Silicone oil-containing composition, oiling agent and preparation method and application thereof

Abstract

The invention relates to the field of silicone oil, and discloses a silicone oil-containing composition and an oiling agent, and a preparation method and application thereof, the composition contains amino modified silicone oil, polyether modified silicone oil, fatty alcohol alkoxylate, a cationic antistatic agent, and aliphatic polyhydroxyalkyl quaternary ammonium salt as shown in formula (1), in the formula (1), R1 is selected from C1-C4 hydroxyalkyl, R2 is selected from C1-C4 hydroxyalkyl, and R3 is selected from C1-C4 hydroxyalkyl. R < 2 > and R < 3 > are independently selected from C1-C4 alkyl groups or C1-C4 hydroxyalkyl groups, R < 4 > is selected from groups with C8-C24 fatty groups, and Z <-> is an anion; wherein based on 100 parts by weight of the composition, the content of the aliphatic polyhydroxyalkyl quaternary ammonium salt is 0.1-5.0 parts by weight. All the components in the silicone oil-containing composition interact, so that the composition has excellent stability and heat resistance.

Description

Technical Field

[0001] This invention relates to the field of silicone oil technology, specifically to a silicone oil-containing composition and oiling agent, its preparation method, and its application. Background Technology

[0002] Carbon fiber is an inorganic polymer fiber with a carbon backbone structure, consisting of over 90% carbon, formed by the pyrolysis and carbonization of organic matrix fibers such as polyacrylonitrile, pitch, and viscose under high-temperature conditions. It possesses numerous excellent properties, including lightweight, high strength, ease of molding, corrosion resistance, and high-temperature resistance, and is widely used in aerospace, wind turbine blades, sports and leisure, pressure vessels, and transportation construction.

[0003] Carbon fiber oil is an important additive in the carbon fiber production process. Its main function is to form a uniformly thick film on the fiber surface, which can effectively prevent or eliminate static electricity generated by friction, reduce the coefficient of friction, and impart properties such as smoothness and softness to the fiber. It also enables the fiber to have appropriate bundle properties, stretchability, fiber splitting, spinnability, oxidation resistance, and heat resistance, allowing it to pass smoothly through processes such as pre-oxidation and low-temperature carbonization. It prevents thermal adhesion or thermal melting on the fiber surface, protects the fiber surface from damage, minimizes microscopic defects in the precursor fiber, and improves the tensile strength and modulus of carbon fiber. It is one of the key technologies for improving the quality of carbon fiber.

[0004] Compared to ordinary civilian spinning oils, carbon fiber manufacturing conditions are more demanding, thus requiring more stringent performance from carbon fiber oils. In particular, the heat resistance of the oil is much higher than that of conventional civilian spinning oils. This is to ensure sufficient oil to protect the fibers during pre-oxidation and low-temperature carbonization, preventing adhesion or tangling due to localized overheating and protecting the fiber surface from damage. For example, the oil in CN200910234655.4 mainly consists of medium-low viscosity, high ammonia value amino silicone oil and polyether, epoxy, and other modified silicone oils, supplemented with other auxiliaries. Although the spinning process is smooth after oiling, without sticking to rollers or fuzzing, the oil's heat resistance is insufficient. Similarly, the oil in CN201410420266.1 mainly consists of high viscosity, low ammonia value amino silicone oil and polyether, epoxy, and other modified silicone oils. The spinning process is smooth after oiling, and heat resistance is improved. However, due to the large amount of high-viscosity silicone oil used, the oil emulsification is more difficult, resulting in poor emulsion stability. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of poor stability and heat resistance of existing silicone oil compositions, and to provide a silicone oil composition and oiling agent, as well as its preparation method and application. By introducing a specific amount of aliphatic polyhydroxyalkyl quaternary ammonium salt into the silicone oil composition, which interacts with other components in the composition, the problem of insufficient stability and heat resistance caused by the interaction of various components in the composition can be better solved.

[0006] To achieve the above objectives, a first aspect of the present invention provides a silicone oil-containing composition comprising amino-modified silicone oil, polyether-modified silicone oil, fatty alcohol alkoxylate, cationic antistatic agent, and aliphatic polyhydroxyalkyl quaternary ammonium salt of formula (1).

[0007] In formula (1), R1 is selected from C1-C4 hydroxyalkyl groups, R2 and R3 are each independently selected from C1-C4 alkyl groups or C1-C4 hydroxyalkyl groups, R4 is selected from a group having aliphatic groups of C8-C24, and Z - The aliphatic polyhydroxyalkyl quaternary ammonium salt is anionic; wherein, based on 100 parts by weight, the aliphatic polyhydroxyalkyl quaternary ammonium salt content is 0.1-5.0 parts by weight.

[0008] A second aspect of the present invention provides an oiling agent comprising water and the silicone oil composition provided in the first aspect of the present invention.

[0009] A third aspect of the present invention provides a method for preparing an oil, the method comprising: contacting water with the silicone oil composition described in the first aspect of the present invention.

[0010] The fourth aspect of the present invention provides the application of the silicone oil composition described in the first aspect or the oiling agent described in the second aspect of the present invention in fiber production.

[0011] Through the above technical solution, the various components in the silicone oil composition of the present invention interact with each other, so that the composition has excellent stability and heat resistance. For example, when the silicone oil composition of the present invention is used as the active ingredient in an oiling agent, the oiling agent has excellent stability and heat resistance. Attached Figure Description

[0012] Figure 1 This is a thermogravimetric analysis of the oil in Example 1. Detailed Implementation

[0013] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0014] In this invention, unless otherwise specified, viscosity refers to viscosity at 20°C.

[0015] The first aspect of this invention provides a silicone oil-containing composition comprising amino-modified silicone oil, polyether-modified silicone oil, fatty alcohol alkoxylate, cationic antistatic agent, and aliphatic polyhydroxyalkyl quaternary ammonium salt of formula (1).

[0016]

[0017] In formula (1), R1 is selected from C1-C4 hydroxyalkyl groups, R2 and R3 are each independently selected from C1-C4 alkyl groups or C1-C4 hydroxyalkyl groups, R4 is selected from a group having aliphatic groups of C8-C24, and Z - The aliphatic polyhydroxyalkyl quaternary ammonium salt is anionic; wherein, based on 100 parts by weight, the aliphatic polyhydroxyalkyl quaternary ammonium salt content is 0.1-5.0 parts by weight.

[0018] In this invention, the interaction of the various components in the silicone oil composition results in the composition having superior stability, heat resistance, and low ash content.

[0019] The specific amount of aliphatic polyhydroxyalkyl quaternary ammonium salt in this invention has a special structure. Its interaction with the amino-modified silicone oil, polyether-modified silicone oil, fatty alcohol alkoxylates, and cationic antistatic agents in the composition can better increase the stability and heat resistance of the composition. The aliphatic polyhydroxyalkyl quaternary ammonium salt content that can be listed in this invention is 0.1 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 1.0 parts by weight, 1.6 parts by weight, 2.0 parts by weight, 3.0 parts by weight, 4.0 parts by weight, 5.0 parts by weight, or any combination of two of the above values, preferably 0.2-2.0 parts by weight. Using the aforementioned embodiments, the silicone oil-containing composition not only has better stability and heat resistance, but also has lower ash content during the use of the composition.

