CN108395675A - A kind of tannic acid modified superhigh molecular weight polyethylene fibers and its composite material and preparation method thereof - Google Patents
A kind of tannic acid modified superhigh molecular weight polyethylene fibers and its composite material and preparation method thereof Download PDFInfo
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- CN108395675A CN108395675A CN201810216007.5A CN201810216007A CN108395675A CN 108395675 A CN108395675 A CN 108395675A CN 201810216007 A CN201810216007 A CN 201810216007A CN 108395675 A CN108395675 A CN 108395675A
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- molecular weight
- weight polyethylene
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- tannic acid
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- 239000000835 fiber Substances 0.000 title claims abstract description 151
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 87
- -1 polyethylene Polymers 0.000 title claims abstract description 87
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 87
- 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 title claims abstract description 39
- 239000001263 FEMA 3042 Substances 0.000 title claims abstract description 39
- 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 title claims abstract description 39
- 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 title claims abstract description 39
- 229940033123 tannic acid Drugs 0.000 title claims abstract description 39
- 235000015523 tannic acid Nutrition 0.000 title claims abstract description 39
- 229920002258 tannic acid Polymers 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 239000007983 Tris buffer Substances 0.000 claims abstract description 19
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000000694 effects Effects 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract 2
- 239000003822 epoxy resin Substances 0.000 claims description 33
- 229920000647 polyepoxide Polymers 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000000536 complexating effect Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 230000003746 surface roughness Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000005060 rubber Substances 0.000 claims 3
- 239000004705 High-molecular-weight polyethylene Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 15
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 2
- 239000002994 raw material Substances 0.000 abstract 2
- 230000009920 chelation Effects 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 229920013657 polymer matrix composite Polymers 0.000 abstract 1
- 239000011160 polymer matrix composite Substances 0.000 abstract 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 19
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 19
- 239000000126 substance Substances 0.000 description 8
- 238000003851 corona treatment Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 235000013824 polyphenols Nutrition 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 102000008946 Fibrinogen Human genes 0.000 description 1
- 108010049003 Fibrinogen Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229940012952 fibrinogen Drugs 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
-
- 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
- D06M13/10—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 oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/238—Tannins, e.g. gallotannic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
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- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a kind of new tannic acid modified superhigh molecular weight polyethylene fibers and its composite material and preparation method thereof.For the present invention using superhigh molecular weight polyethylene fibers as raw material, tannic acid Nacl Tris mixed solutions are modifying agent.By impregnating superhigh molecular weight polyethylene fibers in tannic acid Nacl Tris solution, by chelation by tannic acid and Na+Reaction forms TA Na+；Pass through electrostatic force, covalent bond and non-covalent bond effect again, it is set to form coating on superhigh molecular weight polyethylene fibers surface, after tannic acid coats, the cementitiousness of superhigh molecular weight polyethylene fibers and resin matrix improves, acquired composite materials property enhancing.The raw material sources of the present invention are abundant, preparation method is simple and environmentally-friendly, will have broad application prospects in terms of polymer matrix composites.
Description
【Technical field】：The invention belongs to fiber/resin technical field of composite materials, and in particular to a kind of tannic acid modified
Superhigh molecular weight polyethylene fibers and its composite material and preparation method thereof.
【Background technology】：Ultra-high molecular weight polyethylene (UHMWPE) fiber is to succeed in developing the early 1980s
, the third generation high-performance fiber occurred after carbon fiber and aramid fiber.It is that specific strength and specific modulus be most in the world at present
High fiber.It is with a series of excellent performances, such as：High specific strength, high ratio modulus, specific strength are the ten of same section steel wire
More times, specific modulus is only second to superfine carbon fiber.Extension at break is low, work to break is big, has the very strong ability for absorbing energy, thus
With impact resistance outstanding and anti-cut.Fibre density is low, and density is 0.97-0.98g/cm3, can bubble through the water column.Anti- purple
UV radiation, anti-neutron and gamma-rays, specific energy absorption is high, dielectric constant is low, electromagnetic wave tansmittivity is high.It is wear-resisting, chemically-resistant is rotten
It loses, have longer flex life.UHMWPE fibers can be applied to military affairs, space flight navigation engineering, high-performance light composite wood
The fields such as material and high-grade leisure sports goods.But due to UHMWPE fiber surface non-polar groups, no chemism, surface energy
It is low, the disadvantages such as apolar substance is difficult to infiltrate, and fusing point is low, to limit its application.Especially in reinforced resin base composite wood
In terms of material, the adhesive property between resin matrix is poor, causes shock resistance low, causes composite material using process
In there is fiber and resin matrix degumming and resin matrix problems of crack occur.
