Oiling agent emulsion and oiling agent solution mixture as well as preparation method and application thereof

Abstract

The invention relates to the field of polyacrylonitrile-based precursors, in particular to an oiling agent emulsion, an oiling agent emulsion mixture and a preparation method and application of the oiling agent emulsion mixture. The preparation method of the oiling agent emulsion comprises the following steps: (1) mixing the emulsifier, the cationic antistatic agent and the antioxidant to obtain a composite emulsion; and (2) mixing amino modified polysiloxane, epoxy modified polysiloxane, polyether modified polysiloxane and the composite emulsion to obtain the oiling agent emulsion. And mixing the oiling agent emulsion with water, and adjusting the pH value to be acidic, thereby obtaining the oiling agent emulsion mixture. The oil emulsion mixture has proper viscosity, stability and wettability, and the precursor has proper specific resistance.

Description

Technical Field

[0001] The present invention relates to the field of polyacrylonitrile-based precursor fibers, and in particular to an oil emulsion, a method for preparing the oil emulsion, an oil emulsion prepared by the method, an oil emulsion mixture containing the oil emulsion, a method for preparing the oil emulsion mixture, an oil emulsion mixture prepared by the method, and application of the oil emulsion mixture in preparing polyacrylonitrile-based precursor fibers. Background Art

[0002] As an inorganic fiber with a carbon main chain structure, carbon fiber has many excellent properties, such as good electromagnetic shielding, anisotropy, low density, small thermal expansion coefficient, high axial strength, resistance to ultra-high temperature, corrosion resistance, fatigue resistance, and good specific heat and conductivity.

[0003] Carbon fibers are mostly formed by the cracking and carbonization of polyacrylonitrile (PAN)-based precursors under high temperature. Therefore, the performance of carbon fibers mainly depends on the properties of polyacrylonitrile-based precursors. Polyacrylonitrile-based precursors are spun into fibers through processes such as forming, washing, pickling, stretching, oiling, and densification. The quality of the oil directly affects the quality of carbon fiber precursors and carbon fiber products, and will also have many effects on the production process.

[0004] If the oil has poor smoothness and softness, the finished carbon fiber product will have a poor feel; if the oil has poor antistatic properties, it will easily stick to the rollers and wrap around the rollers; if the oil has poor heat resistance, it will easily evaporate during drying and densification and will not play the protective role it should.

[0005] CN103122585B discloses a large-tow PAN-based carbon fiber precursor oil, which includes amino-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, emulsifier and epoxy adduct of acid amine compound. The invention patent points out that the oil mixture containing the above ingredients can solve the problems of poor antistatic property and low full roll rate of oil for carbon fiber precursor in the prior art. However, the oil still has problems such as poor stability and wettability, large emulsion particle size, etc. Whether the oil is uniform and stable has a very important impact on the long-term storage and quality of carbon fiber precursor.

[0006] Therefore, it is necessary to provide an oil agent for polyacrylonitrile-based precursor fibers with better stability and wettability. Summary of the invention

[0007] The purpose of the present invention is to overcome the problems of poor stability and wettability of existing polyacrylonitrile-based precursors and large emulsion particle size, and provide an oil-emulsion mixture for preparing polyacrylonitrile-based precursors, a preparation method of the oil-emulsion mixture, an oil-emulsion mixture prepared by the preparation method, and an application of the oil-emulsion mixture. The oil-emulsion mixture has low viscosity, excellent antistatic properties, high stability and good wettability, and the preparation process is simple and easy to operate. It can be prepared in general equipment, has good economic benefits, and is conducive to industrial production.

[0008] In order to achieve the above object, the first aspect of the present invention provides an oil emulsion, wherein, based on the total amount of the oil emulsion, the oil emulsion comprises:

[0009]

[0010] A second aspect of the present invention provides a method for preparing an oil emulsion, wherein the method comprises:

[0011] (1) mixing an emulsifier, a cationic antistatic agent, and an antioxidant to obtain a composite emulsion;

[0012] (2) mixing amino-modified polysiloxane, epoxy-modified polysiloxane, polyether-modified polysiloxane and a composite emulsion to obtain an oil emulsion;

[0013] Among them, the amount of amino-modified polysiloxane is 30-70 parts by weight, the amount of epoxy-modified polysiloxane is 15-35 parts by weight, the amount of polyether-modified polysiloxane is 1-10 parts by weight, the amount of emulsifier is 10-15 parts by weight, the amount of cationic antistatic agent is 3-5 parts by weight, and the amount of antioxidant is 1-5 parts by weight.

[0014] The third aspect of the present invention provides an oil emulsion prepared by the method described in the second aspect of the present invention.

[0015] The fourth aspect of the present invention provides an oil-emulsion mixture, wherein the mixture comprises the oil-emulsion of the first aspect or the third aspect and water.

