CN103122585A - Oiling agent of large tow PAN (Polyacrylonitrile)-based carbon fiber precursors - Google Patents
Oiling agent of large tow PAN (Polyacrylonitrile)-based carbon fiber precursors Download PDFInfo
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- CN103122585A CN103122585A CN2011103699565A CN201110369956A CN103122585A CN 103122585 A CN103122585 A CN 103122585A CN 2011103699565 A CN2011103699565 A CN 2011103699565A CN 201110369956 A CN201110369956 A CN 201110369956A CN 103122585 A CN103122585 A CN 103122585A
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- carbon fiber
- dimethyl silicone
- silicone polymer
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Abstract
The invention relates to an oiling agent of large tow PAN (Polyacrylonitrile)-based carbon fiber precursors, which mainly aims at solving the problem in the prior art that an oiling agent for carbon fiber precursors is poor in antistatic property, and thus the possibility of low full-package rate is high. The technical scheme for solving the problem well is that an oiling agent for the large tow PAN based carbon fiber precursors is a mixture of V and W at the mixed weight ratio of 3:(1-3), wherein the V comprises the following components in parts by weight: 5 to 20 parts of amino modified polydimethylsiloxane A, 40 to 60 parts of amino modified polydimethylsiloxane B, 10 to 30 parts of polyether modified polydimethylsiloxane, and 5 to 20 parts of an emulsifying agent; and the W is an epoxy adduct of an amide compound which is obtained from reaction of diethylenetriamine and stearic acid. The oiling agent can be applied to industrial production of the large tow PAN-based carbon fiber precursors.
Description
Technical field
The present invention relates to a kind of large 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.Large tow polyacrylonitrile-based carbon fibre (hereinafter to be referred as large 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.Along with the develop rapidly of sky way, the demand of large tow (greater than 24K) PAN base carbon fibre has obtained swift and violent raising.
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 in the oxidisability atmosphere of 200～400 ℃, precursor carries out pre-oxidation 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 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.This finish antistatic behaviour is poor, easily causes the low problem of full-rolling rate.
Summary of the invention
Technical problem to be solved by this invention is to exist carbon fibre precursor poor with antistatic behaviour in finish in prior art, easily cause the low problem of full-rolling rate, a kind of new large tow PAN base carbon fiber protofilament finish is provided, and this finish has advantages of that in use procedure, the finish antistatic behaviour is good, full-rolling rate is high.
As follows for solving the problems of the technologies described above the technical solution used in the present invention: a kind of large tow PAN base carbon fiber protofilament finish, be the mixture of V and W, V is V: W=3 with the mixed weight ratio of W: 1～3; V comprises following component in parts by weight:
A) 5～20 parts of amino modified dimethyl silicone polymer A;
B) 40～60 parts of amino modified dimethyl silicone polymer B;
C) 10～30 parts of polyether-modified dimethyl silicone polymers;
D) 5～20 parts of emulsifying agents;
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 the viscosity of 25 ℃
2/ s～4000mm
2/ s, amino equivalent are 1000～3000; Described polyether-modified dimethyl silicone polymer is 400mm the viscosity of 25 ℃
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 alkylphenol is 12～16;
W is the epoxy radicals addition product that diethylenetriamine and stearic acid react the amide compound that gets, the synthetic method of the epoxy radicals addition product of described amide compound is: take p-methyl benzenesulfonic acid as catalyst, 1mol diethylenetriamine and 2mol stearic acid were reacted 5 hours under 200～220 ℃, get amide compound, then carry out with 10mol oxirane the epoxy radicals addition product W that addition reaction gets amide compound.
Amino modified dimethyl silicone polymer A described in technique scheme and amino modified dimethyl silicone polymer B are that a part of side chain of the dimethyl-silicon of end with methyl is replaced by the amino of following chemical formula (I) expression the compound that obtains; Described polyether-modified dimethyl silicone polymer is that a part of side chain of the dimethyl-silicon of end with methyl is replaced by the polyether-based of following chemical formula (II) expression the compound that obtains:
-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 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 emulsifier preferable range is 10～15 parts.
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 finish of the present invention, such as benzalkonium bromide, nipalgin etc.; 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 PAN base carbon fiber protofilament finish is: the amino modified dimethyl silicone polymer A in the described component V of finish of the present invention, amino modified dimethyl silicone polymer B, polyether-modified dimethyl silicone polymer and emulsifying agent and bactericide etc. are stirred.When V comprises water, then progressively add entry under stirring after preferably first its active principle 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 the 0.5-3.0 % by weight.The described component W of finish of the present invention is added water, then heat stirring and dissolving, make the emulsion concentration the same with component V, at last component V emulsion and component W emulsion are under agitation mixed, the mixing ratio of V and W is V: W=3: 1-3.
The use step of finish of the present invention is as follows:
(1) with the concentration adjustment of finish emulsion in finishing bathtray and maintain 0.5～3.0 % by weight
Can directly use when finish of the present invention is the emulsion form of 0.5-3.0 % by weight, 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, be impregnated in finish emulsion in 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 to have used in oil formula the epoxy radicals addition product of antistatic good amide compound, improved the antistatic behaviour (the ratio resistance that is carbon fibre precursor descends) of tow, improved full-rolling rate, experimental result shows, the ratio resistance of comparative example is 3 * 10
9Ω cm, full-rolling rate are only 65%, and of the present invention than resistance approximately 1 order of magnitude that descends, full-rolling rate has been obtained technique effect preferably greater than 73%, can be used in the industrial production of large tow PAN base carbon fiber protofilament.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1～10]
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.