[0020] According to the present invention, the content of the amino-modified silicone oil in the composition is not particularly limited, as long as the purpose of the present invention can be achieved. Preferably, the content of the amino-modified silicone oil is 30-50 parts by weight per 100 parts by weight of the composition. By adopting the foregoing embodiments, the components can interact better, giving the composition excellent stability and heat resistance.

[0021] According to the present invention, the content of polyether-modified silicone oil in the composition is not particularly limited, as long as the purpose of the present invention can be achieved. Preferably, the content of polyether-modified silicone oil in the composition is 10-30 parts by weight, based on 100 parts by weight. By adopting the aforementioned embodiments, the various components can interact better, giving the composition excellent stability and heat resistance.

[0022] According to the present invention, the content of fatty alcohol alkoxylates in the composition is not particularly limited, as long as the purpose of the present invention can be achieved. Preferably, the content of fatty alcohol alkoxylates in the composition is 10-20 parts by weight, based on 100 parts by weight. By employing the foregoing embodiments, the various components can interact better, giving the composition excellent stability and heat resistance.

[0023] According to the present invention, the content of the cationic antistatic agent in the composition is not particularly limited, as long as the purpose of the present invention can be achieved. Preferably, the content of the cationic antistatic agent is 10-20 parts by weight based on 100 parts by weight of the composition. By adopting the foregoing embodiments, the various components can interact better, giving the composition excellent stability and heat resistance.

[0024] In this invention, C1-C4 alkyl groups that can be listed include methyl, ethyl, isopropyl, n-propyl, and n-butyl.

[0025] In this invention, "hydroxyalkyl" refers to HO-alkyl-. C1-C4 hydroxyalkyl groups that can be listed in this invention include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, and 4-hydroxybutyl.

[0026] In this invention, the aliphatic group having C8-C24 can be in the form of a straight chain or a branched chain, preferably in the form of a straight chain; the aliphatic group can be saturated or unsaturated (having one or more unsaturated double bonds), preferably a saturated aliphatic group; the number of carbon atoms in the aliphatic group can be 8, 10, 12, 14, 16, 18, 20, 22, 24, or any range of two of the above values.

[0027] According to a preferred embodiment of the present invention, R4 contains at least one functional group selected from ether, ester, amide, and hydroxyl groups. When one of these functional groups is present, the functional group is directly connected to the aliphatic group; when at least two of these functional groups are present, one functional group is directly connected to the aliphatic group, and the remaining functional groups can be connected to the aliphatic group or to the functional group connected to the aliphatic group.

[0028] According to the present invention, as long as the purpose of the present invention can be achieved, there is no special limitation on the specific type of anion in formula (1). In a preferred embodiment, in formula (1), the anion is an inorganic acid ion, an organic acid ion, an ester ion or a halide ion.

[0029] According to a preferred embodiment of the present invention, in formula (1), the anion is a sulfate ion, a phosphate ion, a sulfonate ion, a nitrate ion, or a halide ion.

[0030] In this invention, the sulfate ester ions that can be listed include methyl sulfate ions, ethyl sulfate ions, propyl sulfate ions, and butyl sulfate ions; the phosphate ester ions that can be listed include ethyl phosphate and dibutyl phosphate ions; the sulfonate ester ions that can be listed include methyl sulfonate ions and ethyl sulfonate ions; the nitrate ester ions that can be listed include methyl nitrate ions and ethyl nitrate ions; and the halide ions that can be listed include chloride ions and bromide ions.

[0031] In this invention, amino-modified silicone oil refers to silicone oil with amino-containing organic groups attached to some of its silicon atoms, and polyether-modified silicone oil is formed by chemically bonding polyether segments and polysiloxane segments. In this invention, based on 100 parts by weight of the composition, the value of the weight parts of amino-modified silicone oil × the mass fraction of amino is denoted as a, the value of the weight parts of aliphatic polyhydroxyalkyl quaternary ammonium salt × the mass fraction of hydroxyl groups in the aliphatic polyhydroxyalkyl quaternary ammonium salt is denoted as b, and the value of the weight parts of polyether-modified silicone oil × the mass fraction of ether is denoted as c.

[0032] According to the present invention, it can be understood that the mass fraction of amino groups = molecular weight of each amino group / total molecular weight of amino-modified silicone oil; the mass fraction of hydroxyl groups = number of hydroxyl groups * 17 / total molecular weight of aliphatic polyhydroxyalkyl quaternary ammonium salts; and the mass fraction of ethers = number of ethers in the polyether chain * 16 / total molecular weight of polyether-modified silicone oil.

[0033] According to a preferred embodiment of the present invention, a ≤ b. Using the aforementioned embodiments, the composition exhibits good stability, heat resistance, and low ash content.

[0034] According to a preferred embodiment of the present invention, b ≤ c. Using the aforementioned embodiments, the composition exhibits good stability, heat resistance, and low ash content.

[0035] According to the present invention, the specific values ​​of a, b, and c are not particularly limited as long as the purpose of the present invention can be achieved. Preferably, the difference between a and b is 0-100.0, for example, 0, 0.6, 1.5, 2.6, 3.8, 5.2, 10.0, 15.0, 20.0, 30.0, 49.0, 50.0, 60.0, 70.6, 80.6, 90.0, 100.0, or any two of the above value groups. The range of values ​​for b and c is preferably 0.5-50.0; preferably, the difference between b and c is 0-200.0, for example, 0, 26.8, 37.0, 39.0, 40.4, 48.4, 56.3, 85.4, 113.4, 120.0, 130.5, 145.6, 160.6, 180.5, 200.0, or any combination of two of the above values, preferably 25-120.0. Using the aforementioned embodiments, the composition exhibits better stability, heat resistance, and low ash content.

[0036] According to the present invention, the viscosity of the amino-modified silicone oil is not particularly limited as long as the purpose of the invention can be achieved. Preferably, the viscosity of the amino-modified silicone oil is 100-4000 cp, for example, 100 cp, 1000 cp, 2000 cp, 2500 cp, 3000 cp, 3200 cp, 3500 cp, 4000 cp, or any combination of two of the above values. The compositions in the foregoing embodiments have better stability and heat resistance.

[0037] According to a preferred embodiment of the present invention, the amino-modified silicone oil contains an amino content of 0.1-2.0% by mass, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, or any combination of two of the above values. The compositions described in the foregoing embodiments exhibit better stability and heat resistance.

[0038] In this invention, amino-modified silicone oil refers to silicone oil in which some silicon atoms are attached with an amino-containing organic group. As long as the purpose of this invention can be achieved, there is no special limitation on the specific position of the amino organic group in the silicone oil. Preferably, the amino organic group is a side chain. That is, in one embodiment, the amino-modified silicone oil is a side-chain amino-modified silicone oil.

[0039] According to a particularly preferred embodiment of the present invention, the side-chain amino structure in the side-chain amino-modified silicone oil is selected from C2-C8 monoamino aliphatic hydrocarbon groups or diamino aliphatic hydrocarbon groups. The compositions of the aforementioned embodiments exhibit better stability and heat resistance.

