A phenyl-modified polysiloxane carbon fiber precursor oil and a method for preparing the same

Abstract

The present application relates to the technical field of silicone oil production, and discloses a phenyl-modified polysiloxane carbon fiber precursor oil agent and a preparation method thereof, which comprises the following components by weight: modified silicone oil 5-20 parts, non-ionic emulsifier 5-20 parts, co-emulsifier 1-10 parts, cationic antistatic agent 1-5 parts, and deionized water 50-80 parts. The phenyl, carboxyl and polyether chain modified silicone oil endows the oil agent with excellent high-temperature resistance, improves film tightness, adjusts the balance between affinity and repellency, and enhances emulsion dispersion stability. The non-ionic emulsifier and the co-emulsifier are compounded to reduce the interfacial tension between the oil phase and the water phase, and form a stable emulsion system. The cationic antistatic agent effectively eliminates the static accumulation generated by fiber friction through charge conduction. The present application simultaneously meets the requirements of the carbon fiber precursor oil agent for thermal stability, lubricity, antistatic property and emulsion stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of silicone oil production, in particular to a phenyl-modified polysiloxane carbon fiber precursor oil agent and a preparation method thereof. BACKGROUND

[0002] Carbon fibers have been widely used in aerospace, automotive industry, sports goods and many other fields due to their high strength, high modulus, low density, high temperature resistance, chemical corrosion resistance and other excellent properties. In the production process of carbon fibers, carbon fiber precursor oil agent plays a crucial role.

[0003] Carbon fiber precursor oil agent needs to have multiple properties, such as good lubricity to reduce the friction between the fiber and the equipment parts during production, prevent fiber damage; appropriate antistatic property to avoid the accumulation of static electricity leading to the mutual adsorption and winding of fibers, affecting the production process; and during the high-temperature pre-oxidation and carbonization stages, it can protect the fiber surface, reduce the thermal damage of the fiber, and improve the quality and performance of the carbon fiber.

[0004] At present, the carbon fiber oil agents on the market are mainly divided into silicone oil agents and non-silicone oil agents. Silicone oil agents are widely used in carbon fiber production due to their high heat resistance and lubricity. However, the existing silicone oil agents still have some shortcomings. For example, the heat resistance of some oil agents is not high enough, and the phenomenon of sticking and sticking to the roller easily occurs during the subsequent carbonization stage, affecting the continuity of production and product quality; the antistatic performance of some oil agents is not ideal, and the static problem is more prominent in high humidity or high temperature environment, leading to the decline of the processing performance of the fiber. In addition, the affinity of some oil agents with the fiber needs to be improved, and it is difficult to form a uniform and stable protective film on the fiber surface, thereby affecting the performance of the fiber. In order to meet the needs of high-performance carbon fiber production, it is of great practical significance to develop a carbon fiber precursor oil agent with excellent heat resistance, antistatic property, lubricity and good affinity with the fiber. SUMMARY

[0005] (I) Technical problems to be solved

[0006] In view of the shortcomings of the prior art, the present application provides a phenyl-modified polysiloxane carbon fiber precursor oil agent and a preparation method thereof.

[0007] (II) Technical solutions

[0008] To achieve the above-mentioned purpose, the present application provides the following technical solutions: a phenyl-modified polysiloxane carbon fiber precursor oil agent, comprising the following weight components:

[0009] 5-20 parts of modified silicone oil, 5-20 parts of emulsifier, 1-10 parts of co-emulsifier, 1-5 parts of antistatic agent, 50-80 parts of deionized water;

[0010] The preparation method of the modified silicone oil comprises the following steps:

[0011] A1, mixing octamethylcyclotetrasiloxane, 1,3,5,7-tetramethyltetraphenylcyclotetrasiloxane, methylhydrogencyclotrisiloxane, stirring uniformly, adding tetramethylammonium hydroxide, hexamethyldisiloxane, and obtaining a silicone oil precursor containing phenyl and silicon-hydrogen bond through reaction;

[0012] A2, mixing the silicone oil precursor, anhydrous methylcyclohexane and phenothiazine, passing nitrogen, heating through oil bath, stirring to form a uniform solution, adding catalyst platinum-divinyltetramethyldisiloxane complex and triethylamine, adding 4-pentenoic acid after heating, adding diatomite to adsorb the catalyst after reaction, obtaining a clear filtrate, and obtaining an intermediate product containing phenyl, residual silicon-hydrogen bond and carboxyl through vacuum distillation;

