US009.

476147B2

(12) United States Patent (10) Patent No.: US 9,476,147 B2

Yu et al. (45) Date of Patent: Oct. 25, 2016
(54) GEL SPINNING PROCESS FOR PRODUCING 2101/12 (2013.01): D10B 2101/122 (2013.01);
A PAN-BASED PRECURSOR FIBER D10B 2321/10 (2013.01)
(58) Field of Classification Search
(71) Applicant: DONGHUA UNIVERSITY, Shanghai CPC ............ D01D 1/02: D01D 5/06: D01F 1/02:
(CN) D01F 1/10; D01F 6/18: D01F 9/22: D01F
9/225
(72) Inventors: Muhuo Yu, Shanghai (CN); Huaiping USPC .................................................. 264/182, 211
Rong, Shanghai (CN); Keqing Han, See application file for complete search history.
Shanghai (CN); Yiwei Zhang, Shanghai
(CN); Yincai Tian, Shanghai (CN); (56) References Cited
Qinli Dong, Shanghai (CN); Hui
Zhang, Shanghai (CN) U.S. PATENT DOCUMENTS

(73) Assignee: DONGHUA UNIVERSITY, Shanghai 2,733,121 A 1/1956 Griffith, Jr. et al.
1/1980 Reinehr .................... D01F 1/10
(CN) 4,185,059 A *
264,182
5,560,991 A * 10/1996 Patel ..................... CO4B 35,571
(*) Notice: Subject to any disclaimer, the term of this 264/29.6
patent is extended or adjusted under 35 8,906,278 B2 12/2014 Yu et al.
U.S.C. 154(b) by 0 days. (Continued)
(21) Appl. No.: 14/518,944 FOREIGN PATENT DOCUMENTS
(22) Filed: Oct. 20, 2014 CN 1461829. A 12/2003
CN 1478,930 A 3, 2004
(65) Prior Publication Data
(Continued)
US 2015/OO35196 A1 Feb. 5, 2015
OTHER PUBLICATIONS

Related U.S. Application Data Li, Z., “Study on ionic liquid and PAN/ionic liquid diluted solu
tion.” Chinese Doctoral Dissertations & Master's Theses Full-Text
(62) Division of application No. 13/262,620, filed as Database (Master) Engineering Science and Technology I, Jul. 16.
application No. PCT/CN2010/000036 on Jan. 11, 2005-Aug. 15, 2005.
2010, now Pat. No. 8,906,278.
(Continued)
(30) Foreign Application Priority Data
Mar. 31, 2009 (CN) .......................... 2009 1 OO48.603
Primary Examiner — Leo B Tentoni
Jun. 9, 2009 (CN). ... 2009 1 OO52721 (74) Attorney, Agent, or Firm — Nixon Peabody LLP:
Jun. 17, 2009 (CN) .......................... 2009 1 OO53212 Joseph Bach, Esq.
Sep. 17, 2009 (CN) .......................... 2009 1 O195794 (57) ABSTRACT
Nov. 6, 2009 (CN) .......................... 2009 1 O1984.44
Processes for producing carbon fiber, the filament thereof
(51) Int. C. and pre-oxidized fiber are provided. In one embodiment, the
DOID L/02 (2006.01) gel spinning of polyacrylonitrile filament is achieved by
DOIF 9/22 (2006.01) using Small-molecule gelling agent, and the carbon fiber
D02. I/22 (2006.01) obtained thereby is increased by 15% to 40% in tensile
DOID L/04 (2006.01) strength and by 20% to 35% in toughness. In another
DOID 5/08 (2006.01) embodiment, the melt spinning process of polyacrylonitrile
DOID LO/02 (2006.01) is conducted by using imidazole type ion liquid as plasti
DOIF I/O (2006.01) cizer, the process reduces environment pollution, is Suitable
DOIF 6/8 (2006.01) for industrial production and the fiber produced thereby is
DOID 5/06 (2006.01) improved in its strength. In yet another embodiment, poly
DOID LO/06 (2006.01) acrylonitrile pre-oxidized fiber is produced by melt spin
DOIF I/02 (2006.01) ning, so low cost and controllable pre-oxidization of poly
B05D I/O (2006.01) acrylonitrile can beachieved. In a further embodiment, high
B05D L/18 (2006.01) strength carbon fiber is manufactured by using polymer
(52) U.S. C. thickening agent. In another further embodiment, low cost
CPC ................. D0IF 9/22 (2013.01); B05D I/007 and controllable pre-oxidization of polyacrylonitrile is
(2013.01); B05D 1/18 (2013.01): D01D I/04 achieved by conducting pre-oxidization before spinning,
(2013.01): D01D 5/06 (2013.01): D0ID 5/08 minimizing skin-core structure, so as to produce high per
(2013.01): D0ID 10/02 (2013.01): D01D formance carbon fiber, and reduce the production cost of
10/06 (2013.01): D01F I/02 (2013.01): D0IF carbon fiber greatly.
1/10 (2013.01): D0IF 6/18 (2013.01): D0IF
9/225 (2013.01): D02.J I/224 (2013.01); D10B 4 Claims, 7 Drawing Sheets
 US 9,476,147 B2
Page 2

(56) References Cited WO 2010/111882 A1 10/2010

U.S. PATENT DOCUMENTS OTHER PUBLICATIONS

398-99: A. ck 39; Sist et al . . . . . . . . . . . D01F 6, 18 ShenRui et al., “Study on the Gel-spinning Process for Preparing
524, 236 Polyacrylonitrile Carbon Fiber Filament”, Techno-Economics in
2015.00351.83 A1 2/2015 Yu et al. Petrochemicals, Apr. 2007, vol. 23, No. 2, pp. 41-44.
2015.0035.197 A1 2/2015 Yu et al. Notice of Allowance for U.S. Appl. No. 14/519,002 dated Jan. 25.
2015,003.7509 A1 2/2015 Yu et al. 2016.
Office Action for U.S. Appl. No. 14/519,076 dated Jan. 7, 2016.
FOREIGN PATENT DOCUMENTS International Search Report for PCT/CN2010/000036 dated Apr.
22, 2010.
CN 1740411 3, 2006 International Preliminary Report on Patentability for PCT/CN2010/
CN 1O1250770 8, 2008 000036 dated Oct. 13, 2011.
CN 10 1260575 9, 2008 Restriction Requirement for U.S. Appl. No. 13/262,620 dated Dec.
CN 101545148 9, 2009
CN 101586265 11/2009 11, 2013.
CN 10159782O 12/2009 Office Action for U.S. Appl. No. 13/262,620 dated Apr. 7, 2014.
JP 46-34939 10, 1971 Notice of Allowance for U.S. Appl. No. 13/262,620 dated Jul. 18,
JP 61-69814 4f1986 2014.
JP 10-265674 10, 1998
JP 2005-256.222 9, 2005 * cited by examiner
U.S. Patent Oct. 25, 2016 Sheet 1 of 7 US 9,476,147 B2
U.S. Patent Oct. 25, 2016 Sheet 2 of 7 US 9,476,147 B2

Temperature ("C )

Fig.8
U.S. Patent Oct. 25, 2016 Sheet 3 of 7 US 9,476,147 B2

500 000 1500 2000 2500 3000 3500

Wave number/cm
Fig.13
U.S. Patent Oct. 25, 2016 Sheet 4 of 7 US 9,476,147 B2

00

80

60

20
500 000 1500 2000 2500 3000 3500

Wave number/cm
Fig.14

Fig.15 Fig.16

Fig.17 Fig.18
U.S. Patent Oct. 25, 2016 Sheet S of 7 US 9,476,147 B2

F.

Cottlinoiter Polytetization. Spinning

initiator
Pre-Oxidization(Oxidization. Furnace
FA. Ray Filattent 20-30, it air

Catilization. F.A. ased Cathon Fier

(1-145), in nitrogen)

Fig.19-1
F. Pre-Oxidization(Reactor
Cotton Otter Polymerization -- f-, in air
Initiator

10-45C, in nitrogen

Fig.19-2

145) 334)

393)
18O

1.
.

4.
*&^&.x. A- ^. s
3. 35

Wave number (cm)

Fig.20-1
U.S. Patent Oct. 25, 2016 Sheet 6 of 7 US 9,476,147 B2

5 4 128 3.180
224) 240
ir-Nar--ry v-ty
3- YYYY 3

s: -

a - *\. - ---, /
-v- W/ 5
Y N//
- r in v-A-
V
3. 3.