[0016] The fifth aspect of the present invention provides a method for preparing an oil emulsion mixture, wherein the method comprises: mixing the oil emulsion described in the first aspect or the third aspect with water, and adjusting the pH value to be acidic.

[0017] The sixth aspect of the present invention provides an application of any one of the oil emulsion described in the first aspect or the third aspect, the oil emulsion mixture described in the fourth aspect, and the oil emulsion mixture prepared by the method described in the fifth aspect in preparing polyacrylonitrile-based precursor fibers.

[0018] Through the above technical solution, the present invention has at least the following advantages:

[0019] (1) The oil emulsion mixture of the present invention has lower viscosity, smaller particles and good wettability;

[0020] (2) The oil emulsion mixture of the present invention takes a long time to separate into layers and has high stability;

[0021] (3) The raw silk prepared from the oil emulsion mixture of the present invention has a high specific resistance and excellent antistatic property;

[0022] (4) The raw silk prepared from the oil-emulsion mixture of the present invention has good stability, does not require the addition of antistatic agents, and does not require secondary mixing, which is conducive to the stable production of subsequent processing;

[0023] (5) The preparation method of the oil-emulsion mixture of the present invention has simple process, low cost, easy operation, good economic benefit, and can be prepared in general equipment, which is conducive to industrial production. DETAILED DESCRIPTION

[0024] The endpoints and any values ​​of the ranges disclosed in this article 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 each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0025] The first aspect of the present invention provides an oil emulsion, wherein, based on the total amount of the oil emulsion, the oil emulsion comprises:

[0026]

[0027] The inventors of the present invention have found that the oil emulsion can be mixed with water to obtain an oil emulsion mixture, which can be used to prepare polyacrylonitrile-based precursor fibers.

[0028] In the oil emulsion, adding amino-modified polysiloxane containing amino groups can reduce the viscosity of the oil emulsion mixture obtained after mixing with water; adding epoxy-modified polysiloxane containing active epoxy groups can improve the stability of the oil emulsion mixture obtained after mixing with water; adding polyether-modified polysiloxane containing polyether groups can make the oil emulsion mixture obtained after mixing with water have good wettability; using amino-modified polysiloxane in combination with polyether-modified polysiloxane can improve the resistivity of the raw silk prepared from the oil emulsion mixture obtained after mixing with water, so that the raw silk has excellent antistatic property.

[0029] According to a preferred embodiment of the present invention, the amino-modified polysiloxane is selected from one or more of triamino-modified polysiloxane, N-β-aminoethyl-γ-aminopropylmethyldimethoxypolysiloxane, N-(β-aminoethyliminoethyl)-γ-aminopropylmethyldimethoxypolysiloxane, N-aminoethyl-3-aminopropyltriethoxysilane, aminoalkyl-modified polysiloxane at both ends, side chain N-(β-aminoethyl)iminopropyl-modified polysiloxane, side chain N-(β-aminoethyliminoethyl)iminopropyl-modified polysiloxane, and side chain cyclic diaminoalkyl-modified polysiloxane. Preferably, the amino-modified polysiloxane is selected from one or more of triamino-modified polysiloxane, N-(β-aminoethyl iminoethyl)-γ-aminopropylmethyl dimethoxy polysiloxane, N-β-aminoethyl-γ-aminopropylmethyl dimethoxy polysiloxane, side chain N-(β-aminoethyl iminoethyl) iminopropyl modified polysiloxane, and side chain N-(β-aminoethyl) iminopropyl modified polysiloxane. The use of amino-modified polysiloxane in the preferred range can further reduce the viscosity of the oil emulsion mixture obtained after the oil emulsion is mixed with water.

[0030] According to a preferred embodiment of the present invention, the average molecular weight of the amino-modified polysiloxane is 260-31000 g / mol, preferably 1130-25000 g / mol. The amino-modified polysiloxane contains an amino group, has a strong polarity, and has an average molecular weight of 260-31000 g / mol. The distance between molecules is large, so the intermolecular force is weak, thereby reducing the viscosity of the oil emulsion mixture. When the average molecular weight of the amino-modified polysiloxane is 1130-25000 g / mol, the viscosity of the oil emulsion mixture obtained after the oil emulsion is mixed with water can be further reduced.

[0031] When the content of amino-modified polysiloxane in the oil emulsion is 30-70 wt %, the viscosity of the oil emulsion mixture obtained by mixing the oil emulsion with water can be effectively reduced.

[0032] According to a preferred embodiment of the present invention, the epoxy-modified polysiloxane is selected from glycidyloxypropyl-terminated polydimethylsiloxane and / or epoxy-modified methylphenylvinyl polysiloxane.

[0033] According to a preferred embodiment of the present invention, the average molecular weight of the epoxy-modified polysiloxane is 920-9300 g / mol.

