CN103031734B - Preparation method of oiling agent for small-filament-bundle PAN-based carbon fiber precursor - Google Patents
Preparation method of oiling agent for small-filament-bundle PAN-based carbon fiber precursor Download PDFInfo
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- CN103031734B CN103031734B CN201110301144.7A CN201110301144A CN103031734B CN 103031734 B CN103031734 B CN 103031734B CN 201110301144 A CN201110301144 A CN 201110301144A CN 103031734 B CN103031734 B CN 103031734B
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- silicone polymer
- dimethyl silicone
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Abstract
The invention relates to a preparation method of an oiling agent for a small-filament-bundle PAN-based carbon fiber precursor, and the method is mainly used for solving the problem that the oiling agent emulsion for the PAN-based carbon fiber precursor in the prior art is easily subjected to layering during the storage and transportation process and cannot be re-stabilized by utilizing means such as stirring and shearing. The technical scheme adopted by the invention is as follows: according to the preparation method of the oiling agent for the PAN-based carbon fiber precursor, a 70-90wt% oiling agent emulsion is prepared from water and the oiling agent, wherein the 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 preparation method can be used in the storage and transportation process of the oiling agent for the small-filament-bundle PAN-based carbon fiber precursor.
Description
Technical field
The present invention relates to a kind of preparation method of little tow PAN base carbon fiber protofilament finish.
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 the performance of its excellence.Little tow polyacrylonitrile-based carbon fibre (hereinafter referred to as little tow PAN base carbon fibre) is the one of function admirable in numerous carbon fiber, is the critical material needed for strategic missile, satellite, aerospace craft, large aircraft etc.Little tow PAN base carbon fibre refers to that tow is less than the PAN base carbon fibre of 24K.
Industrially prepare PAN base carbon fibre using following procedures: to the spinning process carrying out one-step method or two-step method spinning as PAN polymer and obtain carbon fibre precursor; Be that in the oxidation atmosphere of 200 ~ 400 DEG C, precursor carries out pre-oxidation in temperature, obtain preoxided thread; And be this preoxided thread of carbonization in 400 ~ 2000 DEG C of inert gases in temperature, change into the carbonation process of carbon fiber.In above-mentioned spinning technique, in order to prevent between filament heating bonding, fiber and the friction of mechanical surface, causing fibre pick, fracture of wire and surface damage, needing use PAN base carbon fiber protofilament finish.
Chinese patent ZL200580044949.0 embodiment 2 discloses a kind of preparation method of carbon fibre precursor finish, and it is made up of the alkylphenol polyoxyethylene of the amino-modified silicone oil of 100 weight portions, 30 weight portions, 8.8 weight portion KM902 (SHIN-ETSU HANTOTAI's chemical industry (strain) system) and 4000 weight parts waters.Wherein water consumption is comparatively large, can cause the easy layering of finish emulsion, and finish emulsion is once occur layering, the problem that finish emulsion cannot be made again stable by means such as stirring, shearings in transporting procedures.
Summary of the invention
Technical problem to be solved by this invention is the PAN base carbon fiber protofilament finish emulsion easy layering in transporting procedures existed in prior art, the problem that finish emulsion cannot be made again stable by means such as stirring, shearings, a kind of preparation method of little tow PAN base carbon fiber protofilament finish is newly provided, the finish emulsion that the method obtains has good stability once there is finish emulsion layering, can make its again stable advantage by methods such as stirring shearings.
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 preparation method of little tow PAN base carbon fiber protofilament finish, with water, finish is mixed with the finish emulsion that weight concentration is 70-90%, wherein said finish is counted by weight and is comprised following component:
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 wherein said viscosity of amino modified dimethyl silicone polymer A 25 DEG C time is 50mm
2/ s ~ 250mm
2/ s, amino equivalent is 4000 ~ 8000; Amino modified dimethyl silicone polymer B is 500mm the viscosity of 25 DEG C
2/ s ~ 4000mm
2/ s, amino equivalent is 1000 ~ 3000; Described polyether-modified dimethyl silicone polymer is 400mm the viscosity of 25 DEG C
2/ s ~ 1000mm
2/ s, HLB are 4.0 ~ 10.0; At least one in the material group be made up of fatty alcohol-polyoxyethylene ether, aliphatic acid polyethenoxy ether, polyoxyethylene alkylphenol ether taken from by described emulsifying agent, 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 is that a part of side chain that end has a dimethyl-silicon of methyl is replaced by the amino that following chemical formula (I) represents the compound obtained; Described polyether-modified dimethyl silicone polymer is that a part of side chain that end has a dimethyl-silicon of methyl is replaced by the polyether-based that following chemical formula (II) represents the compound obtained:
-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 the viscosity 25 DEG C time is 60mm
2/ s ~ 150mm
2/ s, amino equivalent is 4500 ~ 6000; Described amino modified dimethyl silicone polymer B preferable range is the viscosity 25 DEG C time is 1000mm
2/ s ~ 3000mm
2/ s, amino equivalent is 1500 ~ 2000; Described emulsifying agent preferred fat alcohol polyoxyethylene ether; Described emulsifier with weight parts preferable range for 10-15 part.
