CN110904688A - Environment-friendly impregnation system for fiber surface treatment and preparation method thereof - Google Patents
Environment-friendly impregnation system for fiber surface treatment and preparation method thereof Download PDFInfo
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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
- 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
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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
- 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
- D06M11/73—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 carbon or compounds thereof
- D06M11/74—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 carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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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
- 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
- D06M11/77—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 silicon or compounds thereof
- D06M11/79—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 silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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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
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
Abstract
The invention discloses an environment-friendly dipping system for fiber surface treatment and a preparation method thereof. The dipping system comprises 100 parts of deionized water, 5-50 parts of maleic anhydride grafted polyolefin, 1-10 parts of curing agent, 1-10 parts of nano filler and 50-200 parts of rubber latex. The invention adopts an environment-friendly dipping system, nano-filler with better water dispersibility is added in the treatment process of dipping solution, the nano-filler can be well dispersed in the solution by a certain dispersion method, simultaneously, the used nano-filler and the dipping solution have certain reactivity, the improved novel environment-friendly dipping system is used for dipping the fiber cord, a nano-reinforced interface structure can be formed between the fiber and the rubber, a reinforced and toughened interface phase is constructed, the stress is effectively and uniformly transmitted from a matrix to the fiber, the mechanical property of the composite material is improved, and the adhesive strength is effectively improved.
Description
Technical Field
The invention belongs to the field of fiber dipping, and particularly relates to a novel environment-friendly dipping system for fiber surface treatment and a preparation method thereof.
Background
The fiber-rubber composite material is formed by combining a reinforced fiber framework material and a rubber matrix, wherein the good elasticity of the rubber matrix is used for bearing large deformation generated when the composite material is stressed, and the fiber framework material is used for resisting damage of stress to the composite material due to higher strength and rigidity of the fiber framework material. Because the rigidity of the fiber is combined with the elasticity of the rubber, the product has the excellent performances of high strength, high modulus, impact resistance, tear resistance and the like. The fiber rubber composite material is widely used for high-speed high-load automobile/airplane tires, high-pressure-resistant special rubber tubes, high-strength special rubber conveying belts and the like. In the fiber/rubber composite material, the quality of the adhesive property between the fiber framework material and the rubber interface plays a decisive role in the safety performance and the service life of the rubber product.
The traditional method for industrially obtaining firm adhesion between fiber and rubber is resorcinol-formaldehyde-latex (RFL) dipping, but resorcinol and formaldehyde in the RFL dipping formula have great harm to the health and the production environment. As early as 2004, the International agency for research on cancer (IARC) of the world health organization listed it as a carcinogen, easily causing leukemia. In recent years, a large number of reports are made on research on resorcinol removal and formalization of a fiber framework material dipping system at home and abroad, but the system has the problem that an interface layer between a fiber framework material and rubber is easy to damage, so that the adhesive property of a composite material is slightly lower than that of an RFL dipping system, and the application value is influenced.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a novel environment-friendly impregnation system for fiber surface treatment. A small amount of nano filler dispersed well in water is added into the novel environment-friendly gum dipping solution to reinforce the interface layer with higher toughness. By constructing the interface phase for strengthening and toughening, the stress is effectively and uniformly transferred from the matrix to the fiber, the mechanical property of the composite material is improved, and the bonding strength is effectively improved.
The invention aims to provide an environment-friendly impregnation system for fiber surface treatment, which is prepared from the following raw materials in parts by weight:
the grafting rate of the maleic anhydride grafted polyolefin is preferably 10% -30%, and the molecular weight is preferably 3000-10000.
The maleic anhydride grafted polyolefin is preferably at least one of maleic anhydride grafted polybutadiene, maleic anhydride grafted polyisoprene and maleic anhydride grafted styrene-butadiene binary copolymer.
The accelerator can be imidazole accelerator and/or tertiary amine accelerator commonly used in the field, and preferably at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 4-dimethylaminopyridine and dimethylaminomethylalkane.
The nano filler is preferably at least one of attapulgite, montmorillonite, graphene oxide and clay.
The rubber latex is preferably at least one of butadiene-pyridine latex, butadiene-styrene latex, butadiene-pyridine latex, chloroprene latex or butyronitrile latex. The solid content of the rubber latex is 20-40%.