Wave number (cm)

Fig.20-2

5 15 25 3. 35

Wave number (cm)

Fig.21
U.S. Patent Oct. 25, 2016 Sheet 7 Of 7 US 9,476,147 B2

3. 3. O

Wave number (cm)

Fig.22
 US 9,476,147 B2
1. 2
GEL SPINNING PROCESS FOR PRODUCING It was firstly reported by Coxe in 1952 that adding a small
A PAN-BASED PRECURSOR FIBER amount of water into PAN copolymers can lower its melting
point to that required for melt spinning. This report provided
CROSS-REFERENCE TO RELATED a possibility for melt spinning of PAN fibre. Since then,
APPLICATIONS especially, the last 20 years, a lot of researches on melt
spinning of PAN are carried on abroad by many foreign
This application is a divisional application of U.S. patent companies such as ACC Co., Du Pont Co, BP Chemical Co.,
application Ser. No. 13/262,620, now U.S. Pat. No. 8,906, Mitsubishi Rayon Co., Ltd., Exlan Co. Ltd, Asahi Kasei
278, filed on Sep. 30, 2011, which is a National Phase of 10
Corporation, etc.
International Application No. PCT/CN2010/000036, which In general, there are two ways for melt spinning of PAN:
was filed on Jan. 11, 2010, and which claims priority to and plasticized melt spinning and non-plasticized melt spinning,
the benefit of Chinese Patent Application Nos. wherein plasticized melt spinning comprising the following
200910048603.8 filed on Mar. 31, 2009, 2009 10052721.6 aspects: Plasticized by solvent (such as DMSO and PC and
filed on Jun. 9, 2009, 2009 10053212.5 filed on Jun. 17, 15 the like): PAN powder which had been plasticized by PC can
2009, 200910195794.0 filed on Sep. 17, 2009, and be melted and be extruded continuously into filaments. For
2009101984.44.X filed on Nov. 6, 2009, and the disclosures example, the study on Rheological properties of mixture of
of which are hereby incorporated herein by reference in their PAN and PC in weight ratio of 50:50 at 180° C. and 240° C.
entireties. shows that the blend fluid thereof is shear thinning fluid and
its viscosity is lower than that of conventional plastic PE; (2)
TECHNICAL FIELD Plasticized by non-similar polymer such as PEG reported in
literatures: PAN fibre is prepared by melt spinning of PAN
The present invention belongs to the field of processing and PEG mixture by Asahi Chemical Co. Ltd, the tensile
technology of carbon fibres. In particular, the present inven strength of which can be up to 4.68 cN/dtex; (3) Plasticized
tion relates to processes for producing carbon fibre, precur 25 by low molecular weight PAN: 91 parts copolymer of PAN
sor fibre and pre-oxidized fibre thereof. and methyl acrylate (copolymerization ratio being 85:15 by
weight, specific viscosities being 0.68) and 9 parts another
BACKGROUND ART copolymer of PAN and methyl acrylate (copolymerization
ratio being 85:15 by weight, molecular weight being 4800)
Carbon fibre is widely used in high-tech industrial field 30
are mixed and melt extruded at 215° C., and spun at 1200
due to its excellent properties Such as low density, high m/min to obtain fibre, which is drawn in boiling water to 4
strength, high modulus, high temperature resistance, corro times to obtain fibre having a linear density of 1.17 dtex, a
sion resistance, friction resistance, and fatigue resistance, tensile strength of 5.26 cN/dtex, and elongation at break of
etc., especially has a very potential application in aerospace
field. The production of carbon fibre generally comprises 35 12.3%, as reported by Mitsubishi Rayon Co., Ltd. And fibre
spinning, pre-oxidizing and carbonizing process. satisfying certain requirements can also be melt spun by
The properties of carbon fibre, to a great extent, depend on reducing AN unit content of low molecular weight PAN for
its precursor fibre. The low quality of polyacrylonitrile plasticizing appropriately; (4) Plasticized by water, which is
(PAN) based precursor fibre has been a “bottleneck” restrict the most studied method: PAN and certain amount of water
ing the development of carbon fibre industry in china for 40 become melt under a certain pressure and temperature,
many years. It is urgent to effectively improve the quality of which is then extruded into spinning pack and then spinning
PAN precursor fibre, thereby improving the properties of duct through spinning machine, and drawn. There is full of
carbon fibre. Compared with precursor fibre produced water vapour in the spinning duct to prevent fibre foaming
abroad, homemade precursor fibre has larger fineness, lower due to rapidly water evaporation. The obvious characteris
strength, larger dispersion coefficient, more defects, cracks 45 tics of this method lie in that the only use of inexpensive and
and Voids, lower crystallinity and orientation, etc., which are non-toxic water will save recovery procedures and devices
serious problems existing during production of precursor and will not produce pollution to the environment. It was
fibre. As far as quality and yield of precursor fibre are reported in literatures that PAN fibre obtained from melt
concerned, quality is the primary problem at present. The spinning by using water as plasticizer can be used as
tensile strength of most carbon fibres produced from home 50 precursor fibre for carbon fibre and have a molecular weight
made precursor fibre is about 3.5 GPa, which can not fulfil of 100,000-250,000, strength of 3.6 cN/dtex, Young modu
the requirement for use at present, therefore its application lus of 97 cn/dtex, and the carbon fibre obtained by carbon
is limited. Meanwhile, the poor stability of precursor fibre ization has an average strength of 15 ch/dtex, Young modu
quality is an obstacle to scale production. lus of 1080-1310 cN/dtex and Sonic modulus over 1000
A main feature of PAN resin is its high melting point 55 cN/dtex. Recently, aerospace grade carbon fibre prepared
(317° C.). It is decomposed before melted when it is heated, from PAN fibre as precursor fibre obtained from melting
therefore only solution spinning can be used to produce PAN spinning and plasticized by water is also developed by
fibre. A large amount of toxic or corrosive chemical solvents Celion Carbon Fibres Company. However, this method also
are required in industrialized wet spinning and dry spinning, has the following problems: A. The extrusion pressure of
and recovery and purification of the used solvents, washing 60 screw is relatively high due to the poor rheological proper
fibres with water and drying, as well as “three wastes' ties of hydrous melts; B. To prevent the surface of fibre from
treatment are necessary during production. If the melt spin being coarse and microvoids being formed thereon which
ning of PAN fibre can be realized, not only solvent exhaus result in poor mechanical properties of fibre due to too quick
tion but also recovery step and devices for solvent recovery water evaporation during coagulation, Saturated Steam of
and washing step can be saved, therefore the manufacturing 65 certain pressure is required to be maintained in the spinning
cost can be substantially lowered, and the serious environ duct, thereby presenting a requirement for devices; C. It is
mental problems caused by solvents are eliminated. difficult to control the process due to the narrow temperature
 US 9,476,147 B2
3 4
range for melt spinning of hydrous melt, therefore industri pre-oxidization, which is beneficial to properties of carbon
alization of melt spinning of hydrous melt has not been fibre, however, also lowers the production efficiency. Thus
realized yet at present. an excellent process for pre-oxidization has not been devel
During the manufacturing of carbon fibre, pre-oxidization oped yet.
is a key procedure and the most time-consuming process, the 5 During the production of carbon fibre (or graphite fibre),
structure and properties of the final carbon fibre to a great especially carbon fibre obtained by using PAN precursor
extent depend on the structural transformation during pre fibre as starting material, the formation of Voids on Surface
oxidization. Since there is dramatic structural transformation is caused by defects of precursor fibre itself and evenness
during pre-oxidization, defects are easily caused, resulting in problems during production. Those voids induce stress con
a decrease of the mechanical properties of carbon fibre. 10 centration when fibre is subjected to force, which is also the
Therefore the structure transformation and control of struc main reason for break of monofilament. Repairing voids on
ture during pre-oxidization are very important to the control surface has been concerned in carbon fibre production field,
of the structure and properties of carbon fibre. but there is not good means for it until now, and the only way
All processes for pre-oxidizing PAN precursor fibre for at present is to sacrifice monofilaments with voids, therefore
carbon fibre reported in literature till now pre-oxidize pre 15 the overall mechanical properties of carbon fibre are sub
cursor fibre in air. That is to say, all PAN based carbon fibres stantially decreased.
are obtained by spinning, pre-oxidizing and carbonizing As disclosed in Chinese Patent No. 02121070.5, environ
processes sequentially. However, such an order will result in ment of an ethyne reaction is created by heating through
the following shortcomings: 1) During pre-oxidization of focusing electromagnetic field induction to induce ethyne to
PAN precursor fibre, uneven morphological structure of be cracked into hydrogen and carbon atoms near high
fibre will be caused if there is a gradient difference of temperature carbon fibres. Carbon atoms deposits on the
pre-oxidization degree across the cross-section of fibre. Such surface of carbon fibres to repair defects on surface thereby
as common skin-core structure, which will result in uneven reinforcing carbon fibre. However, the equipments for this
radical contraction across the cross-section of fibre and poor process are very complicated and costly, uneasily to handle
preferred orientation and tensile performance, and therefore 25 and the efficiency is low.
decrease of properties of final carbon fibre. 2) The pre
oxidization process is very time-consuming, its temperature SUMMARY OF THE INVENTION
is high and equipments are complicated, resulting in the
