A low-pilary glass fiber film former, its preparation method, impregnant, product and application

Abstract

The application discloses a low-hairiness glass fiber film-forming agent, which comprises the following raw materials in parts by weight: 5-25 parts by weight of hydroxyl silicone oil; 1-10 parts by weight of diisocyanate; 40-80 parts by weight of epoxy resin A; 0.01-0.06 parts by weight of a catalyst; 1-10 parts by weight of an EO / PO block polyether; 1-5 parts by weight of polypropylene glycol; 1-15 parts by weight of epoxy resin B; 1-5 parts by weight of an accelerator; and 2-10 parts by weight of a diluent. The application grafts lubricating monomers to the epoxy resin, develops a suitable non-ionic epoxy resin emulsifier system, and then obtains the low-hairiness glass fiber film-forming agent, reduces the migration of the lubricant to the surface in the baking process, reduces the surface yellowing, reduces the generation of hairiness in the glass fiber production and use process, and reduces the blocking of the film hole and the generation of loose silk and broken yarn.

Description

Technical Field

[0001] This application belongs to the field of polymer materials technology, specifically relating to a low-feather waterborne epoxy resin glass fiber film-forming agent and its preparation method, wetting agent, product and application. Background Technology

[0002] Glass fiber itself is a brittle inorganic material. To meet the requirements of glass fiber drawing and composite material production processes, a sizing agent is applied to the surface of the glass fiber. This sizing agent not only protects the glass fiber but also allows it to be quickly impregnated and well-bonded in polyester and epoxy resins, thereby improving the mechanical properties of the composite material. Currently, sizing agents mainly include film-forming agents, lubricants, coupling agents, antistatic agents, and pH adjusters. The addition of lubricants can improve the smoothness of glass fiber drawing and use, reducing fuzz formation. However, because lubricants have a small molecular structure, they easily migrate to the surface during the drying process. Excessive lubricant can cause yellowing of the outer ring of the yarn and poor impregnation with polyester and epoxy resins, reducing the mechanical properties of the composite material. Insufficient lubricant can lead to fuzz formation during glass fiber production and use, clogging the membrane pores and causing fraying and yarn breakage. Glass fiber products used in winding and pultrusion often generate fuzz due to friction during use, causing membrane pore blockage, fraying, and yarn breakage, severely reducing production efficiency. Summary of the Invention

[0003] The technical problem to be solved by this application is to provide a lubricating glass fiber film-forming agent, which grafts functional groups with lubricating effect into the basic epoxy molecule structure, and then develops a suitable nonionic epoxy resin emulsifier, thereby developing a low-hair glass fiber film-forming agent; the products coated with the sizing agent made using the low-hair glass fiber film-forming agent have moderate softness and hardness, good bundle properties, and few hairs, and the various performance characteristics of the products meet customer approval.

[0004] To achieve the above objectives, this application employs the following technical solution:

[0005] This application provides a low-fuzz glass fiber film-forming agent, comprising the following raw materials, the contents of which are expressed in parts by weight as follows:

[0006]

[0007]

[0008] Preferably, the content of each raw material is expressed in parts by weight as follows:

[0009]

[0010] The hydroxyl silicone oil has a molecular weight of 1000-4000.

[0011] Preferably, the molecular weight of the hydroxyl silicone oil can be selected from at least one of 1000, 2000, 3000, and 4000.

[0012] The diisocyanate is one or more of toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, and naphthalene-1,5-diisocyanate.

[0013] Wherein, the epoxy resin A is one or more of bisphenol A epoxy resin E12, bisphenol A epoxy resin E20, bisphenol A epoxy resin E44, and bisphenol F epoxy resin.

[0014] Wherein, the epoxy resin B is at least one of bisphenol A epoxy resin E44, bisphenol A epoxy resin E51, and bisphenol F epoxy.

[0015] The catalyst is one or more of tetramethylbutanediamine, triethylenediamine, dibutyltin dilaurate, and stannous octoate.

[0016] The molecular weight of the EO / PO block polyether is 1000-8000.

[0017] Preferably, the molecular weight of the EO / PO block polyether can be selected from at least one of 1000, 2000, 3000, 5000, and 8000.

[0018] The molecular weight of the polypropylene glycol is 1000-3000.

[0019] Preferably, the molecular weight of polypropylene glycol can be selected from at least one of 1000, 2000, and 3000.