The fiber cord is preferably a hybrid cord of one or more than two of cotton fiber cord, nylon cord, polyamide cord, polyester cord, aramid cord and ultra-high molecular weight polyethylene fiber cord.
A small amount of nano filler is added in the preparation process of the impregnation system, and the nano filler can be well dispersed in the solution by a certain dispersion method, so that a nano reinforced interface structure is formed between the fiber and the rubber, and the adhesive property of the fiber and the rubber is enhanced.
The invention also aims to provide a preparation method of the environment-friendly dipping system for treating the surface of the fiber, which comprises the following steps:
adding maleic anhydride grafted polyolefin into deionized water, stirring, adding a curing agent, uniformly stirring at normal temperature to obtain uniform reaction liquid, dissolving nano-filler in deionized water to prepare aqueous solution, then adding the aqueous solution of the nano-filler into the reaction liquid, continuously stirring, finally adding rubber latex, and stirring to obtain the environment-friendly dipping system.
Preferably, the preparation method comprises the following steps: adding the maleic anhydride grafted polyolefin into deionized water, stirring for 10-30min to fully dissolve the maleic anhydride grafted polyolefin, continuing to add the curing agent, and uniformly stirring at normal temperature for 1-3 h to obtain a uniform reaction solution; dissolving the nano filler in deionized water, stirring for 10-60 min to prepare a certain aqueous solution, adding the aqueous solution of the nano filler into the reactant, and continuously stirring for 1 h; and finally, adding latex, and continuously stirring for 1-5 hours at normal temperature to obtain the environment-friendly dipping system.
The dispersion method of the nano filler is selected from at least one of the following modes: mechanical agitation, ultrasonic agitation, and the like.
The method for dipping the fiber cord using the eco-friendly dipping system of the present invention may be a method commonly used in the art, and preferably, the dipping is performed using the following process:
placing the fiber cord into the dipping system for dipping, and dipping for 1-5 min at room temperature; and then drying the fiber cord in an oven at 110-160 ℃ for 1-15 min, and curing the fiber cord at 180-230 ℃ for 1-15 min to attach the improved novel environment-friendly dipping solution to the surface of the fiber cord.
The rubber latex selected by the invention is an excellent adhesive for synthetic fibers and rubber products; the selected nano filler is derived from industrial products and does not need to be prepared by self, and the surface of the nano filler contains a plurality of active groups such as: the active groups can react with acid anhydride groups in the environment-friendly dipping solution, so that a nano-reinforced interface structure can be formed between the fiber and the rubber, and the bonding performance between the fiber and the rubber is enhanced.
The impregnation system disclosed by the invention is green and pollution-free, the selected nano filler is wide in source, low in price and simple in preparation process of the impregnation liquid, the improved novel environment-friendly impregnation liquid is good in stability, the viscosity cannot be greatly increased after the novel environment-friendly impregnation liquid is placed at room temperature for a long time, and the long-term storage and transportation of the impregnation liquid in the impregnation production process of the fiber framework material are facilitated.
The advantages and the characteristics of the invention are as follows:
1. the raw materials and the nano filler used in the gum dipping solution are green and pollution-free, are beneficial to the environment and are harmless to human bodies.
2. The nano filler provided by the invention is wide in source, low in price and water-soluble, and the viscosity of the impregnation liquid cannot be greatly increased after the impregnation liquid is placed at room temperature for a long time, so that the long-term storage and transportation of the impregnation liquid in the impregnation production process of the fiber framework material are facilitated.
3. The preparation of the dipping solution and the fiber dipping process are simple, the process is short, and the industrial production is facilitated.
Detailed Description
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention. Various modifications and improvements may be made by those skilled in the art based on the basic idea of the invention, but they are within the scope of the invention as long as they do not depart from the basic idea of the invention.
The rubber latex selected by the embodiment of the invention is purchased from Jiangsu inferior Tai chemical company Limited (the solid content of the rubber latex is 20-40%); maleic anhydride grafted polybutadiene was purchased ex-situ from Cray Valley, usa; maleic anhydride grafted polyisoprene available from Sigma-Aldrich; maleic anhydride grafted styrene-butadiene copolymers are available from shell corporation, usa; the other raw materials are all obtained in the market.