[0013] A3, mixing the above intermediate product and isopropanol, stirring to dissolve, adding 4A molecular sieve, adding catalyst platinum-divinyltetramethyldisiloxane complex, polyethylene glycol monoallyl ether and 2,6-di-tert-butyl-p-cresol after filtration, neutralizing with saturated sodium bicarbonate aqueous solution after reaction, standing to separate, adding antioxidant 1010 to the organic phase, and obtaining the modified silicone oil containing phenyl, carboxyl and polyether chain through vacuum distillation and supercritical CO2 extraction treatment.

[0014] Further, the emulsifier is a non-ionic emulsifier selected from one of Tween-80, Span-80 and polyoxyethylene castor oil.

[0015] Further, the co-emulsifier is selected from one of n-butanol, ethylene glycol monobutyl ether and propylene glycol methyl ether.

[0016] Further, the antistatic agent is a cationic antistatic agent selected from one of dodecyltrimethylammonium chloride, cetylpyridinium bromide and dioctadecyl dimethyl ammonium chloride.

[0017] Further, in step A1, octamethylcyclotetrasiloxane is 100-120 parts, 1,3,5,7-tetramethyltetraphenylcyclotetrasiloxane is 60-80 parts, methylhydrogencyclotrisiloxane is 20-30 parts, tetramethylammonium hydroxide is 1-3 parts, and hexamethyldisiloxane is 4-8 parts.

[0018] Further, in step A2, the silicone oil precursor is 100-120 parts, anhydrous methylcyclohexane is 200-400 parts, phenothiazine is 0.03-0.08 parts, platinum-divinyltetramethyldisiloxane complex is 0.1-0.5 parts, triethylamine is 0.04-0.06 parts, 4-pentenoic acid is 15-20 parts, and diatomite is 5-10 parts.

[0019] Further, in step A3, 100-120 parts of the intermediate product, 300-500 parts of isopropyl alcohol, 15-25 parts of 4A molecular sieves, 0.06-0.12 parts of platinum-divinyltetramethyldisiloxane complex, 10-20 parts of polyethylene glycol monoallyl ether, 0.02-0.05 parts of 2,6-di-tert-butyl-p-cresol, and 0.5-1 parts of antioxidant 1010 are added.

[0020] Further, a preparation method of a phenyl-modified polysiloxane carbon fiber precursor oil agent comprises the following steps:

[0021] S1, preheat the modified silicone oil in a 50℃ oven for 30 min, and prepare it for use; weigh the emulsifier and the co-emulsifier according to the proportion, add them into a beaker, and stir them evenly to form a composite emulsification system; add the antistatic agent into deionized water, and magnetically stir it until it is completely dissolved to prepare an antistatic agent aqueous solution with a mass fraction of 10-20%;

[0022] S2, add the preheated modified silicone oil and the composite emulsification system into an emulsification kettle with a high-speed shearing machine in sequence, start stirring, the rotating speed is 600-800 r / min, mix for 5-10 min, control the temperature of the emulsification kettle to be 40-45℃, slowly add the antistatic agent aqueous solution, the drop speed is 1-2 mL / min, increase the rotating speed to 1200-1500 r / min during the drop process, continue shearing for 10-15 min to form a primary emulsion with relatively coarse emulsion droplet size;

[0023] S3, keep the temperature at 40-45℃, add deionized water into the emulsification kettle in three times, each time interval is 10 min, increase the rotating speed to 2000-2500 r / min after adding the deionized water each time, and shear for 10-20 min, after adding all the deionized water, maintain the rotating speed at 2500 r / min, and continue emulsifying for 30 min;

[0024] S4, transfer the emulsion into a high-pressure homogenizer, cycle homogenization for 3 times under a pressure of 20-25 MPa, cool the system to room temperature after homogenization, adjust the pH to 6.5-7.5, stir for 20-30 min, and filter the emulsion through a 300-mesh nylon filter screen under vacuum to obtain a carbon fiber precursor oil agent.

