CN108951140A - A kind of surface modification method of fiber - Google Patents

A kind of surface modification method of fiber Download PDF

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Publication number
CN108951140A
CN108951140A CN201710351859.0A CN201710351859A CN108951140A CN 108951140 A CN108951140 A CN 108951140A CN 201710351859 A CN201710351859 A CN 201710351859A CN 108951140 A CN108951140 A CN 108951140A
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fiber
surface modification
modification method
water
monomer
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CN108951140B (en
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王文才
王磊
陈思献
田明
张立群
赵秀英
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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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
    • 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
    • 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
    • D06M11/28—Halides of elements of Groups 8, 9, 10 or 18 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
    • D06M13/152—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 having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • 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
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • 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
    • D06M15/55—Epoxy resins
    • 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
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D06M2101/36—Aromatic polyamides

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses a kind of surface modification methods of fiber.It include: that (1) fiber immerses plant polyphenol aqueous solution, stirring, mixing time is no more than 1h；Ferric salt solution is added, continue to stir, mixing time is no more than 1h, adjusting pH with sodium hydroxide solution is 8.0~11, (2) fiber of step (1) after processed is added in active reaction monomer water/ethanol solution, the mass ratio of activated monomer and fibre weight is 1:(2.5~50), at 20 DEG C -80 DEG C, continue to be stirred to react 1~10h, it is dry after cleaning.The bond properties of fiber and rubber interface can be improved in method of the invention, and fibre framework materials is enable preferably to play its excellent comprehensive performance.On the one hand it can improve traditional fibre interface modification means bring environmental problem, on the other hand quickly, low cost, easy operating process has certain prospects for commercial application.

Description

A kind of surface modification method of fiber
Technical field
The present invention relates to fibre technology fields, further say, are to be related to a kind of surface modification method of fiber.Using plant Object polyphenol and metal ion carry out complexing deposition modification to fiber, combine silane coupling agent to carry out graft modification later, introducing Active group can be effectively improved the bond properties between fiber and rubber interface, and the fiber of the processing can be used for tire, pass Send the fields such as band, sebific duct.
Background technique
High-performance fiber has excellent mechanical performance, lower density and preferable thermal stability, is ideal fiber bone Frame material.But since surface lacks active group, so the interfacial adhesion performance of fiber and rubber composite material is very poor, greatly limit Application of the fiber in rubber composite material is made.
The method of fibre modification can substantially be divided into two class of physical method and chemical method, and main effect is on the one hand to mention On the other hand the roughness increased fiber on high microsteping surface and the engagement of matrix introduce active group enhancing in fiber surface The interaction of fiber and matrix.Chemical modification mainly passes through the chemical reaction such as nitrification, oxidation and chlorosulfonation in fiber surface Introducing-OH ,-COOH and-NH2Equal groups, effectively increase fiber surface activity while the active group introduced can be used as instead Site is answered to form chemical bonding between fiber and matrix.Physical modification then mainly passes through high-energy ray, ultrasound, electron beam and waits The physical methods such as gas ions carry out surface etch to fiber, can introduce some polar groups and active reaction position in fiber surface Point, the latter can trigger graft reaction and further achieve the purpose that improve fiber surface activity.But chemical method can be to fiber Structure causes significantly to destroy, and time-consuming, has certain pollution to environment；And physical modification means are to equipment requirement condition Height, severe reaction conditions, higher cost.Resorcin-Formaldehyde-Latex (RFL) dipping system is fiber/rubber composite material system An important interface modification means during standby, it can be traditional rubber framework material nylon, artificial silk and polyester etc. Good interfacial adhesion performance is provided, but for high-performance fiber, since surface inertness is extremely strong, at individual RFL dipping It manages limited to the interfacial adhesion performance improvement of fiber.
The glue protein of bivalves biology can be stable be adhered to various organic and inorganic matrix surfaces, the study found that glue protein Catechol containing higher concentration and amino functional group.Dopamine is a kind of catecholamine, structure and bivalves biology Glue protein is similar, and oxidable auto polymerization forms cross-linked polymer under alkaline environment, and poly-dopamine almost has with all substrates Very good adhesion.Surface is carried out to ultra-high molecular weight polyethylene using dopamine combination silane coupling agent in CN102634986 Processing combines RFL to impregnate so that the interfacial bond strength of itself and rubber is effectively promoted later, but the price of dopamine compared with It is expensive, it is not easy to realize batch operation.