improved cost for pre-oxidization and therefore eventually, The technical problem to be solved by the present inven
the whole cost of manufacturing carbon fibre are Substan 30 tion is to provide processes for producing carbon fibre,
tially increased. Therefore, the pre-oxidization of PAN fibre precursor fibre and pre-oxidized fibre thereof to overcome
is very important. Pre-oxidization is a systemic engineering, the problems existing in current carbon fibre production
revolves in not only equipments and means of pre-oxidiza Such as poor quality of precursor fibre, high cost for pro
tion, but also process parameters (such as temperature, time, ducing pre-oxidized fibre and carbon fibre as well as serious
drawing, medium, flow and direction of medium), reaction 35 environmental pollution.
and change in PAN fibre during pre-oxidization, evaluation In an embodiment, the present invention provides a gel
index of structure and pre-oxidization degree of pre-oxi spinning process for producing a PAN-based precursor fibre,
dized fibre, etc. comprising the following steps: gel spinning
In recent years, researchers at home and abroad take more a) mixing an anhydrous PAN powder and a solvent in a process
and more efforts on pre-oxidization of PAN precursor fibre. 40 weight ratio from 5:100 to 20:100, followed by heating
However, their researches are carried on pre-oxidization of at a temperature between 70° C. and 110° C. until the
PAN precursor fibre after spinning. For example, PAN PAN powder is completely dissolved to obtain a solu
precursor fibre are also pre-oxidized by three huge compa tion;
nies which produce carbon fibre, namely, Toray, TOHO, b) adding a small-molecule gelling agent to the Solution
Mitsubishi Rayon. Pre-oxidization is double diffusion pro 45 from step a) to obtain a mixture, said Small-molecule
cess and oxygen diffuses from Surface to inside of fibre. As gelling agent being in an amount of from 2% to 5% by
the pre-oxidization reaction continues, compact thin layer weight of the solution, and the mixture being mechani
with ladderlike structure is formed on the surface of fibre at cally stirred for 1 hour to obtain a uniformly mixed
first, blocking the diffusion of oxygen, and then a skin-core spinning solution;
structure is formed, resulting in defects of carbon fibre. 50 c) transferring the spinning Solution from step b) to a wet
Manufacturing process using layer-based thermal stabi spinning machine and spinning by using conventional
lized furnace with 6-12 zones for heating and drawing which wet spinning process for producing PAN based precur
can produce pre-oxidization fibre with high quality is dis sor fibre, thereby obtaining the PAN-based precursor
closed in Chinese Patent Nos. 02136722.1 and fibre.
200810036189.4. However, the equipments for this process 55 The solvent in step a) is selected from the group consist
are extremely complicated, the temperature is difficult to ing of dimethylformamide (DMF), dimethylacetamide
control and the cost is high. (DMAc), dimethyl sulfoxide (DMSO), sodium thiocyanate
The industrial objects of carbon fibre production are to (NaSCN), nitric acid (HNO), and Zinc chloride (ZnCl2).
lower the cost, improve the properties and productivity of and preferably DMF or DMSO.
carbon fibre. For quick pre-oxidization and excellent pre 60 The heating in step a) is preformed by means of oil bath
oxidized fibre, the process of pre-oxidization should be or sand bath.
optimized. The key for lowering production cost is shorten The Small-molecule gelling agent in step b) is one or more
the time for pre-oxidization which causes easily skin-core selected from the group consisting of HO, glycerol, glycol,
structure and Subsequently larger voids and defects during urea, and thiourea.
carbonizing procedure, thereby resulting in decrease of 65 In this embodiment, the spinning solution is transformed
mechanical properties of carbon fibre Skin-core structure is to three-dimensional network structure directly in cooled air
not obvious by lowering temperature and prolonging time of by heat-induced gelatinization through adding some non
 US 9,476,147 B2
5 6
Solvents into the spinning solution. Once such structure is a) dissolving a catalyst for pre-oxidation of PAN in an
formed, skin-core structure is avoided because only double ionic liquid in a weight ratio from 1:100 to 0.01:100
diffusion of solvent and non-solvent exists in coagulation followed by adding PAN powder to obtain a mixture,
bath, and phase separation will not occur, thereby the tensile wherein the weight ratio of PAN powder to ionic liquid
strength of precursor fibre for PAN based carbon fibres can 5 is between 1:1 and 1:0.25;
be increased. b) adding the mixture from step a) to hopper of twin
In an embodiment, the present invention provides a melt Screw spinning machine to conduct melting spinning proses
while blowing an oxygen-containing gas into melting melt spinning
melt spinning spinning process for producing a PAN fibre by using an ionic
liquid as plasticizer, comprising the following steps: segment of the twin-screw spinning machine, wherein
a) mixing an anhydrous PAN powder and an ionic liquid 10 the flow rate of the oxygen-containing gas is between
uniformly in a weight ratio from 1:1 to 1:0.25 to obtain 1 ml/min and 5 ml/min, and the rotational velocity of
a mixture; screw is between 40 and 120 r/min, and the temperature
b) adding the mixture from step a) into a hopper of at a feed segment is between 170° C. and 185°C., and
twin-screw spinning machine to conduct melt spinning the temperature for plasticizing is between 185° C. and
with a screw rotation speed of 40-120 r/min at a 15 220° C., and the temperature for melting is between
predetermined spinning temperature ranging from 170° 185° C. and 220° C.;
C. to 220°C.; and a filament from the spinning machine c) dry-heat drawing the spun fibre directly under a tem
being drawn directly by means of dry-heat drawing perature between 110 and 140° C. with a total draw
without a water bath, with a drawing temperature ratio between 4 and 6, then washing the drawn fibre
ranging from 80° C. to 180° C. and a drawing ratio of with water at 70-90° C., followed by thermosetting in
1 to 8: dry hot air at 120-150° C. to give the PAN based
c) washing the drawn fibre with water, thermosetting and pre-oxidized fibre.
winding to obtain the PAN fibre. The catalyst for pre-oxidation of PAN used in step a) is
The plasticizer in step a) is a disubstituted imidazole one or more selected from the group consisting of potassium
based ionic liquid with the structure of 25 permanganate, cobalt dichloride, cobalt Sulphate, potassium
persulfate, benzoyl peroxide, Succinic acid, hydrogen per
oxide, ammonia, and hydroxylamine hydrochloride.
The ionic liquid used in step a) is disubstituted imidazole
based ionic liquid, preferably one or more selected from the
30 group consisting of 1-ethyl-3-methyl imidazolium chloride
(EMIMICl), 1-butyl-3-methyl imidazolium chloride
(BMIMICl), 1-ethyl-3-methyl imidazolium bromide
(EMIMBr), 1-ethyl-3-methyl imidazolium tetrafluorobo
rate (EMIMBF), 1-butyl-3-methyl imidazolium tetrafluo
35 roborate (BMIMIBF), 1-ethyl-3-methyl imidazolium
wherein R is methyl or butyl; R is methyl, ethyl, hexafluorophophate (EMIMPF), 1-methyl-3-butyl imida
n-propyl, iso-propyl. n-butyl, Sec-butyl or iso-butyl; X Zolium hexafluorophophate (BMIMPF).
is chloride ion (Cl), bromide ion (Br), tetrafluorobo Preferably, the oxygen-containing gas is oxygen or air.
rate (BF4) or hexafluorohosphorate (PF6). KMnO is used as a catalyst so that the time for pre
The disubstituted imidazole-based ionic liquid is prefer 40 oxidization is shortened and the final properties of carbon
ably one or more selected from the group consisting of fibre are improved. CoCl2 and CoSO can also be used to
1-ethyl-3-methyl imidazolium chloride (EMIMICl), 1-bu catalytically improve the structure and properties of PAN.
tyl-3-methyl imidazolium chloride (BMIMICl), 1-ethyl-3- BPO, succinic acid and the like can also be used as catalyst
methyl imidazolium bromide (EMIMBr), 1-ethyl-3- for cyclization during the course of pre-oxidization of PAN.
methyl imidazolium tetrafluoroborate (EMIMBF). 45 These catalysts or their combination can reduce the activa
1-butyl-3-methyl imidazolium tetrafluoroborate (BMIM tion energy of oxidization, slower heat release, and shorten
BF), 1-ethyl-3-methyl imidazolium hexafluorophophate the time for pre-oxidization and lower the final temperature
(EMIMPF), and 1-butyl-3-methyl imidazolium hexafluo for pre-oxidization and improve the mechanical properties
rophophate (BMIMPF). of carbon fibre.
The temperature for washing the drawn fibre in step c) is 50 The advantages of this embodiment are as follows:
controlled in a range from 70° C. to 90° C. (1) The skin-core structure is decreased and the compact keuntun
In this embodiment, melt spinning is adopted to avoid the ness of pre-oxidized fibre is substantially increased.
use of a large amount of toxic or corrosive chemical Solvent, The increase of compactness of pre-oxidization is greatly gan
without recovering and purifying the solvent used and three contributed by oxygen content, especially the radial melt-spi
keuntungan wastes treatment during manufacture, thereby saving not 55 distribution of oxygen is related to the skin-core struc nning
melt spinning only solvent but also recovery step and devices for solvent ture along the cross-section of fibre. The key of pre
recovery and washing step, which can Substantially lower oxidization is elimination of skin-core structure of
the manufacturing cost, and eliminate the serious environ pre-oxidized fibre. Oxygen is blow through the melting
mental problems caused by solvent. The plasticizing effect section of twin-screw and diffuses from surface to
of ionic liquid is helpful for drawing PAN fibre. Unlike 60 inside of the melt, Substantially reducing the skin-core
precursor fibre obtained by Solution spinning, which has a structure of pre-oxidized fibre;
large amount of voids caused by double diffusion, the (2) Energy consumption is reduced, and therefore the cost
