Aging-resistant epoxy pipe yarn impregnant and method for preparing the same

Abstract

The present application belongs to the technical field of impregnating agent, and particularly relates to an aging-resistant epoxy pipe yarn impregnating agent and a preparation method thereof. The aging-resistant epoxy pipe yarn impregnating agent is composed of a coupling agent, a lubricant, a film-forming agent, a pH regulator and deionized water, wherein the film-forming agent is a mixture of bisphenol A type epoxy emulsion, polyurethane emulsion and phenolic epoxy emulsion. The glass fiber product produced by using the impregnating agent has good compatibility with epoxy resin, and has the processability of winding pipe, good wear resistance, less hairiness, fast penetration speed; the glass fiber produced by using the impregnating agent has no performance degradation after high-temperature aging, and the performance aging retention rate of the epoxy high-pressure pipe produced by using the glass fiber is higher after boiling in boiling water for 1500 hours.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of impregnating agent, and particularly relates to an aging-resistant epoxy pipe yarn impregnating agent and a preparation method thereof. BACKGROUND

[0002] The epoxy high-pressure glass steel pipe is formed by the continuous glass fiber winding process, is formed by the continuous glass fiber after being impregnated with the epoxy resin, is wound on a mold and is cured by heating, and is simply referred to as GRE pipe.

[0003] The glass steel pipe has been widely applied in the oil field oil transportation, water injection, polymer injection pipeline, natural gas transportation, city water supply and drainage, drinking water pipeline, chemical industry, brine pipeline and fire-fighting pipeline due to its good mechanical and physical properties (light weight, high strength and convenient transportation) and excellent compression resistance.

[0004] The epoxy glass steel pipe manufacturers are distributed all over the world, and the latitude span is large, and the climate distribution is wide. In particular, the temperature in the Middle East is high (the ground temperature is as high as about 50 DEG C) all the year round. In addition to the high requirement for the process performance of the glass fiber, the aging resistance of the fiber is also required to be higher, and the existing product cannot meet the requirement.

[0005] Chinese patent CN 110294600 A discloses a glass fiber impregnating agent and a preparation method and application thereof. The glass fiber impregnating agent comprises the following components, and the content of each component is expressed by mass percentage as follows: 0.10-3.00% of silane coupling agent, 2.00-25.00% of film forming agent, 0-1.00% of plasticizer, 0.01-2.00% of lubricant, 0.01-2.00% of pH value regulator, 67.00-97.88% of water, the film forming agent is a mixture of a first film forming agent and a second film forming agent, and the mass ratio of the first film forming agent to the second film forming agent is 10:1-1:8. The glass fiber impregnating agent prepared by the patent is used to solve the problems of poor compatibility of the glass fiber with the thermoplastic matrix resin and uneven dispersion of the glass fiber in the mixing process, which finally leads to the problem of large fluctuation of the mechanical properties of the produced composite material. However, the glass fiber impregnating agent provided by the patent cannot improve the aging resistance of the pipe.

[0006] Chinese patent CN 112456817 A discloses an enhanced glass fiber sizing agent and its preparation method and application. The sizing agent comprises the following components, the content of each component is expressed as follows: coupling agent 0.1-2.0%; first film forming agent 0.5-2.0%; second film forming agent 1.5-10.0%; crosslinking agent 0.02-1.0%; lubricant 0.01-1.0%; pH value adjusting agent 0.02-1.0%; water 83.0-97.85%; wherein, the coupling agent is a silane coupling agent, and the coupling agent is a mixture of a first coupling agent and a second coupling agent; the first film forming agent is a polyurethane emulsion; and the second film forming agent is an epoxy emulsion. The enhanced glass fiber sizing agent prepared by the patent is used to improve the impregnation of glass fiber and epoxy resin in SMC process, but it cannot improve the aging resistance of the pipeline in high temperature environment.

