CN104179019A - Preparation method of carbon fiber precursor oil agent - Google Patents
Preparation method of carbon fiber precursor oil agent Download PDFInfo
- Publication number
- CN104179019A CN104179019A CN201410420266.1A CN201410420266A CN104179019A CN 104179019 A CN104179019 A CN 104179019A CN 201410420266 A CN201410420266 A CN 201410420266A CN 104179019 A CN104179019 A CN 104179019A
- Authority
- CN
- China
- Prior art keywords
- modified
- preparation
- carbon fibre
- chemical formula
- silicone oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a preparation method of a carbon fiber precursor oil agent. The method comprises the following steps: putting a composite emulsifier and a characteristic composite modified silicone oil in a weight ratio of (1-4) to (3-10) into a high-shear emulsifying machine; evenly stirring; adding a composite assistant; dropwise adding an appropriate amount of deionized water; stirring for 20-120 minutes; and adjusting the pH value to 3-10, thereby obtaining a light blue, light yellow or white emulsion, namely the carbon fiber precursor oil agent. According to the method, the technology operation is simple and can be directly applied to an industrial production line. When in use, the oil agent prepared by the method has good permeability, high temperature resistance and good process stability, and can well enhance the bunching performance of fibers and well protect the fibers in the whole process of pre-oxidation as well as in the initial stage of low-temperature carbonization, thereby greatly reducing the phenomena of monofilament adhesion and doubling, reducing the surface detects of the fibers, and enhancing the performance of the fibers.
Description
Technical field
The present invention relates to a kind of preparation method of finish, particularly a kind of preparation method of carbon fibre precursor finish.
Background technology
Carbon fiber possesses the many merits such as high strength, high-modulus, high temperature resistant, acid-alkali-corrosive-resisting, is widely used in the fields such as Aero-Space, civil construction, new forms of energy.Carbon fibre composite is also being widely used in all trades and professions simultaneously, and along with economic and scientific and technological fast development, the demand of carbon fiber will further improve.
The carbon fibre precursor of high-quality is the key of the high-quality carbon fiber of preparation, and the performance of precursor is directly determining the performance of final carbon fiber.In precursor manufacturing technique, oiling process is an extremely important production technology, and high-quality finish can solve the adhesion of the tow occurring in spinning process; The tow blocking under warming that alleviation produces because of hot-spot in the preoxidation process of 200 ℃～400 ℃ and the hot pre-oxidized fibers blemish of melting and bringing; Minimizing low-temperature carbonization stage of 400～1500 ℃ because of a large amount of accessory substances drain that the fiber heat causing is melted and and blocking under warming; Finish film forming can reduce fluffing, fracture of wire and the surface damage that between tow and machinery, friction causes simultaneously.
Carbon fibre precursor finish should possess good resistance to elevated temperatures, antistatic property, wetting greasy property, boundling and anti-adhesion performance, but the carbon fibre precursor finish of function admirable is but very rarely seen on domestic market, even the manufacturer of the former silk oiling agent of domestic carbon fibre all seldom.At present the most conventional carbon fiber finish has two large classes, and a class is that to take the polyester of LCFA and polyalcohol and the ethylene oxide adduct of higher fatty acid amide etc. be key component, and another kind of is to take the organosilicon finish that dimethyl silicone polymer is main body modification.Organosilicon finish is in heat resistance, and lubricity, shows advantage on antistick characteristic.Different group modified silicone oil has different properties, and amino-modified silicone oil possesses good film forming and hydrophily, and epoxide modified silicone oil possesses good heat resistance, and polyether modified silicon oil possesses good automatic emulsifying performance.Good carbon fibre precursor finish should be multi-functional composite finish, and processability is excellent, and the composite multi-functional finish of good stability is current carbon fibre precursor finish institute urgent need to solve the problem.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, provides a kind of processability excellent, the preparation method of the carbon fibre precursor finish of good stability.
Technical problem to be solved by this invention is to realize by following technical scheme, and the present invention is a kind of preparation method of carbon fibre precursor finish, is characterized in, its step is as follows:
Get the composite modified silicone oil of compound emulsifying agent and feature, according to the weight ratio of 1～4:3～10, drop in high-shear emulsion machine and stir, the composite assistant that adds quality percentage composition 1～2%, drip wherein again appropriate amount of deionized water, control mixing speed is 1500～10000r/min, mixing time is 20～120min, regulates pH value to 3～10, and light blue, the faint yellow or white emulsion of gained is carbon fibre precursor finish;
Described compound emulsifying agent is to be composited by following at least 2 kinds of emulsifying agents: isomery alcohol Polyoxyethylene Ether Nonionic Surfactant, alkylphenol polyoxyethylene type non-ionic surface active agent, fatty alcohol-polyoxyethylene ether type non-ionic surface active agent, polyoxyethylene sorbitan ester type non-ionic surface active agent, alkylolamides type non-ionic surface active agent, C10 ~ C18 straight chain alcohol ether type non-ionic surface active agent; During preparation, above-mentioned at least 2 kinds of emulsifying agents are placed in container, are warming up to 40 ~ 90 ℃, after stirring, be cooled to room temperature, obtain oyster white or faint yellow compound emulsifying agent;
The composite modified silicone oil of described feature is made by following at least 2 kinds of raw materials: 30 ~ 80 parts of amino modified dimethyl silicone polymers, 10 ~ 60 parts of polyether-modified dimethyl silicone polymers, 10 ~ 50 parts of epoxide modified dimethyl silicone polymers, 10 ~ 20 parts of vinyl modified dimethyl silicone polymers;
Described composite assistant respectively in following A group and B group at least a kind of raw material be composited; A group raw material is trihydroxyethyl methyl quaternary ammonium Methylsulfate salt, Dodecyl trimethyl ammonium chloride, different tridecanol ether phosphoric acid methyl esters salt, polyoxyethylene laurate; B group raw material is modification polymethyl siloxane type defoamer, fatty alcohol-polyoxyethylene ether, isoamyl alcohol, tributyl phosphate.