obtained PAN fibre hardly has voids and is compact, which of pre-oxidization is substantially lowered.
is beneficial to the increase of the strength of precursor fibre. The pre-oxidization can be carried in a twin-screw and the
In an embodiment, the present invention provides a melt 65 melt can be uniformly oxidized under rotation of the
spinning process for producing a PAN-based pre-oxidized twin-screw. Compared with the conventional pre-oxi
fibre, comprising the following steps: dization process, the energy consumption of the pro
 US 9,476,147 B2
7 8
cess of the invention is reduced so that the cost of The advantages of this embodiment are as follows:
pre-oxidization and further the manufacturing cost of (1) The defects on the surface of fibres are decreased by
carbon fibres are lowered. repairing the Surface, and therefore stress concentration
(3) Controllable pre-oxidization of PAN is realized. can be effectively eliminated, resulting in an increase of keuntungan
The temperature for pre-oxidization is 170° C.-220° C. 5 15%-30% and 30% in tensile strength and toughness of
and catalyst in certain ratio is added to facilitate the carbon fibre, respectively; high strenght
pre-oxidization. The degree of oxidization of PAN is (2) The process time is short, and the process can be used carbon fiber
effectively controlled by difference retention time of in combination with the online equipment, therefore
melt in a twin-screw, temperature for pre-oxidization investment on equipments and the cost for process are
and catalyst content. The oxidization is strictly con 10 low:
trolled by adjusting the process parameters, i.e. con (3) The ratio of carbon nanotube to solvent and the
trollable pre-oxidization of PAN is realized by control winding speed can be adjusted depending on the degree
ling the time, temperature and catalyst content used for of defect of carbon fibres to obtain a better strength
oxidization, pre-oxidization degree is improved and ening effect;
side reaction Such as cross-linking is reduced. 15 (4) The process effect is good and yield is high;
(4) The devices for process are simple and the process is (5) It is easily to handle and readily to be industrialized.
environmentally friendly. In an embodiment, the present invention provides a pro
The pre-oxidization of the process is carried in a twin cess for producing a PAN based carbon fibre, comprising the
screw extruder which can realize a controllable pre following steps:
oxidization and Sufficiently carry out the pre-oxidiza a) mixing PAN and a solvent in a solid-to-liquid ratio of
tion, thereby avoiding the use of existing expensive and 0.1%-25% in a reactor, and heating and stirring the
complicated devices for pre-oxidization. The melt spin resulting mixture until the PAN is dissolved completely
ning is used to produce PAN pre-oxidized fibre in the to obtain a solution;
process, and avoid the use of a large amount of toxic or b) adding a catalyst KMnO in an amount of 0.05 wt. proses
corrosive chemical Solvent, without recovering and 25 %-0.1 wt.% based on the weight of the PAN to the high
purifying the solvent used and three wastes treatment Solution from Step a), followed by bubbling an oxygen strength
during manufacture. Not only solvent but also recovery containing gas at 5 ml/min to obtain a spinning solu
step and devices for solvent and washing step are tion, then pre-oxidizing the spinning solution for 1-2.5 carbon fiber
saved, therefore the manufacturing cost is substantially hrs at 90° C.-250° C.:
lowered, and the serious environmental problems 30 c) spinning the spinning solution through a spinning
caused by solvent are eliminated. machine, followed by washing with water, drawing and
The tensile strength of carbon fibre obtained by carbon thermosetting to obtain a pre-oxidized fibre with good
izing the pre-oxidized fibre from this embodiment is pre-oxidization degree, which is Subjected to a carbon
increased from 3.3-3.5 GPa to 4.0–4.6 GPa and has an ization process to obtain a high-performance carbon
advantage of lower cost compared with the high strength 35 fibre.
carbon fibres commercial available at present. The solvent used in step a) is selected from the group
In an embodiment, the present invention provides a pro consisting of 1-butyl-3-methylimidazolium chloride, 1-al
HIGH STRENGHT cess for producing a high-strength carbon fibre, comprising lyl-3-methylimidazolium chloride, dimethylformamide
CARBON FIBER the following steps: (DMF), dimethylacetamide (DMAc), dimethylsulfoxide
a) mixing 0.01-2 parts by weight of a carbon nanotube and 40 (DMSO), sodium thiocyanate (NaSCN), nitric acid (HNO),
100 parts by weight of a solvent, and ultrasonic pro and Zinc chloride (ZnCl2).
cessing for 1.5-3 hrs with an ultrasonic cell disrupter at The catalyst used in step b) is one or more selected from
300 w-600 w to obtain a mixture; the group consisting of potassium permanganate (KMnO),
b) adding 0.01-5 parts by weight of a polymer thickener cobalt dichloride (CoCl2), cobalt sulphate (CoSO), benzoyl
to the mixture from step a) followed by ultrasonic 45 peroxide (BPO). Succinic acid, hydrogen peroxide (H2O).
processing for 1-2 hrs with an ultrasonic cell disrupter ammonia, and low molecular weight amine.
at 300 w-600 w to obtain another mixture; The time required for pre-oxidization is shortened and the
step nya c) forming a coating of 100-300 nm on pre-oxidized fibre final properties of carbon fibre are improved by using
with the mixture obtained from step b), followed by KMnO, as a catalyst. CoCl and CoSO can also be used to
carbonizing, to obtain the high-strength carbon fibre. 50 catalytically improve the structure and properties of PAN.
The carbon nanotube used in step a) is a carboxylated BPO and Succinic acid can also be used as a catalyst for
multi-walled carbon nanotube. cyclization during pre-oxidization of PAN. The catalyst
The solvent used in step b) is selected from the group mentioned above may be used either alone or in combination
consisting of dimethyl sulfoxide, N,N-dimethylformamide, to reduce the activation energy of oxidization, slow heat
dimethylacetamide, and distilled water. 55 release, shorten the time for pre-oxidization and lower the
The polymer thickener used in step b) is selected from the temperature for pre-oxidization, thereby improving the
group consisting of polyacrylonitrile, polyvinyl alcohol, and mechanical properties of carbon fibre.
C-cyanoacrylate. The thickener is selected depending on the The oxygen-containing gas used in step b) is oxygen or
Solvent used. a1.
The coating in step c) is formed by immersing the 60 After oxidization of stepb), the structure and properties of
pre-oxidized fibre in the mixture obtained from step b) in a oxidized product is characterized by Fourier Transform
solid-to-liquid ratio of 1:3-1:2 and standing for 1-2 hrs. Infrared Spectroscopy (FTIR), thermogravimetry (TG), dif
The coating in step c) is formed by electrostatic spraying ferential scanning calorimetry (DSC) and NMR, for better
the mixture obtained from step b) onto the surface of the determination of the property of the spinning solution.
fibre with a voltage of 80 kV-120 kV, a spray distance of 25 65 The structure and properties of the pre-oxidized fibre from
cm-40 cm, and a rotation speed of spray gun of 2800 step c) is related to the selection of temperature and time for
r/min-3000 r/min. pre-oxidization. Temperature for pre-oxidization of 60°
 US 9,476,147 B2
9 10
C.-160° C. and time for pre-oxidization of 1 hr-1.5 hrs are FIG. 3 shows a SEM photograph of the cross-section of
conditions for relatively low pre-oxidization degree, and the carbon fibre precursor based precursor fibre spun from a
fibre obtained can be used in civil application. spinning solution containing 4 wt.% gelling agent based on
Temperature for pre-oxidization of 165° C.-250° C. and the total weight of the solution;
time for pre-oxidization of 1.5 hrs-2 hrs are conditions for 5 FIG. 4 shows a SEM photograph of the cross-section of
relatively high pre-oxidization degree, and the fibre obtained carbon fibre precursor based precursor fibre spun from a
can be used in industrial application. spinning solution containing 5 wt.% gelling agent based on
The spinning process used in step c) is wet spinning, the total weight of the solution;
dry-wet spinning, gel spinning, liquid crystal spinning or 10
FIG. 5-1 shows a SEM photograph of the cross-section of
jelly spinning. PAN fibre obtained when PAN/BMIMICl is 1:1 after
The tensile strength of carbon fibres obtained according to washed with water;
this embodiment is 4.0–4.6 Gpa. FIG. 5-2 shows another SEM photograph of the cross
The advantages of this embodiment are as follows: section of PAN fibre obtained when PAN//BMIMICl is 1:1
(1) Fibres can be uniformly oxidized and the skin-core 15 after washed with water;
structure is reduced. FIG. 6 is a DMA curve diagram of the PAN fibre obtained
Oxygen is uniformly diffused from surface to inside of when PAN/IBMIMICl is 1:1;
fibre in the reactor with stirring. The colour gets deeper FIG. 7-1 shows a SEM photograph of the cross-section of
as the pre-oxidization proceeds, and the pre-oxidization PAN fibre obtained when PAN/BMIMICl is 1.2:1 after
degree in fibre is uniform, which is different from the washed with water;
prior art wherein non-uniformly oxidization is occurred FIG. 7-2 shows another SEM photograph of the cross
and skin-core structure is caused. section of PAN fibre obtained when PAN/BMIMICl is 1.2:1
(2) Energy consumption and therefore the cost are after washed with water;
reduced. FIG. 8 is a curve diagram illustrating the relationship
The pre-oxidization can be carried out in a reactor. When 25 between Tg and PAN content of the fibres obtained from
the temperature of pre-oxidization is 160° C.-220°C., PAN/IBMIMIC system before washed with water;
a good pre-oxidization can be reached in a pre-oxidiza FIG. 9 shows a SEM photograph of the cross section of
tion time of 2 hrs. In addition, pre-oxidization can be the fibre obtained when PAN/IBMIMICl is 1:1 and KMnO/
fully completed with stirring. Compared with the con BMIMICl is 0.01:100 after washed with water;
ventional pre-oxidization process, energy consumption 30 FIG. 10 shows a SEM photograph of the cross section of
