CN117306253A - Preparation method of antibacterial creep-resistant strong-adhesion ultra-high molecular weight polyethylene fiber and product thereof - Google Patents
Preparation method of antibacterial creep-resistant strong-adhesion ultra-high molecular weight polyethylene fiber and product thereof Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 148
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 105
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 105
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 125
- 239000000047 product Substances 0.000 claims abstract description 67
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002243 precursor Substances 0.000 claims abstract description 62
- 239000000243 solution Substances 0.000 claims abstract description 56
- 239000013067 intermediate product Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 102000008186 Collagen Human genes 0.000 claims abstract description 41
- 108010035532 Collagen Proteins 0.000 claims abstract description 41
- 229920001436 collagen Polymers 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 33
- 229960003638 dopamine Drugs 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 30
- 238000009987 spinning Methods 0.000 claims abstract description 26
- 238000000605 extraction Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 21
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000002791 soaking Methods 0.000 claims description 92
- 239000000203 mixture Substances 0.000 claims description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000007983 Tris buffer Substances 0.000 claims description 21
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 14
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000005662 Paraffin oil Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 2
- 230000001464 adherent effect Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000499 gel Substances 0.000 description 56
- 239000002131 composite material Substances 0.000 description 37
- 239000003822 epoxy resin Substances 0.000 description 24
- 229920000647 polyepoxide Polymers 0.000 description 24
- -1 polyethylene Polymers 0.000 description 22
- 239000010949 copper Substances 0.000 description 20
- 241000233866 Fungi Species 0.000 description 16
- 230000005764 inhibitory process Effects 0.000 description 16
- 239000004698 Polyethylene Substances 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 238000002604 ultrasonography Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
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- 239000008274 jelly Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 2
- 239000001263 FEMA 3042 Substances 0.000 description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229920006253 high performance fiber Polymers 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000013309 porous organic framework Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002258 tannic acid Polymers 0.000 description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 2
- 229940033123 tannic acid Drugs 0.000 description 2
- 235000015523 tannic acid Nutrition 0.000 description 2
- CPKVUHPKYQGHMW-UHFFFAOYSA-N 1-ethenylpyrrolidin-2-one;molecular iodine Chemical compound II.C=CN1CCCC1=O CPKVUHPKYQGHMW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 229920000153 Povidone-iodine Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper 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
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229960001621 povidone-iodine Drugs 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/368—Hydroxyalkylamines; Derivatives thereof, e.g. Kritchevsky bases
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a preparation method of an antibacterial, creep-resistant and strong-adhesion ultra-high molecular weight polyethylene fiber and a product thereof, wherein the preparation method comprises the steps of reacting UIO-66-NH2 with ethylene glycol diglycidyl ether to obtain an intermediate product A; adding dopamine into the intermediate product A, and reacting to obtain a product B; mixing ultra-high molecular weight polyethylene powder with a solvent, stirring, mixing uniformly, extruding by a double-screw extruder, sequentially spinning by a metering pump and a spinneret plate, and cooling in a water bath to obtain frozen collagen filaments; standing the obtained gel precursor at room temperature, and sequentially placing the gel precursor into a mixed solution C, a mixed solution D and a polar solution E to obtain a surface modified gel precursor; and standing the modified frozen collagen yarn at room temperature, and then extracting, drying and carrying out multistage hot drawing to obtain the surface modified ultra-high molecular weight polyethylene fiber. The UHMWPE fiber with antibacterial creep resistance and improved surface cohesiveness is obtained by processing the gel precursor and then carrying out processes such as extraction drying, super heat drawing and the like.
Description
Technical Field
The invention belongs to the field of high-performance fiber preparation, and particularly relates to a preparation method of an antibacterial creep-resistant and strong-adhesion ultra-high molecular weight polyethylene fiber and a product thereof.
Background
The ultra-high molecular weight polyethylene (UHMWPE) fiber is one of the traditional three-large high-performance fiber, has excellent performances of high strength, high modulus, ultraviolet radiation resistance, chemical corrosion resistance, low dielectric constant and the like, and is widely applied to the fields of military, aviation, aerospace, sports equipment and the like. However, the polyethylene molecular chain in the fiber has high crystallinity and orientation degree, the molecular chain lacks branched chains, is easy to creep under long-time stress, and has smooth and nonpolar surface, so that the polyethylene fiber is difficult to firmly adhere to the surface of the fiber for a long time when the functional coating is coated; in addition, it also results in weak interactions with the resin matrix when used as a reinforcing material, fiber degumming is easy to occur when the stress is applied, the cracking of matrix resin and the like severely restrict the application of the matrix resin in the field of composite materials.
In order to improve the creep resistance of UHMWPE fibers, it is currently mainly achieved by partial crosslinking occurring inside the UHMWPE fibers. The patent application No. CN202011219644.1 discloses a high-modulus creep-resistant ultra-high molecular weight polyethylene fiber and a preparation method thereof, wherein an ultraviolet photosensitizer, a crosslinking agent and a silane coupling agent are added into UHMWPE spinning raw materials to realize light crosslinking, and finally the purpose of improving creep resistance is achieved. Patent application number CN201410142484.3 discloses a preparation method of silane crosslinking modified ultra-high molecular weight polyethylene fiber, which is characterized in that UHMWPE fiber which is not dried is placed in a modified solution, ultrasonic treatment is carried out, and then multistage hot stretching is carried out, so that the modified fiber with creep resistance and surface adhesiveness can be obtained.
In order to improve the antibacterial performance of the UHMWPE fiber, the surface of the UHMWPE fiber is coated with an antibacterial coating. The invention of China patent application No. CN202210187597.X discloses a medical antibacterial UHMWPE suture and a preparation method thereof, wherein a layer of crosslinked network imbibition swelling antibacterial coating consisting of polydimethylsiloxane and povidone iodine is coated on the surface of the fiber, so that the antibacterial performance is realized. The Chinese patent application No. CN 202110504950.8 discloses a bacteriostatic colored fiber of ultra-high molecular weight polyethylene and a preparation method thereof. According to the patent, UHMWPE dry gel fiber is immersed into dispersion liquid containing antibacterial particles and colored particles, so that the antibacterial particles and the colored particles are uniformly loaded into the UHMWPE dry gel fiber, and the antibacterial performance of the fiber is realized. The adhesion performance of UHMWPE fiber is improved mainly by coating a coating layer containing polar groups on the surface of UHMWPE fiber. The Chinese patent application No. CN202111103441.0 discloses a preparation method of a hydrogen bond modified ultra-high molecular weight polyethylene fiber constructed by tannic acid and polyaniline, and the coating of the tannic acid and the polyaniline effectively improves the adhesiveness of the fiber surface.
It is known that at present, the existing treatment means can realize improvement of creep resistance, antibacterial property and surface adhesion property of the fiber, but only a single modification effect can be realized by one treatment means, if multiple property improvements are required, multi-step coating is required, and economic cost is greatly increased.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of the antibacterial, creep-resistant and strongly-adhered ultrahigh molecular weight polyethylene fiber.
