CN103031619A - Small tows PAN-based carbon fiber precursor oiling agent - Google Patents
Small tows PAN-based carbon fiber precursor oiling agent Download PDFInfo
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- CN103031619A CN103031619A CN2011102942634A CN201110294263A CN103031619A CN 103031619 A CN103031619 A CN 103031619A CN 2011102942634 A CN2011102942634 A CN 2011102942634A CN 201110294263 A CN201110294263 A CN 201110294263A CN 103031619 A CN103031619 A CN 103031619A
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- silicone polymer
- dimethyl silicone
- carbon fiber
- modified dimethyl
- amino
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Abstract
The present invention relates to a small tows PAN-based carbon fiber precursor oiling agent, and is mainly to solve the problem that a large amount of emulsifier is used in a carbon fiber precursor oiling agent, causing that the heat resistance of the oiling agent is poor in the using process in the prior art. A technical solution is used by the invention to solve the problem well. The small tows PAN-based carbon fiber precursor oiling agent comprises the following components by weight: a) 40-60 parts of amino-modified polydimethylsiloxane A; b) 5-20 parts of amino-modified poly-dimethylsiloxane B; c) 10-30 parts of polyether-modified polydimethylsiloxane; and d) 5-20 parts of an emulsifier. The agent can be used in the industrial production of small tows PAN-based carbon fiber precursor.
Description
Technical field
The present invention relates to a kind of little tow PAN base carbon fiber protofilament finish.
Background technology
Carbon fiber is used widely at space flight, aviation and automobile, building, light industry etc. with its excellent performance as the fortifying fibre of composite of new generation.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 prepare the PAN base carbon fibre with following operation: to carry out the spinning process that one-step method or two-step method spinning obtain carbon fibre precursor as the PAN polymer; Be that precursor carries out pre-oxidation in 200～400 ℃ the oxidisability atmosphere in temperature, 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, for prevent between the filament that heating is bonding, the friction of fiber and mechanical surface, cause fibre pick, fracture of wire and surface damage, need use PAN base carbon fiber protofilament finish.
Chinese patent ZL200580044949.0 embodiment 2 discloses a kind of carbon fibre precursor finish, and it is comprised of the amino-modified silicone oil of 100 weight portions and alkylphenol polyoxyethylene and the 8.8 weight portion KM902 (SHIN-ETSU HANTOTAI's chemical industry (strain) system) of 30 weight portions.Wherein 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 to exist carbon fibre precursor large with emulsifier in the finish in the prior art, causes the in use problem of poor heat resistance of finish, and a kind of new little tow PAN base carbon fiber protofilament finish is provided.It is few that this finish has an emulsifier, the advantage of finish good heat resistance in the 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 little tow PAN base carbon fiber protofilament finish 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 are 4000～8000; Amino modified dimethyl silicone polymer B is 500mm 25 ℃ viscosity
2/ s～4000mm
2/ s, amino equivalent are 1000～3000; Described polyether-modified dimethyl silicone polymer is 400mm 25 ℃ viscosity
2/ s～1000mm
2/ s, HLB are 4.0～10.0; Described emulsifying agent is taken from least a in the material group that is 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 the alkylphenol is 12～16.
In the technique scheme, described amino modified dimethyl silicone polymer A and amino modified dimethyl silicone polymer B are replaced the compound that obtains for terminal a part of side chain with dimethyl-silicon of methyl by the amino of following chemical formula (I) expression; Described polyether-modified dimethyl silicone polymer is replaced the compound that obtains for terminal a part of side chain with dimethyl-silicon of methyl by the polyether-based of following chemical formula (II) expression:
—CH
2—CH
2—NH—CH
2—CH
2—NH
2 (I)
The preferred HLB value of polyether-modified dimethyl silicone polymer described in the technique scheme is 4-5; Described amino modified dimethyl silicone polymer A preferable range is 60mm for the viscosity in the time of 25 ℃
2/ s～150mm
2/ s, amino equivalent are 4500～6000; Described amino modified dimethyl silicone polymer B preferable range is 1000mm for the viscosity in the time of 25 ℃
2/ s～3000mm
2/ s, amino equivalent are 1500～2000; Described emulsifying agent preferred fat alcohol polyoxyethylene ether; Described emulsifying agent is take parts by weight consumption preferable range as 10-15 part.
Finish of the present invention can also comprise other components well known to those skilled in the art.For example have bactericidal effect in order to give finish, be conducive to long term storage and not corrupt, can comprise bactericide in the finish of the present invention, such as benzalkonium bromide, nipalgin etc.; Has better antistatic effect in order to give finish, finish of the present invention can also comprise antistatic additive commonly used, 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, the betaine type amphoteric antistatic additive; Finish of the present invention uses 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 described amino modified dimethyl silicone polymer A of 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 comprising water in the prescription, then stir the lower entry that progressively adds after preferably first other components being mixed, 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 use step of finish of the present invention is as follows:
(1) with the concentration adjustment of finish emulsion in the finishing bathtray and maintain 0.5～3.0wt%
Can directly use when finish of the present invention is the emulsion form of 0.5-3.0wt%, otherwise need under agitation add the water of amount of calculation, used water is preferably used deionized water.
(2) under 30-50 ℃, condition of normal pressure, be impregnated in the finish emulsion in the step (1) with the carbon fibre precursor through densification 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, can obtain carbon fiber through super-dry, pre-oxidation, carbonization and other processes successively.
