CN115928443A - Carbon fiber oil and preparation method thereof - Google Patents
Carbon fiber oil and preparation method thereof Download PDFInfo
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Abstract
The application provides a carbon fiber oil agent, which comprises quaternized modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, an emulsifier, an organic solvent, an auxiliary agent and deionized water; the mass parts of the components of the oil agent are as follows: 3-14 parts of quaternized modified silicone oil, 5-33 parts of amino modified silicone oil, 3-14 parts of epoxy modified silicone oil, 5-15 parts of emulsifier and organic solvent, 1-5 parts of assistant and 60-70 parts of deionized water; the quaternization modified silicone oil comprises one or more of hydroxyl, polyether modified quaternization silicone oil, alkoxy modified quaternization silicone oil and aminoethyl aminopropyl modified quaternization silicone oil. The carbon fiber produced by coating the oil agent has the advantages of high tensile breaking strength, low impurity content, good fiber separation property, low hairiness in production and use and the like.
Description
Technical Field
The application relates to the field of carbon fiber production, in particular to a carbon fiber oiling agent and a preparation method of the oiling agent.
Background
Polyacrylonitrile (PAN) based carbon fibers are a novel material that has been rapidly developed in the last sixty years, and are widely used in high-end fields such as military industry, aerospace and the like because of their excellent properties such as light weight, high specific strength, high specific modulus, high temperature resistance, corrosion resistance and the like. With the rapid growth of domestic markets, the demand of carbon fibers is increasing day by day, but the tensile strength of the carbon fibers is seriously influenced by the surface defects of the carbon fibers, so that the application of the carbon fibers in composite materials is restricted. In order to prevent surface defects, measures such as high-quality oil agent, effective oiling process and the like are needed, the oil agent is an important auxiliary agent for producing polyacrylonitrile-based carbon fiber precursors, and the contribution rate of the oil agent to the improvement of the carbon fiber strength is about 0.5-1 GPa. However, the oil solution in the current market is difficult to match the carbon fiber production process well, more or less has the problems of high content of impurities such as metal and nonmetal in the precursor, more broken filaments, poor fiber separation property and the like, and even the phenomena of thermal bonding and thermal doubling are easy to occur in a pre-oxidation section, so that the development of the oil solution suitable for dry-jet wet spinning precursor is urgent.
Disclosure of Invention
The application aims at providing a carbon fiber oiling agent, and the carbon fiber produced by coating the oiling agent has the advantages of high tensile breaking strength, low impurity content, good fiber distribution, low hairiness in production and use and the like.
The carbon fiber oil agent can be mainly modified by organic silicon oil emulsion, wherein, the amino modified silicone oil has excellent heat resistance and flexibility and is widely applied to the synthesis of the carbon fiber oil agent because the amino modified silicone oil is easy to form strong hydrogen bonds with polar groups such as hydroxyl groups on carbon fibers. However, the amino group in the molecular structure of the amino modified silicone oil is not uniformly distributed, so that the hydrophilicity of the amino modified silicone oil is poor, uniform and stable emulsion is difficult to obtain, the degree of combination with carbon fibers is too low, the amino modified silicone oil is difficult to uniformly spread on the surfaces of the carbon fibers, and the carbon fibers cannot be well protected. Therefore, the application provides an oiling agent for carbon fiber, has improved oiling agent hydrophilicity and can strengthen the combination with carbon fiber when obtaining homogeneous stable emulsion, has improved carbon fiber tensile rupture strength and mechanical properties, has become the key problem of further improvement carbon fiber production efficiency and quality.
According to one aspect of the application, a carbon fiber oil agent is provided, and the oil agent comprises quaternized modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, an emulsifier, an organic solvent, an auxiliary agent and deionized water;
the mass parts of the components of the oil agent are as follows:
wherein the modification mode of the amino modified silicone oil comprises side chain diamino modification or terminal amino modification.
Wherein the modification mode of the quaternized modified silicone oil comprises side chain modification; the molecular weight of the quaternized modified silicone oil is 3000-15000 g/mol.