In order to solve the technical problems, the invention provides the following technical scheme: a process for preparing antibacterial, creep-resistant and high-adhesion ultrahigh-molecular-weight polyethylene fibres,
UIO-66-NH 2 Reacting with ethylene glycol diglycidyl ether to obtain an intermediate product A;
adding dopamine into the intermediate product A, and reacting to obtain a product B;
mixing ultra-high molecular weight polyethylene powder with a solvent, stirring and mixing uniformly, extruding by a double-screw extruder, sequentially spinning by a metering pump and a spinneret plate, and cooling in a water bath to obtain frozen collagen filaments;
standing the obtained gel precursor at room temperature, and sequentially placing the gel precursor into a mixed solution C, a mixed solution D and a polar solution E to obtain a surface modified gel precursor; wherein the mixed solution C is a mixture of a product B and a solution F, and the solution F is one or a mixture of more of water, alcohol, acetone, methanol and glycerol; the mixed solution D is Tris and solution F, cu containing Tris hydrochloride + Or Ag + One or a mixture of two ions; the polar solution E is one or a mixture of more of methanol, ethanol, isopropanol, n-butanol, dioxane and tetrahydrofuran;
and standing the modified frozen collagen yarn at room temperature, and then extracting, drying and carrying out multistage hot drawing to obtain the surface modified ultra-high molecular weight polyethylene fiber.
As a preferred embodiment of the preparation process according to the invention, there is provided: the UIO-66-NH 2 The molar mass ratio of the intermediate product A to the ethylene glycol diglycidyl ether is 1:1.5-1:5, the reaction time for preparing the intermediate product A is 1-24 h, the reaction temperature is 20-60 ℃, and the pH of the reaction system is 9-12.
As a preferred embodiment of the preparation process according to the invention, there is provided: the UIO-66-NH 2 The molar mass ratio of the catalyst to the glycol diglycidyl ether is 1:1.5-1:3.
As a preferred embodiment of the preparation process according to the invention, there is provided: the molar mass ratio of the intermediate product A to the dopamine is 1:0.5-1:3, the reaction time for preparing the intermediate product B is 1-24 h, the reaction temperature is 20-60 ℃, and the pH of the reaction system is 9-12.
As a preferred embodiment of the preparation process according to the invention, there is provided: the ultra-high molecular weight polyethylene powder accounts for 4-15 wt% of the total mass of the mixed solution, and the solvent in the mixed solution is one or more hydrocarbon compounds, including one or more of decalin, tetralin, kerosene, paraffin oil and white oil.
As a preferred embodiment of the preparation process according to the invention, there is provided: the mass ratio of the product B in the mixture is 0.5-20wt%;
the soaking time of the frozen collagen filaments in the mixed solution C is 0.1-2 h, and the soaking temperature is 10-70 ℃.
As a preferred embodiment of the preparation process according to the invention, there is provided: in the mixed solution D, the mass of Tris accounts for 0.1-2 wt% of the mass of the mixed solution D, the pH value is 6-10, and Cu + Or Ag + The mass of the ions accounts for 1-8wt% of the mass of the mixed solution D;
the soaking time of the frozen collagen filaments in the mixed solution D is 0.2-3 h, and the soaking temperature is 20-60 ℃.
As a preferred embodiment of the preparation process according to the invention, there is provided: and the gel precursor filaments soaked in the mixed solution C and the mixed solution D are soaked in the polar solution E, wherein the soaking time is 2-60 min, and the soaking temperature is 20-60 ℃.
As a preferred embodiment of the preparation process according to the invention, there is provided: the modified frozen collagen yarn is subjected to extraction, drying and multistage hot drawing after standing at room temperature, wherein the extracting agent is one or a mixture of xylene, methylene dichloride, petroleum ether and 120# gasoline, the extraction temperature is 20-40 ℃, the drying temperature is 20-80 ℃, a drawing hot box in the multistage hot drawing process is 3-6 stages, the drawing temperature is 80-148 ℃, and the hot drawing multiple is 10-40 times.
Yet another object of the present invention is to overcome the deficiencies of the prior art and to provide an antimicrobial, creep resistant, strongly adherent, high molecular weight polyethylene fiber prepared by the process for preparing an ultra high molecular weight polyethylene fiber, characterized in that: the surface of the fiber contains polar groups, and has excellent antibacterial, creep-resistant and mechanical properties.
The invention has the beneficial effects that:
(1) The conventional preparation of the UHMWPE fiber with the functions of antibiosis, creep resistance, surface adhesion improvement usually needs multiple steps of treatment to enable the fiber to have the functions, so that the problems of complicated treatment process, increased production cost and the like exist.
(2) The invention immerses the novel filler product B in the gel precursor, and the product B contains a porous organic framework structure UIO-66-NH 2 And contains dopamine structure for promoting adhesion, then makes the product B polymerize under a certain condition, and firmly adhere to the surface of gel precursor, in addition, UIO-66-NH 2 The structure can not only enable the UHMWPE molecular chains to be entangled, but also enable the antibacterial ion Cu to be entangled + Or Ag + And (3) adsorbing ions into UIO-66-NH2 to realize the lasting release of antibacterial performance, and finally, treating by a subsequent process to finally obtain the functional UHMWPE fiber with antibacterial creep resistance and improved surface adhesion.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a diagram showing a process for preparing a novel filler product B in the examples of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The UHMWPE powder of the invention is purchased from Shanghai Bile chemical industry Co., ltd, and has a viscosity average molecular weight of 700 ten thousand.
Fiber density test criteria in the present invention: FZ/T01057.7-2007, density gradient method; fiber strength, elongation at break test standard: GB/T19975-2005; fiber creep resistance test standard: see GB/T19975.10-2005; monofilament pull-out force and interfacial shear strength tests are described in GB 2942-2009; viscosity average molecular weight test criteria: ASTM D4020-2018.
Example 1
(1) UIO-66-NH 2 Reacting with ethylene glycol diglycidyl ether (molar mass ratio is 1:1.5) to obtain an intermediate product A, wherein the reaction time of the intermediate product A is 4 hours, the reaction temperature is 45 ℃, and the pH of a reaction system is 10;
then adding dopamine (the molar mass ratio of the intermediate product A to the dopamine is 1:0.5), and reacting to obtain a product B, wherein the prepared process diagram is shown in figure 1, the reaction time of the intermediate product B is 2.5h, the reaction temperature is 40 ℃, and the pH of a reaction system is 11;
(2) Mixing the selected UHMWPE powder with a solvent (white oil) (the UHMWPE powder accounts for 6wt% of the total mass of the mixed solution), mechanically stirring to uniformly mix, extruding by a double-screw extruder, sequentially spinning by a metering pump and a spinneret plate, and cooling in a water bath to obtain frozen collagen filaments, wherein the concentration of the spinning solution is 6wt%, the spinning temperature of the double screw is 220 ℃, the rotating speed of the double screw is 120RPM, and the distance between the spinneret plate and the water bath is 3cm;
(3) Standing the obtained gel precursor at room temperature, and then sequentially placing the gel precursor into a mixed solution C, a mixed solution D and a polar solution E to obtain a surface modified UHMWPE gel precursor;
wherein the mixed solution C is a mixture of a product B and water, the mass ratio of the product B in the mixture is 0.5wt%, the soaking time of the gel precursor in the mixed solution C is 0.1 hour, and the soaking temperature is 10 ℃;
The mixed solution D is Tris (hydroxymethyl) aminomethane hydrochloride (Tris), alcohol and Ag + The mass of the mixture of ions, tris accounts for 0.1wt% of the mass of the mixed solution D, the pH is 6, the soaking time is 0.2 hours, the soaking temperature is 20 ℃, and the Ag is the same as that of the mixed solution D + The mass of the ions accounts for 1wt% of the mass of the mixed solution D;
the polar solution E is ethanol, the soaking time in the polar solution E is 2 minutes, and the soaking temperature is 20 ℃;
(4) Standing the obtained modified frozen collagen yarn at room temperature, and then extracting, drying and carrying out multi-stage hot drawing to obtain a surface modified UHMWPE fiber, wherein the extracting agent is methylene dichloride, the extracting temperature is 25 ℃, the drying temperature is 40 ℃, a drawing hot box in a multi-stage hot drawing process is three-stage, the temperature of the three-stage drawing hot box is 100, 130 and 147 ℃ respectively, and the hot drawing multiple is 26 times;
wherein the density of the UHMWPE/modified PE composite fiber is 0.96g/cm 3 EDX test was conducted on a fiber cross section having a strength of 36cN/dtex, an elongation at break of 2.7%, a contact angle of the fiber with water of 90 degrees, and found that the fiber center region (circular region with a circular cross section center as a center and a radius of 0.9 r) had a Zr content of 0.3wt%, an Ag content of 0.4wt%, a fiber cross section edge (annular region between 0.9r and r from the circular cross section center) had a Zr content of 0.4wt%, an Ag content of 0.5wt%, and a composite fiber viscosity average molecular weight of 367 ten thousand.