Summary of the invention
To solve the problem in the prior art, the present invention provides a kind of surface modification methods of fiber.Using plant Object polyphenol and metal ion carry out after deposition modification is complexed fiber, then carry out secondary function with activated monomer, pass through introducing Epoxy, double bond and more sulphur isoreactivity groups form in fiber and rubber interface and be chemically bonded, and improves fiber and rubber circle with this The bond properties in face enables fibre framework materials preferably to play its excellent comprehensive performance.On the one hand it can improve traditional fibre Interface modification means bring environmental problem is tieed up, on the other hand quickly, there is low cost, easy operating process certain industry to answer Use prospect.
The object of the present invention is to provide a kind of surface modification methods of fiber.
Include:
(1) complexing deposition modification
Fiber immerses plant polyphenol aqueous solution, stirring, and mixing time is no more than 1h；Ferric salt solution is added, continues to stir It mixes, mixing time is no more than 1h, and adjusting pH with sodium hydroxide solution is 8.0~11,
The mass ratio of trivalent iron salt and plant polyphenol is 0.3~6；Preferably 1~3；The preferred ferric trichloride of trivalent iron salt；
The plant polyphenol is the natural phenolic containing pyrogallol structure；Preferably tannic acid, catechin, galla turcica One kind of theine, catechin and gallate, nutgall catechin gallic acid ester, more preferably tannic acid.
(2) graft modification of function monomer
The fiber of step (1) after processed is added in active reaction monomer water/ethanol solution, 20 DEG C -80 DEG C, continues to stir 1~10h of reaction is mixed, fiber is dry after ethyl alcohol cleans；Activated monomer and the mass ratio of fibre weight are 1:(2.5~50), it is excellent It is selected as 1:(5~20).
Active reaction monomer water/ethanol solution solvent is water and ethyl alcohol, and the volume ratio of water and ethyl alcohol is 1~9；Preferably 1~4；
The volumetric concentration of active reaction monomer is 0.5%~10%；Preferably 1%~3%；
The active reaction monomer is silane coupling agent, glycidyl methacrylate, polyethylene glycol diglycidyl One of ether, aqueous epoxy resins.
The plant polyphenol.
Wherein, preferably:
The concentration of the plant polyphenol aqueous solution is 0.2~1.0mg/ml.
The concentration of ferric salt solution is 0.96~3.2mg/ml；
The fiber is nylon, polyester, aramid fiber, carbon fiber and ultra high molecular weight polyethylene fiber fabric and the above fiber Blended fabric.
Following steps specifically can be used in the present invention:
(1) it is co-deposited modification
Prepare plant polyphenol aqueous solution, plant polyphenol concentration be 0.2~1.0mg/ml, by the fiber cleaned (0.4~ It 2g) is put into above-mentioned solution, is stirred with the speed of 20~100 turns/min, the time is no more than 1h.Then be added ferric iron from The concentration of sub- solution, preparation is 0.96~3.2mg/ml, is stirred with the speed of 20~100 turns/min, the reaction time does not surpass 1h is crossed, and its pH is adjusted to 8.0~11.Polyphenol-complexing of metal ion layer is introduced in fiber surface, after being cleaned with deionized water It takes out.
The polyphenol is preferably tannic acid, catechin, nutgall catechin, catechin and gallate, galla turcica catechu The natural phenolic containing pyrogallol structure such as plain gallate.More preferable tannic acid.
(2) graft modification of function monomer
Active reaction monomer (4ml~80ml) is added to the mixed solution of water/ethyl alcohol (500ml/300ml), then will Fiber after step (1) is processed is added thereto, and under graft reaction temperature (20 DEG C -80 DEG C), continues to be stirred to react 1~10h, After aramid fiber taking-up after reaction is cleaned with ethyl alcohol, dry 12h is placed into 60 DEG C of baking oven.