In order to improve the shortcomings of UHMWPE fiber surface activities are low and adhesive property is poor between resin matrix, both at home and abroad
Scholar has done a large amount of research work.The modification of UHMWPE fibers is mainly handled fiber surface, and common surface changes
Property method has：Chemical oxidation treatment, corona treatment, irradiation grafting processing and Corona discharge Treatment etc..
1. chemical oxidation treatment
Chemical oxidation treatment refers to being handled UHMWPE fiber surfaces using strong oxidizer, is removed using strong oxidation
The weak interface layer for falling fiber surface makes fiber surface generate rough pattern, to increase the roughness and ratio of fiber
Surface area, only fiber is not combined offer physics meshing point with resin matrix, and oxidation can be introduced in fiber surface
The oxygen-containing polar group surface such as carbonyl and carboxyl is modified.This method can be effectively improved the adhesive property between fiber and resin.
Common oxidant has：K2Cr2O7Solution, chromic acid, hydrogen peroxide and KMnO4Solution etc..
2. corona treatment
Plasma method is to one of UHMWPE fibre modification most efficient methods at present, and fiber is through plasma irradiating mistake
Good binding ability is formed with resin matrix afterwards, the cross-linking depth of 30nm can be reached, plasma is passed through under oxygen atmosphere
The effect of chemical bond can be divided after processing with generating unit.In plasma treatment procedure, the weak boundary layer of fiber surface is removed,
This helps to improve the caking property between fiber and resin.Because corona treatment is only to several points of UHMWPE fiber surfaces
The depth of son has an impact, and without being damaged to its internal structure, therefore the strength damage of fiber is smaller.Use such as Yuan Chaoting etc.
Gas ions facture is surface-treated UHMWPE fibers under the conditions of oxygen atmosphere, and by the fiber and ring after before modified
Epoxy resin-based body carries out compound testing caking property between the two.The experimental results showed that unmodified fiber is pulled out from epoxy resin
After going out, fiber and epoxy resin layering are apparent, without resin matrix in fiber sheath, also without residual fiber left in resin matrix
On.And the fiber after plasma modification not only finds the resin of adherency after being extracted in resin matrix in fibrous inside
And it has also been found that there is fiber delamination in resin, illustrate mutual when fiber is combined with epoxy resin-base after plasma modification
It penetrates into, to increase adhesion strength between the two.
3. radiation-induced grafting processing
Radiation-induced grafting processing is to carry out radiation treatment to fiber surface, and second comonomer is added later and be grafted and gathers
It closes, finally generates one layer of boundary layer different from fiber chemistry in fiber surface.The boundary layer, which has, increases fiber and base
The characteristics of body adhesive property and as " tie " between fiber and matrix, improve the adhesion strength between fiber and matrix.Because
UHMWPE fiber surface activities are extremely low, so radiate-induced grafting before pre-processed, pretreated method has：
Gamma-ray irradiation, corona treatment etc..It even smaller receives this is mainly due to fabric surface grain size is suitable with optical wavelength
Rice Argent grain makes the optical absorption of material significantly increase, therefore absorbable some ultra violet rays.But this method will produce containing weight
The discard solution of metal ion pollutes environment.Li et al. people uses Benzophenone (BP) for initiator, methacrylic acid (MAA) and third
Acrylamide (AM) is function monomer, carries out surface modification to UHMWPE fibers using UV photoinitiated grafting copolymerization method, utilizes
Continuous light inducible gradually grafting functional group on the surface of the fiber, and on the performance of fibrinogen influence comparatively compared with
It is small.Since the functional groups of modified UHMWPE fiber surfaces can be reacted with epoxy resin, between the two with chemical bond
Mode combines, to increase the adhesion strength between UHMWPE fibers and epoxy resin-base.
4. Corona discharge Treatment
Corona discharge is most initially the nonpolar film of processing, is exploited for after the eighties at non-polar fibers surface
Reason.Its principle is that high-frequency high-voltage electricity is applied on the electrode of electrification, since the high-frequency high-voltage of application so that electrode is attached
Close electric field becomes very strong, and the gas of neighbouring electrode is made partly to be punctured and generate a large amount of particles, a large amount of particles again with fiber table
Face molecule influences each other, to influence the physical property and chemical property of fiber surface.It is modified through corona discharge
UHMWPE fibers, most important variation, which is the content of the oxygen element of fiber surface, to be increased considerably, and far infrared is further used
The modified UHMWPE fiber surfaces of spectrum analysis, it can be found that there are the characteristic peaks of the groups such as hydroxyl, carboxyl and carbonyl.Together
When, the roughness of the UHMWPE fibers after Corona discharge Treatment, surface increases, this is to improving between fiber and resin matrix
Adhesion strength also has certain help.
