USOO9334586B2

(12) United States Patent (10) Patent No.: US 9,334,586 B2

Yu et al. (45) Date of Patent: May 10, 2016

(54) PROCESS OF MELT-SPINNING D10B2101/12 (2013.01); D10B2101/122

POLYACRYLONTRILE FIBER (2013.01); D10B 2321/10 (2013.01)
(58) Field of Classification Search
(71) Applicant: DONGHUA UNIVERSITY, Shanghai CPC ........... D01D 5/08: D01D 5/098: D01D 5/12:
(CN) D01D 5/16: D01D 7/00: D01D 10/02: D01D
10/06: D01F1/02: D01F 1/10; D01F 6/18:
(72) Inventors: Muhuo Yu, Shanghai (CN); Huaiping D01F 9/22: D02J 1/22: D02J 1/222: D02J
Rong, Shanghai (CN); Keqing Han, 1/224
Shanghai (CN); Zhaohua Wang, USPC ........... 264/210.5, 210.6, 210.8, 211, 211.12,
Shanghai (CN); Yiwei Zhang, Shanghai 264/211.14, 211.17, 233
(CN); Yincai Tian, Shanghai (CN); See application file for complete search history.
Qinli Dong, Shanghai (CN)
(73) Assignee: DONGHUA UNIVERSITY, Shanghai (56) References Cited
(CN) U.S. PATENT DOCUMENTS
(*) Notice: Subject to any disclaimer, the term of this 2,733,121 A 1/1956 Griffith, Jr. et al.
patent is extended or adjusted under 35 4,185,059 A 1/1980 Reinehr et al.
U.S.C. 154(b) by 27 days. 5,560,991 A 10, 1996 Patel et al.
8,906,278 B2 12/2014 Yu et al.
(21) Appl. No.: 14/519,002 (Continued)
(22) Filed: Oct. 20, 2014 FOREIGN PATENT DOCUMENTS
(65) Prior Publication Data CN 1461829. A 12/2003
CN 1478,930 A 3, 2004
US 2015/OO35.197 A1 Feb. 5, 2015
(Continued)
OTHER PUBLICATIONS
Related U.S. Application Data
(62) Division of application No. 13/262,620, filed as International Search Report for PCT/CN2010/000036 dated Apr. 22,
application No. PCT/CN2010/000036 on Jan. 11, 2010.
2010, now Pat. No. 8,906,278. (Continued)
(30) Foreign Application Priority Data
Primary Examiner — Leo B Tentoni
Mar. 31, 2009 (CN) .......................... 2009 1 OO48.603 (74) Attorney, Agent, or Firm — Nixon Peabody LLP:
Jun. 9, 2009 (CN). ... 2009 1 OO52721 Joseph Bach, Esq.
Jun. 17, 2009 (CN) .......................... 2009 1 OO53212
Sep. 17, 2009 (CN) .......................... 2009 1 O195794
Nov. 6, 2009 (CN) .......................... 2009 1 O1984.44 (57) ABSTRACT