Example 1
A novel environment-friendly dipping system for fiber surface treatment is characterized by comprising the following components in parts by weight: deionized water: 100 parts of (A); maleic anhydride grafted polyolefin: 15 parts (10 parts of maleic anhydride grafted polybutadiene and 5 parts of maleic anhydride grafted polyisoprene); 2 parts of curing agent (1 part of 2-methylimidazole and 1 part of 2-ethyl-4-methylimidazole); nano-filler: 3 parts (2 parts of attapulgite and 1 part of graphene oxide); rubber latex: 100 parts of butyl pyridine latex and 50 parts of butadiene pyridine latex. During the preparation process of the dipping solution, the nano filler can be well dispersed in the solution by a certain dispersion method, a nano reinforced interface structure is formed between the fiber and the rubber, and the adhesive property between the fiber and the rubber is enhanced.
The preparation process of the gum dipping solution comprises the following steps:
(1) adding the maleic anhydride grafted polyolefin with the amount into deionized water, stirring for 10min to fully dissolve the maleic anhydride grafted polyolefin, continuing adding the curing agent, and uniformly stirring at normal temperature for 2h to obtain a uniform reaction solution; dissolving the nano filler in deionized water, stirring (ultrasonic stirring) for 20min to prepare a certain aqueous solution, then adding the aqueous solution of the nano filler into the reactant, and continuing stirring for 1 h. Finally, adding latex, and continuously stirring for 5 hours at normal temperature to obtain the novel environment-friendly gum dipping solution;
(2) soaking a nylon 66 fiber cord (nylon 66 cord, Hippocampus fabric development Limited, 1400dtex/2, twist 380T/m) in a dipping solution at room temperature for 2 min; then drying in a drying oven at 120 ℃ for 10min, and curing at 200 ℃ for 5min to attach the improved novel environment-friendly dipping solution to the surface of the fiber cord.
Extraction test specimen preparation: referring to the standard GB/T9101-2002, a standard adhesive (provided by Hill mountain horse cord fabric development Co., Ltd.) is completely coated on a dipping cord to prepare a drawn sample, and finally the drawn sample is placed on a flat plate vulcanizing machine for vulcanization, wherein the vulcanization temperature is 136 ℃, the vulcanization pressure is 15MPa, and the vulcanization time is 50 min.
Example 2
A novel environment-friendly dipping system for fiber surface treatment is characterized by comprising the following components in parts by weight: deionized water: 100 parts of (A); maleic anhydride grafted polyolefin: 15 parts (10 parts of maleic anhydride grafted polybutadiene and 5 parts of maleic anhydride grafted polyisoprene); 2 parts of curing agent (1 part of 2-methylimidazole and 1 part of 2-ethyl-4-methylimidazole); nano-filler: 2 parts (2 parts of attapulgite); rubber latex: 50 parts (butyl Piezin latex 50 parts).
The preparation process of the gum dipping solution comprises the following steps:
(1) adding the maleic anhydride grafted polyolefin with the amount into deionized water, stirring for 10min to fully dissolve the maleic anhydride grafted polyolefin, continuing adding the curing agent, and uniformly stirring at normal temperature for 2h to obtain a uniform reaction solution; dissolving the nano filler in deionized water, stirring (ultrasonic stirring) for 20min to prepare a certain aqueous solution, then adding the aqueous solution of the nano filler into the reactant, and continuing stirring for 1 h. Finally, adding latex, and continuously stirring for 5 hours at normal temperature to obtain the novel environment-friendly gum dipping solution;
(2) soaking a nylon 66 fiber cord (nylon 66 cord, Hippocampus fabric development Limited, 1400dtex/2, twist 380T/m) in a dipping solution at room temperature for 2 min; then drying in a drying oven at 120 ℃ for 10min, and curing at 200 ℃ for 5min to attach the improved novel environment-friendly dipping solution to the surface of the fiber cord.
Extraction test specimen preparation: referring to the standard GB/T9101-2002, a standard adhesive (provided by Hill mountain horse cord fabric development Co., Ltd.) is completely coated on a dipping cord to prepare a drawn sample, and finally the drawn sample is placed on a flat plate vulcanizing machine for vulcanization, wherein the vulcanization temperature is 136 ℃, the vulcanization pressure is 15MPa, and the vulcanization time is 50 min.
