CN101876096B - Production method of proto-filament oiling agent in carbon fiber production process - Google Patents
Production method of proto-filament oiling agent in carbon fiber production process Download PDFInfo
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Abstract
The invention relates to a production method of proto-filament oiling agent in carbon fiber production process, which is characterized in that: the method comprises the following steps: a non-ionic surface active agent formulated matter is used as a complex emulsifying agent, the complex emulsifying agent is arranged in a vessel, the temperature is raised to 60-80 DEG C, the complex emulsifying agent is stirred uniformly and the temperature of the complex emulsifying agent is cooled to room temperature, so as to obtain faint yellow complex emulsifying agent; the complex emulsifying agent and auxiliaries are mixed uniformly, the mixture and modified silicone oil are added in a high-shearing silicone oil and are stirred uniformly, and then silicone oil is added dropwise in the mixture, and then the mixture is stirred pH value is regulated, and the obtained white emulsion is proto-filament oiling agent; the process is rational and the operation is simple. The oiling agent is permeated rapidly when being used, the lubricating property is good, fiber bundling property can be improved, the proto-filament oiling agent can be filmed on the monofilament surface, the proto-filament oiling agent is high-temperature resistant, and the agent is not roll-sticking in the drying densifying process, the fiber can be well protected in the whole pre-oxidation process and the low-temperature carbonization period, monofilament adhesion and doubling phenomenon is greatly reduced, surface defect of the fiber is reduced and the fiber performance is improved.
Description
Technical field
The present invention relates to a kind of production method of finish, the production method of proto-filament oiling agent in particularly a kind of carbon fiber production process.
Background technology
In the production process of carbon fiber, precursor production is the key link of generally acknowledging, the quality quality of precursor has conclusive effect with stable influence to the carbon fiber end properties.The production technology of precursor comprises polymerization, takes off single deaeration, spinning, oil, multiple working procedure such as drawing-off, wherein oiling process is again a ring very important in the precursor production process, and adhesion or the doubling between monofilament can take place in spinning process; Local overheated meeting causes localized heat adhesion or hot doubling initiation blemish between monofilament in preoxidation process; In the low-temperature carbonization process, a large amount of production of by-products be prone to produce between monofilament hot melt also, the blocking under warming phenomenon, the existence of these defectives all can reduce properties of carbon.And the existence meeting of finish protects fiber to avoid damage at the filament surface filming.So the quality of finish quality directly has influence on the quality of precursor, the character to carbon fiber has significant impact simultaneously.
The production of carbon fiber has strict requirement to spinning oil: good resistance to elevated temperatures, to guarantee playing boundling and the effect that prevents the precursor adhesion in pre-oxidation and low-temperature carbonization initial stage; The excellent antistatic ability is given good convergence of precursor and processability; Excellent lubrication property and antiseized isolation can play preventing that the monofilament adhesion is both fiber and is easy to out fibre, reduce lousiness and doubling odds; The fiber with excellent wettability is guaranteed to oil evenly, guarantees the homogeneity of precursor, carbon filament quality.
Be used for the used precursor finish of carbon fiber production at present and mainly contain two big types: one type is organic finish, is key component with the polyester of LCFA and polyalcohol and the ethylene oxide adduct of long-chain fat acid amides etc.; One type is to be the organosilicon finish of main component with the dimethyl silicone polymer.But organic finish is relatively poor in the effect of aspects such as heat resistance, lubricity and antiseized isolation, so the scope of application is very narrow; The organosilicon finish is being superior to organic finish aspect heat resistance, the lubricity; Used finish normally uses with the form of emulsion or aqueous dispersions in carbon fiber production process; But the dimethyl silicone polymer as the finish key component is water insoluble; Be difficult to make very stable aqueous emulsion, think that the production application of precursor finish has caused very big technology barrier.
Summary of the invention
Technical problem to be solved by this invention is the deficiency to prior art, and the production method of proto-filament oiling agent in the carbon fiber production process that a kind of technology is more reasonable, product is heat-resisting and greasy property is good is provided.