By controlling the additional amount of active reaction monomer and the mass ratio of fibre weight, range is 2.5~50, and adjusts water The temperature (20 DEG C -80 DEG C) of bath, can effective regulatory function monomer grafting efficiency, to regulate and control fiber and rubber interface Bond properties.
The active reaction monomer can be reacted with catechol or pyrogallol group, and contained and be may participate in rubber The group of glue vulcanization reaction, selected from any one of following substance: silane coupling agent KH560, silane coupling agent KH570, silicon Alkane coupling agent Si69, silane coupling agent KH590, ethylene glycol diglycidylether, water-base epoxy etc..Due to polyphenol and metal ion The complexing layer of formation can be deposited on fiber surface, therefore the phenolic hydroxyl group introduced can be with the list with hydroxyl, carboxyl, epoxy group etc. Body is reacted.And in order to improve the interfacial interaction with rubber, therefore the other end of selected secondary function monomer Need to containing the group that may participate in vulcanization of rubber reaction, such as double bond, epoxy group, polysulfide bond, so that in sulfidation, rubber with The interface of fiber forms chemical bonding, improves the bond properties at interface.
It is not that fiber surface is destroyed by chemical etching though this method belongs to chemical method, to introduce active group, and It is that fiber surface is deposited on by the complexing of plant polyphenol and ferric ion to introduce a large amount of catechols and even benzene Triphenol group comes activated fiber surface, and the method cost compared to dopamine processing is greatly lowered.This method is to fiber bodies knot Structure does not damage, because plant polyphenol and ferric ion mainly pass through non-covalent bond in the complexing layer that fiber surface is formed The effects of (π-is pi-conjugated, hydrogen bond) and fiber surface phase separation.
It can obviously improve the bond properties with natural rubber and synthetic rubber, synthetic rubber through the pretreated fiber of the present invention It include: butadiene-styrene rubber, nitrile rubber, butadiene rubber, ethylene propylene diene rubber, butyl rubber etc..
Advantage and characteristic of the invention:
(1) method pair with the graft modification of silane coupling agent is modified using the complexing deposition of plant polyphenol and metal ion It is modified that fiber carries out surface, and is quoted in rubber industry, and operating procedure is easy, and low in cost, reaction condition is mildly right Fiber does not damage, at the same it is environmentally protective reduce environmental pollution, and can significantly improve the adhesiveness of fiber and rubber interface Energy.
(2) method pair with the graft modification of silane coupling agent is modified using the complexing deposition of plant polyphenol and metal ion Fiber is surface-treated, and the active group that may participate in vulcanization of rubber cross-linking reaction is introduced in fiber surface, is helped to improve The adhesive strength of fiber and rubber.
(3) high-performance fiber lower for surface free energy such as aramid fiber, ultra-high molecular weight polyethylene etc., compared to traditional Plasma, liquid phase oxidation, latex dipping method, using method of the invention, step operation is simple, equipment requirement is low, at Sheet is low, does not damage substantially to fiber.
Detailed description of the invention
Scanning electron microscope (SEM) figure of Fig. 1,1 aramid fiber of embodiment, the wherein unmodified aramid fiber of Fig. 1 (a), The modified aramid fiber of Fig. 1 (b) tannic acid/ferric iron, Fig. 1 (c) tannic acid/ferric iron complexing deposition modification combine silane coupled The aramid fiber of agent Si69 graft modification.Compared to Fig. 1 (a), the aramid fiber that as can be seen from the figure tannic acid/ferric iron is modified Surface since the appearance roughness of complexing layer is increased, and be further grafted the aramid fiber surface after Si69 occur it is obvious Grafting layer.
X-ray photoelectron spectroscopy (XPS) wide range figure of Fig. 2,1 aramid fiber of embodiment；Fig. 2 (a) is that unmodified aramid fiber is fine The XPS wide range figure of dimension, Fig. 2 (b) are the XPS wide range figure of the aramid fiber of tannic acid and ferric ion complexing modification, Fig. 2 (c) It is the XPS wide range figure for the aramid fiber that tannic acid is combined Si69 graft modification with ferric ion complexing modification.
