Amino-modified resin reinforced carbon fiber precursor oil and method for preparing the same

Abstract

The application discloses an amino-modified resin reinforced oil agent for carbon fiber precursor and a preparation method thereof. The oil agent is composed of 100 parts of amino-modified silicone oil, 20-50 parts of epoxy-modified silicone oil, 10-20 parts of amino-modified resin, 5-10 parts of a catalyst and 40-60 parts of an emulsifier by weight fraction, and is prepared by stirring and uniformly mixing the components, adding water and emulsifying and phase transferring. The modified silicone oil with high amino value and high epoxy value has the characteristics of high polarity and multiple functional groups, and has strong interaction with the organic functional groups on the surface of the precursor; meanwhile, the amino-modified resin is introduced, which plays a role of a reaction enhancement functional component, can chemically cross-link with the modified silicone oil, forms a three-dimensional network oil film structure, reduces the surface damage of the precursor in the drying and steam drawing process, improves the heat resistance and protection of the oil agent to the fiber in the pre-oxidation and carbonization process, and can effectively enhance the mechanical properties of the carbon fiber.

Description

Technical Field

[0001] This invention relates to an oiling agent for amino-modified resin-reinforced carbon fiber precursor, belonging to the field of oiling agent technology. Background Technology

[0002] Oiling agents are key additives used in the production of carbon fiber precursor, playing a crucial role in protecting the fiber surface and preventing thermal bridging. High-performance oiling agents influence fiber drying and densification, drawing, and heat setting, minimizing microscopic defects in the precursor and ensuring pre-oxidation and carbonization, ultimately affecting the fiber's mechanical properties. With the increasing demand for high-performance carbon fibers in aerospace, pressure vessels, and carbon / carbon composites, the industry's need for research and application of high-performance spinning oiling agents for carbon fiber is also gradually increasing. Therefore, it is necessary to find more suitable oiling agents to enhance their protective role in the carbon fiber production process and further improve the mechanical properties of carbon fibers. Summary of the Invention

[0003] The purpose of this invention is to provide an oiling agent for amino-modified resin-reinforced carbon fiber precursor and its preparation method.

[0004] The technical solution for achieving the objective of this invention is as follows:

[0005] The oiling agent for amino-modified resin-reinforced carbon fiber precursor consists of the following components by weight: 100 parts amino-modified silicone oil, 20-50 parts epoxy-modified silicone oil, 10-20 parts amino-modified resin, 5-10 parts catalyst, and 40-60 parts emulsifier.

[0006] Preferably, the oiling agent for amino-modified resin-reinforced carbon fiber precursor is composed of the following components by weight: 100 parts amino-modified silicone oil, 30-50 parts epoxy-modified silicone oil, 15-20 parts amino-modified resin, 8-10 parts catalyst, and 50-60 parts emulsifier.

[0007] The amino-modified silicone oil of the present invention has an ammonia value of 0.90 to 1.60 mmol / g, preferably 1.2 to 1.60 mmol / g.

[0008] The epoxy value of the epoxy-modified silicone oil of the present invention is 1.00 to 2.50 mmol / g, preferably 1.5 to 2.50 mmol / g.

[0009] The amino-modified resin described in this invention is a common amino-modified resin, selected from urea-formaldehyde resin, melamine-formaldehyde resin, or benzo-melamine-formaldehyde resin.

[0010] The catalyst described in this invention is selected from dibutyltin dilaurate or bismuth neodecanoate.

[0011] The emulsifier described in this invention is a commonly used emulsifier in oiling agents for carbon fiber precursors, selected from one or more of fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, and polyoxyethylene sorbitan fatty acid ester.

[0012] The specific steps for preparing the above-mentioned oiling agent for amino-modified resin-reinforced carbon fiber precursor are as follows:

[0013] According to the formula, amino-modified silicone oil, epoxy-modified silicone oil, amino-modified resin, catalyst and emulsifier are stirred evenly and mixed, and then water is added for emulsification and phase inversion to obtain a room temperature stable oil emulsion.