is reduced and so does the cost of pre-oxidization, and the fibre obtained when PAN/IBMIMICl is 1:1 and KMnO/
therefore cost of carbon fibres is reduced. BMIMICl is 0.1:100 after washed with water;
(3) Controllable pre-oxidization of PAN is realized. FIG. 11 shows a SEM photograph of the cross section of
The oxidization is strictly controlled by controlling reac the fibre obtained when PAN/BMIMICl is 1:1 and BPO/
tion conditions, i.e. controllable pre-oxidization of 35 BMIMICl is 0.01:100 after washed with water;
PAN is realized by controlling the time, temperature FIG. 12 shows a SEM photograph of the cross section of
and catalyst content used for oxidization, thereby the fibre obtained when PAN/BMIMICl is 1:1 and BPO/
improving pre-oxidization degree and reducing side BMIMICl is 0.1:100 after washed with water:
reaction Such as cross-linking FIG. 13 shows the infrared spectra of fibres obtained
(4) The devices for process are simple. 40 when PAN/IBMIMICl is 1:1 and KMnO/IBMIMICl is
The pre-oxidization is carried out in a reactor, which is 0.1:100:
beneficial for realization of a controllable and suffi FIG. 14 shows the infrared spectra of fibres obtained
ciently completed pre-oxidization, so that expensive when PAN/IBMIMICl is 1:1 and BPO/IBMIMICl is 0.1:
and complicated devices of prior art are avoided. 100:
By modification on the prior carbon fibres producing line, 45 FIG. 15 shows a filed emission SEM photograph at
the complicated process of pre-oxidization is simplified. The 10000x magnification for carbon fibres treated with poly
pre-oxidization can be carried directly in a reactor, and acrylonitrile:multi-walled carbon nanotube:dimethylsulfox
spinning is carried. The skin-core structure of carbon fibre ide=0.05:0.5:100 by weight;
obtained according to the present process is reduced, which FIG. 16 shows a filed emission SEM photograph at
improves the tensile strength of fibres from 3.3-3.5 GPa to 50 10000x magnification for carbon fibres treated with polyvi
4.0-4.6 GPa and has an advantage of lower cost compared nyl alcohol:multi-walled carbon nanotube:N,N-dimethylfor
with the high strength carbon fibres commercial available at mamide=0.05:0.5:100 by weight;
present. FIG. 17 shows a filed emission SEM photograph at
10000x magnification for carbon fibres treated with polyvi
BRIEF DESCRIPTION OF THE DRAWING 55 nyl alcohol:multi-walled carbon nanotube: water 5:0.05:100
by weight;
The present invention will be further described in details FIG. 18 shows a filed emission SEM photograph at
in connection with certain preferred embodiments with 10000x magnification for carbon fibres treated with C-cya
reference to the accompanying drawings, in which noacrylate:multi-walled carbon nanotube: water 5:0.05:100
FIG. 1 shows a SEM photograph of the cross-section of 60 by weight;
carbon fibre precursor based precursor fibre spun from a FIG. 19-1 is a flow diagram showing a process of pro
spinning Solution containing 2 wt.% gelling agent based on ducing PAN based carbon fibres in prior art;
the total weight of the solution; FIG. 19-2 is a flow diagram showing an improved process
FIG. 2 shows a SEM photograph of the cross-section of of producing PAN based carbon fibres;
carbon fibre precursor based precursor fibre spun from a 65 FIG. 20-1 shows the infrared spectra of PAN/IL pre
spinning Solution containing 3 wt.% gelling agent based on oxidized at 170° C. for different times, 1: not pre-oxidized:
the total weight of the solution; 2: 20 min: 3: 40 min: 4: 60 min; 5: 90 min:
 US 9,476,147 B2
11 12
FIG. 20-2 shows the infrared spectra of PAN/IL pre Upon mechanical stirred for one hour, the slurry is trans
oxidized at 160° C. for different times, 1: 20 min; 2: 40 min; ferred to a spinning machine for spinning, and the PAN
3: 60 min: 4: 90 min; 5: 120 min; 6:150 min: based precursor fibre obtained by the gel spinning (the
FIG. 21 shows the infrared spectra of PAN/DMSO pre spinning condition is the same as those in example 1) has a
oxidized at 175° C. for different times, 1: 4 hrs: 2: 5 hrs; 3: tensile strength of 4.2 GPa. FIG. 3 shows a SEM photograph
not pre-oxidized; (magnification factor of which is 25,000) of PAN based
precursor fibre spun from a spinning solution containing 4
FIG.22 shows the infrared spectra of PAN precursor fibre wt.% gelling agent based on the total weight of the solution.
pre-oxidized in oxidization furnace, 1: pre-oxidized at 250° It can be seen from FIG. 3 that the cross-section of the
C.; 2: not pre-oxidized. 10 obtained PAN based precursor fibre is circle nearly without
Voids across the section and the precursor fibre is structural
EXAMPLES compact.
For a better understanding of embodiments of the present Example 4
invention, together with the technical means, the character 15
istics and the purposes as well as effects thereof, reference First, 5 g anhydrous PAN powder and 95 g NaSCN
is made to the following embodiments. solvent are uniformly mixed in a three-neck flask, while
heated in an oil bath maintained at a temperature of 100°C.,
Example 1 and stirred to completely dissolve the PAN powder. After the
PAN powder is dissolved, 5 g urea is added. Upon mechani
First, 5 g anhydrous PAN powder and 95 g DMSO solvent cal stirred for one hour, the slurry is transferred to a spinning
are uniformly mixed in a three-neck flask, while heated in an machine for spinning, and the PAN based precursor fibre
oil bath maintained at a temperature of 70° C., and stirred to obtained by the gel spinning (the spinning condition is the
completely dissolve PAN powder. After the PAN powder is same as those in example 1) has a tensile strength of 4.5
dissolved, 2 g distilled water is added. Upon mechanical GPa. FIG. 4 shows a SEM photograph (magnification factor
stirred for one hour, the slurry is transferred to a spinning 25
of which being 15,000) of PAN based precursor fibre spun
machine for spinning, and the PAN based precursor fibre from a spinning solution containing 5 wt.% gelling agent
obtained by the gel spinning (in which the spinning tem based on the total weight of the solution. It can be seen from
perature is 60° C., the coagulation bath temperature is FIG. 4 that the cross-section of the obtained PAN based
10-20°C., the primary washing temperature is 75° C., the precursor fibre is uniform nearly without skin-core structure
secondary temperature is 100° C.) has a tensile strength of 30
and Voids, and the precursor fibre is structural compact.
4.31 GPa. FIG. 1 shows a SEM photograph (magnification Therefore, the tensile strength of the PAN based precursor
factor of which is 15,000) of PAN based precursor fibre spun fibre for carbon fibre is substantially increased.
from a spinning solution containing 2 wt.% gelling agent
based on the total weight of the solution. It can be seen from Example 5
FIG. 1 that the cross-section of the obtained PAN based 35
precursor fibre is circle nearly without voids across the First, 5 g anhydrous PAN powder and 95 g ZnCl, solvent
section and the precursor fibre is structural compact. There are uniformly mixed in a three-neck flask, while heated in an
fore, the tensile strength of the PAN based precursor fibre for oil bath maintained at a temperature of 100° C., and stirred
carbon fibre is substantially increased. to completely dissolve the PAN powder. After the PAN
40 powder is dissolved, 2 g thiourea is added. Upon mechanical
Example 2 stirred for one hour, the slurry is transferred to a spinning
machine for spinning, and the PAN based precursor fibre
First, 10 g anhydrous PAN powder and 90 g DMF solvent obtained by the gel spinning (the spinning condition is the
are uniformly mixed in a three-neck flask, while heated in an same as those in example 1) has a tensile strength of 4.51
oil bath maintained at a temperature of 90°C., and stirred to 45 GPa.
completely dissolve the PAN powder. After the PAN powder
is dissolved, 3 g ethylene glycol is added. Upon mechanical Example 6
stirred for one hour, the slurry is transferred to a spinning
machine for spinning, and the PAN based precursor fibre First, PAN powder and BMIMBF4 are uniformly mixed
obtained by the gel spinning (the spinning condition is the 50 in a mass ratio of 1:1 in a high speed mixer. Then the mixture
same as those in example 1) has a tensile strength of 4.4 is transferred to a twin-screw spinning machine for melt
GPa. FIG. 2 shows a SEM photograph (magnification factor spinning (in which screw speed is 50 r/min, the temperatures
of which is 15, 000) of PAN based precursor fibre spun from for feeding section, plasticizing section and melting section
a spinning solution containing 3 wt.% gelling agent based are set at 185° C., 190° C. and 185° C., respectively, the
on the total weight of the solution. It can be seen from FIG. 55 aspect ratio of the spinneret is 1:3 and the orifices in the
2 that the cross-section of the obtained PAN based precursor spinneret is 0.5 mm in diameter). The spun fibre is subjected
fibre is circle nearly without voids across the section, and the to a primary dry-heat drawing, a secondary dry-heat draw
precursor fibre is structural compact and skin-core structure ing, washing with water, oiling and thermosetting (in which
is not observed. the drawing ratio is 2-10 times, the drawing temperature is
60 90° C.-120° C. and the washing temperature is 25° C.-40°
Example 3 C.) to give PAN fibre. The obtained PAN fibre has a tensile
strength of 2.8 cn/dtex and an elongation at break of 19.0%.
First, 10 g anhydrous PAN powder and 90 g DMA.c
solvent are uniformly mixed in a three-neck flask, while Example 7
heated in a sand bath maintained at a temperature of 90° C. 65
and stirred to completely dissolve the PAN powder. After the First, PAN powder and BMIMBF4 are uniformly mixed
PAN powder is dissolved, 4 g ethylene glycol is added. in a mass ratio of 1.2:1 in a high speed mixer. Then the
 US 9,476,147 B2
13 14
mixture is transferred to a twin-screw spinning machine for chloride) in a weight ratio of 1:100. Then anhydrous PAN
melt spinning in which the screw speed is adjusted to 75 powder is added with the weight ratio of PAN powder to