[0007] At present, it is urgent to provide a sizing agent for aging-resistant epoxy pipeline yarn, which not only enables glass fiber to have low hairiness, fast impregnation, high bonding strength with epoxy resin and the like, but also has aging resistance, especially under high temperature storage conditions, still has high mechanical properties. SUMMARY

[0008] The purpose of the present application is to provide a sizing agent for aging-resistant epoxy pipeline yarn, which has good compatibility with epoxy resin, fast impregnation, and good aging resistance, and can make the mechanical property aging retention rate of the product higher. The present application also provides a preparation method of the sizing agent for aging-resistant epoxy pipeline yarn.

[0009] The sizing agent for aging-resistant epoxy pipeline yarn comprises a coupling agent, a lubricant, a film forming agent, a pH adjusting agent and deionized water, wherein the film forming agent is a mixture of bisphenol A type epoxy emulsion, polyurethane emulsion and phenolic epoxy emulsion.

[0010] The molecular weight of the bisphenol A type epoxy emulsion is 200-1000, and the particle size of the bisphenol A type epoxy emulsion is 0.2-3.6 μm.

[0011] The molecular weight of the polyurethane emulsion is 15000-35000, and the particle size of the polyurethane emulsion is 0.5-3.5 μm.

[0012] The molecular weight of the phenolic epoxy emulsion is 300-2000, and the particle size of the phenolic epoxy emulsion is 0.3-3.5 μm.

[0013] The mass ratio of the bisphenol A type epoxy emulsion, the polyurethane emulsion and the phenolic epoxy emulsion is 3-5:0.5-1.5:0.6-1.2, wherein the bisphenol A type epoxy emulsion is based on the solid mass in the bisphenol A type epoxy emulsion, the polyurethane emulsion is based on the solid mass in the polyurethane emulsion, and the phenolic epoxy emulsion is based on the solid mass in the phenolic epoxy emulsion.

[0014] The coupling agent is a mixture of an amino silane coupling agent and an epoxy silane coupling agent.

[0015] The mass ratio of the amino silane coupling agent and the epoxy silane coupling agent is 0.2-5:1, wherein the amino silane coupling agent is based on the solid mass in the amino silane coupling agent, and the epoxy silane coupling agent is based on the solid mass in the epoxy silane coupling agent.

[0016] The lubricant is a mixture of a cationic lubricant, PEG and a silicone oil lubricant, and the cationic lubricant is preferably a polyethylene imine cationic lubricant.

[0017] The pH regulator is one or more of formic acid, glacial acetic acid, citric acid or fluoroboric acid.

[0018] The solid mass of the infiltration agent accounts for 5-15% of the total mass of the infiltration agent, and the solid mass of each component in the infiltration agent accounts for the following percentage of the total solid mass in the infiltration agent:

[0019]

[0020] The solid mass of each component in the infiltration agent accounts for the following percentage of the total solid mass in the infiltration agent:

[0021]

[0022] The preparation method of the infiltration agent of the aging-resistant type epoxy pipeline yarn provided by the application comprises the following steps:

[0023] (1) The pH value regulator is first added to the deionized water and stirred, and then the coupling agent is added and stirred to obtain solution A;

[0024] (2) The bisphenol A type epoxy emulsion is added to the deionized water and stirred uniformly to obtain solution B;

[0025] (3) The polyurethane emulsion is added to the deionized water and stirred uniformly to obtain solution C;

[0026] (4) The phenolic epoxy emulsion is added to the deionized water and stirred uniformly to obtain solution D;

[0027] (5) The lubricant and hot water are stirred uniformly, and then cooled to room temperature to obtain solution E;

[0028] (6) stirring the solution A, the solution B, the solution C, the solution D, the solution E and the remaining deionized water to obtain the aging-resistant epoxy pipe yarn impregnating agent.

[0029] The adding amount of the deionized water in step (1) is 30-40% of the mass of the aging-resistant epoxy pipe yarn impregnating agent.