Technical problem to be solved by this invention is to realize through following technical scheme.The present invention is the production method of proto-filament oiling agent in a kind of carbon fiber production process, is characterized in, its step is following:
(1) get the non-ionic surface active agent compound and make compound emulsifying agent, compound emulsifying agent is placed in the container, the intensification degree is cooled to room temperature to 60-80 ℃ after stirring, and obtains faint yellow compound emulsifying agent; Described compound emulsifying agent is selected from following at least 2 kinds of emulsifying agents and is composited: alkylphenol-polyethenoxy type non-ionic surface active agent; The ethylene oxide adduct of polypropylene glycol; Polyoxyethylene sorbitan ester type non-ionic surface active agent, alkylolamides type non-ionic surface active agent;
(2) get compound emulsifying agent and auxiliary agent weight ratio mixing by 1-4: 0.1-3 after; With stirring in mixture and the weight ratio input high-shear emulsion machine of modified silicon oil by 1-3: 2-8; To wherein dripping deionized water, the control mixing speed is 6000-13000r/min again, stirs 30-90min; Regulating the pH value is 3-7, and the gained white emulsion is the precursor finish; Described auxiliary agent is antistatic additive and antifoaming agent, and the weight proportion of antistatic additive and antifoaming agent is 1-3: 1-2.
In above-described carbon fiber production process in the production method technical scheme of proto-filament oiling agent:
1, in the described compound emulsifying agent, the mixed proportion of various emulsifying agents can add as required in right amount, and the percentage by weight that preferred every kind of emulsifying agent accounts for compound emulsifying agent is greater than 10%;
2, described modified silicon oil can be disclosed any modified silicon oil applicable to carbon fibre precursor in the prior art; Preferred amino-modified silicone oil, epoxide modified silicone oil or polyether modified silicon oil; Can use wherein a kind of; Also can use the mixture of 2 kinds or 3 kinds compositions wherein, when selecting the modified silicon oil mixture for use, preferred every kind of content accounts at least 30% of modified silicon oil total content;
3, the preferred modification ammonia of described amino-modified silicone oil mass fraction is calculated as 0.001-0.05 with end envelope ammonia-NH2, and viscosity is preferably 1000-5000cst; The preferred modification amount of described epoxide modified silicone oil is calculated as 0.001-0.05 with epoxy radicals-CHCH2O, and viscosity is preferably 2000-10000cst; The preferred modification amount of described polyether modified silicon oil is between 0.2-0.7, and viscosity is preferably 300-1000cst.
4, described antistatic additive can be disclosed any antistatic additive applicable to carbon fibre precursor in the prior art; At least a in preferred polyethylene glycol oxide alkylamine or its ester class, sorbitan fatty acid ester, cithrol or the polyoxyethylene laurate; The mixture that also can use at least 2 persons to form, and its mixed proportion can be any.
5, described antifoaming agent can be disclosed any antifoaming agent applicable to carbon fibre precursor in the prior art; At least a in preferred isoamyl alcohol, diisobutyl carbinol (DIBC), ethylenedistearamide or the tributyl phosphate; The mixture that also can use at least 2 persons to form, and its mixed proportion can be any.
6, regulate the used conditioning agent of pH value and can be disclosed any conditioning agent in the prior art applicable to carbon fibre precursor; At least a in preferred glacial acetic acid, oxalic acid, formic acid or the citric acid; The mixture that also can use at least 2 persons to form, and its mixed proportion can be any.
Technical problem to be solved by this invention can also further realize through following technical scheme.
The inventive method technology is reasonable, and is simple to operate, can directly apply on the industrial production line.The quick permeation when finish of processing with the inventive method uses, lubricity is good, can improve collection of filaments property; Can be in the monofilament surface film forming, high temperature resistant, roll banding not in the compacting by drying process; Can be in whole preoxidation process and the low-temperature carbonization initial stage protect fiber well, greatly reduce monofilament adhesion and doubling phenomenon, reduced the blemish of fiber; Improved the performance of fiber, and can all vaporize, can not pollute burner hearth and fiber in the low-temperature carbonization later stage.The inventive method raw material sources are abundant, and cost is lower, can at room temperature operate, and is applicable to suitability for industrialized production.