In the preparation method of carbon fibre precursor finish of the present invention, the amino modified dimethyl silicone polymer of the composite modified silicone oil Raw of described feature possesses following characteristics:
A part of side chain that end has the dimethyl-silicon of methyl is replaced by chemical formula (I) or chemical formula (II)
-CH
2-NH-CH
2-CH
2-NH
2（Ⅰ）
R-NH
2 （Ⅱ）。
In the preparation method of carbon fibre precursor finish of the present invention, the polyether-modified dimethyl silicone polymer of the composite modified silicone oil Raw of feature possesses following characteristics:
A part of side chain that end has the dimethyl-silicon of methyl is replaced by chemical formula (I) or chemical formula (II)
-CH
2（OCH
2-CH
2）
10~15OCH
3（Ⅰ）
-CH
2-NH（CH
2-CH
2）
10~15OCOCH
3 （Ⅱ）。
In the preparation method of carbon fibre precursor finish of the present invention, the epoxide modified dimethyl silicone polymer of the composite modified silicone oil Raw of feature possesses following characteristics:
A part of side chain or terminal methyl group that end has the dimethyl-silicon of methyl are replaced by chemical formula (I), chemical formula (II) or chemical formula (III)
（Ⅰ）
（Ⅱ）
（Ⅲ）。
In the preparation method of carbon fibre precursor finish of the present invention,
In the preparation method of carbon fibre precursor finish of the present invention, the viscosity of described amino-modified silicone oil in the time of 25 ℃ is 10 ~ 6000mm
2/ s, ammonia value is 0.3 ~ 1.0; The viscosity of described epoxide modified silicone oil in the time of 25 ℃ is 50 ~ 10000 mm
2/ s, epoxide equivalent value is 0.001 ~ 0.25; The viscosity of described polyether modified silicon oil in the time of 25 ℃ is 300 ~ 1500 mm
2/ s, the modification amount of polyether group is 0.001 ~ 0.8; The viscosity of described vinyl modified silicone oil in the time of 25 ℃ is 100 ~ 6000 mm
2/ s, the modification amount of vinyl is 0.001 ~ 0.5.
The carbon fibre precursor finish that described in above-mentioned any one, preparation method makes is at little tow, the purposes in the former silk oiling agent of large-tow carbon fiber.
The finish that the present invention makes can regulate working concentration by adding water as required when being applicable to the protofilament of different tow, and adding of water do not exert an influence to the performance of finish own.
After the present invention is equally applicable to modified silicon oil one-component to carry out emulsification and complete, carry out according to the method described above compound, the carbon fibre precursor composite finisher obtaining.
Compared with prior art, the inventive method technological operation is simple, can directly apply on industrial production line.When the finish of making by the inventive method is used, permeability is strong; lubricity is good; can improve the collection of filaments; can be in monofilament surface film forming, and high temperature resistant, technology stability is good; can be in whole preoxidation process and the low-temperature carbonization initial stage protect well fiber; greatly reduce monofilament adhesion and doubling phenomena, reduced the blemish of fiber, improved the performance of carbon fiber.
The specific embodiment
Below further describe concrete technical scheme of the present invention, so that those skilled in the art understands the present invention further, and do not form the restriction to its right.
Embodiment 1, a kind of preparation method of carbon fibre precursor finish, and its step is as follows:
With alkylphenol polyoxyethylene type non-ionic surface active agent and fatty alcohol-polyoxyethylene ether type non-ionic surface active agent compound, make compound emulsifying agent, compound emulsifying agent is placed in container, rise temperature 60 C, after stirring, be cooled to room temperature, obtain oyster white or faint yellow compound emulsifying agent, (25 ℃ of viscosity are 100mm to get compound emulsifying agent and 60 parts of amino modified dimethyl silicone polymers
2/ s, ammonia value is 0.6, modified group chemical formula (I)) and 40 parts of polyether-modified dimethyl silicone polymers (25 ℃ of viscosity are 1500mm
2/ s, modification amount 0.5) composite modified silicone oil drops in high-shear emulsion machine and stirs according to the weight ratio of 3:10, add percentage composition 1%, the compound auxiliary that different tridecanol ether phosphoric acid methyl esters salt and fatty alcohol-polyoxyethylene ether 1:1 form, drip wherein deionized water, control mixing speed is 3000r/min again, stirs 60min, regulate pH value to 8, the faint yellow or white emulsion of gained is former silk oiling agent.
