CN108951140B - Surface modification method of fiber - Google Patents

Surface modification method of fiber Download PDF

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CN108951140B
CN108951140B CN201710351859.0A CN201710351859A CN108951140B CN 108951140 B CN108951140 B CN 108951140B CN 201710351859 A CN201710351859 A CN 201710351859A CN 108951140 B CN108951140 B CN 108951140B
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fiber
water
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ethanol
plant polyphenol
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CN108951140A (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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    • 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)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses a surface modification method of a fiber. The method comprises the following steps: (1) soaking the fiber in plant polyphenol water solution, and stirring for no more than 1 h; adding a trivalent ferric salt solution, continuously stirring for no more than 1h, adjusting the pH to 8.0-11 by using a sodium hydroxide solution, and (2) adding the fiber treated in the step (1) into an active reaction monomer water/ethanol solution, wherein the mass ratio of active monomers to fiber is 1: (2.5-50), continuously stirring and reacting for 1-10 h at 20-80 ℃, and drying after cleaning. The method of the invention can improve the adhesive property of the interface between the fiber and the rubber, so that the fiber framework material can better exert the excellent comprehensive performance. On one hand, the method can improve the environmental problem caused by the traditional fiber interface modification means, and on the other hand, the method is quick, low in cost and simple in operation flow and has a certain industrial application prospect.

Description

Surface modification method of fiber
Technical Field
The invention relates to the technical field of fibers, in particular to a fiber surface modification method. Plant polyphenol and metal ions are adopted to carry out complexing deposition modification on fibers, then a silane coupling agent is combined for carrying out grafting modification, the introduced active groups can effectively improve the adhesive property between the fibers and a rubber interface, and the treated fibers can be used in the fields of tires, conveyor belts, rubber tubes and the like.
Background
The high-performance fiber has excellent mechanical property, lower density and better thermal stability, and is an ideal fiber framework material. However, due to the lack of active groups on the surface, the interfacial adhesion property between the fiber and the rubber composite material is poor, and the application of the fiber in the rubber composite material is greatly limited.
The method of modifying the fibers can be roughly divided intoThe main functions of the method are to improve the roughness of the fiber surface to increase the engagement of the fiber and the matrix, and introduce active groups on the fiber surface to enhance the interaction of the fiber and the matrix. The chemical modification is mainly to introduce-OH, -COOH and-NH on the surface of the fiber through chemical reactions such as nitration, oxidation and chlorosulfonation2And the like, effectively improves the surface activity of the fiber, and simultaneously introduces active groups which can be used as reaction sites to form chemical bonding between the fiber and the matrix. The physical modification is mainly to etch the surface of the fiber by physical methods such as high-energy rays, ultrasound, electron beams and plasmas, and can introduce some polar groups and active reaction sites on the surface of the fiber, and the latter can initiate grafting reaction to further achieve the purpose of improving the surface activity of the fiber. But the chemical method can cause obvious damage to the fiber structure, is long in time consumption and has certain pollution to the environment; the physical modification means has high requirements on equipment, harsh reaction conditions and higher cost. A resorcinol-formaldehyde-latex (RFL) dipping system is an important interface modification means in the preparation process of a fiber/rubber composite material, can provide good interface adhesive property for traditional rubber framework materials such as nylon, rayon and polyester, and has a limited effect of improving the interface adhesive property of the fiber by single RFL dipping treatment due to extremely strong surface inertia for high-performance fiber.
The collagen of the mussel organism can be stably adhered to the surfaces of various organic and inorganic matrixes, and researches show that the collagen contains pyrocatechol and amino functional groups with higher concentration. Dopamine is a kind of o-phenylendiol amine, the structure of which is similar to that of the collagen of mussels, and the dopamine can be oxidized and polymerized automatically to form a cross-linked polymer under an alkaline environment, and the poly-dopamine has good adhesion with almost all substrates. In CN102634986, a dopamine is used to combine with a silane coupling agent to perform surface treatment on ultra-high molecular weight polyethylene, and then RFL impregnation is used to effectively improve the interface bonding strength between the ultra-high molecular weight polyethylene and rubber, but the dopamine is expensive and is not easy to realize batch operation.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a fiber surface modification method. Plant polyphenol and metal ions are adopted to carry out complexing deposition modification on the fiber, then secondary functionalization is carried out by using an active monomer, and chemical bonding is formed between the fiber and a rubber interface by introducing active groups such as epoxy, double bonds, polysulfide and the like, so that the bonding performance between the fiber and the rubber interface is improved, and the excellent comprehensive performance of the fiber framework material can be better exerted. On one hand, the method can improve the environmental problem caused by the traditional fiber interface modification means, and on the other hand, the method is quick, low in cost and simple in operation flow and has a certain industrial application prospect.