[0014] Compared with the prior art, the present invention has the following advantages:

[0015] This invention utilizes modified silicone oil with high ammonia and high epoxy values, characterized by high polarity and numerous functional groups, exhibiting strong interaction with organic functional groups on the surface of the precursor fiber. Furthermore, an amino-modified resin is introduced, acting as a reaction-enhancing functional component. During drying, pre-oxidation, and carbonization processes, it undergoes chemical cross-linking with the modified silicone oil to form a three-dimensional network structure. This effectively ensures the protective film formation on the precursor fiber surface during drying, the stretching resistance during steam stretching, and the heat protection capability of the fiber during carbonization, thereby effectively improving the mechanical properties of carbon fibers. Detailed Implementation

[0016] The following detailed embodiments further illustrate the content and technical solutions of the present invention, but should not be construed as limiting the invention. Any simple modifications or substitutions made to the methods, steps, or conditions of the present invention without departing from the spirit of the invention are within the scope of the invention.

[0017] The raw materials and reagents used in the following examples and comparative examples are all commercially available.

[0018] Example 1

[0019] 100 parts by weight of amino-modified silicone oil with an ammonia value of 1.20 mmol / g; 30 parts by weight of epoxy-modified silicone oil with an epoxy value of 1.50 mmol / g; 15 parts by weight of urea-formaldehyde resin with an amino-modified resin; 8 parts by weight of dibutyltin dilaurate as catalyst; and 50 parts by weight of fatty alcohol polyoxyethylene ether as emulsifier. After mixing the above components evenly, water was added for emulsification and phase inversion to obtain a room-temperature stable oil emulsion. The evaluation results on the production line using the prepared oil are shown in Table 1. The carbon fiber precursor contained 0.98% oil, and the precursor fiber filament grade was 1.0 (divided into grades 1.0-5.0, with grade 1.0 being the best and grade 5.0 being the worst). There was no sticking to the rollers during the drying process of the precursor fiber. The carbon fiber tensile strength was 6618 MPa, and the carbon fiber filament grade was 1.5 (divided into grades 1.0-5.0, with grade 1.0 being the best and grade 5.0 being the worst).

[0020] Example 2

[0021] 100 parts by weight of amino-modified silicone oil with an ammonia value of 0.90 mmol / g; 20 parts by weight of epoxy-modified silicone oil with an epoxy value of 1.00 mmol / g; 10 parts by weight of urea-formaldehyde resin for amino-modified resin; 5 parts by weight of dibutyltin dilaurate catalyst; and 40 parts by weight of fatty alcohol polyoxyethylene ether emulsifier. After uniform mixing of the above components, water was added for emulsification and phase inversion to obtain a room-temperature stable oil emulsion. The evaluation results on the production line using the prepared oil are shown in Table 1. The carbon fiber precursor contained 1.04% oil, with a precursor fiber filament grade of 1.2. No sticking to the rollers occurred during the drying process. The carbon fiber tensile strength was 6537 MPa, and the carbon fiber filament grade was 1.6.

[0022] Example 3

[0023] 100 parts by weight of amino-modified silicone oil with an ammonia value of 1.60 mmol / g; 50 parts by weight of epoxy-modified silicone oil with an epoxy value of 2.50 mmol / g; 20 parts by weight of urea-formaldehyde resin with an amino-modified resin; 10 parts by weight of dibutyltin dilaurate as catalyst; and 60 parts by weight of fatty alcohol polyoxyethylene ether as emulsifier. After uniform mixing of the above components, water was added for emulsification and phase inversion to obtain a room-temperature stable oil emulsion. The evaluation results on the production line using the prepared oil are shown in Table 1. The carbon fiber precursor contained 0.97% oil, with a precursor fiber filament grade of 1.0. No sticking to the rollers occurred during the drying process. The carbon fiber tensile strength was 6712 MPa, and the carbon fiber filament grade was 1.5.

