WO2022000432A1 - 环保型二浴法纤维浸渍处理体系及其制备方法和应用及浸胶纤维织物的制备方法 - Google Patents

环保型二浴法纤维浸渍处理体系及其制备方法和应用及浸胶纤维织物的制备方法 Download PDF

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WO2022000432A1
WO2022000432A1 PCT/CN2020/099972 CN2020099972W WO2022000432A1 WO 2022000432 A1 WO2022000432 A1 WO 2022000432A1 CN 2020099972 W CN2020099972 W CN 2020099972W WO 2022000432 A1 WO2022000432 A1 WO 2022000432A1
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bath
fiber
treatment system
friendly
environment
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PCT/CN2020/099972
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English (en)
French (fr)
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田明
程学文
宁南英
王文才
张立群
黄伟
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北京化工大学
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Priority to PCT/CN2020/099972 priority Critical patent/WO2022000432A1/zh
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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
    • D06M13/152—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
    • 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
    • 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
    • D06M15/59—Polyamides; Polyimides
    • 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
    • D06M15/61—Polyamines polyimines
    • 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
    • D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof

Definitions

  • the invention belongs to the field of fiber dipping, and relates to a fiber dipping treatment system, in particular to an environment-friendly two-bath fiber dipping treatment system, a preparation method and application thereof, and a preparation method of a dipped fiber fabric.
  • fiber-rubber composite materials are widely used in high-speed and high-load automobile/aircraft tires, high-pressure resistant special rubber hoses and high-strength special rubber conveyor belts.
  • the fiber-reinforced material has high stiffness and strength and can be used to resist external stress, while the rubber matrix has good elasticity and can be used to withstand strain.
  • Fiber-rubber interfacial adhesion is the key to determining the stress transfer efficiency and enhancement of fiber reinforced materials.
  • the traditional fiber impregnation treatment method adopts the resorcinol-formaldehyde-rubber latex (RFL) impregnation method, and the treated fibers and the rubber matrix show excellent bonding effect.
  • RTL resorcinol-formaldehyde-rubber latex
  • resorcinol and formaldehyde used in this method have been classified as carcinogens by the International Agency for Research on Cancer (IARC), and more and more countries are beginning to ban the use of resorcinol and formaldehyde in tire production.
  • IARC International Agency for Research on Cancer
  • U.S. Patent US0041113 discloses a dipping system composed of blocked isocyanate, amino curing agent, epoxy resin and butyl pyridine latex, which is mainly used for one-bath treatment of polyester and nylon fibers to improve the adhesion between them and rubber materials.
  • the adhesion performance of the dipping system is comparable to that of RFL.
  • US Patent US0315410 discloses a fiber impregnation liquid composed of acrylic resin with carboxylic acid group, epoxy resin, blocked polyisocyanate and styrene-butadiene latex, styrene pyridine latex, one-bath dipping treated fiber cord and rubber The adhesion performance between them reached a level comparable to RFL.
  • U.S. Patent 2004/0249053 A1 discloses an adhesive system mainly composed of half-esterified maleic anhydride grafted polybutadiene resin and VP latex, which is used to promote the bonding between polyester industrial yarn and rubber matrix after epoxy activation. Adhesion between the two, but the treatment effect is not as good as the traditional RFL impregnation system.
  • WO1996000749A1 discloses a dipping system for enhancing the adhesion between fiber fabrics and rubber, the system comprises epoxy compounds with trifunctionality and above, and rubber latex with carboxyl, amino or pyridine groups composition, the effect of fiber/rubber adhesion after treatment with the impregnation system is unknown.
  • US20150314644 discloses a dipping solution composed of epoxy resin, polyamine with a molecular weight greater than 190 Daltons, and rubber latex, which is used to improve the adhesion between cords and rubber, and its adhesion effect is comparable to that of the RFL system.
  • the purpose of the present invention is to provide a kind of environment-friendly two-bath fiber impregnation treatment system, to be suitable for industrialized production use;
  • Another object of the present invention is to provide the preparation method of the above-mentioned environment-friendly two-bath fiber dipping treatment system
  • Another object of the present invention is to provide the application of the above-mentioned environment-friendly two-bath fiber dipping treatment system.
  • the last object of the present invention is to provide a preparation method of dipped fiber fabric.
  • An environment-friendly two-bath fiber impregnation treatment system includes one-bath dipping solution and two-bath dipping solution;
  • the one-bath dipping solution includes: 1) phenolic compound and water; or 2) phenolic compound, filler and water;
  • the two-bath dipping solution includes epoxy resin, amine compound, rubber latex and water.
  • the one-bath dipping solution in parts by weight, includes 0.5-20 parts of phenolic compounds, 0-30 parts of fillers and 295-305 parts of water ; Preferably, in parts by weight, the one-bath dipping solution comprises 0.5-8 parts of phenolic compounds, 0.5-20 parts of fillers and 295-305 parts of water. Further preferably, in parts by weight, the one-bath dipping solution comprises 2-5 parts of phenolic compounds, 3-17 parts of fillers and 295-305 parts of water.
  • the two-bath dipping solution comprises 2-25 parts of epoxy resin, 0.2-15 parts of amine compounds, 80-220 parts of parts rubber latex and 95-105 parts water.
  • the two-bath dipping solution includes 2-20 parts of epoxy resin, 0.2-8 parts of amine compound, 100-200 parts of rubber latex and 95-105 parts of water; more preferably, it includes 3-18 parts epoxy resin, 0.2-8 parts amine compound, 100-200 parts rubber latex and 95-105 parts water.
  • the phenolic compound is a polyphenolic compound, preferably selected from raspberry polyphenol, chrysophanol, kaempferol, apple polyphenol, grape polyphenol, One or more of pomegranate peel polyphenol, flying grass polyphenol, tea polyphenol, catechol; more preferably chrysophanol, kaempferol, apple polyphenol, grape polyphenol, flying grass polyphenol, tea One or more of polyphenols and catechols.
  • the epoxy resin is bisphenol A epoxy resin, epoxidized novolac resin, ethylene glycol diglycidyl ether, polyethylene glycol Diglycidyl ether, 1,2-propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, diglycidyl ether, glycerol glycidyl ether, trimethylol One or more of propane glycidyl ether, tetraphenol ethane tetraglycidyl ether epoxy resin, resorcinol bisglycidyl ether type epoxy resin, and bisresorcinol formal tetraglycidyl ether .
  • the amine compound is a hyperbranched or macromolecular amine compound, preferably selected from hyperbranched polyamides (number of amino groups: 7-9 mol/mol, molecular weight : 800-1000g/mol), hyperbranched polyethyleneimine (purity: MW1000, 98%, CAS: 9002-98-6, content: 98%), polyoxyethylene bisamine (purity: MW: 2000, CAS : 24991-53-5), polyamide-amine (PAMAM dendrimer, ethylenediamine core, 3.5 generation solution, purity: 10wt.% in methanol, CAS: 192948-77-9) one or two more than one species.
