A novel modified RF resin emulsion for the fiber skeleton material dipping solution RFL and its preparation method

Abstract

The present invention provides a modified thermoplastic RF resin for an RFL dipping solution for fiber skeleton materials, a modified thermosetting RF resin solution for an RFL dipping solution for fiber skeleton materials, a modified RF resin emulsion for an RFL dipping solution for fiber skeleton materials, and a preparation method and application thereof. The modified RF resin emulsion prepared by the present invention can not only reduce the volatilization of resorcinol monomers during the operation process, but also improve the adhesion between rubber and fiber and the heat aging performance of the fiber skeleton material-reinforced rubber material at the same time. This modified RF resin emulsion can be directly mixed with latex to prepare a fiber skeleton material dipping solution RFL, which has better adhesion performance and aging resistance than the existing RFL, and thus has broad application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical field of RFL dipping solutions, and relates to a modified thermoplastic RF resin for RFL dipping solutions for fiber skeleton materials, a modified thermosetting RF resin solution for RFL dipping solutions for fiber skeleton materials, a modified RF resin emulsion for RFL dipping solutions for fiber skeleton materials, and a preparation method and application thereof. In particular, the present invention relates to a novel modified RF resin emulsion for RFL dipping solutions for fiber skeleton materials and a preparation method thereof. Background Art

[0002] With the development of China's tire industry, conveyor belt and rubber hose rubber product industries, fiber skeleton materials play a very important role in the development of the rubber industry, and mainly play the role of bearing load and maintaining the dimensional stability of products in reinforcing rubber products. In fiber / rubber composites, the adhesion performance between the fiber skeleton material and the rubber interface plays a decisive role in the safety performance and service life of rubber products.

[0003] In order to form an effective bond between fibers and rubber with very different polarities and rigidities, resorcinol-formaldehyde-latex (RFL) is used to impregnate fiber skeleton materials. In the RFL dipping layer, the functional groups on the RF resin can combine with the polar groups on the fiber surface, and at the same time, the rubber components in the cross-linked network structure of the RF resin can cross-link with the rubber matrix through co-vulcanization, so as to form an adhesive transition layer between the fiber and the rubber matrix.

[0004] At present, in the preparation of tire polyester cord fabric, the traditional RFL dipping technology (directly mixing resorcinol, formaldehyde and latex solution) is quite mature and has a low production cost. However, resorcinol and formaldehyde in the RFL dipping solution are both harmful to physical health and the production environment, and both have been included in the "Catalog of Substitutes for Toxic and Hazardous Raw Materials (Products) Encouraged by the State (2016 Edition)". At the same time, the adhesive layer prepared by traditional RFL dipping is prone to degradation under high strength, high heat and high humidity conditions, resulting in dimensional instability and low interfacial adhesion strength. Unsafe phenomena such as tire blistering, delamination and blowout will occur.

[0005] Therefore, how to find a more suitable way to solve the above problems existing in the prior art, propose an effective solution, and develop a new environmentally friendly RFL fiber surface treatment process is extremely urgent, and it is also a problem that all domestic tire suppliers in the industry need to face at present. At the same time, it is of great significance to build a beautiful ecological society. Summary of the Invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a modified thermoplastic RF resin for RFL dipping solution of fiber skeleton materials, a modified thermosetting RF resin solution for RFL dipping solution of fiber skeleton materials, a modified RF resin emulsion for RFL dipping solution of fiber skeleton materials and its preparation method and application, in particular a novel modified RF resin emulsion for RFL dipping solution of fiber skeleton materials. The present invention copolymerizes multiple monomers and emulsifies the copolymerization product to obtain a modified RF resin emulsion. Due to the introduction of copolymer monomers, antioxidants and fillers with excellent heat resistance, the obtained modified RF resin emulsion can effectively solve the problems of high toxicity, low adhesion and poor heat aging performance of the current dipping solution RFL, and the process is simple and easy to control, which is conducive to realizing industrial continuous production.

[0007] The present invention provides a modified thermoplastic RF resin for RFL dipping solution of fiber skeleton materials, which, calculated by mass fraction of raw materials, includes:

[0008]

[0009] The third monomer includes one or more of hydroquinone, catechol, tea polyphenols, tert-butylphenol, eugenol, 2,6-dimethylphenol, p-chlorophenol, biphenol, bisphenol A and bisphenol S.

[0010] Preferably, the catalyst includes one or more of hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, oxalic acid, acetic acid, p-toluenesulfonic acid, phosphotungstic acid, oxalic acid and formic acid;

[0011] The molecular weight of the methoxyalkyl diphenyl ether oligomer is 200-3000;

[0012] The modified thermoplastic RF resin is a modified thermoplastic RF resin containing a phenyl ether structure.

[0013] The present invention provides a modified thermosetting RF resin solution for RFL dipping solution of fiber skeleton materials, which, calculated by mass fraction of raw materials, includes:

[0014]

[0015] The modified thermoplastic RF resin includes the modified thermoplastic RF resin described in any one of the above technical solutions.

[0016] Preferably, the formaldehyde includes aqueous formaldehyde solution or paraformaldehyde;

[0017] The mass concentration of the aqueous formaldehyde solution is 37%;

[0018] The catalyst includes one or more of hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, oxalic acid, formic acid, acetic acid, p-toluenesulfonic acid, phosphotungstic acid, oxalic acid, ammonia water, sodium hydroxide, barium hydroxide, potassium hydroxide, magnesium hydroxide, and magnesium oxide;

[0019] The solvent includes one or more of toluene, xylene, ethylbenzene, acetone, butanone, methanol, ethanol, ethylene glycol, glycerol, environmental protection aromatic oil, and paraffin oil.

[0020] The present invention provides a modified RF resin emulsion for an RFL dipping solution of a fiber skeleton material, which, calculated by mass fraction of raw materials, includes:

[0021]

[0022] The modified thermosetting RF resin solution includes the modified thermosetting RF resin solution described in any one of the above technical solutions.

[0023] Preferably, the emulsifier includes one or more of cationic surfactants, anionic surfactants, non-ionic surfactants, and amphoteric surfactants;

[0024] The aqueous thickener is one or more of methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxyethyl cellulose, starch, gelatin, chitosan, polyvinyl alcohol, polyvinylpyrrolidone, and polyethylene oxide;

[0025] The antioxidant includes one or more of phenolic antioxidants, amine antioxidants, and heterocyclic antioxidants;

[0026] The hydrophilic filler includes one or more of titanium dioxide, silicon dioxide, montmorillonite, calcium carbonate, and talc powder;

[0027] The modifier includes one or more of aqueous phenolic aldehyde, aqueous epoxy, polyacrylamide, and polyacrylic acid.