r/min, the temperatures for feeding section, plasticizing ionic liquid being 1:1. The obtained mixture is feed into a
section and melting section are set at 180° C., 185° C. and twin-screw spinning machine for melt spinning while blow
180°C., respectively, the aspect ratio of the spinneret is 1:3 ing air through the melting section of the twin-screw spin
and the orifices in the spinneret is 0.5 mm in diameter. The ning machine, wherein the air flow is 1 ml/min, the screw
spun fibre is subjected to a primary dry-heat drawing, a
secondary dry-heat drawing, washing with water, oiling and speed is 40 r/min, the temperatures for the feeding section,
thermosetting to give PAN fibre. The obtained PAN fibre has plasticizing section and melting section are 170° C., 185°C.
a tensile strength of 3.6 cn/dtex and an elongation at break 10
and 185°C., respectively, the aspect ratio of the spinneret is
of 8.9%. 1:3 and the orifices in the spinneret is 0.5 mm in diameter.
The spun fibre is directly subjected to dry-heat drawing
Example 8 (wherein the drawing temperature is 110° C., the total
First, PAN powder and BMIMBF4 are uniformly mixed drawing ratio is 4 times). The drawn fibre is washed with
in a mass ratio of 1:1 in a high speed mixer. Then the mixture 15 water at 70° C., followed by thermoset in dry and hot air at
is transferred to a twin-screw spinning machine for melt 150° C. to give PAN pre-oxidization fibre with a pre
spinning in which the screw speed is adjusted to 70 r/min, oxidization degree of 31%.
the temperatures for feeding section, plasticizing section and Example 11
melting section are set at 185° C., 190° C. and 190° C.,
respectively, the aspect ratio of the spinneret is 1:3 and the
orifices in the spinneret is 0.5 mm in diameter. The spun First, cobalt sulphate, a catalyst of PAN pre-oxidization is
fibre is subjected to a primary dry-heat drawing, a secondary dissolved in an ionic liquid (1-butyl-3-methyl imidazolium
dry-heat drawing, washing with water, oiling and thermo tetrafluoroborate) in a weight ratio of 0.01:100. Then anhy
setting to give PAN fibres. The obtained PAN fibre has a drous PAN powder is added with the weight ratio of PAN
tensile strength of 4.0 ch/dtex and an elongation at break of 25 powder to ionic liquid being 1:1. The obtained mixture is
16.9%. FIG. 5 shows a SEM photograph of the cross-section feed into a twin-screw spinning machine for melt spinning
of PAN fibre after washed with water. It can be concluded
from the SEM photograph that the cross section of the fibre while blowing oxygen through the melting section of the
is circle without skin-core structure. FIG. 6 is the DMA twin-screw spinning machine, wherein the oxygen flow is 5
curve diagram of the PAN fibre obtained with PAN/IBMIM] ml/min, the screw speed is 120 r/min, the temperatures for
Cl of 1:1. It can be deduced from FIG. 6 that the glass 30 the feeding section, plasticizing section and melting section
transition temperature of PAN is decreased upon the addition are 185° C., 220° C. and 220° C., respectively, the aspect
of plasticizer and it is beneficial to drawing of macromol ratio of the spinneret is 1:3 and the orifices in the spinneret
ecule chain. is 0.5 mm in diameter. The spun fibre is directly subjected
to dry-heat drawing (wherein the drawing temperature is
Example 9 35 140°C., the total drawing ratio is 6 times). The drawn fibre
is washed with water at 90° C., followed by thermoset in dry
First, PAN powder and BMIMICl are uniformly mixed in and hot air at 150° C. to give PAN pre-oxidization fibre with
a mass ratio of 1.2:1 in a high speed mixer. Then the mixture a pre-oxidization degree of 31%.
is transferred to a twin-screw spinning machine for melt
spinning in which the screw speed is adjusted to 60 r/min, 40 Example 12
the temperatures for feeding section, plasticizing section and
melting section are set at 180° C., 185° C. and 185° C., First, potassium permanganate particles and BMIMIC1
respectively, the aspect ratio of the spinneret is 1:3 and the are uniformly mixed in a three-neck flask in a weight ratio
orifices in the spinneret is 0.5 mm in diameter. The spun of 0.01:100. After the potassium permanganate is com
fibre is subjected to a primary dry-heat drawing, a secondary 45 pletely dissolved, the dried PAN powder and BMIMICl are
dry-heat drawing, washing with water, oiling and thermo uniformly mixed in a high speed mixer in a weight ratio of
setting to give PAN fibres. The obtained PAN fibre has a 1:1, followed by transferred to a twin-screw spinning
tensile strength of 4.0 ch/dtex and an elongation at break of machine for melt spinning while blowing oxygen through
14.3%. FIG. 7 shows a SEM photograph of the cross-section the melting section of the twin-screw spinning machine,
of PAN fibre after washed with water. It can be seen from the
SEM photograph that the cross section of the fibre is nearly 50 wherein the oxygen flow is 2 ml/min, the screw speed is 50
circle and the core is relatively structural compact resulting r/min, the temperatures for the feeding section, plasticizing
in the PAN based precursor fibre with relatively excellent section and melting section are 185°C., 190° C. and 185°C.,
physical and mechanical properties. FIG. 8 is a curve respectively, the aspect ratio of the spinneret is 1:3 and the
diagram illustrating the relationship between Tg and PAN orifices in the spinneret is 0.5 mm in diameter. The spun
content of the fibres obtained from PAN/IBMIMICl system 55 fibre is subjected to dry-heat drawing (wherein the drawing
before washed with water. It can be deduced from FIG. 8 temperature is 120° C., the total drawing ratio is 45 times).
that the glass transition temperature of PAN decreases with The drawn fibre is washed with water at 80°C., followed by
the decrease of the PAN content, i.e. BMIMICl functions as thermoset in dry and hot air at 120-150° C. to give PAN
a plasticizer during the melt spinning, the higher the pre-oxidization fibre with a pre-oxidization degree of 31%.
BMIMICl content, the lower the glass transition of the melt, 60 FIG. 9 shows a SEM photograph of the cross section of the
and the more beneficial to drawing of the fibre during fibre obtained when PAN/BMIMICl is 1:1 and KMnO4/
Subsequent procedure. BMIMICl is 0.01:100 after washed with water. It can be
seen from FIG. 9 that the cross section of the pre-oxidized
Example 10 fibre is very compact in structure and nearly circle in shape,
65 and that there is nearly no voids in the core, the density is
First, Cobalt dichloride, a catalyst of PAN pre-oxidization increased and the pre-oxidized fibre has relatively excellent
is dissolved in an ionic liquid (1-butyl-3 methyl-imidazolium physical and mechanical properties.
 US 9,476,147 B2
15 16
Example 13 the benzoyl peroxide is completely dissolved, the dried PAN
powder and BMIMICl are uniformly mixed in a high speed
First, potassium permanganate particles and BMIMIC1 mixer in a weight ratio of 1:1, followed by transferred to a
are uniformly mixed in a three-neck flask in a weight ratio twin-screw spinning machine for melt spinning while blow
of 0.1:100. After the potassium permanganate is completely ing oxygen through the melting section of the twin-screw
dissolved, the dried PAN powder and BMIMICl are uni spinning machine, wherein the oxygen flow is 2 ml/min, the
formly mixed in a high speed mixer in a weight ratio of 1:1, screw speed is 50 r/min, the temperatures for the feeding
followed by transferred to a twin-screw spinning machine
for melt spinning while blowing oxygen through the melting section, plasticizing section and melting section are 185°C.,
section of the twin-screw spinning machine, wherein the 10
190° C. and 185° C., respectively, the aspect ratio of the
oxygen flow is 2 ml/min, the screw speed is 50 r/min, the spinneret is 1:3 and the orifices in the spinneret is 0.5 mm
temperatures for the feeding section, plasticizing section and in diameter. The spun fibre is subjected to dry-heat drawing
melting section are 185°C., 190° C. and 185°C., respec (wherein the drawing temperature is 120° C., the total
tively, the aspect ratio of the spinneret is 1:3 and the orifices drawing ratio is 45 times). The drawn fibres is washed with
in the spinneret is 0.5 mm in diameter. The spun fibre is water at 80°C., followed by thermoset in dry and hot air at
Subjected to dry-heat drawing (wherein the drawing tem 15
150° C. to give PAN pre-oxidization fibre with a pre
perature is 120° C., the total drawing ratio is 45 times). The oxidization degree of 73%. FIG. 12 shows a SEM photo
drawn fibres is washed with water at 80° C., followed by graph of part of the cross section of the fibre obtained when
thermoset in dry and hot air at 150° C. to give PAN PAN/BMIMICl is 1:1 and BPO/IBMIMICl is 0.1:100 after
pre-oxidization fibre with a pre-oxidization degree of 67%. washed with water. It can be seen from FIG. 12 that the cross
FIG. 10 shows a SEM photograph of part of the cross section section of the pre-oxidized fibre is very compact in structure
of the fibre obtained when PAN/BMIMICl is 1:1 and and there is no skin-core structure and no voids, the pre
KMnO4/BMIMICl is 0.1:100 after washed with water. FIG. oxidized fibre is structural uniform from surface to inside,
13 shows the infrared spectra of fibres obtained when and without skin-core structure as obtained by wet spinning
PAN/BMIMICl is 1:1 and KMnO4/BMIMICl is 0.1:100, FIG. 14 shows infrared spectra of fibres obtained when
wherein curve 1 is for pre-oxidized fibre and curve 2 is for 25
precursor fibre. It can be concluded from FIG. 13 that the PAN/BMIMICl is 1:1 and BPO/IBMIMICl is 0.1:100,
absorption peak of cyano group (2240 cm-1) upon oxidiza wherein curve 1 is for pre-oxidized fibre and curve 2 is for
tion decreases while the absorption peak of—C—N (1630 precursor fibre. It can be concluded from FIG. 14 that the
cm-1) increases, indicating that part of cyano groups are absorption peak of cyano group (2240 cm-1) upon oxidiza
converted to —C=N upon pre-oxidization, facilitating the 30
tion decreases while the absorption peak of—C—N (1630
formation of intramolecular ring. It can be seen from FIG. 10 cm-1) increases, indicating that part of cyano groups are