The quaternization modified silicone oil comprises one or more of hydroxyl, polyether modified quaternization silicone oil, alkoxy modified quaternization silicone oil and aminoethyl aminopropyl modified quaternization silicone oil.
If the quaternized modified silicone oil comprises hydroxyl and polyether modified quaternized silicone oil, the mass part of the hydroxyl and polyether modified quaternized silicone oil is 3-8, and the mass part ratio of the hydroxyl and polyether modified quaternized silicone oil to the amino modified silicone oil is 1.5-1;
if the quaternized modified silicone oil comprises the alkoxy modified quaternized silicone oil, the mass part of the alkoxy modified quaternized silicone oil is 8-14 parts, and the mass part ratio of the alkoxy modified quaternized silicone oil to the amino modified silicone oil is 1;
if the quaternized modified silicone oil comprises the aminoethyl aminopropyl modified quaternized silicone oil, the mass part of the aminoethyl aminopropyl modified quaternized silicone oil is 3-8, and the mass part ratio of the aminoethyl aminopropyl modified quaternized silicone oil to the amino modified silicone oil is 1.5-1.
When the quaternized modified silicone oil comprises the hydroxyl group, the polyether modified quaternized silicone oil, the alkoxy modified quaternized silicone oil and the aminoethyl aminopropyl modified quaternized silicone oil, the mass part ratio of the hydroxyl group, the polyether modified quaternized silicone oil, the alkoxy modified quaternized silicone oil and the aminoethyl aminopropyl modified quaternized silicone oil is 1.5.
Wherein the modification mode of the epoxy modified silicone oil comprises side chain multifunctional group modification or double-end modification.
Wherein the epoxy value of the epoxy modified silicone oil is 0.005-0.25 mmol/100g; the molecular weight of the epoxy modified silicone oil is 50000-200000 g/mol; the ratio of the mass portion of the epoxy modified silicone oil to the sum of the mass portions of the quaternized modified silicone oil and the amino modified silicone oil is 1.5-1.
The oil agent comprises the following components in parts by weight:
wherein the quaternized modified silicone oil comprises hydroxyl, polyether modified quaternized silicone oil, alkoxy modified quaternized silicone oil and aminoethyl aminopropyl modified quaternized silicone oil; wherein the mass parts of the hydroxyl and polyether modified quaternized silicone oil are 1.3-2.0 parts, the mass parts of the alkoxy modified quaternized silicone oil are 2.6-4.0 parts, and the mass parts of the aminoethyl aminopropyl modified quaternized silicone oil are 1.3-2.0 parts; wherein the mass part ratio of the hydroxyl, the polyether modified quaternized silicone oil, the alkoxy modified quaternized silicone oil and the aminoethyl aminopropyl modified quaternized silicone oil is 1.7.
In the carbon fiber oiling agent, the organic silicone oil comprises quaternized modified silicone oil, amino modified silicone oil and epoxy modified silicone oil, wherein the quaternized modified silicone oil comprises hydroxyl, polyether modified quaternized silicone oil, alkoxy modified quaternized silicone oil and aminoethyl aminopropyl modified quaternized silicone oil, after hydrophilic quaternary ammonium salt groups are introduced, the original good hand feeling of the amino silicone oil can be kept, the carbon fiber is endowed with better hydrophilicity, and the yellowing phenomenon of the carbon fiber during high-temperature treatment is reduced.
The functions and contents of the components in the carbon fiber oil agent are described as follows:
the carbon fiber oil agent comprises quaternized modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, an emulsifier, an organic solvent, an auxiliary agent and deionized water; the effective components of the carbon fiber oil agent comprise quaternized modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, an emulsifier, an organic solvent and an auxiliary agent.
The amino modified silicone oil has excellent heat resistance and flexibility, is easy to form strong hydrogen bonds with polar groups such as hydroxyl groups on carbon fibers, improves the film forming property and the hydrophilicity of the carbon fibers, and has decisive influence on the continuous production and the subsequent application of the carbon fibers. Preferably, the modification mode of the amino modified silicone oil in the application comprises side chain double amino modification or end amino modification; more preferably, the modifying group of the amino-modified silicone oil comprises one or more of a primary amine group, a secondary amine group, a pyrazinyl group and an phenylamino group; further preferably, the ammonia value is 0.1 to 0.7mmol/g and the molecular weight is 10000 to 150000g/mol. The carbon fiber oil agent is characterized in that the mass part of amino modified silicone oil is limited to 5-33 parts; preferably, the amino modified silicone oil is 5 to 20 parts by weight.