The extraction force of the monofilament of the epoxy resin embedding test is 8cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 18MPa. And after 2 hours of ultrasound, the retention of the filament pullout force and interfacial shear strength was 97%.
Creep resistance: creep was 2% after 30 minutes of exposure to 1000MPa tension at 70 ℃;
antibacterial properties: the fungi inhibition rate is 99% by using GB/T20944.2-2007 absorption method, and after washing for 50 times, the fungi inhibition rate is 99% according to FZ/T73023-2006 standard.
Example 2
(1) UIO-66-NH 2 Reacting with ethylene glycol diglycidyl ether (molar mass ratio is 1:5) to obtain an intermediate product A, wherein the reaction time of the intermediate product A is 2h, the reaction temperature is 55 ℃, and the pH of a reaction system is 11;
adding dopamine (the molar mass ratio of the intermediate product A to the dopamine is 1:3), and reacting to obtain a product B, wherein the reaction time of the intermediate product B is 3 hours, the reaction temperature is 49 ℃, and the pH of a reaction system is 10.5;
(2) Mixing the selected UHMWPE powder with a solvent (decalin) (the UHMWPE powder accounts for 8wt% of the total mass of the mixed solution), mechanically stirring to uniformly mix, extruding by a double-screw extruder, sequentially spinning by a metering pump and a spinneret plate, and cooling in a water bath to obtain frozen collagen filaments, wherein the concentration of the spinning solution is 8wt%, the spinning temperature of the double screw is 205 ℃, the rotating speed of the double screw is 110RPM, and the distance between the spinneret plate and the water bath is 2.5cm;
(3) Standing the obtained gel precursor at room temperature, and then sequentially placing the gel precursor into a mixed solution C, a mixed solution D and a polar solution E to obtain the surface modified UHMWPE gel precursor;
wherein the mixed solution C is a mixture of a product B and acetone, the mass ratio of the product B in the mixture is 20wt%, the soaking time of the gel precursor in the mixed solution C is 2 hours, and the soaking temperature is 70 ℃;
the mixed solution D is Tris (hydroxymethyl) aminomethane hydrochloride (Tris), glycerol and Cu + The mass of the mixture of ions is 2wt% of the mass of the mixed solution D, the pH is 10, the soaking time is 3 hours, the soaking temperature is 60 ℃, and the mass of Cu+ ions is 8wt% of the mass of the mixed solution D;
the polar solution E is dioxane, the soaking time in the polar solution E is 60 minutes, and the soaking temperature is 60 ℃;
(4) Standing the obtained modified frozen collagen yarn at room temperature, and then extracting, drying and carrying out multi-stage hot drawing to obtain a surface modified UHMWPE fiber, wherein the extracting agent is dimethylbenzene, the extracting temperature is 35 ℃, the drying temperature is 50 ℃, a drawing hot box in the multi-stage hot drawing process is five stages, and the temperature of the five-stage drawing hot box is 90, 110, 130, 140 and 148 ℃ respectively, and the hot drawing multiple is 34 times;
wherein the density of the UHMWPE/modified PE composite fiber is 0.98g/cm 3 EDX test was conducted on a fiber cross section having a strength of 39cN/dtex, an elongation at break of 2.5%, a contact angle of the fiber with water of 90 degrees, and found that the fiber center region (circular region with a circular cross section center as a center and a radius of 0.9 r) had a Zr content of 0.2wt%, a Cu content of 0.1wt%, a fiber cross section edge (annular region between 0.9r and r from the circular cross section center) had a Zr content of 8wt%, a Cu content of 5wt%, and a composite fiber viscosity average molecular weight of 390 ten thousand.
The extraction force of the monofilament of the epoxy resin embedding test is 10cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 20MPa. And after 2 hours of ultrasound, the retention of the filament pullout force and interfacial shear strength was 98%.
Creep resistance: creep was 1% after 30 minutes of exposure to 1000MPa tension at 70 ℃;
antibacterial properties: the fungi inhibition rate is 100% by using GB/T20944.2-2007 absorption method, and after washing for 50 times, the fungi inhibition rate is 100% according to FZ/T73023-2006 standard.
Example 3
(1) Reacting UIO-66-NH2 with ethylene glycol diglycidyl ether (molar mass ratio is 1:3) to obtain an intermediate product A, wherein the reaction time of the intermediate product A is 8 hours, the reaction temperature is 35 ℃, and the pH of a reaction system is 11;
Then adding dopamine (the molar mass ratio of the intermediate product A to the dopamine is 1:2), and reacting to obtain a product B, wherein the reaction time of the intermediate product B is 5 hours, the reaction temperature is 46 ℃, and the pH of a reaction system is 10;
(2) Mixing the selected UHMWPE powder with a solvent (tetralin) (the UHMWPE powder accounts for 7wt% of the total mass of the mixed solution), mechanically stirring to uniformly mix, extruding by a double-screw extruder, sequentially spinning by a metering pump and a spinneret plate, and cooling in a water bath to obtain frozen collagen filaments, wherein the concentration of the spinning solution is 7wt%, the spinning temperature of the double screw is 215 ℃, the rotating speed of the double screw is 140RPM, and the distance between the spinneret plate and the water bath is 3.5cm;
(3) Standing the obtained gel precursor at room temperature, and then sequentially placing the gel precursor into a mixed solution C, a mixed solution D and a polar solution E to obtain the surface modified UHMWPE gel precursor;
wherein the mixed solution C is a mixture of a product B and acetone, the mass ratio of the product B in the mixture is 10wt%, the soaking time of the gel precursor in the mixed solution C is 1 hour, and the soaking temperature is 40 ℃;
the mixed solution D is Tris (hydroxymethyl) aminomethane hydrochloride (Tris), methanol and Ag + The mass of the mixture of ions is 1wt% of the mass of the mixed solution D, the pH is 8, the soaking time is 1.5 hours, the soaking temperature is 40 ℃, and the mass of Ag+ ions is 4.5wt% of the mass of the mixed solution D;
The polar solution E is tetrahydrofuran, the soaking time in the polar solution E is 31 minutes, and the soaking temperature is 40 ℃;
(4) Standing the obtained modified frozen collagen yarn at room temperature, and then extracting, drying and carrying out multistage hot drawing to obtain a surface modified UHMWPE fiber, wherein the extractant is 120# gasoline, the extraction temperature is 30 ℃, the drying temperature is 50 ℃, a drawing hot box in the multistage hot drawing process is four stages, the temperatures of the four stages of drawing hot boxes are 100, 120, 140 and 145 ℃ respectively, and the hot drawing multiple is 32 times;
the density of the UHMWPE/modified PE composite fiber is 0.97g/cm < 3 >, the strength is 37cN/dtex, the elongation at break is 2.9%, the contact angle of the fiber with water is 80 degrees, EDX test is carried out on the fiber section, the Zr content in the central area of the fiber (the circular area taking the center of the circular section as the center and 0.9r as the radius) is 0.2wt%, the Ag content is 0.2wt%, the Zr content in the edge of the fiber section (the annular area between 0.9r and r from the center of the circular section) is 4wt%, the Ag content is 2.5wt%, and the viscosity average molecular weight of the composite fiber is 374 ten thousand.
