CN103031623B - Method for oiling small-filament-bundle PAN-based carbon fiber precursor - Google Patents
Method for oiling small-filament-bundle PAN-based carbon fiber precursor Download PDFInfo
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- CN103031623B CN103031623B CN201110300939.6A CN201110300939A CN103031623B CN 103031623 B CN103031623 B CN 103031623B CN 201110300939 A CN201110300939 A CN 201110300939A CN 103031623 B CN103031623 B CN 103031623B
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- silicone polymer
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- dimethyl silicone
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Abstract
The invention relates to a method for oiling a small-filament-bundle PAN-based carbon fiber precursor, and the method is mainly used for solving the problem that an oiling agent has poor heat resistance during the use process caused by that the adopted oiling agent for the carbon fiber precursor in the prior art is large in emulsifying agent dosage. The technical scheme adopted by the invention is as follows: under the conditions of temperature of 30-50 DEG C and normal pressure, soaking compacted PAN-based carbon fiber precursor with a filament bundle of less than 24K by utilizing a 0.5-3.0wt% oiling agent, wherein the used oiling agent comprises the following components in parts by weight: a) 40-60 parts of amido modified dimethyl polysiloxane A, b) 5-20 parts of amido modified dimethyl polysiloxane B, c) 10-30 parts of polyether modified dimethyl polysiloxane and d) 5-20 parts of emulsifying agent, so that the problem in the prior art is well solved. The method can be used in the industrial production of the small-filament-bundle PAN-based carbon fiber precursor.
Description
Technical field
The present invention relates to a kind of method that oils of little tow PAN base carbon fiber protofilament.
Background technology
Carbon fiber, as the fortifying fibre of composite of new generation, is used widely at space flight, aviation and automobile, building, light industry etc. with its excellent performance.Little tow polyacrylonitrile-based carbon fibre (hereinafter to be referred as little tow PAN base carbon fibre) is good a kind of of numerous carbon fiber performances, is the required critical materials such as strategic missile, satellite, aerospace craft, large aircraft.Little tow PAN base carbon fibre refers to that tow is less than the PAN base carbon fibre of 24K.
Industrially using following operation and prepare PAN base carbon fibre: to carry out the spinning process that one-step method or two-step method spinning obtain carbon fibre precursor as PAN polymer; In temperature, be that in the oxidisability atmosphere of 200～400 ℃, precursor carries out pre-oxidation, obtain preoxided thread; And be this preoxided thread of carbonization in 400～2000 ℃ of inert gases in temperature, change into the carbonation process of carbon fiber.In above-mentioned spinning technique, the friction of, fiber bonding in order to prevent from generating heat between filament and mechanical surface, causes fibre pick, fracture of wire and surface damage, need to use PAN base carbon fiber protofilament finish.
Chinese patent ZL200580044949.0 embodiment 2 discloses a kind of method that oils of carbon fibre precursor, the amino-modified silicone oil of 100 weight portions and the alkylphenol polyoxyethylene of 30 weight portions and 8.8 weight portion KM902 (SHIN-ETSU HANTOTAI's chemical industry (strain) system) finish will be consisted of, with 4000 parts of water, be made into finish emulsion, carbon fibre precursor stretches after 3 times in the warm water of 70 ℃, make again it pass through during finish that the finish by above-mentioned preparation forms bathes, by infusion process, to oil.During finish that it adopts forms, alkylphenol polyoxyethylene is non-ionic surface active agent, can play the effect of emulsifying agent, and its large usage quantity in use can cause the problem of finish poor heat resistance.
Summary of the invention
Technical problem to be solved by this invention is that the carbon fibre precursor of the employing that exists in prior art is large with emulsifier in finish, causes the in use problem of poor heat resistance of finish, and a kind of method that oils of new little tow PAN base carbon fiber protofilament is provided.It is few that the finish that the method adopts has emulsifier, the advantage of finish good heat resistance in use procedure.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that oils of little tow PAN base carbon fiber protofilament, under 30-50 ℃, condition of normal pressure, the PAN base carbon fiber protofilament that 0.5～3.0wt% finish emulsion dipping tow after densification is less than to 24K, wherein finish used comprises following component in parts by weight:
A) the amino modified dimethyl silicone polymer A of 40-60 part;
B) the amino modified dimethyl silicone polymer B of 5-20 part;
C) the polyether-modified dimethyl silicone polymer of 10-30 part;
D) 5-20 part emulsifying agent;
The viscosity of wherein said amino modified dimethyl silicone polymer A in the time of 25 ℃ is 50mm
2/ s～250mm
2/ s, amino equivalent is 4000～8000; Amino modified dimethyl silicone polymer B is 500mm2/s～4000mm the viscosity of 25 ℃
2/ s, amino equivalent is 1000～3000; Described polyether-modified dimethyl silicone polymer is 400mm the viscosity of 25 ℃
2/ s～1000mm
2/ s, HLB is 4.0～10.0; Described emulsifying agent is taken from least one in the material group being comprised of fatty alcohol-polyoxyethylene ether, aliphatic acid polyethenoxy ether, polyoxyethylene alkylphenol ether, its ethoxymer distribution is 3～8, and the carbon number in its fatty alcohol, aliphatic acid or alkylphenol is 12～16.