The specific embodiment
Below further describe concrete technical scheme of the present invention,, and do not constitute restriction its right so that those skilled in the art understands the present invention further.
Embodiment 1.The production method of proto-filament oiling agent in a kind of carbon fiber production process, its step is following:
(1) get the non-ionic surface active agent compound and make compound emulsifying agent, compound emulsifying agent is placed in the container, intensification degree to 60 ℃ is cooled to room temperature after stirring, and obtains faint yellow compound emulsifying agent; Described compound emulsifying agent is selected from following 2 kinds of emulsifying agents and is composited: alkylphenol-polyethenoxy type non-ionic surface active agent; The ethylene oxide adduct of polypropylene glycol; Polyoxyethylene sorbitan ester type non-ionic surface active agent, alkylolamides type non-ionic surface active agent;
(2) get compound emulsifying agent and auxiliary agent by 1: 0.1 weight ratio mixing after; Mixture and modified silicon oil dropped in the high-shear emulsion machine by 1: 8 weight ratio stir; To wherein dripping deionized water, the control mixing speed is 6000r/min again, stirs 30min; Regulating the pH value is 3, and the gained white emulsion is the precursor finish; Described auxiliary agent is antistatic additive and antifoaming agent, and the weight proportion of antistatic additive and antifoaming agent is 1: 2.
Embodiment 2.The production method of proto-filament oiling agent in a kind of carbon fiber production process, its step is following:
(1) get the non-ionic surface active agent compound and make compound emulsifying agent, compound emulsifying agent is placed in the container, intensification degree to 80 ℃ is cooled to room temperature after stirring, and obtains faint yellow compound emulsifying agent; Described compound emulsifying agent is selected from following 3 kinds of emulsifying agents and is composited: alkylphenol-polyethenoxy type non-ionic surface active agent; The ethylene oxide adduct of polypropylene glycol; Polyoxyethylene sorbitan ester type non-ionic surface active agent, alkylolamides type non-ionic surface active agent;
(2) get compound emulsifying agent and auxiliary agent by 4: 3 weight ratio mixing after; Mixture and modified silicon oil dropped in the high-shear emulsion machine by 3: 8 weight ratio stir; To wherein dripping deionized water, the control mixing speed is 13000r/min again, stirs 90min; Regulating the pH value is 7, and the gained white emulsion is the precursor finish; Described auxiliary agent is antistatic additive and antifoaming agent, and the weight proportion of antistatic additive and antifoaming agent is 3: 1.
Embodiment 3.The production method of proto-filament oiling agent in a kind of carbon fiber production process, its step is following:
(1) get the non-ionic surface active agent compound and make compound emulsifying agent, compound emulsifying agent is placed in the container, intensification degree to 70 ℃ is cooled to room temperature after stirring, and obtains faint yellow compound emulsifying agent; Described compound emulsifying agent is selected from following 4 kinds of emulsifying agents and is composited: alkylphenol-polyethenoxy type non-ionic surface active agent; The ethylene oxide adduct of polypropylene glycol; Polyoxyethylene sorbitan ester type non-ionic surface active agent, alkylolamides type non-ionic surface active agent;
(2) get compound emulsifying agent and auxiliary agent by 1: 1 weight ratio mixing after; Mixture and modified silicon oil dropped in the high-shear emulsion machine by 2: 5 weight ratio stir; To wherein dripping deionized water, the control mixing speed is 10000r/min again, stirs 60min; Regulating the pH value is 5, and the gained white emulsion is the precursor finish; Described auxiliary agent is antistatic additive and antifoaming agent, and the weight proportion of antistatic additive and antifoaming agent is 4: 3.
