Resin-based paraffin impregnating compound as well as preparation method and application thereof

Abstract

The invention relates to the technical field of impregnating compounds, in particular to a resin-based paraffin impregnating compound as well as a preparation method and application thereof. The preparation method comprises the following steps: mixing paraffin emulsion, transformer oil emulsion, dibutyl phthalate emulsion, epoxy emulsion, epoxy resin and water to obtain the resin-based paraffin impregnating compound; the preparation method comprises the following steps: preparing a paraffin emulsion, a transformer oil emulsion or a dibutyl phthalate emulsion: pre-emulsifying paraffin / transformer oil / dibutyl phthalate and a No.2 emulsifier to obtain a paraffin pre-emulsified liquid / transformer oil pre-emulsified liquid / dibutyl phthalate pre-emulsified liquid; and mixing a No.1 emulsifier aqueous solution with the paraffin / transformer oil / dibutyl phthalate pre-emulsion, and then emulsifying to obtain the product. The resin-based paraffin impregnating compound prepared by the preparation method disclosed by the invention is relatively small in viscosity, can improve the bundling property and dispersion uniformity of glass fibers, reduces the phenomenon of filament dispersion, and also can enhance the chemical stability and corrosion resistance of the glass fibers.

Description

Technical Field

[0001] The present invention relates to the technical field of sizing agents, and in particular to a resin-based paraffin sizing agent, a preparation method thereof, and an application thereof. Background Art

[0002] Glass fiber is an inorganic non-metallic composite material with very excellent properties and friendly to the environment. With the rapid development of economy and technology, the market has a relatively high demand for this composite material of glass fiber, and it has been applied in many fields and has become an indispensable raw material in many industries. Among them, binary glass fiber has attracted much attention in the glass fiber industries of various countries due to its advantages of high performance, low cost, and low pollution. Currently, it has been widely used in spacecraft thermal ablation materials, high-temperature resistant and heat-insulating bodies. However, binary high-silica glass fiber has poor chemical stability, is easily corroded by environmental media, is difficult to store, and the tensile fracture strength will rapidly decrease in the air, and the fibers will coagulate with each other, making it impossible to perform reeling and weaving. And the sizing agent plays a role of protection, lubrication, and bundling in glass fiber.

[0003] Currently, paraffin-based sizing agents are mainly used in the market. However, the glass fibers treated with the paraffin-based sizing agents prepared by the prior art have relatively poor bundling properties, and the phenomenon of loose filaments is serious. Summary of the Invention

[0004] Aiming at the problems existing in the prior art, the present invention provides a resin-based paraffin sizing agent, a preparation method thereof, and an application thereof. In the present invention, paraffin, transformer oil, and dibutyl phthalate are respectively made into emulsions, and these emulsions are compounded with the film-forming agent epoxy resin and epoxy emulsion to obtain a resin-based paraffin sizing agent. Compared with the paraffin-based sizing agent, the resin-based paraffin sizing agent obtained by this method has less viscosity, can not only significantly improve the bundling property and dispersion uniformity of glass fiber, reduce the phenomenon of loose filaments, but also effectively enhance the chemical stability and corrosion resistance of glass fiber, and extend its service life in a complex environment.

[0005] In order to achieve the above object, the technical solution adopted in the present application is as follows:

[0006] The first object of the present invention is to provide a preparation method of a resin-based paraffin sizing agent, including the following steps:

[0007] Mix the paraffin emulsion, transformer oil emulsion, dibutyl phthalate emulsion, epoxy emulsion, epoxy resin and water to obtain a resin-based paraffin sizing agent.

[0008] The paraffin emulsion, transformer oil emulsion or dibutyl phthalate emulsion is prepared according to the following steps:

[0009] Mix water and emulsifier No. 1 to obtain a mixed solution; pre-emulsify paraffin / transformer oil / dibutyl phthalate with emulsifier No. 2 to obtain paraffin pre-emulsion / transformer oil pre-emulsion / dibutyl phthalate pre-emulsion; mix the mixed solution with paraffin pre-emulsion / transformer oil pre-emulsion / dibutyl phthalate pre-emulsion and then carry out emulsification treatment to obtain paraffin emulsion / transformer oil emulsion / dibutyl phthalate emulsion.

[0010] The solid content of the paraffin emulsion is 27.21% - 41.63%, the solid content of the transformer oil emulsion is 27.21% - 41.63%, and the solid content of the dibutyl phthalate emulsion is 17.34% - 33.85%.

[0011] In the resin-based paraffin sizing agent, the mass percentages of paraffin emulsion, transformer oil emulsion, dibutyl phthalate emulsion, epoxy emulsion and epoxy resin are 1.7% - 2.1%, 7% - 9%, 6% - 8%, 5% - 6% and 0.3% - 0.7% respectively, and the balance is water; and the sum of the mass percentages of paraffin emulsion, transformer oil emulsion, dibutyl phthalate emulsion, epoxy emulsion, epoxy resin and water is 100%.

[0012] Preferably, the conditions for the mixing treatment are: stirring at 80°C - 90°C and 400 r / min - 600 r / min for 30 min - 50 min.

[0013] Preferably, emulsifier No. 1 is selected from Tween 80.

[0014] Preferably, the mass ratio of emulsifier No. 1 to water is 0.8 - 1.2:12 - 15.

[0015] Preferably, emulsifier No. 2 is selected from one or two of Span 80 and Peregal O, and Tween 80, Span 80 and Peregal O can all keep the paraffin emulsion / transformer oil emulsion / dibutyl phthalate emulsion from separating.

[0016] Preferably, the mass ratio of emulsifier No. 2 to paraffin / transformer oil / dibutyl phthalate is 8 - 10:46 - 54.

[0017] Preferably, the conditions for the emulsification treatment are: stirring at 70°C - 95°C and 400 r / min - 650 r / min for 30 min - 80 min.

[0018] The second object of the present invention is to provide a resin-based paraffin sizing agent prepared by the above preparation method.

[0019] The third object of the present invention is to provide the application of the above resin-based paraffin sizing agent in the preparation of resin-based paraffin sizing agent glass fibers.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] 1. The present invention provides a preparation method of a resin-based paraffin-type sizing agent. Mix paraffin emulsion, transformer oil emulsion, dibutyl phthalate emulsion, epoxy emulsion, epoxy resin and water to obtain the resin-based paraffin-type sizing agent. The paraffin emulsion, transformer oil emulsion or dibutyl phthalate emulsion is prepared according to the following steps: Mix water and the first emulsifier to obtain a mixed solution; Pre-emulsify paraffin / transformer oil / dibutyl phthalate with the second emulsifier to obtain a paraffin pre-emulsion / transformer oil pre-emulsion / dibutyl phthalate pre-emulsion; Mix the mixed solution with the paraffin / transformer oil / dibutyl phthalate pre-emulsion and then perform emulsification treatment to obtain a paraffin emulsion / transformer oil emulsion / dibutyl phthalate emulsion. The solid content of the paraffin emulsion is 27.21% - 41.63%, the solid content of the transformer oil emulsion is 27.21% - 41.63%, and the solid content of the dibutyl phthalate emulsion is 17.34% - 33.85%. In the resin-based paraffin-type sizing agent, the mass percentages of the paraffin emulsion, transformer oil emulsion, dibutyl phthalate emulsion, epoxy emulsion and epoxy resin are 1.7% - 2.1%, 7% - 9%, 6% - 8%, 5% - 6%, 0.3% - 0.7% respectively, and the balance is water; and the sum of the mass percentages of the paraffin emulsion, transformer oil emulsion, dibutyl phthalate emulsion, epoxy emulsion, epoxy resin and water is 100%.