[0040] In this invention, the C2-C8 monoamino aliphatic hydrocarbon groups or diamino aliphatic hydrocarbon groups that can be listed include C2 monoamino aliphatic hydrocarbon groups or diamino aliphatic hydrocarbon groups, C4 monoamino aliphatic hydrocarbon groups or diamino aliphatic hydrocarbon groups, C6 monoamino aliphatic hydrocarbon groups or diamino aliphatic hydrocarbon groups, and C8 monoamino aliphatic hydrocarbon groups or diamino aliphatic hydrocarbon groups; as a non-limiting illustration, the amino organic groups in the side-chain amino-modified silicone oil include: -CH2CH2CH2NH2, -CH2CH2CH2NHCH2CH2NH2.

[0041] According to the present invention, the viscosity of the polyether-modified silicone oil is not particularly limited as long as the purpose of the present invention can be achieved. Preferably, the viscosity of the polyether-modified silicone oil is 300-2000 cp, for example, 300 cp, 500 cp, 800 cp, 1100 cp, 1500 cp, 1800 cp, 2000 cp, or any combination of two of the above values. The compositions in the foregoing embodiments have better stability and heat resistance.

[0042] In this invention, polyether-modified silicone oil is formed by chemically bonding polyether segments and polysiloxane segments. The bonding can be Si-OC or Si-C. There is no special limitation in this invention. This invention uses SiC-type polyether-modified silicone oil as an example to illustrate the advantages of this invention, but this invention is not limited thereto.

[0043] According to a preferred embodiment of the present invention, the polyether-modified silicone oil is selected from at least one of side-chain polyether-modified silicone oil, double-ended polyether-modified silicone oil, single-ended polyether-modified silicone oil, and side-chain end-group co-modified polyether silicone oil.

[0044] According to a particularly preferred embodiment of the present invention, the polyether-modified silicone oil is a side-chain polyether-modified silicone oil. The compositions described in the foregoing embodiments exhibit better stability and heat resistance.

[0045] According to a preferred embodiment of the present invention, the polyether structural units in the polyether-modified silicone oil include ethylene oxide structural units and optionally propylene oxide structural units.

[0046] In this invention, optionally, the propylene oxide structural unit means that it may contain propylene oxide structural units or not.

[0047] According to a particularly preferred embodiment of the present invention, the number of ethylene oxide additions in the polyether structural unit is 4-16 (e.g., 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or any two of the above values), preferably 12-16 and / or the number of propylene oxide additions is 0-4 (e.g., 0, 1, 2, 3, 4, or any two of the above values).

[0048] According to a preferred embodiment of the present invention, based on the total mass of the polyether-modified silicone oil, the mass fraction of ether in the polyether-modified silicone oil is 0.5-20.0 wt%, for example, 0.5 wt%, 1.0 wt%, 2.0 wt%, 5.0 wt%, 10.0 wt%, 15.0 wt%, 20.0 wt%, or any range of two of the above values, preferably 1.0-3.0 wt%. The composition under the aforementioned embodiment has better stability and heat resistance.

[0049] In this invention, those skilled in the art will know that fatty alcohol alkoxylates refer to products obtained by the addition reaction of fatty alcohols with ethylene oxide and / or propylene oxide. In fatty alcohol alkoxylates: the fatty alcohol segment can be a straight chain or a branched chain structure; the fatty alcohol segment can be a saturated fatty alcohol segment or an unsaturated fatty alcohol segment, preferably a saturated fatty alcohol segment, and more preferably, the fatty alcohol segment is selected from C8-C16 fatty alcohol segments. Examples of C8-C16 fatty alcohol segments include straight-chain octanol segments, isomeric decaylol segments, isomeric tridecylol segments, and straight-chain hexadecylol segments.

[0050] According to a particularly preferred embodiment of the present invention, the fatty alcohol alkoxylate contains an alkoxy segment and optionally a propoxy segment.

[0051] In this invention, optionally, the propoxy segment refers to the presence or absence of a propoxy segment. Preferably, the number of ethoxy groups is 2-8 (e.g., 2, 3, 4, 5, 6, 7, 8, or any combination of two of the above values), and more preferably 8 and / or the number of propoxy groups is 0-4 (e.g., 0, 1, 2, 3, 4, or any combination of two of the above values). The compositions of the foregoing embodiments have better stability and heat resistance.

[0052] In this invention, cationic antistatic agent refers to antistatic agent with a hydrophilic group that is cationic. As long as the purpose of this invention can be achieved, there is no special limitation on the specific type of cationic antistatic agent. Preferably, the cationic antistatic agent is selected from quaternary ammonium salt antistatic agents.

[0053] According to a preferred embodiment of the present invention, the quaternary ammonium salt antistatic agent is selected from at least one of C6-C24 hydrocarbon-based aliphatic ammonium, hydrocarbon-based acid aliphatic ammonium, and hydrocarbon-based amide aliphatic ammonium, preferably selected from C6-C24 hydrocarbon-based acid aliphatic ammonium, wherein the hydrocarbon group can be an unsaturated hydrocarbon group or a saturated hydrocarbon group, preferably a saturated hydrocarbon group. Cationic antistatic agents listed as non-limiting embodiments include hexadecanoic acid-ammonium propyltrimethylammonium chloride and oleoic acid-ammonium propyltrimethylammonium chloride. The compositions of the aforementioned embodiments have better stability and heat resistance.

[0054] The compositions of the present invention can be formulated into various forms as needed for application, and the present invention does not have any particular limitation in this regard. A second aspect of the present invention provides an oil containing water and the silicone oil composition described in the first aspect of the present invention.

[0055] In this invention, a silicone oil composition is used as an effective component in an oiling agent, which exhibits excellent stability and heat resistance.

[0056] According to the present invention, the content of the silicone oil composition in the oil is not particularly limited as long as the purpose of the present invention can be achieved. Preferably, the content of the silicone oil composition in the oil is 10-30 wt%.

[0057] According to the present invention, the preparation method of the oil is not particularly limited as long as the purpose of the present invention can be achieved. The third aspect of the present invention provides a method for preparing an oil, which includes contacting water with the silicone oil composition described in the first aspect of the present invention.

[0058] In this invention, the oil obtained by contacting water with the silicone oil composition described in this invention has the advantages of uniformity, stability, and good heat resistance.

[0059] In this invention, the contact is sufficient to allow water and the silicone oil composition described in this invention to mix thoroughly. Preferably, the contact method includes: mixing water and oil and then homogenizing.

[0060] In this invention, water-to-oil mixing refers to gradually adding water to the silicone oil composition for mixing. Specifically, water can be added while stirring. Preferably, the water-to-oil mixing time is controlled between 0.5 and 5 hours. Preferred mixing conditions include a stirring speed of 500-3000 r / min. After the water is added, stirring can continue for another 0.5-2 hours as needed. Using the aforementioned reverse emulsification method of water-to-oil, the resulting oil is homogeneous and has good stability.

[0061] According to the present invention, the homogenization conditions are not particularly limited as long as the purpose of the present invention can be achieved. Preferably, the homogenization conditions include: a homogenization pressure of 1-150 MPa and / or a flow rate of 1-5 L / h. By combining the aforementioned implementation with high-speed mechanical stirring and high-pressure homogenization technology, the resulting oil is homogeneous and has good stability.

[0062] According to the present invention, it is understood that the homogenization of the present invention can be performed once or multiple times as needed.

[0063] The fourth aspect of the present invention provides the application of the silicone oil composition described in the first aspect or the oiling agent described in the second aspect of the present invention in fiber production.