The amino modified silicone oil has excellent performance, but the hydrophilicity of the amino modified silicone oil is insufficient due to the uneven distribution of the amino groups in the molecular structure, uniform and stable emulsion is difficult to obtain, the emulsion is not combined with carbon fibers to a sufficient degree, and the emulsion is difficult to spread on the surfaces of the carbon fibers uniformly. Preferably, the modification mode of the quaternized modified silicone oil comprises side chain modification; more preferably, the molecular weight of the quaternized modified silicone oil is 3000 to 15000g/mol. Further preferably, the quaternized modified silicone oil includes one or more of a hydroxyl group, a polyether-modified quaternized silicone oil, an alkoxy-modified quaternized silicone oil, and an aminoethyl aminopropyl-modified quaternized silicone oil. Wherein, in the carbon fiber oil agent, the mass part of the quaternary ammonium modified silicone oil is limited to be 3-14 parts; preferably, the mass portion of the quaternized modified silicone oil is 5-10.
In the research process, the selection and the mass part of different types of quaternized modified silicone oil and the mass part of quaternized modified silicone oil and amino modified silicone oil have different influences on the using effect of the carbon fiber oil agent. If the quaternized modified silicone oil comprises hydroxyl and polyether modified quaternized silicone oil, the mass part of the hydroxyl and polyether modified quaternized silicone oil is 3-8, and the mass part ratio of the hydroxyl and polyether modified quaternized silicone oil to the amino modified silicone oil is 1.5-1.5, the range has the effects of improving the hydrophilicity of the carbon fiber fabric and the carbon fiber oiling agent emulsion, and effectively controlling the particle size of the carbon fiber oiling agent emulsion in an application range, so that the carbon fiber oiling agent emulsion can be quickly and uniformly oiled on the surface of carbon fiber precursors; if the quaternized modified silicone oil comprises 8-14 parts by weight of alkoxy modified quaternized silicone oil, the mass part ratio of the alkoxy modified quaternized silicone oil to the amino modified silicone oil is defined as 1.8-1, the yellowing degree of the carbon fiber fabric can be effectively reduced, and the hydrophilicity of the carbon fiber fabric is improved at the same time; if the quaternized modified silicone oil comprises aminoethyl aminopropyl modified quaternized silicone oil, the mass part of the aminoethyl aminopropyl modified quaternized silicone oil is 3-8, and the mass part ratio of the aminoethyl aminopropyl modified quaternized silicone oil to the amino modified silicone oil is 1.5-1.5, the range of the effects can ensure that the carbon fiber fabric has soft and smooth hand feeling and good rebound resilience, and simultaneously the carbon fiber oil emulsion has excellent stability. If the quaternized modified silicone oil comprises hydroxyl, polyether modified quaternized silicone oil, alkoxy modified quaternized silicone oil and aminoethyl aminopropyl modified quaternized silicone oil, the mass parts of the hydroxyl and polyether modified quaternized silicone oil are 1.3-2.0 parts, the mass parts of the alkoxy modified quaternized silicone oil are 2.6-4.0 parts, the mass parts of the aminoethyl aminopropyl modified quaternized silicone oil are 1.3-2.0 parts, and the mass part ratio of the hydroxyl, polyether modified quaternized silicone oil, alkoxy modified quaternized silicone oil and aminoethyl aminopropyl modified quaternized silicone oil is 1.5; preferably, the mass part ratio of the hydroxyl, the polyether modified quaternized silicone oil, the alkoxy modified quaternized silicone oil and the aminoethyl aminopropyl modified quaternized silicone oil is 1.7; through different quaternization modification modes, hydrophilic quaternary ammonium salt groups of different types are introduced, the hydrophilic groups of quaternization modified silicone oil can be distributed more uniformly, the hydrophilicity of the modified silicone oil is improved, uniform and stable carbon fiber oil emulsion is obtained, the modified silicone oil is uniformly spread on the surface of the fiber, the combination of the modified silicone oil and the carbon fiber is enhanced, and the carbon fiber is effectively protected to improve the tensile breaking strength and the mechanical property of the carbon fiber.