[0025] (Three) Beneficial technical effects

[0026] The phenyl, carboxyl and polyether chain modified silicone oil is used in the present application, the rigid conjugated structure of the phenyl gives the oil agent excellent high temperature resistance, can keep stability in the high temperature environment of carbon fiber precursor processing, avoids lubrication failure or pollution caused by thermal decomposition; the carboxyl enhances the adsorption force with the fiber surface through polarity, improves the film forming tightness, reduces the friction damage in the spinning process; the polyether chain adjusts the balance of hydrophilicity and hydrophobicity, optimizes the spreadability of the oil agent on the fiber surface, and at the same time enhances the emulsion dispersion stability. The combination of the non-ionic emulsifier and the co-emulsifier can reduce the interfacial tension between the oil phase and the water phase, form a stable emulsion system, and ensure that the oil agent is uniformly attached to the fiber surface; the cationic antistatic agent effectively eliminates the static accumulation generated by fiber friction through charge conduction, avoids the yarn dispersion or breakage caused by static electricity.

[0027] In summary, the combination of the phenyl, carboxyl and polyether chain modified silicone oil and the non-ionic emulsion system can meet the requirements of the carbon fiber precursor oil agent for thermal stability, lubricity, antistatic property and emulsion stability. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0029] The components of the carbon fiber precursor oil agent formula in the present application are all commercially available, unless otherwise specified.

[0030] The parts used in the present application are all parts by weight.

[0031] In example 1, the emulsifier is a non-ionic emulsifier, which is selected from Tween-80.

[0032] The co-emulsifier is selected from n-butanol.

[0033] The antistatic agent is a cationic antistatic agent, which is selected from dodecyltrimethylammonium chloride.

[0034] A phenyl modified polysiloxane carbon fiber precursor oil agent, comprising the following components by weight:

[0035] 5 parts of modified silicone oil, 5 parts of emulsifier, 1 part of co-emulsifier, 1 part of antistatic agent and 50 parts of deionized water;

[0036] The preparation method of the modified silicone oil comprises the following steps:

[0037] A1, in a dry four-necked flask, 100 parts of octamethylcyclotetrasiloxane, 60 parts of 1,3,5,7-tetramethyltetraphenylcyclotetrasiloxane, 20 parts of methylhydrogen cyclosiloxane were added in turn, stirred uniformly, nitrogen was introduced, the temperature was raised to 60℃, 1 part of tetramethylammonium hydroxide was added dropwise, the temperature was continuously raised to 100℃, and the reaction was carried out for 4 hours, 4 parts of hexamethyldisiloxane was added, the temperature was raised to 130℃, and maintained for 1 hour, and then distilled under reduced pressure to obtain a silicone oil precursor containing phenyl and silicon-hydrogen bonds;

[0038] A2, 100 parts of the silicone oil precursor, 200 parts of anhydrous methylcyclohexane, and 0.03 parts of phenothiazine were added in turn into a four-necked flask, nitrogen was introduced, the stirring rate was adjusted to 250 r / min, the oil bath was heated to 40℃, the silicone oil precursor was completely dissolved to form a uniform solution, 0.1 parts of the catalyst platinum-divinyltetramethyldisiloxane complex and 0.04 parts of triethylamine were added, the temperature was continuously raised to 70℃, and maintained for 10 minutes, 15 parts of 4-pentenoic acid was slowly added through a constant pressure dropping funnel, the dropping speed was controlled at 0.8 mL / min, and the temperature was kept unchanged during the dropping process, after the dropping was completed, the temperature was raised to 85℃, and the reaction was carried out for 4 hours, the reaction liquid was cooled to room temperature, 5 parts of diatomite was added to adsorb the catalyst, stirred for 30 minutes, and then filtered under vacuum to obtain a clear filtrate, the filtrate was transferred to a rotary evaporator, distilled at 70℃ and 0.09 MPa for 30 minutes to remove the methylcyclohexane and unreacted 4-pentenoic acid, and an intermediate product containing phenyl, residual silicon-hydrogen bonds and carboxyl groups was obtained;