And the present invention proposes a kind of method of new tannic acid modified superhigh molecular weight polyethylene fibers, i.e., by supra polymer
Weight polyethylene fiber immerses in tannic acid-Nacl-Tris solution, tannic acid and metal Na+Complexing occurs, then by altogether
Valence link or non-covalent bond effect, TA-Na+Firmly it is adsorbed on superhigh molecular weight polyethylene fibers surface.Tannic acid is as in recent years
The Novel modifier to grow up, it is a kind of water-soluble, high molecular weight natural plants polyphenol, is widely present in draft and wood
In this plant.Its chemical constitution is similar to hyperbranched aromatic polyester, has abundant phenolic hydroxyl group reactive group.Due to this spy
Different structure, tannic acid have a wide range of applications, such as coating, absorption and anti-biotic material and nano material.Tannic acid also can
Enough at ambient temperature, formation coating spontaneous in trishydroxymethylaminomethane (Tris) buffering, and because of the structure of tannic acid
In have a large amount of phenol structure unit, coating that can greatly improve the hydrophily on modified material surface.
【Invention content】：In view of the deficiencies of the prior art, which uses a kind of side easy to operate, green non-pollution
Method, it is therefore an objective to complexing be occurred by tannic acid and metal ion, superelevation is adhered to by covalent bond or non-covalent bond effect
Molecular weight polyethylene fiber surface provides abundant phenolic hydroxyl group, come improve superhigh molecular weight polyethylene fibers and composite material it
Between adhesion strength.
The present invention is first by tannic acid and metal Na+Complexing occurs, forms TA-Na+Complex, ligand compound
Object is deposited on organic and inorganic matrix surface and forms colourless coating by covalent bond or non-covalent bond effect formation oligomer,
It is adhered to superhigh molecular weight polyethylene fibers surface, to make superhigh molecular weight polyethylene fibers surface there are a large amount of phenolic hydroxyl groups,
To improve the cementitiousness between epoxy resin.This method is strong with bonding force compared to traditional blending and modifying, is not easy
The advantages of falling, and fiber original mechanical property will not be changed.
To reach this purpose, the technology path that the present invention uses is：
1) pretreatment of superhigh molecular weight polyethylene fibers：
Superhigh molecular weight polyethylene fibers are impregnated into a period of time in ethanol, are removed on superhigh molecular weight polyethylene fibers
Remaining organic solvent then takes out drying.
2) adherency of tannic acid：
The Tris for weighing 0.06-0.20g is dissolved in 200ml water, is adjusted pH value 5-10, is then weighed the tannin of 0.1-0.8g
Acid, 3-7gNacl are dissolved in above-mentioned Tris solution and stir.Superhigh molecular weight polyethylene fibers are immersed into this solution, herein mistake
Tannic acid solution can become blackish green from brown color in journey, and superhigh molecular weight polyethylene fibers can become faint yellow from white.
After reacting 3-24h, superhigh molecular weight polyethylene fibers are taken out, are repeatedly rinsed with deionized water, dried, is made tannic acid modified
Superhigh molecular weight polyethylene fibers afterwards.
3) preparation of superhigh molecular weight polyethylene fibers/epoxy resin composite material
Superhigh molecular weight polyethylene fibers monofilament is passed through in cylindrical mold, then injects epoxy resin/solidification into mold
Agent system demoulds after curing 24-48h at room temperature, obtains superhigh molecular weight polyethylene fibers/epoxy resin composite material.
The principle of the invention is：Tannic acid and metal Na+Complexing occurs, forms TA-Na+Complex, ligand compound
Object is deposited on organic and inorganic matrix surface and forms colourless coating by covalent bond or non-covalent bond effect formation oligomer,
It is adhered to superhigh molecular weight polyethylene fibers surface, there are a large amount of active groups to make superhigh molecular weight polyethylene fibers surface
Phenolic hydroxyl group simultaneously increases superhigh molecular weight polyethylene fibers surface roughness, to improve the bonding energy between epoxy resin
Power.
The method applied in the present invention, the surface that can be applied to most of materials is modified, easy to operate, to appointed condition
It is required that low, green non-pollution, and the original mechanical property of fiber will not be changed, it can be widely applied to various polymer.
【Specific embodiment】
Embodiment 1：
1) pretreatment of superhigh molecular weight polyethylene fibers.Superhigh molecular weight polyethylene fibers are cut to certain length,
It is soaked for a period of time in ethanol, removes remaining organic solvent on superhigh molecular weight polyethylene fibers, then take out drying and wait for
With.