  • hyperbranched polyamides number of amino groups: 7-9 mol/mol, molecular weight : 800-1000g/mol
  • hyperbranched polyethyleneimine purity: MW1000, 98%, CAS: 9002-98-6, content: 98%)
  • polyoxyethylene bisamine purity: MW: 2000, CAS : 24991-53-5
  • the rubber latex is styrene-butadiene latex, pyridine-butadiene latex, styrene-butadiene latex, nitrile-butadiene latex, chloroprene latex, chlorosulfonated polyethylene latex and One or more of natural rubber latex; preferably one or more of styrene-butadiene latex, butyl-pyridine latex, styrene-butadiene latex, neoprene latex, nitrile latex and natural rubber latex; the styrene-butadiene latex Preferably, it is carboxylated styrene-butadiene latex; the nitrile latex is preferably carboxylated nitrile-butadiene latex; and the natural latex is preferably epoxidized natural latex.
  • the solid content of the rubber latex is 30-50 wt%.
  • the filler is selected from attapulgite, nanocellulose, halloysite, graphene oxide, montmorillonite, nano-silica, carbon black, One or more of carbon nanotubes, nano-aramid fibers, basalt fibers, nano-whiskers, mica, kaolin, hydrotalcite, nano-titanium dioxide, nano-zinc oxide, nano-iron oxide, nano-calcium oxide and nano-calcium carbonate; preferably It is one or more of halloysite, graphene oxide, nano-cellulose, nano-aramid fiber, montmorillonite, nano-silica, attapulgite, nano-zinc oxide and graphene oxide.
  • the filler is a filler treated with a surface modifier.
  • the surface modifier is selected from one or both of amino silane coupling agent, epoxy silane coupling agent, alkyl silane coupling agent, isocyanato silane coupling agent and polyether silane coupling agent more preferably, the surface modifier is selected from 3-aminopropyltriethoxysilane (KH550: CAS: 919-30-2, molecular weight: 221.37), 3-glycidyl etheroxypropyl Trimethoxysilane (KH560, CAS: 2530-83-8, molecular weight: 236.34), ⁇ -methacryloyloxypropyltrimethoxysilane (KH570, CAS: 2530-85-0, molecular weight: 248.35), Bis-[ ⁇ -(triethoxysilyl)propyl]tetrasulfide (Si69, molecular weight: 538.94, CAS: 40372-72-3, content (%): ⁇ 22.5) and vinyltriethoxysilane (KH550
  • the surface modifier treatment includes the following steps: adding the solution containing the surface modifier to the dispersion liquid containing the filler for ultrasonication,
  • the solution containing the surface modifier is a solution formed by a surface modifier and ethanol
  • the dispersion liquid containing the filler is a dispersion liquid formed by a filler and water
  • the material of the surface modifier is a filler
  • the dosage is 1-20wt%
  • the temperature of the ultrasonic is 25-60°C
  • the time of the ultrasonic is 0.5-2h.
  • the water may be deionized water.
  • the present invention also provides a method for preparing the above-mentioned environmentally friendly two-bath fiber impregnation treatment system, comprising the following steps:
  • the present invention further provides the application of the above-mentioned environment-friendly two-bath fiber impregnation treatment system in preparing the dipped fiber fabric.
  • the present invention further provides a preparation method of a dipped fiber fabric, which adopts the above-mentioned environmentally friendly two-bath fiber dipping treatment system to treat the fiber fabric.
  • Described application or preparation method can comprise the steps:
  • the fabric M is subjected to surface dipping treatment and curing in the two-bath dipping solution of the environment-friendly two-bath fiber impregnation treatment system to obtain a dipping fiber fabric.
  • the surface immersion treatment conditions may include: the treatment temperature is room temperature, for example, it may be 15-35°C, preferably 20-30°C, and the treatment time Both can be 1-15s.
  • the fibers are fiber cords
  • the surface dipping treatment includes immersing the fiber cords in a bath of dipping solution for routing, and the routing speed is Can be 4-10m/min.
  • the drying temperature may be 120-160° C. and the time may be 1-5 min.
  • the curing temperature may be 160-250° C. and the time may be 1-5 min.
  • the fibers are selected from rayon, nylon 6, nylon 66, meta- or para-aramid fibers, polyethylene terephthalate (PET), polyethylene Polyethylene naphthalate (PEN), polyimide, carbon fibers, and mixed twisted cords of the above fibers; preferably aramid cords, polyester cords or nylon cords.
  • the form of the fibers is selected from the group consisting of monofilament, tow, twisted cord, canvas, and cord fabric.
  • the epoxy resins, amine compounds and phenolic compounds used in the environment-friendly two-bath fiber impregnation treatment system of the present invention are all industrial products, with wide sources, low prices, green, pollution-free, and good water solubility.
  • the environment-friendly two-bath fiber impregnation treatment system provided by the invention has simple preparation process and short process flow.
  • the prepared environment-friendly two-bath fiber impregnation treatment system has good stability and can be stored at room temperature for a long time.
  • the dipped fiber fabric prepared by the environment-friendly two-bath fiber impregnation treatment system provided by the present invention has a slightly better adhesion between fibers and rubber than the dipped fiber fabric treated by the RFL system, and the change of the tensile strength of the fiber is higher than that of the RFL system. Small, the overall effect exceeds that of dipped fiber fabrics made using the RFL system.
  • the dipped fiber fabric prepared by the invention is suitable for rubber skeleton material.
  • the raw materials used in the examples and comparative examples of the present invention are all commercially available, and the equipment used is conventional production equipment.
  • the standard rubber (standard rubber rubber formula refers to GBT9101-2017) is completely covered on the dipping cord, and the extraction pattern is prepared, and finally it is placed on a flat vulcanizing machine for vulcanization.
  • the vulcanization temperature is 136 °C
  • the vulcanization pressure is 15MPa
  • the vulcanization time is 50min.
  • the preparation method of the peel force test strip is as follows:
  • the peeling method of Shenma Industrial Co., Ltd. to measure the adhesion standard of nylon 66 dipped single cord, completely wrap the standard rubber on the dipped cord, prepare the peeling sample, and finally put it on the flat vulcanizing machine
  • the vulcanization temperature is 160°C
  • the vulcanization pressure is 2.354MPa
  • the vulcanization time is 20min.
  • the preparation method of the cord tensile strength sample is as follows:
  • the dipped cord is clamped under the tensile testing machine for testing, and the tensile speed is 300 ⁇ 5mm/min.
  • the tensile strength test of cord is tested according to GB/T32108-2015; the H pull-out force is tested according to GB/T2942-2009; the method of peeling test is as follows:
  • the depth of the film cavity is 2mm, the length is 250mm, and the width is 170mm.
  • the width of each sample is 20mm.
  • Vulcanization process 1) After preheating the mold at 136°C for 15-20 minutes, put a single cord into the groove to make the cord vertically tensioned; 2) Put a long cord at the lower end of the mold near the frame 20mm, 160mm wide, 0.5mm thick film and attach a cellophane slightly larger than the film on it; 3) Put a 240mm long, 160mm wide, 1.7mm thick film on the cellophane, and attach a lining of the same size on it. Vulcanization is performed after the gland is closed. Cool for at least 2 hours after vulcanization, and then trim the samples to test the peel force (each sample contains 5 cords).
  • Test process The part separated by cellophane is clamped into the upper and lower chucks of the tensile machine at an angle of 180° for tensile peeling.
  • the tensile machine speed was set to 300 mm/min, and the peel length was (150 ⁇ 10) mm.
  • the average adhesion (N) was read from the peel curve, and the peel adhesion of a single cord was calculated.
  • Example 1 An environmentally friendly two-bath fiber impregnation treatment system and its preparation method and application
  • the environment-friendly two-bath fiber dipping treatment system is composed of one-bath dipping solution and two-bath dipping solution.