[0039] A3, 100 parts of the intermediate product and 300 parts of isopropanol were added into a four-necked flask, stirred and dissolved, 15 parts of 4Å molecular sieves were added, stirred for 1 hour, the molecular sieves were removed by filtration, the filtrate was returned to the flask, nitrogen was introduced for protection, the temperature was raised to 60℃, 0.06 parts of the catalyst platinum-divinyltetramethyldisiloxane complex was added, stirred and activated for 20 minutes, 10 parts of polyethylene glycol monoallyl ether and 0.02 parts of 2,6-di-tert-butyl-p-cresol were added, the temperature was raised to 80℃, and the reaction was carried out for 3 hours, the reaction liquid was cooled, neutralized with saturated sodium bicarbonate aqueous solution, and then allowed to stand and separate, the organic phase was washed with 0.1 mol / L hydrochloric acid to adjust the pH to 5.0, and then washed with deionized water until neutral, 0.5 parts of antioxidant 1010 was added to the organic phase, stirred and dissolved, and then transferred to a reduced pressure distillation device, distilled at 90℃ and 0.085 MPa for 1.5 hours, and finally treated by supercritical CO2 extraction for 2 hours at a temperature of 40℃, a pressure of 15 MPa, and a CO2 flow rate of 20 g / h to obtain a modified silicone oil containing phenyl, carboxyl and polyether chains.

[0040] A method for preparing a phenyl-modified polysiloxane carbon fiber precursor oil agent, comprising the following steps:

[0041] S1, the modified silicone oil is placed in a 50°C oven for preheating for 30 min, standby; the emulsifier and the co-emulsifier are weighed according to the proportion, added into a beaker and stirred uniformly to form a composite emulsifying system; the antistatic agent is added into deionized water, and magnetically stirred until completely dissolved to prepare an antistatic agent aqueous solution with a mass fraction of 10%;

[0042] S2, into the emulsifying kettle with a high-speed shearing machine, the preheated modified silicone oil, the composite emulsifying system are added in sequence, the stirring is started, the rotating speed is 600 r / min, the mixing is carried out for 5 min, the temperature of the emulsifying kettle is controlled to be 40°C, the antistatic agent aqueous solution is slowly added dropwise, the dropwise adding speed is 1 mL / min, the rotating speed is increased to 1200 r / min during the dropwise adding process, the shearing is continuously carried out for 10 min, and the primary emulsion with relatively coarse emulsion droplet size is formed;

[0043] S3, the temperature is kept to be 40°C, the deionized water is added into the emulsifying kettle in three times, each time interval is 10 min, the rotating speed is increased to 2000 r / min after each time of adding water, the shearing is carried out for 10 min, after all the deionized water is added, the rotating speed is maintained to be 2500 r / min, and the emulsifying is continuously carried out for 30 min;

[0044] S4, the emulsion is transferred to a high-pressure homogenizer, is circularly homogenized for 3 times under the pressure of 20 MPa, the system is cooled to room temperature after the homogenization, the pH value is adjusted to be 6.5, the stirring is carried out for 20 min, the emulsion is filtered under vacuum through a 300 mesh nylon filter screen, and the carbon fiber precursor oil agent is obtained.

[0045] In example 2, the emulsifier is a non-ionic emulsifier, which is selected from Span-80.

[0046] The co-emulsifier is selected from ethylene glycol monobutyl ether.

[0047] The antistatic agent is a cationic antistatic agent, which is selected from cetyl pyridine bromide.

[0048] A phenyl-modified polysiloxane carbon fiber precursor oil agent includes the following weight components:

[0049] 10 parts of modified silicone oil, 10 parts of emulsifier, 5 parts of co-emulsifier, 3 parts of antistatic agent, and 60 parts of deionized water;

[0050] The preparation method of the modified silicone oil includes the following steps:

[0051] A1, in a dry four-necked flask, 110 parts of octamethylcyclotetrasiloxane, 70 parts of 1,3,5,7-tetramethyltetraphenylcyclotetrasiloxane and 25 parts of methylhydrogen cyclosiloxane are sequentially added, stirred uniformly, nitrogen is introduced, the temperature is increased to 70°C, 2 parts of tetramethylammonium hydroxide is added dropwise, the temperature is continuously increased to 105°C, and reaction is carried out for 5 h; 6 parts of hexamethyldisiloxane is added, the temperature is increased to 135°C, and maintained for 1 h; and then pressure reduction distillation is carried out to obtain a silicone oil precursor containing phenyl and silicon-hydrogen bonds.