The invention aims to provide a surface modification method of a fiber.
The method comprises the following steps:
(1) modification by complex deposition
Soaking the fiber in plant polyphenol water solution, and stirring for no more than 1 h; adding a trivalent ferric salt solution, continuously stirring for no more than 1h, adjusting the pH value to 8.0-11 by using a sodium hydroxide solution,
the mass ratio of the trivalent ferric salt to the plant polyphenol is 0.3-6; preferably 1 to 3; ferric salt is preferably ferric trichloride;
the plant polyphenol is natural phenols containing pyrogallol structures; preferably one of tannic acid, catechin, gallocatechin, catechin gallate and gallocatechin gallate, more preferably tannic acid.
(2) Graft modification of functional monomers
Adding the fiber treated in the step (1) into an active reaction monomer water/ethanol solution, continuously stirring and reacting for 1-10 h at 20-80 ℃, and cleaning the fiber with ethanol and then drying; the mass ratio of the active monomer to the fiber amount is 1: (2.5-50), preferably 1: (5-20).
The solvent of the active reaction monomer water/ethanol solution is water and ethanol, and the volume ratio of the water to the ethanol is 1-9; preferably 1-4;
the volume concentration of the active reaction monomer is 0.5-10%; preferably 1 to 3 percent;
the active reaction monomer is one of silane coupling agent, glycidyl methacrylate, polyethylene glycol diglycidyl ether and water-based epoxy resin.
The plant polyphenol.
Among them, preferred are:
the concentration of the plant polyphenol water solution is 0.2-1.0 mg/ml.
The concentration of the ferric salt solution is 0.96-3.2 mg/ml;
the fiber is nylon, polyester, aramid fiber, carbon fiber, ultra-high molecular weight polyethylene fiber fabric and mixed fabric of the above fibers.
The invention can specifically adopt the following steps:
(1) co-deposition modification
Preparing an aqueous solution of plant polyphenol, wherein the concentration of the plant polyphenol is 0.2-1.0 mg/ml, putting the cleaned fiber (0.4-2 g) into the aqueous solution, and stirring at the speed of 20-100 revolutions per minute for not more than 1 hour. And then adding a ferric ion solution, wherein the prepared concentration is 0.96-3.2 mg/ml, stirring at the speed of 20-100 revolutions/min, the reaction time is not more than 1 hour, and adjusting the pH value to 8.0-11. Introducing a polyphenol-metal ion complexing layer on the surface of the fiber, cleaning with deionized water and taking out.
The polyphenol is preferably natural phenols containing pyrogallol structure such as tannic acid, catechin, gallocatechin, catechin gallate, and gallocatechin gallate. More preferably tannic acid.
(2) Graft modification of functional monomers
Adding an active reaction monomer (4-80 ml) into a mixed solution of water/ethanol (500ml/300ml), adding the fiber treated in the step (1), continuously stirring and reacting for 1-10 h at a grafting reaction temperature (20-80 ℃), taking the aramid fiber after the reaction out, cleaning with ethanol, and placing in an oven at 60 ℃ for drying for 12 h.
By controlling the mass ratio of the addition amount of the active reaction monomer to the fiber amount within the range of 2.5-50 and adjusting the temperature of the water bath kettle (20-80 ℃), the grafting efficiency of the functional monomer can be effectively adjusted, and thus the adhesive property of the fiber and rubber interface can be adjusted and controlled.