Embodiment 2, a kind of preparation method of carbon fibre precursor finish, and its step is as follows:
With C13 straight chain alcohol ether type non-ionic surface active agent and fatty alcohol-polyoxyethylene ether type non-ionic surface active agent compound, make compound emulsifying agent, compound emulsifying agent is placed in container, rise temperature 60 C, after stirring, be cooled to room temperature, obtain oyster white or faint yellow compound emulsifying agent, (25 ℃ of viscosity are 100mm to get compound emulsifying agent and 60 parts of amino modified dimethyl silicone polymers
2/ s, ammonia value is 0.6, modified group chemical formula (I)) and 40 parts of polyether-modified dimethyl silicone polymers (25 ℃ of viscosity are 1500mm
2/ s, modification amount 0.5) composite modified silicone oil drops in high-shear emulsion machine and stirs according to the weight ratio of 3:10, add the different tridecanol ether phosphoric acid methyl esters salt of percentage composition 1% and the compound auxiliary that fatty alcohol-polyoxyethylene ether 1:1 forms, drip wherein again deionized water, control mixing speed is 3000r/min, stir 60min, regulate pH value to 7, the faint yellow or white emulsion of gained is former silk oiling agent.
Embodiment 3, a kind of preparation method of carbon fibre precursor finish, and its step is as follows:
With C13 straight chain alcohol ether type non-ionic surface active agent and fatty alcohol-polyoxyethylene ether type non-ionic surface active agent compound, make compound emulsifying agent, compound emulsifying agent is placed in container, rise temperature 60 C, after stirring, be cooled to room temperature, obtain oyster white or faint yellow compound emulsifying agent, (25 ℃ of viscosity are 100mm to get compound emulsifying agent and 50 parts of amino modified dimethyl silicone polymers
2/ s, ammonia value is 0.6, modified group chemical formula (I)), (25 ℃ of viscosity are 1500mm to 30 parts of polyether-modified dimethyl silicone polymers
2/ s, modification amount 0.5), (viscosity 25 ℃ time is 3000mm for 20 parts of epoxide modified dimethyl silicone polymers
2/ s, epoxide equivalent value is 0.15, modified group chemical formula (I)) composite modified silicone oil drops in high-shear emulsion machine and stirs according to the weight ratio of 3:10, add the different tridecanol ether phosphoric acid methyl esters salt of percentage composition 1% and the compound auxiliary that fatty alcohol-polyoxyethylene ether 1:1 forms, drip wherein deionized water, control mixing speed is 3000r/min again, stirs 60min, regulate pH value to 7, the faint yellow or white emulsion of gained is former silk oiling agent.
Embodiment 4, a kind of preparation method of carbon fibre precursor finish, and its step is as follows:
With C13 straight chain alcohol ether type non-ionic surface active agent and fatty alcohol-polyoxyethylene ether type non-ionic surface active agent compound, make compound emulsifying agent, compound emulsifying agent is placed in container, rise temperature 60 C, after stirring, be cooled to room temperature, obtain oyster white or faint yellow compound emulsifying agent, (25 ℃ of viscosity are 100mm to get compound emulsifying agent and 50 parts of amino modified dimethyl silicone polymers
2/ s, ammonia value is 0.6, modified group chemical formula (I)), (25 ℃ of viscosity are 1500mm to 20 parts of polyether-modified dimethyl silicone polymers
2/ s, modification amount 0.5), (viscosity 25 ℃ time is 3000mm for 20 parts of epoxide modified dimethyl silicone polymers
2/ s, epoxide equivalent value is 0.15, modified group chemical formula (I)), (viscosity 25 ℃ time is 5000 mm for 10 parts of vinyl modified dimethyl silicone polymers
2/ s, the modification amount of vinyl is 0.1) composite modified silicone oil according to the weight ratio of 3:10, drop in high-shear emulsion machine and stir, add the different tridecanol ether phosphoric acid methyl esters salt of percentage composition 1% and the compound auxiliary that fatty alcohol-polyoxyethylene ether 1:1 forms, drip wherein again deionized water, control mixing speed is 3000r/min, stir 60min, regulate pH value to 9, the faint yellow or white emulsion of gained is former silk oiling agent.
Embodiment 5, a kind of preparation method of carbon fibre precursor finish, and its step is as follows:
With C13 straight chain alcohol ether type non-ionic surface active agent and fatty alcohol-polyoxyethylene ether type non-ionic surface active agent compound, make compound emulsifying agent, compound emulsifying agent is placed in container, rise temperature 60 C, after stirring, be cooled to room temperature, obtain oyster white or faint yellow compound emulsifying agent, (25 ℃ of viscosity are 100mm to get compound emulsifying agent and 50 parts of amino modified dimethyl silicone polymers
2/ s, ammonia value is 0.6, modified group chemical formula (I)), (25 ℃ of viscosity are 1500mm to 20 parts of polyether-modified dimethyl silicone polymers
2/ s, modification amount 0.5), (viscosity 25 ℃ time is 3000mm for 20 parts of epoxide modified dimethyl silicone polymers
2/ s, epoxide equivalent value is 0.15, modified group chemical formula (I)), (viscosity 25 ℃ time is 5000 mm for 10 parts of vinyl modified dimethyl silicone polymers
2/ s, the modification amount of vinyl is 0.1) composite modified silicone oil according to the weight ratio of 3:10, drop in high-shear emulsion machine and stir, add the trihydroxyethyl methyl quaternary ammonium Methylsulfate salt of percentage composition 1% and the 1:1 compound auxiliary that modification polymethyl siloxane type defoamer forms, drip wherein again deionized water, control mixing speed is 3000r/min, stir 60min, regulate pH value to 7, the faint yellow or white emulsion of gained is former silk oiling agent.