[0052] A2, 110 parts of the silicone oil precursor, 300 parts of anhydrous methylcyclohexane, 0.06 parts of phenothiazine were sequentially added into a four-necked flask, nitrogen was introduced, the stirring rate was adjusted to 300 r / min, the oil bath was heated to 45℃, the silicone oil precursor was completely dissolved to form a uniform solution, 0.3 parts of platinum-divinyltetramethyldisiloxane complex and 0.05 parts of triethylamine were added, the temperature was continuously increased to 75℃, and the temperature was kept for 15 min, 18 parts of 4-pentenoic acid was slowly added through a constant pressure dropping funnel, the dropping speed was controlled at 0.9 mL / min, and the temperature was kept unchanged during the dropping period, after the dropping was completed, the temperature was increased to 90℃, and the reaction was kept for 5 h, the reaction liquid was cooled to room temperature, 8 parts of diatomite was added to adsorb the catalyst, stirring was carried out for 40 min, and then vacuum filtration was carried out, a clear filtrate was obtained, the filtrate was transferred to a rotary evaporator, and distillation was carried out at 75℃ and 0.09 MPa for 45 min, methylcyclohexane and unreacted 4-pentenoic acid were removed, and an intermediate product containing phenyl, residual silicon-hydrogen bond and carboxyl was obtained;

[0053] A3, 110 parts of the intermediate product, 400 parts of isopropanol were added into a four-necked flask, after stirring and dissolving, 20 parts of 4A molecular sieve was added, stirring was carried out for 2 h, the molecular sieve was removed by filtration, the filtrate was returned to the flask, nitrogen was introduced for protection, the temperature was increased to 65℃, 0.09 parts of platinum-divinyltetramethyldisiloxane complex was added, stirring was carried out for 25 min, 15 parts of polyethylene glycol monoallyl ether and 0.04 parts of 2,6-di-tert-butyl-p-cresol were added, the temperature was increased to 80℃, and the reaction was kept for 4 h, after the reaction liquid was cooled, it was neutralized with saturated sodium bicarbonate aqueous solution, and was allowed to stand and separate, the organic phase was washed with 0.1 mol / L hydrochloric acid, the pH was adjusted to 5.5, and then the organic phase was washed with deionized water until it was neutral, 0.8 parts of antioxidant 1010 was added to the organic phase, stirring and dissolving were carried out, and then the organic phase was transferred into a reduced pressure distillation device, distillation was carried out at 95℃ and 0.09 MPa for 2 h, and finally supercritical CO2 extraction treatment was carried out for 2 h, the temperature was 40℃, the pressure was 15 MPa, and the CO2 flow rate was 20 g / h, and a modified silicone oil containing phenyl, carboxyl and polyether chain was obtained.

[0054] A method for preparing a phenyl-modified polysiloxane carbon fiber precursor oil, comprising the following steps:

[0055] S1, the modified silicone oil was preheated in a 50℃ oven for 30 min, and was prepared for use; the emulsifier and the co-emulsifier were weighed according to the proportion, were added into a beaker, and were stirred uniformly to form a composite emulsifying system; the antistatic agent was added into deionized water, and was magnetically stirred until it was completely dissolved, and was prepared into an antistatic agent aqueous solution with a mass fraction of 15%;

[0056] S2, into the emulsification kettle with high-speed shearing machine, sequentially add preheated modified silicone oil, composite emulsifier system, start stirring, speed 700 r / min, mix 10 min, control the temperature of the emulsification kettle to be 45℃, slowly drop the antistatic agent aqueous solution, drop speed 1 mL / min, during the drop process, increase the speed to 1300 r / min, continue shearing for 10 min, form the primary emulsion with relatively coarse emulsion droplet size;

[0057] S3, keep the temperature to be 40℃, add deionized water into the emulsification kettle in 3 times, interval 10 min, after each time of adding water, increase the speed to 2200 r / min, shear for 15 min, after adding all the deionized water, maintain the speed to be 2500 r / min, continue emulsifying for 30 min;

[0058] S4, transfer the emulsion to the high-pressure homogenizer, cycle homogenization for 3 times under the pressure of 22 MPa, after homogenization, cool the system to room temperature, adjust the pH to be 7, stir for 30 min, vacuum filter the emulsion through the 300 mesh nylon filter screen, obtain the carbon fiber precursor oil agent.

[0059] In example 3, the emulsifier is a non-ionic emulsifier, which is selected from polyoxyethylene castor oil.

[0060] The co-emulsifier is selected from propylene glycol methyl ether.