The scanning electron microscope (SEM) of Fig. 3,1 aramid fiber of embodiment and rubber extraction style: Fig. 3 (a) is unmodified The extraction interface of aramid fiber and rubber composite material, Fig. 3 (b) are the aramid fibers of tannic acid and ferric ion complexing modification With the extraction interface of rubber composite material, Fig. 3 (c), which is tannic acid, is combined Si69 graft modification with ferric ion complexing modification The extraction interface of aramid fiber and rubber composite material, from comparison it can be found that by tannic acid and ferric iron complexing modification after Aramid fiber surface attachment glue it is most, it was demonstrated that it is most strong with the interface interaction power of rubber.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.
Raw materials used in embodiment is commercially available.
Embodiment 1
1) 1.6g aramid fiber and canvas are immersed in the aqueous solution of 0.4mg/ml tannic acid, are stirred, mixing time 1min；Iron(III) chloride hexahydrate solution is added, the concentration of preparation is 3.2mg/ml, continues to stir, then mixing time 1min is used It is 9.0 that sodium hydroxide solution, which adjusts pH, and the amount of substance ratio of trivalent iron salt and tannic acid is 3.13.Polyphenol-is introduced in fiber surface Complexing of metal ion layer takes out after being cleaned with deionized water.
2) active reaction monomer Si69 (16ml) is added to the mixed solution of water/ethyl alcohol (500ml/300ml), then will Aramid fiber and canvas after step (1) is processed are added thereto, and the mass ratio of activated monomer and fiber is 10, in graft reaction At 80 DEG C of temperature, continue to be stirred to react 2h, after aramid fiber taking-up after reaction is cleaned with ethyl alcohol, is placed into 60 DEG C Dry 12h in baking oven.
3) preparation of rubber compound: taking natural rubber (SMR10) mass parts 30, and butadiene-styrene rubber (SBR1502) mass parts 70 exist It plasticates in mixer, sequentially adds activating agent: zinc oxide mass parts 5, stearic acid mass parts 2；Antioxidant 4010NA mass parts 1； Coumarone indene resin mass parts 1；Tackifier: RA mass parts 1, RS mass parts 1；Reinforcing agent: carbon black N330 mass parts 25, vapor phase method is white Carbon black mass part 10；Plasticizer: aromatic naphtha mass parts 10；It is eventually adding sulphur mass parts 1 and accelerant CZ mass parts 4.It will mix The sizing material refined beats triangle bag with open mill, and slice obtains the film of 5mm.
4) preparation of sample and peel test specimen is extracted out:
The size for extracting sample out is made referring to ISO 4647.Rubber compound is cut into the bar shaped to match with extraction mold, It is filled into the die cavity of extraction experiment mould.Fiber after before modified is embedded into adhesive tape and mold, then places one layer of adhesive tape. Closed die.The preparation of disbonded test batten: the aramid fiber canvas after dipping process is cut into two pieces having a size of 23.5cm × 23.5cm, Two layers of aramid fiber canvas is upper and lower and intermediate by the adhesive glue progress interlayer fitting for the 0.8mm thickness being kneaded, then in aramid fiber Peel test batten is made in the rubber cover that canvas upper and lower surface attaches the 8mm thickness being kneaded.
5) vulcanization of sample and peel test specimen is extracted out:
Extraction Test strips are vulcanized on vulcanizing press, 150 DEG C of curing temperature, sulfide stress 15Mpa, vulcanization Time 30min.The conditions of vulcanization of peel test specimen are as follows: curing temperature is 140 DEG C, sulfide stress 15MPa, and vulcanization time is 40min。
Embodiment 2
Process is chosen to be 0.47 with embodiment 1, by the amount of substance ratio of the trivalent iron salt and tannic acid in step 1), tannic acid Concentration is 0.8mg/ml, pH value 8.0, and it is 4.0vol%, the mass ratio of monomer and fiber that water and proportion of ethanol, which are 2, Si69 concentration, It is 20, graft reaction temperature is 30 DEG C, reaction time 4h.