[0034] Epoxy-modified polysiloxane contains active epoxy groups, which can effectively alleviate the stratification of the oil emulsion, and the epoxy-modified polysiloxane with an average molecular weight of 920-9300 g / mol has a good coupling effect, thereby improving the stability of the oil emulsion mixture. When the content of epoxy-modified polysiloxane in the oil emulsion is 15-35wt%, the number of days required for the oil emulsion to stratify can be effectively increased, and the stability of the emulsion mixture can be improved.

[0035] According to a preferred embodiment of the present invention, the polyether-modified polysiloxane is selected from 3-[hydroxy(polyoxyethylene)propyl]heptamethyltrisiloxane and / or 3-[methoxypoly(ethoxy)]propyl-methyl-bis(trimethylsiloxy)silane.

[0036] According to a preferred embodiment of the present invention, the average molecular weight of the polyether-modified polysiloxane is 290-460 g / mol.

[0037] The polyether-modified polysiloxane contains a polyether group, which can increase the hydrophilicity of the oil emulsion, and the polyether-modified polysiloxane with an average molecular weight of 290-460 g / mol can effectively reduce the surface tension, so that the oil emulsion mixture has good wettability. When the content of the polyether-modified polysiloxane in the oil emulsion is 1-10wt%, the wetting and spreading performance of the oil emulsion mixture can be further improved.

[0038] According to a preferred embodiment of the present invention, the emulsifier is selected from nonionic surfactants C 12 -C 18 Fatty alcohol polyoxyethylene (10) ether, C 12 -C 18 Fatty alcohol polyoxyethylene (15) ether, C 12 -C 18 One or more of fatty alcohol polyoxyethylene (35) ether, castor oil polyoxyethylene (10) ether, castor oil polyoxyethylene (30) ether and castor oil polyoxyethylene (90) ether; more preferably, the emulsifier is selected from C 12 Fatty alcohol polyoxyethylene (10) ether, C 15 Fatty alcohol polyoxyethylene (10) ether, C 12 Fatty alcohol polyoxyethylene (15) ether, C 15 Fatty alcohol polyoxyethylene (15) ether, C 12 Fatty alcohol polyoxyethylene (35) ether, C 15 Fatty alcohol polyoxyethylene (35) ether, C 16 Fatty alcohol polyoxyethylene (35) ether, C 18 One or more of fatty alcohol polyoxyethylene (35) ethers.

[0039] According to a preferred embodiment of the present invention, the cationic antistatic agent is selected from one or more of dodecyltrimethylammonium chloride, methyltrihydroxyethylmethylammonium sulfate, and dibenzylbis(octadecylamideethyl)ammonium salt.

[0040] According to a preferred embodiment of the present invention, the antioxidant is selected from one or more of antioxidant 1076, antioxidant 1035, phenolic antioxidant and antioxidant BHT; preferably, the antioxidant is selected from one or more of antioxidant 1076 and antioxidant 1035.

[0041] A second aspect of the present invention provides a method for preparing an oil emulsion, wherein the method comprises:

[0042] (1) mixing an emulsifier, a cationic antistatic agent, and an antioxidant to obtain a composite emulsion;

[0043] (2) mixing amino-modified polysiloxane, epoxy-modified polysiloxane, polyether-modified polysiloxane and a composite emulsion to obtain an oil emulsion;

[0044] Among them, the amount of amino-modified polysiloxane is 30-70 parts by weight, the amount of epoxy-modified polysiloxane is 15-35 parts by weight, the amount of polyether-modified polysiloxane is 1-10 parts by weight, the amount of emulsifier is 10-15 parts by weight, the amount of cationic antistatic agent is 3-5 parts by weight, and the amount of antioxidant is 1-5 parts by weight.

[0045] The total amount of the above-mentioned materials is 100 wt%.

[0046] According to a preferred embodiment of the present invention, the amino-modified polysiloxane is selected from one or more of triamino-modified polysiloxane, N-β-aminoethyl-γ-aminopropylmethyldimethoxypolysiloxane, N-(β-aminoethyliminoethyl)-γ-aminopropylmethyldimethoxypolysiloxane, N-aminoethyl-3-aminopropyltriethoxysilane, aminoalkyl-modified polysiloxane at both ends, side chain N-(β-aminoethyl)iminopropyl-modified polysiloxane, side chain N-(β-aminoethyliminoethyl)iminopropyl-modified polysiloxane, and side chain cyclic diaminoalkyl-modified polysiloxane.

[0047] According to a preferred embodiment of the present invention, the epoxy-modified polysiloxane is selected from glycidyloxypropyl-terminated polydimethylsiloxane and / or epoxy-modified methylphenylvinyl polysiloxane.

[0048] According to a preferred embodiment of the present invention, the polyether-modified polysiloxane is selected from 3-[hydroxy(polyoxyethylene)propyl]heptamethyltrisiloxane and / or 3-[methoxypoly(ethoxy)]propyl-methyl-bis(trimethylsiloxy)silane.