The extraction force of the monofilament of the epoxy resin embedding test is 7cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 16MPa. And after 2 hours of ultrasound, the retention of the filament pullout force and interfacial shear strength was 99%.
Creep resistance: creep was 3% after 30 minutes of 1000MPa tension at 70 ℃;
antibacterial properties: the fungi inhibition rate is 99% by using GB/T20944.2-2007 absorption method, and 100% by using FZ/T73023-2006 standard after washing for 50 times.
Example 4
(1) UIO-66-NH 2 Reacting with ethylene glycol diglycidyl ether (molar mass ratio is 1:3) to obtain an intermediate product A, wherein the reaction time of the intermediate product A is 4.5h, the reaction temperature is 38 ℃, and the pH of a reaction system is 10.5;
then adding dopamine (the molar mass ratio of the intermediate product A to the dopamine is 1:1), and reacting to obtain a product B, wherein the reaction time of the intermediate product B is 3.5h, the reaction temperature is 45 ℃, and the pH of a reaction system is 9.5;
(2) Mixing the selected UHMWPE powder with a solvent (paraffin oil) (the UHMWPE powder accounts for 5wt% of the total mass of the mixed solution), mechanically stirring to uniformly mix, extruding by a double-screw extruder, sequentially spinning by a metering pump and a spinneret plate, and cooling in a water bath to obtain frozen collagen filaments, wherein the concentration of the spinning solution is 5wt%, the double-screw spinning temperature is 200 ℃, the rotating speed of the double screw is 128RPM, and the distance between the spinneret plate and the water bath is 2.8cm;
(3) Standing the obtained gel precursor at room temperature, and then sequentially placing the gel precursor into a mixed solution C, a mixed solution D and a polar solution E to obtain the surface modified UHMWPE gel precursor;
Wherein the mixed solution C is a mixture of a product B and water, the mass ratio of the product B in the mixture is 2wt%, the soaking time of the gel precursor in the mixed solution C is 0.5 hour, and the soaking temperature is 20 ℃;
the mixed solution D is Tris (hydroxymethyl) aminomethane hydrochloride (Tris), methanol and Cu + The mass of the mixture of ions is 1wt% of the mass of the mixed solution D, the pH is 9, the soaking time is 2 hours, the soaking temperature is 30 ℃, and the mass of Cu+ ions is 3wt% of the mass of the mixed solution D;
the polar solution E is isopropanol, the soaking time in the polar solution E is 10 minutes, and the soaking temperature is 30 ℃;
(4) Standing the obtained modified frozen collagen yarn at room temperature, and then extracting, drying and carrying out multi-stage hot drawing to obtain a surface modified UHMWPE fiber, wherein the extracting agent is petroleum ether, the extracting temperature is 34 ℃, the drying temperature is 60 ℃, a drawing hot box in the multi-stage hot drawing process is four stages, the temperatures of the four stages of drawing hot boxes are respectively 100, 115, 135 and 145 ℃, and the hot drawing multiple is 31 times;
wherein the density of the UHMWPE/modified PE composite fiber is 0.97g/cm < 3 >, the strength is 36cN/dtex, the elongation at break is 3.0%, the contact angle of the fiber with water is 72 degrees, EDX test is carried out on the fiber section, the Zr content in the central area of the fiber (the circular area taking the center of the circular section as the center and 0.9r as the radius) is 0.05wt%, the Cu content is 0.03wt%, the Zr content in the edge of the fiber section (the annular area between 0.9r and r from the center of the circular section) is 7wt%, the Cu content is 4wt%, and the viscosity average molecular weight of the composite fiber is 358 ten thousand.
The extraction force of the monofilament of the epoxy resin embedding test is 7cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 16MPa. And after 2 hours of ultrasound, the retention of the filament pullout force and interfacial shear strength was 96%.
Creep resistance: creep was 3% after 30 minutes of 1000MPa tension at 70 ℃;
antibacterial properties: the fungi inhibition rate is 100% by using GB/T20944.2-2007 absorption method, and 98% by using FZ/T73023-2006 standard after washing for 50 times.
Example 5
(1) UIO-66-NH 2 Reacting with ethylene glycol diglycidyl ether (molar mass ratio is 1:2.5) to obtain an intermediate product A, wherein the reaction time of the intermediate product A is 10 hours, the reaction temperature is 25 ℃, and the pH of a reaction system is 11;
then adding dopamine (the molar mass ratio of the intermediate product A to the dopamine is 1:1.5), and reacting to obtain a product B, wherein the reaction time of the intermediate product B is 6 hours, the reaction temperature is 30 ℃, and the pH of a reaction system is 10;
(2) Mixing the selected UHMWPE powder with a solvent (white oil) (the UHMWPE powder accounts for 8wt% of the total mass of the mixed solution), mechanically stirring to uniformly mix, extruding by a double-screw extruder, sequentially spinning by a metering pump and a spinneret plate, and cooling in a water bath to obtain frozen collagen filaments, wherein the concentration of the spinning solution is 8wt%, the spinning temperature of the double screw is 220 ℃, the rotating speed of the double screw is 100RPM, and the distance between the spinneret plate and the water bath is 3.2cm;
(3) Standing the obtained gel precursor at room temperature, and then sequentially placing the gel precursor into a mixed solution C, a mixed solution D and a polar solution E to obtain the surface modified UHMWPE gel precursor;
wherein the mixed solution C is a mixture of a product B and methanol, the mass ratio of the product B in the mixture is 6wt%, the soaking time of the gel precursor in the mixed solution C is 1 hour, and the soaking temperature is 30 ℃;
the mixed solution D is a mixture of Tris (hydroxymethyl) aminomethane hydrochloride (Tris), alcohol and Ag+ ions, wherein the mass of the Tris accounts for 0.5wt% of the mass of the mixed solution D, the pH value is 8, the soaking time is 1 hour, the soaking temperature is 40 ℃, and the mass of the Ag+ ions accounts for 6wt% of the mass of the mixed solution D;
the polar solution E is a mixture of ethanol and isopropanol, the soaking time in the polar solution E is 25 minutes, and the soaking temperature is 45 ℃;
(4) Standing the obtained modified frozen collagen yarn at room temperature, and then extracting, drying and carrying out multi-stage hot drawing to obtain a surface modified UHMWPE fiber, wherein the extracting agent is methylene dichloride, the extracting temperature is 32 ℃, the drying temperature is 45 ℃, a drawing hot box in the multi-stage hot drawing process is five stages, and the temperature of the five-stage drawing hot box is 90, 110, 125, 135 and 146 ℃ respectively, and the hot drawing multiple is 37 times;
The density of the UHMWPE/modified PE composite fiber is 0.97g/cm < 3 >, the strength is 40cN/dtex, the elongation at break is 2.6%, the contact angle of the fiber with water is 78 degrees, EDX test is carried out on the fiber section, the Zr content in the central area of the fiber (the circular area taking the center of the circular section as the center and 0.9r as the radius) is 0.3wt%, the Ag content is 0.3wt%, the Zr content in the edge of the fiber section (the annular area between 0.9r and r from the center of the circular section) is 5wt%, the Ag content is 2wt%, and the viscosity average molecular weight of the composite fiber is 394 ten thousand.