[0024] Example 4

[0025] 100 parts by weight of amino-modified silicone oil with an ammonia value of 1.20 mmol / g; 30 parts by weight of epoxy-modified silicone oil with an epoxy value of 1.50 mmol / g; 15 parts by weight of melamine-formaldehyde resin; 8 parts by weight of bismuth neodecanoate catalyst; 10 parts by weight of fatty acid polyoxyethylene ester and 40 parts by weight of polyoxyethylene sorbitan fatty acid ester emulsifier. After the above components were thoroughly mixed, water was added for emulsification and phase inversion to obtain a room-temperature stable oil emulsion. The evaluation results on the production line using the prepared oil are shown in Table 1. The carbon fiber precursor contained 1.02% oil, the precursor fiber filament grade was 1.0, and there was no sticking to the rollers during the drying process; the carbon fiber tensile strength was 6647 MPa, and the carbon fiber filament grade was 1.5.

[0026] Example 5

[0027] 100 parts by weight of amino-modified silicone oil with an ammonia value of 1.20 mmol / g; 30 parts by weight of epoxy-modified silicone oil with an epoxy value of 1.50 mmol / g; 15 parts by weight of benzoic acid melamine-formaldehyde resin as the amino-modified resin; 8 parts by weight of bismuth neodecanoate as the catalyst; 10 parts by weight of fatty acid polyoxyethylene ester and 40 parts by weight of polyoxyethylene sorbitan fatty acid ester as the emulsifier. After the above components were thoroughly mixed, water was added for emulsification and phase inversion to obtain a room-temperature stable oil emulsion. The evaluation results on the production line using the prepared oil are shown in Table 1. The carbon fiber precursor contained 0.95% oil, the precursor filament grade was 1.0, and there was no sticking to the rollers during the drying process; the carbon fiber tensile strength was 6521 MPa, and the carbon fiber filament grade was 1.6.

[0028] Comparative Example 1

[0029] 100 parts by weight of amino-modified silicone oil with an ammonia value of 1.20 mmol / g; 30 parts by weight of epoxy-modified silicone oil with an epoxy value of 1.50 mmol / g; 8 parts by weight of dibutyltin dilaurate as catalyst; and 50 parts by weight of fatty alcohol polyoxyethylene ether as emulsifier. After uniform mixing of the above components, water was added for emulsification and phase inversion to obtain a room-temperature stable oil emulsion. The evaluation results on the production line using the prepared oil are shown in Table 1. The carbon fiber precursor contained 0.97% oil, with a precursor fiber fuzz grade of 2.5. During the precursor fiber operation, drying sticking to the rollers occurred. The carbon fiber tensile strength was 5980 MPa, and the carbon fiber fuzz grade was 3.0. Compared with Example 1, without the addition of amino-modified resin, the oil's binding and cross-linking properties to the precursor fiber decreased, leading to carbon fiber precursor fiber sticking to the rollers, increased fuzz, and reduced heat resistance of the oil during the carbonization stage, resulting in a significant decrease in the carbon fiber tensile strength.

[0030] Comparative Example 2

[0031] 100 parts by weight of amino-modified silicone oil with an ammonia value of 1.20 mmol / g; 30 parts by weight of epoxy-modified silicone oil with an epoxy value of 1.50 mmol / g; 15 parts by weight of urea-formaldehyde resin (amino-modified resin); and 50 parts by weight of fatty alcohol polyoxyethylene ether (emulsifier). After uniform mixing of the above components, water was added for emulsification and phase inversion to obtain a room-temperature stable oil emulsion. The evaluation results on the production line using the prepared oil are shown in Table 1. The carbon fiber precursor contained 1.02% oil, with a precursor fiber filament grade of 2.0. Drying and roller sticking phenomena also occurred during the precursor fiber operation. The carbon fiber tensile strength was 6011 MPa, and the carbon fiber filament grade was 2.5. Compared with Example 1, the lack of a catalyst led to a significant decrease in the film-forming rate of the oil, reduced the oil's binding and anti-sticking properties on the precursor, resulting in increased carbon fiber precursor filament filament size, weakened heat protection of the oil during the carbonization stage, and a decrease in the tensile strength of the carbon fiber.