[0049] According to a preferred embodiment of the present invention, the emulsifier is selected from nonionic surfactants C 12 -C 18 Fatty alcohol polyoxyethylene (10) ether, C 12 -C 18 Fatty alcohol polyoxyethylene (15) ether, C 12 -C 18 One or more of fatty alcohol polyoxyethylene (35) ether, castor oil polyoxyethylene (10) ether, castor oil polyoxyethylene (30) ether and castor oil polyoxyethylene (90) ether.

[0050] According to a preferred embodiment of the present invention, the cationic antistatic agent is selected from one or more of dodecyltrimethylammonium chloride, methyltrihydroxyethylmethylammonium sulfate, and dibenzylbis(octadecylamideethyl)ammonium salt.

[0051] According to a preferred embodiment of the present invention, the antioxidant is selected from a compound selected from antioxidant 1076, antioxidant 1035, phenolic antioxidant and antioxidant BHT.

[0052] According to a preferred embodiment of the present invention, in step (1), the stirring temperature is 40-65°C, preferably 50-55°C; the stirring speed is 1800-3800r / min, preferably 2200-2800r / min; and the stirring time is 80-120 minutes, preferably 90-110 minutes.

[0053] According to a preferred embodiment of the present invention, in step (2), the stirring temperature is 40-65°C, preferably 50-55°C; the stirring speed is 1800-3800r / min, preferably 2200-2800r / min; and the stirring time is 80-120 minutes, preferably 90-110 minutes.

[0054] The above stirring temperature can make the oil emulsion have a suitable surface tension and improve the oiling efficiency. If the stirring temperature is lower or higher than the above range, the surface tension of the oil will be too large, thereby reducing the oiling efficiency. The above stirring speed and stirring time can well prevent the generation of a large amount of foam and can also effectively avoid the demulsification of the oil emulsion.

[0055] The third aspect of the present invention provides an oil emulsion prepared by the method described in the second aspect of the present invention.

[0056] The fourth aspect of the present invention provides an oil-emulsion mixture, wherein the mixture comprises the oil-emulsion of the first aspect or the third aspect and water.

[0057] According to a preferred embodiment of the present invention, the weight ratio of water to the oil emulsion is 2-5:1, and the pH value of the oil emulsion mixture is <7.

[0058] According to a preferred embodiment of the present invention, the average particle size of the oil-emulsion mixture is 0.1-0.3 μm, the time required for stratification is 110-150 days, the wetting time is 7-11 s, and the viscosity is 90-130 mPa·s.

[0059] The fifth aspect of the present invention provides a method for preparing an oil emulsion mixture, wherein the method comprises: mixing the oil emulsion described in the first aspect or the third aspect with water, and adjusting the pH value to be acidic.

[0060] According to a preferred embodiment of the present invention, the weight ratio of water to the oil emulsion is 2-5:1.

[0061] According to a preferred embodiment of the present invention, the pH value is 5-5.5.

[0062] When the pH value is less than 7, the oil-emulsion mixture is relatively stable; preferably, when the pH value is 5-5.5, the interface film of the oil-emulsion mixture has considerable strength, which effectively improves the stability of the emulsion mixture.

[0063] In the oil emulsion mixture, adding amino-modified polysiloxane containing amino groups can reduce its viscosity; adding epoxy-modified polysiloxane containing active epoxy groups can improve its stability; adding polyether-modified polysiloxane containing polyether groups can make it have good wettability; using amino-modified polysiloxane in combination with polyether-modified polysiloxane can improve the resistivity of the prepared raw silk, so that the raw silk has excellent antistatic properties.

[0064] If the amino-modified polysiloxane in the oil emulsion mixture is selected from one or more of triamino-modified polysiloxane, N-(β-aminoethyliminoethyl)-γ-aminopropylmethyldimethoxypolysiloxane, N-β-aminoethyl-γ-aminopropylmethyldimethoxypolysiloxane, side chain N-(β-aminoethyliminoethyl)iminopropyl-modified polysiloxane, and side chain N-(β-aminoethyl)iminopropyl-modified polysiloxane, the viscosity of the oil emulsion mixture obtained after mixing the oil emulsion with water can be further reduced.

[0065] The amino-modified polysiloxane contains an amino group, has a strong polarity, and has an average molecular weight of 260-31000 g / mol, a large distance between molecules, and thus a weak intermolecular force, thereby reducing the viscosity of the oil emulsion mixture. When the average molecular weight of the amino-modified polysiloxane is 1130-25000 g / mol, the viscosity of the oil emulsion mixture obtained by mixing the oil emulsion with water can be further reduced.

[0066] When the content of amino-modified polysiloxane in the oil emulsion is 30-70 wt %, the viscosity of the oil emulsion mixture obtained by mixing the oil emulsion with water can be effectively reduced.