2) deposition of tannic acid.It weighs 0.121gTris to be dissolved into 200ml deionized waters, then weighs 0.4g tannic acid,
3gNacl is dissolved into Tris solution, and it is 8.5 to adjust pH value, then quickly impregnates superhigh molecular weight polyethylene fibers into solution
In, reaction condition is：Room temperature, 3h.It is repeatedly rinsed, is dried with deionized water after taking-up, it is poly- that the modified ultra-high molecular mass is made
Vinyl fiber.
3) preparation of superhigh molecular weight polyethylene fibers/epoxy resin composite material.By superhigh molecular weight polyethylene fibers
Monofilament passes through in cylindrical mold, then epoxy resin/curing agent system is injected into mold, cures demould afterwards for 24 hours at room temperature, obtain
To superhigh molecular weight polyethylene fibers/epoxy resin composite material.
Embodiment 2：
1) pretreatment of superhigh molecular weight polyethylene fibers.Superhigh molecular weight polyethylene fibers are cut to certain length,
It is soaked for a period of time in ethanol, removes remaining organic solvent on superhigh molecular weight polyethylene fibers, then take out drying and wait for
With.
2) deposition of tannic acid.It weighs 0.121g Tris to be dissolved into 200ml deionized waters, then weighs 0.2g tannic acid,
4gNacl is dissolved into Tris solution, and it is 7 to adjust pH value, then quickly impregnates superhigh molecular weight polyethylene fibers into solution
In, reaction condition is：Room temperature, 6h.It is repeatedly rinsed, is dried with deionized water after taking-up, it is poly- that the modified ultra-high molecular mass is made
Vinyl fiber.
3) preparation of superhigh molecular weight polyethylene fibers/epoxy resin composite material.By superhigh molecular weight polyethylene fibers
Monofilament passes through in cylindrical mold, then epoxy resin/curing agent system is injected into mold, cures demould afterwards for 24 hours at room temperature, obtain
To superhigh molecular weight polyethylene fibers/epoxy resin composite material.
Embodiment 3：
1) pretreatment of superhigh molecular weight polyethylene fibers.Superhigh molecular weight polyethylene fibers are cut to certain length,
It is soaked for a period of time in ethanol, removes remaining organic solvent on superhigh molecular weight polyethylene fibers, then take out drying and wait for
With.
2) deposition of tannic acid.It weighs 0.121g Tris to be dissolved into 200ml deionized waters, then weighs 0.4g tannic acid,
5gNacl is dissolved into Tris solution, and it is 5 to adjust pH value, then quickly impregnates superhigh molecular weight polyethylene fibers into solution
In, reaction condition is：Room temperature, for 24 hours.It is repeatedly rinsed, is dried with deionized water after taking-up, it is poly- that the modified ultra-high molecular mass is made
Vinyl fiber.
3) preparation of superhigh molecular weight polyethylene fibers/epoxy resin composite material.By superhigh molecular weight polyethylene fibers
Monofilament passes through in cylindrical mold, then epoxy resin/curing agent system is injected into mold, demoulds, obtains after curing 36h at room temperature
To superhigh molecular weight polyethylene fibers/epoxy resin composite material.
Embodiment 4：
1) pretreatment of superhigh molecular weight polyethylene fibers.Superhigh molecular weight polyethylene fibers are cut to certain length,
It is soaked for a period of time in ethanol, removes remaining organic solvent on superhigh molecular weight polyethylene fibers, then take out drying and wait for
With.
2) deposition of tannic acid.It weighs 0.121g Tris to be dissolved into 200ml deionized waters, then weighs 0.6g tannic acid,
6gNacl is dissolved into Tris solution, and it is 10 to adjust pH value, then quickly impregnates superhigh molecular weight polyethylene fibers into solution
In, reaction condition is：Room temperature, for 24 hours.It is repeatedly rinsed, is dried with deionized water after taking-up, it is poly- that the modified ultra-high molecular mass is made
Vinyl fiber.
3) preparation of superhigh molecular weight polyethylene fibers/epoxy resin composite material.By superhigh molecular weight polyethylene fibers
Monofilament passes through in cylindrical mold, then epoxy resin/curing agent system is injected into mold, demoulds, obtains after curing 36h at room temperature
To superhigh molecular weight polyethylene fibers/epoxy resin composite material.
Embodiment 5：
1) pretreatment of superhigh molecular weight polyethylene fibers.Superhigh molecular weight polyethylene fibers are cut to certain length,
It is soaked for a period of time in ethanol, removes remaining organic solvent on superhigh molecular weight polyethylene fibers, then take out drying and wait for
With.