that the cross section of the pre-oxidized fibre is very converted to —C=N upon pre-oxidization, facilitating the
compact in structure and there is no skin-core structure and formation of intramolecular ring.
no voids, the pre-oxidized fibre is structural uniform from
Surface to inside, and without skin-core structure as obtained Examples 16-20
by wet spinning. 35
Examples 16-20 are performed as Example 15 except that
Example 14 using different catalyst for PAN pre-oxidization and ionic
liquids, as listed in the following table 1.
First, benzoyl peroxide and BMIMICl are uniformly
mixed in a three-neck flask in a weight ratio of 0.01:100. 40
TABLE 1.
After the benzoyl peroxide is completely dissolved, the
dried PAN powder and IBMIMICl are uniformly mixed in a The catalyst for PAN pre-oxidation and ionic liquids as well as the pre
high speed mixer in a weight ratio of 1:1, followed by Oxidization degree of the obtained fibres
transferred to a twin-screw spinning machine for melt spin Catalyst for PAN Pre-oxidization
ning while blowing oxygen through the melting section of 45 No. preoxidization Ionic liquid degree (%)
the twin-screw spinning machine, wherein the oxygen flow Example 16 K2S2O8 (EMIMIC| 50
is 2 ml/min, the screw speed is 50 r/min, the temperatures for Example 17 Succinic acid BMIMBr 63
the feeding section, plasticizing section and melting section Example 18 Hydrogen peroxide (EMIMIBF4 82
are 185° C., 190° C. and 185° C., respectively, the aspect Example 19 Ammonia (EMIMIBF6 68
ratio of the spinneret is 1:3 and the orifices in the spinneret 50 Example 20 Hydroxylamine BMIMIBF4 79
hydrochloride
is 0.5 mm in diameter. The spun fibre is subjected to dry-heat
drawing (wherein the drawing temperature is 120° C., the
total drawing ratio is 45 times). The drawn fibres is washed
with water at 80°C., followed by thermoset in dry and hot Example 21
air at 150° C. to give PAN pre-oxidization fibre with a 55
pre-oxidization degree of 47%. FIG. 11 shows a SEM 0.05 parts by weight of carboxylated multi-walled carbon
photograph of the cross section of the fibre obtained when nanotube (available from Chengdu Institute of Organic
PAN/BMIMICl is 1:1 and BPO/IBMIMICl is 0.01:100 after Chemistry of Chinese Academy of Sciences, with length of
washed with water. It can be seen from FIG. 11 that the cross 10-30 um, inner diameter of 10-20 nm, outer diameter of
section of the pre-oxidized fibre is nearly circle in shape and 60 5-10 nm) and 100 parts by weight of dimethylsulfoxide
is relatively compact in core and, and the pre-oxidized fibre Solvent are mixed, ultrasonic processed for 3 hrs in an
has relatively excellent physical and mechanical properties. ultrasonic cell disrupter operating at 300 w; to the resulting
solution is added 0.05 parts by weight of polymer thickener
Example 15 PAN (with polymerization degree of 88,000 and particle size
65 of 230 nm-250 nm) and ultrasonic processed for 2 hrs in an
First, benzoyl peroxide and BMIMICl are uniformly ultrasonic cell disrupter operating at 300 w. The oxidized
mixed in a three-neck flaskin a weight ratio of 0.1:100. After PAN pre-oxidized fibre is dipped into the obtained solution
 US 9,476,147 B2
17 18
in a solid-to-liquid ratio of 1:3 for 1 hr., and a coating of 200 Chemistry of Chinese Academy of Sciences, with length of
nm is formed on the surface of the oxidized PAN pre 10-30 um, inner diameter of 10-20 nm, outer diameter of
oxidized fibre. The oxidized PAN pre-oxidized fibre is 5-10 nm) and 100 parts by weight of water solvent are
carbonized at 1000° C. to give high strength carbon fibre. mixed, ultrasonic processed for 1.5 hrs in an ultrasonic cell
FIG. 15 shows a filed emission SEM photograph (magnifi- 5 disrupter operating at 500 w. To the resulting solution is
cation factor of which is 10,000) of carbon fibres treated added 5 parts by weight of polymer thickener C-cyanoacry
with PAN: multi-walled carbon nanotube:dimethylsulfox
ide=0.05:0.05:100 by weight. It can be seen from FIG. 15 late (with molecular weight of 400-800, available from
that carbon nanotubes are uniformly attached to the surface Shanghai Tailuo Company Ltd.) and ultrasonic processed for
of fibres and can repair voids on the surface of fibre so that 10 1 hr in an ultrasonic cell disrupter operating at 500 w. The
the tensile strength of carbon fibre can be effectively obtained solution is electrostatically sprayed onto the Sur
increased. face of the oxidized PAN pre-oxidized fibre with a voltage
of 120 kV, a spray distance of 40 cm and a rotation speed of
Example 22 spray gun of 3000 r/min to form a coating of 100 nm
0.5 parts by weight of carboxylated multi-walled carbon 15 1000° The
thereon. oxidized PAN pre-oxidized fibre is carbonized
nanotube (available from Chengdu Institute of Organic at C. to give high strength carbon fibre. FIG. 18 shows
Chemistry of Chinese Academy of Sciences, with length of a filed emission SEM photograph (magnification factor of
10-30 um, inner diameter of 10-20 nm, outer diameter of which is 10,000) of carbon fibres treated with C.-cyanoacry
5-10 nm) and 100 parts by weight of N,N-dimethylforma late:multi-walled carbon nanotube:water 5:0.05:100 by
mide solvent are mixed, ultrasonic processed for 1.5 hrs in weight. It can be seen from FIG. 18 that multi-walled carbon
an ultrasonic cell disrupter operating at 600 w. To the nanotubes are uniformly attached to the surface of carbon
resulting solution is added 0.05 parts by weight of polymer fibres and repair voids on the surface of carbon fibres, which
thickener polyvinyl alcohol (with polymerization degree of is beneficial to increase of the tensile strength of carbon
88,000 and particle size of 230 nm-250 nm) and ultrasonic fibre.
processed for 1 hrs in an ultrasonic cell disrupter operating 25
at 600 w. The oxidized PAN pre-oxidized fibre is dipped into
the obtained solution in a solid-to-liquid ratio of 1:2 for 2 Example 25
hrs; a coating of 200 nm is formed on the surface of the
oxidized PAN pre-oxidized fibre. The oxidized PAN pre
oxidized fibre is carbonized at 1000°C. to give high strength 30 0.01 parts by weight of carboxylated Multi-walled Carbon
carbon fibre. FIG. 16 shows a filed emission SEM photo nanotube (available from Chengdu Institute of Organic
graph (magnification factor of which is 10,000) of carbon Chemistry of Chinese Academy of Sciences, with length of
fibres treated with polyvinyl alcohol:multi-walled carbon 10-30 um, inner diameter of 10-20 nm, outer diameter of
nanotube:N,N-dimethylformamide=0.05:0.5:100 by weight. 5-10 nm) and 100 parts by weight of water solvent are
It can be seen from FIG. 16 that multi-walled carbon mixed, ultrasonic processed for 1.5 hrs in an ultrasonic cell
nanotubes are uniformly attached to the surface of carbon 35 disrupter operating at 500 w. To the resulting solution is
fibre and repair voids on the surface of carbon fibre, which added 0.01 parts by weight of polymer thickener C.-cyano
is beneficial to increase of the tensile strength of carbon acrylate and ultrasonic processed for 1 hr in an ultrasonic
fibres. cell disrupter operating at 500 w. The obtained solution is
Example 23 40 electrostatically sprayed onto the surface of the oxidized
PAN pre-oxidized fibre with a voltage of 100 kV, a spray
0.05 parts by weight of carboxylated multi-walled carbon distance of 30 cm and a rotation speed of spray gun of 2900
nanotube (available from Chengdu Institute of Organic r/min to form a coating of 100 nm thereon. The oxidized
Chemistry of Chinese Academy of Sciences, with length of PAN pre-oxidized fibre is carbonized at 1000° C. to give
10-30 um, inner diameter of 10-20 nm, outer diameter of 45 high strength carbon fibre.
5-10 nm) and 100 parts by weight of water solvent are
mixed, ultrasonic processed for 2 hrs in an ultrasonic cell Example 26
disrupter operating at 500 w. To the resulting solution is
added 5 parts by weight of polymer thickener polyvinyl
alcohol (with polymerization degree of 88,000 and particle 50 2 parts by weight of carboxylated multi-walled carbon
size of 230 nm-250 nm) and ultrasonic processed for 1.5 hrs nanotube (available from Chengdu Institute of Organic
in an ultrasonic cell disrupter operating at 600 w. The Chemistry of Chinese Academy of Sciences, with length of
obtained solution is electrostatically sprayed onto the Sur 10-30 um, inner diameter of 10-20 nm, and outer diameter
face of the oxidized PAN pre-oxidized fibre with a voltage of 5-10 nm) and 100 parts by weight of dimethylacetamide
of 80 kV, a spray distance of 25 cm and a rotation speed of 55 Solvent are mixed, ultrasonic processed for 1.5 hrs in an
spray gun of 2800 r/min to form a coating of 300 nm ultrasonic cell disrupter operating at 500 w. To the resulting
thereon. The oxidized PAN pre-oxidized fibre is carbonized solution is added 2 parts by weight of polymer thickener
at 1000° C. to give high strength carbon fibre. FIG. 17 shows C-cyanoacrylate and ultrasonic processed for 1 hr in an
a filed emission SEM photograph (magnification factor of ultrasonic cell disrupter operating at 500 w. The obtained
which is 10,000) of carbon fibres treated with polyvinyl 60 solution is electrostatically sprayed onto the surface of the
alcohol:multi-walled carbon nanotube:water 5:0.05:100 by oxidized PAN pre-oxidized fibre with a voltage of 120 kV, a
weight. spray distance of 30 cm and a rotation speed of spray gun of
2900 r/min to form a coating of 100 nm thereon. The
Example 24 oxidized PAN pre-oxidized fibre is carbonized at 1000° C. to
65 give high Strength carbon fibre. The mechanical properties
0.05 parts by weight of carboxylated multi-walled carbon of carbon fibres obtained from Examples 21-26 are shown in
nanotube (available from Chengdu Institute of Organic table 2.
 US 9,476,147 B2
19 20
TABLE 2
Mechanical properties of carbon fibres obtained
Mechanical properties
Tensile strength Elongation at break
Strength GPa. Variation range (%) Elongation (%) Variation range %
Contrast (untreated) 3.18 8.90
Example 21 3.80 +22.64 13.5 +51.6
Example 22 4.35 +36.79 14.3 +60.6
Example 23 4.40 +38.36. 1S.O --68.5
Example 24 4.67 +46.85 16.3 +83.1
Example 25 4.78 --50.30 16.9 --89.8
Example 26 4.71 +48.11 16.0 79.7