(51) Int. C. Processes for producing carbon fiber, the filament thereofand
DOID 5/098 (2006.01) pre-oxidized fiber are provided. In one embodiment, the gel
spinning of polyacrylonitrile filament is achieved by using
DOID 5/2 (2006.01) Small-molecule gelling agent, and the carbon fiber obtained
D02. I/22 (2006.01) thereby is increased by 15% to 40% intensile strength and by
DOIF 9/22 (2006.01) 20% to 35% in toughness. In another embodiment, the melt
DOID L/04 (2006.01) spinning process of polyacrylonitrile is conducted by using
DOID 5/08 (2006.01) imidazole type ion liquid as plasticizer, the process reduces
DOID LO/02 (2006.01) environment pollution, is Suitable for industrial production
DOIF I/O (2006.01) and the fiber produced thereby is improved in its strength. In
DOIF 6/18 (2006.01) yet another embodiment, polyacrylonitrile pre-oxidized fiber
DOID 5/06 (2006.01) is produced by melt spinning, so low cost and controllable
DOID LO/06 (2006.01) pre-oxidization of polyacrylonitrile can be achieved. In a
DOIF I/02 (2006.01) further embodiment, high strength carbon fiber is manufac
B05D I/00 (2006.01) tured by using polymer thickening agent. In another further
B05D L/18 (2006.01) embodiment, low cost and controllable pre-oxidization of
(52) U.S. C. polyacrylonitrile is achieved by conducting pre-oxidization
CPC DOIF 9/22 (2013.01); B05D I/007 (2013.01); before spinning, minimizing skin-core structure, so as to pro
B05D 1/18 (2013.01): D0ID I/04 (2013.01); duce high performance carbon fiber, and reduce the produc
D0ID5/06 (2013.01): D0ID5/08 (2013.01); tion cost of carbon fiber greatly.
D0ID 10/02 (2013.01): D0ID 10/06 (2013.01);
D0IF I/02 (2013.01): D0IF I/10 (2013.01);
D0IF 6/18 (2013.01): D02.J I/224 (2013.01); 5 Claims, 7 Drawing Sheets
 US 9,334,586 B2
Page 2

(56) References Cited JP 61-69814 A 4f1986

JP 10-265674. A 10, 1998
U.S. PATENT DOCUMENTS JP 2005-256.222 A 9, 2005
WO 2010/111882 A1 10/2010
2006/0100323 A1 5, 2006 Schmidt et al. OTHER PUBLICATIONS
2007/O142515 A1 6, 2007 Higuchi et al.
2015.00351.83 A1 2, 2015 Yu et al.
2015.0035196 A1 2, 2015 Yu et al. International Preliminary Report on Patentability for PCT/CN2010/
2015,003.7509 A1 2, 2015 Yu et al. 000036 dated Oct. 13, 2011.
ShenRui et al., “Study on the Gel-spinning Process for Preparing
FOREIGN PATENT DOCUMENTS Polyacrylonitrile Carbon Fiber Filament”,Techno-Economics in Pet
rochemicals, Apr. 2007, vol. 23, No. 2, pp. 41-44.
CN 1740411 A 3, 2006 Restriction Requirement for U.S. Appl. No. 13/262,620 dated Dec.
CN 1.0125077O A 8, 2008 11, 2013.
CN 10 1260575 A 9, 2008 Office Action for U.S. Appl. No. 13/262,620 dated Apr. 7, 2014.
CN 101545148 A 9, 2009 Notice of Allowance for U.S. Appl. No. 13/262,620 dated Jul. 18,
CN 101586265 A 11, 2009 2014.
CN 10159782O A 12/2009 Office Action for U.S. Appl. No. 14/518,944 dated Dec. 8, 2015.
JP 46-34939 B 10, 1971 Office Action for U.S. Appl. No. 14/519,076 dated Jan. 7, 2016.
U.S. Patent May 10, 2016 Sheet 1 of 7 US 9,334,586 B2
U.S. Patent May 10, 2016 Sheet 2 of 7 US 9,334,586 B2

Temperature ( )
Fig.6
U.S. Patent May 10, 2016 Sheet 3 of 7 US 9,334,586 B2

Fig.9 Fig.10

x3 . sess is 888; 8.

Fig.11

500 000 500 2000 2500 3000 3500

Wave numbericm
Fig.13
U.S. Patent May 10, 2016 Sheet 4 of 7 US 9,334,586 B2

90

4.

20 8
500 1000 1500 2000 250 3000 3500

Wave number/cm
Fig.14

Fig.15 Fig.16

Fig.17 Fig.18
U.S. Patent May 10, 2016 Sheet 5 Of 7 US 9,334,586 B2

FA,

Initiator
Pre-Oxidization(xidization. Furnace
F. Ray Filattent (200-3COC, it air

Cathorization FA as at Oil Fief

(1-143, it initiei

Fig.19.1
F.
Pre-Oxidization(Reactor
Coition. Other Polymerization - 1-2, in air
Initiator

Cathonization F. 888 at Oil Fif

1-145OC, it fittget

Fig.19-2

14) 334

15 3. 3.