[0067] Epoxy-modified polysiloxane contains active epoxy groups, which can effectively alleviate the stratification of the oil emulsion, and the epoxy-modified polysiloxane with an average molecular weight of 920-9300 g / mol has a good coupling effect, thereby improving the stability of the oil emulsion mixture. When the content of epoxy-modified polysiloxane in the oil emulsion is 15-35wt%, the number of days required for the oil emulsion to stratify can be effectively increased, and the stability of the emulsion mixture can be improved.

[0068] The polyether-modified polysiloxane contains a polyether group, which can increase the hydrophilicity of the oil emulsion, and the polyether-modified polysiloxane with an average molecular weight of 290-460 g / mol can effectively reduce the surface tension, so that the oil emulsion mixture has good wettability. When the content of the polyether-modified polysiloxane in the oil emulsion is 1-10wt%, the wetting and spreading performance of the oil emulsion mixture can be further improved.

[0069] According to a preferred embodiment of the present invention, the mixing is stirring, wherein the stirring speed is 1800-3800 r / min, preferably 2200-2800 r / min.

[0070] According to a preferred embodiment of the present invention, the stirring time is 80-120 minutes, preferably 90-110 minutes.

[0071] The sixth aspect of the present invention provides an application of any one of the oil emulsion described in the first aspect or the third aspect, the oil emulsion mixture described in the fourth aspect, and the oil emulsion mixture prepared by the method described in the fifth aspect in preparing polyacrylonitrile-based precursor fibers.

[0072] The present invention will be described in detail below through examples.

[0073] Example 1

[0074] (1) Preparation of composite emulsion:

[0075] In a 50L stirred tank, add C 12 Fatty alcohol polyoxyethylene (10) ether (Wuhan Kemik Biopharmaceutical Technology Co., Ltd.) 900g, dodecyltrimethylammonium chloride (Pulov Biotechnology Co., Ltd.) 300g, antioxidant 1076 (Nanjing Milan Chemical Co., Ltd.) 300g, control the stirring temperature to 40°C, stir at a stirring rate of 1800r / min for 80 minutes to obtain a composite emulsion.

[0076] (2) Preparation of oil emulsion:

[0077] 1800 g of N-aminoethyl-3-aminopropyltriethoxysilane (Wuhan Jixinyibang Biotechnology Co., Ltd.), 2100 g of glycidyloxypropyl-terminated polydimethylsiloxane (Hubei Jiufenglong Chemical Co., Ltd.), and 600 g of 3-[hydroxy(polyoxyethylene)propyl]heptamethyltrisiloxane (Guangzhou Ruishi Biotechnology Co., Ltd.) were slowly added into a high shear emulsifier. After starting stirring, the composite emulsion prepared in (1) was slowly added into the emulsifier, and the stirring temperature was controlled to be 40°C.

[0078] (3) Preparation of oil emulsion mixture:

[0079] Deionized water was added dropwise to the oil emulsion prepared in (2) to adjust the pH to 5.0, and the mixture was stirred at a stirring rate of 1800 r / min for 80 minutes. After cooling to room temperature, the mixture was filtered to obtain an oil emulsion mixture.

[0080] Embodiment 2-8

[0081] The preparation steps are the same as those in Example 1, wherein the names and molecular weights of amino-modified polysiloxane, epoxy-modified polysiloxane, and polyether-modified polysiloxane are shown in Table 1, the names of emulsifiers, cationic antistatic agents, and antioxidants are shown in Table 2, the contents of the components of the oil emulsion are shown in Table 3, and the process parameters for preparing the oil emulsion are shown in Table 4.

[0082] Comparative Example 1

[0083] (1) 35 parts of amino-modified polydimethylsilane A, 35 parts of amino-modified polydimethylsilane B, 15 parts of polyether-modified polydimethylsiloxane, 10 parts of fatty alcohol polyoxyethylene ether and 5 parts of dimethyldodecylbenzylammonium chloride were stirred at 50° C. and 2200 r / min for 80 minutes until the mixture was uniform, to obtain a composite emulsion 1.

[0084] (2) Using p-toluenesulfonic acid as a catalyst, 1 mol of diethylenetriamine and 2 mol of stearic acid are reacted at 200-220° C. for 5 hours to obtain an amide compound, which is then subjected to an addition reaction with 10 mol of ethylene oxide to obtain an epoxy adduct of the amide compound.

[0085] (3) gradually adding deionized water to the composite emulsion 1 obtained in (1) to obtain an oil-emulsion mixture 1, wherein the concentration of the oil-emulsion mixture 1 should be 0.5 to 3.0 wt%.