The finish that the inventive method obtains can also comprise other components well known to those skilled in the art.Such as in order to give finish, there is bactericidal effect, being conducive to long term storage and not corrupt, bactericide can also be comprised in finish of the present invention, 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, the anionic antistatic agents such as such as alkyl phosphoric acid ester ammonium salt, alkyl phosphate diethanolamine salt, alkyl phosphate triethanolamine salt, the cationic antistatic agent such as octadecyldimethyl ethoxy quaternary ammonium nitrate, betaine type amphoteric antistatic additive; Finish of the present invention uses with the form of aqueous dispersion, and in order to easy to use, this finish can also comprise water.
The preparation method of described PAN base carbon fiber protofilament finish for: 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, then under agitation progressively add water, the weight concentration of finish emulsion is mixed with 70-90%.The finish emulsion working concentration that the inventive method obtains is generally 0.5-3.0wt%.
The step that oils of the finish that the inventive method obtains is as follows:
(1) concentration of finish emulsion in finishing bathtray is adjusted and maintains 0.5 ~ 3.0wt%.
(2) 30-50 DEG C, under condition of normal pressure, be impregnated into the carbon fibre precursor through densification in the finish emulsion in step (1) and oil to carbon fibre precursor.
One skilled in the art will appreciate that the precursor processed through above-mentioned steps (1) and (2), can carbon fiber be obtained through super-dry, pre-oxidation, carbonization and other processes successively.
Key of the present invention is only to have added the water of 10-30wt% in finish preparation process, the emulsion of the stable two-arch tunnel structure between O/W and W/O may be defined, once there is layering, it can be made again to stablize by methods such as stirring shearings, be particularly suitable for the storing of little tow PAN base carbon fiber protofilament finish.Two kinds of amino modified dimethyl silicone polymers that amino equivalent is different are employed in oil formula, reduce emulsification gradient, reduce the consumption of emulsifying agent, thus improve the heat resistance of finish, heat-resisting residual mass mark improves more than 20% than prior art, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1 ~ 10]
Amino modified for component dimethyl silicone polymer A, amino modified dimethyl silicone polymer B, polyether-modified dimethyl silicone polymer and emulsifying agent are uniformly mixed 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 5h is processed in 105 DEG C of baking ovens, be absolute dry condition.Accurate weighing above-mentioned over dry finish 15mg-20mg, is placed in the aluminium crucible of TGA (thermogravimetric analysis), surveys its heat-resisting residual mass mark.First under moving air state, be heated to 240 DEG C, and keep 60min, record heat-resisting residual mass mark r1; And then switch atmosphere (switching to nitrogen by air), in nitrogen atmosphere, be heated to 450 DEG C, and keep 30s, record heat-resisting residual mass mark r2.Total heat-resisting residual mass mark r=r1 × r2.
Amino modified for component dimethyl silicone polymer A, amino modified dimethyl silicone polymer B, polyether-modified dimethyl silicone polymer and emulsifying agent are uniformly mixed 30 minutes in required ratio in the composite still of finish, are mixed with the finish emulsion that weight concentration is 70-90%.The finish emulsion prepared is put into the static placement of 100ml vial, observe emulsion and place the stability after 72 hours and the stability after 1 month.If emulsion has lamination, again stir 30 minutes, then observe the stability of the static placement of emulsion after 72 hours.
In embodiment 1, emulsifying agent adopts laurate polyoxyethylene ether surface active agent; In example 2, emulsifying agent adopts polyoxyethylene nonylphenol ether (6) 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 finish heat resistance evaluation result is in table 3, and finish emulsion stability performance evaluation result is in table 4.Can be found out by evaluation result, 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 mark improves more than 20% than prior art.
[comparative example 1 ~ 3]
In comparative example 1, oil formula is with embodiment 1; In comparative example 2, oil formula is with embodiment 5; In comparative example 3, oil formula is with embodiment 10.