The epoxy modified silicone oil can improve the heat resistance of the carbon fiber oil agent in the carbonization and graphitization high-temperature treatment process in the carbon fiber production. Preferably, the modification mode of the epoxy modified silicone oil in the application comprises side chain multifunctional group modification or double-end modification; more preferably, the epoxy value of the epoxy-modified silicone oil is from 0.005 to 0.25mmol/100g; the molecular weight of the epoxy modified silicone oil is 50000-200000 g/mol. The carbon fiber oil agent is characterized in that 3-14 parts by mass of epoxy modified silicone oil is limited; preferably, the epoxy modified silicone oil is 5 to 10 parts by weight. The application further limits the ratio of the mass part of the epoxy modified silicone oil to the sum of the mass parts of the quaternized modified silicone oil and the amino modified silicone oil to be 1.5-1.5, and the carbon fiber oil emulsion has better bundling property on carbon fiber fabrics and higher heat resistance in the range of effects.
The emulsifier is a non-ionic surfactant, and can improve the stability of the carbon fiber oil emulsion. Preferably, the emulsifier can be one or more of isomeric alcohol polyoxyethylene ether or fatty alcohol polyoxyethylene ether. The organic solvent has the functions of dissolving and lubricating the emulsifier, and can well disperse the emulsifier in the carbon fiber oil. Preferably, the organic solvent may be isopropyl alcohol. In the carbon fiber oil agent, the sum of the mass parts of the emulsifier and the organic solvent is limited to be 5-15 parts; preferably, the sum of the mass parts of the emulsifier and the organic solvent is 8 to 12 parts.
The auxiliaries used herein may include antifoaming agents, antistatic agents, pH adjusting agents. The defoaming agent can carry out defoaming treatment on the carbon fiber oil emulsion, so that adverse effects on the subsequent production process and the product quality due to the fact that the carbon fiber oil emulsion contains foam are avoided. The antistatic agent can enable the carbon fiber oil agent to have a better antistatic effect. The pH regulator can regulate the pH value of the carbon fiber oil. In the carbon fiber oiling agent, the mass part of the limiting auxiliary agent is 1-5 parts.
Deionized water in this application is the disperse phase of each component in the carbon fiber finish, can make carbon fiber finish system viscosity reduction through adding deionized water in an appropriate amount. In the carbon fiber oil agent, the mass part of deionized water is limited to be 60-70 parts.
According to another aspect of the application, a preparation method of the carbon fiber oiling agent comprises the following steps:
s1: mixing and stirring the quaternized modified silicone oil and the amino modified silicone oil to obtain a first mixture;
s2: adding an emulsifier and an organic solvent into the first mixture obtained in the step S1, and stirring to obtain a second mixture;
s3: adding epoxy modified silicone oil into the second mixture obtained in the step S2, and stirring to obtain a third mixture;
s4: adding deionized water into the third mixture obtained in the step S3, reducing viscosity of the third mixture, and stirring to obtain a fourth mixture;
s5: and (5) adding the balance of deionized water and auxiliary agent into the fourth mixture obtained in the step (S4), and stirring to obtain the carbon fiber oiling agent.
Preferably, the reaction system adopts a stirring kettle with a wall scraping device and a high-speed dispersion disc, or an emulsifying kettle with a wall scraping device, a stirring paddle and a high-speed homogenizing head, wherein the wall scraping device can fully mix the material components, and the high-speed dispersion disc and the homogenizing head can provide high-speed shearing to realize the phase inversion process.
Preferably, the stirring time after the viscosity of the system is reduced in step S4 is 0.5 to 2 hours.
The beneficial effects of selecting the above ranges of the contents of the components in the carbon fiber finish of the present application will be illustrated by giving specific experimental data through examples.
The following is an example of preferable value ranges of each component contained in the carbon fiber finish according to the present application.