[0028] The present invention provides a preparation method of a modified RF resin emulsion for an RFL dipping solution of a fiber skeleton material as described in any one of the above technical solutions, which is characterized by including the following steps:

[0029] 1) Mix resorcinol, methoxyalkyl diphenyl ether oligomer, a third monomer, and a catalyst, and then carry out a reaction to obtain a modified thermoplastic RF resin containing a phenyl ether structure;

[0030] 2) Continuously mix the thermoplastic RF resin containing a phenyl ether structure obtained in the above step, a solvent, formaldehyde, and a catalyst, and then carry out a reaction again to obtain a modified thermosetting RF resin solution containing a phenyl ether structure;

[0031] 3) After remixing the emulsifier, antioxidant, and the modified thermosetting RF resin solution obtained in the above step, add water for emulsification, and then add a water-based thickener, hydrophilic filler, and modifier and mix them evenly to obtain a modified RF resin emulsion.

[0032] Preferably, the reaction temperature in step 1) is 30 - 120 °C;

[0033] The reaction time in step 1) is 0.5 - 10 hours;

[0034] The re-reaction temperature in step 2) is 60 - 100 °C;

[0035] The re-reaction time in step 2) is 0.5 - 4 hours;

[0036] The emulsification method includes high-speed stirring emulsification;

[0037] The emulsification temperature is 20 - 70 °C;

[0038] The emulsification rotation speed is 1000 - 10000 r / min;

[0039] The emulsification time is 10 - 30 min.

[0040] The present invention provides an RFL dipping solution, which includes the modified RF resin emulsion described in any one of the above technical solutions or the modified RF resin emulsion prepared by the preparation method described in any one of the above technical solutions, latex, and water;

[0041] The pH value of the modified RF emulsion is 8 - 12.

[0042] The present invention also provides the application of the modified thermoplastic RF resin, the modified thermosetting RF resin solution, the modified RF resin emulsion, the modified RF resin emulsion prepared by the preparation method described in any one of the above technical solutions, or the RFL dipping solution described in the above technical solutions in the adhesion of fiber skeleton materials.

[0043] The present invention provides a modified thermoplastic RF resin for RFL dipping solution of fiber skeleton materials. Calculated by mass fraction of raw materials, it includes 100 parts by weight of resorcinol, 60 - 150 parts by weight of methoxyalkyl diphenyl ether oligomer, 0 - 20 parts by weight of a third monomer, and 0.01 - 5 parts by weight of a catalyst; the third monomer includes one or more of hydroquinone, catechol, tea polyphenol, tert-butylphenol, eugenol, 2,6-dimethylphenol, p-chlorophenol, biphenol, bisphenol A, and bisphenol S. Compared with the prior art, the present invention provides a modified thermoplastic RF resin copolymerized from multiple monomers, and then the copolymer is emulsified to obtain a modified RF emulsion, which has excellent aging resistance and does not reduce its bonding performance. The present invention first reacts a monomer with excellent heat resistance with resorcinol, and then reacts with formaldehyde to prepare a modified RF resin with excellent heat resistance. Then the modified RF resin is emulsified, and an appropriate amount of additives is added to obtain a modified RF resin emulsion. This modified RF resin emulsion can be directly mixed with latex to prepare a fiber skeleton material dipping solution RFL, which has better bonding performance and aging resistance than the existing RFL and has broad application prospects.

[0044] Based on the modified RF resin emulsion, the present invention can reduce the volatilization of resorcinol monomer during the operation process; and by the method of physical blending modification, components with excellent bonding performance, such as waterborne epoxy, are introduced to improve the bonding performance with the fiber surface. Moreover, antioxidants and hydrophilic fillers with excellent heat resistance are introduced into the resin system, which can further improve the aging resistance of the RFL dipping solution.

[0045] The present invention combines three modification methods of copolymerization modification, blending modification, and inorganic filler modification to improve the bonding performance and aging resistance of the existing RFL dipping solution. This modified RF resin emulsion can simultaneously improve the adhesion between rubber and fiber and the heat aging resistance of the fiber skeleton material reinforced rubber material, and thus can be applied to many high-end fiber skeleton material fields, such as high-performance tires, high-performance conveyor belts, etc., and will have many application fields and good application prospects.

[0046] The experimental results show that the retention rate of the bonding strength (160 °C / 180 min) of the RFL dipping solution prepared with the modified RF resin provided by the present invention is greater than 60%. Detailed Embodiments

[0047] To further understand the present invention, the preferred embodiments of the present invention will be described below in conjunction with examples. However, it should be understood that these descriptions are only for further explaining the features and advantages of the present invention and not for limiting the claims of the invention.

[0048] There are no particular restrictions on the sources of all raw materials of the present invention, and they can be purchased on the market or prepared by conventional methods well-known to those skilled in the art.

[0049] There are no particular restrictions on the purity of all raw materials of the present invention. The present invention preferably uses analytically pure or the purity requirements conventional in the field of preparing RFL dipping solutions for fiber skeleton materials.

[0050] All raw materials of the present invention, their trade names and abbreviations belong to the conventional trade names and abbreviations in the art, and each trade name and abbreviation is clear and definite within the field of its relevant uses. Those skilled in the art can purchase them from the market or prepare them by conventional methods according to the trade name, abbreviation and corresponding uses.

[0051] The present invention provides a modified thermoplastic RF resin for RFL dipping solution for fiber skeleton materials, which includes, by mass fraction of raw materials:

[0052]

[0053] The third monomer includes one or more of hydroquinone, catechol, tea polyphenols, tert-butylphenol, eugenol, 2,6-dimethylphenol, p-chlorophenol, biphenol, bisphenol A and bisphenol S.

[0054] In the present invention, the addition amount of resorcinol is 100 parts by weight.

[0055] In the present invention, the addition amount of the methoxyalkyl diphenyl ether oligomer is 60 - 150 parts by weight, can be 70 - 140 parts by weight, preferably 80 - 130 parts by weight, and more preferably 90 - 120 parts by weight.

[0056] In the present invention, the addition amount of the third monomer is 0 - 20 parts by weight, preferably 0.01 - 20 parts by weight, can be 1 - 18 parts by weight, or 5 - 15 parts by weight, or 7 - 13 parts by weight.