[0030] The adding amount of the deionized water in step (2) is 0.5-1 times of the mass of the bisphenol A type epoxy emulsion.

[0031] The adding amount of the deionized water in step (3) is 0.5-1 times of the mass of the polyurethane emulsion.

[0032] The adding amount of the deionized water in step (4) is 0.5-1 times of the mass of the phenolic epoxy emulsion.

[0033] The adding amount of the water in step (5) is 10-15 times of the mass of the lubricant.

[0034] The impregnating agent of the present application can be applied to the epoxy pipe glass fiber.

[0035] The coupling agent in the present application has strong reactivity, and generates silicon hydroxyl through its own hydrolysis reaction, on one hand, the silicon hydroxyl can chemically react with the hydroxyl on the surface of the glass fiber, on the other hand, the other groups of the silane coupling agent chemically react with the resin matrix, through the coupling agent acting on the fiber and the resin matrix respectively at both ends, a dense spatial network structure is formed, the function of the fiber reinforcing the resin matrix is fully played, and the mechanical properties of the composite material are improved.

[0036] The coupling agent in the present application is a mixture of amino silane coupling agent and epoxy silane coupling agent, and both of the selected coupling agents have good compatibility with epoxy resin. The amino silane coupling agent can react with the epoxy groups in the bisphenol A type epoxy emulsion and the epoxy silane coupling agent, and part of the amino silane coupling agent can react with the epoxy groups in the bisphenol A type epoxy emulsion and the epoxy silane coupling agent at room temperature. The reaction of the amino silane coupling agent and the epoxy silane coupling agent increases the reaction sites of the glass fiber surface and the resin base, and forms high and low reaction sites on the glass fiber surface. The reaction of part of the amino silane coupling agent and the epoxy groups in the bisphenol A type epoxy emulsion forms a relatively long molecular chain structure. The relatively long molecular chain is dissolved in the epoxy resin during the process of resin penetrating the fiber, and increases the connection between the glass fiber and the resin after the resin is cured, so that the spatial network structure of the formed composite material interface is more compact. Moreover, the relatively long molecular structure formed by the reaction is closer to the glass fiber surface during the long-term storage and transportation of the original wire, which reduces the problem of performance degradation of the glass fiber due to temperature change and water vapor erosion, better protects the glass fiber surface, and basically does not age during storage and transportation. The amino silane coupling agent selected in the present application is mainly aromatic amino silane, amino silane containing secondary amine, tertiary amine, amide or urea-based silane. The amino silane coupling agent is preferably polyamide silane, modified amino silane or aniline silane, such as Momentive A-1387, A-1126 and A-1128. The urea-based silane is preferably gamma-urea propyl trialkoxy silane, such as Momentive A-1160. The epoxy silane coupling agent is preferably gamma-glycidyl ether propyl trimethoxy silane or 3-glycidyl ether propyl methyl diethoxy silane, such as Momentive A-187 and Wetlink 78.

[0037] In the present application, the coupling agent is a mixture of coupling agent A and coupling agent B. Coupling agent A is an amino silane coupling agent, and coupling agent B is an epoxy silane coupling agent. The solid mass of coupling agent A accounts for 2-12% of the total solid mass in the infiltration agent, preferably 3-10%. The solid mass of coupling agent B accounts for 3-13% of the total solid mass in the infiltration agent, preferably 5-12%.

[0038] The film forming agent, also known as the adhesive, is the main component of the infiltration agent system. For the yarn used for aging-resistant high-pressure pipes, the film forming agent can not only realize the bundling of single filaments and maintain the integrity of the original wire, but also can give the glass fiber good processability, and can also make the glass fiber quickly and completely penetrate the epoxy resin and have good compatibility with the epoxy resin. In addition to the above functions, the film forming agent selected in the present application also needs to consider that the glass fiber yarn has good initial performance and stable aging-resistant performance (long-term storage or high-temperature use performance does not decrease) after the composite material high-pressure pipe is made.