[0022] Among them, the paraffin emulsion mainly plays the roles of lubrication and film formation, which can reduce the friction of glass fibers during processing and at the same time form a protective film to prevent glass fibers from being damaged; the transformer oil emulsion can endow glass fibers with good lubricity, so that when the glass fibers are mechanically worn during deep processing, no obvious hairiness appears; the dibutyl phthalate emulsion acts as a plasticizer, which can increase the flexibility and weather resistance of the resin-based paraffin-type sizing agent film layer and prevent cracks from occurring in the resin-based paraffin-type sizing agent film layer during the drying process; the epoxy emulsion and epoxy resin are used as the main film-forming substances, which enhance the bonding force between the resin-based paraffin-type sizing agent and glass fibers and improve the adhesion and durability of the resin-based paraffin-type sizing agent on the surface of glass fibers.

[0023] By preparing paraffin wax, transformer oil, and dibutyl phthalate into emulsions respectively and then compounding them with epoxy emulsion and epoxy resin, the present invention effectively avoids the direct aggregation and precipitation of each component in the resin-based paraffin sizing agent, improves the stability and hydrophilicity of the resin-based paraffin sizing agent, enables the resin-based paraffin sizing agent to be coated more uniformly on the surface of glass fibers, enhances the interaction force between the resin-based paraffin sizing agent and glass fibers, and thus improves the mechanical properties and bundling property of glass fibers. In addition, by introducing epoxy resin and epoxy emulsion, the film layer formed by the resin-based paraffin sizing agent on the surface of glass fibers is more flexible and not easily broken, effectively improving the bundling property of the resin-based paraffin sizing agent for glass fibers and the unwinding performance of the yarn bobbin.

[0024] 2. The resin-based paraffin sizing agent provided by the present invention has a potential value as high as 23.47 mV, indicating that there is a strong electrostatic force between the droplets of the resin-based paraffin sizing agent of the present invention. This strong electrostatic force further consolidates the stability of the resin-based paraffin sizing agent, effectively preventing the occurrence of adverse phenomena such as coagulation or stratification during its use, and ensuring the long-term stability and excellent performance of the resin-based paraffin sizing agent.

[0025] 3. The present invention also applies the obtained resin-based paraffin sizing agent to the preparation of resin-based paraffin sizing agent glass fibers. Compared with the paraffin sizing agent glass fibers used in the current technology, the resin-based paraffin sizing agent glass fibers of the present invention exhibit more excellent mechanical properties. Specifically, its breaking strength is as high as 11 N, and the linear shrinkage rate is precisely controlled at 3.06%; in terms of hydrophilic performance, the water contact angle is as low as 6°, showing excellent hydrophilicity; in addition, the resin-based paraffin sizing agent glass fibers also have higher bundling property, and their performance is significantly better than that of paraffin sizing agent glass fibers. Description of the Drawings

[0026] Figure 1 It is the appearance diagram of the paraffin emulsion, transformer oil emulsion, and dibutyl phthalate emulsion in Example 1 of the present invention.

[0027] Figure 2 It is the diagram of the emulsion skin formation of the transformer oil emulsion standing for 24 h under different stirring rates in the present invention, where (a) is 400 r / min, (b) is 600 r / min, and (c) is 650 r / min.

[0028] Figure 3 It is the diagram of the emulsion stratification of the transformer oil emulsion standing for 24 h under different stirring rates in the present invention, where (a) is 400 r / min, (b) is 600 r / min, and (c) is 650 r / min.

[0029] Figure 4Diagram of the stratification situation of the transformer oil emulsion after centrifugation at different stirring rates in the present invention, where (a) is 400 r / min, (b) is 600 r / min, and (c) is 650 r / min.

[0030] Figure 5 Diagrams of the pH, particle size, solid content, and potential of the transformer oil emulsion at different stirring rates in the present invention, where (a) is the pH diagram of the transformer oil emulsion, (b) is the particle size diagram of the transformer oil emulsion, (c) is the solid content diagram of the transformer oil emulsion, and (d) is the potential diagram of the transformer oil emulsion.

[0031] Figure 6 Diagram of the skin formation situation of the transformer oil emulsion after standing for 24 h at different stirring times in the present invention, where (a) is 40 min, (b) is 60 min, and (c) is 80 min.

[0032] Figure 7 Diagram of the stratification situation of the transformer oil emulsion after standing for 24 h at different stirring times in the present invention, where (a) is 40 min, (b) is 60 min, and (c) is 80 min.

[0033] Figure 8 Diagram of the stratification situation of the transformer oil emulsion after centrifugation at different stirring times in the present invention, where (a) is 40 min, (b) is 60 min, and (c) is 80 min.

[0034] Figure 9 Diagrams of the pH, particle size, solid content, and potential of the transformer oil emulsion at different stirring times in the present invention, where (a) is the pH diagram of the transformer oil emulsion, (b) is the particle size diagram of the transformer oil emulsion, (c) is the solid content diagram of the transformer oil emulsion, and (d) is the potential diagram of the transformer oil emulsion.

[0035] Figure 10 Diagram of the skin formation situation of the transformer oil emulsion after standing for 24 h at different stirring temperatures in the present invention, where (a) is 75 °C, (b) is 85 °C, and (c) is 95 °C.

[0036] Figure 11 Diagram of the stratification situation of the transformer oil emulsion after standing for 24 h at different stirring temperatures in the present invention, where (a) is 75 °C, (b) is 85 °C, and (c) is 95 °C.

[0037] Figure 12 Diagram of the stratification situation of the transformer oil emulsion after centrifugation at different stirring temperatures in the present invention, where (a) is 75 °C, (b) is 85 °C, and (c) is 95 °C.

[0038] Figure 13pH, particle size, solid content, and potential diagrams of transformer oil emulsions at different stirring temperatures of the present invention. Among them, (a) is the pH diagram of the transformer oil emulsion, (b) is the particle size diagram of the transformer oil emulsion, (c) is the solid content diagram of the transformer oil emulsion, and (d) is the potential diagram of the transformer oil emulsion.

[0039] Figure 14 Diagram of the skin formation situation of dibutyl phthalate emulsions after standing for 24h at different stirring temperatures of the present invention. Among them, (a) is at 75°C, (b) is at 85°C, and (c) is at 95°C.