[0086] (4) Deionized water was added to the epoxy adduct of the amide compound, and the mixture was heated to 55° C. The mixture was stirred at a speed of 2200 r / min for 80 minutes until dissolved to obtain an oil-emulsion mixture 2. The concentration of the oil-emulsion mixture 2 should be the same as that of the oil-emulsion mixture 1.

[0087] (5) The oil-emulsion mixture 1 and the oil-emulsion mixture 2 are stirred and mixed at a temperature of 55° C. and a rotation speed of 2200 r / min for 80 minutes, wherein the mass ratio of the oil-emulsion mixture 1 to the oil-emulsion mixture 2 is 3:1-3, to obtain a final oil-emulsion mixture.

[0088] Table 1 Names and molecular weights of three polysiloxanes

[0089]

[0090]

[0091] Table 2 Names of emulsifiers, antistatic agents and antioxidants

[0092] Emulsifier Cationic antistatic agent Antioxidants Comparative Example 1 <![CDATA[C 12 Fatty alcohol polyoxyethylene (15) ether]]> Dodecyltrimethylammonium chloride Antioxidant 1076 Comparative Example 2 <![CDATA[C 12 Fatty alcohol polyoxyethylene (15) ether]]> Dodecyltrimethylammonium chloride Antioxidant 1076 Comparative Example 3 <![CDATA[C 16 Fatty alcohol polyoxyethylene (35) ether]]> Dibenzyl di(octadecylamideethyl)ammonium salt Antioxidant 1035 Comparative Example 4 <![CDATA[C 16 Fatty alcohol polyoxyethylene (35) ether]]> Dibenzyl di(octadecylamideethyl)ammonium salt Antioxidant 1035 Comparative Example 5 <![CDATA[C 16 Fatty alcohol polyoxyethylene (35) ether]]> Dibenzyl di(octadecylamideethyl)ammonium salt Antioxidant 1035 Comparative Example 6 <![CDATA[C 16 Fatty alcohol polyoxyethylene (35) ether]]> Dibenzyl di(octadecylamideethyl)ammonium salt Antioxidant 1035 Example 1 <![CDATA[C 12 Fatty alcohol polyoxyethylene (10) ether]]> Dodecyltrimethylammonium chloride Antioxidant 1076 Example 2 <![CDATA[C 15 Fatty alcohol polyoxyethylene (10) ether]]> Dodecyltrimethylammonium chloride Antioxidant 1076 Example 3 <![CDATA[C 12 Fatty alcohol polyoxyethylene (15) ether]]> Dodecyltrimethylammonium chloride Antioxidant 1076 Example 4 <![CDATA[C 15 Fatty alcohol polyoxyethylene (15) ether]]> Methyltrihydroxyethylammonium methylsulfate Antioxidant 1076 Example 5 <![CDATA[C 12 Fatty alcohol polyoxyethylene (35) ether]]> Methyltrihydroxyethylammonium methylsulfate Antioxidant 1035 Example 6 <![CDATA[C 15 Fatty alcohol polyoxyethylene (35) ether]]> Methyltrihydroxyethylammonium methylsulfate Antioxidant 1035 Example 7 <![CDATA[C 16 Fatty alcohol polyoxyethylene (35) ether]]> Dibenzyl di(octadecylamideethyl)ammonium salt Antioxidant 1035 Example 8 <![CDATA[C 18 Fatty alcohol polyoxyethylene (35) ether]]> Dibenzyl di(octadecylamideethyl)ammonium salt Antioxidant 1035 Example 9 <![CDATA[C 12 Fatty alcohol polyoxyethylene (15) ether]]> Dodecyltrimethylammonium chloride Antioxidant 1076 Example 10 <![CDATA[C 12 Fatty alcohol polyoxyethylene (15) ether]]> Dodecyltrimethylammonium chloride Antioxidant 1076

[0093] Table 3 Content of each component of oil emulsion

[0094]

[0095]

[0096] Table 4 Process parameters for preparing oil emulsion

[0097] Stirring temperature (℃) Stirring time (min) Stirring speed (r / min) pH Comparative Example 1 50 90 2200 6.5 Comparative Example 2 50 90 2200 6.2 Comparative Example 3 55 110 2800 6.8 Comparative Example 4 55 110 2800 6.4 Comparative Example 5 55 110 2800 6.6 Comparative Example 6 55 110 2800 6.7 Example 1 40 80 1800 5.0 Example 2 46 85 2080 5.1 Example 3 50 90 2200 5.2 Example 4 52 93 2350 5.3 Example 5 53 102 2560 5.3 Example 6 53 106 2620 5.4 Example 7 55 110 2800 5.5 Example 8 65 120 3800 5.5 Example 9 50 90 2650 5.5 Example 10 50 90 2800 5.5

[0098] The properties of the oil emulsion and the raw silk are shown in Table 5.