The reactive monomer can react with catechol or pyrogallol groups and contains groups which can participate in rubber vulcanization reaction and is selected from any one of the following substances: silane coupling agent KH560, silane coupling agent KH570, silane coupling agent Si69, silane coupling agent KH590, ethylene glycol diglycidyl ether, aqueous epoxy, and the like. Because the complex layer formed by polyphenol and metal ions can be deposited on the surface of the fiber, the introduced phenolic hydroxyl can react with the monomer with hydroxyl, carboxyl, epoxy and the like. In order to improve the interfacial interaction with rubber, the other end of the selected secondary functional monomer needs to contain a group capable of participating in rubber vulcanization reaction, such as a double bond, an epoxy group, a polysulfide bond and the like, so that the rubber and the fiber interface form chemical bonding in the vulcanization process, and the interfacial adhesion performance is improved.
Although the method belongs to a chemical method, active groups are introduced by destroying the surface of the fiber through chemical etching, plant polyphenol and ferric ions are deposited on the surface of the fiber through the complexing effect of the plant polyphenol and the ferric ions, so that a large number of catechol and pyrogallol groups are introduced to activate the surface of the fiber, and compared with a dopamine treatment method, the cost is greatly reduced. The method has no damage to the structure of the fiber body, because the complexing layer formed on the surface of the fiber by the plant polyphenol and the ferric ions mainly acts with the surface of the fiber through non-covalent bonds (pi-pi conjugation, hydrogen bonds and the like).
The fibers pretreated in accordance with the present invention can significantly improve the adhesion to natural and synthetic rubbers, including: styrene butadiene rubber, nitrile butadiene rubber, ethylene propylene diene monomer rubber, butyl rubber and the like.
The advantages and the characteristics of the invention are as follows:
(1) the surface modification is carried out on the fiber by adopting the method of the complexing deposition modification of plant polyphenol and metal ions and the grafting modification of a silane coupling agent, and the method is introduced into the rubber industry, so that the operation process is simple and convenient, the cost is low, the reaction condition is mild, the fiber is not damaged, the environment is protected, the environmental pollution is reduced, and the adhesive property of the fiber and the rubber interface can be greatly improved.
(2) The surface treatment is carried out on the fiber by adopting the method of the complexing deposition modification of plant polyphenol and metal ions and the grafting modification of the silane coupling agent, and an active group which can participate in the vulcanization crosslinking reaction of rubber is introduced on the surface of the fiber, thereby being beneficial to improving the bonding strength of the fiber and the rubber.
(3) Compared with the traditional plasma, liquid phase oxidation and latex dipping methods, the method has the advantages of simple step operation, low equipment requirement, low cost and no damage to the fibers.
Drawings
Fig. 1, Scanning Electron Microscope (SEM) image of aramid fiber of example 1, wherein fig. 1(a) unmodified aramid fiber, fig. 1(b) tannic acid/ferric iron modified aramid fiber, and fig. 1(c) tannic acid/ferric iron complex deposition modifies aramid fiber graft-modified in combination with silane coupling agent Si 69. Compared with fig. 1(a), it can be seen from the figure that the surface of the tannic acid/ferric iron modified aramid fiber is increased in roughness due to the occurrence of the complexing layer, and the surface of the aramid fiber after further grafting with Si69 shows a distinct grafted layer.
FIG. 2 is an X-ray photoelectron spectroscopy (XPS) broad spectrum of an aramid fiber of example 1; fig. 2(a) is an XPS broad spectrum of an unmodified aramid fiber, fig. 2(b) is an XPS broad spectrum of an aramid fiber modified by complexing tannic acid with ferric ions, and fig. 2(c) is an XPS broad spectrum of an aramid fiber modified by grafting tannic acid with Si69 in combination with ferric ion complexing modification.
Fig. 3, Scanning Electron Microscope (SEM) of aramid fiber and rubber extraction pattern of example 1: fig. 3(a) is a drawing interface of an unmodified aramid fiber and a rubber composite material, fig. 3(b) is a drawing interface of an aramid fiber and a rubber composite material modified by complexing tannic acid and ferric ions, and fig. 3(c) is a drawing interface of an aramid fiber and a rubber composite material modified by grafting tannic acid and ferric ions in combination with Si 69.
Detailed Description
The present invention will be further described with reference to the following examples.
The starting materials used in the examples are all commercially available.
Example 1
1) Soaking 1.6g of aramid fiber and canvas into 0.4mg/ml of tannic acid water solution, and stirring for 1 min; adding ferric trichloride hexahydrate solution with the prepared concentration of 3.2mg/ml, continuously stirring for 1min, then adjusting the pH to 9.0 by using sodium hydroxide solution, wherein the mass ratio of ferric salt to tannic acid is 3.13. Introducing a polyphenol-metal ion complexing layer on the surface of the fiber, cleaning with deionized water and taking out.