[0020] The accelerator is at least one of diethanolamine, triethanolamine, and N,N-dimethylbenzylamine.

[0021] The diluent is at least one of acetone, propylene glycol methyl ether, and xylene.

[0022] According to a second aspect of this application, a method for preparing the aforementioned low-fuzz glass fiber film-forming agent is provided, comprising the following steps:

[0023] S1: Synthesis of lubricating modified epoxy resin: Hydroxy silicone oil is added to a four-necked flask, heated to 110-130℃ and vacuumed for 1.5-2.5 hours with a vacuum degree of -0.08 to -0.1 MPa. The temperature is then lowered to 60-70℃ and a catalyst is added. Diisocyanate is added dropwise. After the addition is complete, the temperature is maintained for 2-3 hours and the NCO is tested. Then, dehydrated epoxy resin A is added dropwise at a temperature of 60-70℃. After the addition is complete, the temperature is maintained for 2-5 hours and the NCO is tested to be 0.

[0024] S2: Preparation of epoxy resin emulsifier: EO / PO block polyether, polypropylene glycol and epoxy resin are put into the kettle according to the ratio and stirred. The mixture is heated to 90-120℃, and the accelerator is added dropwise over 1-2 hours. After the addition is complete, the mixture is kept at 100-120℃ for 3-5 hours. The mixture is then cooled to 50-60℃ and the diluent is added.

[0025] S3: Emulsification: Using the phase inversion method, weigh out S1 resin and S2 emulsifier according to the ratio and add them to the emulsification kettle. Before phase inversion, add water for 30 min to 40 min, the material temperature is 55℃ to 60℃, and the shearing speed is 2000-4000 r / min. After phase inversion, continue high-speed stirring for 10 min, slowly add water, and adjust the solid content to 39-41% to obtain the low-fuzz glass fiber film-forming agent emulsion.

[0026] The following explains the selection of raw materials for this application:

[0027] This application uses hydroxyl silicone oil grafted onto epoxy resin to obtain a flexible and lubricating matrix epoxy resin, which can improve the smoothness of glass fiber drawing and use, and reduce fuzzing. When hydroxyl silicone oil is grafted and copolymerized with epoxy resin, if the hydroxyl silicone oil content is too high, the performance of the composite material will be reduced; if the content is too low, the smoothness will be insufficient, and the processing performance will not meet the requirements. Therefore, in this application, the content of hydroxyl silicone oil is 5-25 parts by weight; preferably, the content of hydroxyl silicone oil is 10-20 parts by weight. Furthermore, hydroxyl silicone oil with a high molecular weight has a long molecular chain and good flexibility, but the content of urethane groups decreases, resulting in a decrease in strength. Therefore, selecting a suitable structure and ratio according to the performance requirements, with a molecular weight of 1000-4000 for the hydroxyl silicone oil, ensures easier emulsification and obtains a suitable particle size.

[0028] This application uses a self-made epoxy emulsifier, grafting hydrophilic groups onto the epoxy resin. The size of the emulsifier molecules is adjusted according to the molecular structure to be emulsified, thereby ensuring high emulsion stability and preventing migration on the glass fiber surface during baking. The EO / PO block polyether molecular weight of 1000-8000 ensures the emulsion's dilution and storage stability.

[0029] This application uses a phase inversion method to synthesize a film-forming agent emulsion, which is then water-based. The resulting emulsion meets the requirements of glass fiber production processes. The emulsion particle size distribution conforms to the molding process requirements, and it exhibits good stability.

[0030] Compared with the prior art, the beneficial effects of this application are as follows:

[0031] By grafting organosilicon from hydroxyl silicone oil with lubricating effects into the basic epoxy molecular structure, lubricating structural groups are grafted to increase slipability and reduce fuzzing. Then, a nonionic epoxy resin emulsifier with a matching molecular structure and molecular weight is experimentally developed, and a low-fuzz glass fiber film-forming agent is developed. Products coated with sizing agents made using this low-fuzz glass fiber film-forming agent have moderate softness and hardness, good bundle properties, and less fuzzing. The various performance characteristics of the products meet customer approval. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of this application will be clearly and completely described below in conjunction with the embodiments of this application. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of this application can be arbitrarily combined with each other.