In technique scheme, described amino modified dimethyl silicone polymer A and amino modified dimethyl silicone polymer B are that the amino that a part of side chain of the end dimethyl-silicon with methyl is represented by following chemical formula (I) replaces the compound obtaining; Described polyether-modified dimethyl silicone polymer is that the polyether-based that a part of side chain of the end dimethyl-silicon with methyl is represented by following chemical formula (II) replaces the compound obtaining:
-CH
2-CH
2-NH-CH
2-CH
2-NH
2 (I)
The preferred HLB value of polyether-modified dimethyl silicone polymer described in technique scheme is 4-5; Described amino modified dimethyl silicone polymer A preferable range is that the viscosity in the time of 25 ℃ is 60mm
2/ s～150mm
2/ s, amino equivalent is 4500～6000; Described amino modified dimethyl silicone polymer B preferable range is that the viscosity in the time of 25 ℃ is 1000mm
2/ s～3000mm
2/ s, amino equivalent is 1500～2000; Described emulsifying agent preferred fat alcohol polyoxyethylene ether; Described emulsifier be take parts by weight preferable range as 10-15 part.
The finish adopting in the inventive method can also comprise other components well known to those skilled in the art.For example in order to give finish, there is bactericidal effect, be conducive to long term storage and not corrupt, in finish of the present invention, can also comprise bactericide, such as benzalkonium bromide, nipalgin etc.; In order to give finish, there is better antistatic effect, finish of the present invention can also comprise conventional antistatic additive, such as anionic antistatic agents such as alkyl phosphoric acid ester ammonium salt, alkyl phosphate diethanolamine salt, alkyl phosphate triethanolamine salts, the cationic antistatic additive such as octadecyl dimethyl ethoxy quaternary ammonium nitrate, betaine type amphoteric antistatic additive; Finish of the present invention is used with the form of aqueous dispersion, and for easy to use, this finish can also comprise water.
The preparation method of described little tow PAN base carbon fiber protofilament finish is: the amino modified dimethyl silicone polymer A described in finish of the present invention, amino modified dimethyl silicone polymer B, polyether-modified dimethyl silicone polymer and emulsifying agent and bactericide and antistatic additive etc. are stirred.When formula comprises water, then under stirring after preferably first other components being mixed, progressively add water, be beneficial to make more uniform emulsion, the maximum adding quantity of water is to make the concentration of finish emulsion be not less than working concentration, and the emulsion working concentration of finish of the present invention is generally 0.5-3.0wt%.
The present invention's method step that oils is as follows:
(1) by the concentration adjustment of finish emulsion in finishing bathtray and maintain 0.5～3.0wt%
When emulsion form that finish of the present invention is 0.5-3.0wt%, can directly use, otherwise need under agitation add the water of amount of calculation, water used is preferably used deionized water.
(2), under 30-50 ℃, condition of normal pressure, with the carbon fibre precursor through densification, be impregnated in the finish emulsion in step (1) and oil to carbon fibre precursor.
One skilled in the art will appreciate that through the precursor of above-mentioned steps (1) and (2) processing, through super-dry, pre-oxidation, carbonization and other processes, can obtain carbon fiber successively.
In the oil formula that the key problem in technology of the inventive method is to use, two kinds of different amino modified dimethyl silicone polymers of amino equivalent have been used, dwindled emulsification gradient, reduced the consumption of emulsifying agent, thereby improved the heat resistance of finish, heat-resisting residual mass fraction improves more than 20% than prior art, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[embodiment 1～10]
The amino modified dimethyl silicone polymer A of component, amino modified dimethyl silicone polymer B, polyether-modified dimethyl silicone polymer and emulsifying agent are uniformly mixed to 30 minutes in required ratio in the composite still of finish, taking the finish that 1g is uniformly mixed is placed in aluminium crucible, and process 5h in 105 ℃ of baking ovens, be over dry state.The above-mentioned over dry finish of accurate weighing 15mg-20mg, is placed in the aluminium crucible of TGA (thermogravimetric analysis), surveys its heat-resisting residual mass fraction.First under moving air state, be heated to 240 ℃, and keep 60min, record heat-resisting residual mass fraction r1; And then switch atmosphere (switching to nitrogen by air), in nitrogen atmosphere, be heated to 450 ℃, and keep 30s, record heat-resisting residual mass fraction r2.Total heat-resisting residual mass fraction r=r1 * r2.