Embodiment 6, a kind of preparation method of carbon fibre precursor finish, and its step is as follows:
With the compound of C13 straight chain alcohol ether type non-ionic surface active agent, fatty alcohol-polyoxyethylene ether type non-ionic surface active agent, isomery alcohol Polyoxyethylene Ether Nonionic Surfactant, make compound emulsifying agent, compound emulsifying agent is placed in container, rise temperature 60 C, after stirring, be cooled to room temperature, obtain oyster white or faint yellow compound emulsifying agent, (25 ℃ of viscosity are 100mm to get compound emulsifying agent and 50 parts of amino modified dimethyl silicone polymers
2/ s, ammonia value is 0.6, modified group chemical formula (I)), (25 ℃ of viscosity are 1500mm to 20 parts of polyether-modified dimethyl silicone polymers
2/ s, modification amount 0.5), (viscosity 25 ℃ time is 3000mm for 20 parts of epoxide modified dimethyl silicone polymers
2/ s, epoxide equivalent value is 0.15, modified group chemical formula (I)), (viscosity 25 ℃ time is 5000 mm for 10 parts of vinyl modified dimethyl silicone polymers
2/ s, the modification amount of vinyl is 0.1) composite modified silicone oil according to the weight ratio of 2:9, drop in high-shear emulsion machine and stir, add the trihydroxyethyl methyl quaternary ammonium Methylsulfate salt of percentage composition 1% and the 1:1 compound auxiliary that modification polymethyl siloxane type defoamer forms, drip wherein again deionized water, control mixing speed is 3500r/min, stir 60min, regulate pH value to 7, the faint yellow or white emulsion of gained is former silk oiling agent.
Embodiment 7, a kind of preparation method of carbon fibre precursor finish, and its step is as follows:
With the compound of C13 straight chain alcohol ether type non-ionic surface active agent, fatty alcohol-polyoxyethylene ether type non-ionic surface active agent, isomery alcohol Polyoxyethylene Ether Nonionic Surfactant, make compound emulsifying agent, compound emulsifying agent is placed in container, rise temperature 60 C, after stirring, be cooled to room temperature, obtain oyster white or faint yellow compound emulsifying agent, (25 ℃ of viscosity are 100mm to get compound emulsifying agent and 60 parts of amino modified dimethyl silicone polymers
2/ s, ammonia value is 0.6, modified group chemical formula (I)), (25 ℃ of viscosity are 1500mm to 15 parts of polyether-modified dimethyl silicone polymers
2/ s, modification amount 0.5), (viscosity 25 ℃ time is 3000mm for 15 parts of epoxide modified dimethyl silicone polymers
2/ s, epoxide equivalent value is 0.15, modified group chemical formula (I)), (viscosity 25 ℃ time is 5000 mm for 10 parts of vinyl modified dimethyl silicone polymers
2/ s, the modification amount of vinyl is 0.1) composite modified silicone oil according to the weight ratio of 2:9, drop in high-shear emulsion machine and stir, add the trihydroxyethyl methyl quaternary ammonium Methylsulfate salt of percentage composition 1% and the 1:1 compound auxiliary that modification polymethyl siloxane type defoamer forms, drip wherein again deionized water, control mixing speed is 3000r/min, stir 60min, regulate pH value to 7, the faint yellow or white emulsion of gained is former silk oiling agent.
Embodiment 8, a kind of preparation method of carbon fibre precursor finish, and its step is as follows:
With the compound of C13 straight chain alcohol ether type non-ionic surface active agent, fatty alcohol-polyoxyethylene ether type non-ionic surface active agent, isomery alcohol Polyoxyethylene Ether Nonionic Surfactant, make compound emulsifying agent, compound emulsifying agent is placed in container, rise temperature 60 C, after stirring, be cooled to room temperature, obtain oyster white or faint yellow compound emulsifying agent, (25 ℃ of viscosity are 3000mm to get compound emulsifying agent and 60 parts of amino modified dimethyl silicone polymers
2/ s, ammonia value is 0.3), (25 ℃ of viscosity are 1500mm to 15 parts of polyether-modified dimethyl silicone polymers
2/ s, modification amount 0.5), (viscosity 25 ℃ time is 3000mm for 15 parts of epoxide modified dimethyl silicone polymers
2/ s, epoxide equivalent value is 0.15, modified group chemical formula (I)), (viscosity 25 ℃ time is 5000 mm for 10 parts of vinyl modified dimethyl silicone polymers
2/ s, the modification amount of vinyl is 0.1) composite modified silicone oil according to the weight ratio of 2:9, drop in high-shear emulsion machine and stir, add the trihydroxyethyl methyl quaternary ammonium Methylsulfate salt of percentage composition 1% and the 2:1:1 compound auxiliary that modification polymethyl siloxane type defoamer, tributyl phosphate form, drip wherein again deionized water, control mixing speed is 3500r/min, stir 60min, regulate pH value to 8, the faint yellow or white emulsion of gained is former silk oiling agent.