[0040] Figure 15 Diagram of the layering situation of dibutyl phthalate emulsions after standing for 24h at different stirring temperatures of the present invention. Among them, (a) is at 75°C, (b) is at 85°C, and (c) is at 95°C.

[0041] Figure 16 Diagram of the layering situation of dibutyl phthalate emulsions after centrifugation at different stirring temperatures of the present invention. Among them, (a) is at 75°C, (b) is at 85°C, and (c) is at 95°C.

[0042] Figure 17 pH, particle size, solid content, and potential diagrams of dibutyl phthalate emulsions at different stirring temperatures of the present invention. Among them, (a) is the pH diagram of the dibutyl phthalate emulsion, (b) is the particle size diagram of the dibutyl phthalate emulsion, (c) is the solid content diagram of the dibutyl phthalate emulsion, and (d) is the potential diagram of the dibutyl phthalate emulsion.

[0043] Figure 18 Diagram of the skin formation situation of dibutyl phthalate emulsions after standing for 24h at different stirring times of the present invention. Among them, (a) is 60 min, (b) is 70 min, and (c) is 80 min.

[0044] Figure 19 Diagram of the layering situation of dibutyl phthalate emulsions after standing for 24h at different stirring times of the present invention. Among them, (a) is 60 min, (b) is 70 min, and (c) is 80 min.

[0045] Figure 20 Diagram of the layering situation of dibutyl phthalate emulsions after centrifugation at different stirring times of the present invention. Among them, (a) is 60 min, (b) is 70 min, and (c) is 80 min.

[0046] Figure 21pH, particle size, solid content, and potential diagrams of dibutyl phthalate emulsion under different stirring times of the present invention. Among them, (a) is the pH diagram of dibutyl phthalate emulsion, (b) is the particle size diagram of dibutyl phthalate emulsion, (c) is the solid content diagram of dibutyl phthalate emulsion, and (d) is the potential diagram of dibutyl phthalate emulsion.

[0047] Figure 22 Diagram of the skin formation of dibutyl phthalate emulsion after standing for 24 h under different stirring rates of the present invention. Among them, (a) is 400 r / min, (b) is 600 r / min, and (c) is 650 r / min.

[0048] Figure 23 Diagram of the layer separation of dibutyl phthalate emulsion after standing for 24 h under different stirring rates of the present invention. Among them, (a) is 400 r / min, (b) is 600 r / min, and (c) is 650 r / min.

[0049] Figure 24 Diagram of the layer separation of dibutyl phthalate emulsion after centrifugation under different stirring rates of the present invention. Among them, (a) is 400 r / min, (b) is 600 r / min, and (c) is 650 r / min.

[0050] Figure 25 pH, particle size, solid content, and potential diagrams of dibutyl phthalate emulsion under different stirring rates of the present invention. Among them, (a) is the pH diagram of dibutyl phthalate emulsion, (b) is the particle size diagram of dibutyl phthalate emulsion, (c) is the solid content diagram of dibutyl phthalate emulsion, and (d) is the potential diagram of dibutyl phthalate emulsion.

[0051] Figure 26 SEM morphology diagrams of water-soaked monofilaments, water-soaked stranded filaments, acid-soaked monofilaments, and acid-soaked stranded filaments. Among them, (a) is the SEM morphology diagram of water-soaked monofilaments, (b) is the SEM morphology diagram of water-soaked stranded filaments, (c) is the SEM morphology diagram of acid-soaked monofilaments, and (d) is the SEM morphology diagram of acid-soaked stranded filaments.

[0052] Figure 27 Contact angle diagrams of paraffin-type sizing glass fiber and resin-based paraffin-type sizing glass fiber. Among them, (a) is the contact angle diagram of paraffin-type sizing glass fiber, and (b) is the contact angle diagram of resin-based paraffin-type sizing glass fiber.

[0053] Figure 28 Micrographs of paraffin-type sizing glass fiber and resin-based paraffin-type glass fiber. Among them, (a) is the micrograph of paraffin-type sizing glass fiber, and (b) is the micrograph of resin-based paraffin-type sizing glass fiber. Detailed implementation manners

[0054] The technical solution of the present invention will be clearly and completely described below in conjunction with the data in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention. Among them, paraffin wax, Peregal O, epoxy resin, epoxy emulsion were purchased from Shaanxi Huate New Materials Co., Ltd.; transformer oil was purchased from Dongguan Zhongtang Feima White Oil Trading Department; Tween 80 and dibutyl phthalate were purchased from Shanghai Macklin Biochemical Co., Ltd.

[0055] The paraffin-based sizing agent prepared by the prior art has a relatively large viscosity and is likely to form a hard film on the surface of the roving. This hard film will become hard and prone to cracking after drying, resulting in poor bundling property of the fibers and serious fiber dispersion phenomenon. In addition, a large amount of paraffin-based sizing agent will splash onto the surface of the bobbin during the processing, making the bobbin sticky, thus prone to interlayer breakage problems during unwinding.

[0056] In view of the problems existing in the prior art, the present invention provides a preparation method of a resin-based paraffin sizing agent, which includes the following steps: mixing paraffin emulsion, transformer oil emulsion, dibutyl phthalate emulsion, epoxy emulsion, epoxy resin and water to obtain a resin-based paraffin sizing agent.

[0057] In the present invention, after paraffin, transformer oil, and dibutyl phthalate are respectively made into emulsions and then compounded with epoxy emulsion and epoxy resin, it effectively avoids the direct aggregation and precipitation of each component in the resin-based paraffin sizing agent, improves the stability and hydrophilicity of the resin-based paraffin sizing agent, enables the resin-based paraffin sizing agent to be more evenly coated on the surface of glass fiber, enhances the interaction force between the resin-based paraffin sizing agent and glass fiber, thereby improving the mechanical properties and bundling property of glass fiber. In addition, by introducing epoxy resin and epoxy emulsion, the film layer formed by the resin-based paraffin sizing agent on the surface of glass fiber is more flexible and not prone to cracking, effectively improving the bundling property of the resin-based paraffin sizing agent for glass fiber and the unwinding performance of the bobbin.

[0058] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in conjunction with specific embodiments.

[0059] Example 1

[0060] A preparation method of a resin-based paraffin sizing agent includes the following steps:

[0061] Mix 1.9% paraffin emulsion, 8.0% transformer oil emulsion, 7.0% dibutyl phthalate emulsion, 5.5% epoxy emulsion and 0.5% epoxy resin with water at 85°C, and shear at 500 r / min for 40 min to obtain a resin-based paraffin sizing agent.

[0062] Example 2

[0063] A preparation method of a resin-based paraffin sizing agent is the same as that of Example 1, except that 1.9% paraffin emulsion, 8.0% transformer oil emulsion, 7.0% dibutyl phthalate emulsion, 5.5% epoxy emulsion and 0.5% epoxy resin are replaced with 1.7% paraffin emulsion, 7.0% transformer oil emulsion, 6.0% dibutyl phthalate emulsion, 5% epoxy emulsion and 0.3% epoxy resin to obtain a resin-based paraffin sizing agent.

