Fiber impregnation liquid for improving bonding effect between nylon fiber and rubber and preparation method thereof

Abstract

The present application provides a fiber impregnation liquid for improving the bonding effect between nylon fiber and rubber, which is mixed with multiple raw materials, including 5 to 10 parts by mass of glycidyl ether, 1 to 3 parts by mass of dopamine derivatives, 2 to 6 parts by mass of diamine, 100 to 150 parts by mass of water and 100 parts by mass of rubber latex; a preparation method of the fiber impregnation liquid is also provided; the fiber impregnation liquid can be uniformly attached to the surface of the nylon fiber to enhance the bonding performance between the nylon fiber and the rubber, the main raw materials are environmentally friendly and non-toxic, and the pollution of traditional RFL fiber impregnation liquid to human body and environment is avoided, and the preparation and impregnation process of the fiber impregnation liquid are simple and controllable, and the bonding strength between the obtained nylon fiber and rubber is close to the level of traditional RFL impregnation liquid.

Description

Technical Field

[0001] The invention relates to the technical field of fiber impregnation, and in particular to a fiber impregnation liquid for improving the bonding effect between nylon fiber and rubber and a preparation method thereof. Background Art

[0002] Rubber is widely used in tires, conveyor belts, air springs and other products due to its excellent elasticity, physical and mechanical properties, fatigue resistance and chemical corrosion resistance. Nylon fiber has high strength and good fatigue resistance, and is an important rubber matrix reinforcement material. Fiber-reinforced rubber composites are composed of fiber skeleton materials and rubber matrix. The higher strength and modulus of the fiber skeleton material can resist the complex stress of the composite material, and the excellent elasticity of the rubber matrix can withstand the deformation of the composite material caused by external forces.

[0003] However, due to the difference in polarity and modulus between rubber and fiber, the fiber surface treatment is usually required to improve the bonding effect between the fiber and rubber. Resorcinol-formaldehyde-latex (RFL) impregnation liquid is a fiber impregnation liquid widely used in recent decades. However, the toxicity of resorcinol and formaldehyde has caused great harm to the human body and the environment. Faced with increasingly stringent environmental protection requirements, there is an urgent need to develop new environmentally friendly fiber impregnation liquids.

[0004] Although the prior art has made some research on the impregnation liquid for improving the bonding performance between fiber and rubber, there are still some problems, including that the bonding effect of the impregnation liquid does not reach the RFL level; some raw materials used in the formula are expensive or have complex processes. Therefore, there is a need for an environmentally friendly fiber impregnation liquid that is low in cost, non-toxic and environmentally friendly, and can generate considerable physical and chemical activity between fiber and rubber. Summary of the invention

[0005] The object of the present invention is to provide a fiber impregnation liquid for improving the bonding effect between nylon fiber and rubber. Another object of the present invention is to provide a method for preparing the fiber impregnation liquid for improving the bonding effect between nylon fiber and rubber.

[0006] In order to achieve the above object, the technical solution of the present invention is as follows:

[0007] A fiber impregnation liquid for improving the bonding effect between nylon fiber and rubber. The fiber impregnation liquid is mixed with multiple raw materials, including 5 to 10 parts by mass of glycidyl ether, 1 to 3 parts by mass of dopamine derivatives, 2 to 6 parts by mass of diamine, 100 to 150 parts by mass of water and 100 parts by mass of rubber latex.

[0008] Preferably, the glycidyl ether is one or more of diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycerol triglycidyl ether, and pentaerythritol glycidyl ether.

[0009] Preferably, the dopamine derivative is one or more of dopamine, dopamine hydrochloride, coumaroyl dopamine, 5-hydroxydopamine, 6-hydroxydopamine, and N-methyl dopamine.

[0010] Preferably, the diamine is one or more of hexamethylenediamine, o-phenylenediamine, m-phenylenediamine and p-phenylenediamine.

[0011] Preferably, the rubber latex is one or a mixed latex of chloroprene rubber latex, butylpyrrolidone latex, and epoxidized natural rubber latex.

[0012] A method for preparing a fiber impregnation liquid for improving the bonding effect between nylon fiber and rubber as described in any one of the above, comprising the following steps performed in sequence:

[0013] 1) Take glycidyl ether, add dopamine derivatives while stirring, and stir and mix well to obtain intermediate product A;

[0014] 2) adding diamine to the intermediate product A, stirring while adding, then adding water and continuing to stir, and after completion, obtaining the intermediate product B;

[0015] 3) Add rubber latex to the intermediate product B, stir and mix evenly, and obtain the finished fiber impregnation liquid.

[0016] Preferably, the stirring rate is 50 rpm to 300 rpm.

[0017] This application has achieved the following beneficial technical effects:

[0018] (1) The impregnation liquid provided by the present invention does not contain resorcinol and formaldehyde, has low cost, is non-toxic and environmentally friendly, and is conducive to reducing the pollution of the RFL impregnation liquid to the environment.