Embodiment 9, a kind of preparation method of carbon fibre precursor finish, and its step is as follows:
With the compound of C13 straight chain alcohol ether type non-ionic surface active agent, fatty alcohol-polyoxyethylene ether type non-ionic surface active agent, isomery alcohol Polyoxyethylene Ether Nonionic Surfactant, make compound emulsifying agent, compound emulsifying agent is placed in container, rise temperature 60 C, after stirring, be cooled to room temperature, obtain oyster white or faint yellow compound emulsifying agent, (25 ℃ of viscosity are 5000mm to get compound emulsifying agent and 60 parts of amino modified dimethyl silicone polymers
2/ s, ammonia value is 0.8, modified group chemical formula (I)), (25 ℃ of viscosity are 500mm to 15 parts of polyether-modified dimethyl silicone polymers
2/ s, modification amount 0.3), (viscosity 25 ℃ time is 6000mm for 15 parts of epoxide modified dimethyl silicone polymers
2/ s, epoxide equivalent value is 0.1, modified group chemical formula (I)), (viscosity 25 ℃ time is 3000 mm for 10 parts of vinyl modified dimethyl silicone polymers
2/ s, the modification amount of vinyl is 0.15) composite modified silicone oil according to the weight ratio of 1:4, drop in high-shear emulsion machine and stir, add the trihydroxyethyl methyl quaternary ammonium Methylsulfate salt of percentage composition 1.5% and the 1:1 compound auxiliary that modification polymethyl siloxane type defoamer forms, drip wherein again deionized water, control mixing speed is 3500r/min, stir 80min, regulate pH value to 7, the faint yellow or white emulsion of gained is former silk oiling agent.
Embodiment 10, a kind of preparation method of carbon fibre precursor finish, and its step is as follows:
In embodiment 9, emulsifying agent adopts the compound of polyoxyethylene sorbitan ester type non-ionic surface active agent, C13 straight chain alcohol ether type non-ionic surface active agent, fatty alcohol-polyoxyethylene ether type non-ionic surface active agent, isomery alcohol Polyoxyethylene Ether Nonionic Surfactant to make compound emulsifying agent; Compound auxiliary changes different tridecanol ether phosphoric acid methyl esters salt into, polyoxyethylene laurate, and modification polymethyl siloxane type defoamer, fatty alcohol-polyoxyethylene ether equal proportion is mixed composite, adds percentage composition 1%.
Embodiment 11, a kind of preparation method of carbon fibre precursor finish, and its step is as follows:
In embodiment 6, (viscosity 25 ℃ time is 1500mm for 20 parts of epoxide modified dimethyl silicone polymers
2/ s, epoxide equivalent value is 0.1, modified group chemical formula (II)), all the other feature invariants.
Embodiment 12, a kind of preparation method of carbon fibre precursor finish, and its step is as follows:
In embodiment 7, (viscosity 25 ℃ time is 1500mm for 15 parts of epoxide modified dimethyl silicone polymers
2/ s, epoxide equivalent value is 0.1, modified group chemical formula (II)), all the other feature invariants.
Embodiment 13, a kind of preparation method of carbon fibre precursor finish, and its step is as follows:
In embodiment 8, (viscosity 25 ℃ time is 1500mm for 15 parts of epoxide modified dimethyl silicone polymers
2/ s, epoxide equivalent value is 0.1, modified group chemical formula (II)), all the other feature invariants.
Embodiment 14, a kind of preparation method of carbon fibre precursor finish, and its step is as follows:
In embodiment 9, (viscosity 25 ℃ time is 2000mm for 15 parts of epoxide modified dimethyl silicone polymers
2/ s, epoxide equivalent value is 0.2, modified group chemical formula (II)), all the other feature invariants.
Embodiment 15, a kind of preparation method of carbon fibre precursor finish, and its step is as follows:
In embodiment 7, (25 ℃ of viscosity are 180mm to 60 parts of amino modified dimethyl silicone polymers
2/ s, ammonia value is 0.5, modified group chemical formula (II)), (viscosity 25 ℃ time is 1500mm for 15 parts of epoxide modified dimethyl silicone polymers
2/ s, epoxide equivalent value is 0.1, modified group chemical formula (II)), all the other feature invariants.
Comparative example.Adopt single purchase amino-modified silicone oil, gained precursor carries out pre-oxidation carbonization.
Emulsifying agent and auxiliary agent reference numeral see attached list 1, each embodiment gained finish use and this finish gained precursor gained carbon fiber mechanical performance data after pre-oxidation carbonization sees attached list 2, each embodiment specific embodiments sees attached list 3.