[comparative example 4]
In comparative example 4, adopt the oil formula that Chinese patent ZL200580044949.0 embodiment 2 provides.Wherein, amino modified silicon 100 weight portion, emulsifying agent (polyoxyethylene nonylphenol ether (6)) 30 weight portions, KM902 (SHIN-ETSU HANTOTAI's chemical industry (strain) system) 8.8 weight portions, the 1.2 parts of emulsifying agents added in order to emulsification KM902, the percetage by weight that emulsification dosage accounts for finish total surfactant is 22wt%; Amino-modified silicone oil kinematic viscosity at 25 DEG C is 3500mm
2/ s, amino equivalent is 2000.Measuring the heat-resisting residual mass mark of finish in the absence of water, depositing the stability of observing emulsion in case there being 4000 parts of water.
The character of the key component of table 1 finish of the present invention
The composition of table 2 finish of the present invention
Table 3 finish heat resistance is evaluated
| Total heat-resisting residual mass mark r | Heat-resisting residual mass mark improves % than prior art | |
| Embodiment 1 | 0.50 | 25 |
| Embodiment 2 | 0.61 | 52 |
| Embodiment 3 | 0.53 | 32 |
| Embodiment 4 | 0.52 | 30 |
| Embodiment 5 | 0.54 | 35 |
| Embodiment 6 | 0.59 | 47 |
| Embodiment 7 | 0.50 | 25 |
| Embodiment 8 | 0.63 | 57 |
| Embodiment 9 | 0.59 | 47 |
| Embodiment 10 | 0.56 | 40 |
| Comparative example 1 | 0.40 | - |
Table 4 finish emulsion stability performance is evaluated
Claims (5)
1. a preparation method for little tow PAN base carbon fiber protofilament finish, with water, finish is mixed with the finish emulsion that weight concentration is 70-90%, wherein said finish is counted composed as follows 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 wherein said viscosity of amino modified dimethyl silicone polymer A 25 DEG C time is 60mm
2/ s ~ 150mm
2/ s, amino equivalent is 4500 ~ 6000; Amino modified dimethyl silicone polymer B is 1000mm the viscosity of 25 DEG C
2/ s ~ 3000mm
2/ s, amino equivalent is 1500 ~ 2000; Described polyether-modified dimethyl silicone polymer is 400mm the viscosity of 25 DEG C
2/ s ~ 1000mm
2/ s, HLB are 4.0 ~ 10.0; At least one in the material group be made up of fatty alcohol-polyoxyethylene ether, aliphatic acid polyethenoxy ether, polyoxyethylene alkylphenol ether taken from by described emulsifying agent, its ethoxymer distribution is 3 ~ 8, and the carbon number in its fatty alcohol, aliphatic acid or alkylphenol is 12 ~ 16.
2. the preparation method of little tow PAN base carbon fiber protofilament finish according to claim 1, is characterized in that described amino modified dimethyl silicone polymer A and amino modified dimethyl silicone polymer B is that a part of side chain that end has a dimethyl-silicon of methyl is replaced the compound obtained by the amino of following represented by formula I; Described polyether-modified dimethyl silicone polymer is that a part of side chain that end has a dimethyl-silicon of methyl is replaced by the polyether-based that following Formulae II represents the compound obtained:
-CH
2-CH
2-NH-CH
2-CH
2-NH
2(I)、
3. the preparation method of little tow PAN base carbon fiber protofilament finish according to claim 1, is characterized in that the HLB value of described polyether-modified dimethyl silicone polymer is 4-5.
4. the preparation method of little tow PAN base carbon fiber protofilament finish according to claim 1, is characterized in that described emulsifying agent is fatty alcohol-polyoxyethylene ether.
5. the preparation method of little tow PAN base carbon fiber protofilament finish according to claim 1, is characterized in that described emulsifier counts 10-15 part with parts by weight.
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| JP7021071B2 (en) * | 2016-03-30 | 2022-02-16 | 松本油脂製薬株式会社 | Acrylic fiber treatment agent and its uses |
| 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 |
| CN113445324A (en) * | 2021-06-30 | 2021-09-28 | 中复神鹰碳纤维西宁有限公司 | Carbon fiber oil agent suitable for alpine regions |
| 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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| 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 |
| 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 |
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| JP4801546B2 (en) * | 2006-09-11 | 2011-10-26 | 三菱レイヨン株式会社 | Oil agent for carbon fiber precursor acrylic fiber |
| JP4856724B2 (en) * | 2007-11-07 | 2012-01-18 | 三菱レイヨン株式会社 | Oil agent composition for carbon fiber precursor acrylic fiber, carbon fiber precursor acrylic fiber bundle, and method for producing the same |
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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 |
| 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 |
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