[0019] (2) The preparation process of the environmentally friendly fiber impregnation liquid provided by the present invention is simple, the process conditions are easy to control, and the preparation time is short.

[0020] (3) The environmentally friendly fiber impregnation liquid provided by the present invention can achieve the same bonding performance as the RFL impregnation liquid treatment after the rubber and fiber are co-vulcanized.

[0021] (4) The present invention is suitable for the preparation of nylon fiber impregnation liquid, which is used to replace resorcinol and formaldehyde in traditional RFL dipping, thereby reducing the harm to human body and environment, and improving the interface bonding performance between nylon fiber and rubber matrix. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The graph is a test result of the adhesion between the fiber impregnation liquid prepared in the embodiment of the present invention and the nylon fiber of the comparative example and chloroprene rubber. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. The described embodiments are only part of the embodiments of the present invention, not all of them. Therefore, based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0024] The present application provides a fiber impregnation liquid for improving the bonding effect between nylon fiber and rubber. The fiber impregnation liquid is mixed with multiple raw materials, including 5 to 10 parts by mass of glycidyl ether, 1 to 3 parts by mass of dopamine derivatives, 2 to 6 parts by mass of diamine, 100 to 150 parts by mass of water and 100 parts by mass of rubber latex.

[0025] In one embodiment of the present application, the glycidyl ether is one or more of diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycerol triglycidyl ether, and pentaerythritol glycidyl ether.

[0026] In one embodiment of the present application, the dopamine derivative is one or more of dopamine, dopamine hydrochloride, coumaroyl dopamine, 5-hydroxydopamine, 6-hydroxydopamine, and N-methyl dopamine.

[0027] In one embodiment of the present application, the diamine is one or more of hexamethylenediamine, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine.

[0028] In one embodiment of the present application, the rubber latex is one or a mixed latex of chloroprene rubber latex, butylpyrrolidone latex, and epoxidized natural rubber latex.

[0029] The present application provides a method for preparing a fiber impregnation liquid for improving the bonding effect between nylon fiber and rubber as described in any one of the above, comprising the following steps performed in sequence:

[0030] 1) Take glycidyl ether, add dopamine derivatives while stirring, and stir and mix well to obtain intermediate product A;

[0031] 2) adding diamine to the intermediate product A, stirring while adding, then adding water and continuing to stir, and after completion, obtaining the intermediate product B;

[0032] 3) Add rubber latex to the intermediate product B, stir and mix evenly, and obtain the finished fiber impregnation liquid.

[0033] In one embodiment of the present application, the stirring rate is 50 rpm to 300 rpm.

[0034] The working principle of the fiber impregnation liquid of the present invention for improving the bonding effect between nylon fiber and rubber is as follows: the abundant epoxy groups in glycidyl ether can react with the amino groups in diamine to generate an epoxy resin-type skeleton structure, the bonding force between the skeleton structure modified by dopamine derivatives and the fiber is greatly improved, and the catechol groups in the dopamine derivatives have a strong adhesion effect with polar materials, rubber latex is added to the system, the rubber latex particles are stably and evenly dispersed in the network structure, and the latex molecular chains are co-vulcanized with the rubber matrix in the vulcanization stage, which further improves the bonding force between the fiber and the rubber;

[0035] The fiber impregnation solution contains a large number of epoxy and catechol groups, and nylon fibers contain a large number of amide, hydroxyl and amino groups;

[0036] On the one hand, the highly active catechol groups in the fiber impregnation solution are oxidized to orthoquinone and diquinone structures. The quinone structures can react with the amino groups on the nylon fibers through Schiff base or Michael addition reaction, so that the fiber impregnation solution and the nylon fibers are chemically cross-linked. In addition, during the vulcanization process, the epoxy groups can cross-link with the amide groups to form chemical bonds.

[0037] On the other hand, rubber latex particles can be co-vulcanized with the rubber matrix to form an interpenetrating network structure, thereby obtaining excellent fiber / rubber interface adhesion properties;

[0038] In addition, hydrogen bonds also play an important role in adhesion performance due to the presence of a large number of polar atoms in the fiber impregnation solution and on the surface of nylon fibers.

[0039] The methods and devices not described in detail in the present invention are all prior art and will not be described in detail.

[0040] In order to better understand the present invention, the present invention is further specifically described below through the following examples, but it should not be understood as a limitation of the present invention. Some non-essential improvements and adjustments made by technicians in this field based on the above invention content are also considered to fall within the protection scope of the present invention.

[0041] Example 1

[0042] A method for preparing a fiber impregnation liquid for improving the bonding effect between nylon fiber and rubber comprises the following steps performed in sequence:

[0043] 1) Take 5 g of propylene glycol triglycidyl ether in a beaker, add 1 g of dopamine while stirring at 200 rpm, and stir for 20 minutes to obtain intermediate product A;

[0044] 2) Slowly add 2 g of m-phenylenediamine to the intermediate product A several times while stirring, stir at 150 rpm for 15 min, then add 100 g of deionized water and continue stirring for 30 min to obtain the intermediate product B;

[0045] 3) Add 100 g of chloroprene rubber latex to the intermediate product B, and stir at 150 rpm for 1 hour to obtain a homogeneous product, which is a fiber impregnation liquid for improving the adhesion between nylon fiber and chloroprene rubber.