  • the preparation method of the system is as follows:
  • the phenolic compound A 1 was added to 300 kg of deionized water, and vigorously stirred at room temperature for 1 h to obtain a one-bath dipping solution.
  • the epoxy resin B 1 , the amine compound C 1 , and the rubber latex D 1 were added to 100 kg of deionized water, and vigorously stirred at room temperature for 2 hours to fully dissolve, and then a two-bath dipping solution was prepared.
  • the above-mentioned one-bath dipping solution and two-bath dipping solution constitute an environment-friendly two-bath fiber dipping treatment system for preparing dipped fiber fabric.
  • the fabric M 1 is subjected to surface dipping treatment at room temperature for 6 s in the second-bath dipping solution, and then cured in an oven at 210° C. for 4 min to obtain a dipped fiber fabric.
  • Embodiments 2-9 are respectively a kind of environment-friendly two-bath fiber dipping treatment system and preparation method and application thereof, their steps are basically the same as those of embodiment 1, and the difference is only in the process parameters, see Table 1 for details, wherein:
  • Kaempferol purchased from Shaanxi Yikanglong Biotechnology Co., Ltd., CAS: 520-18-3, purity: 98%;
  • Grape polyphenol purchased from Xi'an Tianguangyuan Biotechnology Co., Ltd., purity: 50%, CAS: 1-542-8600;
  • Styrene-butadiene latex purchased from Jiangsu Yatai Chemical Co., Ltd., pH value (25°C): 10-12, viscosity (25°C): 25-45mpa.S;
  • Carboxylated styrene-butadiene latex purchased from Jiangsu Yatai Chemical Co., Ltd., pH value (25°C): 8-10, viscosity (25°C): ⁇ 200mpa.S;
  • Carboxylated nitrile latex purchased from Jiangsu Yatai Chemical Co., Ltd., pH value (25°C): 7-9, viscosity (25°C): ⁇ 50mpa.S;
  • Polyethylene glycol diglycidyl ether purchased from Shanghai McLean Biochemical Technology Co., Ltd., CAS: 39443-66-8, purity: epoxy value: 0.70 ⁇ 0.80mol/100g, viscosity (25°C): 5 ⁇ 25mpa. s;
  • Ethylene glycol glycidyl ether purchased from Shanghai McLean Biochemical Technology Co., Ltd., CAS: 2224-15-9, purity: epoxy value: ⁇ 0.7;
  • Trimethylolpropane glycidyl ether purchased from Shanghai McLean Biochemical Technology Co., Ltd., CAS: 30499-70-8, epoxy value eq/100g: 0.70;
  • 1,2-cyclohexanediol diglycidyl ether purchased from Wuhan Fengyao Tonghui Chemical Co., Ltd., CAS: 37763-26-1, purity: 99% HPLC
  • Comparative example 1 is compared with embodiment 1, adopts RFL one-bath method dipping treatment system to process fiber, and the preparation method of the system is as follows:
  • a2) Add the phenolic pre-polycondensate to the mixed solution of 80.0kg of butyl pyridine latex and 20.0kg of deionized water, and add 1.0kg of ammonia water dropwise to adjust the pH value of the solution, and continue to stir and mature at room temperature for 20h.
  • the resorcinol-formaldehyde-butyropyridine latex (RFL) dipping solution can be prepared.
  • the above resorcinol-formaldehyde-butyropyridine latex (RFL) dipping solution constitutes an RFL fiber dipping treatment system for preparing dipped fiber fabrics.
  • Comparative example 2 is compared with embodiment 2, adopts RFL two-bath dipping treatment system to process fiber, and the preparation method of the system is as follows:
  • the above-mentioned resorcinol-formaldehyde-butyropyridine latex (RFL) two-bath dipping solution constitutes an RFL fiber dipping treatment system for preparing the dipping fiber fabric.
  • the application method of the above-mentioned resorcinol-formaldehyde-butyropyridine latex (RFL) fiber dipping treatment system in the preparation of the dipping fiber fabric comprises the following steps:
  • the modified fabric is subjected to a two-bath dipping treatment on the surface of the modified fabric at room temperature for 6 s with a two-bath dipping solution, and then cured in an oven at 210° C. for 4 min to obtain a dipped fiber fabric.
  • Comparative example 3 is compared with embodiment 3, adopts RFL two-bath dipping treatment system to process fiber, and the preparation method of the system is as follows:
  • the above-mentioned resorcinol-formaldehyde-butyropyridine latex (RFL) two-bath dipping solution constitutes an RFL fiber dipping treatment system for preparing the dipping fiber fabric.
  • polyester fiber cords (1670dtex) Take polyester fiber cords (1670dtex) at a running speed of 6m/min, first perform surface dipping treatment in a bath of dipping solution for 6s at room temperature, and then dry them in an oven at 140°C for 4min to prepare a bath Impregnated fabrics;
  • the modified fabric is subjected to a two-bath dipping treatment on the surface of the modified fabric at room temperature for 6 s with a two-bath dipping solution, and then cured in an oven at 210° C. for 4 min to obtain a dipped fiber fabric.
  • the adhesive effect of the dipped fiber fabric prepared by using the environment-friendly two-bath fiber impregnation treatment system of the present invention is higher than that of the dipped fiber fabric prepared by using the RFL system, and the strength of the dipped fiber fabric prepared by the present invention is not greatly lost.
  • the environment-friendly two-bath fiber dipping treatment system is composed of one-bath dipping solution and two-bath dipping solution.
  • the preparation method of the system is as follows:
  • a2) take by weighing 4kg of glycerol glycidyl ether and 2kg of 1,4-butanediol diglycidyl ether as epoxy resin B 1 ;
  • the epoxy resin B 1 , the amine compound C 1 , and the rubber latex D 1 were added to 100 kg of deionized water, stirred at room temperature for 2 hours, and fully dissolved to obtain a two-bath dipping solution.
  • the above-mentioned one-bath dipping solution and two-bath dipping solution constitute an environment-friendly two-bath fiber dipping treatment system for preparing dipped fiber fabric.
  • the fabric M 1 is subjected to surface dipping treatment at room temperature for 6 s in the second-bath dipping solution, and then cured in an oven at 210° C. for 4 min to obtain a dipped fiber fabric.
  • Embodiments 11-17 are respectively an environment-friendly two-bath fiber impregnation treatment system and its preparation method and application, and their steps are basically the same as those in Embodiment 10.
  • the filler and deionized water are added to the beaker, and the modifier/
  • the mixed solution of ethanol (modifier/ethanol volume ratio 2:1, ethanol (purity ⁇ 95wt%)) (modifier dosage is 10wt% of filler dosage) is slowly added to the mixed solution of filler and deionized water, and ultrasonic Stirring, the power of the ultrasonic equipment is 400W, and the time of ultrasonic stirring is 1h to obtain the dispersed modified nano-filler.
  • Graphene oxide purchased from Changzhou Sixth Element Materials Technology Co., Ltd., model: SE2430W, solid content (%): 43 ⁇ 5, pH: 1.5-1.8, viscosity (Pa ⁇ S): 1.5-5.0, oxygen carbon mole Ratio O/C: 0.6 ⁇ 0.1;
  • Attapulgite purchased from Jiangsu Shengyi Nano Technology Co., Ltd., purified type 601;
  • Nano-silica purchased from West Asia Chemical Technology (Shandong) Co., Ltd., purity: >99.5%, average particle size: 15 ⁇ 5nm)
  • Examples 10, 11, 12 added unsurface-modified fillers, while Examples 13, 14, 15 added surface-modified fillers, and Examples 16, 17 added surface-modified mixed fillers.