[0099] Table 5 Oil emulsion mixture and raw silk properties

[0100]

[0101]

[0102] It can be seen from the results in the table that the oil-emulsion mixture provided by the present invention has lower viscosity, smaller average particle size and longer stratification time, and the raw silk prepared therefrom has smaller specific resistance and better antistatic property.

[0103] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. An oil emulsion, characterized in that: Based on the total amount of the oil emulsion, the oil emulsion comprises:

2. The oil emulsion according to claim 1, wherein The amino-modified polysiloxane is selected from one or more of triamino-modified polysiloxane, N-β-aminoethyl-γ-aminopropylmethyldimethoxy polysiloxane, N-(β-aminoethyliminoethyl)-γ-aminopropylmethyldimethoxy polysiloxane, N-aminoethyl-3-aminopropyltriethoxysilane, aminoalkyl-modified polysiloxane at both ends, side chain N-(β-aminoethyl)iminopropyl-modified polysiloxane, side chain N-(β-aminoethyliminoethyl)iminopropyl-modified polysiloxane, and side chain cyclic diaminoalkyl-modified polysiloxane; Preferably, the amino-modified polysiloxane is selected from one or more of triamino-modified polysiloxane, N-(β-aminoethyliminoethyl)-γ-aminopropylmethyldimethoxypolysiloxane, N-β-aminoethyl-γ-aminopropylmethyldimethoxypolysiloxane, side chain N-(β-aminoethyliminoethyl)iminopropyl modified polysiloxane, and side chain N-(β-aminoethyl)iminopropyl modified polysiloxane; And / or, the epoxy-modified polysiloxane is selected from glycidyloxypropyl-terminated polydimethylsiloxane and / or epoxy-modified methylphenylvinyl polysiloxane; and / or, the polyether-modified polysiloxane is selected from 3-[hydroxy(polyoxyethylene)propyl]heptamethyltrisiloxane and / or 3-[methoxypoly(ethoxy)]propyl-methyl-bis(trimethylsiloxy)silane; And / or, the emulsifier is selected from nonionic surfactant C 12 -C 18 Fatty alcohol polyoxyethylene (10) ether, C 12 -C 18 Fatty alcohol polyoxyethylene (15) ether, C 12 -C 18 One or more of fatty alcohol polyoxyethylene (35) ether, castor oil polyoxyethylene (10) ether, castor oil polyoxyethylene (30) ether and castor oil polyoxyethylene (90) ether; Preferably, the emulsifier is selected from C 12 Fatty alcohol polyoxyethylene (10) ether, C 15 Fatty alcohol polyoxyethylene (10) ether, C 12 Fatty alcohol polyoxyethylene (15) ether, C 15 Fatty alcohol polyoxyethylene (15) ether, C 12 Fatty alcohol polyoxyethylene (35) ether, C 15 Fatty alcohol polyoxyethylene (35) ether, C 16 Fatty alcohol polyoxyethylene (35) ether, C 18 One or more of fatty alcohol polyoxyethylene (35) ethers; And / or, the cationic antistatic agent is selected from one or more of dodecyltrimethylammonium chloride, methyltrihydroxyethylmethylammonium sulfate, and dibenzylbis(octadecylamideethyl)ammonium salt; And / or, the antioxidant is selected from one or more of antioxidant 1076, antioxidant 1035, phenolic antioxidant and antioxidant BHT; Preferably, the antioxidant is selected from one or more of antioxidant 1076 and antioxidant 1035.

3. The oil emulsion according to claim 1 or 2, wherein The average molecular weight of the amino-modified polysiloxane is 260-31000 g / mol, preferably 1130-25000 g / mol; And / or, the average molecular weight of the epoxy-modified polysiloxane is 920-9300 g / mol; And / or, the average molecular weight of the polyether-modified polysiloxane is 290-460 g / mol.

4. A method for preparing an oil emulsion, characterized in that: The method includes: (1) mixing an emulsifier, a cationic antistatic agent, and an antioxidant to obtain a composite emulsion; (2) mixing amino-modified polysiloxane, epoxy-modified polysiloxane, polyether-modified polysiloxane and a composite emulsion to obtain an oil emulsion; Among them, the amount of amino-modified polysiloxane is 30-70 parts by weight, the amount of epoxy-modified polysiloxane is 15-35 parts by weight, the amount of polyether-modified polysiloxane is 1-10 parts by weight, the amount of emulsifier is 10-15 parts by weight, the amount of cationic antistatic agent is 3-5 parts by weight, and the amount of antioxidant is 1-5 parts by weight.