Example 3
A novel environment-friendly dipping system for fiber surface treatment is characterized by comprising the following components in parts by weight: deionized water: 100 parts of (A); maleic anhydride grafted polyolefin: 30 parts (20 parts of maleic anhydride grafted polybutadiene and 10 parts of maleic anhydride grafted styrene-butadiene binary copolymer); 6 parts of curing agent (4 parts of 2-methylimidazole and 2 parts of 4-dimethylaminopyridine); nano-filler: 5 parts of montmorillonite and 2 parts of graphene oxide; rubber latex: 150 parts (80 parts of butadiene-pyridine latex, 40 parts of butadiene-styrene latex and 30 parts of butadiene-pyridine latex). During the preparation process of the dipping solution, the nano filler can be well dispersed in the solution by a certain dispersion method, a nano reinforced interface structure is formed between the fiber and the rubber, and the adhesive property between the fiber and the rubber is enhanced.
The preparation process of the gum dipping solution comprises the following steps:
(1) adding the maleic anhydride grafted polyolefin with the amount into deionized water, stirring for 25min to fully dissolve the maleic anhydride grafted polyolefin, continuing adding the curing agent, and uniformly stirring at normal temperature for 3h to obtain a uniform reaction solution; dissolving the nano filler in deionized water, stirring (physically stirring) for 60min to prepare a certain aqueous solution, then adding the aqueous solution of the nano filler into the reactant, and continuing stirring for 1 h. Finally, adding latex, and continuously stirring for 5 hours at normal temperature to obtain the novel green environmental-friendly gum dipping solution;
(2) dipping the nylon 66 fiber cord in a dipping solution for 3min at room temperature; then drying the fiber cord in an oven at 150 ℃ for 8min, and curing the fiber cord at 230 ℃ for 2min to attach the improved novel environment-friendly dipping solution to the surface of the fiber cord.
Extraction test specimen preparation: referring to the standard GB/T9101-2002, a standard adhesive (provided by Hill mountain horse cord fabric development Co., Ltd.) is completely coated on a dipping cord to prepare a drawn sample, and finally the drawn sample is placed on a flat plate vulcanizing machine for vulcanization, wherein the vulcanization temperature is 136 ℃, the vulcanization pressure is 15MPa, and the vulcanization time is 50 min.
Example 4
A novel environment-friendly dipping system for fiber surface treatment is characterized by comprising the following components in parts by weight: deionized water: 100 parts of (A); maleic anhydride grafted polyolefin: 50 parts (30 parts of maleic anhydride grafted polybutadiene and 20 parts of maleic anhydride grafted styrene-butadiene binary copolymer); 8 parts of curing agent (5 parts of 2-methylimidazole and 3 parts of 4-dimethylaminopyridine); nano-filler: 5 parts of montmorillonite and 2 parts of graphene oxide; rubber latex: 150 parts (80 parts of butadiene-pyridine latex, 40 parts of butadiene-styrene latex and 30 parts of butadiene-pyridine latex).
The preparation process of the gum dipping solution comprises the following steps:
(1) adding the maleic anhydride grafted polyolefin with the amount into deionized water, stirring for 25min to fully dissolve the maleic anhydride grafted polyolefin, continuing adding the curing agent, and uniformly stirring at normal temperature for 3h to obtain a uniform reaction solution; dissolving the nano filler in deionized water, stirring (physically stirring) for 60min to prepare a certain aqueous solution, then adding the aqueous solution of the nano filler into the reactant, and continuing stirring for 1 h. Finally, adding latex, and continuously stirring for 5 hours at normal temperature to obtain the novel green environmental-friendly gum dipping solution;
(2) dipping the nylon 66 fiber cord in a dipping solution for 3min at room temperature; then drying the fiber cord in an oven at 150 ℃ for 8min, and curing the fiber cord at 230 ℃ for 2min to attach the improved novel environment-friendly dipping solution to the surface of the fiber cord.
Extraction test specimen preparation: referring to the standard GB/T9101-2002, a standard adhesive (provided by Hill mountain horse cord fabric development Co., Ltd.) is completely coated on a dipping cord to prepare a drawn sample, and finally the drawn sample is placed on a flat plate vulcanizing machine for vulcanization, wherein the vulcanization temperature is 136 ℃, the vulcanization pressure is 15MPa, and the vulcanization time is 50 min.