  • the contents of other parts of Embodiments 11-17 are the same as those of Embodiment 10.
  • the H-extraction force test specimens, the peeling force test specimens and the cord tensile strength samples were prepared according to the above methods for the materials of Examples 10-17, and the H-extraction force, the peeling force and the cord tensile strength were tested respectively, and the results were shown in Table 4:
  • the H extraction force and peeling force of the unmodified filler and the impregnation system and the impregnation system with the modified filler were 5-10% higher than those of Examples 1, 2, and 3 without fillers, respectively, and 10-10%. 15%, indicating that adding nano-filler to the impregnation system of the present invention can further improve the adhesion between the treated fiber and rubber, which is obviously better than the treatment effect of the RFL system and the impregnating system without nano-filler of the present invention.
  • the adhesion effect of the impregnated fiber fabric prepared by the environmentally friendly two-bath fiber impregnation treatment system of the present invention is also better than that of the impregnated fiber fabric prepared by the RFL system, and the tensile strength of the impregnated fiber fabric does not change significantly.

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

Abstract

本发明公开了一种环保型二浴法纤维浸渍处理体系及其制备方法和应用，该体系包括一浴浸胶液和二浴浸胶液，其中一浴浸胶液的包括酚类化合物A和水或者酚类化合物A、填料和水，二浴浸胶液包括环氧树脂、胺类化合物、橡胶胶乳和去离子水。所述浸渍处理体系可用于制备浸胶纤维织物。本发明提供的环保型二浴法纤维浸渍处理体系制得的浸胶纤维织物，纤维与橡胶之间的粘合性能略优于RFL体系处理的浸胶纤维织物，纤维的拉断强度变化较小，综合效果超过使用RFL体系制得的浸胶纤维织物。

Description

环保型二浴法纤维浸渍处理体系及其制备方法和应用及浸胶纤维织物的制备方法 技术领域
本发明属于纤维浸胶领域，涉及一种纤维浸渍处理体系，具体地说是一种环保型二浴法纤维浸渍处理体系及其制备方法和应用及浸胶纤维织物的制备方法。
背景技术
目前，纤维橡胶复合材料广泛用于高速高载汽车/飞机轮胎、抗高压特种胶管和高强力特种橡胶输送带等。其中，纤维增强材料具有较高的刚度和强度可以用来抵抗外来应力，而橡胶基体具有良好的弹性可以用来承受应变。
纤维－橡胶界面粘合是决定纤维增强材料发挥应力传递效率起到增强的关键。在橡胶工业中，传统纤维浸渍处理方法采用间苯二酚－甲醛－橡胶乳液(RFL)浸渍法，处理的纤维与橡胶基体表现优良的粘合效果。但该方法使用的间苯二酚和甲醛已被国际癌症研究机构(IARC)列为致癌物质，越来越多国家开始禁止在轮胎生产中使用间苯二酚和甲醛。
针对这一问题，近几年开发新型的无毒无害非RFL浸渍处理技术成为发展趋势。美国专利US0041113公开了一种由封闭型异氰酸酯、氨基固化剂、环氧树脂和丁吡胶乳组成的浸胶体系，主要用于一浴法处理聚酯和尼龙纤维，来提高其与橡胶材料之间的粘合性能，其浸胶体系处理后的效果与RFL相当。美国专利US0315410公开了一种由带羧酸基团的丙烯酸树脂、环氧树脂、封闭的聚异氰酸酯和丁苯胶乳、苯乙烯吡胶乳组成的纤维浸渍液，一浴浸渍处理的纤维帘线与橡胶之间的粘合性能达到了RFL相当的水平。美国专利2004/0249053 A1公开了一种主要由半酯化的马来酸酐接枝聚丁二烯树脂和VP胶乳组成的粘合体系，用于促进环氧活化后聚酯工业丝与橡胶基体之间的粘合，但处理效果不如传统RFL浸渍体系。WO1996000749A1中公开了一种用于增强纤维织布与橡胶之间的粘合性能的浸胶体系，该体系包含三官能度及以上的环氧化合物、带有羧基、氨基或吡啶基团的橡胶胶乳组成，其浸渍体系处理后的纤维/橡胶间的粘合效果未知。US20150314644公开了一种由环氧树脂、分子量大于190道尔顿的多胺、橡胶胶乳组成的浸胶液，用于提高帘线和橡胶间的粘合性能，其粘合效果与RFL体系相当。
发明内容
本发明的目的是要提供一种环保型二浴法纤维浸渍处理体系，以适合工业化生产使用；
本发明的另一个目的，是要提供上述环保型二浴法纤维浸渍处理体系的制备方法；
本发明的还有一个目的，是要提供上述环保型二浴法纤维浸渍处理体系的应用。
本发明的最后一个目的，是要提供一种浸胶纤维织物的制备方法。
为了实现上述目的，本发明采用的技术方案是：
一种环保型二浴法纤维浸渍处理体系，包括一浴浸胶液和二浴浸胶液；
所述一浴浸胶液包括：1)酚类化合物和水；或者2)酚类化合物、填料和水；
所述二浴浸胶液包括：环氧树脂、胺类化合物、橡胶胶乳和水。
根据所述的环保型二浴法纤维浸渍处理体系的实施方式，以重量份数计，所述一浴浸胶液包括0.5-20份酚类化合物、0-30份填料和295-305份水；优选地，以重量份数计，所述一浴浸胶液包括0.5-8份酚类化合物、0.5-20份填料和295-305份水。进一步优选地，以重量份数计，所述一浴浸胶液包括2-5份酚类化合物、3-17份填料和295-305份水。