Preferred examples 1
The carbon fiber oil agent comprises quaternized modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, an emulsifier, an organic solvent, an auxiliary agent and deionized water, and is expressed by the following mass parts:
preferred example two
The carbon fiber oil agent comprises quaternized modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, an emulsifier, an organic solvent, an auxiliary agent and deionized water, and is expressed by the following mass parts:
wherein the quaternized modified silicone oil comprises one or more of hydroxyl, polyether modified quaternized silicone oil, alkoxy modified quaternized silicone oil and aminoethyl aminopropyl modified quaternized silicone oil;
if the quaternized modified silicone oil comprises hydroxyl and polyether modified quaternized silicone oil, the mass part of the hydroxyl and polyether modified quaternized silicone oil is 3-8, and the mass part ratio of the hydroxyl and polyether modified quaternized silicone oil to the amino modified silicone oil is 1.5-1;
if the quaternized modified silicone oil comprises the alkoxy modified quaternized silicone oil, the mass parts of the alkoxy modified quaternized silicone oil are 8-14 parts, and the mass part ratio of the alkoxy modified quaternized silicone oil to the amino modified silicone oil is 1;
if the quaternized modified silicone oil comprises the aminoethyl aminopropyl modified quaternized silicone oil, the mass part of the aminoethyl aminopropyl modified quaternized silicone oil is 3-8, and the mass part ratio of the aminoethyl aminopropyl modified quaternized silicone oil to the amino modified silicone oil is 1.5-1.
Preferred example three
The carbon fiber oil agent comprises quaternized modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, an emulsifier, an organic solvent, an auxiliary agent and deionized water, and is represented by the following components in parts by mass:
when the quaternized modified silicone oil comprises the hydroxyl group, the polyether modified quaternized silicone oil, the alkoxy modified quaternized silicone oil and the aminoethyl aminopropyl modified quaternized silicone oil, the mass part ratio of the hydroxyl group, the polyether modified quaternized silicone oil, the alkoxy modified quaternized silicone oil and the aminoethyl aminopropyl modified quaternized silicone oil is 1.5.
Preferred example four
The carbon fiber oil agent comprises quaternized modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, an emulsifier, an organic solvent, an auxiliary agent and deionized water, and is expressed by the following mass parts:
wherein the ratio of the mass parts of the epoxy modified silicone oil to the sum of the mass parts of the quaternized modified silicone oil and the amino modified silicone oil is 1.5-1.
Preferred example five
The carbon fiber oil agent comprises quaternized modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, an emulsifier, an organic solvent, an auxiliary agent and deionized water, and is expressed by the following mass parts:
wherein the quaternized modified silicone oil comprises hydroxyl, polyether modified quaternized silicone oil, alkoxy modified quaternized silicone oil and aminoethyl aminopropyl modified quaternized silicone oil; wherein the mass parts of the hydroxyl and polyether modified quaternized silicone oil are 1.3-2.0 parts, the mass parts of the alkoxy modified quaternized silicone oil are 2.6-4.0 parts, and the mass parts of the aminoethyl aminopropyl modified quaternized silicone oil are 1.3-2.0 parts; wherein the mass part ratio of the hydroxyl, the polyether modified quaternized silicone oil, the alkoxy modified quaternized silicone oil and the aminoethyl aminopropyl modified quaternized silicone oil is 1.7.
Preferred example six
The carbon fiber oil agent comprises quaternized modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, an emulsifier, an organic solvent, an auxiliary agent and deionized water, and is expressed by the following mass parts:
when the quaternized modified silicone oil comprises the hydroxyl group, the polyether modified quaternized silicone oil, the alkoxy modified quaternized silicone oil and the aminoethyl aminopropyl modified quaternized silicone oil, the mass part ratio of the hydroxyl group, the polyether modified quaternized silicone oil, the alkoxy modified quaternized silicone oil and the aminoethyl aminopropyl modified quaternized silicone oil is 1.7.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.