Example 5
A novel environment-friendly dipping system for fiber surface treatment is characterized by comprising the following components in parts by weight: deionized water: 100 parts of (A); maleic anhydride grafted polyolefin: 8 parts of (4 parts of maleic anhydride grafted polyisoprene and 4 parts of maleic anhydride grafted styrene-butadiene binary copolymer); 2 parts of curing agent (0.5 part of 4-dimethylamino pyridine and 1.5 parts of dimethylamino dimethane); nano-filler: 8 parts (6 parts of attapulgite and 2 parts of clay); rubber latex: 180 parts (butyl pyridine latex 90 parts, butyronitrile latex 90 parts). During the preparation process of the dipping solution, the nano filler can be well dispersed in the solution by a certain dispersion method, a nano reinforced interface structure is formed between the fiber and the rubber, and the adhesive property between the fiber and the rubber is enhanced.
The preparation process of the gum dipping solution comprises the following steps:
(1) adding the maleic anhydride grafted polyolefin with the amount into deionized water, stirring for 20min to fully dissolve the maleic anhydride grafted polyolefin, continuing adding the curing agent, and uniformly stirring at normal temperature for 1h to obtain a uniform reaction solution; dissolving the nano filler in deionized water, stirring (ultrasonic stirring for 10min, physical stirring for 20min) for 30min to prepare a certain aqueous solution, then adding the aqueous solution of the nano filler into the reactant, and continuing stirring for 1 h. Finally, adding latex, and continuously stirring for 2h at normal temperature to obtain the novel green environmental-friendly gum dipping solution;
(2) dipping the nylon 66 fiber cord in a dipping solution for 2min at room temperature; then drying the fiber cord in an oven at 130 ℃ for 8min, and curing the fiber cord at 220 ℃ for 4min to attach the improved novel environment-friendly dipping solution to the surface of the fiber cord.
Extraction test specimen preparation: referring to the standard GB/T9101-2002, a standard adhesive (provided by Hill mountain horse cord fabric development Co., Ltd.) is completely coated on a dipping cord to prepare a drawn sample, and finally the drawn sample is placed on a flat plate vulcanizing machine for vulcanization, wherein the vulcanization temperature is 136 ℃, the vulcanization pressure is 15MPa, and the vulcanization time is 50 min.
Comparative example 1
Traditional RFL dipping solution
Gum dipping treatment: the nylon 66 fiber cord (provided by Hill mountain magic horse cord development Co., Ltd.) dipped by the traditional RFL dipping system is directly used.
Extraction test specimen preparation: referring to the standard GB/T9101-2002, a standard adhesive (provided by Hill mountain horse cord fabric development Co., Ltd.) is completely coated on a dipping cord to prepare a drawn sample, and finally the drawn sample is placed on a flat plate vulcanizing machine for vulcanization, wherein the vulcanization temperature is 136 ℃, the vulcanization pressure is 15MPa, and the vulcanization time is 50 min.
Comparative example 2
Unmodified environmental-friendly gum dipping solution: the formula is characterized by comprising the following components in parts by weight: deionized water: 100 parts of (A); maleic anhydride grafted polyolefin: 15 parts (10 parts of maleic anhydride grafted polybutadiene and 5 parts of maleic anhydride grafted polyisoprene); 2 parts of curing agent (1 part of 2-methylimidazole and 1 part of 2-ethyl-4-methylimidazole); rubber latex: 50 parts (butyl Piezin latex 50 parts).
Adding the maleic anhydride grafted polyolefin with the amount into deionized water, stirring for 10min to fully dissolve the maleic anhydride grafted polyolefin, continuing adding the curing agent, and uniformly stirring at normal temperature for 2h to obtain a uniform reaction solution; adding latex, and continuously stirring for 5 hours at normal temperature to obtain the environment-friendly dipping solution;
(2) dipping the nylon 66 fiber cord in a dipping solution for 2min at room temperature; then drying the fiber cord in a drying oven at 120 ℃ for 10min, and curing the fiber cord at 200 ℃ for 5min to ensure that the improved environment-friendly dipping solution is attached to the surface of the fiber cord.
Extraction test specimen preparation: referring to the standard GB/T9101-2002, a standard adhesive (provided by Hill mountain horse cord fabric development Co., Ltd.) is completely coated on a dipping cord to prepare a drawn sample, and finally the drawn sample is placed on a flat plate vulcanizing machine for vulcanization, wherein the vulcanization temperature is 136 ℃, the vulcanization pressure is 15MPa, and the vulcanization time is 50 min.