根据所述的环保型二浴法纤维浸渍处理体系的实施方式，以重量份数计，所述二浴浸胶液包括2-25份环氧树脂、0.2-15份胺类化合物、80-220份橡胶胶乳和95-105份水。优选地，以重量份数计，所述二浴浸胶液包括2-20份环氧树脂、0.2-8份胺类化合物、100-200份橡胶胶乳和95-105份水；进一步优选为括3-18份环氧树脂、0.2-8份胺类化合物、100-200份橡胶胶乳和95-105份水。
根据所述的环保型二浴法纤维浸渍处理体系的实施方式，所述酚类化合物为多酚化合物，优选选自覆盆子多酚、大黄酚、山柰酚、苹果多酚、葡萄多酚、石榴皮多酚、飞扬草多酚、茶多酚、儿茶酚中的一种或两种以上；进一步优选为大黄酚、山柰酚、苹果多酚、葡萄多酚、飞扬草多酚、茶多酚和儿茶酚中的一种或两种以上。
根据所述的环保型二浴法纤维浸渍处理体系的实施方式，所述环氧树脂为双酚A型环氧树脂、环氧化线性酚醛树脂、乙二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、1,2-丙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、1,4-丁二醇二缩水甘油醚、二缩水甘油醚、丙三醇缩水甘油醚、三羟甲基丙烷缩水甘油醚、四酚基乙烷四缩水甘油醚环氧树脂、间苯二酚双缩水甘油醚型环氧树脂、双间苯二酚缩甲醛四缩水甘油醚中的一种或两种以上。
根据所述的环保型二浴法纤维浸渍处理体系的实施方式，所述胺类化合物为超支化或 大分子胺类化合物，优选选自超支化聚酰胺(氨基数：7-9mol/mol，分子量：800-1000g/mol)、超支化聚乙烯亚胺(纯度：M.W.1000，98％，CAS:9002-98-6，含量：98％)、聚氧乙烯双胺(纯度：MW：2000，CAS:24991-53-5)、聚酰胺-胺(PAMAM树枝状聚合物，乙二胺核，3.5代溶液，纯度:甲醇中10wt.％，CAS:192948-77-9)中的一种或两种以上。
根据所述的环保型二浴法纤维浸渍处理体系的实施方式，所述橡胶胶乳为丁苯胶乳、丁吡胶乳、丁苯吡胶乳、丁腈胶乳、氯丁胶乳、氯磺化聚乙烯胶乳和天然胶乳中的一种或两种以上；优选为丁苯吡胶乳、丁吡胶乳、丁苯胶乳、氯丁胶乳、丁腈胶乳和天然胶乳中的一种或两种以上；所述丁苯胶乳优选为羧基丁苯胶乳；所述丁腈胶乳优选为羧基丁腈胶乳；所述天然胶乳优选为环氧化天然胶乳。
根据所述的环保型二浴法纤维浸渍处理体系的实施方式，所述橡胶胶乳的固含量为30-50wt％。
根据所述的环保型二浴法纤维浸渍处理体系的实施方式，所述填料选自凹凸棒石、纳米纤维素、埃洛石、氧化石墨烯、蒙脱石、纳米二氧化硅、炭黑、碳纳米管、纳米芳纶纤维、玄武岩纤维、纳米晶须、云母、高岭土、水滑石、纳米二氧化钛、纳米氧化锌、纳米氧化铁、纳米氧化钙和纳米碳酸钙的一种或两种以上；优选为埃洛石、氧化石墨烯、纳米纤维素、纳米芳纶纤维、蒙脱石、纳米二氧化硅、凹凸棒石、纳米氧化锌和氧化石墨烯中的一种或两种以上。
根据所述的环保型二浴法纤维浸渍处理体系的实施方式，所述填料为经表面改性剂处理的填料。
优选地，所述表面改性剂选自氨基硅烷偶联剂、环氧基硅烷偶联剂、烷基硅烷偶联剂、异氰酸酯基硅烷偶联剂和聚醚硅烷偶联剂的一种或两种以上；更优选地，所述表面改性剂选自3-氨基丙基三乙氧基硅烷(KH550：CAS：919-30-2，分子量:221.37)、3-缩水甘油醚氧基丙基三甲氧基硅烷(KH560，CAS：2530-83-8，分子量:236.34)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570，CAS：2530-85-0，分子量:248.35)、双-[γ-(三乙氧基硅)丙基]四硫化物(Si69，分子量:538.94，CAS:40372-72-3，含量(％)：≥22.5)和乙烯基三乙氧基硅烷(分子量:148.23，CAS:2768-02-7，含量(％)：≥98.0)中一种或两种以上。
根据所述的环保型二浴法纤维浸渍处理体系的实施方式，所述经表面改性剂处理包括以下步骤：将含有表面改性剂的溶液加入到含有填料的分散液中进行超声，
优选地，所述含有表面改性剂的溶液为表面改性剂和乙醇形成的溶液，所述含有填料 的分散液为填料与水形成的分散液，所述表面改性剂的用料为填料用量的1-20wt％，所述超声的温度为25-60℃，所述超声的时间为0.5-2h。
根据所述的环保型二浴法纤维浸渍处理体系的实施方式，所述水可以为去离子水。
本发明还提供了一种用于制备上述的环保型二浴法纤维浸渍处理体系的方法，包括以下步骤：
a1)将酚类化合物与水和任选地填料混合，以得到所述的一浴浸胶液；
a2)将环氧树脂、胺类化合物和橡胶胶乳与水混合，以得到所述的二浴浸胶液。
本发明进一步提供了上述环保型二浴法纤维浸渍处理体系在制备浸胶纤维织物中的应用。
本发明进一步提供了一种浸胶纤维织物的制备方法，其采用上述的环保型二浴法纤维浸渍处理体系处理纤维织物。
所述的应用或制备方法可以包括如下步骤：
b1)将纤维于所述环保型二浴法纤维浸渍处理体系的一浴浸胶液中进行表面浸渍处理和烘干，制得织物M；
b2)将织物M于所述环保型二浴法纤维浸渍处理体系的二浴浸胶液中进行表面浸渍处理和固化，制得浸胶纤维织物。
根据所述的应用或制备方法的一些实施方式，步骤b1)和b2)中，表面浸渍处理条件可以包括：处理温度均为室温，例如可以为15-35℃，优选20-30℃，处理时间均可以为1-15s。
根据所述的应用或制备方法的一些实施方式，步骤b1)中，所述纤维为纤维帘线，所述表面浸渍处理包括将纤维帘线浸入一浴浸胶液中进行走线，走线速度可以为4-10m/min。
根据所述的应用或制备方法的一些实施方式，步骤b1)中，烘干的温度可以为120-160℃、时间可以为1-5min。
根据所述的应用或制备方法的一些实施方式，步骤b2)中，固化的温度可以为160-250℃、时间可以为1-5min。
根据所述的应用或制备方法的一些实施方式，所述纤维选自人造丝、尼龙6、尼龙66、间位或对位芳纶纤维、聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯 (PEN)、聚酰亚胺、碳纤维以及上述纤维的混编加捻帘线；优选为芳纶帘线、聚酯帘线或尼龙帘线。
根据所述的应用或制备方法的一些实施方式，所述纤维的形式选自单丝、束丝、加捻帘线、帆布和帘子布。
本发明环保型二浴法纤维浸渍处理体系中所用的环氧树脂、胺类化合物、酚类化合物均为工业产品，来源广、价格低廉且绿色无污染、水溶性好。本发明提供的环保型二浴法纤维浸渍处理体系，制备工艺简单，流程较短。制得的环保型二浴法纤维浸渍处理体系稳定性好，能够在室温下长期储存。用本发明提供的环保型二浴法纤维浸渍处理体系制得的浸胶纤维织物，纤维与橡胶之间的粘合性能略优于RFL体系处理的浸胶纤维织物，纤维的拉断强度变化较小，综合效果超过使用RFL体系制得的浸胶纤维织物。本发明制得的浸胶纤维织物适用于橡胶骨架材料。