[0039] The film forming agent in the present application is the main film forming agent and auxiliary film forming agent in the infiltrating agent, the main film forming agent is bisphenol A type epoxy emulsion, and the auxiliary film forming agent is polyurethane emulsion and phenolic epoxy emulsion. The phenolic epoxy emulsion has a molecular weight of 300-2000, preferably 500-1500, and an emulsion particle size of 0.3-3.5 μm; the purpose of adding the phenolic epoxy emulsion is to enable the glass fiber to have good flexibility and permeability while having good heat resistance, thereby improving the anti-aging performance of the produced composite material pipeline under high temperature environment; the polyurethane emulsion has a molecular weight of 15000-35000, preferably 20000-30000, and an emulsion particle size of 0.5-3.5 μm; the micro-crosslinking reaction between the hydroxyl and the urethane in the polyurethane molecule and the epoxy group in the epoxy emulsion improves the toughness and tensile strength of the glass fiber, and enables the glass fiber to have good process performance and water resistance.

[0040] The film forming agent in the present application is the main film forming agent and auxiliary film forming agent in the infiltrating agent, the main film forming agent is bisphenol A type epoxy emulsion, and the auxiliary film forming agent is polyurethane emulsion and phenolic epoxy emulsion.

[0041] The film forming agent in the present application is the main film forming agent and auxiliary film forming agent in the infiltrating agent, the main film forming agent is bisphenol A type epoxy emulsion, and the auxiliary film forming agent is polyurethane emulsion and phenolic epoxy emulsion.

[0042] The film forming agent in the present application is the main film forming agent and auxiliary film forming agent in the infiltrating agent, the main film forming agent is bisphenol A type epoxy emulsion, and the auxiliary film forming agent is polyurethane emulsion and phenolic epoxy emulsion.

[0043] The pH adjusting agent is used to adjust the pH value of the infiltrating agent, so that the infiltrating agent can be stably stored without delamination.

[0044] The solid content of the infiltrating agent is 5-15%, and the pH value is 3-7.

[0045] The combustible content (LOI) of the glass fiber prepared by using the sizing agent of the present application is generally controlled between 0.35-0.85%, preferably between 0.40-0.70%, which is mainly a theoretical reference value for the performance of the final product composite material.

[0046] The beneficial effects of the present application are as follows:

[0047] Compared with the prior art, the sizing agent system of the present application has two innovations: the first innovation is to use amino silane and epoxy silane coupling agent to match the epoxy emulsion system of bisphenol A type epoxy emulsion and phenolic epoxy emulsion, the amino group reacts with the epoxy group, this reaction can increase the reaction sites on the surface of the glass fiber, and form a more compact composite material interface with the resin, thus better protecting the composite material interface and reducing the performance decline and other aging phenomena caused by high temperature and high humidity erosion; the second innovation is to use a mixture of bisphenol A type epoxy emulsion as the main film former, and polyurethane emulsion and phenolic epoxy emulsion as the auxiliary, selecting a relatively low molecular weight bisphenol A type epoxy emulsion as the main film former can ensure good softness and permeability of the glass fiber, adding auxiliary phenolic epoxy emulsion can make the composite material pipe made of the glass fiber coated with the sizing agent have more excellent aging resistance in high temperature environment, and adding polyurethane emulsion with relatively high molecular weight is because the polyurethane emulsion and the epoxy emulsion have a micro-crosslinking reaction, which improves the toughness and tensile strength of the glass fiber, and makes the glass fiber have good process performance and water resistance.

[0048] The glass fiber produced by using the sizing agent of the present application has good compatibility with epoxy resin, good production process performance, and stable aging resistance performance, and is suitable for producing epoxy pipes, especially in areas with high temperature all year round. Chemical reactions occur between the film formers and between the coupling agents, and appropriate raw material combination can ensure good infiltration of the glass fiber in the resin, unify the softness and stiffness of the fiber, reduce the hairiness of the glass fiber during pipe production, and the produced pipe has high strength retention rate after high temperature boiling.