The using equipment is conventional production equipment.
Table 1: comparison of adhesive Properties of samples obtained in examples of the present invention and comparative examples
The material preparation and test method of the embodiment of the invention comprises the following steps: the H extraction test sample is prepared according to the regulations of GB/T9101-2002 national standard, and the H extraction force adhesive property and the cord breaking strength are tested according to the regulations of GB/T2942-2009 national standard.
As can be seen from the data in the table above, the adhesion performance between the cord treated by the environment-friendly dipping solution system and the rubber is slightly insufficient and the strength difference is not large compared with the cord treated by the RFL dipping solution; when the formula of the fiber cord thread dipping solution is modified by a nano interface strengthening method, although the nano filler is added into the dipping solution, the filler has good dispersibility, the tensile strength of the cord thread is not obviously influenced, the adhesive property of the cord thread can be improved, the level of an RFL system is reached, meanwhile, the process is simple, and the production efficiency is not influenced.
In summary, the nano filler with better water dispersibility is added in the treatment process of the dipping solution, so that the nano filler is well dispersed in the solution, the improved dipping solution is used for dipping the fiber cord, a nano reinforced interface structure can be formed between the fiber and the rubber, and the stress is effectively and uniformly transmitted from the matrix to the fiber by constructing a reinforced and toughened interface phase, so that the mechanical property of the composite material is improved, and the adhesive strength is effectively improved. And the excellent performances of the rubber matrix and the framework material are not lost, and the raw materials selected by the dipping solution are nontoxic and pollution-free, thereby being more beneficial to implementation and application.
Claims (9)
1. The environment-friendly impregnation system for the fiber surface treatment is characterized by being prepared from the following raw materials in parts by weight:
2. the impregnation system according to claim 1, characterized in that it is prepared from raw materials comprising, in parts by weight:
3. milk infusion system according to claim 1 or 2, characterized in that:
the nano filler is selected from at least one of attapulgite, montmorillonite, graphene oxide and clay.
4. Impregnation system according to claim 1 or 2, characterized in that:
the solid content of the rubber latex is 20-40%, and the rubber latex is selected from at least one of butadiene-pyridine latex, butadiene-styrene pyridine latex, chloroprene latex and butyronitrile latex.
5. Impregnation system according to claim 1 or 2, characterized in that:
the grafting rate of the maleic anhydride grafted polyolefin is 10% -30%, the molecular weight is 3000-10000, and the maleic anhydride grafted polyolefin is at least one of maleic anhydride grafted polybutadiene, maleic anhydride grafted polyisoprene and maleic anhydride grafted styrene-butadiene binary copolymer.
6. Impregnation system according to claim 1 or 2, characterized in that:
the curing agent is at least one selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 4-dimethylaminopyridine and dimethylamino-dimethane.
7. Impregnation system according to claim 1 or 2, characterized in that:
the fiber cord is a mixed knitting cord of one or more than two of cotton fiber cord, nylon cord, polyamide cord, polyester cord, aramid cord and ultra-high molecular weight polyethylene fiber cord.
8. A method for preparing the environment-friendly dipping system for fiber surface treatment according to any one of claims 1 to 7, characterized by comprising the following steps:
adding maleic anhydride grafted polyolefin into deionized water, stirring, adding a curing agent, uniformly stirring at normal temperature to obtain uniform reaction liquid, dissolving nano-filler in deionized water to prepare aqueous solution, then adding the aqueous solution of the nano-filler into the reaction liquid, continuously stirring, finally adding rubber latex, and stirring to obtain the environment-friendly dipping system.
9. The method for preparing an impregnation system according to claim 8, characterized in that:
the dispersion method of the nano filler is at least one of mechanical stirring and ultrasonic stirring.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112160169A (en) * | 2020-09-30 | 2021-01-01 | 北京化工大学 | Environment-friendly fiber dipping solution, preparation method and application |
| WO2021000918A1 (en) * | 2019-07-03 | 2021-01-07 | 北京化工大学 | Composition for surface treatment of fibers and fiber treatment method |
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| CN112160169A (en) * | 2020-09-30 | 2021-01-01 | 北京化工大学 | Environment-friendly fiber dipping solution, preparation method and application |
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