The extraction force of the monofilament of the epoxy resin embedding test is 9cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 19MPa. And after 2 hours of ultrasound, the retention of the filament pullout force and interfacial shear strength was 98%.
Creep resistance: creep was 2% after 30 minutes of exposure to 1000MPa tension at 70 ℃;
antibacterial properties: the fungi inhibition rate is 100% by using GB/T20944.2-2007 absorption method, and 99% by using FZ/T73023-2006 standard after washing for 50 times.
Comparative example 1 (unmodified fiber)
(1) Mixing the selected UHMWPE powder with a solvent (the UHMWPE powder accounts for 4wt% of the total mass of the mixed solution), mechanically stirring to uniformly mix, extruding by a double-screw extruder, sequentially spinning by a metering pump and a spinneret plate, and cooling in a water bath to obtain the frozen collagen yarn.
(2) Standing the obtained modified frozen collagen yarn at room temperature, and then extracting, drying and carrying out multi-stage hot drawing to obtain a surface modified UHMWPE fiber, wherein the extracting agent is methylene dichloride, the extracting temperature is 35 ℃, the drying temperature is 50 ℃, a drawing hot box in the multi-stage hot drawing process is four stages, the temperatures of the four stages of drawing hot boxes are respectively 100, 115, 135 and 145 ℃, and the hot drawing multiple is 28 times;
(3) The density of the UHMWPE/modified PE composite fiber is 0.96g/cm < 3 >, the strength is 35cN/dtex, the elongation at break is 3.4%, the contact angle of the fiber with water is 110 degrees, EDX test is carried out on the fiber section, the Zr content of zirconium element in the central area of the fiber (the circular area taking the center of the circular section as the center and 0.9r as the radius) is 0wt%, the Ag (or copper) content of silver element (or Cu) is 0wt%, the Zr content of the edge of the fiber section (the annular area between 0.9r and r from the center of the circular section) is 0wt%, the Ag (or Cu) content is 0wt%, and the viscosity average molecular weight of the composite fiber is 354 ten thousand.
The extraction force of the monofilament of the epoxy resin embedding test is 2cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 6MPa;
and after 2 hours of ultrasound, the retention of the filament pullout force and interfacial shear strength was 80%.
Creep resistance: creep was 15% after 30 minutes of 1000MPa tension at 70 ℃;
antibacterial properties: the fungi inhibition rate is 1% by using GB/T20944.2-2007 absorption method, and is 3% by using FZ/T73023-2006 standard after washing for 50 times.
Comparative example 2 (soaking time of mixed solution C was too long and temperature was too low)
(1) UIO-66-NH 2 Reacting with ethylene glycol diglycidyl ether (molar mass ratio is 1:1.5) to obtain an intermediate product A, and then adding dopamine (molar mass ratio of the intermediate product A to the dopamine is 1:1), and reacting to obtain a product B;
(2) Mixing the selected UHMWPE powder with a solvent (the UHMWPE powder accounts for 5wt% of the total mass of the mixed solution), mechanically stirring to uniformly mix, extruding by a double-screw extruder, sequentially spinning by a metering pump and a spinneret plate, and cooling in a water bath to obtain frozen collagen filaments;
(3) Standing the obtained gel precursor at room temperature, and then sequentially placing the gel precursor into a mixed solution C, a mixed solution D and a polar solution E to obtain the surface modified UHMWPE gel precursor;
wherein the mixed solution C is a mixture of a product B and water, the mass ratio of the product B in the mixture is 10wt%, the soaking time of the gel precursor in the mixed solution C is 4 hours, and the soaking temperature is 0 ℃;
The mixed solution D is a mixture of Tris (hydroxymethyl) aminomethane hydrochloride (Tris), alcohol and Ag+ ions, wherein the mass of the Tris accounts for 1wt% of the mass of the mixed solution D, the pH is 7, the soaking time is 2 hours, the soaking temperature is 50 ℃, and the mass of the Ag+ ions accounts for 4wt% of the mass of the mixed solution D;
the polar solution E is methanol, the soaking time in the polar solution E is 60 minutes, and the soaking temperature is 40 ℃;
(4) Standing the obtained modified frozen collagen yarn at room temperature, and then extracting, drying and carrying out multi-stage hot drawing to obtain a surface modified UHMWPE fiber, wherein the extracting agent is dimethylbenzene, the extracting temperature is 30 ℃, the drying temperature is 40 ℃, a drawing hot box in the multi-stage hot drawing process is three stages, the temperature of the three-stage drawing hot box is 100, 130 and 147 ℃ respectively, and the hot drawing multiple is 23 times;
wherein the density of the UHMWPE/modified PE composite fiber is 0.96g/cm 3 The strength is 23cN/dtex, the elongation at break is 3.2 percent, the contact angle of the fiber and water is 78 degrees, and the fiber is cutEDX test was conducted on the surface, and it was found that the Zr content in the fiber center region (circular region with the center of the circular cross section as the center and 0.9r as the radius) was 3wt%, the Ag content was 2wt%, the Zr content in the fiber cross-sectional edge (annular region between 0.9r and r from the center of the circular cross section) was 10wt%, the Ag content was 8wt%, and the composite fiber viscosity average molecular weight was 338 ten thousand.
The extraction force of the monofilament of the epoxy resin embedding test is 5cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 12MPa.
And after 2 hours of ultrasound, the retention of the filament pullout force and interfacial shear strength was 96%.
Creep resistance: creep was 3% after 30 minutes of 1000MPa tension at 70 ℃;
antibacterial properties: the fungi inhibition rate is 99% by using GB/T20944.2-2007 absorption method, and 98% by using FZ/T73023-2006 standard after washing for 50 times.
Comparative example 3 (soaking time of mixed solution C is too short and temperature is too high)
(1) UIO-66-NH 2 Reacting with ethylene glycol diglycidyl ether (molar mass ratio is 1:1.5) to obtain an intermediate product A, and then adding dopamine (molar mass ratio of the intermediate product A to the dopamine is 1:1), and reacting to obtain a product B;
(2) Mixing the selected UHMWPE powder with a solvent (the UHMWPE powder accounts for 5wt% of the total mass of the mixed solution), mechanically stirring to uniformly mix, extruding by a double-screw extruder, sequentially spinning by a metering pump and a spinneret plate, and cooling in a water bath to obtain frozen collagen filaments;
(3) Standing the obtained gel precursor at room temperature, and then sequentially placing the gel precursor into a mixed solution C, a mixed solution D and a polar solution E to obtain the surface modified UHMWPE gel precursor;
Wherein the mixed solution C is a mixture of a product B and water, the mass ratio of the product B in the mixture is 10wt%, the soaking time of the gel precursor in the mixed solution C is 0.05 hours (compared with comparative example 2, the parameter is changed), and the soaking temperature is 80 ℃;
the mixed solution D is a mixture of Tris (hydroxymethyl) aminomethane hydrochloride (Tris), alcohol and Ag+ ions, wherein the mass of the Tris accounts for 1wt% of the mass of the mixed solution D, the pH is 7, the soaking time is 3 hours, the soaking temperature is 40 ℃, and the mass of the Ag+ ions accounts for 5wt% of the mass of the mixed solution D;
the polar solution E is methanol, the soaking time in the polar solution E is 30 minutes, and the soaking temperature is 10 ℃;
(4) The obtained modified frozen collagen yarn is subjected to standing at room temperature, and then is subjected to extraction, drying and multistage hot drawing to obtain surface modified UHMWPE fibers, wherein the extracting agent is petroleum ether, the extraction temperature is 38 ℃, the drying temperature is 45 ℃, a drawing hot box in the multistage hot drawing process is five stages, and the temperature of the five-stage drawing hot box is 90, 110, 125, 135 and 146 ℃ respectively, and the hot drawing multiple is 26 times;
wherein the density of the UHMWPE/modified PE composite fiber is 0.97g/cm 3 EDX test was conducted on a fiber cross section having a strength of 26cN/dtex and an elongation at break of 11% and a contact angle of 100℃with water, and found that the fiber center region (circular region having a radius of 0.9r as the center of the circular cross section) had a Zr content of 0.2% by weight, an Ag content of 0.3% by weight, the fiber cross-sectional edge (annular region between 0.9r and r from the center of the circular cross section) had a Zr content of 0.1% by weight, an Ag content of 0.2% by weight, and a composite fiber viscosity average molecular weight of 319 ten thousand.