Key problem in technology of the present invention is two kinds of amino modified dimethyl silicone polymers having used amino equivalent different in the oil formula, dwindled the 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 preferably technique effect.
The present invention is further elaborated below by embodiment.
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 mixed 30 minutes in required ratio in the composite still of finish, taking by weighing the finish that 1g mixes is placed in the aluminium crucible, and in 105 ℃ of baking ovens, process 5h, be the 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.At first under the 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 mixed in the 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 the laurate polyoxyethylene ether surface active agent; In embodiment 2, emulsifying agent adopts the nonyl phenol polyoxyethylene ether surface active agent; In embodiment 3-10, emulsifying agent adopts the fatty alcohol-polyoxyethylene ether surfactant.
The concrete component of each embodiment sees Table 1, and the content of each component sees Table 2, and evaluation result sees Table 3.Can be found out that by evaluation result little tow PAN base carbon fiber protofilament finish of the present invention has clear improvement than stability of emulsion and the heat resistance of prior art, its heat-resisting residual mass fraction improves more than 20% than prior art.
[comparative example 1]
In comparative example 11, 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 the finish total surfactant is 22wt%; Amino-modified silicone oil is 3500mm 25 ℃ of lower kinematic viscosity
2/ s, amino equivalent are 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 (7)
1. one kind little tow PAN base carbon fiber protofilament finish 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 are 4000～8000; Amino modified dimethyl silicone polymer B is 500mm 25 ℃ viscosity
2/ s～4000mm
2/ s, amino equivalent are 1000～3000; Described polyether-modified dimethyl silicone polymer is 400mm 25 ℃ viscosity
2/ s～1000mm
2/ s, HLB are 4.0～10.0; Described emulsifying agent is taken from least a in the material group that is 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 the alkylphenol is 12～16.
2. described 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 are replaced the compound that obtains for terminal a part of side chain with dimethyl-silicon of methyl by the amino of following represented by formula I; Described polyether-modified dimethyl silicone polymer is replaced the compound that obtains for terminal a part of side chain with dimethyl-silicon of methyl by the polyether-based that following Formulae II represents:
—CH
2—CH
2—NH—CH
2—CH
2—NH
2 (I)
3. 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. little tow PAN base carbon fiber protofilament finish according to claim 1 is characterized in that the viscosity of described amino modified dimethyl silicone polymer A in the time of 25 ℃ is 60mm
2/ s～150mm
2/ s, amino equivalent are 4500～6000.
5. little tow PAN base carbon fiber protofilament finish according to claim 1 is characterized in that the viscosity of described amino modified dimethyl silicone polymer B in the time of 25 ℃ is 1000mm
2/ s～3000mm
2/ s, amino equivalent are 1500～2000.
6. little tow PAN base carbon fiber protofilament finish according to claim 1 is characterized in that described emulsifying agent is fatty alcohol-polyoxyethylene ether.
7. little tow PAN base carbon fiber protofilament finish according to claim 1 is characterized in that described emulsifying agent is take the parts by weight consumption as 10-15 part.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110294263.4A CN103031619B (en) | 2011-09-30 | 2011-09-30 | Small tows PAN-based carbon fiber precursor oiling agent |
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|---|---|---|---|
| CN201110294263.4A CN103031619B (en) | 2011-09-30 | 2011-09-30 | Small tows PAN-based carbon fiber precursor oiling agent |
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| CN103031619A true CN103031619A (en) | 2013-04-10 |
| CN103031619B CN103031619B (en) | 2014-12-10 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN115787147A (en) * | 2022-11-30 | 2023-03-14 | 上海丰泽源科技有限公司 | Oiling agent for polyacrylonitrile-based carbon fiber precursor and preparation method thereof |
| CN116103790A (en) * | 2022-11-18 | 2023-05-12 | 北京宝冠助剂有限公司 | Heat-resistant and high-compatibility carbon fiber precursor oiling agent and preparation method thereof |
Citations (2)
| 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 |
| JP2008063705A (en) * | 2006-09-11 | 2008-03-21 | Mitsubishi Rayon Co Ltd | Lubricant for acrylic fiber as carbon fiber precursor |
-
2011
- 2011-09-30 CN CN201110294263.4A patent/CN103031619B/en active Active
Patent Citations (2)
| 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 |
| JP2008063705A (en) * | 2006-09-11 | 2008-03-21 | Mitsubishi Rayon Co Ltd | Lubricant for acrylic fiber as carbon fiber precursor |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN116103790A (en) * | 2022-11-18 | 2023-05-12 | 北京宝冠助剂有限公司 | Heat-resistant and high-compatibility carbon fiber precursor oiling agent and preparation method thereof |
| CN116103790B (en) * | 2022-11-18 | 2023-09-22 | 北京宝冠助剂有限公司 | Heat-resistant and high-compatibility carbon fiber precursor oiling agent and preparation method thereof |
| CN115787147A (en) * | 2022-11-30 | 2023-03-14 | 上海丰泽源科技有限公司 | Oiling agent for polyacrylonitrile-based carbon fiber precursor and preparation method thereof |
| CN115787147B (en) * | 2022-11-30 | 2024-05-17 | 上海丰泽源科技有限公司 | Oiling agent for polyacrylonitrile-based carbon fiber precursor and preparation method thereof |
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| CN103031619B (en) | 2014-12-10 |
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