具体实施方式
下面通过具体实施例对本发明做进一步详细说明，应当理解所描述的实施例仅用于解释本发明，并不限定本发明。
本发明实施例和对比例中所用原料均为市售所得，所用设备均为常规生产设备。
以下实施例和对比例中的H抽出力试验样条制备方法如下：
参考标准GB/T2942-2009，将标准胶(标准胶橡胶配方参照GBT9101-2017)完全包覆在浸胶帘线上，制备抽出式样，最后将其放在平板硫化机上进行硫化，硫化温度为136℃，硫化压力为15MPa，硫化时间为50min。
剥离力试验样条制备方法如下：
参考神马实业股份有限公司的剥离法测定锦纶66浸胶单根帘线粘合力标准，将标准胶完全包覆在浸胶帘线上，制备剥离试样，最后将其放在平板硫化机上进行硫化，硫化温度为160℃，硫化压力为2.354MPa，硫化时间为20min。
帘线拉断强度试样制备方法如下：
参考标准GB/T32108-2015，将浸胶帘线夹持在拉力试验机下进行测试，拉伸速度为300±5mm/min。
其中，帘线拉断强度测试按照GB/T32108-2015测试；H抽出力按照GB/T2942-2009测试；剥离测试的方法如下：
(1)硫化模具尺寸：膜腔深2mm，长250mm，宽170mm，每片试样宽20mm，片与片间隔 6mm，模具两边各保留10mm，盖板与模具底板厚度均不小于10mm。
(2)硫化所用橡胶胶料配方与H抽出力测试相同。
(3)硫化工艺：160℃×20min，压力2.354Mpa。
(4)硫化过程：1)将模具在136℃下预热15～20min后，将单根帘线装入凹槽内，使帘线垂直张紧；2)在模具下端靠近边框处放入长20mm、宽160mm、厚0.5mm的胶片并在上面附上稍大于胶片的玻璃纸；3)在玻璃纸上放上长240mm、宽160mm、厚1.7mm的胶片，同时在上面附上相同尺寸的衬布。压盖合模后进行硫化。硫化后至少冷却2h，再修剪试样测试剥离力(每片试样含有5根帘线)。
(5)测试过程：将用玻璃纸分离的部分以180°角夹入拉力机上、下夹头，进行拉伸剥离。拉力机速度设置为300mm/min，剥离长度为(150±10)mm。根据剥离曲线读取平均粘合力(N)，计算得到单根帘线的剥离粘合力。
实施例1 一种环保型二浴法纤维浸渍处理体系及其制备方法和应用
1)环保型二浴法纤维浸渍处理体系及其制备方法
环保型二浴法纤维浸渍处理体系，由一浴浸胶液和二浴浸胶液构成，体系的制备方法如下：
a1)称取1.5kg苹果多酚(购自陕西帕尼尔生物科技有限公司，纯度：98％)及0.5kg茶多酚(购自北京祥云兴业科技有限公司，纯度：98％)，作为酚类化合物A 1；
将酚类化合物A 1加至300kg去离子水中，室温强力搅拌1h，制得一浴浸胶液。
a2)称取4kg丙三醇缩水甘油醚(购自金锦乐化学，CAS：25038-04-4，环氧值0.65-0.70)和2kg的1,4-丁二醇二缩水甘油醚(购自上海麦克林生化科技有限公司，CAS：2425-79-8，纯度：95％，密度:1.1g/mL at 25℃)，作为环氧树脂B 1；
称取0.3kg超支化聚乙烯亚胺和0.2kg聚酰胺胺，作为胺类化合物C 1；
称取50kg重量百分比为40％的丁吡胶乳(购自江苏亚泰化工有限公司，粘度(25℃)：25-60mpa.S，pH值(25℃)：10-12)和50kg重量百分比为40％丁腈胶乳(购自江苏亚泰化工有限公司，粘度(25℃)：≤500mpa.S，pH值(25℃)：9-12)，作为橡胶胶乳D 1；
将环氧树脂B 1、胺类化合物C 1、橡胶胶乳D 1加至100kg去离子水中，室温强力搅拌2h，使之充分溶解后，制得二浴浸胶液。
上述一浴浸胶液和二浴浸胶液，构成用于制备浸胶纤维织物的环保型二浴法纤维浸 渍处理体系。
2)环保型二浴法纤维浸渍处理体系的应用
b1)取尼龙帘线(1870dtex/2)以6m/min的走线速度在一浴浸胶液中进行室温表面浸渍处理6s，再于140℃的烘箱中烘干4min，制得织物M 1；
b2)织物M 1于二浴浸胶液中进行室温表面浸渍处理6s，再于210℃的烘箱中固化4min，制得浸胶纤维织物。
实施例2-9 环保型二浴法纤维浸渍处理体系及其制备方法和应用
实施例2-9分别为一种环保型二浴法纤维浸渍处理体系及其制备方法和应用，它们的步骤与实施例1基本相同，不同之处仅在于工艺参数，详见表1，其中：
儿茶酚：购自四川省维克奇生物科技有限公司，CAS：52936-64-8，纯度：HPLC>＝98％；
山奈酚：购自陕西亿康龙生物技术有限公司，CAS：520-18-3，纯度：98％；
大黄酚：购自上海澄绍生物科技有限公司，CAS：518-82-1，纯度：HPLC>＝98％；
葡萄多酚，购自西安天广源生物科技有限公司，纯度：50％，CAS：1-542-8600；
丁苯胶乳：购自江苏亚泰化工有限公司，pH值(25℃)：10-12，粘度(25℃)：25-45mpa.S；
羧基丁苯胶乳：购自江苏亚泰化工有限公司，pH值(25℃)：8-10，粘度(25℃)：≤200mpa.S；
羧基丁腈胶乳：购自江苏亚泰化工有限公司，pH值(25℃)：7-9，粘度(25℃)：≤50mpa.S；
聚乙二醇二缩水甘油醚：购自上海麦克林生化科技有限公司，CAS：39443-66-8，纯度：环氧值:0.70～0.80mol/100g，粘度(25℃):5～25mpa.s；
乙二醇缩水甘油醚：购自上海麦克林生化科技有限公司，CAS：2224-15-9，纯度：环氧值:≥0.7；
三羟甲基丙烷缩水甘油醚：购自上海麦克林生化科技有限公司，CAS：30499-70-8，环氧值eq/100g:0.70；
1,2-环己二醇二缩水甘油醚：购自武汉峰耀同辉化学制品有限公司，CAS：37763-26-1，纯度：99％HPLC)
表1 实施例2-9中各项工艺参数一览表
Figure PCTCN2020099972-appb-000001
Figure PCTCN2020099972-appb-000002
Figure PCTCN2020099972-appb-000003
实施例2-9其它部分的内容，与实施例1相同。
对比例1
1)传统RFL纤维浸渍处理体系及其制备方法
对比例1与实施例1进行对比，采用RFL一浴法浸渍处理体系处理纤维，体系的制备方法如下：
a1)分别称取5.4kg甲醛(37wt％)，3.7kg间苯二酚，0.1kg氢氧化钠，将其溶解于80.0kg去离子水中，在40℃水浴条件下持续使用强力搅拌器充分搅拌4h，混合均匀后，得到酚醛的预缩聚物。
a2)将酚醛的预缩聚物加入到80.0kg丁吡胶乳和20.0kg去离子水的混合溶液中，并滴加1.0kg的氨水调节溶液pH值，在室温下持续搅拌熟化20h，充分混合均匀后，即可制得间苯二酚-甲醛-丁吡胶乳(RFL)浸胶液。