[0049] The glass fiber product produced by using the sizing agent of the present application has good compatibility with epoxy resin, and also has good process performance for winding pipes, good wear resistance, less hairiness, and fast penetration speed; the glass fiber produced by using the sizing agent has no performance decline after high temperature aging, and the epoxy high pressure pipe produced by using the glass fiber has higher aging retention rate of composite material performance after boiling in boiling water for 1500h.

[0050] According to the technical characteristics of the epoxy pipe winding process, by selecting raw materials and optimizing the proportion of formula components, and using suitable and mature glass fiber production process, the product has better aging resistance stability, and meets the production requirements of high pressure pipes. DETAILED DESCRIPTION

[0051] The application is further described below in conjunction with examples.

[0052] The components of the infiltrating agent are as follows:

[0053] The coupling agents A / B are respectively: Meitu A-1160, A-187;

[0054] The film forming agents A / B / C are respectively: HY-208, HY-391, HY-282, all produced by Taishan Glass Fiber Co., Ltd.;

[0055] The lubricants A / B / C are respectively: PMX200-500CST of Kaimeng Chemical, 6760L of Cognis Chemical, and PEG400MO of Nanjing Well;

[0056] The pH regulator is: glacial acetic acid.

[0057] The preparation method of the infiltrating agent of examples 1-5 and comparative examples 1-5 comprises the following steps:

[0058] (1) 30% of the total preparation amount of room temperature deionized water is added to the first preparation container, and the pH regulator is added while stirring; coupling agent A is added to the first preparation container under the condition of ensuring uniform stirring and no air bubbles, and stirring is continued until there are no oil flowers on the water surface and the solution is clear and not turbid, then coupling agent B is added, and stirring is continued until there are no oil flowers on the water surface and the solution is clear and not turbid, to obtain solution A;

[0059] (2) room temperature deionized water is added to the second preparation container, and film forming agent A is added and stirred uniformly to obtain solution B; the amount of deionized water added is 1 times the mass of film forming agent A;

[0060] (3) room temperature deionized water is added to the third preparation container, and film forming agent B is added and stirred uniformly to obtain solution C; the amount of deionized water added is 1 times the mass of film forming agent B;

[0061] (4) room temperature deionized water is added to the fourth preparation container, and film forming agent C is added and stirred uniformly to obtain solution D; the amount of deionized water added is 1 times the mass of film forming agent C;

[0062] (5) lubricant is added to the fifth preparation container, and hot water is added to the container, stirred uniformly, and cooled to room temperature to obtain solution E; the lubricant is a mixture of lubricant A, lubricant B, and lubricant C, and the amount of water added is 10 times the mass of the lubricant;

[0063] (6) solution A, solution B, solution C, solution D, and solution E are sequentially added to the sixth preparation container, and the remaining amount of room temperature deionized water is added, and the mixture is stirred uniformly to obtain the infiltrating agent.

[0064] The specific infiltration agent formula, glass fiber performance and composite material performance are shown in Table 1 (the proportion of each component is calculated based on the proportion of the effective solid mass of each component in the total solid mass in the infiltration agent):

[0065] Table 1 Infiltration agent formula, glass fiber performance and composite material performance of Examples 1-5 and Comparative Examples 1-5

[0066]

[0067]

[0068] The high-pressure pipe was produced by a high-pressure pipe production line produced by Haerbin Yidao, the epoxy resin was Nanya 127H, the pipe tensile strength test standard was ASTM D638, and the pipe shear strength test standard was ASTM D2344.