[0061] The antistatic agent is a cationic antistatic agent, which is selected from dioctadecyl dimethyl ammonium chloride.

[0062] A phenyl-modified polysiloxane carbon fiber precursor oil agent, which comprises the following components by weight:

[0063] Modified silicone oil 20 parts, emulsifier 20 parts, co-emulsifier 10 parts, antistatic agent 5 parts, deionized water 80 parts;

[0064] The preparation method of the modified silicone oil comprises the following steps:

[0065] A1, in a dry four-necked flask, sequentially add 120 parts of octamethylcyclotetrasiloxane, 80 parts of 1,3,5,7-tetramethyltetraphenylcyclotetrasiloxane, 30 parts of methylhydrogen cyclosiloxane, stir uniformly, introduce nitrogen, increase the temperature to 80℃, drop 3 parts of tetramethylammonium hydroxide, continue to increase the temperature to 110℃, react for 6 h, add 8 parts of hexamethyldisiloxane, increase the temperature to 140℃, maintain for 1 h, reduce pressure distillation, obtain the silicone oil precursor containing phenyl and silicon-hydrogen bond;

[0066] A2, add 120 parts of silicone oil precursor, 400 parts of anhydrous methylcyclohexane and 0.08 parts of phenothiazine into a four-necked flask in turn, introduce nitrogen, adjust the stirring rate to 350 r / min, heat the oil bath to 50℃, and make the silicone oil precursor completely dissolved to form a uniform solution, then add 0.5 parts of platinum-divinyltetramethyldisiloxane complex and 0.06 parts of triethylamine, continue to heat to 80℃, and keep the temperature for 20 min, then slowly drop 20 parts of 4-pentenoic acid through a constant pressure dropping funnel at a dropping speed of 1 mL / min, keep the temperature unchanged during the dropping, after the dropping is completed, heat to 90℃, keep the temperature for 6 h, cool the reaction liquid to room temperature, add 10 parts of diatomite to adsorb the catalyst, stir for 40 min, then vacuum filter to obtain a clear filtrate, transfer the filtrate to a rotary evaporator, distill under the condition of 80℃ and 0.1 MPa for 45 min to remove methylcyclohexane and unreacted 4-pentenoic acid, and obtain an intermediate product containing phenyl, residual silicon-hydrogen bond and carboxyl;

[0067] A3, add 120 parts of the intermediate product and 500 parts of isopropanol into a four-necked flask, stir and dissolve, then add 25 parts of 4A molecular sieve, stir for 2 h, filter to remove the molecular sieve, return the filtrate to the flask, introduce nitrogen protection, heat to 65℃, add 0.12 parts of platinum-divinyltetramethyldisiloxane complex as a catalyst, stir and activate for 30 min, add 20 parts of polyethylene glycol monoallyl ether and 0.05 parts of 2,6-di-tert-butyl-p-cresol, heat to 85℃, keep the temperature for 5 h, cool the reaction liquid, first neutralize with saturated sodium bicarbonate aqueous solution, stand and separate, wash the organic phase with 0.1 mol / L hydrochloric acid, adjust the pH to 6.0, then wash with deionized water until neutral, add 1 part of antioxidant 1010 to the organic phase, stir and dissolve, then transfer into a reduced pressure distillation device, distill under the condition of 100℃ and 0.095 MPa for 2 h, and finally treat by supercritical CO2 extraction for 2 h under the condition of a temperature of 40℃, a pressure of 15 MPa and a CO2 flow rate of 20 g / h to obtain modified silicone oil containing phenyl, carboxyl and polyether chain.

[0068] A method for preparing a phenyl-modified polysiloxane carbon fiber precursor oil, comprising the following steps:

[0069] S1, preheat the modified silicone oil in a 50℃ oven for 30 min, and prepare; weigh the emulsifier and the co-emulsifier according to the proportion, add them into a beaker, stir uniformly to form a composite emulsifying system; add the antistatic agent into deionized water, and magnetically stir until it is completely dissolved to prepare an antistatic agent aqueous solution with a mass fraction of 20%;

[0070] S2, into the emulsification kettle with high-speed shearing machine, sequentially add preheated modified silicone oil, composite emulsifying system, start stirring, speed 800 r / min, mix for 10 min, control the temperature of the emulsification kettle to be 45℃, slowly add the antistatic agent aqueous solution, drop speed 2 mL / min, during the drop process, increase the speed to 1500 r / min, continue shearing for 15 min, form the primary emulsion with relatively coarse emulsion droplet size;