Wave number (cm)

Fig.20-1
U.S. Patent May 10, 2016 Sheet 6 of 7 US 9,334,586 B2

59 14 1280
1.

4.
5
8

O 1. &O 3. 3.

Wave number (cm)

Fig.20-2

1.

5 i &O 3. 3.

Wave number (cm)

Fig.21
U.S. Patent May 10, 2016 Sheet 7 Of 7 US 9,334,586 B2

3. 3. .

Wave number (cm)

Fig.22
 US 9,334,586 B2
1. 2
PROCESS OF MIELTSPINNING It was firstly reported by Coxe in 1952 that adding a small
POLYACRYLONTRILE 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 spin
ning of PAN are carried on abroad by many foreign compa
This application is a divisional application of U.S. patent nies such as ACC Co., Du Pont Co, BP Chemical Co., Mit
application Ser. No. 13/262,620 filed on Sep. 30, 2011, now subishi Rayon Co., Ltd., Exlan Co. Ltd, Asahi Kasei
U.S. Pat. No. 8,906,278 B2 which is a National Phase of Corporation, etc.
International Application No. PCT/CN2010/000036, which 10 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,
wherein plasticized melt spinning comprising the following
the benefit of Chinese Patent Application Nos. aspects: Plasticized by solvent (such as DMSO and PC and
200910048603.8 filed on Mar. 31, 2009, 2009 10052721.6 the like): PAN powder which had been plasticized by PC can
filed on Jun. 9, 2009, 2009 10053212.5 filed on Jun. 17, 2009, 15 be melted and be extruded continuously into filaments. For
200910195794.0 filed on Sep. 17, 2009, and example, the study on Rheological properties of mixture of
2009101984.44.X filed on Nov. 6, 2009, and the disclosures of PAN and PC in weight ratio of 50:50 at 180° C. and 240° C.
which are hereby incorporated herein by reference in their shows that the blend fluid thereof is shear thinning fluid and
entireties. its viscosity is lower than that of conventional plastic PE; 2
Plasticized by non-similar polymer such as PEG reported in
TECHNICAL FIELD literatures: PAN fibre is prepared by melt spinning of PAN
and PEG mixture by Asahi Chemical Co. Ltd, the tensile
The present invention belongs to the field of processing strength of which can be up to 4.68 cn/dtex; (3) Plasticized by
technology of carbon fibres. In particular, the present inven low molecular weight PAN: 91 parts copolymer of PAN and
tion relates to processes for producing carbon fibre, precursor 25 methyl acrylate (copolymerization ratio being 85:15 by
fibre and pre-oxidized fibre thereof. weight, specific viscosities being 0.68) and 9 parts another
copolymer of PAN and methyl acrylate (copolymerization
BACKGROUND ART ratio being 85:15 by weight, molecular weight being 4800)
are mixed and melt extruded at 215° C., and spun at 1200
Carbon fibre is widely used in high-tech industrial field due 30 m/min to obtain fibre, which is drawn in boiling water to 4
to its excellent properties such as low density, high strength, times to obtain fibre having a linear density of 1.17 dtex, a
high modulus, high temperature resistance, corrosion resis tensile strength of 5.26 cN/dtex, and elongation at break of
tance, friction resistance, and fatigue resistance, etc., espe 12.3%, as reported by Mitsubishi Rayon Co., Ltd. And fibre
cially has a very potential application in aerospace field. The satisfying certain requirements can also be melt spun by
production of carbon fibre generally comprises spinning, pre 35 reducing AN unit content of low molecular weight PAN for
oxidizing and carbonizing process. plasticizing appropriately; 4 Plasticized by water, which is the
The properties of carbon fibre, to a great extent, depend on most studied method: PAN and certain amount of water
its precursor fibre. The low quality of polyacrylonitrile (PAN) become melt under a certain pressure and temperature, which
based precursor fibre has been a “bottleneck” restricting the is then extruded into spinning pack and then spinning duct
development of carbon fibre industry in china for many years. 40 through spinning machine, and drawn. There is full of water
It is urgent to effectively improve the quality of PAN precur vapour in the spinning duct to prevent fibre foaming due to
sor fibre, thereby improving the properties of carbon fibre. rapidly water evaporation. The obvious characteristics of this