上述间苯二酚-甲醛-丁吡胶乳(RFL)浸胶液，构成用于制备浸胶纤维织物的RFL纤维浸渍处理体系。
2)间苯二酚-甲醛-丁吡胶乳(RFL)一浴纤维浸渍处理体系的应用。
取尼龙帘线(1870dtex/2)以6m/min的走线速度在一浴浸胶液中进行室温表面浸渍处理6s，再于140℃的烘箱中烘干4min；再于210℃的烘箱中固化4min，制得浸胶纤维织物。
对比例2
1)传统RFL纤维浸渍处理体系及其制备方法
对比例2与实施例2进行对比，采用RFL二浴法浸渍处理体系处理纤维，体系的制备方法如下：
a1)称取1.8kg丙三醇缩水甘油醚与4.5kg苯酚封端的异佛尔酮二异氰酸酯加入100.0kg的去离子水中，在25℃下强力搅拌1h，混合均匀后可制得一浴纤维预浸液。
a2)分别称取5.1kg甲醛37wt％)，4.0kg间苯二酚，0.1kg氢氧化钠，并溶解于80.0kg去离子水中，在40℃水浴条件下持续使用强力搅拌器充分搅拌4h，混合均匀后，得到酚醛的预缩聚物。
a3)将上述预缩聚的酚醛树脂加入到80.0kg丁吡胶乳和20.0kg去离子水的混合溶液中，并滴加0.9kg的氨水调节溶液pH值，在室温下持续搅拌熟化20h，充分混合均匀后，即可制得间苯二酚-甲醛-丁吡胶乳(RFL)二浴浸胶液。
上述间苯二酚-甲醛-丁吡胶乳(RFL)二浴浸胶液，构成用于制备浸胶纤维织物的RFL纤维浸渍处理体系。
2)间苯二酚-甲醛-丁吡胶乳(RFL)二浴浸渍处理体系的应用
上述间苯二酚-甲醛-丁吡胶乳(RFL)纤维浸渍处理体系在制备浸胶纤维织物中的应用方法包括如下步骤：
b1)取芳纶纤维帘线(1670dtex)以6m/min的走线速度，先在一浴浸胶液中进行室温表面浸渍处理6s，再于140℃的烘箱中烘干4min，制得一浴浸渍处理织物；
b2)采用二浴浸胶液对改性织物进行室温表面二浴浸渍处理6s，再于210℃的烘箱中固化4min，制得浸胶纤维织物。
对比例3
1)传统RFL纤维浸渍处理体系及其制备方法
对比例3与实施例3进行对比，采用RFL二浴法浸渍处理体系处理纤维，体系的制备方法如下：
a1)称取1.5kg乙二醇缩水甘油醚与5.0kgε-己内酰胺封端的二苯基甲烷二异氰酸酯(CAS 5101-68-8，牌号CBI 50，购自常州市科英化工有限公司)加入100.0kg的去离子水中，在25℃下强力搅拌1h，混合均匀后可制得一浴纤维预浸液。
a2)分别称取5.7kg甲醛(37wt％)，3.3kg间苯二酚，0.1kg氢氧化钠，并溶解于80.0kg去离子水中，在40℃水浴条件下持续使用强力搅拌器充分搅拌4h，混合均匀后，得到酚醛的预缩聚物。
a3)将上述预缩聚的酚醛树脂加入到80.0kg丁吡胶乳和20.0kg去离子水的混合溶液中，并滴加1.2kg的氨水来调节溶液pH值，在室温下持续搅拌熟化20h，充分混合均匀后，即可制得间苯二酚-甲醛-丁吡胶乳(RFL)二浴浸胶液。
上述间苯二酚-甲醛-丁吡胶乳(RFL)二浴浸胶液，构成用于制备浸胶纤维织物的RFL纤维浸渍处理体系。
2)间苯二酚-甲醛-丁吡胶乳(RFL)二浴浸渍处理体系的应用
上述间苯二酚-甲醛-丁吡胶乳(RFL)纤维浸渍处理体系在制备浸胶纤维织物中的应用方法，包括如下步骤：
b1)取聚酯纤维帘线(1670dtex)以6m/min的走线速度，先在一浴浸胶液中进行室温表面浸渍处理6s，再于140℃的烘箱中烘干4min，制得一浴浸渍处理织物；
b2)采用二浴浸胶液对改性织物进行室温表面二浴浸渍处理6s，再于210℃的烘箱中固化4min，制得浸胶纤维织物。
将实施例1-9以及对比例1-3所得浸胶纤维织物按照以上方法制备H抽出力试验样条、剥离力试验样条以及帘线拉断强度试样，分别测试H抽出力、剥离力及帘线拉断强度，结果示于表2：
表2 实施例1-9制得的浸胶纤维织物与传统RFL浸胶液制备的浸胶纤维织物的粘合性能对照表
Figure PCTCN2020099972-appb-000004
由表2可知，本发明浸渍体系处理纤维与橡胶之间的粘合性能，略优于RFL体系处理效果(实施例1、2、3相比对比例1、2、3高出5％左右)，纤维的拉断强度变化较小。
使用本发明的环保型二浴法纤维浸渍处理体系制备的浸胶纤维织物粘合效果超过使用RFL体系制得的浸胶纤维织物，且本发明制得的浸胶纤维织物强度没有较大损失。
实施例10 环保型二浴法纤维浸渍处理体系及其制备方法和应用
1)环保型二浴法纤维浸渍处理体系及其制备方法
环保型二浴法纤维浸渍处理体系，由一浴浸胶液和二浴浸胶液构成，体系的制备方法如下：
a1)称取1.5kg苹果多酚及0.5kg茶多酚，作为酚类化合物A 1；
称取3.0kg氧化石墨烯，作为填料F 1；
将酚类化合物A 1和填料F 1加至300kg去离子水中，室温均匀搅拌1h，制得一浴浸 胶液。
a2)称取4kg丙三醇缩水甘油醚和2kg的1,4-丁二醇二缩水甘油醚，作为环氧树脂B 1；
称取0.3kg超支化聚乙烯亚胺和0.2kg聚酰胺胺，作为胺类化合物C 1；
称取50kg重量百分比为40％的丁吡胶乳和50kg重量百分比为40％丁腈胶乳，作为橡胶胶乳D 1；
将环氧树脂B 1、胺类化合物C 1、橡胶胶乳D 1加至100kg去离子水中，室温搅拌2h，使之充分溶解后，制得二浴浸胶液。
上述一浴浸胶液和二浴浸胶液，构成用于制备浸胶纤维织物的环保型二浴法纤维浸渍处理体系。
2)环保型二浴法纤维浸渍处理体系的应用
b1)取尼龙帘线(1870dtex/2)以6m/min的走线速度在一浴浸胶液中进行室温表面浸渍处理6s，再于140℃的烘箱中烘干4min，制得织物M 1；
b2)织物M 1于二浴浸胶液中进行室温表面浸渍处理6s，再于210℃的烘箱中固化4min，制得浸胶纤维织物。
实施例11-17 环保型二浴法纤维浸渍处理体系及其制备方法和应用
实施例11-17分别为一种环保型二浴法纤维浸渍处理体系及其制备方法和应用，它们的步骤与实施例10基本相同，将填料和去离子水加入烧杯中，将改性剂/乙醇(改性剂/乙醇体积比2:1，乙醇(纯度≥95wt％))的混合溶液(改性剂用量为填料用量的10wt％)缓慢加入填料和去离子水的混合溶液中，进行超声搅拌，超声设备的功率为400W，超声搅拌的时间为1h，得到分散的改性纳米填料。
其他不同工艺参数之处，详见表3，其中：
氧化石墨烯：购自常州第六元素材料科技股份有限公司，型号：SE2430W，固含量(％)：43±5，pH：1.5-1.8，黏度(Pa·S)：1.5-5.0，氧碳摩尔比O/C：0.6±0.1；
凹凸棒石：购自江苏圣一纳米科技有限公司，提纯601型；
纳米二氧化硅：购自西亚化学科技(山东)有限公司，纯度：＞99.5％，平均粒径：15±5nm)
表3 实施例11-17中各项工艺参数一览表
Figure PCTCN2020099972-appb-000005
Figure PCTCN2020099972-appb-000006
Figure PCTCN2020099972-appb-000007