[0046] Example 2

[0047] The propylene glycol triglycidyl ether in step 1) is replaced by ethylene glycol diglycidyl ether, dopamine is replaced by coumaroyl dopamine, the meta-phenylenediamine in step 2) is replaced by o-phenylenediamine, the chloroprene latex in step 3) is replaced by epoxidized natural rubber latex, and the rest of the preparation method is the same as that in Example 1, and after completion, a fiber impregnation solution is obtained.

[0048] Example 3

[0049] The propylene glycol triglycidyl ether in step 1) is replaced by pentaerythritol glycidyl ether, dopamine is replaced by N-methyl dopamine, the meta-xylylenediamine in step 2) is replaced by ethylenediamine, the chloroprene rubber latex in step 3) is replaced by butylpyrrolidone latex, and the rest of the preparation method is the same as that in Example 1, and after completion, a fiber impregnation solution is obtained.

[0050] Example 4

[0051] The glycerol triglycidyl ether in step 1) is replaced with bisphenol A diglycidyl ether, dopamine is replaced with 5-hydroxydopamine, and the m-xylylenediamine in step 2) is replaced with p-xylylenediamine. The rest of the preparation method is the same as that in Example 1, and after completion, a fiber impregnation solution is obtained.

[0052] Comparative Example 1

[0053] The cleaned nylon fibers are directly compounded with rubber to prepare fiber-reinforced rubber composite materials.

[0054] According to GB / T2942-2009 Determination of static bonding strength between vulcanized rubber and fiber cord H extraction method, bonding samples of Examples 1-4 and Comparative Example 1 were prepared and the bonding performance was tested. Extraction test description: The fiber-rubber bonding test was conducted on an electronic tensile testing machine produced by Zwick / Roell in Germany in accordance with GB / T2942-2009 standard. The test speed was 100mm / min, and the maximum force when the fiber was pulled out from the rubber was recorded. No less than 8 samples were tested, and the average value of at least 8 valid data was recorded. The measured results are as follows: Figure 1 shown.

[0055] like Figure 1 As shown in the figure, comparative example 1 is a strip of unmodified nylon fiber and chloroprene rubber, and examples 1-4 are strips of nylon fiber and chloroprene rubber treated with different glycidyl ether and diamine monomers;

[0056] Example 1 is a nylon fiber modified by a fiber impregnation solution of glycerol triglycidyl ether, dopamine and m-xylylenediamine;

[0057] Example 2 is a nylon fiber modified by a fiber impregnation solution of ethylene glycol diglycidyl ether, coumaroyl dopamine and o-phenylenediamine;

[0058] Example 3 is a nylon fiber modified by a fiber impregnation solution of pentaerythritol glycidyl ether, N-methyl dopamine and ethylenediamine;

[0059] Example 4 is a nylon fiber modified by a fiber impregnation solution of bisphenol A diglycidyl ether, 5-hydroxydopamine, and p-phenylenediamine;

[0060] It can be seen that compared with the unmodified nylon fiber in Comparative Example 1, the adhesion properties of the composite materials samples of modified nylon fiber and rubber in Examples 1-4 are improved by 92%, 87%, 91% and 90%, respectively. The test results show that the fiber impregnation liquid prepared in the present application can greatly improve the adhesion effect between nylon fiber and rubber after treating nylon fiber.

[0061] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a fiber impregnation liquid for improving the bonding effect between nylon fiber and rubber, characterized in that: The method includes the following steps in sequence: 1) Take glycidyl ether, add dopamine derivatives while stirring, and stir and mix well to obtain intermediate product A; 2) Add diamine to the intermediate product A while stirring, then add water and continue stirring to obtain the intermediate product B; 3) adding rubber latex to the intermediate product B, stirring and mixing evenly, and obtaining a finished fiber impregnation liquid; The fiber impregnation liquid is mixed with a variety of raw materials, including 5 to 10 parts by weight of glycidyl ether, 1 to 3 parts by weight of dopamine derivatives, 2 to 6 parts by weight of diamine, 100 to 150 parts by weight of water and 100 parts by weight of rubber latex; The glycidyl ether is one or more of diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycerol triglycidyl ether, and pentaerythritol glycidyl ether; The dopamine derivative is one or more of dopamine, dopamine hydrochloride, coumaroyl dopamine, 5-hydroxydopamine, 6-hydroxydopamine, and N-methyl dopamine; The diamine is one or more of hexamethylenediamine, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine; The stirring rate is 50 rpm to 300 rpm; The rubber latex is one or a mixed latex of chloroprene rubber latex, butylpyrrolidone latex and epoxidized natural rubber latex.

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