Embodiment 4.The production method of proto-filament oiling agent in a kind of carbon fiber production process, its step is following:
(1) get the non-ionic surface active agent compound and make compound emulsifying agent, compound emulsifying agent is placed in the container, intensification degree to 65 ℃ is cooled to room temperature after stirring, and obtains faint yellow compound emulsifying agent; Described compound emulsifying agent is selected from following any 2 kinds of emulsifying agents and is composited: alkylphenol-polyethenoxy type non-ionic surface active agent; The ethylene oxide adduct of polypropylene glycol; Polyoxyethylene sorbitan ester type non-ionic surface active agent, alkylolamides type non-ionic surface active agent;
(2) get compound emulsifying agent and auxiliary agent by 1: 3 weight ratio mixing after; Mixture and modified silicon oil dropped in the high-shear emulsion machine by 1: 2 weight ratio stir; To wherein dripping deionized water, the control mixing speed is 8000r/min again, stirs 50min; Regulating the pH value is 4, and the gained white emulsion is the precursor finish; Described auxiliary agent is antistatic additive and antifoaming agent, and the weight proportion of antistatic additive and antifoaming agent is 1: 1.
Embodiment 5.The production method of proto-filament oiling agent in a kind of carbon fiber production process, its step is following:
(1) get the non-ionic surface active agent compound and make compound emulsifying agent, compound emulsifying agent is placed in the container, intensification degree to 75 ℃ is cooled to room temperature after stirring, and obtains faint yellow compound emulsifying agent; Described compound emulsifying agent is selected from following 2 kinds of emulsifying agents and is composited: alkylphenol-polyethenoxy type non-ionic surface active agent; The ethylene oxide adduct of polypropylene glycol; Polyoxyethylene sorbitan ester type non-ionic surface active agent, alkylolamides type non-ionic surface active agent;
(2) get compound emulsifying agent and auxiliary agent by 1: 3 weight ratio mixing after; Mixture and modified silicon oil dropped in the high-shear emulsion machine by 3: 2 weight ratio stir; To wherein dripping deionized water, the control mixing speed is 11000r/min again, stirs 70min; Regulating the pH value is 6, and the gained white emulsion is the precursor finish; Described auxiliary agent is antistatic additive and antifoaming agent, and the weight proportion of antistatic additive and antifoaming agent is 3: 2.
Embodiment 6.In any one described production method of embodiment 1-5, in the described compound emulsifying agent, the percentage by weight that every kind of emulsifying agent accounts for compound emulsifying agent is greater than 10%.
Embodiment 7.In any one described production method of embodiment 1-6, described modified silicon oil is selected from a kind in amino-modified silicone oil, epoxide modified silicone oil or the polyether modified silicon oil.
Embodiment 8.In any one described production method of embodiment 1-6, described modified silicon oil is selected from the mixture of 2 kinds of compositions in amino-modified silicone oil, epoxide modified silicone oil or the polyether modified silicon oil, and its mixed proportion is 1: 1.
Embodiment 9.In any one described production method of embodiment 1-6, described modified silicon oil is selected from the mixture of 3 kinds of compositions in amino-modified silicone oil, epoxide modified silicone oil or the polyether modified silicon oil, and its mixed proportion is 1: 1: 1.
Embodiment 10.In any one described production method of embodiment 1-6, described modified silicon oil is selected from the mixture of 2 kinds of compositions in amino-modified silicone oil, epoxide modified silicone oil or the polyether modified silicon oil, and its mixed proportion is 1: 2.
Embodiment 11.In any one described production method of embodiment 1-6, described modified silicon oil is selected from the mixture of 2 kinds or 3 kinds compositions in amino-modified silicone oil, epoxide modified silicone oil or the polyether modified silicon oil, and every kind of (weight) content all is not less than 30% of total content.