The extraction force of the monofilament of the epoxy resin embedding test is 2cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 9MPa.
And after 2 hours of ultrasound, the filament pullout force and interfacial shear strength retention were 50%.
Creep resistance: creep was 30% after 30 minutes of exposure to 1000MPa tension at 70 ℃;
antibacterial properties: the fungi inhibition rate is 80% by using GB/T20944.2-2007 absorption method, and 50 times of water washing, the fungi inhibition rate is 50% according to FZ/T73023-2006 standard.
Comparative example 4 (soaking time of mixed liquor D is too short and temperature is too low)
(1) UIO-66-NH 2 With ethylene glycol diglycidyl ether (molar mass ratio 1:3) to give intermediate a, and then adding dopamine (molar ratio of intermediate a to dopamineThe mass ratio is 1:2), and the product B is obtained by reaction;
(2) Mixing the selected UHMWPE powder with a solvent (the UHMWPE powder accounts for 10wt% of the total mass of the mixed solution), mechanically stirring to uniformly mix, extruding by a double-screw extruder, sequentially spinning by a metering pump and a spinneret plate, and cooling in a water bath to obtain frozen collagen filaments;
(3) Standing the obtained gel precursor at room temperature, and then sequentially placing the gel precursor into a mixed solution C, a mixed solution D and a polar solution E to obtain the surface modified UHMWPE gel precursor;
Wherein the mixed solution C is a mixture of a product B and water, the mass ratio of the product B in the mixture is 7wt%, the soaking time of the gel precursor in the mixed solution C is 2 hours, and the soaking temperature is 60 ℃;
the mixed solution D is a mixture of Tris hydrochloride (Tris), alcohol and Ag+ ions, wherein the mass of the Tris accounts for 0.8wt% of the mass of the mixed solution D, the pH value is 9, the soaking time is 0.1 hour, the soaking temperature is 5 ℃, and the mass of the Ag+ ions accounts for 6wt% of the mass of the mixed solution D;
the polar solution E is methanol, the soaking time in the polar solution E is 40 minutes, and the soaking temperature is 50 ℃;
(4) Standing the obtained modified frozen collagen yarn at room temperature, and then extracting, drying and carrying out multistage hot drawing to obtain a surface modified UHMWPE fiber, wherein the extractant is 120# gasoline, the extraction temperature is 32 ℃, the drying temperature is 48 ℃, a drawing hot box in the multistage hot drawing process is four stages, the temperatures of the four stages of drawing hot boxes are 100, 115, 135 and 145 ℃ respectively, and the hot drawing multiple is 23 times;
wherein the density of the UHMWPE/modified PE composite fiber is 0.98g/cm 3 EDX test was conducted on a fiber cross section having a strength of 24cN/dtex, an elongation at break of 9%, a contact angle of the fiber with water of 95℃and found that the fiber center region (circular region with a radius of 0.9r as the center of the circular cross section) had a Zr content of 0.3% by weight, an Ag content of 0.4% by weight, the fiber cross-sectional edge (annular region between 0.9r and r from the center of the circular cross section) had a Zr content of 0.5% by weight, an Ag content of 0.7% by weight, and a composite fiber viscosity average molecular weight of 305 ten thousand.
The extraction force of the monofilament of the epoxy resin embedding test is 3cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 8MPa.
And after 2 hours of ultrasound, the retention of the filament pullout force and interfacial shear strength was 70%.
Creep resistance: creep was 40% after 30 minutes of 1000MPa tension at 70 ℃;
antibacterial properties: the fungi inhibition rate is 70% by using GB/T20944.2-2007 absorption method, and 65% by using FZ/T73023-2006 standard after washing with water for 50 times.
Comparative example 5 (soaking time of mixed solution D is too long and temperature is too high)
(1) UIO-66-NH 2 Reacting with ethylene glycol diglycidyl ether (molar mass ratio is 1:3) to obtain an intermediate product A, and then adding dopamine (molar mass ratio of the intermediate product A to the dopamine is 1:2), and reacting to obtain a product B;
(2) Mixing the selected UHMWPE powder with a solvent (the UHMWPE powder accounts for 10wt% of the total mass of the mixed solution), mechanically stirring to uniformly mix, extruding by a double-screw extruder, sequentially spinning by a metering pump and a spinneret plate, and cooling in a water bath to obtain frozen collagen filaments;
(3) Standing the obtained gel precursor at room temperature, and then sequentially placing the gel precursor into a mixed solution C, a mixed solution D and a polar solution E to obtain the surface modified UHMWPE gel precursor;
Wherein the mixed solution C is a mixture of a product B and water, the mass ratio of the product B in the mixture is 7wt%, the soaking time of the gel precursor in the mixed solution C is 2 hours, and the soaking temperature is 60 ℃;
the mixed solution D is a mixture of Tris (hydroxymethyl) aminomethane hydrochloride (Tris), alcohol and Ag+ ions, wherein the mass of the Tris accounts for 0.8wt% of the mass of the mixed solution D, the pH is 9, the soaking time is 4 hours, the soaking temperature is 80 ℃, and the mass of the Ag+ ions accounts for 7wt% of the mass of the mixed solution D;
the polar solution E is methanol, the soaking time in the polar solution E is 50 minutes, and the soaking temperature is 60 ℃;
(4) Standing the obtained modified frozen collagen yarn at room temperature, and then extracting, drying and carrying out multi-stage hot drawing to obtain a surface modified UHMWPE fiber, wherein the extracting agent is dimethylbenzene, the extracting temperature is 30 ℃, the drying temperature is 45 ℃, a drawing hot box in the multi-stage hot drawing process is four stages, the temperatures of the four stages of drawing hot boxes are 110, 120, 135 and 147 ℃ respectively, and the hot drawing multiple is 21 times;
wherein the density of the UHMWPE/modified PE composite fiber is 0.98g/cm 3 EDX test was conducted on a fiber cross section having a strength of 13cN/dtex, an elongation at break of 6% and a contact angle of 75℃with water, and found that the fiber center region (circular region having a radius of 0.9r around the center of the circular cross section) had a Zr content of 1% by weight, an Ag content of 1% by weight, the fiber cross-sectional edge (annular region between 0.9r and r from the center of the circular cross section) had a Zr content of 3% by weight, an Ag content of 4% by weight, and a composite fiber viscosity average molecular weight of 295 ten thousand.
The extraction force of the monofilament of the epoxy resin embedding test is 2cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 15MPa.
And after 2 hours of ultrasound, the retention of the filament pullout force and interfacial shear strength was 96%.