2) Adding an active reaction monomer Si69(16ml) into a mixed solution of water/ethanol (500ml/300ml), adding the aramid fiber and the canvas which are treated in the step (1) into the mixed solution, wherein the mass ratio of the active monomer to the fiber is 10, continuously stirring and reacting for 2 hours at the grafting reaction temperature of 80 ℃, taking out the aramid fiber after the reaction is finished, cleaning the aramid fiber with ethanol, and placing the aramid fiber in an oven at 60 ℃ for drying for 12 hours.
3) Preparation of rubber compound: taking 30 parts by mass of natural rubber (SMR10) and 70 parts by mass of styrene butadiene rubber (SBR1502) to plasticate in an internal mixer, and sequentially adding active agents: 5 parts by mass of zinc oxide and 2 parts by mass of stearic acid; 1 part by mass of an anti-aging agent 4010 NA; 1 part by mass of coumarone resin; tackifier: RA 1 part by mass and RS 1 part by mass; reinforcing agent: 25 parts of carbon black N330 and 10 parts of fumed silica; plasticizer: 10 parts of aromatic oil; finally adding 1 part by mass of sulfur and 4 parts by mass of promoter CZ. And (4) triangular packaging the mixed rubber material by using an open mill, and discharging to obtain a 5mm rubber sheet.
4) Preparation of extraction sample and peeling sample:
the dimensions of the drawn-out test specimens are made in accordance with ISO 4647. And cutting the rubber compound into strips matched with the extraction mold, and filling the strips into a mold cavity of the extraction experimental mold. And embedding the fibers before and after modification into the adhesive tape and the mold, and then placing a layer of adhesive tape. And (5) closing the mold. Preparation of peel test specimens: cutting the aramid fiber canvas after gum dipping into two pieces with the size of 23.5cm multiplied by 23.5cm, laminating the upper, the lower and the middle of the two layers of aramid fiber canvas by mixed adhesive with the thickness of 0.8mm, and then attaching the mixed covering rubber with the thickness of 8mm to the upper and the lower surfaces of the aramid fiber canvas to prepare stripping experiment sample strips.
5) Vulcanization of the withdrawn and peeled specimens:
and vulcanizing the extracted experimental sample strips on a flat vulcanizing machine at the vulcanization temperature of 150 ℃ and the vulcanization pressure of 15MPa for 30 min. The vulcanization conditions for the peeled specimens were: the vulcanization temperature is 140 ℃, the vulcanization pressure is 15MPa, and the vulcanization time is 40 min.
Example 2
The procedure is as in example 1, the mass ratio of ferric salt to tannic acid in step 1) is selected to be 0.47, the tannic acid concentration is 0.8mg/ml, the pH value is 8.0, the ratio of water to ethanol is 2, the concentration of Si69 is 4.0 vol%, the mass ratio of monomer to fiber is 20, the grafting reaction temperature is 30 ℃, and the reaction time is 4 hours.
Example 3
The procedure is as in example 1, the mass ratio of the ferric salt and the tannic acid in step 1) is selected to be 5.2, the tannic acid concentration is 0.1mg/ml, the pH value is 10.0, the ratio of water to ethanol is 8, the concentration of Si69 is 8.0 vol%, the mass ratio of the monomer to the fiber is 40, the grafting reaction temperature is 60 ℃, and the reaction time is 8 hours.
Example 4
The procedure is as in example 1, the silane coupling agent Si69 in step 2) is replaced by KH560, the mass ratio of ferric salt to tannic acid is 3.13, the tannic acid concentration is 0.4mg/ml, the pH value is 11.0, the ratio of water to ethanol is 4, the KH560 concentration is 1.0 vol%, the mass ratio of monomer to fiber is 5, the grafting reaction temperature is 60 ℃, and the reaction time is 4 h. And the aramid fiber modified by the combination of tannic acid/ferric iron complexing deposition modification and silane coupling agent KH560 grafting is obtained.