[0071] S3, keep the temperature at 45℃, add deionized water into the emulsification kettle in 3 times, interval 10 min each time, after adding water each time, increase the speed to 2500 r / min, shear for 20 min, after adding all the deionized water, maintain the speed at 2500 r / min, continue emulsifying for 30 min;

[0072] S4, transfer the emulsion to the high-pressure homogenizer, cycle homogenization for 3 times under the pressure of 25 MPa, after homogenization, cool the system to room temperature, adjust the pH to 7.5, stir for 30 min, vacuum filter the emulsion through a 300 mesh nylon filter screen, to obtain the carbon fiber precursor oil.

[0073] Comparative Example 1: replace the modified silicone oil with octamethylcyclotetrasiloxane and methylhydrogen cyclosiloxane, the rest of the components and preparation method are the same as Example 1.

[0074] Comparative Example 2: use the silicone oil precursor containing phenyl and silicon-hydrogen bond prepared by step A1, without step A2 and A3, the rest of the components and preparation method are the same as Example 1.

[0075] Comparative Example 3: replace the emulsifier with sodium dodecyl sulfate, the rest of the components and preparation method are the same as Example 1.

[0076] Performance test:

[0077] Thermal stability: adopt thermogravimetric analysis method (TGA), in nitrogen atmosphere, heat to 500℃ at 10℃ / min, record the weight loss rate at 300℃;

[0078] Lubricity: measure the dynamic friction coefficient of the carbon fiber precursor coated with oil by fiber friction coefficient instrument (test speed 10 m / min, tension 5 cN);

[0079] Antistatic property: use surface resistance meter to measure the surface resistance of the fiber coated with oil (environmental humidity 50%, temperature 25℃);

[0080] Emulsion stability: place the oil in the oven at 50℃ for 72 h, observe whether it is layered; centrifuge at 3000 r / min for 30 min, record the volume ratio of the layered part;

[0081] Film-forming property: The oil agent was coated on a glass sheet, dried at room temperature for 24 h, and the film surface flatness (Ra value) was observed by atomic force microscopy (AFM);

[0082] Table 1

[0083] .

[0084] Table 2

[0085] .

[0086] From the above table, it can be seen that the silicone oil without phenyl group has significantly decreased thermal stability and poor lubricity due to the lack of rigid groups, indicating that phenyl group is the key to improve the high-temperature resistance and lubricity of the oil agent. The pure phenyl silicone oil has poor emulsion stability, rough film formation and decreased antistatic property due to the lack of carboxyl group and polyether chain, indicating that carboxyl group and polyether chain can ensure the dispersibility of the oil agent and the synergy of functions. The charge conflict between anionic emulsifier and cationic antistatic agent leads to decreased emulsion stability and film flatness, indicating that the compatibility of non-ionic emulsifier and cationic antistatic agent is better.

[0087] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and changes can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A phenyl-modified polysiloxane carbon fiber precursor oil characterized by comprising: The following weight components are included: Modified silicone oil 5~20 parts, emulsifier 5~20 parts, co-emulsifier 1~10 parts, antistatic agent 1~5 parts, deionized water 50~80 parts; The preparation method of the modified silicone oil includes the following steps: A1, octamethylcyclotetrasiloxane, 1, 3, 5, 7-tetramethyltetraphenylcyclotetrasiloxane, methyl hydrogen cyclotrisiloxane is mixed, stirred uniformly, dropwise added with tetramethylammonium hydroxide and hexamethyldisiloxane, and a silicone oil precursor containing phenyl and silicon hydrogen bonds is obtained by reaction; A2, the silicone oil precursor, anhydrous methylcyclohexane and phenothiazine are mixed, nitrogen is introduced, the oil bath is heated, stirring is performed to form a uniform solution, a catalyst platinum-divinyltetramethyldisiloxane complex and triethylamine are added, 4-pentenoic acid is added dropwise after heating, diatomite is added to adsorb the catalyst after reaction, a clear filtrate is obtained, vacuum distillation is performed, and an intermediate product containing phenyl, residual silicon hydrogen bonds and carboxyl groups is obtained; A3, the intermediate product, isopropanol are mixed, stirring and dissolution are performed, 4A molecular sieve is added, filtration is performed, a catalyst platinum-divinyltetramethyldisiloxane complex, polyethylene glycol monoallyl ether and 2, 6-di-tert-butyl-p-cresol are added after filtration, neutralization is performed with saturated sodium bicarbonate aqueous solution after reaction, standing and liquid separation are performed, an antioxidant 1010 is added to the organic phase, vacuum distillation is performed, supercritical CO2 extraction treatment is performed, and a modified silicone oil containing phenyl, carboxyl and polyether chains is obtained.