实施例10、11、12添加了未表面改性的填料，而实施例13、14、15添加了表面改性的填料，实施例16、17添加了表面改性的混合填料。实施例11-17其它部分的内容，与实施例10相同。
将实施例10-17物按照以上方法制备H抽出力试验样条、剥离力试验样条以及帘线拉断强度试样，分别测试H抽出力、剥离力及帘线拉断强度，结果示于表4：
表4 实施例10-17制得的浸胶纤维织物性能数据
Figure PCTCN2020099972-appb-000008
由表3可知，实施例10、11、12添加了未改性的填料，而实施例13、14、15添加了改性的填料，实施例16、17添加了改性的混合填料。由表2和4数据可以看出添加了未改性填料的浸渍体系的H抽出力、剥离力比对比例1，2，3高出10～15％，纤维的拉断强度变化很小，而添加了经过改性填料的浸渍体系的H抽出力、剥离力比对比例1，2，3高出15～20％，这是由于表面处理过后的填料能够分散的更加均匀，更加有利于提高处理纤维与橡胶之间的粘合性能。同时，添加了未改性填料和浸渍体系和添加了改性填料的浸渍体系的H抽出力、剥离力比未添加填料的实施例1，2，3分别高出了5～10％，10～15％，表明在本发明浸渍体系中加入纳米填料可以进一步提高处理纤维与橡胶之间的粘合性能，明显优于RFL体系及本发明未加纳米填料浸渍体系的处理效果。此外，本发明的环保二浴纤维浸渍处理系统制备的浸渍纤维织物的粘合效果也比RFL系统制备的浸渍纤维织物的粘合效果更好，且浸渍纤维织物的拉断强度没有明显变化。

Claims (14)

  1. 一种环保型二浴法纤维浸渍处理体系，包括一浴浸胶液和二浴浸胶液；
    所述一浴浸胶液包括：1)酚类化合物和水；或者2)酚类化合物、填料和水；
    所述二浴浸胶液包括：环氧树脂、胺类化合物、橡胶胶乳和水。
  2. 根据权利要求1所述的环保型二浴法纤维浸渍处理体系，其特征在于，
    以重量份数计，所述一浴浸胶液包括：0.5-20份酚类化合物、0-30份填料和295-305份水；
    以重量份数计，所述二浴浸胶液包括为：2-25份环氧树脂、0.2-15份胺类化合物、80-220份橡胶胶乳和95-105份水。
  3. 根据权利要求1或2所述的环保型二浴法纤维浸渍处理体系，其特征在于，所述酚类化合物为多酚化合物，优选选自覆盆子多酚、山柰酚、大黄酚、苹果多酚、葡萄多酚、石榴皮多酚、飞扬草多酚、茶多酚和儿茶酚中的一种或两种以上。
  4. 根据权利要求1-3中任一项所述的环保型二浴法纤维浸渍处理体系，其特征在于，所述环氧树脂为双酚A型环氧树脂、环氧化线性酚醛树脂、乙二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、1,2-丙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、1,4-丁二醇二缩水甘油醚、二缩水甘油醚、丙三醇缩水甘油醚、三羟甲基丙烷缩水甘油醚、四酚基乙烷四缩水甘油醚环氧树脂、间苯二酚双缩水甘油醚型环氧树脂和双间苯二酚缩甲醛四缩水甘油醚中的一种或两种以上。
  5. 根据权利要求1-4中任一项所述的环保型二浴法纤维浸渍处理体系，其特征在于，所述胺类化合物为超支化或大分子胺类化合物，优选选自超支化聚酰胺、超支化聚乙烯亚胺、超分子聚氧乙烯胺、聚氧乙烯双胺和聚酰胺-胺中的一种或两种以上。
  6. 根据权利要求1-5中任一项所述的环保型二浴法纤维浸渍处理体系，其特征在于，所述橡胶胶乳为丁苯胶乳、丁吡胶乳、丁苯吡胶乳、丁腈胶乳、氯丁胶乳、氯磺化聚乙烯胶乳和天然胶乳中的一种或两种以上；和/或所述橡胶胶乳的固含量为30-50wt％。
  7. 根据权利要求2-6中任一项所述的环保型二浴法纤维浸渍处理体系，其特征在于，所述填料的重量份数为0.5-20份；
    所述填料选自凹凸棒石、纳米纤维素、埃洛石、氧化石墨烯、蒙脱石、纳米二氧化硅、炭黑、碳纳米管、纳米芳纶纤维、玄武岩纤维、纳米晶须、云母、高岭土、水滑石，纳米二氧化钛、纳米氧化锌、纳米氧化铁、纳米氧化钙和纳米碳酸钙的一种或两种以上。
  8. 根据权利要求2-7中任一项所述的环保型二浴法纤维浸渍处理体系，其特征在于， 所述填料为经表面改性剂处理的填料；
    优选地，所述表面改性剂选自氨基硅烷偶联剂、环氧基硅烷偶联剂、烷基硅烷偶联剂、异氰酸酯基硅烷偶联剂和聚醚硅烷偶联剂的一种或两种以上；更优选地，所述表面改性剂选自3-氨基丙基三乙氧基硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、双-[γ-(三乙氧基硅)丙基]四硫化物和乙烯基三乙氧基硅烷中一种或两种以上。
  9. 一种用于制备权利要求1-8中任一项所述的环保型二浴法纤维浸渍处理体系的方法，包括以下步骤：
    a1)将酚类化合物与水和任选地填料混合，以得到所述的一浴浸胶液；
    a2)将环氧树脂、胺类化合物和橡胶胶乳与水混合，以得到所述的二浴浸胶液。
  10. 权利要求1-8中任一项所述的环保型二浴法纤维浸渍处理体系在制备浸胶纤维织物中的应用。
  11. 一种浸胶纤维织物的制备方法，其使用权利要求1-8中任一项所述的环保型二浴法纤维浸渍处理体系处理纤维织物。
  12. 根据权利要求10或11所述的应用或制备方法，其特征在于，包括如下步骤：
    b1)将纤维于所述环保型二浴法纤维浸渍处理体系的一浴浸胶液中进行表面浸渍处理和烘干，制得织物M；
    b2)将织物M于所述环保型二浴法纤维浸渍处理体系的二浴浸胶液中进行表面浸渍处理和固化，制得浸胶纤维织物。
  13. 根据权利要求12所述的应用或制备方法，其特征在于，步骤b1)和b2)中，表面浸渍处理的条件包括：处理温度为15-35℃，处理时间为1-15s；
    步骤b1)中，所述纤维为纤维帘线，所述表面浸渍处理包括将纤维帘线浸入一浴浸胶液中进行走线，走线速度为4-10m/min；
    步骤b1)中，烘干的温度为120-160℃、时间为1-5min；
    步骤b2)中，固化的温度为160-250℃、时间为1-5min。
  14. 根据权利要求11-13中任一项所述的应用或制备方法，其特征在于
    所述纤维选自人造丝、尼龙6、尼龙66、间位或对位芳纶纤维、聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚酰亚胺、碳纤维以及上述纤维的混编加捻帘线；
    所述纤维的形式选自单丝、束丝、加捻帘线、帆布和帘子布。
PCT/CN2020/099972 2020-07-02 2020-07-02 环保型二浴法纤维浸渍处理体系及其制备方法和应用及浸胶纤维织物的制备方法 WO2022000432A1 (zh)

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