Subordinate list 1 emulsifying agent and auxiliary agent reference numeral
Subordinate list 2 embodiment finish serviceabilities and gained carbon fiber mechanical property
Subordinate list 3 embodiment specific embodiments
Claims (6)
1. a preparation method for carbon fibre precursor finish, is characterized in that, its step is as follows:
Get the composite modified silicone oil of compound emulsifying agent and feature, according to the weight ratio of 1～4:3～10, drop in high-shear emulsion machine and stir, the composite assistant that adds quality percentage composition 1～2%, drip wherein again appropriate amount of deionized water, control mixing speed is 1500～10000r/min, mixing time is 20～120min, regulates pH value to 3～10, and light blue, the faint yellow or white emulsion of gained is carbon fibre precursor finish;
Described compound emulsifying agent is to be composited by following at least 2 kinds of emulsifying agents: isomery alcohol Polyoxyethylene Ether Nonionic Surfactant, alkylphenol polyoxyethylene type non-ionic surface active agent, fatty alcohol-polyoxyethylene ether type non-ionic surface active agent, polyoxyethylene sorbitan ester type non-ionic surface active agent, alkylolamides type non-ionic surface active agent, C10 ~ C18 straight chain alcohol ether type non-ionic surface active agent; During preparation, above-mentioned at least 2 kinds of emulsifying agents are placed in container, are warming up to 40 ~ 90 ℃, after stirring, be cooled to room temperature, obtain oyster white or faint yellow compound emulsifying agent;
The composite modified silicone oil of described feature is made by following at least 2 kinds of raw materials: 30 ~ 80 parts of amino modified dimethyl silicone polymers, 10 ~ 60 parts of polyether-modified dimethyl silicone polymers, 10 ~ 50 parts of epoxide modified dimethyl silicone polymers, 10 ~ 20 parts of vinyl modified dimethyl silicone polymers;
Described composite assistant respectively in following A group and B group at least a kind of raw material be composited; A group raw material is trihydroxyethyl methyl quaternary ammonium Methylsulfate salt, Dodecyl trimethyl ammonium chloride, different tridecanol ether phosphoric acid methyl esters salt, polyoxyethylene laurate; B group raw material is modification polymethyl siloxane type defoamer, fatty alcohol-polyoxyethylene ether, isoamyl alcohol, tributyl phosphate.
2. the preparation method of carbon fibre precursor finish according to claim 1, is characterized in that, the amino modified dimethyl silicone polymer of the composite modified silicone oil Raw of described feature possesses following characteristics:
A part of side chain that end has the dimethyl-silicon of methyl is replaced by chemical formula (I) or chemical formula (II)
-CH
2-NH-CH
2-CH
2-NH
2（Ⅰ）
R-NH
2 （Ⅱ）。
3. the preparation method of carbon fibre precursor finish according to claim 1, is characterized in that, the polyether-modified dimethyl silicone polymer of the composite modified silicone oil Raw of feature possesses following characteristics:
A part of side chain that end has the dimethyl-silicon of methyl is replaced by chemical formula (I) or chemical formula (II)
-CH
2（OCH
2-CH
2）
10~15OCH
3（Ⅰ）
-CH
2-NH（CH
2-CH
2）
10~15OCOCH
3 （Ⅱ）。
4. the preparation method of carbon fibre precursor finish according to claim 1, is characterized in that, the epoxide modified dimethyl silicone polymer of the composite modified silicone oil Raw of feature possesses following characteristics:
A part of side chain or terminal methyl group that end has the dimethyl-silicon of methyl are replaced by chemical formula (I), chemical formula (II) or chemical formula (III)
（Ⅰ）
（Ⅱ）
（Ⅲ）。
5. the preparation method of carbon fibre precursor finish according to claim 1, is characterized in that, the viscosity of described amino-modified silicone oil in the time of 25 ℃ is 10 ~ 6000mm
2/ s, ammonia value is 0.3 ~ 1.0; The viscosity of described epoxide modified silicone oil in the time of 25 ℃ is 50 ~ 10000 mm
2/ s, epoxide equivalent value is 0.001 ~ 0.25; The viscosity of described polyether modified silicon oil in the time of 25 ℃ is 300 ~ 1500 mm
2/ s, the modification amount of polyether group is 0.001 ~ 0.8; The viscosity of described vinyl modified silicone oil in the time of 25 ℃ is 100 ~ 6000 mm
2/ s, the modification amount of vinyl is 0.001 ~ 0.5.