Example 27 The mixture is stirred at 175° C., oxygen-containing gas is

blown into the reactor at a rate of 5 ml/min. The temperature
1-butyl-3-methylimidazolium chloride ionic liquid and and time of pre-oxidization is controlled, and pre-oxidiza
PAN powder are added in a reactor with mechanical stirrer. tion is proceeded for about 4-5 hrs to get PAN spinning
Upon the polymer is completely dissolved, a catalyst solution. FIG. 21 shows infrared spectra of PAN/DMSO
KMnO4 is added to facilitate cyclization of PAN. The pre-oxidized at 175° C. for different time. It can be seen
weight percent of the above material are as follows: PAN, from the spectra that as the pre-oxidization time increases,
5%; solvent, 95%. KMnO is added at 0.05 wt.% of PAN. 25
the intensity of the absorption peak of —C=N group
The mixture is stirred at 170° C., oxygen is blown into the decreases and that of —C=N group increases, and the
reactor at certain flow rate. The temperature and time of intramolecular cyclization degree increases.
pre-oxidization is controlled and samples are collected when
the reaction time is 20 min, 40 min, 60 min and 90 min,
respectively, to get PAN spinning solutions with different Comparative Example 1
pre-oxidization degree. FIG. 19-2 shows an improved pro 30
cess of producing PAN based carbon fibre used in this First, a PAN/DMSO spinning solution is wet spun by
example. FIG. 20-1 shows infrared spectra of PAN/IL pre conventional process. Then PAN precursor fibres are
oxidized at 170° C. for different time. It can be seen from the
spectra that as the pre-oxidization time increases, the inten obtained after a series of post-treatments. PAN precursor
sity of the absorption peak of—C=N group decreases and 35 fibre is pre-oxidized in a pre-oxidization furnace with 6
that of —C=N group increases, and the intramolecular heating sections with the onset temperature of 170° C., the
cyclization degree increases. temperature is warmed up 10° C./10 min, while samples of
pre-oxidized fibres are collected at different temperature,
Example 28 and finally maintained at 260° C. for 0.5 hr. The samples of
40 pre-oxidized fibres are subjected to infrared analysis and
1-butyl-3-methylimidazolium chloride ionic liquid and compared with that obtained from the above two systems in
PAN are added in a reactor with mechanical stirrer. Upon the terms of pre-oxidization degree. It has been found that the
polymer is completely dissolved, a catalyst KMnO4 is added new process of spinning after the spinning Solution being
to facilitate cyclization of PAN. The weight percent of the pre-oxidized can reach the same pre-oxidization degree as
above material are as follows: PAN, 5%; solvent, 95%. 45
that obtained from conventional process, however, the pre
KMnO, is added at 0.05 wt.% of PAN. The mixture is oxidization cost of the new process can be substantially
stirred at 160° C., oxygen is blown into the reactor at 5 decreased, and therefore the manufacturing cost of carbon
ml/min. The temperature and time of pre-oxidization is fibres is decreased. FIG. 22 shows infrared spectra of PAN
controlled and samples are collected when the reaction time precursor fibre pre-oxidized in oxidization furnace. Com
is 20 min, 40 min, 60 min, 90 min, 120 min and 150 min, 50
pared with Examples 27, 28 and 29, the oxidization degree
respectively, to get PAN spinning solutions with different of comparative example 1 is comparative with that of
pre-oxidization degree. FIG. 20-2 shows infrared spectra of Examples 27, 28 and 29, however the oxidization effect of
PAN/IL pre-oxidized at 160° C. for different time. It can be examples 27, 28 and 29 is better and the process is simpler,
seen from the spectra that as the pre-oxidization time
increases, the intensity of the absorption peak of—C=N 55 therefore the cost of the subsequent carbon fibres manufac
group decreases and that of —C=N group increases, and turing can be decreased.
the intramolecular cyclization degree increases. However, The basic principle, main characteristics and advantages
the cyclization degree at 160° C. is lower than that at 170° of the invention are illustrated and described above. It
C. should be understood by the skilled in the art that the
60 examples and description are used to illustrate the principle
Example 29 of the invention and should not be taken as limiting the
Scope of the invention, and there will be various changes and
DMSO and PAN are added in a reactor with mechanical modifications without departing the sprit and scope of the
stirrer. Upon the polymer is completely dissolved, a catalyst invention and those changes and modifications fall within
KMnO4 is added to facilitate cyclization of PAN. The 65 the scope of the invention. The scope of the invention is
weight percent of the above material are as follows: PAN, defined by the accompanying claims and equivalents
10%; DMSO, 90%. KMnO is added at 0.05 wt.% of PAN. thereof.
 US 9,476,147 B2
21 22
The invention claimed is:
1. A gel spinning process for producing a PAN-based
precursor fibre consisting of the following steps:
a) mixing an anhydrous PAN powder and a solvent in a
weight ratio from 5:100 to 20:100, followed by heating
at a temperature between 70° C. and 110°C. until the
PAN powder is completely dissolved to obtain a solu
tion;
b) adding a small-molecule gelling agent to the Solution
from step a) to obtain a mixture, said Small-molecule 10
gelling agent being in an amount of from 2% to 5% by
weight of the solution, and the mixture being mechani
cally stirred for 1 hour to obtain a uniformly mixed
spinning solution;
c) transferring the spinning solution from step b) to a wet 15
spinning machine and spinning by using conventional
wet spinning process for producing PAN based precur
sor fibre, thereby obtaining the PAN-based precursor
fibre.
2. The gel spinning process according to claim 1, char
acterised in that the solvent in step a) is selected from the
group consisting of dimethylformamide (DMF), dimethyl
acetamide (DMAc), dimethyl sulfoxide (DMSO), sodium
thiocyanate (NaSCN), nitric acid (HNO), and Zinc chloride
(ZnCl2). 25
3. The gel spinning process according to claim 1, char
acterised in that the heating in Step a) is performed by means
of oil bath or sand bath.
4. The gel spinning process according to claim 1, char
acterised in that the Small-molecule gelling agent in step b) 30
is one or more selected from the group consisting of H2O,
glycerol, glycol, urea, and thiourea.
k k k k k