[0064] Example 3

[0065] A preparation method of a resin-based paraffin sizing agent is the same as that of Example 1, except that 1.9% paraffin emulsion, 8.0% transformer oil emulsion, 7.0% dibutyl phthalate emulsion, 5.5% epoxy emulsion and 0.5% epoxy resin are replaced with 2.1% paraffin emulsion, 9.0% transformer oil emulsion, 8.0% dibutyl phthalate emulsion, 6% epoxy emulsion and 0.7% epoxy resin to obtain a resin-based paraffin sizing agent.

[0066] Example 4

[0067] A preparation method of a resin-based paraffin sizing agent is the same as that of Example 1, except that the mixing temperature is replaced from 85°C to 80°C to obtain a resin-based paraffin sizing agent.

[0068] Example 5

[0069] A preparation method of a resin-based paraffin sizing agent is the same as that of Example 1, except that the mixing temperature is replaced from 85°C to 90°C to obtain a resin-based paraffin sizing agent.

[0070] Example 6

[0071] A preparation method of a resin-based paraffin sizing agent is the same as that of Example 1, except that shearing at 500 r / min for 40 min is replaced with shearing at 400 r / min for 50 min to obtain a resin-based paraffin sizing agent.

[0072] Example 7

[0073] A preparation method of a resin-based paraffin sizing agent is the same as that of Example 1, except that shearing at 500 r / min for 40 min is replaced by shearing at 600 r / min for 30 min to obtain the resin-based paraffin sizing agent.

[0074] The paraffin emulsion, transformer oil emulsion or dibutyl phthalate emulsion used is prepared according to the following steps:

[0075] Weigh 20 g of paraffin / transformer oil / dibutyl phthalate solid respectively and place them in a three-necked flask. Stir and melt them in a water bath at 85 °C. Add 3.6 g of Span 80 to the molten paraffin and stir. Then weigh 74 g of distilled water in a beaker, add 5.4 g of Tween 80 to the distilled water, and place it in a constant temperature water bath to heat. When the temperature rises to about 85 °C, slowly drop it into the three-necked flask. After dropping, stir at high speed for 40 min, remove the water bath, and cool to room temperature to obtain the paraffin emulsion / transformer oil emulsion / dibutyl phthalate emulsion. Seal and reserve it.

[0076] On the basis of the above preparation methods of paraffin emulsion, transformer oil emulsion and dibutyl phthalate emulsion, the present invention also designs a single-factor influence experiment for emulsification time, emulsification temperature and emulsification shear rate.

[0077] Figure 1 It is the appearance diagram of the paraffin emulsion, transformer oil emulsion and dibutyl phthalate emulsion in Example 1 of the present invention. According to the HLB calculation formula, the best compounding ratio of the three surface emulsifiers Tween 80, Span 80 and Peregal is m(Span 80):m(Tween 80):m(Peregal)=12:15:5, and finally water-in-oil paraffin emulsion, transformer oil emulsion and dibutyl phthalate emulsion with higher stability are developed.

[0078] Perform appearance, solid content, pH, centrifugation, static settlement, particle size and potential treatment operations on paraffin emulsion, transformer oil emulsion, dibutyl phthalate emulsion and epoxy emulsion respectively. The results are shown in Tables 1 to 8.

[0079] Table 1 Physical property result table of paraffin emulsion

[0080] Name Solid content pH Static settling Particle size Potential Appearance Paraffin emulsion 37.73％ 5.16 No skinning 12.97μm 29.79mV Milky white

[0081] As shown in Table 1, the paraffin emulsions prepared by the present invention are all milky white liquids. After being placed at room temperature for 24 h, the paraffin emulsions do not form a skin and do not stratify, which preliminarily indicates their good static stability. Measured by a pH meter, its pH is 5.16, and the paraffin emulsion is acidic. Its particle size is 12.97 μm, the solid content is 37.73%, and the potential is 29.79 mV; the potential value is relatively large, which proves that the electrostatic force generated between the paraffin emulsion droplets is large, making the paraffin emulsion have good stability; the smaller particle size weakens the interaction between the paraffin emulsion particles, reduces the risk of particle aggregation and precipitation, and further enhances the kinetic stability of the paraffin emulsion.

[0082] Table 2 Test Table of Different Stirring Rates

[0083] Name pH Solid content Static settling Centrifugation Particle size (μm) Potential (mV) 400r / min 5.08 41.63％ Skinning Stratification 76.43 0.44 450r / min 5.13 37.33％ Skinning No stratification 20.22 -3.75 500r / min 5.14 35.48％ Skinning No stratification 18.34 6.93 550r / min 5.19 27.21％ No skinning No stratification 9.13 33.84 600r / min 5.21 29.57％ No skinning No stratification 10.19 43.59 650r / min 5.52 31.69％ Skinning No stratification 12.98 19.32

[0084] As Figure 2 shown in Table 2, after standing for 24 h and observing, the stabilities of the transformer oil emulsions prepared at different stirring rates are different. Among them, the transformer oil emulsion prepared at a stirring rate of 400 r / min forms a serious skin, and there is a slight skin at 650 r / min, both showing instability. The transformer oil emulsion prepared at a stirring rate of 600 r / min does not form a skin, indicating that this speed is the best choice for preparing a stable transformer oil emulsion.

[0085] As Figure 3 shown in Table 2, after standing for 24 h, the transformer oil emulsion prepared at a stirring rate of 400 r / min stratifies, while the transformer oil emulsions prepared at stirring rates of 600 r / min and 650 r / min do not stratify and are relatively stable. According to the skin formation and stratification conditions, the best stirring rate for the transformer oil emulsion is 600 r / min.

[0086] As Figure 4 shown in Table 2, after centrifuging for 5 min on a centrifuge at 3000 r / min, the transformer oil emulsion prepared at 400 r / min stratifies, while the transformer oil emulsions prepared at stirring rates of 600 r / min and 650 r / min do not stratify and are relatively stable. According to the skin formation and stratification conditions, the best stirring rates for the transformer oil emulsion are 550 r / min and 600 r / min.

[0087] As Figure 5As shown in Table 2, under the experimental condition of standing for 24 h, the transformer oil emulsions prepared at the rotation speeds of 550 r / min and 600 r / min did not show skinning phenomenon, while skinning occurred at the other rotation speeds, indicating that the preparation environments at these two rotation speeds were relatively stable. Further, after continuous stirring at 3000 r / min for 5 min, only the transformer oil emulsion at the rotation speed of 400 r / min showed stratification, and the others remained stable. It should be noted that the transformer oil emulsions prepared at the rotation speeds of 550 r / min and 600 r / min were both acidic (pH < 7), which was beneficial to improving the stability of the transformer oil emulsion. Especially at the rotation speed of 600 r / min, the potential of the transformer oil emulsion was as high as 43.59 mV, showing strong electrostatic force, which further enhanced the stability of the transformer oil emulsion. In addition, the particle size of the transformer oil emulsion at this rotation speed was 10.19 μm, and the solid content was 29.57%. The high solid content endows it with excellent hardness and toughness, making it less likely to break or fracture. Therefore, 600 r / min is the optimal stirring rate for preparing the transformer oil emulsion.