Creep resistance: creep was 3% after 30 minutes of 1000MPa tension at 70 ℃;
antibacterial properties: the fungi inhibition rate is 99% by using GB/T20944.2-2007 absorption method, and 98% by using FZ/T73023-2006 standard after washing for 50 times.
Comparative example 6 (Cu) + The ions have too high mass in the mixture D)
(1) UIO-66-NH 2 Reacting with ethylene glycol diglycidyl ether (molar mass ratio is 1:3) to obtain an intermediate product A, and then adding dopamine (molar mass ratio of the intermediate product A to the dopamine is 1:1), and reacting to obtain a product B;
(2) Mixing the selected UHMWPE powder with a solvent (the UHMWPE powder accounts for 5wt% of the total mass of the mixed solution), mechanically stirring to uniformly mix, extruding by a double-screw extruder, sequentially spinning by a metering pump and a spinneret plate, and cooling in a water bath to obtain frozen collagen filaments;
(3) Standing the obtained gel precursor at room temperature, and then sequentially placing the gel precursor into a mixed solution C, a mixed solution D and a polar solution E to obtain the surface modified UHMWPE gel precursor;
Wherein the mixed solution C is a mixture of a product B and water, the mass ratio of the product B in the mixture is 2wt%, the soaking time of the gel precursor in the mixed solution C is 0.5 hour, and the soaking temperature is 20 ℃;
the mixed solution D is Tris (hydroxymethyl) aminomethane hydrochloride (Tris), methanol and Cu + The mass of the mixture of ions is 1wt% of the mass of the mixed solution D, the pH is 9, the soaking time is 1 hour, the soaking temperature is 40 ℃, and the mass of Cu+ ions is 20wt% of the mass of the mixed solution D;
the polar solution E is isopropanol, the soaking time in the polar solution E is 30 minutes, and the soaking temperature is 40 ℃;
(4) Standing the obtained modified frozen collagen yarn at room temperature, and then extracting, drying and carrying out multistage hot drawing to obtain a surface modified UHMWPE fiber, wherein the extracting agent is methylene dichloride, the extracting temperature is 36 ℃, the drying temperature is 40 ℃, a drawing hot box in the multistage hot drawing process is three stages, the temperature of the three stages of drawing hot boxes is 100, 135 and 144 ℃ respectively, and the hot drawing multiple is 18 times;
the density of the UHMWPE/modified PE composite fiber is 0.97g/cm < 3 >, the strength is 10cN/dtex, the elongation at break is 1.0%, the contact angle of the fiber with water is 78 degrees, EDX test is carried out on the fiber section, the Zr content in the central area of the fiber (the circular area taking the center of the circular section as the center and 0.9r as the radius) is 1wt%, the Cu content is 1wt%, the Zr content in the edge of the fiber section (the annular area between 0.9r and r from the center of the circular section) is 10wt%, the Cu content is 7wt%, and the viscosity average molecular weight of the composite fiber is 306 ten thousand.
The extraction force of the monofilament of the epoxy resin embedding test is 6cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 13MPa. And after 2 hours of ultrasound, the retention of the filament pullout force and interfacial shear strength was 97%.
Creep resistance: creep was 2% after 30 minutes of exposure to 1000MPa tension at 70 ℃;
antibacterial properties: the fungi inhibition rate is 100% by using GB/T20944.2-2007 absorption method, and 98% by using FZ/T73023-2006 standard after washing for 50 times.
Comparative example 7 (Cu) + The ions have too low a mass in the mixture D)
(1) UIO-66-NH 2 Reacting with ethylene glycol diglycidyl ether (molar mass ratio is 1:3) to obtain an intermediate product A, and then adding dopamine (molar mass ratio of the intermediate product A to the dopamine is 1:1), and reacting to obtain a product B;
(2) Mixing the selected UHMWPE powder with a solvent (the UHMWPE powder accounts for 5wt% of the total mass of the mixed solution), mechanically stirring to uniformly mix, extruding by a double-screw extruder, sequentially spinning by a metering pump and a spinneret plate, and cooling in a water bath to obtain frozen collagen filaments;
(3) Standing the obtained gel precursor at room temperature, and then sequentially placing the gel precursor into a mixed solution C, a mixed solution D and a polar solution E to obtain the surface modified UHMWPE gel precursor;
Wherein the mixed solution C is a mixture of a product B and water, the mass ratio of the product B in the mixture is 2wt%, the soaking time of the gel precursor in the mixed solution C is 0.5 hour, and the soaking temperature is 20 ℃;
the mixed solution D is Tris (hydroxymethyl) aminomethane hydrochloride (Tris), methanol and Cu + The mass of the mixture of ions is 1wt% of the mass of the mixed solution D, the pH is 9, the soaking time is 1 hour, the soaking temperature is 50 ℃, and the mass of Cu+ ions is 1wt% of the mass of the mixed solution D;
the polar solution E is isopropanol, the soaking time in the polar solution E is 10 minutes, and the soaking temperature is 30 ℃;
(4) Standing the obtained modified frozen collagen yarn at room temperature, and then extracting, drying and carrying out multi-stage hot drawing to obtain a surface modified UHMWPE fiber, wherein the extracting agent is petroleum ether, the extracting temperature is 35 ℃, the drying temperature is 55 ℃, a drawing hot box in the multi-stage hot drawing process is four stages, the temperatures of the four stages of drawing hot boxes are respectively 100, 110, 130 and 145 ℃, and the hot drawing multiple is 26 times;
the density of the UHMWPE/modified PE composite fiber is 0.97g/cm < 3 >, the strength is 30cN/dtex, the elongation at break is 11%, the contact angle of the fiber with water is 97 degrees, EDX test is carried out on the fiber section, the Zr content in the central area of the fiber (the circular area taking the center of the circular section as the center and 0.9r as the radius) is 0.1wt%, the Cu content is 0.1wt%, the Zr content in the edge of the fiber section (the annular area between 0.9r and r from the center of the circular section) is 0.3wt%, the Cu content is 0.4wt%, and the viscosity average molecular weight of the composite fiber is 326 ten thousand. .
The extraction force of the monofilament of the epoxy resin embedding test is 8cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 17MPa. And after 2 hours of ultrasound, the retention of the filament pullout force and interfacial shear strength was 98%.
Creep resistance: creep was 7% after 30 minutes of 1000MPa tension at 70 ℃;
antibacterial properties: the fungi inhibition rate is 80% by using GB/T20944.2-2007 absorption method, and after washing for 50 times, the fungi inhibition rate is 78% according to FZ/T73023-2006 standard.
The conventional preparation of the UHMWPE fiber with the functions of antibiosis, creep resistance and surface adhesion improvement often needs multiple steps of treatment to enable the fiber to have the functions, so that the problems of complicated treatment process, increased production cost and the like exist. The UHMWPE fiber with antibacterial creep resistance and improved surface cohesiveness is obtained by processing the gel precursor and then carrying out processes such as extraction drying, super heat drawing and the like.
According to the invention, a novel filler product B is soaked in a jelly fiber, the product B not only contains a porous organic framework structure UIO-66-NH2, but also contains a dopamine structure for improving adhesion, then the product B is polymerized under a certain condition and firmly adhered to the surface of the jelly fiber, in addition, the UIO-66-NH2 structure can enable UHMWPE molecular chains to be entangled, and antibacterial ions Cu+ or Ag+ ions can be adsorbed into the UIO-66-NH2, so that the lasting release of antibacterial performance is realized, and finally, the functional UHMWPE fiber with antibacterial, creep resistance and surface adhesion improvement is finally obtained through subsequent process treatment.