[0064] In this invention, the silicone oil composition or oiling agent of this invention is used in fiber production. Because the composition or oiling agent has excellent stability and heat resistance, it will not affect the final quality of the fiber when used, and the fiber produced in the end has better cohesion, smoothness and antistatic properties.

[0065] According to the present invention, the fiber may be a textile fiber, preferably a carbon fiber.

[0066] In this invention, when the oil is used as a carbon fiber oil in carbon fiber production, it can be diluted by a certain factor as needed before being used in carbon fiber production. For example, the oil in this invention can be diluted by a certain factor as needed to obtain a carbon fiber oil with a silicone oil composition content of 1-5 wt%. The carbon fiber finally produced has better cohesion, smoothness, and antistatic properties.

[0067] According to the present invention, it is understood that water is used for dilution.

[0068] The present invention will be described in detail below through embodiments. In the following embodiments and comparative examples:

[0069] The method for testing the heat resistance of the oil is as follows: The oil concentrate is heated at 105℃ for 3 hours in a forced-air drying oven. Then, 20-30 mg of the sample to be tested is accurately weighed for thermogravimetric analysis. The experimental conditions are as follows: First stage: air atmosphere, 0-240℃, heating rate 10℃ / min, reaching 240℃ and holding for 1 hour, the instrument displays the sample weight residual rate as r1; Second stage: switch to nitrogen atmosphere, 240-450℃, heating rate 10℃ / min, reaching 450℃ and holding for 30 seconds, the instrument displays the sample weight residual rate as r2; Third stage: nitrogen atmosphere, 450-900℃, heating rate 10℃ / min, cooling and purging, and then the instrument is turned off.

[0070] The method for determining the average particle size of the oil was as follows: A Mastersizer 2000 laser particle size analyzer (UK) was used. Open the file by selecting "File" in the initial interface menu. Then, replace the deionized water in the beaker located on the lower left side of the accessory with approximately 800 mL of water. Press the green button on the front of the accessory to start the pump. At this point, you can select "Manual (M)" under "Measurement" in the menu bar. You can observe the background of the instrument's automatic testing. If the background display is less than 80 (ideally less than 40), the sample cell is considered clean (otherwise, the water in the beaker should be replaced, and the sample cell should be repeatedly cleaned). In the measurement display interface menu bar, select "Document" and enter the sample information, setting the file name. The dispersant option is "Water." Press "Start" in the menu bar. The instrument will automatically detect the background. According to the prompts in the lower left corner of the operation interface, add the pretreated sample, click "Test Sample," and the instrument will automatically provide the results.

[0071] The method for determining the ash content of oil is as follows: accurately weigh a certain amount of oil sample m1, place it in a constant weight crucible, calcine it in a muffle furnace at 900℃ for 5 hours, cool it down, and accurately weigh it m2. The ash content of the oil is m2 / m1.

[0072] Example 1

[0073] By weight, 45 parts of amino-modified silicone oil 1 (viscosity 2500cp, amino mass fraction 0.2wt%, side chain amino structure is -CH2CH2CH2NH2), 25 parts of SiC type side chain polyether modified silicone oil 1 (viscosity 1100cp, ether mass fraction 2.0wt%, polyether structural unit contains 10 ethoxy groups), 15 parts of isomeric tridecyl alcohol polyoxyethylene ether 8 (8 represents 8 ethylene oxide addition number), 14 parts of hexadecanoic acid propyltrimethylammonium chloride, and 1 part of aliphatic polyhydroxyalkyl quaternary ammonium salt 1 (as shown in formula (11), CAS: 35239-12-4, hydroxyl mass fraction is 11.6%). Accurately add the above components to the mixing vessel, turn on the high-speed stirrer, select the stirring speed of 1200 r / min, slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20 wt%. After completion, continue stirring for 1 hour. Then immediately use a high-pressure homogenizer to further homogenize the carbon fiber oil agent obtained by high-speed stirring. Select a homogenization pressure of 120 MPa, a homogenizer flow rate of 2 L / h, and homogenize 3 times to finally obtain the oil agent.

[0074] Thermogravimetric analysis of the oil is shown below. Figure 1 As shown.

[0075] The obtained oil was homogeneous and stable, showing no stratification after standing at room temperature for 415 days. The average particle size of the oil was 121 nm. Stratification began to appear after 415 days. The heat resistance test results were: r1 = 88.61%, r2 = 55.01%. The ash content was 1.48%.

[0076] The oil formulation was prepared with water to a concentration of 2 wt% for carbon fiber oiling evaluation. The resulting fibers were smooth, soft, and free of fuzz and adhesion.

[0077]

[0078] Example 2

[0079] By weight, 45 parts of amino-modified silicone oil 1 (viscosity 2500cp, amino mass fraction 0.2wt%, side chain amino structure is -CH2CH2CH2NH2), 25 parts of SiC type side chain polyether modified silicone oil 1 (viscosity 1100cp, ether mass fraction 2.0wt%, polyether structural unit contains 10 ethoxy groups), 15 parts of isomeric tridecyl alcohol polyoxyethylene ether 8 (8 represents 8 ethylene oxide addition number), 14 parts of hexadecanoic acid propyltrimethylammonium chloride, and 1 part of aliphatic polyhydroxyalkyl quaternary ammonium salt 2 (as shown in formula (12), CAS: 22340-01-8, hydroxyl mass fraction is 10.5%). Accurately add the above components to the mixing vessel, turn on the high-speed stirrer, select the stirring speed of 1200 r / min, slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20 wt%. After completion, continue stirring for 1 hour. Then immediately use a high-pressure homogenizer to further homogenize the carbon fiber oil agent obtained by high-speed stirring. Select a homogenization pressure of 120 MPa, a homogenizer flow rate of 2 L / h, and homogenize 3 times to finally obtain the oil agent.

[0080] The obtained oil was homogeneous and stable, showing no stratification after 409 days of standing at room temperature. The average particle size of the oil was 123 nm. Stratification began to appear after 409 days. The heat resistance test results were: r1 = 88.24%, r2 = 50.15%. The ash content was 1.53%.

[0081] The oil formulation was prepared with water to a concentration of 2 wt% for carbon fiber oiling evaluation. The resulting fibers were smooth, soft, and free of fuzz and adhesion.

[0082]

[0083] Example 3

[0084] By weight, 45 parts of amino-modified silicone oil 1 (viscosity 2500cp, amino mass fraction 0.2wt%, side chain amino structure is -CH2CH2CH2NH2), 25 parts of SiC type side chain polyether modified silicone oil 1 (viscosity 1100cp, ether mass fraction 2.0wt%, polyether structural unit contains 10 ethoxy groups), 15 parts of isomeric tridecyl alcohol polyoxyethylene ether 8 (8 represents 8 ethylene oxide addition number), 14 parts of hexadecanoic acid propyltrimethylammonium chloride, and 1 part of aliphatic polyhydroxyalkyl quaternary ammonium salt 3 (as shown in formula (13), CAS: 6200-40-4, hydroxyl mass fraction is 12.8%). Accurately add the above components to the mixing vessel, turn on the high-speed stirrer, select the stirring speed of 1200 r / min, slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20 wt%. After completion, continue stirring for 1 hour. Then immediately use a high-pressure homogenizer to further homogenize the carbon fiber oil agent obtained by high-speed stirring. Select a homogenization pressure of 120 MPa, a homogenizer flow rate of 2 L / h, and homogenize 3 times to finally obtain the oil agent.

