a temperature of 140-150 ℃ to obtain a sixth material, wherein the stretching multiple of the primary stretching is 3-4 times, the stretching multiple of the secondary stretching is 2-3 times, and the stretching multiple of the tertiary stretching is 1.5-2 times;
and S134, feeding the sixth material into a winding machine for winding to obtain the ultra-high molecular weight polyethylene fiber cable material.
7. Process for the preparation of an ultra high molecular weight polyethylene fibre cable material as claimed in any one of claims 1 to 4, characterized in that the modifier is prepared by the following steps:
s21, mixing titanium tetrachloride, polyvinyl alcohol and ethanol to obtain a first mixture;
s22, mixing silicon nitride, vinyl trimethoxy silane and ethanol to obtain a second mixture;
s23, mixing the first mixture and the second mixture to obtain a third mixture, and dropwise adding a sodium hydroxide solution into the third mixture and synchronously stirring until the pH value of the third mixture is adjusted to 10-12;
s24, feeding the third mixture into a reaction kettle, reacting for 3 to 4 hours at the temperature of between 180 and 200 ℃, and then cooling, filtering, washing and drying to obtain a precipitate;
s25, mixing paraffin, sodium dodecyl benzene sulfonate and water, and ultrasonically emulsifying to obtain a fourth mixture;
s26, mixing and ultrasonically emulsifying sodium hexametaphosphate, the precipitate and the fourth mixture to obtain a fifth mixture, and adjusting the pH value of the fifth mixture to 5-6;
s27, mixing melamine, a formaldehyde aqueous solution and water to obtain a sixth mixture, and adjusting the pH value of the sixth mixture to 8-9;
s28, dropwise adding the sixth mixture into the fifth mixture, synchronously stirring, standing after dropwise adding is finished, adjusting the pH value to 7-8 after standing is finished, and filtering, washing and drying after the pH value is adjusted to obtain the modifier.
8. Process for the preparation of an ultra high molecular weight polyethylene fibre cable material as claimed in any one of claims 1 to 4, characterized in that the modifier is prepared by the following steps:
s31, preparing titanium tetrachloride: polyvinyl alcohol: ethanol ═ (10-20): 15: 100 by mass, mixing the titanium tetrachloride, the polyvinyl alcohol and the ethanol to obtain a first mixture;
s32, according to the silicon nitride: vinyl trimethoxy silane: ethanol ═ (10-20): 15: 100 by mass, mixing the silicon nitride, the vinyltrimethoxysilane and the ethanol to obtain a second mixture;
s33, according to the first mixture: second mixture ═ (20-40): 100 to obtain a third mixture, and dropwise adding a sodium hydroxide solution into the third mixture at a rate of 6 ml/min to 10 ml/min while stirring until the pH of the third mixture is adjusted to 10 to 12;
s34, feeding the third mixture into a reaction kettle, reacting for 3 to 4 hours at the temperature of between 180 and 200 ℃, and then cooling, filtering, washing and drying to obtain a precipitate;
s35, according to paraffin: sodium dodecylbenzenesulfonate: water ═ 10-20: (10-15): 100, mixing the paraffin, the sodium dodecyl benzene sulfonate and the water at the temperature of 55-65 ℃, and ultrasonically emulsifying for 20-40 minutes to obtain a fourth mixture;
s36, mixing sodium hexametaphosphate: and (3) precipitation: fourth mixture ═ (0.5-1): (8-12): 100, mixing and ultrasonically emulsifying the sodium hexametaphosphate, the precipitate and the fourth mixture at the temperature of 80-85 ℃ for 20-40 minutes, cooling to room temperature to obtain a fifth mixture, and adjusting the pH value of the fifth mixture to 5-6;
s37, adding melamine: aqueous formaldehyde solution: water ═ 40-50: (50-80): 100, mixing the melamine, the aqueous formaldehyde solution with a concentration of 35 to 40 wt% and the water to obtain a sixth mixture, and adjusting the pH of the sixth mixture to 8 to 9;
s38, heating the fifth mixture to 55-65 ℃, dropwise adding the sixth mixture into the fifth mixture at a speed of 12-18 ml/min, synchronously stirring, stopping heating after dropwise adding, standing for 1-2 hours, adjusting the pH value to 7-8 after standing, and filtering, washing and drying after pH value adjustment to obtain the modifier, wherein the dropwise adding amount of the sixth mixture is 1.5-1.6 times of the adding mass of the paraffin.
9. An ultra high molecular weight polyethylene fiber cable material obtained by the production method as claimed in any one of claims 1 to 8.
10. An ultra-high molecular weight polyethylene fiber cable, characterized in that the material used for the cable is obtained by the preparation method of any one of claims 1 to 8.
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