[0032] Comparative Example 3

[0033] 100 parts by weight of amino-modified silicone oil with an ammonia value of 1.20 mmol / g; 30 parts by weight of epoxy-modified silicone oil with an epoxy value of 1.50 mmol / g; 30 parts by weight of urea-formaldehyde resin as the amino-modified resin; 8 parts by weight of dibutyltin dilaurate as the catalyst; and 50 parts by weight of fatty alcohol polyoxyethylene ether as the emulsifier. After uniform mixing of the above components, water was added for emulsification and phase inversion to obtain a room-temperature stable oil emulsion. The evaluation results on the production line using the prepared oil are shown in Table 1. The carbon fiber precursor contained 0.99% oil, and the precursor fiber filament grade was 2.0. Slight sticking to the drying rollers occurred during the precursor fiber operation. The carbon fiber tensile strength was 6207 MPa, and the carbon fiber filament grade was 2.5. Compared with Example 1, excessive amino-modified resin was added. It is speculated that during the crosslinking reaction, the excess component could not fully participate in the reinforcement reaction and remained on the drying rollers, leading to a deterioration in the precursor fiber's processability and a decrease in the carbon fiber filament grade and tensile strength.

[0034]

[0035] In summary, this invention utilizes modified silicone oil with high ammonia and high epoxy values, characterized by high polarity and numerous functional groups, exhibiting strong interaction with the organic functional groups on the surface of the precursor fiber. Furthermore, the introduction of amino resin acts as a reactive reinforcing component, chemically cross-linking with the modified silicone oil during drying, pre-oxidation, and carbonization processes to form a three-dimensional network oil film structure. This reduces surface damage to the precursor fiber during drying and steam stretching, while simultaneously enhancing the heat resistance and protection of the fiber during pre-oxidation and carbonization, effectively strengthening the mechanical properties of carbon fibers.

Claims

1. An oiling agent for amino-modified resin-reinforced carbon fiber precursor, characterized in that, The amino-modified silicone oil is 100 parts by weight, the epoxy-modified silicone oil is 20-50 parts by weight, the amino-modified resin is 10-20 parts by weight, the catalyst is 5-10 parts by weight, and the emulsifier is 40-60 parts by weight, wherein the amino value of the amino-modified silicone oil is 0.90-1.60 mmol / g, the epoxy value of the epoxy-modified silicone oil is 1.00-2.50 mmol / g, and the catalyst is selected from dibutyl tin dilaurate or bismuth neodecanoate.

2. The amino-modified resin reinforced carbon fiber precursor oil agent according to claim 1, characterized by, The amino-modified silicone oil is 100 parts by weight, the epoxy-modified silicone oil is 30-50 parts by weight, the amino-modified resin is 15-20 parts by weight, the catalyst is 8-10 parts by weight, and the emulsifier is 50-60 parts by weight.

3. The amino-modified resin reinforced carbon fiber precursor oil agent according to claim 1, characterized by, The amino value of the amino-modified silicone oil is 1.20-1.60 mmol / g.

4. The amino-modified resin reinforced carbon fiber precursor oil agent according to claim 1, characterized by, The epoxy value of the epoxy-modified silicone oil is 1.50-2.50 mmol / g.

5. The amino-modified resin reinforced carbon fiber precursor oil agent according to claim 1, characterized by, The amino-modified resin is selected from urea-formaldehyde resin, melamine-formaldehyde resin or benzotriazene-formaldehyde resin.

6. The amino-modified resin reinforced carbon fiber precursor oil agent according to claim 1, characterized by, The emulsifier is selected from one or more of fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester and polyoxyethylene sorbitan fatty acid ester.

7. The process for producing an oil agent for an aminomodified resin-reinforced carbon fiber precursor according to any one of claims 1 to 6, characterized by, The specific steps are as follows: According to the formula, the amino-modified silicone oil, the epoxy-modified silicone oil, the amino-modified resin, the catalyst and the emulsifier are uniformly mixed by stirring, and then water is added for emulsification and phase inversion to obtain a room temperature stable oil agent emulsion.

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