The amino modified dimethyl silicone polymer A of component, amino modified dimethyl silicone polymer B, polyether-modified dimethyl silicone polymer and emulsifying agent are uniformly mixed in 100ml beaker in required ratio, then when stirring, progressively add normal temperature deionization pure water, be mixed with the emulsion of 10.0wt% concentration, static placement 72hr, the stability of observing emulsion.Emulsion stability is not stratified, is judged as, and emulsion has lamination, is judged as bad.
In embodiment 1, emulsifying agent adopts laurate polyoxyethylene ether surface active agent; In embodiment 2, emulsifying agent adopts polyoxyethylene nonylphenol ether surfactant; In embodiment 3-10, emulsifying agent adopts fatty alcohol-polyoxyethylene ether surfactant.
The concrete component of each embodiment is in Table 1, and the content of each component is in Table 2, and evaluation result is in Table 3.By evaluation result, can be found out, little tow PAN base carbon fiber protofilament finish of the present invention has clear improvement than the stability of emulsion of prior art and heat resistance, and its heat-resisting residual mass fraction improves more than 20% than prior art.
[comparative example 1]
In comparative example 1, the oil formula that adopts Chinese patent ZL200580044949.0 embodiment 2 to provide.Wherein, amino modified silicon 100 weight portions, emulsifying agent (polyoxyethylene nonylphenol ether (6)) 30 weight portions, KM902 (SHIN-ETSU HANTOTAI's chemical industry (strain) system) 8.8 weight portions, 1.2 parts of emulsifying agents that add for emulsification KM902, the percetage by weight that emulsification dosage accounts for finish total surfactant is 22wt%; Amino-modified silicone oil kinematic viscosity at 25 ℃ is 3500mm
2/ s, amino equivalent is 2000.
The character of the key component of table 1 finish of the present invention
The composition of table 2 finish of the present invention
The evaluation of table 3 oil performance
Claims (5)
1. the method that oils of one kind little tow PAN base carbon fiber protofilament, under 30-50 ℃, condition of normal pressure, the PAN base carbon fiber protofilament that 0.5～3.0wt% finish emulsion dipping tow after densification is less than to 24K, wherein finish used is composed as follows in parts by weight:
A) the amino modified dimethyl silicone polymer A of 40-60 part;
B) the amino modified dimethyl silicone polymer B of 5-20 part;
C) the polyether-modified dimethyl silicone polymer of 10-30 part;
D) 5-20 part emulsifying agent;
The viscosity of wherein said amino modified dimethyl silicone polymer A in the time of 25 ℃ is 60mm
2/ s～150mm
2/ s, amino equivalent is 4500～6000; Amino modified dimethyl silicone polymer B is 1000mm the viscosity of 25 ℃
2/ s～3000mm
2/ s, amino equivalent is 1500～2000; Described polyether-modified dimethyl silicone polymer is 400mm the viscosity of 25 ℃
2/ s～1000mm
2/ s, HLB is 4.0～10.0; Described emulsifying agent is taken from least one in the material group being comprised of fatty alcohol-polyoxyethylene ether, aliphatic acid polyethenoxy ether, polyoxyethylene alkylphenol ether, its ethoxymer distribution is 3～8, and the carbon number in its fatty alcohol, aliphatic acid or alkylphenol is 12～16.
2. the method that oils of according to claim 1 little tow PAN base carbon fiber protofilament, is characterized in that described amino modified dimethyl silicone polymer A and amino modified dimethyl silicone polymer B are that a part of side chain of the end dimethyl-silicon with methyl is replaced the compound obtaining by the amino of following represented by formula I; Described polyether-modified dimethyl silicone polymer is that the polyether-based that a part of side chain of the end dimethyl-silicon with methyl is represented by following Formulae II replaces the compound obtaining:
-CH
2-CH
2-NH-CH
2-CH
2-NH
2 (I)、
3. the method that oils of little tow PAN base carbon fiber protofilament according to claim 1, the HLB value that it is characterized in that described polyether-modified dimethyl silicone polymer is 4-5.
4. the method that oils of little tow PAN base carbon fiber protofilament according to claim 1, is characterized in that described emulsifying agent is fatty alcohol-polyoxyethylene ether.
5. the method that oils of little tow PAN base carbon fiber protofilament according to claim 1, is characterized in that described emulsifier counts 10-15 part with parts by weight.
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|---|---|---|---|
| CN201110300939.6A CN103031623B (en) | 2011-09-30 | 2011-09-30 | Method for oiling small-filament-bundle PAN-based carbon fiber precursor |
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| CN103031623B true CN103031623B (en) | 2014-11-26 |
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| CN101091010A (en) * | 2004-12-27 | 2007-12-19 | 东丽株式会社 | Oil agent for carbon fiber precursor fiber, carbon fiber and method for producing carbon fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101091010A (en) * | 2004-12-27 | 2007-12-19 | 东丽株式会社 | Oil agent for carbon fiber precursor fiber, carbon fiber and method for producing carbon fiber |
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