Embodiment 12.In any one described production method of embodiment 7-11, the modification ammonia mass fraction of described amino-modified silicone oil is calculated as 0.001-0.05 with end envelope ammonia-NH2, and viscosity is 1000-5000cst; The modification amount of described epoxide modified silicone oil is calculated as 0.001-0.05 with epoxy radicals-CHCH2O, and viscosity is 2000-10000cst; The modification amount of described polyether modified silicon oil is between 0.2-0.7, and viscosity is 300-1000cst.
Embodiment 13.In any one described production method of embodiment 1-12; Described antistatic additive is selected from a kind or 2 kinds or 3 kinds or 4 kinds in polyethylene glycol oxide alkylamine or its ester class, sorbitan fatty acid ester, cithrol or the polyoxyethylene laurate; When selecting for use mixture to make antistatic additive, its mixed proportion can be arbitrary proportion.
Embodiment 14.In any one described production method of embodiment 1-13; Described antifoaming agent is selected from a kind or 2 kinds or 3 kinds or 4 kinds in isoamyl alcohol, diisobutyl carbinol (DIBC), ethylenedistearamide or the tributyl phosphate; When selecting for use mixture to make antifoaming agent, its mixed proportion can be arbitrary proportion.
Embodiment 15.In any one described production method of embodiment 1-14, regulate the used conditioning agent of pH value and be selected from a kind or 2 kinds or 3 kinds or 4 kinds in glacial acetic acid, oxalic acid, formic acid or the citric acid, when selecting for use mixture to make conditioning agent, its mixed proportion can be arbitrary proportion.
Experimental example 1.Alkylphenol-polyethenoxy type non-ionic surface active agent mixes by weight 1: 2 with the ethylene oxide adduct of polypropylene glycol, is warming up to 70 ℃, after stirring; Be cooled to room temperature and obtain faint yellow transparent compound emulsifying agent, compound emulsifying agent and auxiliary agent add the mechanical agitation mixing by 1: 0.1 part by weight; Mixture and amino-modified silicone oil add the high-shear emulsion machine high-speed stirred by 1: 3 part by weight, and mixing speed is 10000r/min, begin to drip water behind the stirring 30min; When taking place, phase inversion stops to add water; Continue to stir, phase inversion finishes the back and drips remaining water, continues to stir 30min; Using glacial acetic acid to regulate the pH value is 5.6, obtains white amino-modified silicone oil emulsion uniformly.
It is stable to get in the centrifuge of the amino-modified silicone oil emulsion 4000r/min that makes centrifugal 30min, no demulsifying phenomenon; Room temperature was placed one month, and is stable; Measuring the silicone oil emulsion surface tension is 30mN/m, and thin up to concentration is 3% to oil, and the precursor oil content is 0.54%, and oxygen silk hair fracture of wire is few in advance, does not have molten stickingly, and the test of T300 grade carbon fiber TENSILE STRENGTH is 3.84GPa.
Experimental example 2.Alkylphenol-polyethenoxy type non-ionic surface active agent and polyoxyethylene sorbitan ester type non-ionic surface active agent were mixed by weight 5: 6, be warming up to 70 ℃, after stirring, be cooled to room temperature and obtain faint yellow transparent compound emulsifying agent; Compound emulsifying agent and auxiliary agent are pressed 1: 0.5 part by weight adding mixing, and mixture and amino-modified silicone oil add by 1: 2 part by weight, and high-shear emulsion machine is carried out emulsification; Mixing speed is 10000r/min, begins to drip water behind the stirring 15min, stops to add water when phase inversion takes place; Continue to stir, phase inversion finishes the back and drips remaining water, continues to stir 30min; Using glacial acetic acid to regulate the pH value is 4.8, obtains white amino-modified silicone oil emulsion uniformly.
It is stable to get in the centrifuge of the amino-modified silicone oil emulsion 4000r/min that makes centrifugal 30min, no demulsifying phenomenon, and room temperature was placed one month, and is stable, and mensuration silicone oil emulsion surface tension is 31mN/m; Thin up to concentration is 4.5% to oil, and the precursor oil content is 1.7%, and oxygen silk hair fracture of wire is few in advance, does not have molten stickingly, and the test of T300 grade carbon fiber TENSILE STRENGTH is 3.76GPa.