[0057] In the present invention, the addition amount of the catalyst is 0.01 - 5 parts by weight, can be 0.1 - 4 parts by weight, and preferably 1 - 3 parts by weight.

[0058] In the present invention, the catalyst preferably includes one or more of hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, oxalic acid, acetic acid, p-toluenesulfonic acid, phosphotungstic acid, oxalic acid and formic acid, and more preferably hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, oxalic acid, acetic acid, p-toluenesulfonic acid, phosphotungstic acid, oxalic acid or formic acid.

[0059] In the present invention, the molecular weight of the methoxyalkyl diphenyl ether oligomer is preferably 200 - 3000, more preferably 500 - 2500, and still more preferably 1000 - 2000.

[0060] In the present invention, the third monomer includes one or more of hydroquinone, catechol, tea polyphenols, tert-butylphenol, eugenol, 2,6-dimethylphenol, p-chlorophenol, biphenol, bisphenol A and bisphenol S, preferably hydroquinone, catechol, tea polyphenols, tert-butylphenol, eugenol, 2,6-dimethylphenol, p-chlorophenol, biphenol, bisphenol A or bisphenol S.

[0061] In the present invention, the modified thermoplastic RF resin is preferably a modified thermoplastic RF resin containing a phenyl ether structure.

[0062] The present invention provides a modified thermosetting RF resin solution for an RFL impregnating solution for a fiber skeleton material, which includes, by mass fraction of raw materials:

[0063]

[0064]

[0065] The modified thermoplastic RF resin includes the modified thermoplastic RF resin described in any one of the above technical solutions.

[0066] In the present invention, the addition amount of the modified thermoplastic RF resin is 100 parts by weight.

[0067] In the present invention, the addition amount of formaldehyde is 1 to 30 parts by weight, can be 5 to 25 parts by weight, and is preferably 10 to 20 parts by weight.

[0068] In the present invention, the addition amount of the catalyst is 0.01 to 5 parts by weight, can be 0.1 to 4 parts by weight, and is preferably 1 to 3 parts by weight. To distinguish from the catalyst in the aforementioned modified thermoplastic RF resin, the catalyst in the modified thermosetting RF resin solution can be a first catalyst.

[0069] In the present invention, the addition amount of the solvent is 30 to 50 parts by weight, can be 34 to 46 parts by weight, and is preferably 38 to 42 parts by weight.

[0070] In the present invention, the formaldehyde preferably includes an aqueous formaldehyde solution or paraformaldehyde.

[0071] In the present invention, the mass concentration of the aqueous formaldehyde solution is preferably 37%.

[0072] In the present invention, the catalyst preferably comprises one or more of hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, oxalic acid, formic acid, acetic acid, p-toluenesulfonic acid, phosphotungstic acid, oxalic acid, ammonia water, sodium hydroxide, barium hydroxide, potassium hydroxide, magnesium hydroxide and magnesium oxide, and more preferably hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, oxalic acid, formic acid, acetic acid, p-toluenesulfonic acid, phosphotungstic acid, oxalic acid, ammonia water, sodium hydroxide, barium hydroxide, potassium hydroxide, magnesium hydroxide or magnesium oxide.

[0073] In the present invention, the solvent preferably comprises one or more of toluene, xylene, ethylbenzene, acetone, methyl ethyl ketone, methanol, ethanol, ethylene glycol, glycerol, environmental protection aromatic oil and paraffin oil, and more preferably toluene, xylene, ethylbenzene, acetone, methyl ethyl ketone, methanol, ethanol, ethylene glycol, glycerol, environmental protection aromatic oil or paraffin oil.

[0074] The present invention provides a modified RF resin emulsion for an RFL dipping solution of a fiber skeleton material, which, calculated by mass fraction of raw materials, comprises:

[0075]

[0076]

[0077] The modified thermosetting RF resin solution comprises the modified thermosetting RF resin solution described in any one of the above technologies.

[0078] In the present invention, the addition amount of the modified thermosetting RF resin solution is 100 parts by weight.

[0079] In the present invention, the addition amount of the emulsifier is 1 to 20 parts by weight, may be 5 to 16 parts by weight, and is preferably 9 to 12 parts by weight.

[0080] In the present invention, the addition amount of the aqueous thickener is 0.2 to 5 parts by weight, may be 0.5 to 4 parts by weight, and is preferably 1 to 3 parts by weight.

[0081] In the present invention, the addition amount of the antioxidant is 1 to 8 parts by weight, may be 2 to 7 parts by weight, is preferably 3 to 6 parts by weight, and more preferably 4 to 5 parts by weight.

[0082] In the present invention, the addition amount of the hydrophilic filler is 0.5 to 5 parts by weight, may be 1 to 4 parts by weight, and is preferably 2 to 3 parts by weight.

[0083] In the present invention, the addition amount of the modifier is 1 to 10 parts by weight, may be 3 to 8 parts by weight, and is preferably 5 to 6 parts by weight.

[0084] In the present invention, the addition amount of the water is 50 to 100 parts by weight, may be 60 to 90 parts by weight, and is preferably 70 to 80 parts by weight.

[0085] In the present invention, the emulsifier preferably includes one or more of cationic surfactants, anionic surfactants, non-ionic surfactants and amphoteric surfactants, and more preferably is a cationic surfactant, anionic surfactant, non-ionic surfactant or amphoteric surfactant.

[0086] In the present invention, the aqueous thickener preferably includes one or more of methylcellulose, hydroxypropyl methylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, starch, gelatin, chitosan, polyvinyl alcohol, polyvinylpyrrolidone and polyethylene oxide, and more preferably is methylcellulose, hydroxypropyl methylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, starch, gelatin, chitosan, polyvinyl alcohol, polyvinylpyrrolidone or polyethylene oxide.

[0087] In the present invention, the antioxidant preferably includes one or more of phenolic antioxidants, amine antioxidants and heterocyclic antioxidants, and more preferably is a phenolic antioxidant, amine antioxidant or heterocyclic antioxidant.

[0088] In the present invention, the hydrophilic filler preferably includes one or more of titanium dioxide, silicon dioxide, montmorillonite, calcium carbonate and talc powder, and more preferably is titanium dioxide, silicon dioxide, montmorillonite, calcium carbonate or talc powder.