Embodiment 3
Process is chosen to be 5.2 with embodiment 1, by the amount of substance ratio of the trivalent iron salt and tannic acid in step 1), tannic acid Concentration is 0.1mg/ml, pH value 10.0, and it is 8.0vol%, the mass ratio of monomer and fiber that water and proportion of ethanol, which are 8, Si69 concentration, It is 40, graft reaction temperature is 60 DEG C, reaction time 8h.
Embodiment 4
Process changes KH560 into embodiment 1, by the silane coupling agent Si69 in step 2), trivalent iron salt and tannic acid Amount of substance ratio is 3.13, and tannin acid concentration is 0.4mg/ml, and pH value 11.0, water and proportion of ethanol are that 4, KH560 concentration is The mass ratio of 1.0vol%, monomer and fiber is 5, and graft reaction temperature is 60 DEG C, reaction time 4h.Obtain tannic acid/tri- The complexing deposition modification of valence iron combines the aramid fiber of silane coupling agent KH560 graft modification.
Embodiment 5
Process is with embodiment 1, and by polyphenol selection catechin in step 1), the amount of substance ratio of trivalent iron salt and catechin is 3.13, catechin concentration 0.4mg/ml, pH value 11.0, water and proportion of ethanol are 4, and the concentration of aqueous epoxy resins EGDE is The mass ratio of 2.0vol%, monomer and fiber is 10, and graft reaction temperature is 80 DEG C, reaction time 2h.Obtain catechin/tri- The complexing deposition modification of valence iron combines the aramid fiber of EGDE graft modification.
Comparative example 1
The aramid fiber cleaned and aramid fiber canvas are directly carried out with rubber it is compound, process with step 2) in example 1 and Step 3).
Extraction test explanation: fiber and rubber adhesion power are tested according to 4647 standard of ISO in Shenzhen Rui Geer instrument company It is tested on the universal testing machine of production.Test speed 100mm/min, maximum when record fiber is extracted from rubber Power, test are no less than 8 samples, record the average value of minimum 8 valid data.
Disbonded test explanation: being cut into batten the size of 250mm × 250mm, according to side as defined in national standard GB/T6759-86 Method carries out peel test to batten.
Table 1: the performance comparison of batten obtained by the embodiment of the present invention and comparative example
As shown in table 1, the unmodified aramid fiber of comparative example 1 and the batten of rubber, embodiment are tannic acid/trivalent Iron complexing deposition modification combines the aramid fiber of different silane coupling agent graft modifications and the batten of rubber, embodiment 1 and implementation Example 2 is respectively Si69 and KH560.As can be seen that unmodified aramid fiber is compared, by tannic acid/ferric iron complexing deposition Modification combines the bond properties of the aramid fiber and rubber composite material sample of silane coupling agent graft modification successively to improve 73.6% and 55.4%, furthermore tannic acid/ferric iron complexing deposition modification combines the aramid fiber canvas of silane coupling agent graft modification 185% and 136% are successively improved with the bond properties of rubber composite material sample.Illustrate that this method of modifying can effectively change The interfacial bond strength of kind aramid fiber and rubber.

Claims (10)

1. a kind of surface modification method of fiber, it is characterised in that the described method includes:
(1) complexing deposition modification
Fiber immerses plant polyphenol aqueous solution, stirring, and mixing time is no more than 1h；Ferric salt solution is added, continues to stir, stir The time is mixed no more than 1h, adjusting pH with sodium hydroxide solution is 8.0~11,
The mass ratio of trivalent iron salt and plant polyphenol is 1:(0.3~6)；
The plant polyphenol is the natural phenolic containing pyrogallol structure；
(2) graft modification of function monomer
The fiber of step (1) after processed is added in active reaction monomer water/ethanol solution, the matter of activated monomer and fibre weight Amount is than being 1:(2.5~50), at 20 DEG C -80 DEG C, continue to be stirred to react 1~10h, it is dry after cleaning；
Active reaction monomer water/ethanol solution solvent is water and ethyl alcohol, and the volume ratio of water and ethyl alcohol is 1~9；
The volumetric concentration of active reaction monomer is 0.5%~10%；
The active reaction monomer is silane coupling agent, glycidyl methacrylate, polyethyleneglycol diglycidylether, water One of property epoxy resin.