2. The phenyl-modified polysiloxane carbon fiber precursor oil according to claim 1, characterized by, The emulsifier is a non-ionic emulsifier, and is selected from one of Tween-80, Span-80 and polyoxyethylene castor oil.

3. The phenyl-modified polysiloxane carbon fiber precursor oil according to claim 1, characterized by, The co-emulsifier is selected from one of n-butanol, ethylene glycol monobutyl ether and propylene glycol methyl ether.

4. The phenyl-modified polysiloxane carbon fiber precursor oil according to claim 1, characterized by, The antistatic agent is a cationic antistatic agent, and is selected from one of dodecyltrimethylammonium chloride, cetylpyridinium bromide and dioctadecyldimethylammonium chloride.

5. The phenyl-modified polysiloxane carbon fiber precursor oil according to claim 1, characterized by, In step A1, octamethylcyclotetrasiloxane 100~120 parts, 1, 3, 5, 7-tetramethyltetraphenylcyclotetrasiloxane 60~80 parts, methyl hydrogen cyclotrisiloxane 20~30 parts, tetramethylammonium hydroxide 1~3 parts and hexamethyldisiloxane 4~8 parts are used.

6. The phenyl-modified polysiloxane carbon fiber precursor oil according to claim 1, characterized by In step A2, the silicone oil precursor 100~120 parts, anhydrous methylcyclohexane 200~400 parts, phenothiazine 0.03~0.08 parts, platinum-divinyltetramethyldisiloxane complex 0.1~0.5 parts, triethylamine 0.04~0.06 parts, 4-pentenoic acid 15~20 parts and diatomite 5~10 parts are used.

7. The phenyl-modified polysiloxane carbon fiber precursor oil according to claim 1, characterized by, In step A3, the intermediate product 100~120 parts, isopropanol 300~500 parts, 4A molecular sieve 15~25 parts, platinum-divinyltetramethyldisiloxane complex 0.06~0.12 parts, polyethylene glycol monoallyl ether 10~20 parts, 2, 6-di-tert-butyl-p-cresol 0.02~0.05 parts and antioxidant 1010 0.5~1 parts are used.

8. A process for the preparation of a phenyl-modified polysiloxane oil for carbon fiber precursors according to any one of claims 1 to 7, characterized in that The following steps are included: S1, the modified silicone oil is preheated in a 50℃ oven for 30 min and is ready for use; the emulsifier and the co-emulsifier are weighed according to the proportion, are added into a beaker and are stirred uniformly to form a composite emulsification system; the antistatic agent is added into deionized water, and is stirred magnetically until completely dissolved to prepare an antistatic agent aqueous solution with a mass fraction of 10~20%; S2, into the emulsification kettle with high-speed shearing machine, sequentially add preheated modified silicone oil, composite emulsifying system, start stirring, speed 600~800 r / min, mixed 5~10 min, control the temperature of emulsification kettle 40~45℃, slowly drop the antistatic agent aqueous solution, drop speed 1~2 mL / min, during the drop process, the speed is increased to 1200~1500 r / min, continue shearing 10~15 min, form the primary emulsion with coarse emulsion droplet size; S3, keep the temperature 40~45℃, add deionized water into the emulsification kettle in 3 times, interval 10 min, after each time of adding water, increase the speed to 2000~2500 r / min, shear 10~20 min, after adding all deionized water, maintain the speed 2500 r / min, continue emulsification 30 min; S4, transfer the emulsion to high pressure homogenizer, cycle homogenization 3 times under 20~25 MPa pressure, after homogenization, cool the system to room temperature, adjust pH to 6.5~7.5, stir 20~30 min, filter the emulsion through 300 mesh nylon filter screen under vacuum, get carbon fiber precursor oil agent.