Experimental example 3.Alkylphenol-polyethenoxy type non-ionic surface active agent and alkylolamides type non-ionic surface active agent were mixed by weight 1: 5, be warming up to 70 ℃, after stirring, be cooled to room temperature and obtain faint yellow transparent compound emulsifying agent; Compound emulsifying agent and auxiliary agent add by 1: 0.1 part by weight, the mechanical agitation mixing, and compound and epoxide modified silicone oil add by 1: 2 part by weight; High-shear emulsion machine is carried out emulsification, and mixing speed is 10000r/min, begins to drip water behind the stirring 30min; Stop to add water when phase inversion takes place, continue to stir, phase inversion finishes the back and drips remaining water; Continue to stir 30min, using glacial acetic acid to regulate the pH value is 4.8, obtains the uniform epoxide modified silicone oil emulsion of white.
Get the epoxide modified silicone oil emulsion room temperature that makes and place a week; Stable, measuring the silicone oil emulsion surface tension is 42mN/m, and thin up to concentration is 5% to oil; The precursor oil content is 0.8%; The oxygen silk has a little lousiness, fracture of wire in advance, and molten slightly sticking, the test of T300 grade carbon fiber TENSILE STRENGTH is 3.50GPa.
Experimental example 4.The ethylene oxide adduct and the polyoxyethylene sorbitan ester type non-ionic surface active agent of polypropylene glycol were mixed by weight 1: 6, be warming up to 70 ℃, after stirring, be cooled to room temperature and obtain faint yellow transparent compound emulsifying agent; Compound emulsifying agent and auxiliary agent add by 1: 0.5 part by weight, the mechanical agitation mixing, and mixture and epoxide modified silicone oil add by 1: 3 part by weight; High-shear emulsion machine is carried out emulsification, and mixing speed is 10000r/min, begins to drip water behind the stirring 30min; Stop to add water when phase inversion takes place, continue to stir, phase inversion finishes the back and drips remaining water; Continue to stir 30min, using glacial acetic acid to regulate the pH value is 5.2, obtains the uniform epoxide modified silicone oil emulsion of white.
The epoxide modified silicone oil emulsion room temperature that makes is placed a week; Stable, measuring the silicone oil emulsion surface tension is 45mN/m, and thin up to concentration is 4.5% to oil; The precursor oil content is 0.6%; Lousiness, fracture of wire appear in the oxygen silk in advance, and molten sticking phenomenon is arranged, and the test of T300 grade carbon fiber TENSILE STRENGTH is 3.45GPa.
Experimental example 5.The ethylene oxide adduct of polypropylene glycol is mixed by weight 1: 3 with alkylolamides type non-ionic surface active agent, be warming up to 80 ℃, after stirring, be cooled to room temperature and obtain faint yellow transparent compound emulsifying agent; Compound emulsifying agent and auxiliary agent are pressed 1: 0.2 part by weight adding mixing, and mixture and polyether modified silicon oil add by 1: 2 part by weight, and high-shear emulsion machine is carried out emulsification; Mixing speed is 8000r/min, begins to drip water behind the stirring 20min, stops to add water when phase inversion takes place; Continue to stir, phase inversion finishes the back and drips remaining water, continues to stir 30min; Using glacial acetic acid to regulate the pH value is 5.6, obtains white polyether modified silicon oil emulsion uniformly.
Centrifugal 30min in the centrifuge of prepared polyether modified silicon oil emulsion 4000r/min is stable, no demulsifying phenomenon, room temperature was placed one month; Stable, measuring the silicone oil emulsion surface tension is 28mN/m, and thin up to concentration is 3.0% to oil; The precursor oil content is 0.8%; Oxygen silk hair fracture of wire is few in advance, does not have molten gluing, and the test of T300 grade carbon fiber TENSILE STRENGTH is 3.81GPa.