[0085] The obtained oil was uniform and stable, and no stratification was observed after standing at room temperature for 394 days. The average particle size of the oil was 128 nm. Stratification began to appear after 394 days. The heat resistance of the oil was tested, and the results were: r1 = 87.69% and r2 = 48.34%. The ash content of 1.58% was included for statistical purposes.

[0086] The oil formulation was prepared with water to a concentration of 2 wt% for carbon fiber oiling evaluation. The resulting fibers were smooth, soft, and free of fuzz and adhesion.

[0087]

[0088] Example 4

[0089] By weight, 45 parts of amino-modified silicone oil 1 (viscosity 2500cp, amino mass fraction 0.2wt%, side chain amino structure is -CH2CH2CH2NH2), 25 parts of SiC type side chain polyether modified silicone oil 1 (viscosity 1100cp, ether mass fraction 2.0wt%, polyether structural unit contains 10 ethoxy groups), 15 parts of isomeric tridecyl alcohol polyoxyethylene ether 8 (8 represents 8 ethylene oxide addition number), 14 parts of hexadecanoic acid propyltrimethylammonium chloride, and 1 part of aliphatic polyhydroxyalkyl quaternary ammonium salt 4 (as shown in formula (14), CAS: 125464-18-8, hydroxyl mass fraction is 9.6%). Accurately add the above components into the mixing vessel, turn on the high-speed stirrer, select the stirring speed of 1200 r / min, slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20 wt%, and continue stirring for 1 hour after completion; then immediately use a high-pressure homogenizer to further homogenize the carbon fiber oil agent obtained by high-speed stirring, select a homogenization pressure of 120 MPa, a homogenizer flow rate of 2 L / h, and homogenize 3 times to finally obtain the carbon fiber oil agent.

[0090] The obtained carbon fiber oil was uniform and stable, and no stratification was observed after standing at room temperature for 402 days. The average particle size of the oil was 117 nm. Stratification began to appear after 402 days. The heat resistance of the oil was tested, and the results were: r1 = 87.53%, r2 = 49.12%. The ash content was 1.43%.

[0091] The oil formulation was prepared with water to a concentration of 2 wt% for carbon fiber oiling evaluation. The resulting fibers were smooth, soft, and free of fuzz and adhesion.

[0092]

[0093] Example 5

[0094] By weight, 45 parts of amino-modified silicone oil 2 (viscosity 3200cp, amino mass fraction 0.4wt%, side chain amino structure -CH2CH2CH2NHCH2CH2NH2), 25 parts of SiC type side chain polyether modified silicone oil 1 (viscosity 1100cp, ether mass fraction 2.0wt%, polyether structural unit contains 10 ethoxy groups), 15 parts of isomeric tridecyl alcohol polyoxyethylene ether 8 (8 represents 8 ethylene oxide addition number), 13 parts of hexadecanoic acid propyltrimethylammonium chloride, and 2 parts of aliphatic polyhydroxyalkyl quaternary ammonium salt 1 (CAS: 35239-12-4). Accurately add the above components to the mixing vessel, turn on the high-speed stirrer, select the stirring speed of 1200 r / min, slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20 wt%. After completion, continue stirring for 1 hour. Then immediately use a high-pressure homogenizer to further homogenize the carbon fiber oil agent obtained by high-speed stirring. Select a homogenization pressure of 120 MPa, a homogenizer flow rate of 2 L / h, and homogenize 3 times to finally obtain the oil agent.

[0095] The obtained oil was homogeneous and stable, showing no stratification after standing at room temperature for 396 days. The average particle size of the oil was 125 nm. Stratification began to appear after 396 days. The oil underwent heat resistance testing, with results of r1 = 88.72% and r2 = 53.24%. The ash content was 1.61%.

[0096] The oil formulation was prepared with water to a concentration of 2 wt% for carbon fiber oiling evaluation. The resulting fibers were smooth, soft, and free of fuzz and adhesion.

[0097] Example 6

[0098] By weight, 45 parts of amino-modified silicone oil 1 (viscosity 2500cp, amino mass fraction 0.2wt%, side chain amino structure -CH2CH2CH2NH2), 25 parts of SiC-type side chain polyether-modified silicone oil 2 (viscosity 600cp, ether mass fraction 5.0wt%, polyether structural unit contains 10 ethoxy groups), 15 parts of isomeric tridecyl alcohol polyoxyethylene ether 8 (8 represents 8 ethylene oxide addition number), 14 parts of hexadecanoic acid propyltrimethylammonium chloride, and 1 part of aliphatic polyhydroxyalkyl quaternary ammonium salt 1 (CAS: 35239-12-4). Accurately add the above components into the mixing vessel, turn on the high-speed stirrer, select the stirring speed of 1200 r / min, slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20 wt%, and continue stirring for 1 hour after completion; then immediately use a high-pressure homogenizer to further homogenize the carbon fiber oil agent obtained by high-speed stirring, select a homogenization pressure of 120 MPa, a homogenizer flow rate of 2 L / h, and homogenize 3 times to finally obtain the carbon fiber oil agent.

[0099] The obtained oil was uniform and stable, and no stratification was observed after standing at room temperature for 373 days. The average particle size of the oil was 131 nm. Stratification began to appear after 373 days. The heat resistance of the oil was tested, and the results were: r1 = 87.94% and r2 = 51.72%. The ash content of 1.66% was included for statistical purposes.

[0100] The oil formulation was prepared with water to a concentration of 2 wt% for carbon fiber oiling evaluation. The resulting fibers were smooth, soft, and free of fuzz and adhesion.

[0101] Example 7

[0102] By weight, 45 parts of amino-modified silicone oil 1 (viscosity 2500cp, amino mass fraction 0.2wt%, side chain amino structure -CH2CH2CH2NH2), 25 parts of SiC-type side chain polyether-modified silicone oil 1 (viscosity 1100cp, ether mass fraction 2.0wt%, polyether structural unit contains 10 ethoxy groups), 15 parts of isomeric decaol polyoxyethylene ether 6 (6 represents 6 ethylene oxide addition number), 14 parts of hexadecanoic acid propyltrimethylammonium chloride, and 1 part of aliphatic polyhydroxyalkyl quaternary ammonium salt 1 (CAS: 35239-12-4, hydroxyl mass fraction 11.6%). Accurately add the above components to the mixing vessel, turn on the high-speed stirrer, select the stirring speed of 1200 r / min, slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20 wt%. After completion, continue stirring for 1 hour. Then immediately use a high-pressure homogenizer to further homogenize the carbon fiber oil agent obtained by high-speed stirring. Select a homogenization pressure of 120 MPa, a homogenizer flow rate of 2 L / h, and homogenize 3 times to finally obtain the oil agent.

[0103] The obtained oil was homogeneous and stable, showing no stratification after standing at room temperature for 342 days. The average particle size of the oil was 136 nm. Stratification began to appear after 342 days. The oil underwent heat resistance testing, with results of r1 = 86.15% and r2 = 47.30%. The ash content was 1.72%.