The formula raw materials of the carbon fiber oil used in the embodiments 1 to 6 of the application are as follows:
quaternization modified silicone oil: hydroxyl and polyether modified quaternary ammonium silicone oil with the molecular weight of 14000g/mol is selected in the embodiments 1 and 4-5, alkoxy modified quaternary ammonium silicone oil with the molecular weight of 14000g/mol is selected in the embodiments 2 and 6, and aminoethyl aminopropyl modified quaternary ammonium silicone oil with the molecular weight of 3000g/mol is selected in the embodiment 3;
amino-modified silicone oil: in the embodiments 1 to 6, terminal phenylamino modified silicone oil is selected;
epoxy modified silicone oil: in the embodiments 1-5, side chain multifunctional epoxy modified silicone oil with the molecular weight of 200000g/mol is selected, and in the embodiment 6, double-end epoxy modified silicone oil with the molecular weight of 100000g/mol is selected;
emulsifier + organic solvent: in the embodiments 1-6, a fatty alcohol-polyoxyethylene ether emulsifier and an isopropanol organic solvent are selected;
auxiliary agent: examples 1 to 6 used antistatic agents, defoaming agents and pH adjusting agents.
Deionized water;
the mass parts of the components in the examples of the carbon fiber finish of the present application are shown in table 1.
Table 1 formulation of carbon fiber finish for examples 1-6
| Component (in parts) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Quaternized modified silicone oil | 5 | 10 | 5 | 3 | 8 | 14 |
| Amino modified silicone oil | 10 | 10 | 10 | 5 | 16 | 21 |
| Epoxy modified silicone oil | 6 | 8 | 6 | 4 | 14 | 14 |
| Emulsifier + organic solvent | 10 | 10 | 10 | 5 | 15 | 15 |
| Auxiliary agent | 3 | 3 | 3 | 1 | 5 | 5 |
| Deionized water | 65 | 66.5 | 65 | 60 | 67 | 70 |
The preparation of examples 1 to 6 was as follows:
s1: adding the quaternized modified silicone oil and the amino modified silicone oil into a stirring kettle at one time, and stirring for 20 minutes at a constant temperature of 40 ℃ and a high-speed dispersion disc rotating speed of 1500rpm/min to obtain a first mixture;
s2: slowly adding an emulsifier and an organic solvent into the first mixture obtained in the step S1, and stirring at the rotating speed of 1500rpm/min for 10 minutes to obtain a second mixture;
s3: adding epoxy modified silicone oil into the second mixture obtained in the step S2, stirring at the rotating speed of 1500rpm/min for 10 minutes to obtain a third mixture, and reducing the stirring rotating speed to 1000rpm/min after the third mixture becomes sticky;
s4: slowly adding deionized water into the third mixture obtained in the step S3, reducing viscosity of the third mixture, adjusting the rotating speed to 1500rpm/min, and continuously stirring for 2 hours to obtain a fourth mixture;
s5: and (5) adding the rest deionized water and the auxiliary agent into the fourth mixture obtained in the step (S4) in 3 batches in equal amount, and stirring at the rotating speed of 1500rpm/min for 20 minutes to obtain the carbon fiber oil agent.
In order to further illustrate the beneficial effects of the application, comparative example 1 (carbon fiber oil prepared without using quaternized modified silicone oil) and comparative example 2 (preparation method of carbon fiber oil is not stepped, and preparation method of "one pot boiling" is adopted) are given as comparative examples, and the carbon fiber oil of comparative example 1 and comparative example 2 comprises the following components in parts and preparation method:
comparative example 1:
amino-modified silicone oil: 15 parts of terminal phenylamino modified silicone oil;
epoxy modified silicone oil: 6 parts by weight of side chain multifunctional epoxy modified silicone oil with the molecular weight of 200000g/mol;
emulsifier + organic solvent: 8 parts of fatty alcohol-polyoxyethylene ether emulsifier and 2 parts of isopropanol organic solvent;
auxiliary agent: 3 parts by weight of antistatic agent, defoaming agent and pH regulator;
deionized water: 65 parts by weight.
The preparation method comprises the following steps: the same procedure was used for the preparation of examples 1 to 6.