[0088] Table 3 Test results of transformer oil emulsion under different stirring durations

[0089] Name pH Solid content Static settling Centrifugation Particle size (μm) Potential (mV) 30min 5.41 75.34％ Skinning Stratification 105.33 -3.6 40min 5.46 62.48％ Skinning Stratification 88.84 -0.61 50min 5.58 37.95％ Skinning No stratification 30.66 7.6 60min 5.62 22.34％ No skinning No stratification 10.19 39.79 70min 5.84 20.22％ No skinning No stratification 9.66 21.65 80min 6.32 20.59％ Skinning No stratification 9.98 13.49

[0090] As Figure 6 shown in Table 3, after standing for 24 h, the transformer oil emulsion prepared under the stirring time of 40 min had serious skinning, and the transformer oil emulsion prepared under the stirring time of 80 min had slight skinning, both of which were unstable. According to the skinning situation, the optimal stirring time for emulsifying transformer oil is 60 min.

[0091] As Figure 7 shown in Table 3, after standing for 24 h, the transformer oil emulsion prepared with the stirring time of 40 min showed stratification, while the transformer oil emulsions prepared with the stirring times of 60 min and 80 min did not show stratification and were relatively stable. According to the skinning and stratification situations, the optimal stirring time for the transformer oil emulsion is 60 min.

[0092] As Figure 8 shown in Table 3, after centrifuging for 5 min on a centrifuge with a rotation speed of 3000 r / min, it was found that the transformer oil emulsion prepared with the stirring time of 40 min showed stratification, while the transformer oil emulsions prepared with the stirring times of 60 min and 80 min did not show stratification and were relatively stable. According to the skinning and stratification situations, the optimal stirring time is 60 min.

[0093] As Figure 9As shown in Table 3, after standing for 24 h, the transformer oil emulsions prepared with stirring times of 60 min and 10 min did not show skinning, while skinning occurred at the other stirring times. Further, after continuously stirring at a speed of 3000 r / min for 5 min, only the transformer oil emulsions prepared with stirring times of 30 min and 40 min showed delamination, and the others remained stable. Among them, the transformer oil emulsions prepared with stirring times of 60 min and 70 min showed relatively high stability, and both were acidic (pH < 7), which was beneficial to improving the stability of the resin-based paraffin sizing agent. It should be noted that the particle size of the transformer oil emulsion prepared with a stirring time of 60 min was 39.79 μm, the solid content was 22.34%, and the potential was 39.79 mV. Compared with the transformer oil emulsion prepared with a stirring time of 70 min, it had a larger particle size, a higher solid content, and stronger stability. The high solid content not only enhanced the environmental protection and reduced the solvent evaporation amount but also brought good economic benefits. Therefore, the optimal stirring time for the transformer oil emulsion is 60 min.

[0094] Table 4 Test results of emulsifying transformer oil at different temperatures

[0095] Name pH Solid content Static settling Centrifugation Particle size (μm) Potential (mV) 70℃ 5.38 79.60％ Skinning Stratification 108.69 1.59 75℃ 5.58 74.48％ Skinning Stratification 101.38 4.51 80℃ 5.60 31.49％ Skinning No stratification 10.54 10.35 85℃ 5.69 29.58％ No skinning No stratification 9.93 32.8 90℃ 5.79 33.65％ Skinning No stratification 6.47 15.83 95℃ 6.08 29.73％ Skinning No stratification 4.53 17.59

[0096] As Figure 10 shown in Table 4, after standing for 24 h, the transformer oil emulsions prepared at stirring temperatures of 75 °C and 95 °C showed skinning, while the transformer oil emulsion prepared at a stirring temperature of 85 °C did not show skinning. According to the skinning situation, the optimal temperature for emulsifying transformer oil is 85 °C.

[0097] As Figure 11 shown in Table 4, after standing for 24 h, the transformer oil emulsion prepared at a stirring temperature of 75 °C showed delamination, while the transformer oil emulsions prepared at stirring temperatures of 85 °C and 95 °C did not show delamination and were relatively stable. Therefore, according to the skinning and delamination situations, the optimal temperature for emulsifying transformer oil is 85 °C.

[0098] As Figure 12 shown in Table 4, after centrifuging at a speed of 3000 r / min for 5 min, the transformer oil emulsion prepared at a stirring temperature of 75 °C showed delamination, while the transformer oil emulsions prepared at stirring temperatures of 85 °C and 95 °C did not show delamination. Considering the skinning and delamination situations, the optimal temperature for emulsifying transformer oil is determined to be 85 °C.

[0099] As Figure 13 shown in Table 4, after standing for 24 h, only the transformer oil emulsion prepared at a stirring temperature of 85 °C did not show skinning. Its particle size was 9.93 μm, the solid content was 29.58%, and the potential reached 32.8 mV, indicating that there was a large electrostatic repulsion between the droplets of the transformer oil emulsion, effectively preventing coagulation and delamination, and showing good stability.

[0100] Table 5 Emulsification test results of dibutyl phthalate emulsion at different stirring rates

[0101] Name pH Solid content Static settling Centrifugation Particle size (μm) Potential (mV) 400r / min 5.33 39.22％ Skinning Stratification 54.66 3.39 450r / min 5.48 36.68％ Skinning No stratification 43.34 7.09 500r / min 5.63 22.11％ No skinning No stratification 10.76 28.67 550r / min 5.79 21.21％ No skinning No stratification 9.22 26.49 600r / min 6.11 19.22％ No skinning No stratification 8.21 -27.31 650r / min 6.27 17.34％ No skinning No stratification 7.23 21.89

[0102] As Figure 14 shown in Table 5, after standing for 24 h, the dibutyl phthalate emulsions prepared at stirring temperatures of 75 °C and 95 °C formed a skin, while the dibutyl phthalate emulsion prepared at 85 °C did not form a skin and was relatively stable. Combining with Table 5, the optimal temperature for emulsifying dibutyl phthalate is 85 °C.

[0103] As Figure 15 shown in Table 5, after standing for 24 h, the dibutyl phthalate emulsion prepared at a stirring temperature of 75 °C stratified, while the dibutyl phthalate emulsions prepared at stirring temperatures of 85 °C and 95 °C did not stratify and were relatively stable. According to the skin formation and stratification conditions, the optimal temperature for emulsifying dibutyl phthalate is 85 °C.

[0104] As Figure 16 shown in Table 5, after centrifuging for 5 min on a centrifuge with a rotation speed of 3000 r / min, the dibutyl phthalate emulsion prepared at a stirring temperature of 75 °C stratified, while the dibutyl phthalate solutions prepared at stirring temperatures of 80 °C, 85 °C and 90 °C did not stratify. According to the skin formation and stratification conditions, the optimal temperature for emulsifying dibutyl phthalate is 85 °C.