[0104] The oil formulation was prepared with water to a concentration of 2 wt% for carbon fiber oiling evaluation. The resulting fibers were smooth, soft, and free of fuzz and adhesion.

[0105] Example 8

[0106] By weight, 45 parts of amino-modified silicone oil 1 (viscosity 2500cp, amino mass fraction 0.2wt%, side chain amino structure -CH2CH2CH2NH2), 25 parts of SiC type side chain polyether modified silicone oil 1 (viscosity 1100cp, ether mass fraction 2.0wt%, polyether structural unit contains 10 ethoxy groups), 15 parts of isomeric tridecyl alcohol polyoxyethylene ether 8 (8 represents 8 ethylene oxide addition number), 14 parts of oleamidopropyltrimethylammonium chloride, and 1 part of aliphatic polyhydroxyalkyl quaternary ammonium salt 1 (CAS: 35239-12-4, hydroxyl mass fraction 11.6%). Accurately add the above components to the mixing vessel, turn on the high-speed stirrer, select the stirring speed of 1200 r / min, slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20 w% and continue stirring for 1 hour after completion; then immediately use a high-pressure homogenizer to further homogenize the carbon fiber oil agent obtained by high-speed stirring, select a homogenization pressure of 120 MPa, a homogenizer flow rate of 2 L / h, and homogenize 3 times to finally obtain the oil agent.

[0107] The obtained oil was homogeneous and stable, showing no stratification after standing at room temperature for 335 days. The average particle size of the oil was 141 nm. Stratification began to appear after 335 days. The heat resistance test results were: r1 = 86.38%, r2 = 47.51%. The ash content was 1.54%.

[0108] The oil formulation was prepared with water to a concentration of 2 wt% for carbon fiber oiling evaluation. The resulting fibers were smooth, soft, and free of fuzz and adhesion.

[0109] Example 9

[0110] By weight, 45 parts of amino-modified silicone oil 1 (viscosity 2500cp, amino mass fraction 0.2wt%, side chain amino structure -CH2CH2CH2NH2), 25 parts of SiC-type side chain polyether-modified silicone oil 1 (viscosity 1100cp, ether mass fraction 2.0wt%, polyether structural unit contains 10 ethoxy groups), 13 parts of isomeric tridecyl alcohol polyoxyethylene ether 8 (8 represents 8 ethylene oxide addition number), 12 parts of hexadecanoic acid propyltrimethylammonium chloride, and 5 parts of aliphatic polyhydroxyalkyl quaternary ammonium salt 1 (CAS: 35239-12-4, hydroxyl mass fraction 11.6%). Accurately add the above components to the mixing vessel, turn on the high-speed stirrer, select the stirring speed of 1200 r / min, slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20 wt%. After completion, continue stirring for 1 hour. Then immediately use a high-pressure homogenizer to further homogenize the carbon fiber oil agent obtained by high-speed stirring. Select a homogenization pressure of 120 MPa, a homogenizer flow rate of 2 L / h, and homogenize 3 times to finally obtain the oil agent.

[0111] The obtained oil was homogeneous and stable, showing no stratification after 405 days of standing at room temperature. The average particle size of the oil was 130 nm. Stratification began to appear after 405 days. The oil underwent heat resistance testing, with results of r1 = 87.18% and r2 = 48.97%. The ash content was 2.87%.

[0112] The oil formulation was prepared with water to a concentration of 2 wt% for carbon fiber oiling evaluation. The resulting fibers were smooth, soft, and free of fuzz and adhesion.

[0113] Example 10

[0114] By weight, 45 parts of amino-modified silicone oil 1 (viscosity 2500cp, amino mass fraction 0.2wt%, side chain amino structure -CH2CH2CH2NH2), 25 parts of SiC type side chain polyether modified silicone oil 1 (viscosity 1100cp, ether mass fraction 2.0wt%, polyether structural unit contains 10 ethoxy groups), 15 parts of isomeric tridecyl alcohol polyoxyethylene ether 8 (8 represents 8 ethylene oxide addition number), 14.9 parts of hexadecanoic acid propyltrimethylammonium chloride, and 0.1 parts of aliphatic polyhydroxyalkyl quaternary ammonium salt 1 (CAS: 35239-12-4, hydroxyl mass fraction 11.6%). Accurately add the above components to the mixing vessel, turn on the high-speed stirrer, select the stirring speed of 1200 r / min, slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20 wt%. After completion, continue stirring for 1 hour. Then immediately use a high-pressure homogenizer to further homogenize the carbon fiber oil agent obtained by high-speed stirring. Select a homogenization pressure of 120 MPa, a homogenizer flow rate of 2 L / h, and homogenize 3 times to finally obtain the oil agent.

[0115] The obtained oil was homogeneous and stable, showing no stratification after standing at room temperature for 348 days. The average particle size of the oil was 133 nm. Stratification began to appear after 348 days. The heat resistance test results were: r1 = 76.42%, r2 = 43.16%. The ash content was 1.57%.

[0116] The oil formulation was prepared with water to a concentration of 2 wt% for carbon fiber oiling evaluation. The resulting fibers were smooth, soft, and free of fuzz and adhesion.

[0117] Example 11

[0118] By weight, 45 parts of amino-modified silicone oil 1 (viscosity 5000cp, amino mass fraction 0.6wt%, side chain amino structure is -CH2CH2CH2NH2), 25 parts of SiC type side chain polyether modified silicone oil 1 (viscosity 1100cp, ether mass fraction 2.0wt%, polyether structural unit contains 10 ethoxy groups), 15 parts of isomeric tridecyl alcohol polyoxyethylene ether 8 (8 represents 8 ethylene oxide addition number), 14 parts of hexadecanoic acid propyltrimethylammonium chloride, and 1 part of aliphatic polyhydroxyalkyl quaternary ammonium salt 1 (as shown in formula (11), CAS: 35239-12-4, hydroxyl mass fraction is 11.6%). Accurately add the above components to the mixing vessel, turn on the high-speed stirrer, select the stirring speed of 1200 r / min, slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20 wt%. After completion, continue stirring for 1 hour. Then immediately use a high-pressure homogenizer to further homogenize the carbon fiber oil agent obtained by high-speed stirring. Select a homogenization pressure of 120 MPa, a homogenizer flow rate of 2 L / h, and homogenize 3 times to finally obtain the oil agent.

[0119] The obtained oil was homogeneous and stable, showing no stratification after 328 days of standing at room temperature. The average particle size of the oil was 121 nm. Stratification began to appear after 328 days. The heat resistance test results were: r1 = 75.66%, r2 = 42.25%. The ash content was 1.52%.

[0120] The oil formulation was prepared with water to a concentration of 2 wt% for carbon fiber oiling evaluation. The resulting fibers were smooth, soft, and free of fuzz and adhesion.