[0033] Example 1

[0034] In some optional embodiments, a glass fiber film-forming agent is provided. Example 1 describes a method for preparing the film-forming agent, comprising the following steps:

[0035] S1: Synthesis of lubricating modified epoxy resin: 10 parts of hydroxyl silicone oil with a molecular weight of 1000 were added to a four-necked flask, heated to 110-130℃ and vacuumed for 2 hours with a vacuum degree of -0.08 to -0.1 MPa. The temperature was then lowered to 60-70℃ and 0.03 parts of catalyst were added. 5 parts of diisocyanate were added dropwise. After the addition was complete, the temperature was maintained for 2-3 hours and the NCO value was tested to reach the theoretical value of 7.0. Then, 63 parts of dehydrated epoxy resin A were added dropwise at a temperature of 60-70℃. After the addition was complete, the temperature was maintained for 2-5 hours and the NCO value was tested to be 0.

[0036] S2: Preparation of epoxy resin emulsifier: 3.2 parts of EO / PO block polyether with a molecular weight of 2000, 2.1 parts of polypropylene glycol with a molecular weight of 3000, and 8.4 parts of epoxy resin B were added to a reactor and stirred. The mixture was heated to 90-120℃, and 1.97 parts of accelerator were added dropwise over 1-2 hours. After the addition was complete, the mixture was kept at 100-120℃ for 3-5 hours, then cooled to 50-60℃ and 6.3 parts of diluent were added.

[0037] S3: Emulsification: Using the phase inversion method, weigh out S1 resin and S2 emulsifier according to the ratio and add them to the emulsification kettle. Before phase inversion, add water for 30-40 minutes, the material temperature is 55℃-60℃, and the shearing speed is 3000r / min. After phase inversion, continue high-speed stirring for 10 minutes, slowly add water, and adjust the solid content to 39-41% to obtain a low-fuzz glass fiber film-forming agent emulsion.

[0038] Examples 2-8 are prepared using the same methods as Example 1, except for differences in raw material content and molecular weight, as shown in the table below.

[0039] In Examples 2-4, the molecular weight of hydroxyl silicone oil is 3000, the molecular weight of EO / PO block polyether is 5000, and the molecular weight of polypropylene glycol is 2000.

[0040] In Examples 5-6, the molecular weight of the hydroxyl silicone oil was 2000, the molecular weight of the EO / PO block polyether was 1000, and the molecular weight of the polypropylene glycol was 2000.

[0041] In Examples 7-9, the molecular weight of the hydroxyl silicone oil is 4000, the molecular weight of the EO / PO block polyether is 3000, and the molecular weight of the polypropylene glycol is 1000.

[0042] Table 1. Composition and proportions of each component in the embodiment.

[0043]

[0044]

[0045] To better illustrate the technical effects of this application, a commercially available film-forming agent commonly used in this application is used as Comparative Example 1. The film-forming agent prepared in this application and the film-forming agent in the comparative example are prepared according to conventional sizing agent preparation methods. The stability of the sizing agents is tested, and glass fiber drawing operations are performed to test the amount of hairiness. The stability test method involves preparing the film-forming agent with lubricant, pH adjuster, and antistatic agent in a ratio of 20:5:1:1, and tracking the stability for 24 hours. The relevant test results are shown in Table 2.

[0046] Table 2. Performance test results of the examples and comparative products.

[0047]

[0048] As shown in Table 2, the performance data of Examples 1-9 are all superior to those of the comparative examples. Among them, Example 3 exhibits the best overall performance. The emulsion particle size of Examples 1-9 is moderate, ranging from 98-232 nm, which is lower than the 251 nm of the comparative example. This moderate particle size broadens its applicability, especially when used in composite materials. Furthermore, this particle size range results in good mechanical properties, being neither too hard nor too brittle, and exhibiting good flexibility, leading to optimal performance. The dilution stability of Examples 3 and 8 reached 100%, while that of the purchased film-forming agent was only 95.7%. This indicates that the film-forming agent used in the preparation of the sizing agent has high stability, is easy to store, and is suitable for most sizing agent formulations. The film-forming agent of this application imparts certain flexibility and low-fuzz properties to glass fiber products, resulting in composite material products with high mechanical strength and excellent aging resistance.

[0049] In summary, the glass fiber film-forming agent formulation of this application is scientifically sound and the preparation process is effective. The glass fiber products produced by coating with a glass fiber sizing agent containing the glass fiber film-forming agent have good flexibility and low fuzzing properties. The composite material products have high mechanical strength and excellent aging resistance.