5. The method according to claim 4, wherein: The amino-modified polysiloxane is selected from one or more of triamino-modified polysiloxane, N-β-aminoethyl-γ-aminopropylmethyldimethoxy polysiloxane, N-(β-aminoethyliminoethyl)-γ-aminopropylmethyldimethoxy polysiloxane, N-aminoethyl-3-aminopropyltriethoxysilane, aminoalkyl-modified polysiloxane at both ends, side chain N-(β-aminoethyl)iminopropyl-modified polysiloxane, side chain N-(β-aminoethyliminoethyl)iminopropyl-modified polysiloxane, and side chain cyclic diaminoalkyl-modified polysiloxane; Preferably, the amino-modified polysiloxane is selected from one or more of triamino-modified polysiloxane, N-(β-aminoethyliminoethyl)-γ-aminopropylmethyldimethoxypolysiloxane, N-β-aminoethyl-γ-aminopropylmethyldimethoxypolysiloxane, side chain N-(β-aminoethyliminoethyl)iminopropyl modified polysiloxane, and side chain N-(β-aminoethyl)iminopropyl modified polysiloxane; and / or, the average molecular weight of the amino-modified polysiloxane is 260-31000 g / mol, preferably 1130-25000 g / mol; And / or, the epoxy-modified polysiloxane is selected from glycidyloxypropyl-terminated polydimethylsiloxane and / or epoxy-modified methylphenylvinyl polysiloxane; And / or, the average molecular weight of the epoxy-modified polysiloxane is 920-9300 g / mol; and / or, the polyether-modified polysiloxane is selected from 3-[hydroxy(polyoxyethylene)propyl]heptamethyltrisiloxane and / or 3-[methoxypoly(ethoxy)]propyl-methyl-bis(trimethylsiloxy)silane; and / or, the average molecular weight of the polyether-modified polysiloxane is 290-460 g / mol; And / or, the emulsifier is selected from nonionic surfactant C 12 -C 18 Fatty alcohol polyoxyethylene (10) ether, C 12 -C 18 Fatty alcohol polyoxyethylene (15) ether, C 12 -C 18 One or more of fatty alcohol polyoxyethylene (35) ether, castor oil polyoxyethylene (10) ether, castor oil polyoxyethylene (30) ether and castor oil polyoxyethylene (90) ether; Preferably, the emulsifier is selected from C 12 Fatty alcohol polyoxyethylene (10) ether, C 15 Fatty alcohol polyoxyethylene (10) ether, C 12 Fatty alcohol polyoxyethylene (15) ether, C 15 Fatty alcohol polyoxyethylene (15) ether, C 12 Fatty alcohol polyoxyethylene (35) ether, C 15 Fatty alcohol polyoxyethylene (35) ether, C 16 Fatty alcohol polyoxyethylene (35) ether, C 18 One or more of fatty alcohol polyoxyethylene (35) ethers; And / or, the cationic antistatic agent is selected from one or more of dodecyltrimethylammonium chloride, methyltrihydroxyethylmethylammonium sulfate, and dibenzylbis(octadecylamideethyl)ammonium salt; And / or, the antioxidant is selected from a compound of antioxidant 1076, antioxidant 1035, phenolic antioxidant and antioxidant BHT; Preferably, the antioxidant is selected from one or more of antioxidant 1076 and antioxidant 1035.

6. The method according to claim 4, wherein: In step (1), the stirring temperature is 40-65°C, preferably 50-55°C; and / or, the stirring speed is 1800-3800 r / min, preferably 2200-2800 r / min; And / or, the stirring time is 80-120 minutes, preferably 90-110 minutes.

7. The method according to claim 4, wherein: In step (2), the stirring temperature is 40-65°C, preferably 50-55°C; and / or, the stirring speed is 1800-3800 r / min, preferably 2200-2800 r / min; And / or, the stirring time is 80-120 minutes, preferably 90-110 minutes.

8. An oil emulsion obtained by the method according to any one of claims 4 to 7.

9. An oil emulsion mixture, characterized in that: The mixture comprises the oil emulsion according to any one of claims 1 to 3 and 8 and water; wherein the weight ratio of water to the oil emulsion is 2-5:1, and the pH value of the oil emulsion mixture is less than 7; Preferably, the oil-emulsion mixture has an average particle size of 0.1-0.3 μm, a stratification time of 110-150 days, a wetting time of 7-11 s, and a viscosity of 90-130 mPa·s.

10. A method for preparing an oil-emulsion mixture, characterized in that: Mixing the oil emulsion according to any one of claims 1 to 3 and 8 with water, and adjusting the pH value to be acidic, to obtain the oil emulsion mixture; Wherein, the weight ratio of water to the oil emulsion is 2-5:1; Preferably, the pH value is 5-5.5; Preferably, the mixing is stirring, wherein the stirring speed is 1800-3800 r / min, preferably 2200-2800 r / min; Preferably, the stirring time is 80-120 minutes, preferably 90-110 minutes.

11. Use of the oil emulsion according to any one of claims 1 to 3 and 8, the oil emulsion mixture according to claim 9, or the oil emulsion mixture obtained by the method according to claim 10 in preparing polyacrylonitrile-based precursor fibers.

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