Experimental example 6.Other presses 1: 0.2 part by weight adding mixing with experimental example 1 with compound emulsifying agent and auxiliary agent, and mixture and polyether modified silicon oil add by 1: 4 part by weight; High-shear emulsion machine is carried out emulsification, and mixing speed is 8000r/min, begins to drip water behind the stirring 30min; Stop to add water when phase inversion takes place, continue to stir, phase inversion finishes the back and drips remaining water; Continue to stir 30min, using glacial acetic acid to regulate the pH value is 5.0, obtains white polyether modified silicon oil emulsion uniformly.
It is stable to get in the centrifuge of polyether modified silicon oil emulsion 4000r/min centrifugal 30min, no demulsifying phenomenon, room temperature placement one month; Stable, measuring the silicone oil emulsion surface tension is 28mN/m, and thin up to concentration is 3.5% to oil; The precursor oil content is 1.1%; Oxygen silk hair fracture of wire is few in advance, does not have molten gluing, and the test of T300 grade carbon fiber TENSILE STRENGTH is 3.69GPa.
Experimental example 7.Other presses 1: 0.2 part by weight adding mixing with experimental example 2 with compound emulsifying agent and auxiliary agent, and amino-modified silicone oil and epoxide modified silicone oil mixed by weight 1: 1; Mixture and modified silicon oil mixture add by 1: 2 part by weight, and high-shear emulsion machine is carried out emulsification, and mixing speed is 12000r/min; Begin to drip water after stirring 30min, stop to add water when phase inversion takes place, continue to stir; Phase inversion finishes the back and drips remaining water; Continue to stir 30min, using glacial acetic acid to regulate the pH value is 4.7, obtains the uniform mixed and modified silicone oil emulsion of white.
It is stable to get in the centrifuge of mixed and modified silicone oil emulsion 4000r/min centrifugal 30min, has a little deposition to separate out, and room temperature is placed a week; Demulsifying phenomenon is arranged, and measuring the silicone oil emulsion surface tension is 48mN/m, and thin up to concentration is 6% to oil; The precursor oil content is 1.2%; Lousiness, fracture of wire appear in the oxygen silk in advance, occur adhesion between the monofilament, and the test of T300 grade carbon fiber TENSILE STRENGTH is 3.42GPa.
Experimental example 8.Other presses 1: 0.2 part by weight adding mixing with experimental example 3 with compound emulsifying agent and auxiliary agent, and amino-modified silicone oil and polyether modified silicon oil mixed by weight 1: 1; Mixture and modified silicon oil mixture add by 1: 2 part by weight, and high-shear emulsion machine is carried out emulsification, and mixing speed is 12000r/min; Begin to drip water after stirring 30min, stop to add water when phase inversion takes place, continue to stir; Phase inversion finishes the back and drips remaining water; Continue to stir 30min, using glacial acetic acid to regulate the pH value is 5.3, obtains the uniform mixed and modified silicone oil emulsion of white.
It is stable to get in the centrifuge of mixed and modified silicone oil emulsion 4000r/min centrifugal 30min, and room temperature is placed a week, and is stable; Measuring the silicone oil emulsion surface tension is 38mN/m; Thin up to concentration is 5% to oil, and the precursor oil content is 1.15%, and the oxygen silk does not have lousiness, fracture of wire in advance; Do not have adhesion between the monofilament, the test of T300 grade carbon fiber TENSILE STRENGTH is 3.81GPa.
Claims (8)
1. the production method of proto-filament oiling agent in the carbon fiber production process is characterized in that its step is following:
(1) get the non-ionic surface active agent compound and make compound emulsifying agent, compound emulsifying agent is placed in the container, the intensification degree is cooled to room temperature to 60-80 ℃ after stirring, and obtains faint yellow compound emulsifying agent; Described compound emulsifying agent is selected from following at least 2 kinds of emulsifying agents and is composited: alkylphenol-polyethenoxy type non-ionic surface active agent; The ethylene oxide adduct of polypropylene glycol; Polyoxyethylene sorbitan ester type non-ionic surface active agent, alkylolamides type non-ionic surface active agent;
(2) get compound emulsifying agent and auxiliary agent weight ratio mixing by 1-4: 0.1-3 after; With stirring in mixture and the weight ratio input high-shear emulsion machine of modified silicon oil by 1-3: 2-8; To wherein dripping deionized water, the control mixing speed is 6000-13000r/min again, stirs 30-90min; Regulating the pH value is 3-7, and the gained white emulsion is the precursor finish; Described auxiliary agent is antistatic additive and antifoaming agent, and the weight proportion of antistatic additive and antifoaming agent is 1-3: 1-2.