[0089] In the present invention, the modifier preferably includes one or more of aqueous phenolic aldehyde, aqueous epoxy, polyacrylamide and polyacrylic acid, and more preferably is aqueous phenolic aldehyde, aqueous epoxy, polyacrylamide or polyacrylic acid.

[0090] In order to better complete and refine the overall technical solution of the present invention, better reduce the volatilization of resorcinol monomers during the production process, and further improve the adhesion between rubber and fiber and the heat aging resistance of the fiber skeleton material reinforcing the rubber material in subsequent applications, the modified RF resin emulsion of the above-mentioned RFL dipping solution for fiber skeleton materials may specifically include the following components:

[0091] A modified RF resin emulsion for an RFL dipping solution for fiber skeleton materials, first prepare a thermoplastic RF resin containing a phenyl ether structure:

[0092] Prepare a thermoplastic RF resin containing a phenyl ether structure. The formula is based on the mass fraction of raw materials and includes:

[0093]

[0094] The third monomer includes one or more of hydroquinone, catechol, tea polyphenols, tert-butylphenol, eugenol, 2,6-dimethylphenol, p-chlorophenol, biphenol, bisphenol A and bisphenol S.

[0095] Specifically, the catalyst includes one or more of hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, oxalic acid, acetic acid, p-toluenesulfonic acid, phosphotungstic acid, oxalic acid, and formic acid.

[0096] Specifically, the preparation process of the modified thermoplastic RF resin can be the following steps:

[0097] Weigh 100 parts of resorcinol, 60 - 150 parts of methoxyalkyl diphenyl ether oligomer, 0 - 20 parts of the third monomer, and 0.01 - 5 parts of the catalyst by weight; in a reaction kettle, first add the methoxyalkyl diphenyl ether oligomer, and then add resorcinol and the third monomer into it, and stir evenly; add an appropriate amount of catalyst, react at 60 - 120 °C for 2 - 8 hours, and after the reaction is completed, cool to room temperature to obtain a thermoplastic RF resin containing a phenyl ether structure.

[0098] In the second step of the present invention, a thermosetting RF resin or a thermosetting RF resin solution containing a phenyl ether structure is prepared:

[0099] Dissolve the thermoplastic RF resin (100 parts by weight) containing a phenyl ether structure in the above step in a solvent (30 - 50 parts by weight), add formaldehyde (1 - 30 parts by weight) and a catalyst (0.01 - 5 parts by weight), and react to generate a thermosetting RF resin solution.

[0100] Specifically, the formaldehyde includes aqueous formaldehyde or paraformaldehyde.

[0101] Specifically, the mass concentration of the aqueous formaldehyde solution is 37%.

[0102] Specifically, the catalyst includes one or more of hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, oxalic acid, formic acid, acetic acid, p-toluenesulfonic acid, phosphotungstic acid, oxalic acid, ammonia water, sodium hydroxide, barium hydroxide, potassium hydroxide, magnesium hydroxide, and magnesium oxide.

[0103] Specifically, the solvent includes one or more of toluene, xylene, ethylbenzene, acetone, butanone, methanol, ethanol, ethylene glycol, glycerol, environmental protection aromatic oil, and paraffin oil.

[0104] Specifically, the preparation process of the thermosetting RF resin or resin solution containing a phenyl ether structure can be the following steps:

[0105] Weigh 100 parts of the thermoplastic RF resin containing a phenyl ether structure prepared in step (1) and dissolve it in 30 - 50 parts of a solvent, add 1 - 30 parts of formaldehyde and 0.01 - 5 parts of a catalyst, and react to generate a thermosetting RF resin solution.

[0106] Specifically, the reaction temperature range is 60 - 100 °C, and the reaction time is 1 - 5 hours.

[0107] The third step of the present invention is to prepare a modified RF resin emulsion:

[0108] Emulsify the thermosetting RF resin solution containing a phenyl ether structure, additives and water prepared in the second step to obtain a modified RF resin emulsion;

[0109] Its formula, by mass fraction of raw materials, is:

[0110]

[0111] Specifically, the water-based thickener is one or more of methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxyethyl cellulose, starch, gelatin, chitosan, polyvinyl alcohol, polyvinylpyrrolidone, and polyethylene oxide.

[0112] Specifically, the emulsifier is one or more of cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants.

[0113] Specifically, the hydrophilic filler includes one or more of titanium dioxide, silicon dioxide, montmorillonite, calcium carbonate, and talc powder.

[0114] Specifically, the antioxidant includes one or more of phenolic antioxidants, amine antioxidants, and heterocyclic antioxidants.

[0115] Specifically, the modifier includes one or more of water-based phenolic aldehyde, water-based epoxy, polyacrylamide, and polyacrylic acid.

[0116] Specifically, the preparation process of the modified RF resin emulsion can be the following steps:

[0117] Add the emulsifier and antioxidant to the above thermosetting RF resin solution, disperse evenly, and then slowly add water, and use high-speed stirring for emulsification; after complete emulsification, add the water-based thickener, water-based filler, and modifier.

[0118] More specifically, add 1-20 parts of emulsifier and 1-8 parts of antioxidant to the above 100 parts of thermosetting RF resin solution, disperse evenly, and then slowly add water, and use high-speed stirring for emulsification; after complete emulsification, add the water-based thickener, water-based filler, and modifier, and stir evenly to obtain a modified RF resin emulsion. The emulsification temperature range is 20-70°C, the rotation speed of the high-speed mixing for emulsification is 1000-10000 r / min; the time of the high-speed mixing for emulsification is 10-30 min.

[0119] Finally, adjust the pH of the modified RF resin emulsion to make the pH between 8 and 12, and then add latex and water to prepare the impregnating liquid RFL.

[0120] The present invention provides a method for preparing a modified RF resin emulsion for an RFL dipping solution for fiber skeleton materials according to any one of the above technical solutions, comprising the following steps:

[0121] 1) Mix resorcinol, a methoxyalkyl diphenyl ether oligomer, a third monomer, and a catalyst, and then carry out a reaction to obtain a modified thermoplastic RF resin containing a phenyl ether structure;

[0122] 2) Continuously mix the thermoplastic RF resin containing a phenyl ether structure obtained in the above step, a solvent, formaldehyde, and a catalyst, and then carry out a reaction again to obtain a modified thermosetting RF resin solution containing a phenyl ether structure;

[0123] 3) Mix an emulsifier, an antioxidant, and the modified thermosetting RF resin solution obtained in the above step again, add water for emulsification, and then add an aqueous thickener, a hydrophilic filler, and a modifier and mix them evenly to obtain a modified RF resin emulsion.