Comparative example 2:
quaternization modified silicone oil: 5 parts by weight of hydroxyl and polyether modified quaternized silicone oil with the molecular weight of 14000 g/mol;
amino-modified silicone oil: 10 parts of terminal phenylamino modified silicone oil;
epoxy modified silicone oil: 6 parts by weight of side chain multifunctional epoxy modified silicone oil with the molecular weight of 200000g/mol;
emulsifier + organic solvent: 8 parts of fatty alcohol-polyoxyethylene ether emulsifier and 2 parts of isopropanol organic solvent;
auxiliary agent: 3 parts by weight of antistatic agent, defoaming agent and pH regulator;
deionized water: 65 parts by weight.
The preparation method comprises the following steps: adding the quaternized modified silicone oil, the amino modified silicone oil, the epoxy modified silicone oil, the emulsifier and the organic solvent into a stirring kettle at one time, stirring for 20 minutes at a constant temperature of 40 ℃ at a high-speed dispersion disc rotating speed of 1500rpm/min to obtain a first reaction mixture, and reducing the stirring rotating speed to 1000rpm/min after the obtained first reaction mixture becomes sticky; slowly adding deionized water into the first reaction mixture, reducing viscosity of the reaction mixture, adjusting the rotating speed to 1500rpm/min, and continuously stirring for 2 hours to obtain a second reaction mixture; and adding the rest of deionized water and the auxiliary agent into the second reaction mixture in 3 batches in equal amount, and stirring at the rotating speed of 1500rpm/min for 20 minutes to obtain the carbon fiber oil.
Table 2 shows the characteristics and the use effects of the carbon fiber oil solutions described in examples 1 to 6 and comparative examples 1 to 2, and in order to ensure the comparability of the test results, the preparation processes not listed in each example and comparative example are ensured to be completely consistent, so as to facilitate the parallel comparison of the mechanical properties.
Table 2 characteristics and effects of using carbon fiber oil solutions described in examples and comparative examples
Comparative example 1 shows that the stability of the carbon fiber oil emulsion is poor and the using effect is poor due to no addition of the quaternized modified silicone oil; comparative example 2 shows that the carbon fiber oil emulsion synthesized by all raw materials in one pot has poor stability and is subjected to layering demulsification in a short time.
From the test results of the above examples and comparative examples, it can be seen that the carbon fiber oil prepared by using the component ratios and the preparation method provided by the application has higher stability and better using effect, and in addition, the carbon fiber oil has the advantages of good bundling property, improvement of the tensile breaking strength and mechanical property of the carbon fiber and the like.
Finally, it should be noted that: in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one of 8230" does not exclude the presence of additional identical elements in the process, method, article, or apparatus that comprises the element.
The above examples are only for illustrating the technical solutions of the present application, and are not limited thereto. Although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions in the embodiments of the present application.
Claims (10)
1. The carbon fiber oil agent is characterized by comprising quaternized modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, an emulsifier, an organic solvent, an auxiliary agent and deionized water;
the mass parts of the components of the oil agent are as follows:
2. an oil agent according to claim 1, characterized in that the modification mode of the amino-modified silicone oil comprises side chain bisamino modification or terminal amino modification.
3. An oil agent according to claim 1, wherein the quaternary modified silicone oil is modified in a manner including side chain modification; the molecular weight of the quaternized modified silicone oil is 3000-15000 g/mol.
4. An oil agent according to claim 3, wherein the quaternized modified silicone oil comprises one or more of a hydroxyl group, a polyether modified quaternized silicone oil, an alkoxy modified quaternized silicone oil, and an aminoethyl aminopropyl modified quaternized silicone oil.
5. An oil agent according to claim 3,
if the quaternized modified silicone oil comprises hydroxyl and polyether modified quaternized silicone oil, the mass part of the hydroxyl and polyether modified quaternized silicone oil is 3-8, and the mass part ratio of the hydroxyl and polyether modified quaternized silicone oil to the amino modified silicone oil is 1.5-1;
if the quaternized modified silicone oil comprises the alkoxy modified quaternized silicone oil, the mass part of the alkoxy modified quaternized silicone oil is 8-14 parts, and the mass part ratio of the alkoxy modified quaternized silicone oil to the amino modified silicone oil is 1;
if the quaternized modified silicone oil comprises the aminoethyl aminopropyl modified quaternized silicone oil, the mass part of the aminoethyl aminopropyl modified quaternized silicone oil is 3-8, and the mass part ratio of the aminoethyl aminopropyl modified quaternized silicone oil to the amino modified silicone oil is 1.5-1.