2. production method according to claim 1 is characterized in that, in the described compound emulsifying agent, the percentage by weight that every kind of emulsifying agent accounts for compound emulsifying agent is greater than 10%.
3. production method according to claim 1 is characterized in that described modified silicon oil is selected from one or more in amino-modified silicone oil, epoxide modified silicone oil or the polyether modified silicon oil.
4. production method according to claim 3 is characterized in that, the modification ammonia mass fraction of described amino-modified silicone oil is with end envelope ammonia-NH
2Be calculated as 0.001-0.05, viscosity is 1000-5000cst; The modification amount of described epoxide modified silicone oil is with epoxy radicals-CHCH
2O is calculated as 0.001-0.05, and viscosity is 2000-10000cst; The modification amount of described polyether modified silicon oil is between 0.2-0.7, and viscosity is 300-1000cst.
5. according to claim 3 or 4 described production methods, it is characterized in that described modified silicon oil is selected from least 2 kinds in amino-modified silicone oil, epoxide modified silicone oil or the polyether modified silicon oil, and every kind of content accounts at least 30% of modified silicon oil total content.
6. production method according to claim 1 is characterized in that, described antistatic additive is selected from least a in polyethylene glycol oxide alkylamine, sorbitan fatty acid ester, cithrol or the polyoxyethylene laurate.
7. production method according to claim 1 is characterized in that, described antifoaming agent is selected from least a in isoamyl alcohol, diisobutyl carbinol (DIBC), ethylenedistearamide or the tributyl phosphate.
8. production method according to claim 1 is characterized in that, regulates the used conditioning agent of pH value and is selected from least a in glacial acetic acid, oxalic acid, formic acid or the citric acid.
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| 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 |
| JP6798734B1 (en) * | 2020-02-12 | 2020-12-09 | 竹本油脂株式会社 | Treatment agent for carbon fiber precursor, carbon fiber precursor, and method for producing flame-resistant fiber |
| CN113338041A (en) * | 2021-06-29 | 2021-09-03 | 江苏品和石油科技有限公司 | Production and preparation method of novel emulsifier for spinning oil |
| TWI763566B (en) * | 2021-07-23 | 2022-05-01 | 臺灣塑膠工業股份有限公司 | Manufacturing method for carbon fiber |
| CN114232139A (en) * | 2021-12-16 | 2022-03-25 | 连云港神鹰复合材料科技有限公司 | Preparation method of carbon fiber oil for dry-jet wet-spun precursor |
| CN114214841B (en) * | 2021-12-17 | 2023-05-23 | 开封大学 | Heat-resistant antistatic carbon fiber oiling agent, and preparation and application thereof |
| CN114622417B (en) * | 2022-03-21 | 2023-05-30 | 中复神鹰碳纤维股份有限公司 | Carbon fiber oiling agent capable of being rapidly crosslinked into film |
| 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 |
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| 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 |
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106868616A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | The method that fiber oils |
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Address after: 222000 No.6 Yunqiao Road, Dapu Industrial Zone, Lianyungang Economic and Technological Development Zone, Jiangsu Province Patentee after: Zhongfu Shenying Carbon Fiber Co.,Ltd. Address before: 222000 No.6 Yunqiao Road, Dapu Industrial Zone, Lianyungang Economic and Technological Development Zone, Jiangsu Province Patentee before: ZHONGFU SHENYING CARBON FIBER Co.,Ltd. |