[0121] Comparative Example 1

[0122] By weight, 45 parts of amino-modified silicone oil 1 (viscosity 2500cp, amino mass fraction 0.2wt%, side chain amino structure -CH2CH2CH2NH2), 25 parts of SiC-type side chain polyether-modified silicone oil 1 (viscosity 1100cp, ether mass fraction 2.0wt%, polyether structural unit contains 10 ethoxy groups), 15.5 parts of isomeric tridecyl alcohol polyoxyethylene ether 8 (8 represents ethylene oxide addition number 8), and 14.5 parts of hexadecylaminopropyltrimethylammonium chloride were accurately added to a stirred tank. The high-speed stirrer was turned on, and the stirring speed was set to 1200 r / min. Deionized water was slowly added in the required proportion over 3 hours to prepare an oil agent with an effective concentration of 20wt%. After completion, stirring was continued for 1 hour. Then, the carbon fiber oil agent obtained by high-speed stirring was immediately further homogenized using a high-pressure homogenizer. The homogenization pressure was set to 120 MPa, the homogenizer flow rate was 2 L / h, and the homogenization was performed 3 times to finally obtain the oil agent.

[0123] The obtained oil was uniform and stable, and no stratification was observed after standing at room temperature for 341 days. The average particle size of the oil was 118 nm. Stratification began to appear after 341 days. The heat resistance of the oil was tested, and the results were: r1 = 86.54% and r2 = 22.41%. The ash content of 1.22% was included for statistical purposes.

[0124] The oil formulation was prepared with water to a concentration of 2 wt% for carbon fiber oiling evaluation. The resulting fibers showed a certain degree of adhesion.

[0125] Comparative Example 2

[0126] By weight, 45 parts of amino-modified silicone oil 1 (viscosity 2500cp, amino mass fraction 0.2wt%, side chain amino structure -CH2CH2CH2NH2), 25 parts of SiC-type side chain polyether-modified silicone oil 1 (viscosity 1100cp, ether mass fraction 2.0wt%, polyether structural unit contains 10 ethoxy groups), 15 parts of isomeric tridecyl alcohol polyoxyethylene ether 8 (8 represents the number of ethylene oxide additions of 8), 14 parts of hexadecanoic acid propyltrimethylammonium chloride, and 1 part of diethylmethyl dodecyl ammonium chloride (as shown in formula (D2), CAS: 98342-48-4). Accurately add the above components into the mixing vessel, turn on the high-speed stirrer, select the stirring speed of 1200 r / min, slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20 wt%, and continue stirring for 1 hour after completion; then immediately use a high-pressure homogenizer to further homogenize the carbon fiber oil agent obtained by high-speed stirring, select a homogenization pressure of 120 MPa, a homogenizer flow rate of 2 L / h, and homogenize 3 times to finally obtain the carbon fiber oil agent.

[0127] The obtained carbon fiber oil was uniform and stable, and no stratification was observed after standing at room temperature for 32 days. The average particle size of the oil was 217 nm. After 32 days, stratification began to appear. The heat resistance of the oil was tested, and the results were: r1 = 81.16%, r2 = 25.37%, and ash content 1.19%.

[0128] The oil formulation was prepared with water to a concentration of 2 wt% for carbon fiber oiling evaluation. The resulting fibers showed a certain degree of fuzziness and adhesion.

[0129]

[0130] Comparative Example 3

[0131] By weight, 45 parts of amino-modified silicone oil 1 (viscosity 2500cp, amino mass fraction 0.2wt%, side chain amino structure -CH2CH2CH2NH2), 25 parts of SiC-type side chain polyether-modified silicone oil 1 (viscosity 1100cp, ether mass fraction 2.0wt%, polyether structural unit contains 10 ethoxy groups), 15 parts of isomeric tridecyl alcohol polyoxyethylene ether 8 (8 represents 8 ethylene oxide addition number), 14 parts of hexadecanoic acid propyltrimethylammonium chloride, and 1 part of bis-2-hydroxyethyl dimethylammonium chloride. Accurately add the above components to the mixing vessel, turn on the high-speed stirrer, select the stirring speed of 1200 r / min, slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20 wt%. After completion, continue stirring for 1 hour. Then immediately use a high-pressure homogenizer to further homogenize the carbon fiber oil agent obtained by high-speed stirring. Select a homogenization pressure of 120 MPa, a homogenizer flow rate of 2 L / h, and homogenize 3 times to finally obtain the oil agent.

[0132] The obtained oil was homogeneous and stable, showing no stratification after standing at room temperature for 276 days. The average particle size of the oil was 127 nm. Stratification began to appear after 276 days. The oil underwent heat resistance testing, with results of r1 = 82.97% and r2 = 23.63%. The ash content was 3.59%.

[0133] The oil formulation was prepared with water to a concentration of 2 wt% for evaluation of carbon fiber oiling. The resulting fibers showed signs of fuzzing and adhesion.

[0134] Comparative Example 4

[0135] By weight, 45 parts of amino-modified silicone oil 1 (viscosity 2500cp, amino mass fraction 0.2wt%, side chain amino structure -CH2CH2CH2NH2), 25 parts of side chain polyether-modified silicone oil 1 (viscosity 1100cp, ether mass fraction 2.0wt%, polyether structural unit contains 10 ethoxy groups), 10 parts of isomeric tridecyl alcohol polyoxyethylene ether 8 (8 represents 8 ethylene oxide addition number), 10 parts of hexadecanoic acid propyltrimethylammonium chloride, and 10 parts of aliphatic polyhydroxyalkyl quaternary ammonium salt 1 (CAS: 35239-12-4, hydroxyl mass fraction 11.6%). Accurately add the above components to the mixing vessel, turn on the high-speed stirrer, select the stirring speed of 1200 r / min, slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20 wt%. After completion, continue stirring for 1 hour. Then immediately use a high-pressure homogenizer to further homogenize the carbon fiber oil agent obtained by high-speed stirring. Select a homogenization pressure of 120 MPa, a homogenizer flow rate of 2 L / h, and homogenize 3 times to finally obtain the oil agent.

[0136] The obtained oil was homogeneous and stable, showing no stratification after standing at room temperature for 313 days. The average particle size of the oil was 130 nm. Stratification began to appear after 313 days. The oil underwent heat resistance testing, with results of r1 = 90.05% and r2 = 60.23%. The ash content was 10.71%.

[0137] The formulation oil was prepared with water to a concentration of 2wt% for carbon fiber oiling evaluation. During the spinning process, the fiber sticking to the roller was obvious, and the resulting fiber had more fuzz and broken fibers.

[0138] Comparative Example 5

[0139] By weight, 45 parts of amino-modified silicone oil 1 (viscosity 2500cp, amino mass fraction 0.2wt%, side chain amino structure -CH2CH2CH2NH2), 25 parts of epoxy-modified polyether silicone oil 1 (viscosity 1000, epoxy mass fraction 5wt%, ether mass fraction 2.0wt%, polyether structural unit contains 10 ethoxy groups), 15 parts of isomeric tridecyl alcohol polyoxyethylene ether 8 (8 represents the number of ethylene oxide additions is 8), 14 parts of hexadecanoic acid propyltrimethylammonium chloride, and 1 part of aliphatic polyhydroxyalkyl quaternary ammonium salt 1 (CAS: 35239-12-4). Accurately add the above components to the mixing vessel, turn on the high-speed stirrer, select the stirring speed of 1200 r / min, slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20 wt%. After completion, continue stirring for 1 hour. Then immediately use a high-pressure homogenizer to further homogenize the carbon fiber oil agent obtained by high-speed stirring. Select a homogenization pressure of 120 MPa, a homogenizer flow rate of 2 L / h, and homogenize 3 times to finally obtain the oil agent.