[0124] The method for preparing the modified RF resin emulsion in the present invention includes a method for preparing a modified thermoplastic RF resin (i.e., step 1)), a method for preparing a modified thermosetting RF resin solution (i.e., step 2)), and a method for preparing a modified RF resin emulsion (i.e., step 3) or steps 1), 2), and 3)).

[0125] The present invention first mixes resorcinol, a methoxyalkyl diphenyl ether oligomer, a third monomer, and a catalyst, and then carries out a reaction to obtain a modified thermoplastic RF resin containing a phenyl ether structure.

[0126] In the present invention, the temperature of the reaction in step 1) is preferably 30 - 120°C, more preferably 60 - 120°C, and still more preferably 60 - 90°C.

[0127] In the present invention, the reaction time in step 1) is preferably 0.5 - 10 hours, more preferably 2.5 - 8 hours, and still more preferably 4.5 - 6 hours.

[0128] The present invention then continuously mixes the thermoplastic RF resin containing a phenyl ether structure obtained in the above step, a solvent, formaldehyde, and a catalyst, and then carries out a reaction again to obtain a modified thermosetting RF resin solution containing a phenyl ether structure.

[0129] In the present invention, the temperature of the reaction again in step 2) is preferably 60 - 100°C, more preferably 65 - 95°C, and still more preferably 75 - 85°C.

[0130] In the present invention, the reaction time again in step 2) is preferably 0.5 - 4 hours, more preferably 1 - 3.5 hours, still more preferably 1.5 - 3 hours, and most preferably 2 - 2.5 hours.

[0131] Finally, in the present invention, after re - mixing the emulsifier, antioxidant and the modified thermosetting RF resin solution obtained in the above steps, water is added for emulsification, and then an aqueous thickener, hydrophilic filler and modifier are added and uniformly mixed to obtain a modified RF resin emulsion.

[0132] In the present invention, the emulsification method preferably includes high - speed stirring emulsification.

[0133] In the present invention, the emulsification temperature is preferably 20 - 70 °C, more preferably 30 - 60 °C, and even more preferably 40 - 50 °C.

[0134] In the present invention, the emulsification rotation speed is preferably 1000 - 10000 r / min, more preferably 3000 - 8000 r / min, and even more preferably 5000 - 6000 r / min.

[0135] In the present invention, the emulsification time is preferably 10 - 30 min, more preferably 14 - 26 min, and even more preferably 18 - 22 min.

[0136] In order to better complete and refine the overall technical solution of the present invention, better reduce the volatilization of resorcinol monomers during the production process, and further improve the adhesion between rubber and fiber and the heat - aging resistance of the fiber - skeleton - material - reinforced rubber material in subsequent applications, the preparation method of the modified RF resin emulsion for the above - mentioned RFL dipping solution for fiber - skeleton materials may specifically include the following steps:

[0137] 1) React resorcinol, methoxy - alkyl diphenyl ether oligomer, the third monomer and a catalyst after mixing to obtain a thermoplastic RF resin containing a phenyl ether structure. Specifically, the reaction temperature range is 60 - 120 °C.

[0138] 2) Dissolve the thermoplastic RF resin containing a phenyl ether structure obtained in the above step in a solvent, add formaldehyde and a catalyst and react to obtain a thermosetting RF resin solution containing a phenyl ether structure. Specifically, the reaction temperature range is 60 - 100 °C.

[0139] 3) Add an emulsifier and an antioxidant to the above thermosetting RF resin solution, disperse evenly, and then slowly add water, and use the method of high - speed stirring for emulsification; after complete emulsification, add an aqueous thickener, aqueous filler and modifier, and stir evenly to obtain a modified RF resin emulsion. Specifically, the emulsification temperature range is 20 - 70 °C, the rotation speed of high - speed mixing during emulsification is 1000 - 10000 r / min; the time of high - speed mixing is 10 - 30 min.

[0140] Further, the methoxyalkyl diphenyl ether oligomer and the third monomer of the thermoplastic RF resin containing a phenyl ether structure obtained in the step (1) are for improving the antioxidant performance of the resin, and the third monomer includes one or two of hydroquinone, catechol, tea polyphenols, tert-butylphenol, eugenol, 2,6-dimethylphenol, p-chlorophenol, and biphenol.

[0141] Preferably, the catalyst in the step (1) can be one of hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, oxalic acid, acetic acid, p-toluenesulfonic acid, phosphotungstic acid, oxalic acid, and formic acid.

[0142] Further, the formaldehyde in the step (2) is an aqueous formaldehyde solution or paraformaldehyde;

[0143] Further, the catalyst in the step (2) includes one of hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, oxalic acid, formic acid, acetic acid, p-toluenesulfonic acid, phosphotungstic acid, oxalic acid, ammonia water, sodium hydroxide, barium hydroxide, potassium hydroxide, magnesium hydroxide, and magnesium oxide;

[0144] Further, the solvent in the step (2) includes one of toluene, xylene, ethylbenzene, acetone, butanone, methanol, ethanol, ethylene glycol, glycerol, environmental protection aromatic oil, and paraffin oil;

[0145] Further, the aqueous thickener in the step (3) is one of methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxyethyl cellulose, starch, gelatin, chitosan, polyvinyl alcohol, polyvinylpyrrolidone, and polyethylene oxide.

[0146] Further, the emulsifier in the step (3) is one of cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants.

[0147] Further, the hydrophilic filler in the step (3) includes one of titanium dioxide, silicon dioxide, montmorillonite, calcium carbonate, and talc powder.

[0148] Further, the antioxidant in the step (3) includes one of phenolic antioxidants, amine antioxidants, and heterocyclic antioxidants.

[0149] Further, the modifier in the step (3) includes one of aqueous phenolic aldehyde, aqueous epoxy, polyacrylamide, and polyacrylic acid.

[0150] Further, the reaction temperature in the step (1) is 60-120 °C, and the reaction time is 2-8 hours.

[0151] Further, in the preparation of the thermosetting RF resin containing a phenyl ether structure in step (2), the reaction temperature is 60 - 100 °C, and the reaction time is 1 - 5 hours.

[0152] Further, in the preparation of the modified RF resin emulsion in step (3), high-speed stirring is required to obtain a uniform emulsion, and antioxidants, stabilizers, and modifiers can be added to the emulsion.