[0105] As Figure 17 shown in Table 5, after standing for 24 h, only the dibutyl phthalate emulsion prepared at a stirring temperature of 85 °C did not show skin formation. The pH value of this emulsion was 5.56, showing acidity, which helped to improve its performance and reduce the surface tension of the resin-based paraffin sizing agent. The particle size of the dibutyl phthalate emulsion was 9.34 μm, and the solid content was 33.85%, with a relatively high viscosity. Therefore, the optimal temperature for emulsifying dibutyl phthalate is 85 °C.

[0106] Table 6 Emulsification test results of dibutyl phthalate emulsion at different stirring rates

[0107] Name pH Solid content Static settling Centrifugation Particle size (μm) Potential (mV) 70℃ 5.08 75.78％ Skinning Stratification 102.34 0.61 75℃ 5.31 71.89％ Skinning Stratification 88.35 2.69 80℃ 5.42 43.50％ Skinning No stratification 21.66 10.21 85℃ 5.56 33.85％ No skinning No stratification 9.34 29.83 90℃ 5.88 35.68％ Skinning No stratification 13.22 21.67 95℃ 5.93 58.41％ Skinning Stratification 60.34 15.69

[0108] As Figure 18 shown in Table 6, after standing for 24 h, the dibutyl phthalate emulsions prepared at stirring times of 40 min and 80 min formed a skin more seriously, while the dibutyl phthalate emulsion prepared at a stirring time of 60 min did not form a skin. Therefore, the optimal stirring time for emulsifying dibutyl phthalate is 60 min.

[0109] As Figure 19As shown in Table 6, after standing for 24 h, the dibutyl phthalate emulsion prepared with a stirring time of 40 min was stratified, while the dibutyl phthalate emulsions prepared with stirring times of 60 min and 80 min were not stratified. According to the skin formation and stratification conditions, the optimal stirring duration for emulsifying dibutyl phthalate is 60 min.

[0110] As Figure 20 As shown in Table 6, after centrifuging for 5 min on a centrifuge with a rotation speed of 3000 r / min, the dibutyl phthalate emulsion prepared with a stirring time of 40 min was stratified, while the dibutyl phthalate emulsions prepared with stirring times of 60 min and 80 min were not stratified. Therefore, according to the skin formation and stratification conditions, the optimal stirring duration for emulsifying dibutyl phthalate is 60 min.

[0111] As Figure 21 As shown in Table 6, after a 24-h standing experiment, only when the stirring time was 60 min did the dibutyl phthalate emulsion not show skin formation, indicating that it was the most stable at this stirring duration. The particle size of the dibutyl phthalate emulsion was 11.34 μm, and the solid content was as high as 29.62%; meanwhile, its potential value was 30.65 mV, showing strong electrostatic repulsion, effectively preventing the aggregation or stratification of the dibutyl phthalate emulsion and further enhancing its stability. In summary, the optimal stirring duration for emulsifying the dibutyl phthalate emulsion was determined to be 60 min.

[0112] Table 7 Emulsification test results of dibutyl phthalate emulsion at different stirring durations

[0113] Name pH Solid content Static settling Centrifugation Particle size (μm) Potential (mV) 30min 5.34 48.22％ Skinning Stratification 70.35 9.31 40min 5.49 49.74％ Skinning Stratification 72.46 8.63 50min 5.57 42.39％ Skinning Stratification 69.44 3.89 60min 5.89 29.62％ No skinning No stratification 11.34 30.65 70min 6.08 34.89％ Skinning No stratification 15.28 26.92 80min 6.21 32.30％ Skinning No stratification 13.94 21.84

[0114] As Figure 22 As shown in Table 7, after standing for 24 h, the dibutyl phthalate emulsion prepared with a stirring rate of 400 r / min had serious skin formation, while the dibutyl phthalate emulsions prepared with stirring rates of 600 r / min and 650 r / min did not have skin formation.

[0115] As Figure 23 As shown in Table 7, after standing for 24 h, the dibutyl phthalate emulsion prepared with a stirring rate of 400 r / min was stratified, while the dibutyl phthalate emulsions prepared with stirring rates of 600 r / min and 650 r / min were not stratified. Considering the skin formation situation, the optimal stirring rate for emulsifying dibutyl phthalate is 500 r / min.

[0116] As Figure 24As shown in Table 7, after centrifuging for 5 min on a centrifuge at a rotational speed of 3000 r / min, the dibutyl phthalate emulsion prepared at a stirring rate of 400 r / min showed layering, while the dibutyl phthalate emulsions prepared at stirring rates of 600 r / min and 650 r / min did not show layering. According to the skin formation and layering conditions, the optimal stirring rate for emulsifying dibutyl phthalate was 500 r / min.

[0117] As Figure 25 As shown in Table 7, in the 24-hour static experiment, the dibutyl phthalate emulsions prepared at stirring rates of 400 r / min and 450 r / min showed skin formation; while after continuous stirring at a rotational speed of 3000 r / min for 5 min, only the dibutyl phthalate emulsion prepared at 400 r / min showed layering. Therefore, it was determined that the dibutyl phthalate emulsions prepared at stirring rates of 500 r / min, 550 r / min, 600 r / min, and 650 r / min were relatively stable. Among them, the dibutyl phthalate emulsion prepared at 500 r / min had the highest solid content, reaching 29.57%, and a relatively large potential value. For the resin-based paraffin sizing agent, the higher the solid content, the better the economic benefits. Combining Table 7, the optimal stirring rate for emulsifying dibutyl phthalate was 500 r / min.

[0118] The resin-based paraffin sizing agent was subjected to operations such as appearance, solid content, pH, centrifugation, static state, particle size, and potential, and the results are shown in Table 8.

[0119] Table 8 Physical Property Results of the Resin-Based Paraffin Sizing Agent in Example 1

[0120] Name Solid content pH Centrifuged solid content Static settling Particle size Potential Appearance Resin-based paraffin sizing agent 5.93％ 6.00 2.0％ No skinning 2.14μm 23.74mV Milky white

[0121] As shown in Table 8, the prepared resin-based paraffin sizing agent presented the appearance of a homogeneous milky white liquid. After being placed at room temperature for 24 hours, the resin-based paraffin sizing agent emulsion neither formed a skin nor separated, showing good stability. Detected by a pH meter, its pH value was 6.00, showing acidity, which indicated that the epoxy resin played a good role in the resin-based paraffin sizing agent, effectively reducing the surface tension of the resin-based paraffin sizing agent, thereby enhancing the wettability of the resin-based paraffin sizing agent on glass fibers. In addition, the particle size of the resin-based paraffin sizing agent was 2.14 μm, and the solid content was 5.93%. The relatively low solid content gave the resin-based paraffin sizing agent better fluidity, which was conducive to its penetration to the surface of glass fibers, and the chemical resistance was relatively weak. After centrifugation testing, the precipitation amount of the resin-based paraffin sizing agent was only 2.0%, showing a high degree of uniformity and stability of the resin-based paraffin sizing agent. At the same time, the potential value was 23.74 mV, indicating that there was a strong electrostatic force between the droplets of the resin-based paraffin sizing agent, which further enhanced the stability of the resin-based paraffin sizing agent and made it not easy to occur coagulation or stratification phenomena.