[0069] In Table 1, 50℃ / 49d aging refers to that the glass fiber is aged at 50℃ / 49d, then wound on the high-pressure pipe, cut and tested; 95℃ / 1500h aging refers to that the glass fiber yarn is wound on the high-pressure pipe composite material, cut and tested after the sample is boiled in 95℃ water for 1500 hours.

[0070] As shown in Table 1, the pipe tensile strength, shear strength, high-temperature aging resistance of the glass fiber yarn and the high-temperature water boiling resistance of the pipe of Examples 1-5 are obviously superior to those of Comparative Examples 1-5.

Claims

1. A sizing agent for aging-resistant epoxy pipe yarn, characterized in that... It is composed of coupling agent, lubricant, film-forming agent, pH adjuster and deionized water, wherein the film-forming agent is a mixture of bisphenol A type epoxy emulsion, polyurethane emulsion and phenolic epoxy emulsion; The molecular weight of the bisphenol A type epoxy emulsion is 200-1000; The molecular weight of the polyurethane emulsion is 15,000-35,000; The molecular weight of the phenolic epoxy emulsion is 300-2000; The coupling agent is a mixture of aminosilane coupling agents and epoxysilane coupling agents; The solid mass of the wetting agent accounts for 5-15% of the total mass of the wetting agent. The percentage of the solid mass of each component in the total solid mass of the wetting agent is as follows: Coupling agent 5-25% Film-forming agent 55-80% Lubricant 7-21% pH adjuster 1-3%.

2. The impregnating agent for the aging-resistant epoxy pipe yarn according to claim 1, characterized in that... The particle size of the bisphenol A type epoxy emulsion is 0.2-3.6 μm.

3. The impregnating agent for the aging-resistant epoxy pipe yarn according to claim 1, characterized in that... The particle size of the polyurethane emulsion is 0.5-3.5 μm.

4. The impregnating agent for the aging-resistant epoxy pipe yarn according to claim 1, characterized in that... The particle size of the phenolic epoxy emulsion is 0.3-3.5 μm.

5. The impregnating agent for the aging-resistant epoxy pipe yarn according to claim 1, characterized in that... The mass ratio of the bisphenol A type epoxy emulsion, polyurethane emulsion, and phenolic epoxy emulsion is 3-5:0.5-1.5:0.6-1.2, wherein the bisphenol A type epoxy emulsion is based on the solid mass of the bisphenol A type epoxy emulsion, the polyurethane emulsion is based on the solid mass of the polyurethane emulsion, and the phenolic epoxy emulsion is based on the solid mass of the phenolic epoxy emulsion.

6. The impregnating agent for the aging-resistant epoxy pipe yarn according to claim 1, characterized in that... The mass ratio of the aminosilane coupling agent to the epoxysilane coupling agent is 0.2-5:1, wherein the aminosilane coupling agent is based on the solid mass of the aminosilane coupling agent, and the epoxysilane coupling agent is based on the solid mass of the epoxysilane coupling agent.

7. The impregnating agent for the aging-resistant epoxy pipe yarn according to claim 1, characterized in that... The lubricant is a mixture of cationic lubricant, PEG and silicone oil lubricant, and the pH adjuster is one or more of formic acid, glacial acetic acid, citric acid or fluoroboric acid.

8. A method for preparing an impregnating agent for an aging-resistant epoxy pipe yarn according to any one of claims 1-7, characterized in that... Includes the following steps: (1) First, add a pH adjuster to deionized water and stir, then add a coupling agent and stir to obtain solution A; (2) Add bisphenol A type epoxy emulsion to deionized water and stir evenly to obtain solution B; (3) Add polyurethane emulsion to deionized water and stir until homogeneous to obtain solution C; (4) Add phenolic epoxy emulsion to deionized water and stir well to obtain solution D; (5) Stir the lubricant and hot water evenly, cool to room temperature, and obtain solution E; (6) Mix solutions A, B, C, D, E and the remaining deionized water evenly to obtain an impregnating agent for aging-resistant epoxy pipe yarn.

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