The evaluation of antistatic property.The YG321 fiber of producing with Co., Ltd of Changzhou Textile Machinery Plant No.2 is than resistance instrument, and adopting oil content is the PAN base carbon fiber protofilament of the 36K of 1 % by weight, measures the ratio resistance of fiber with the method for GB/T14342-93, and evaluation result sees Table 3.
The spinnability that represents the PAN base carbon fiber protofilament with full-rolling rate.The test condition of full-rolling rate is, adopt the PAN base carbon fiber protofilament of 500 ton/years to produce evaluating apparatus, be the PAN base carbon fiber protofilament of the 36K of 1 % by weight with oil content, reel with the winding speed of 200 m/mins, reach 30 kilograms as full volume take PAN base carbon fiber protofilament winding weight.Fracture of wire occurs in winding process namely to be obtained rolling up less than curled hair, fracture of wire does not occur in winding process obtain full curled hair volume, the computing formula of full-rolling rate is: full-rolling rate=[full curled hair volume number/(less than curled hair volume number+full curled hair volume number)] * 100%.Evaluation result sees Table 3.
[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 (Nonyl pheno base 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 22 % by weight; Amino-modified silicone oil is 3500mm 25 ℃ of lower kinematic viscosity
2/ s, amino equivalent are 2000.
Except the finish that adopts comparative example 1, the evaluation of antistatic property and the test of full-rolling rate the results are shown in Table 3 with embodiment 1～10.
Ratio resistance data from table 3 can find out, the antistatic property of large tow PAN base carbon fiber protofilament finish of the present invention has clear improvement than prior art.
Full-rolling rate data from table 3 can find out, the tow full-rolling rate of large tow PAN base carbon fiber protofilament finish of the present invention is significantly improved than prior art, has spinnability preferably.
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
| Carbon fibre precursor is than resistance, Ω cm | Full-rolling rate % | |
| Embodiment 1 | 8×10 8 | 75 |
| Embodiment 2 | 8×10 8 | 76 |
| Embodiment 3 | 8×10 8 | 73 |
| Embodiment 4 | 6×10 8 | 80 |
| Embodiment 5 | 5×10 8 | 85 |
| Embodiment 6 | 3×10 8 | 90 |
| Embodiment 7 | 3×10 8 | 93 |
| Embodiment 8 | 1×10 8 | 98 |
| Embodiment 9 | 9×10 7 | 95 |
| Embodiment 10 | 7×10 7 | 94 |
| Comparative example 1 | 3×10 9 | 65 |
Claims (7)
1. a large tow PAN base carbon fiber protofilament finish, be the mixture of V and W, and V is V: W=3 with the mixed weight ratio of W: 1～3; V comprises following component in parts by weight:
A) 5～20 parts of amino modified dimethyl silicone polymer A;
B) 40～60 parts of amino modified dimethyl silicone polymer B;
C) 10～30 parts of polyether-modified dimethyl silicone polymers;
D) 5～20 parts of emulsifying agents;
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 the viscosity of 25 ℃
2/ s～4000mm
2/ s, amino equivalent are 1000～3000; Described polyether-modified dimethyl silicone polymer is 400mm the viscosity of 25 ℃
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 alkylphenol is 12～16;
W is the epoxy radicals addition product that diethylenetriamine and stearic acid react the amide compound that gets, the synthetic method of the epoxy radicals addition product of described amide compound is: take p-methyl benzenesulfonic acid as catalyst, 1mol diethylenetriamine and 2mol stearic acid were reacted 5 hours under 200～220 ℃, get amide compound, then carry out with 10mol oxirane the epoxy radicals addition product W that addition reaction gets amide compound.
2. large 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 that a part of side chain of the dimethyl-silicon of end with methyl is replaced the compound that obtains by the amino of following represented by formula I; Described polyether-modified dimethyl silicone polymer is that a part of side chain of the dimethyl-silicon of end with methyl is replaced by the polyether-based that following Formulae II represents the compound that obtains:
-CH
2-CH
2-NH-CH
2-CH
2-NH
2(I)
3. large tow PAN base carbon fiber protofilament finish according to claim 1, the HLB value that it is characterized in that described polyether-modified dimethyl silicone polymer is 4～5.
4. large 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. large 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. large tow PAN base carbon fiber protofilament finish according to claim 1, is characterized in that described emulsifying agent is fatty alcohol-polyoxyethylene ether.
7. large tow PAN base carbon fiber protofilament finish according to claim 1, is characterized in that described emulsifier is 10～15 parts.
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|---|---|---|---|
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|---|---|---|---|
| CN201110369956.5A CN103122585B (en) | 2011-11-18 | 2011-11-18 | Oiling agent of large tow PAN (Polyacrylonitrile)-based carbon fiber precursors |
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| CN103122585B CN103122585B (en) | 2015-01-07 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104452270A (en) * | 2014-12-19 | 2015-03-25 | 四川创越炭材料有限公司 | Spinning finish for asphalt carbon fiber |
| CN106544760A (en) * | 2015-09-18 | 2017-03-29 | 中国石油天然气股份有限公司 | A kind of carbon fibre precursor is oil solution dedicated and preparation method thereof |
Citations (3)
| 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 |
| 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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2011
- 2011-11-18 CN CN201110369956.5A patent/CN103122585B/en active Active
Patent Citations (3)
| 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 |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104452270A (en) * | 2014-12-19 | 2015-03-25 | 四川创越炭材料有限公司 | Spinning finish for asphalt carbon fiber |
| CN106544760A (en) * | 2015-09-18 | 2017-03-29 | 中国石油天然气股份有限公司 | A kind of carbon fibre precursor is oil solution dedicated and preparation method thereof |
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| CN103122585B (en) | 2015-01-07 |
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