[0153] The present invention provides an RFL dipping solution, which includes the modified RF resin emulsion described in any one of the above technical solutions or the modified RF resin emulsion prepared by the preparation method described in any one of the above technical solutions, latex, and water.

[0154] The pH value of the modified RF emulsion is 8 - 12, it can be 8.5 - 11.5, preferably 9 - 11, and more preferably 9.5 - 10.5.

[0155] The RFL dipping solution provided by the present invention can be prepared by adding latex and water to the above modified RF resin emulsion to obtain an RFL dipping solution for fiber skeleton materials; the pH value of the modified RF resin emulsion is 8 - 12. The application of the modified RF resin emulsion of this fiber skeleton material dipping solution in the adhesion of fiber skeleton materials has better adhesion performance and aging resistance than the existing RFL.

[0156] The present invention also provides the application of the modified thermoplastic RF resin described in any one of the above technical solutions, the modified thermosetting RF resin solution described in any one of the above technical solutions, the modified RF resin emulsion described in any one of the above technical solutions, the modified RF resin emulsion prepared by the preparation method described in any one of the above technical solutions, or the RFL dipping solution described in the above technical solutions in the adhesion of fiber skeleton materials.

[0157] The above content of the present invention provides a modified thermoplastic RF resin for an RFL dipping solution for fiber skeleton materials, a modified thermosetting RF resin solution for an RFL dipping solution for fiber skeleton materials, a modified RF resin emulsion for an RFL dipping solution for fiber skeleton materials, its preparation method, and application. The present invention first designs a modified thermoplastic RF resin copolymerized from multiple monomers, and then emulsifies the copolymer to obtain a modified RF emulsion, making it have excellent aging resistance without reducing its adhesion performance. The present invention first reacts a monomer with excellent heat resistance with resorcinol, and then reacts with formaldehyde to prepare a modified RF resin with excellent heat resistance, and then emulsifies the modified RF resin and adds appropriate additives to obtain a modified RF resin emulsion. This modified RF resin emulsion can be directly mixed with latex to prepare an RFL dipping solution for fiber skeleton materials, which has better adhesion performance and aging resistance than the existing RFL and has broad application prospects.

[0158] Based on the modified RF resin emulsion, the present invention can reduce the volatilization of resorcinol monomers during the operation process; and through the method of physical blending modification, components with excellent bonding properties, such as waterborne epoxy, are introduced to enhance the bonding performance with the fiber surface. Moreover, antioxidants and hydrophilic fillers with excellent heat resistance are introduced into the resin system, which can further improve the aging resistance of the RFL dipping solution.

[0159] The present invention combines copolymerization modification, blending modification and inorganic filler modification to comprehensively improve the bonding performance and aging resistance of the existing RFL dipping solution. This modified RF resin emulsion can simultaneously improve the adhesion between rubber and fiber and the heat aging resistance of the fiber skeleton material to enhance the rubber material, and thus can be applied to many high-end fiber skeleton material fields, such as high-performance tires, high-performance conveyor belts, etc., and will have many application fields and good application prospects.

[0160] The experimental results show that the adhesion strength retention rate (160 °C / 180 min) of the RFL dipping solution prepared with the modified RF resin provided by the present invention is greater than 60%.

[0161] To further illustrate the present invention, the following describes in detail a modified thermoplastic RF resin for an RFL dipping solution for fiber skeleton materials, a modified thermosetting RF resin solution for an RFL dipping solution for fiber skeleton materials, a modified RF resin emulsion for an RFL dipping solution for fiber skeleton materials and its preparation method, and applications in conjunction with embodiments. However, it should be understood that these embodiments are implemented on the premise of the technical solution of the present invention, and give detailed implementation manners and specific operation processes, only to further illustrate the features and advantages of the present invention, rather than a limitation on the claims of the present invention. The protection scope of the present invention is not limited to the following embodiments.

[0162] Example 1

[0163] Weigh resorcinol, methoxyalkyl diphenyl ether oligomer, catechol and p-toluenesulfonic acid by weight; in a reaction kettle, first add 100 parts of methoxyalkyl diphenyl ether oligomer, then add 100 parts of resorcinol and 10 parts of catechol, and stir evenly; add 1 part of p-toluenesulfonic acid and react at 110 °C for 4 hours. After the reaction is completed, cool to room temperature to obtain a thermoplastic RF resin containing a phenyl ether structure.

[0164] Weigh 100 parts of the thermoplastic RF resin containing a phenyl ether structure and dissolve it in 40 parts of toluene, add 10 parts of formaldehyde and 1 part of catalyst, and react to generate a thermosetting RF resin solution. The reaction temperature is 90 °C and the reaction time is 2 hours.

[0165] By weight, 10 parts of an emulsifier (anionic emulsifier: non-ionic emulsifier = 1:1) and 2 parts of an antioxidant were added to the above 100 parts of the thermosetting RF resin solution, dispersed evenly, and then water was slowly added, and emulsification was carried out by means of high-speed stirring; after complete emulsification, methyl cellulose, silica and waterborne epoxy were added and stirred evenly to obtain a modified RF resin emulsion. The emulsification temperature was 30 °C, and the rotation speed of high-speed mixing was 6000 r / min; the mixing time was 10 min.

[0166] The pH of the modified RF resin emulsion was adjusted to pH = 9, and then latex and water were added to prepare the impregnating liquid RFL-1.

[0167] Example 2

[0168] Weigh resorcinol, methoxyalkyl diphenyl ether oligomer, catechol and p-toluenesulfonic acid by weight; in a reaction kettle, first add 120 parts of methoxyalkyl diphenyl ether oligomer, and then add 100 parts of resorcinol and 10 parts of catechol thereto, and stir evenly; add 1 part of p-toluenesulfonic acid and react at 110 °C for 4 hours. After the reaction is completed, cool to room temperature to obtain a thermoplastic RF resin containing a phenyl ether structure.

[0169] Weigh 100 parts of the thermoplastic RF resin containing a phenyl ether structure by weight and dissolve it in 40 parts of toluene, add 20 parts of formaldehyde and 1 part of a catalyst, and react to form a thermosetting RF resin solution. The reaction temperature was 80 °C, and the reaction time was 2 hours.