Example 5
The process is the same as example 1, the polyphenol in step 1) is catechin, the mass ratio of ferric salt to catechin is 3.13, the concentration of catechin is 0.4mg/ml, the pH value is 11.0, the ratio of water to ethanol is 4, the concentration of water-based epoxy resin EGDE is 2.0 vol%, the mass ratio of monomer to fiber is 10, the grafting reaction temperature is 80 ℃, and the reaction time is 2 hours. And obtaining the aramid fiber modified by catechin/ferric iron complexing deposition modification and EGDE grafting.
Comparative example 1
The washed aramid fibers and aramid canvas were directly compounded with rubber in the same manner as in step 2) and step 3) of example 1.
Extraction of experimental description: fiber to rubber adhesion testing was performed in accordance with ISO 4647 standard on a universal material testing machine manufactured by Shenzhen Rungel instruments. The speed of the test was 100mm/min, the maximum force at which the fiber was pulled from the rubber was recorded, no less than 8 samples were tested, and the average of a minimum of 8 valid data was recorded.
Description of the peeling test: the sample strips were cut to a size of 250mm by 250mm, and peel-off test was carried out according to the method prescribed in the national standard GB/T6759-86.
Table 1: comparison of the Properties of the sample strips obtained in the examples of the present invention and the comparative examples
Figure BDA0001298026220000081
As shown in table 1, the unmodified aramid fiber and rubber bars of comparative example 1, examples are tannin/ferric complex deposition modification combined with different silane coupling agents graft modified aramid fiber and rubber bars, examples 1 and 2 are Si69 and KH560, respectively. Compared with unmodified aramid fibers, the bonding performance of the aramid fibers modified by the combination of the tannin/ferric iron complexing deposition modification and the silane coupling agent grafting is sequentially improved by 73.6% and 55.4%, and in addition, the bonding performance of the aramid canvas modified by the combination of the tannin/ferric iron complexing deposition modification and the silane coupling agent grafting and the rubber composite material sample is sequentially improved by 185% and 136%. The modification method can effectively improve the interfacial bonding strength of the aramid fiber and the rubber.

Claims (6)

1. A method of surface modification of a fibre, characterised in that the method comprises:
(1) modification by complex deposition
Soaking the fiber in plant polyphenol water solution, and stirring for no more than 1 h; adding a trivalent ferric salt solution, continuously stirring for no more than 1h, adjusting the pH value to 8.0-11 by using a sodium hydroxide solution,
the mass ratio of the trivalent ferric salt to the plant polyphenol is 1: (0.3-6);
the plant polyphenol is natural phenols containing catechol or pyrogallol structures;
the concentration of the plant polyphenol water solution is 0.2-1.0 mg/mL;
the plant polyphenol is one of tannic acid, catechin, gallocatechin, epicatechin gallate and gallocatechin gallate;
the concentration of the ferric salt solution is 0.96-3.2 mg/mL;
(2) graft modification of functional monomers
Adding the fiber treated in the step (1) into an active reaction monomer water/ethanol solution, wherein the mass ratio of the fiber to the active monomer is 1: (2.5-50), continuously stirring and reacting for 1-10 h at 20-80 ℃, and drying after cleaning;
the solvent of the active reaction monomer water/ethanol solution is water and ethanol, and the volume ratio of the water to the ethanol is 1-9;
the volume concentration of the active reaction monomer is 0.5-10%;
the active reaction monomer is one of a silane coupling agent KH560, a silane coupling agent KH570, a silane coupling agent Si69, a silane coupling agent KH590, glycidyl methacrylate, polyethylene glycol diglycidyl ether and water-based epoxy resin.
2. A method of surface modification of a fiber as defined in claim 1, wherein:
the mass ratio of the fiber to the active monomer is 1: (5-20).
3. A method of surface modification of a fiber as defined in claim 1, wherein:
the plant polyphenol is tannic acid.
4. A method of surface modification of a fiber as defined in claim 1, wherein:
the mass ratio of the trivalent ferric salt to the plant polyphenol is 1: (1-3).
5. A method of surface modification of a fiber as defined in claim 1, wherein:
the solvent of the active reaction monomer water/ethanol solution is water and ethanol, and the volume ratio of the water to the ethanol is 1-4.
6. A method of surface modification of a fiber as defined in claim 1, wherein:
the volume concentration of the reactive monomer is 1-3%.
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