[0122] The application research was carried out on the resin-based paraffin sizing agent obtained in Example 1 of the present invention and the paraffin sizing agent obtained in Comparative Example 1 as follows:

[0123] a. Drawing process: Nine glass balls were respectively placed in nine drawing crucibles, and the full cylinder rate of each crucible position was tested. The average value was taken after repeating 7 times, and the drawing was carried out using the crucible position with the highest full cylinder rate; Subsequently, the paraffin sizing agent glass fiber of Comparative Example 1 and the resin-based paraffin sizing agent glass fiber of Example 1 were used for drawing experiments in a slit-type wire arrangement method, and the paraffin sizing agent glass fiber and the resin-based paraffin sizing agent glass fiber were obtained respectively.

[0124] b. Wire drawing-back process: The resin-based paraffin sizing agent glass fiber was left standing for 12 hours at room temperature and a humidity of 50%, and then positive raw wire drawing-back and free raw wire drawing-back were carried out respectively.

[0125] c. Glass fiber properties: ① Single filament detection: The diameter, linear density, strength, combustible content, and water content of the single filaments of the paraffin sizing agent glass fiber and the resin-based paraffin sizing agent glass fiber were tested.

[0126] ② Stranded wire detection: The diameter, linear density, strength, and combustible content of the stranded wires of the paraffin sizing agent glass fiber and the resin-based paraffin sizing agent glass fiber were tested.

[0127] ③ Post-treatment stranded wire detection: The linear density, breaking strength, silicon content, heat loss rate, and linear shrinkage rate of the stranded wires of the paraffin sizing agent glass fiber and the resin-based paraffin sizing agent glass fiber were tested.

[0128] Table 9 Full cylinder rate table of each crucible position

[0129] Drawing crucible No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 5.3 55.5 30 5.5 41 49.5 2 52.5 43.5 16 5.4 48.5 42 17 43 40 10 45 30 9 5.5 46.5 45 35.5 42.5 33 42.5 33 40.5 21.5 5.6 52.5 41.5 23 38 29.5 9.5 40 11.5 7 5.7 44.5 39.5 37.5 37 31.5 14.5 37 24 8 5.8 64.5 42.5 8.5 25.5 51 17.5 33.5 38.5 4 5.9 50 42 16.5 35 47 11 66 30 5.5 Average value 51.71 40.36 20.50 37.43 40.21 12.43 44.14 31.14 10.14

[0130] Through the statistical comparison of the data in Table 9, the full bobbin rate of the 1st crucible position is the highest. A high full bobbin rate proves that the actual production time of the machine is fully utilized, the production efficiency is high, and at the same time, it also fully proves the stability of the quality of the resin-based paraffin wax sizing agent. Most importantly, the higher the full bobbin rate, the less waste of raw materials and energy consumption, thus greatly reducing the production cost. Therefore, the 1st crucible position is determined as the experimental crucible position. The operating conditions of the paraffin wax sizing agent and the resin-based paraffin wax sizing agent in the slot-type wire winding and drawing are shown in Table 10.

[0131] Table 10 Operating Conditions of Paraffin Wax Sizing Agent and Resin-Based Paraffin Wax Sizing Agent in Slot-Type Wire Winding and Drawing

[0132] Experiment Number of flying filaments Number of broken ends Number of full bobbins Number of non-full bobbins Full bobbin rate Resin-based paraffin sizing agent 4 7 17 17 50％ Paraffin sizing agent 7 11 18 21 46.15％

[0133] It can be seen from Table 10 that by comparing the slot-type wire winding of glass fiber with the resin-based paraffin wax sizing agent and that with the paraffin wax sizing agent, the full bobbin rate of the glass fiber with the resin-based paraffin wax sizing agent is relatively high, the production efficiency is high, and the waste of resources is reduced. The main reason for the low full bobbin rate of the glass fiber with the paraffin wax sizing agent is flying filaments and broken ends, among which the broken ends account for more than 50%.

[0134] After the obtained glass fiber with the resin-based paraffin wax sizing agent is left standing for 12 h at room temperature and a humidity of 50%, positive-type roving unwinding and free-type roving unwinding are carried out respectively, and the unwinding conditions are shown in Table 11.

[0135] Table 11 Roving Unwinding Conditions of Glass Fiber with Resin-Based Paraffin Wax Sizing Agent

[0136] Name Drawing wire arrangement Winding-off method Number of unwound spindles Number of flying filaments Number of roving yarns Qualified rate Resin-based paraffin sizing agent glass fiber Gap progressive Positive type 94 22 5 89.36％ Resin-based paraffin sizing agent glass fiber Steel wire reciprocating Positive type 157 45 11 83.64％ Resin-based paraffin sizing agent glass fiber Gap progressive Free type 72 13 4 92.44％

[0137] It can be seen from Table 11 that the qualified rate of the positive-type unwinding of the resin-based paraffin wax sizing agent is lower than that of the free-type unwinding. The main reason for the unwinding of the resin-based paraffin wax sizing agent is that the glass fiber with the resin-based paraffin wax sizing agent is sticky and breaks at the roller. This is because the original filament bobbin produced by slot-type wire winding is heavier, and the film-forming property of the glass fiber original filament with the resin-based paraffin wax sizing agent is poor during the conditioning process, resulting in stickiness and breakage during unwinding.

[0138] The diameter, linear density, strength, and combustible content of the single filaments of the glass fiber with the paraffin wax sizing agent and the glass fiber with the resin-based paraffin wax sizing agent are tested, and the test results are shown in Table 12.

[0139] Table 12 Single Filament Performance Test Table

[0140] Test items Unit Paraffin sizing agent glass fiber Resin-based paraffin sizing agent glass fiber Single fiber diameter μm 7.2 7.0 Linear density tex 14.9 14.4 Strength N 7.6 8.7 Combustible content ％ 1.22 1.06

[0141] It can be concluded from Table 12 that the single fiber diameter of the resin-based paraffin-type sizing glass fiber is slightly smaller than that of the paraffin-type sizing glass fiber. The increase in the single fiber diameter of the paraffin-type sizing glass fiber leads to a decrease in the contact area, and then the stress is reduced, which weakens the strength of the paraffin-type sizing glass fiber. In view of the low combustible content of high-quality materials, the resin-based paraffin-type sizing glass fiber contains less impurities and flammables, and exhibits better mechanical properties.

[0142] The diameter, linear density, strength and combustible content of paraffin wax sizing glass fiber and resin-based paraffin wax sizing glass fiber plied yarn were tested. The test results are shown in Table 13.