[0170] By weight, 10 parts of an emulsifier (anionic emulsifier: non-ionic emulsifier = 1:1) and 2 parts of an antioxidant were added to the above 100 parts of the thermosetting RF resin solution, dispersed evenly, and then water was slowly added, and emulsification was carried out by means of high-speed stirring; after complete emulsification, polyvinyl alcohol, silica and waterborne epoxy were added and stirred evenly to obtain a modified RF resin emulsion. The emulsification temperature was 30 °C, and the rotation speed of high-speed mixing was 6000 r / min; the mixing time was 10 min

[0171] The pH of the modified RF resin emulsion was adjusted to pH = 9, and then latex and water were added to prepare the impregnating liquid RFL-2.

[0172] Example 3

[0173] Weigh resorcinol, methoxyalkyl diphenyl ether oligomer, catechol and p-toluenesulfonic acid by weight; in a reaction kettle, first add 140 parts of methoxyalkyl diphenyl ether oligomer, and then add 100 parts of resorcinol and 10 parts of catechol thereto, and stir evenly; add 1 part of p-toluenesulfonic acid and react at 110 °C for 4 hours. After the reaction is completed, cool to room temperature to obtain a thermoplastic RF resin containing a phenyl ether structure.

[0174] Weigh 100 parts by weight of a thermoplastic RF resin containing a phenyl ether structure and dissolve it in 40 parts of toluene. Add 20 parts of formaldehyde and 1 part of catalyst, and react to form a thermosetting RF resin solution. The reaction temperature is 80 °C and the reaction time is 2 hours.

[0175] By weight, add 10 parts of emulsifier (anionic emulsifier: non-ionic emulsifier = 1:1) and 2 parts of antioxidant to the above 100 parts of thermosetting RF resin solution, disperse evenly, and then slowly add water, and use high-speed stirring for emulsification; after complete emulsification, add polyvinyl alcohol, silica and waterborne acrylic resin, stir evenly to obtain a modified RF resin emulsion. The emulsification temperature is 30 °C, the rotation speed of high-speed mixing is 6000 r / min; the mixing time is 10 min.

[0176] Adjust the pH of the modified RF resin emulsion to pH = 9, and then add latex and water to prepare the impregnating solution RFL-3.

[0177] Example 4

[0178] Weigh resorcinol, methoxyalkyl diphenyl ether oligomer, catechol and sulfuric acid by weight; in a reaction kettle, first add 60 parts of methoxyalkyl diphenyl ether oligomer, then add 100 parts of resorcinol and 5 parts of catechol, stir evenly; add 1 part of sulfuric acid, react at 100 °C, the reaction time is 4 hours, and after the reaction is completed, cool to room temperature to obtain a thermoplastic RF resin containing a phenyl ether structure.

[0179] Weigh 100 parts by weight of a thermoplastic RF resin containing a phenyl ether structure and dissolve it in 40 parts of ethanol. Add 30 parts of formaldehyde and 1 part of catalyst, and react to form a thermosetting RF resin solution. The reaction temperature is 60 °C and the reaction time is 2 hours.

[0180] By weight, add 10 parts of emulsifier (anionic emulsifier: non-ionic emulsifier = 1:1) and 2 parts of antioxidant to the above 100 parts of thermosetting RF resin solution, disperse evenly, and then slowly add water, and use high-speed stirring for emulsification; after complete emulsification, add polyvinyl alcohol, silica and waterborne epoxy, stir evenly to obtain a modified RF resin emulsion. The emulsification temperature is 30 °C, the rotation speed of high-speed mixing is 6000 r / min; the mixing time is 10 min

[0181] Adjust the pH of the modified RF resin emulsion to pH = 9, and then add latex and water to prepare the impregnating solution RFL-4.

[0182] Example 5

[0183] Weigh resorcinol, methoxyalkyl diphenyl ether oligomer, tea polyphenols and p-toluenesulfonic acid by weight parts; in a reaction kettle, first add 100 parts of methoxyalkyl diphenyl ether oligomer, then add 100 parts of resorcinol and 10 parts of tea polyphenols into it, and stir evenly; add 1 part of p-toluenesulfonic acid, react at 100 °C, and the reaction time is 4 hours. After the reaction is completed, cool to room temperature to obtain a thermoplastic RF resin containing a phenyl ether structure.

[0184] Weigh 100 parts of the thermoplastic RF resin containing a phenyl ether structure by weight and dissolve it in 40 parts of xylene, add 20 parts of formaldehyde and 1 part of catalyst, and react to form a thermosetting RF resin solution. The reaction temperature is 80 °C and the reaction time is 2 hours.

[0185] By weight, add 10 parts of emulsifier (anionic emulsifier: non-ionic emulsifier = 1:1) and 4 parts of antioxidant to the above 100 parts of thermosetting RF resin solution, disperse evenly, and then slowly add water, and carry out emulsification by high-speed stirring; after complete emulsification, add polyvinyl alcohol, titanium dioxide silicate and waterborne acrylic resin, and stir evenly to obtain a modified RF resin emulsion. The emulsification temperature is 30 °C, the rotation speed of high-speed mixing is 6000 r / min; the mixing time is 20 min

[0186] Adjust the pH of the modified RF resin emulsion to make pH = 9, and then add latex and water to prepare the impregnating liquid RFL-5.

[0187] Example 6

[0188] Weigh resorcinol, methoxyalkyl diphenyl ether oligomer, hydroquinone and hydrochloric acid by weight parts; in a reaction kettle, first add 100 parts of methoxyalkyl diphenyl ether oligomer, then add 100 parts of resorcinol and 10 parts of hydroquinone into it, and stir evenly; add 1 part of hydrochloric acid, react at 120 °C, and the reaction time is 4 hours. After the reaction is completed, cool to room temperature to obtain a thermoplastic RF resin containing a phenyl ether structure.

[0189] Weigh 100 parts of the thermoplastic RF resin containing a phenyl ether structure by weight and dissolve it in 40 parts of xylene, add 20 parts of formaldehyde and 1 part of catalyst, and react to form a thermosetting RF resin solution. The reaction temperature is 90 °C and the reaction time is 2 hours.

[0190] By weight, add 10 parts of emulsifier (anionic emulsifier: non-ionic emulsifier = 1:1) and 4 parts of antioxidant to the above 100 parts of thermosetting RF resin solution, disperse evenly, and then slowly add water, and carry out emulsification by high-speed stirring; after complete emulsification, add polyvinyl alcohol, titanium dioxide and waterborne epoxy, and stir evenly to obtain a modified RF resin emulsion. The emulsification temperature is 30 °C, the rotation speed of high-speed mixing is 6000 r / min; the mixing time is 20 min

[0191] Adjust the pH of the modified RF resin emulsion to pH = 9, then add latex and water to prepare the impregnating solution RFL-6.