Compared with precursor fibre produced abroad, homemade method lie in that the only use of inexpensive and non-toxic
precursor fibre has larger fineness, lower strength, larger dis water will save recovery procedures and devices and will not
persion coefficient, more defects, cracks and Voids, lower 45 produce pollution to the environment. It was reported in lit
crystallinity and orientation, etc., which are serious problems eratures that PAN fibre obtained from melt spinning by using
existing during production of precursor fibre. As far as quality water as plasticizer can be used as precursor fibre for carbon
and yield of precursor fibre are concerned, quality is the fibre and have a molecular weight of 100,000-250,000,
primary problem at present. The tensile strength of most strength of 3.6 cN/dtex, Young modulus of 97 cn/dtex, and
carbon fibres produced from homemade precursor fibre is 50 the carbon fibre obtained by carbonization has an average
about 3.5 GPa, which can not fulfil the requirement for use at strength of 15 cN/dtex, Young modulus of 1080-1310
present, therefore its application is limited. Meanwhile, the cN/dtex and sonic modulus over 1000 cn/dtex. Recently,
poor stability of precursor fibre quality is an obstacle to Scale aerospace grade carbon fibre prepared from PAN fibre as
production. precursor fibre obtained from melting spinning and plasti
A main feature of PAN resin is its high melting point (317° 55 cized by water is also developed by Celion Carbon Fibres
C.). It is decomposed before melted when it is heated, there Company. However, this method also has the following prob
fore only solution spinning can be used to produce PAN fibre. lems: A. The extrusion pressure of screw is relatively high due
A large amount of toxic or corrosive chemical Solvents are to the poor rheological properties of hydrous melts; B. To
required in industrialized wet spinning and dry spinning, and prevent the surface of fibre from being coarse and microvoids
recovery and purification of the used solvents, washing fibres 60 being formed thereon which result in poor mechanical prop
with water and drying, as well as “three wastes' treatment are erties of fibre due to too quick water evaporation during
necessary during production. If the melt spinning of PAN coagulation, Saturated Steam of certain pressure is required to
fibre can be realized, not only solvent exhaustion but also be maintained in the spinning duct, thereby presenting a
recovery step and devices for solvent recovery and washing requirement for devices; C. It is difficult to control the process
step can be saved, therefore the manufacturing cost can be 65 due to the narrow temperature range for melt spinning of
substantially lowered, and the serious environmental prob hydrous melt, therefore industrialization of melt spinning of
lems caused by solvents are eliminated. hydrous melt has not been realized yet at present.
 US 9,334,586 B2
3 4
During the manufacturing of carbon fibre, pre-oxidization During the production of carbon fibre (or graphite fibre),
is a key procedure and the most time-consuming process, the especially carbon fibre obtained by using PAN precursor fibre
structure and properties of the final carbon fibre to a great as starting material, the formation of Voids on Surface is
extent depend on the structural transformation during pre caused by defects of precursor fibre itself and evenness prob
oxidization. Since there is dramatic structural transformation 5 lems during production. Those Voids induce stress concentra
during pre-oxidization, defects are easily caused, resulting in tion when fibre is subjected to force, which is also the main
a decrease of the mechanical properties of carbon fibre. reason for break of monofilament. Repairing Voids on Surface
Therefore the structure transformation and control of struc
ture during pre-oxidization are very important to the control has been concerned in carbon fibre production field, but there
is not good means for it until now, and the only way at present
of the structure and properties of carbon fibre. 10
is to sacrifice monofilaments with voids, therefore the overall