[0143] Table 13 Plied yarn performance test table

[0144]

[0145]

[0146] The data in Table 13 show that the diameter of the resin-based paraffin-type sizing glass fiber strands is larger than that of the paraffin-type sizing glass fiber strands. The larger diameter resin-based paraffin-type sizing glass fiber has advantages in strength, stiffness and linear density. In addition, the large diameter resin-based paraffin-type sizing glass fiber exhibits better fracture resistance when subjected to impact or bending forces. Its performance is also relatively stable in high temperature environments. It is particularly worth mentioning that the resin-based paraffin-type sizing strands have a lower combustible content, which means that they contain relatively less combustibles and impurities, thus ensuring their excellent performance.

[0147] The post-treated paraffin wax sizing glass fiber and resin-based paraffin wax sizing glass fiber plied yarn were tested for linear density, breaking strength, silicon content, thermal vector rate and linear shrinkage. The results are shown in Table 14.

[0148] Table 14 Post-processing plied yarn performance test table

[0149] Test items Unit Paraffin sizing agent glass fiber Resin-based paraffin sizing agent glass fiber Linear density tex 83.1 89.1 Breaking strength N 8.0 11.0 Silicon content ％ 96.77 97.38 Thermal vector ％ 0.78 0.71 Linear shrinkage rate ％ 3.08 3.06

[0150] It can be concluded from Table 14 that the post-treated resin-based paraffin-type sizing glass fiber strands are slightly better than the post-treated paraffin-type sizing strands in terms of linear density and breaking strength. Generally speaking, the greater the linear density, the thicker the glass fiber strands, and the greater the breaking strength, indicating that the resin-based paraffin-type sizing glass fiber has a stronger ability to resist tensile damage. In addition, its thermal vector rate is lower than that of the paraffin-type sizing glass fiber, indicating that it has better thermal insulation performance and can effectively prevent heat transfer. As an important indicator for measuring dimensional stability, the linear shrinkage rate of the resin-based paraffin-type sizing glass fiber is lower, so it has higher dimensional stability and better mechanical properties.

[0151] The appearance of the resin-based wax-type sizing glass fiber obtained by soaking it in distilled water, 3mol / L HCl and 3mol / L NaOH for 15 days. Among them, the resin-based wax-type sizing glass fiber was completely corroded after being soaked in 3mol / L NaOH for 15 days, so it was concluded that the resin-based wax-type sizing glass fiber was not alkali-resistant.

[0152] like Figure 26 As shown in the figure, after the resin-based wax-type sizing glass fiber was treated with acid, obvious cracks and pits appeared on the surface, which indicates that it was severely corroded after the acid treatment, resulting in a significant reduction in its strength. From the composition and structure analysis of the resin-based wax-type sizing glass fiber, its network-forming unit has poor acid resistance. When the resin-based wax-type sizing glass fiber encounters acid corrosion, the Na in its internal network structure + With H in acid corrosion medium + Ion exchange occurs. The surface of the resin-based wax-type sizing glass fiber treated with deionized water is smooth and flat, proving that deionized water has little effect on it. Therefore, it is concluded that the acid and alkali resistance of the resin-based wax-type sizing glass fiber is not good.

[0153] Figure 27 Figure (a) shows a paraffin-type impregnated glass fiber with a contact angle of 5°. Figure 27 Figure (b) shows a glass fiber with a resin-based wax-type sizing agent, and the contact angle is 6°. The glass fiber with a resin-based wax-type sizing agent has better hydrophilicity, and the resin-based wax-type sizing agent can improve the bonding force between the sizing agent and the glass fiber, further improve its stability, and improve compatibility.

[0154] observe Figure 28 Figure (a) shows that the surface of the glass fiber with paraffin-type sizing agent is seriously scattered and the bundling is poor. Figure 28 Figure (b) shows that the surface of the resin-based paraffin-type paraffin-type sizing agent glass fiber is smooth and flat, the single fiber bonding ability is strong, and the twisted yarn structure is compact.

[0155] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A method for preparing a resin-based paraffin-type wetting agent, characterized in that: The following steps are involved: Paraffin wax emulsion, transformer oil emulsion, dibutyl phthalate emulsion, epoxy emulsion, epoxy resin and water are mixed to obtain a resin-based paraffin type wetting agent; The paraffin wax emulsion, transformer oil emulsion or dibutyl phthalate emulsion is prepared according to the following steps: Mixing water and emulsifier No. 1 to obtain a mixed solution; Pre-emulsifying paraffin wax / transformer oil / dibutyl phthalate with No. 2 emulsifier to obtain paraffin wax pre-emulsion / transformer oil pre-emulsion / dibutyl phthalate pre-emulsion; The mixed liquid is mixed with paraffin pre-emulsion liquid / transformer oil pre-emulsion liquid / dibutyl phthalate pre-emulsion liquid and then emulsified to obtain paraffin emulsion / transformer oil emulsion / dibutyl phthalate emulsion; The solid content of paraffin emulsion is 27.21% to 41.63%, the solid content of transformer oil emulsion is 27.21% to 41.63%, and the solid content of dibutyl phthalate emulsion is 17.34% to 33.85%; In the resin-based paraffin-type wetting agent, the mass percentages of paraffin emulsion, transformer oil emulsion, dibutyl phthalate emulsion, epoxy emulsion and epoxy resin are 1.7%-2.1%, 7%-9%, 6%-8%, 5%-6%, 0.3%-0.7% respectively, and the balance is water; and the sum of the mass percentages of paraffin emulsion, transformer oil emulsion, dibutyl phthalate emulsion, epoxy emulsion, epoxy resin and water is 100%.

2. A method for preparing a resin-based paraffin-type sizing agent according to claim 1, characterized in that: The mixing treatment conditions are: stirring at 80°C to 90°C and 400 r / min to 600 r / min for 30 min to 50 min.

3. A method for preparing a resin-based wax-type sizing agent according to claim 1, characterized in that: The first emulsifier is selected from Tween 80.

4. A method for preparing a resin-based wax-type sizing agent according to claim 1, characterized in that: The mass ratio of emulsifier No. 1 to water is 0.8-1.2:12-15.

5. A method for preparing a resin-based wax-type sizing agent according to claim 1, characterized in that: The second emulsifier is selected from one or two of Siban 80 and Pingpingjia.

6. A method for preparing a resin-based wax-type sizing agent according to claim 1, characterized in that: The mass ratio of No. 2 emulsifier to paraffin / transformer oil / dibutyl phthalate is 8-10:46-54.

7. A method for preparing a resin-based wax-type sizing agent according to claim 1, characterized in that: The conditions for the emulsification treatment are: stirring at 70°C to 95°C and 400 r / min to 650 r / min for 30 min to 80 min.

8. A resin-based paraffin-type wetting agent obtained by the preparation method according to any one of claims 1 to 7.

9. Use of the resin-based wax-type sizing agent according to claim 8 in the preparation of resin-based wax-type sizing agent glass fiber.

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