2. the surface modification method of fiber as described in claim 1, it is characterised in that:
The plant polyphenol is tannic acid, catechin, nutgall catechin, L-Epicatechin gallate, nutgall catechin One kind of gallate.
3. the surface modification method of fiber as described in claim 1, it is characterised in that:
The concentration of the plant polyphenol aqueous solution is 0.2~1.0mg/ml.
4. the surface modification method of fiber as claimed in claim 3, it is characterised in that:
The concentration of ferric salt solution is 0.96~3.2mg/ml.
5. the surface modification method of fiber as claimed in claim 4, it is characterised in that:
The mass ratio of fibre weight and activated monomer is 1:(5~20).
6. the surface modification method of fiber as claimed in claim 2, it is characterised in that:
The plant polyphenol is tannic acid.
7. the surface modification method of fiber as described in claim 1, it is characterised in that:
The mass ratio of trivalent iron salt and polyphenol is 1:(1~3).
8. the surface modification method of fiber as described in claim 1, it is characterised in that:
Active reaction monomer water/ethanol solution solvent is water and ethyl alcohol, and the volume ratio of water and ethyl alcohol is 1~4.
9. the surface modification method of fiber as claimed in claim 8, it is characterised in that:
The volumetric concentration of active reaction monomer is 1%~3%.
10. the surface modification method of the fiber as described in one of claim 1~9, it is characterised in that:
The fiber is the mixed of nylon, polyester, aramid fiber, carbon fiber and ultra high molecular weight polyethylene fiber fabric and the above fiber Braided fabric.
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CN109722886A (en) * 2018-12-21 2019-05-07 江苏普泰克新材料科技有限公司 A kind of preparation method of tannic acid modified aramid fiber and its composite material
CN110592942A (en) * 2019-09-20 2019-12-20 中国林业科学研究院木材工业研究所 Reagent for improving dimensional stability of natural fiber material and treatment method thereof
CN112500619A (en) * 2020-10-22 2021-03-16 青岛科技大学 Aramid fiber reinforced nitrile rubber composite material and preparation method thereof
CN113025056A (en) * 2021-02-25 2021-06-25 浙江恒业成有机硅有限公司 Conductive silicone rubber and preparation method thereof
CN113089320A (en) * 2021-05-20 2021-07-09 盐城工学院 Surface appearance controllable high-adhesion modified fiber and preparation method and application thereof
CN113863001A (en) * 2021-11-09 2021-12-31 长春工业大学 Carbon fiber surface complexing modification method
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CN109722886A (en) * 2018-12-21 2019-05-07 江苏普泰克新材料科技有限公司 A kind of preparation method of tannic acid modified aramid fiber and its composite material
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CN112500619A (en) * 2020-10-22 2021-03-16 青岛科技大学 Aramid fiber reinforced nitrile rubber composite material and preparation method thereof
CN113025056A (en) * 2021-02-25 2021-06-25 浙江恒业成有机硅有限公司 Conductive silicone rubber and preparation method thereof
CN113089320A (en) * 2021-05-20 2021-07-09 盐城工学院 Surface appearance controllable high-adhesion modified fiber and preparation method and application thereof
WO2022252198A1 (en) * 2021-05-31 2022-12-08 苏州大学 Polythiophene composite nylon conductive fiber and preparation method therefor
CN113863001A (en) * 2021-11-09 2021-12-31 长春工业大学 Carbon fiber surface complexing modification method
CN114411417A (en) * 2022-01-28 2022-04-29 郑州中远氨纶工程技术有限公司 Washing-resistant alginate fiber and preparation method thereof
CN114411417B (en) * 2022-01-28 2024-01-30 郑州中远氨纶工程技术有限公司 Washing-resistant alginate fiber and preparation method thereof
CN117552145A (en) * 2024-01-04 2024-02-13 昆山东利新材料科技有限公司 Tire regenerated environment-friendly fabric and preparation method thereof
CN117552145B (en) * 2024-01-04 2024-04-02 昆山东利新材料科技有限公司 Tire regenerated environment-friendly fabric and preparation method thereof

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