All processes for pre-oxidizing PAN precursor fibre for mechanical properties of carbon fibre are substantially
carbon fibre reported in literature till now pre-oxidize precur decreased.
sor fibre in air. That is to say, all PAN based carbon fibres are As disclosed in Chinese Patent No. 02121070.5, environ
obtained by spinning, pre-oxidizing and carbonizing pro
cesses sequentially. However, such an order will result in the 15 ment of an ethyne reaction is created by heating through
following shortcomings: 1) During pre-oxidization of PAN focusing electromagnetic field induction to induce ethyne to
precursor fibre, uneven morphological structure of fibre will be cracked into hydrogen and carbon atoms near high tem
becaused if there is a gradient difference of pre-oxidization perature carbon fibres. Carbon atoms deposits on the surface
degree across the cross-section of fibre, such as common of carbon fibres to repair defects on surface thereby reinforc
skin-core structure, which will result in uneven radical con ing carbon fibre. However, the equipments for this process are
traction across the cross-section of fibre and poor preferred very complicated and costly, uneasily to handle and the effi
orientation and tensile performance, and therefore decrease ciency is low.
of properties of final carbon fibre. 2) The pre-oxidization
process is very time-consuming, its temperature is high and SUMMARY OF THE INVENTION
equipments are complicated, resulting in the improved cost 25
for pre-oxidization and therefore eventually, the whole cost of The technical problem to be solved by the present invention
manufacturing carbon fibre are Substantially increased. is to provide processes for producing carbon fibre, precursor
Therefore, the pre-oxidization of PAN fibre is very important. fibre and pre-oxidized fibrethereof to overcome the problems
Pre-oxidization is a systemic engineering, revolves in not existing in current carbon fibre production such as poor qual
only equipments and means of pre-oxidization, but also pro 30 ity of precursor fibre, high cost for producing pre-oxidized
cess parameters (such as temperature, time, drawing, fibre and carbon fibre as well as serious environmental pol
medium, flow and direction of medium), reaction and change lution.
in PAN fibre during pre-oxidization, evaluation index of In an embodiment, the present invention provides a gel
structure and pre-oxidization degree of pre-oxidized fibre, spinning process for producing a PAN-based precursor fibre,
etc. 35 comprising the following steps:
In recent years, researchers at home and abroad take more a) mixing an anhydrous PAN powder and a solvent in a
and more efforts on pre-oxidization of PAN precursor fibre. weight ratio from 5:100 to 20:100, followed by heating at a
However, their researches are carried on pre-oxidization of temperature between 70° C. and 110° C. until the PAN pow
PAN precursor fibre after spinning. For example, PAN pre der is completely dissolved to obtain a solution;
cursor fibre are also pre-oxidized by three huge companies 40 b) adding a small-molecule gelling agent to the Solution
which produce carbon fibre, namely, Toray, TOHO, Mitsub from step a) to obtain a mixture, said Small-molecule gelling
ishi Rayon. Pre-oxidization is double diffusion process and agent being in an amount of from 2% to 5% by weight of the
oxygen diffuses from surface to inside of fibre. As the pre Solution, and the mixture being mechanically stirred for 1
oxidization reaction continues, compact thin layer with lad hour to obtain a uniformly mixed spinning Solution;
derlike structure is formed on the surface of fibre at first, 45 c) transferring the spinning Solution from step b) to a wet
blocking the diffusion of oxygen, and then a skin-core struc spinning machine and spinning by using conventional wet
ture is formed, resulting in defects of carbon fibre. spinning process for producing PAN based precursor fibre,
Manufacturing process using layer-based thermal stabi thereby obtaining the PAN-based precursor fibre.
lized furnace with 6-12 zones for heating and drawing which The solvent in step a) is selected from the group consisting