[0050] Finally, it should be noted that in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0051] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit it. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application.

Claims

1. A low-pilifer glass fiber film former characterized by, It comprises the following raw materials, the content of each raw material being expressed in parts by weight as follows: 5-25 parts by weight of hydroxyl silicone oil 1-10 parts by weight of diisocyanate Epoxy resin A 40-80 parts by weight Catalyst 0.01-0.06 parts by weight 1-10 parts by weight of EO / PO block polyether 1-5 parts by weight of polypropylene glycol Epoxy resin B1-15 parts by weight Accelerator 1-5 parts by weight 2-10 parts by weight of diluent; The preparation method of the low-fuzz glass fiber film-forming agent includes the following steps: S1: Synthesis of lubricating modified epoxy resin: The hydroxyl silicone oil is put into a four-necked flask, heated to 110-130℃ and vacuumed for 1.5-2.5 hours with a vacuum degree of -0.08~-0.1MPa. The temperature is then lowered to 60-70℃ and the catalyst is added. The diisocyanate is added dropwise. After the addition is complete, the temperature is maintained for 2-3 hours and the NCO is tested. Then, the dehydrated epoxy resin A is added dropwise at a temperature of 60-70℃. After the addition is complete, the temperature is maintained for 2-5 hours and the NCO is tested to be 0. S2: Preparation of epoxy resin emulsifier: The EO / PO block polyether, the polypropylene glycol, and the epoxy resin B are added to a kettle according to the ratio and stirred. The mixture is heated to 90-120°C, and the accelerator is added dropwise over 1-2 hours. After the addition is complete, the mixture is kept at 100-120°C for 3-5 hours. The mixture is then cooled to 50-60°C and the diluent is added. S3: Emulsification: Using the phase inversion method, weigh out S1 resin and S2 emulsifier according to the ratio and add them to the emulsification kettle. Before phase inversion, add water for 30 min to 40 min, the material temperature is 55℃ to 60℃, and the shearing speed is 2000-4000 r / min. After phase inversion, continue high-speed stirring for 10 min, slowly add water, and adjust the solid content to 39-41% to obtain the low-fuzz glass fiber film-forming agent emulsion.

2. The low-pilifer glass fiber film former according to claim 1, characterized in that, The content of each raw material is expressed in parts by weight as follows: 10-20 parts by weight of hydroxyl silicone oil 3-5 parts by weight of diisocyanate Epoxy resin A 50-70 parts by weight Catalyst 0.02-0.05 parts by weight 2-5 parts by weight of EO / PO block polyether 1-3 parts by weight of polypropylene glycol Epoxy resin B5-10 parts by weight Accelerator 1-3 parts by weight Diluent 4-8 parts by weight.

3. The low-fuzz glass fiber film-forming agent according to claim 1 or 2, characterized in that, The molecular weight of the hydroxyl silicone oil is 1000-4000.

4. The low-fuzz glass fiber film-forming agent according to claim 1 or 2, characterized in that, The diisocyanate is one or more of toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, and naphthalene-1,5-diisocyanate.

5. The low-fuzz glass fiber film-forming agent according to claim 1 or 2, characterized in that, The epoxy resin A is one or more of bisphenol A epoxy resin E12, bisphenol A epoxy resin E20, bisphenol A epoxy resin E44, and bisphenol F epoxy resin; the epoxy resin B is at least one of bisphenol A epoxy resin E44, bisphenol A epoxy resin E51, and bisphenol F epoxy resin.

6. The low-fuzz glass fiber film-forming agent according to claim 1 or 2, characterized in that, The molecular weight of the EO / PO block polyether is 1000-8000.

7. The low-fuzz glass fiber film-forming agent according to claim 1 or 2, characterized in that, The catalyst is one or more of tetramethylbutanediamine, triethylenediamine, dibutyltin dilaurate, and stannous octoate. The molecular weight of the polypropylene glycol is 1000-3000; The accelerator is at least one of diethanolamine, triethanolamine, and N,N-dimethylbenzylamine; The diluent is at least one of acetone, propylene glycol methyl ether, and xylene.

8. A sizing agent for glass fibers prepared using the low-fuzz glass fiber film-forming agent according to any one of claims 1-7 as one of the raw materials.

9. A glass fiber product produced by coating the glass fiber with the sizing agent according to claim 8.

10. An application of the glass fiber product of claim 9 in the field of pultruded composite materials.

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