2) deposition of tannic acid.It weighs 0.121g Tris to be dissolved into 200ml deionized waters, then weighs 0.8g tannic acid,
7gNacl is dissolved into Tris solution, and it is 9 to adjust pH value, then quickly impregnates superhigh molecular weight polyethylene fibers into solution
In, reaction condition is：Room temperature, for 24 hours.It is repeatedly rinsed, is dried with deionized water after taking-up, it is poly- that the modified ultra-high molecular mass is made
Vinyl fiber.
3) preparation of superhigh molecular weight polyethylene fibers/epoxy resin composite material.By superhigh molecular weight polyethylene fibers
Monofilament passes through in cylindrical mold, then epoxy resin/curing agent system is injected into mold, demoulds, obtains after curing 48h at room temperature
To superhigh molecular weight polyethylene fibers/epoxy resin composite material.
Experiment effect：
Modified ultra-high molecular weight polyethylene fiber surface has carried out Static water contact angles test in example 1, as a result shows modification
The water contact angle of superhigh molecular weight polyethylene fibers is 83.3 ° afterwards, and without modified superhigh molecular weight polyethylene fibers
Water contact angle is 95 °, and the water contact angle relative to virgin ultrahigh molecular weight polyethylene fibre reduces 12.3%, is prepared for superelevation
Molecular weight polyethylene fiber/epoxy resin composite material, and shear strength is tested, as a result show that modified super high molecular weight is poly-
Vinyl fiber/epoxy resin composite material shear strength is 1.09MPa, and fine without modified ultra-high molecular weight polyethylene
Dimension/epoxy resin composite material shear strength be 0.736MPa, relative to without modified superhigh molecular weight polyethylene fibers/
Epoxy resin composite material shear strength increases 32.5%.And be compared to unmodified superhigh molecular weight polyethylene fibers/
Epoxy resin composite material, modified ultrahigh-molecular-weight polyethylene/epoxy resin composite material tensile break strength have apparent increasing
Add.
Claims (4)
1. a kind of new tannic acid modified superhigh molecular weight polyethylene fibers and its composite material and preparation method thereof, including walk as follows
Suddenly：
1) cleaning of superhigh molecular weight polyethylene fibers
It will be soaked for a period of time in ethyl alcohol in superhigh molecular weight polyethylene fibers, remove the remaining organic solvent of fiber surface,
Then take out drying；
2) deposition of tannic acid
The Tris for weighing 0.06-0.20g is dissolved in 200ml water, is adjusted solution ph, is then weighed 0.1-0.8g tannic acid, 3-
7gNacl is dissolved in above-mentioned Tris solution and stirs, superhigh molecular weight polyethylene fibers immersed in this solution, in the process
Tannic acid solution can become blackish green from brown color, and superhigh molecular weight polyethylene fibers can become faint yellow from white, 3-24h
Afterwards, superhigh molecular weight polyethylene fibers are taken out and is dried, superhigh molecular weight polyethylene fibers after being made tannic acid modified.
3) preparation of superhigh molecular weight polyethylene fibers/resin or superhigh molecular weight polyethylene fibers/rubber composite material
Superhigh molecular weight polyethylene fibers monofilament is passed through in cylindrical mold, then injects resin or rubbery system into mold,
It is demoulded after curing 24-48h at room temperature, obtains superhigh molecular weight polyethylene fibers/epoxy resin composite material.
2. a kind of method of new tannic acid modified superhigh molecular weight polyethylene fibers according to claim 1, feature
It is：The modifying agent used is tannic acid-Nacl-Tris mixed solutions.
3. a kind of method of new tannic acid modified superhigh molecular weight polyethylene fibers according to claim 1, feature
It is：Tannic acid and metal Na+Generation complexing is adhered to super by covalent bond or non-covalent bond effect in Tris solution
The surface of high molecular weight polyethylene fiber.
4. a kind of superhigh molecular weight polyethylene fibers/epoxy resin obtained based on claim 1 method of modifying or rubber are base
The preparation of the composite material of body, it is characterised in that：Tannic acid is adhered to superhigh molecular weight polyethylene fibers surface, makes supra polymer
Weight polyethylene fiber surface is there are a large amount of active group phenolic hydroxyl groups and increases superhigh molecular weight polyethylene fibers surface roughness,
The progress of the matrixes such as the fiber and epoxy resin is compound, to obtain modified superhigh molecular weight polyethylene fibers and resin compounded
Material.This method can effectively improve the cementitiousness between superhigh molecular weight polyethylene fibers and resin or rubber.
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