[0140] The obtained oil was homogeneous and stable, showing no stratification after 98 days of standing at room temperature. The average particle size of the oil was 157 nm. Stratification began to appear after 98 days. The oil underwent heat resistance testing, with results of r1 = 81.45% and r2 = 33.79%. The ash content was 7.83%.

[0141] The formulation oil was prepared with water to a concentration of 2wt% for carbon fiber oiling evaluation. During the spinning process, the fiber sticking to the roller was obvious, and the resulting fiber had more fuzz and broken fibers.

[0142] Comparative Example 6

[0143] By weight, 45 parts of amino-modified silicone oil 1 (viscosity 2500cp, amino mass fraction 0.2wt%, side chain amino structure -CH2CH2CH2NH2), 25 parts of glycerol polyoxyethylene ether 30 (30 represents the number of ethylene oxide additions in the ethylene ether), 15 parts of isomeric tridecyl alcohol polyoxyethylene ether 8 (8 represents the number of ethylene oxide additions of 8), 14 parts of hexadecanoic acid propyltrimethylammonium chloride, and 1 part of aliphatic polyhydroxyalkyl quaternary ammonium salt 1 (CAS: 35239-12-4, hydroxyl mass fraction 11.6%). Accurately add the above components to the mixing vessel, turn on the high-speed stirrer, select the stirring speed of 1200 r / min, slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20 wt%. After completion, continue stirring for 1 hour. Then immediately use a high-pressure homogenizer to further homogenize the carbon fiber oil agent obtained by high-speed stirring. Select a homogenization pressure of 120 MPa, a homogenizer flow rate of 2 L / h, and homogenize 3 times to finally obtain the oil agent.

[0144] The obtained oil was homogeneous and stable, showing no stratification after 95 days of standing at room temperature. The average particle size of the oil was 178 nm. Stratification began to appear after 95 days. The heat resistance test results were: r1 = 80.56%, r2 = 38.62%. The ash content was 1.48%.

[0145] The oil formulation was prepared with water to a concentration of 2 wt% for carbon fiber oiling evaluation. The resulting fibers had a certain degree of fuzziness.

[0146] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A silicone oil-containing composition, characterized in that, The composition contains amino-modified silicone oil, polyether-modified silicone oil, fatty alcohol alkoxylate, cationic antistatic agent, and aliphatic polyhydroxyalkyl quaternary ammonium salt as shown in formula (1). In formula (1), R1 is selected from C1-C4 hydroxyalkyl groups, R2 and R3 are each independently selected from C1-C4 alkyl groups or C1-C4 hydroxyalkyl groups, R4 is selected from a group having aliphatic groups of C8-C24, and Z - It is an anion; The composition is based on 100 parts by weight, and the content of the aliphatic polyhydroxyalkyl quaternary ammonium salt is 0.1-5.0 parts by weight.

2. The composition according to claim 1, wherein, The composition is based on 100 parts by weight, and the content of the aliphatic polyhydroxyalkyl quaternary ammonium salt is 0.2-2.0 parts by weight; and / or In the composition: The content of amino-modified silicone oil is 30-50 parts by weight; and / or The content of polyether-modified silicone oil is 10-30 parts by weight; and / or The content of fatty alcohol alkoxylates is 10-20 parts by weight; and / or The content of cationic antistatic agent is 10-20 parts by weight.

3. The composition according to claim 1 or 2, wherein, In formula (1), R4 contains at least one functional group selected from ether, ester, amide, and hydroxyl groups; and / or In formula (1), the anion is an inorganic acid ion, an organic acid ion, an ester ion, or a halide ion, preferably a sulfate ester ion, a phosphate ester ion, a sulfonate ester ion, a nitrate ester ion, or a halide ion; and / or Preferably, based on 100 parts by weight of the composition, the value of the weight parts of amino-modified silicone oil × the mass fraction of amino is denoted as a, the value of the weight parts of aliphatic polyhydroxyalkyl quaternary ammonium salt × the mass fraction of hydroxyl groups in the aliphatic polyhydroxyalkyl quaternary ammonium salt is denoted as b, and the value of the weight parts of polyether-modified silicone oil × the mass fraction of ether is denoted as c, wherein: a≤b, preferably the difference between a and b is 0-100.0, more preferably the difference between a and b is 0.5-50.0; and / or b≤c, preferably the difference between b and c is 0-200.0, more preferably the difference between b and c is 25-120.

0.

4. The composition according to any one of claims 1-3, wherein, The viscosity of the amino-modified silicone oil is 100-4000 cp; and / or The amino-modified silicone oil contains 0.1-2.0% amino by mass; and / or The amino-modified silicone oil is a side-chain amino-modified silicone oil, preferably with the side-chain amino structure selected from C2-C8 monoamino aliphatic hydrocarbon groups or diamino aliphatic hydrocarbon groups.

5. The composition according to any one of claims 1-4, wherein, The viscosity of the polyether-modified silicone oil is 300-2000 cp; and / or The polyether-modified silicone oil is selected from at least one of side-chain polyether-modified silicone oil, double-ended polyether-modified silicone oil, single-ended polyether-modified silicone oil, and side-chain end-group co-modified polyether silicone oil, preferably side-chain polyether-modified silicone oil; and / or The polyether-modified silicone oil contains ethylene oxide structural units and optionally propylene oxide structural units, preferably with an ethylene oxide addition number of 4-16 and / or a propylene oxide addition number of 0-4 in the polyether structural units; and / or Based on the total mass of the polyether-modified silicone oil, the mass fraction of ether in the polyether-modified silicone oil is 0.5-20.0 wt%.

6. The composition according to any one of claims 1-5, wherein, In the fatty alcohol alkoxylates, the fatty alcohol segment is selected from C8-C16 fatty alcohol segments; and / or In the fatty alcohol alkoxylate, the alkoxylate fragment contains an ethoxy segment and optionally a propoxy segment, preferably with an ethoxy addition number of 2-8 and / or a propoxy addition number of 0-4; and / or The cationic antistatic agent is selected from quaternary ammonium salt antistatic agents, preferably selected from at least one of C6-C24 hydrocarbon aliphatic ammonium, hydrocarbon acid aliphatic ammonium and hydrocarbon amide aliphatic ammonium, more preferably selected from C6-C24 hydrocarbon acid aliphatic ammonium.

7. An oil-based agent, characterized in that, The oil comprises water and the silicone-containing oil composition according to any one of claims 1-6; Preferably, the content of the silicone oil composition in the oil is 10-30 wt%.

8. A method for preparing an oil-based agent, characterized in that, The preparation method includes: contacting water with the silicone oil composition according to any one of claims 1-6; Preferably, the contact method includes: mixing water and oil and then homogenizing; More preferably, The water-to-oil mixing time is 0.5-5 hours, and the preferred mixing conditions include: a stirring speed of 500-3000 r / min; and / or The homogenization conditions include: a homogenization pressure of 1-150 MPa and / or a flow rate of 1-5 L / h.

9. The use of the silicone oil composition according to any one of claims 1-6 or the oiling agent according to claim 7 in fiber production.

10. The application according to claim 9, wherein, The fiber is a textile fiber, preferably carbon fiber; and / or When the oil is used as a carbon fiber oil in carbon fiber production, the content of the silicone oil composition in the carbon fiber oil is 1-5 wt%.

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