6. the carbon fibre precursor finish that described in claim 1-5 any one, preparation method makes is at little tow, the purposes in the former silk oiling agent of large-tow carbon fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410420266.1A CN104179019A (en) | 2014-08-25 | 2014-08-25 | Preparation method of carbon fiber precursor oil agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410420266.1A CN104179019A (en) | 2014-08-25 | 2014-08-25 | Preparation method of carbon fiber precursor oil agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104179019A true CN104179019A (en) | 2014-12-03 |
Family
ID=51960342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410420266.1A Pending CN104179019A (en) | 2014-08-25 | 2014-08-25 | Preparation method of carbon fiber precursor oil agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104179019A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104499098A (en) * | 2014-12-11 | 2015-04-08 | 桐乡市恒隆化工有限公司 | Filament finish emulsifier |
| CN104910388A (en) * | 2015-06-24 | 2015-09-16 | 吉林大学 | Polyol ester/polyether co-modified silicone oil and special oil agent for carbon fibers |
| CN107829306A (en) * | 2017-10-31 | 2018-03-23 | 中复神鹰碳纤维有限责任公司 | Covering property carbon fibre precursor finish and preparation method thereof |
| CN111139555A (en) * | 2019-12-26 | 2020-05-12 | 中复神鹰碳纤维有限责任公司 | High-heat-resistance oil agent and preparation method of polyacrylonitrile carbon fiber |
| CN111321599A (en) * | 2020-04-10 | 2020-06-23 | 江门市润祥纺织科技有限公司 | High-temperature-resistant alkali-resistant composite emulsifier for silicone oil emulsification and preparation method thereof |
| CN112424418A (en) * | 2019-05-30 | 2021-02-26 | 竹本油脂株式会社 | Treatment agent for carbon fiber precursor and carbon fiber precursor |
| CN112725941A (en) * | 2020-12-27 | 2021-04-30 | 中复神鹰碳纤维股份有限公司 | Carbon fiber precursor oiling agent capable of bearing high-power steam drafting |
| CN113677847A (en) * | 2019-10-07 | 2021-11-19 | 竹本油脂株式会社 | Aqueous liquid of treating agent for carbon fiber precursor, and carbon fiber precursor |
| CN113897708A (en) * | 2021-11-18 | 2022-01-07 | 中复神鹰碳纤维股份有限公司 | Oiling agent for polyacrylonitrile carbon fiber precursor and preparation method thereof |
| CN114075702A (en) * | 2020-08-19 | 2022-02-22 | 中国石油化工股份有限公司 | Protofilament oiling agent for producing polyacrylonitrile-based carbon fiber |
| CN114182532A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Polyacrylonitrile-based carbon fiber low-ash protofilament oiling agent |
| CN114941243A (en) * | 2022-03-18 | 2022-08-26 | 中复神鹰碳纤维股份有限公司 | Special oil agent for polyacrylonitrile-based carbon fiber and preparation method thereof |
| CN115679481A (en) * | 2022-09-08 | 2023-02-03 | 中复神鹰碳纤维股份有限公司 | Oil agent for polyacrylonitrile carbon fiber precursor with low friction coefficient and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280475A (en) * | 2008-05-21 | 2008-10-08 | 威海东方润德新材料有限公司 | Lubricating antistatic high-performance oil for drawing production of carbon fibre |
| JP4543931B2 (en) * | 2005-01-07 | 2010-09-15 | 東レ株式会社 | Silicone oil agent for carbon fiber precursor fiber, carbon fiber precursor fiber, flame resistant fiber, carbon fiber and method for producing the same |
| CN101876096A (en) * | 2009-11-26 | 2010-11-03 | 中复神鹰碳纤维有限责任公司 | Production method of proto-filament oiling agent in carbon fiber production process |
| CN103014922A (en) * | 2011-09-22 | 2013-04-03 | 中国科学院化学研究所 | Organosilicon spinning oil agent used for preparing polyacrylonitrile-based carbon fiber, and preparation method thereof |
-
2014
- 2014-08-25 CN CN201410420266.1A patent/CN104179019A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4543931B2 (en) * | 2005-01-07 | 2010-09-15 | 東レ株式会社 | Silicone oil agent for carbon fiber precursor fiber, carbon fiber precursor fiber, flame resistant fiber, carbon fiber and method for producing the same |
| CN101280475A (en) * | 2008-05-21 | 2008-10-08 | 威海东方润德新材料有限公司 | Lubricating antistatic high-performance oil for drawing production of carbon fibre |
| CN101876096A (en) * | 2009-11-26 | 2010-11-03 | 中复神鹰碳纤维有限责任公司 | Production method of proto-filament oiling agent in carbon fiber production process |
| CN103014922A (en) * | 2011-09-22 | 2013-04-03 | 中国科学院化学研究所 | Organosilicon spinning oil agent used for preparing polyacrylonitrile-based carbon fiber, and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杨铁军: "《产业专利分析报告（第14册）——高性能纤维》", 31 March 2013 * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104499098A (en) * | 2014-12-11 | 2015-04-08 | 桐乡市恒隆化工有限公司 | Filament finish emulsifier |
| CN104910388A (en) * | 2015-06-24 | 2015-09-16 | 吉林大学 | Polyol ester/polyether co-modified silicone oil and special oil agent for carbon fibers |
| CN104910388B (en) * | 2015-06-24 | 2017-06-20 | 吉林大学 | A kind of polyol ester/polyethers co-modified silicone oil and carbon fiber are oil solution dedicated |
| CN107829306A (en) * | 2017-10-31 | 2018-03-23 | 中复神鹰碳纤维有限责任公司 | Covering property carbon fibre precursor finish and preparation method thereof |
| CN107829306B (en) * | 2017-10-31 | 2020-04-10 | 中复神鹰碳纤维有限责任公司 | Coated carbon fiber precursor oiling agent and preparation method thereof |