In the invention, the molar mass ratio of the UIO-66-NH2 to the ethylene glycol diglycidyl ether is important; only if the ratio of UIO-66-NH2 to ethylene glycol diglycidyl ether is in a proper range, the intermediate product A can be successfully obtained, and if the content of UIO-66-NH2 is too high, epoxy groups at two ends of the ethylene glycol diglycidyl ether can fully react with amino groups of the UIO-66-NH2, so that the intermediate product A can not be obtained; when the content of UIO-66-NH2 is too low, the UIO-66-NH2 cannot react with ethylene glycol diglycidyl ether, and an intermediate product A cannot be generated; likewise, the molar mass ratio of the intermediate product A to the dopamine also influences the structure of the product B, and when the dopamine content is too high or too low, the product B is difficult to obtain;
the soaking time of the frozen collagen filaments in the mixed solution C can influence the distribution of the product B in the frozen collagen filaments, the soaking time is too long, the product B can infiltrate into the core of the frozen collagen filaments, the oriented crystallization of the fibers is hindered during hot drawing, the mechanical properties of UHMWPE are finally influenced, the soaking time is too short, and the product B only infiltrates into the surface of the frozen collagen filaments or less into the frozen collagen filaments, so that the purposes of creep resistance, antibiosis and adhesion promotion can not be finally achieved. Similarly, the soaking temperature also affects the infiltration amount of the product B in the gel precursor, the product B is oxidized at too high temperature, the structure is destroyed, and the infiltration of the product B in the gel precursor is not facilitated due to too low temperature.
Then the gel precursor containing the product B is polymerized in the mixed solution D, the product B can be firmly adhered to an UHMWPE molecular chain by utilizing the catechol structure of dopamine, and meanwhile Cu+ or Ag+ ions can enter a porous structure of UIO-66-NH2, so that the stable adsorption of the Cu+ or Ag+ ions is realized;
the soaking time and the soaking temperature of the jelly fiber of the product B in the mixed solution D also influence the performance of the final product, the soaking time is too short, the product B cannot be polymerized in the jelly fiber, the adhesion performance of the fiber is difficult to improve, the soaking time is too long, the product B is polymerized too much to cause bonding of UHMWPE molecular chains together, the subsequent hot drawing is influenced, the oriented crystallization of the fiber is further not facilitated, and the mechanical property of the fiber is reduced; the soaking temperature is too high, the oxidation structure of the product B is destroyed, self-polymerization cannot occur, the soaking temperature is too low, and polymerization reaction is difficult to occur; similarly, too high quality of Cu+ or Ag+ ions in the mixed solution D can affect the final mechanical properties of the fiber, and too low quality cannot enter the porous structure of UIO-66-NH2, so that the antibacterial performance is difficult to realize.
Unexpectedly, the product obtained after addition of product B and polymerization, extraction and hot drawing also has better creep resistance, since the UIO-66-NH2 in product B is a porous compound, which not only can contain Cu + Or Ag + The ion plays an antibacterial role, the UHMWPE molecular chain can be entangled in the ion, and finally the slippage of the PE molecular chain is restrained, so that the creep resistance of the fiber is enhanced.
In summary, compared with the prior art, the invention has the following advantages and positive effects: the UHMWPE fibers have antibacterial property; the creep resistance is improved; the surface adhesiveness is improved; the excellent mechanical properties are maintained.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, and it should be covered in the scope of the present invention.
Claims (10)
1. A preparation method of an antibacterial creep-resistant strong-adhesion ultra-high molecular weight polyethylene fiber is characterized by comprising the following steps: comprising the steps of (a) a step of,
UIO-66-NH 2 Reacting with ethylene glycol diglycidyl ether to obtain an intermediate product A;
adding dopamine into the intermediate product A, and reacting to obtain a product B;
mixing ultra-high molecular weight polyethylene powder with a solvent, stirring and mixing uniformly, extruding by a double-screw extruder, sequentially spinning by a metering pump and a spinneret plate, and cooling in a water bath to obtain frozen collagen filaments;
Standing the obtained gel precursor at room temperature, and sequentially placing the gel precursor into a mixed solution C, a mixed solution D and a polar solution E to obtain a surface modified gel precursor; wherein the mixed solution C is a mixture of a product B and a solution F, and the solution F is one or a mixture of more of water, alcohol, acetone, methanol and glycerol; by a means ofThe mixed solution D is Tris and solution F, cu containing Tris hydrochloride + Or Ag + One or a mixture of two ions; the polar solution E is one or a mixture of more of methanol, ethanol, isopropanol, n-butanol, dioxane and tetrahydrofuran;
and standing the modified frozen collagen yarn at room temperature, and then extracting, drying and carrying out multistage hot drawing to obtain the surface modified ultra-high molecular weight polyethylene fiber.
2. The method of manufacturing according to claim 1, wherein: the UIO-66-NH 2 The molar mass ratio of the intermediate product A to the ethylene glycol diglycidyl ether is 1:1.5-1:5, the reaction time for preparing the intermediate product A is 1-24 h, the reaction temperature is 20-60 ℃, and the pH of the reaction system is 9-12.
3. The preparation method according to claim 1 or 2, characterized in that: the UIO-66-NH 2 The molar mass ratio of the catalyst to the glycol diglycidyl ether is 1:1.5-1:3.
4. The method of manufacturing according to claim 1, wherein: the molar mass ratio of the intermediate product A to the dopamine is 1:0.5-1:3, the reaction time for preparing the intermediate product B is 1-24 h, the reaction temperature is 20-60 ℃, and the pH of the reaction system is 9-12.
5. The method of any one of claims 1, 2 or 4, wherein: the ultra-high molecular weight polyethylene powder accounts for 4-15 wt% of the total mass of the mixed solution, and the solvent in the mixed solution is one or more hydrocarbon compounds, including one or more of decalin, tetralin, kerosene, paraffin oil and white oil.
6. The method of manufacturing according to claim 5, wherein: the mass ratio of the product B in the mixture is 0.5-20wt%;
the soaking time of the frozen collagen filaments in the mixed solution C is 0.1-2 h, and the soaking temperature is 10-70 ℃.
7. The method of manufacturing according to claim 6, wherein: in the mixed solution D, the mass of Tris accounts for 0.1-2 wt% of the mass of the mixed solution D, the pH value is 6-10, and Cu + Or Ag + The mass of the ions accounts for 1-8wt% of the mass of the mixed solution D;
the soaking time of the frozen collagen filaments in the mixed solution D is 0.2-3 h, and the soaking temperature is 20-60 ℃.
8. The method of manufacturing according to claim 7, wherein: and the gel precursor filaments soaked in the mixed solution C and the mixed solution D are soaked in the polar solution E, wherein the soaking time is 2-60 min, and the soaking temperature is 20-60 ℃.
9. The method of preparing as claimed in claim 8, wherein: the modified frozen collagen yarn is subjected to extraction, drying and multistage hot drawing after standing at room temperature, wherein the extracting agent is one or a mixture of xylene, methylene dichloride, petroleum ether and 120# gasoline, the extraction temperature is 20-40 ℃, the drying temperature is 20-80 ℃, a drawing hot box in the multistage hot drawing process is 3-6 stages, the drawing temperature is 80-148 ℃, and the hot drawing multiple is 10-40 times.
10. The antibacterial, creep-resistant, strongly adherent ultra-high molecular weight polyethylene fiber produced by the production process of any one of claims 1 to 9, characterized in that: the surface of the fiber contains polar groups, and has excellent antibacterial, creep-resistant and mechanical properties.
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