[0192] Perform performance testing on the RFL impregnating solution prepared in the examples of the present invention.

[0193] Test the H extraction force in accordance with GB / T 2942-2009, and the fibers used are polyester fibers or nylon fibers.

[0194] Refer to Table 1. Table 1 shows the performance testing data of the RFL impregnating solutions prepared in Examples 1 to 6 of the present invention when bonding fibers and rubber matrices.

[0195] Table 1

[0196]

[0197] The above has introduced in detail a modified RF resin emulsion for a novel fiber skeleton material impregnating solution RFL and its preparation method provided by the present invention. Specific examples are used herein to elaborate on the principle and implementation manner of the present invention. The description of the above examples is only used to help understand the method and its core idea of the present invention, including the best mode, and also enables any person skilled in the art to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that for those of ordinary skill in the art in this technical field, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. The protection scope of the present invention patent is defined by the claims and may include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements that are not different from the literal description of the claims, or if they include equivalent structural elements that have no substantial difference from the literal description of the claims, then these other embodiments should also be included within the scope of the claims.

Claims

1. A modified RF resin emulsion for an RFL dipping solution of a fiber skeleton material, characterized in that, By mass fraction of raw materials, it includes: 100 parts by weight of modified thermosetting RF resin solution; 1 - 20 parts by weight of emulsifier; 0.2 - 5 parts by weight of aqueous thickener; 1 - 8 parts by weight of antioxidant; 0.5 - 5 parts by weight of hydrophilic filler 1 - 10 parts by weight of modifier 50 - 100 parts by weight of water; The modified thermosetting RF resin solution, by mass fraction of raw materials, includes: 100 parts by weight of modified thermoplastic RF resin; 1 - 30 parts by weight of formaldehyde; 0.01 - 5 parts by weight of catalyst 30 - 50 parts by weight of solvent; The modified thermoplastic RF resin, by mass fraction of raw materials, includes: 100 parts by weight of resorcinol; 60 - 150 parts by weight of methoxyalkyl diphenyl ether oligomer; 0 - 20 parts by weight of the third monomer; 0.01 - 5 parts by weight of catalyst; The molecular weight of the methoxyalkyl diphenyl ether oligomer is 200 - 3000; The third monomer includes one or more of hydroquinone, catechol, tea polyphenol, tert - butylphenol, eugenol, 2,6 - dimethylphenol, p - chlorophenol, biphenol, bisphenol A and bisphenol S; The catalyst in the raw materials of the modified thermoplastic RF resin includes one or more of hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, oxalic acid, acetic acid, p - toluenesulfonic acid, phosphotungstic acid and formic acid; The modified thermoplastic RF resin is a modified thermoplastic RF resin containing a phenyl ether structure.

2. The modified RF resin emulsion according to claim 1, wherein The formaldehyde includes aqueous formaldehyde solution or paraformaldehyde; The mass concentration of the aqueous formaldehyde solution is 37%.

3. The modified RF resin emulsion according to claim 1, the catalyst in the raw materials of the modified thermosetting RF resin solution includes one or more of hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, oxalic acid, formic acid, acetic acid, p - toluenesulfonic acid, phosphotungstic acid, ammonia water, sodium hydroxide, barium hydroxide, potassium hydroxide, magnesium hydroxide and magnesium oxide; The solvent includes one or more of toluene, xylene, ethylbenzene, acetone, butanone, methanol, ethanol, ethylene glycol, glycerol, environmental protection aromatic oil and paraffin oil.

4. The modified RF resin emulsion according to claim 1, wherein The emulsifier includes one or more of cationic surfactants, anionic surfactants, non - ionic surfactants and amphoteric surfactants.

5. The modified RF resin emulsion according to claim 1, wherein The aqueous thickener is one or more of methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxyethyl cellulose, starch, gelatin, chitosan, polyvinyl alcohol, polyvinylpyrrolidone and polyethylene oxide; The antioxidant includes one or more of phenolic antioxidants, amine antioxidants and heterocyclic antioxidants.

6. The modified RF resin emulsion according to claim 1, wherein The hydrophilic filler includes one or more of titanium dioxide, silicon dioxide, montmorillonite, calcium carbonate and talc powder; The modifier includes one or more of aqueous phenolic aldehyde, aqueous epoxy, polyacrylamide and polyacrylic acid.

7. A method for preparing a modified RF resin emulsion of an RFL dipping solution for a fiber skeleton material according to any one of claims 1 to 6, characterized in that, It includes the following steps: 1) After mixing resorcinol, methoxyalkyl diphenyl ether oligomer, the third monomer and the catalyst, carry out a reaction to obtain a modified thermoplastic RF resin containing a phenyl ether structure; 2) After continuously mixing the thermoplastic RF resin containing a phenyl ether structure, solvent, formaldehyde, and catalyst obtained in the above steps, react again to obtain a modified thermosetting RF resin solution containing a phenyl ether structure; 3) After remixing the emulsifier, antioxidant, and the modified thermosetting RF resin solution obtained in the above steps, add water for emulsification, and then add a water-based thickener, hydrophilic filler, and modifier and mix evenly to obtain a modified RF resin emulsion.

8. The preparation method according to claim 7, characterized in that, The temperature of the reaction in step 1) is 30 - 120 °C; The reaction time in step 1) is 0.5 - 10 hours; The temperature of the re-reaction in step 2) is 60 - 100 °C; The re-reaction time in step 2) is 0.5 - 4 hours; The emulsification method includes high-speed stirring emulsification; The temperature of the emulsification is 20 - 70 °C; The rotation speed of the emulsification is 1000 - 10000 r / min; The emulsification time is 10 - 30 min.

9. An RFL impregnating solution, characterized in that, It includes the modified RF resin emulsion described in any one of claims 1 - 6 or the modified RF resin emulsion prepared by the preparation method described in any one of claims 7 - 8, latex, and water; The pH value of the modified RF resin emulsion is 8 - 12.

10. Application of the modified RF resin emulsion described in any one of claims 1 - 6, the modified RF resin emulsion prepared by the preparation method described in any one of claims 7 - 8, or the RFL dipping solution described in claim 9 in the adhesion of fiber skeleton materials.

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