| CN112424418B (en) * | 2019-05-30 | 2021-11-19 | 竹本油脂株式会社 | Treatment agent for carbon fiber precursor and carbon fiber precursor |
| CN112424418A (en) * | 2019-05-30 | 2021-02-26 | 竹本油脂株式会社 | Treatment agent for carbon fiber precursor and carbon fiber precursor |
| CN113677847A (en) * | 2019-10-07 | 2021-11-19 | 竹本油脂株式会社 | Aqueous liquid of treating agent for carbon fiber precursor, and carbon fiber precursor |
| CN111139555A (en) * | 2019-12-26 | 2020-05-12 | 中复神鹰碳纤维有限责任公司 | High-heat-resistance oil agent and preparation method of polyacrylonitrile carbon fiber |
| CN111139555B (en) * | 2019-12-26 | 2022-09-09 | 中复神鹰碳纤维股份有限公司 | High-heat-resistance oil agent and preparation method of polyacrylonitrile carbon fiber thereof |
| CN111321599A (en) * | 2020-04-10 | 2020-06-23 | 江门市润祥纺织科技有限公司 | High-temperature-resistant alkali-resistant composite emulsifier for silicone oil emulsification and preparation method thereof |
| CN114075702A (en) * | 2020-08-19 | 2022-02-22 | 中国石油化工股份有限公司 | Protofilament oiling agent for producing polyacrylonitrile-based carbon fiber |
| CN114075702B (en) * | 2020-08-19 | 2023-08-08 | 中国石油化工股份有限公司 | Precursor oiling agent for polyacrylonitrile-based carbon fiber production |
| CN114182532A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Polyacrylonitrile-based carbon fiber low-ash protofilament oiling agent |
| CN114182532B (en) * | 2020-09-14 | 2023-08-08 | 中国石油化工股份有限公司 | Polyacrylonitrile-based carbon fiber low-ash precursor oiling agent |
| CN112725941A (en) * | 2020-12-27 | 2021-04-30 | 中复神鹰碳纤维股份有限公司 | Carbon fiber precursor oiling agent capable of bearing high-power steam drafting |
| CN113897708A (en) * | 2021-11-18 | 2022-01-07 | 中复神鹰碳纤维股份有限公司 | Oiling agent for polyacrylonitrile carbon fiber precursor and preparation method thereof |
| CN114941243A (en) * | 2022-03-18 | 2022-08-26 | 中复神鹰碳纤维股份有限公司 | Special oil agent for polyacrylonitrile-based carbon fiber and preparation method thereof |
| CN115679481A (en) * | 2022-09-08 | 2023-02-03 | 中复神鹰碳纤维股份有限公司 | Oil agent for polyacrylonitrile carbon fiber precursor with low friction coefficient and preparation method thereof |
| CN115679481B (en) * | 2022-09-08 | 2023-08-08 | 中复神鹰碳纤维股份有限公司 | Oiling agent for polyacrylonitrile carbon fiber precursor with low friction coefficient and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104179019A (en) | Preparation method of carbon fiber precursor oil agent | |
| CN101876096B (en) | Production method of proto-filament oiling agent in carbon fiber production process | |
| CN107829306A (en) | Covering property carbon fibre precursor finish and preparation method thereof | |
| CN105019244B (en) | A kind of high-tenacity polyester yarn fiber and preparation method thereof | |
| TWI437028B (en) | Organo-functional silicone in emulsion systems and process for preparing same | |
| US5428089A (en) | Diorganopolysiloxane composition with excellent heat resistance | |
| CN105002603B (en) | A kind of super fine denier polyester fiber and preparation method thereof | |
| CN102776786A (en) | Non-emulsion type pure oiling agent for high speed spinning of polyamide-6 filaments | |
| JP2019515095A (en) | Modified polyester and method for producing the same | |
| CN105064042A (en) | Spinning oil for endowing polyurethane elastic fiber with unwinding property and preparation method of spinning oil | |
| CN105297446B (en) | A kind of carbon fiber oil preparation of non-silicon oil preparation/siliceous oil preparation compounding use and preparation method thereof | |
| CN105541126A (en) | Resin compatible type glass fiber yarn impregnation agent, and preparation method thereof | |
| CN115369649A (en) | Special oil for low-oil-smoke high-speed spinning of heat-humidity comfortable polyester fiber and preparation process thereof | |
| CN104562694A (en) | Super-low-shrinkage water-repellent polyester industrial yarn and preparation method thereof | |
| CN102432948B (en) | Antistatic resin | |
| JP2010174409A (en) | Oil agent for acrylic fiber for producing carbon fiber, and method for producing carbon fiber using the same | |
| CN111943527B (en) | Starch type impregnating compound for electronic yarn and preparation method and application thereof | |
| CN107190400B (en) | A kind of high intensity outdoor goods fabric | |
| CN105155016B (en) | A kind of super soft dense dye type polyester HOY fibers and preparation method thereof | |
| CN105064029B (en) | A kind of superbright light polyester DTY fiber and preparation method thereof | |
| CN116657286A (en) | Oil solution for ultrahigh-strength carbon fiber precursor and preparation method thereof | |
| JP2010174408A (en) | Oil agent for acrylic fiber for producing carbon fiber, and method for producing carbon fiber using the same | |
| CN111041585A (en) | Water-repellent polyester functional master batch and preparation method thereof | |
| CN106544760B (en) | A kind of carbon fibre precursor is oil solution dedicated and preparation method thereof | |
| CN108866713A (en) | A kind of cotton blended yarn and preparation method thereof of corrosion-resistant anti-aging PP fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141203 |