6. An oil agent according to claim 3, wherein when the quaternized modified silicone oil comprises the hydroxyl group, polyether modified quaternized silicone oil, alkoxy modified quaternized silicone oil and aminoethyl aminopropyl modified quaternized silicone oil, the mass part ratio of the hydroxyl group, polyether modified quaternized silicone oil, alkoxy modified quaternized silicone oil and aminoethyl aminopropyl modified quaternized silicone oil is 1 to 1.5.
7. An oil agent according to claim 1, wherein the modification mode of the epoxy-modified silicone oil comprises side chain multifunctional group modification or double-end modification.
8. An oil agent according to claim 7, wherein the epoxy value of the epoxy-modified silicone oil is from 0.005 to 0.25mmol/100g; the molecular weight of the epoxy modified silicone oil is 50000-200000 g/mol; the ratio of the mass portion of the epoxy modified silicone oil to the sum of the mass portions of the quaternized modified silicone oil and the amino modified silicone oil is 1.5-1.
9. An oil agent according to claim 1, characterized in that the mass parts of the components of the oil agent are as follows:
wherein the quaternized modified silicone oil comprises hydroxyl, polyether modified quaternized silicone oil, alkoxy modified quaternized silicone oil and aminoethyl aminopropyl modified quaternized silicone oil; wherein the mass parts of the hydroxyl and polyether modified quaternized silicone oil are 1.3-2.0 parts, the mass parts of the alkoxy modified quaternized silicone oil are 2.6-4.0 parts, and the mass parts of the aminoethyl aminopropyl modified quaternized silicone oil are 1.3-2.0 parts; wherein the mass part ratio of the hydroxyl, the polyether modified quaternized silicone oil, the alkoxy modified quaternized silicone oil and the aminoethyl aminopropyl modified quaternized silicone oil is 1.7.
10. A method for preparing a carbon fiber finish according to any one of claims 1 to 8, comprising the steps of:
s1: mixing and stirring the quaternized modified silicone oil and the amino modified silicone oil to obtain a first mixture;
s2: adding an emulsifier and an organic solvent into the first mixture obtained in the step S1, and stirring to obtain a second mixture;
s3: adding epoxy modified silicone oil into the second mixture obtained in the step S2, and stirring to obtain a third mixture;
s4: adding deionized water into the third mixture obtained in the step S3, reducing viscosity of the third mixture, and stirring to obtain a fourth mixture;
s5: and (5) adding the balance of deionized water and auxiliary agent into the fourth mixture obtained in the step (S4), and stirring to obtain the carbon fiber oiling agent.
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| CN202211499248.8A Pending CN115928443A (en) | 2022-11-28 | 2022-11-28 | Carbon fiber oil and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116657287A (en) * | 2023-07-14 | 2023-08-29 | 中复神鹰碳纤维股份有限公司 | High heat-resistant carbon fiber oiling agent and preparation method thereof |
| CN116657286A (en) * | 2023-06-30 | 2023-08-29 | 中复神鹰碳纤维股份有限公司 | Oil solution for ultrahigh-strength carbon fiber precursor and preparation method thereof |
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- 2022-11-28 CN CN202211499248.8A patent/CN115928443A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116657286A (en) * | 2023-06-30 | 2023-08-29 | 中复神鹰碳纤维股份有限公司 | Oil solution for ultrahigh-strength carbon fiber precursor and preparation method thereof |
| CN116657287A (en) * | 2023-07-14 | 2023-08-29 | 中复神鹰碳纤维股份有限公司 | High heat-resistant carbon fiber oiling agent and preparation method thereof |
| CN116657287B (en) * | 2023-07-14 | 2024-05-07 | 中复神鹰碳纤维股份有限公司 | High heat-resistant carbon fiber oiling agent and preparation method thereof |
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