can produce pre-oxidization fibre with high quality is dis 50 of dimethylformamide (DMF), dimethylacetamide (DMAc),
closed in Chinese Patent Nos. 02136722.1 and dimethyl sulfoxide (DMSO), sodium thiocyanate (NaSCN),
200810036189.4. However, the equipments for this process nitric acid (HNO), and Zinc chloride (ZnCl), and preferably
are extremely complicated, the temperature is difficult to DMF or DMSO.
control and the cost is high. The heating in step a) is preformed by means of oil bath or
The industrial objects of carbon fibre production are to 55 sandbath.
lower the cost, improve the properties and productivity of The Small-molecule gelling agent in step b) is one or more
carbon fibre. For quick pre-oxidization and excellent pre selected from the group consisting of H2O, glycerol, glycol,
oxidized fibre, the process of pre-oxidization should be opti urea, and thiourea.
mized. The key for lowering production cost is shorten the In this embodiment, the spinning solution is transformed to
time for pre-oxidization which causes easily skin-core struc 60 three-dimensional network structure directly in cooled air by
ture and Subsequently larger voids and defects during carbon heat-induced gelatinization through adding some non-sol
izing procedure, thereby resulting in decrease of mechanical vents into the spinning solution. Once Such structure is
properties of carbon fibre Skin-core structure is not obvious formed, skin-core structure is avoided because only double
by lowering temperature and prolonging time of pre-oxidiza diffusion of Solvent and non-solvent exists in coagulation
tion, which is beneficial to properties of carbon fibre, how 65 bath, and phase separation will not occur, thereby the tensile
ever, also lowers the production efficiency. Thus an excellent strength of precursor fibre for PAN based carbon fibres can be
process for pre-oxidization has not been developed yet. increased.
 US 9,334,586 B2
5 6
In an embodiment, the present invention provides a melt screw spinning machine, wherein the flow rate of the oxygen
spinning process for producing a PAN fibre by using an ionic containing gas is between 1 ml/min and 5 ml/min, and the
liquid as plasticizer, comprising the following steps: rotational velocity of screw is between 40 and 120 r/min, and
a) mixing an anhydrous PAN powder and an ionic liquid the temperature at a feed segment is between 170° C. and
uniformly in a weight ratio from 1:1 to 1:0.25 to obtain a 185°C., and the temperature for plasticizing is between 185°
mixture; C. and 220° C., and the temperature for melting is between
b) adding the mixture from step a) into a hopper of twin 185° C. and 220° C.;
screw spinning machine to conduct melt spinning with a c) dry-heat drawing the spun fibre directly under a tem
screw rotation speed of 40-120 r/min at a predetermined perature between 110 and 140° C. with a total draw ratio
spinning temperature ranging from 170° C. to 220°C.; and a 10 between 4 and 6, then washing the drawn fibre with water at
filament from the spinning machine being drawn directly by 70-90° C., followed by thermosetting in dry hot air at 120
means of dry-heat drawing without a water bath, with a draw 150° C. to give the PAN based pre-oxidized fibre.
ing temperature ranging from 80°C. to 180° C. and a drawing The catalyst for pre-oxidation of PAN used in step a) is one
ratio of 1 to 8: or more selected from the group consisting of potassium
c) washing the drawn fibre with water, thermosetting and 15 permanganate, cobalt dichloride, cobalt Sulphate, potassium
winding to obtain the PAN fibre. persulfate, benzoyl peroxide, Succinic acid, hydrogen peroX
The plasticizer in step a) is a disubstituted imidazole-based ide, ammonia, and hydroxylamine hydrochloride.
ionic liquid with the structure of The ionic liquid used in step a) is disubstituted imidazole
based ionic liquid, preferably one or more selected from the
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
25 roborate (BMIM BF), 1-ethyl-3-methyl imidazolium
hexafluorophophate (EMIMPF), 1-methyl-3-butyl imida
Zolium hexafluorophophate (BMIMPF).
Preferably, the oxygen-containing gas is oxygen or air.
wherein R is methyl or butyl; R is methyl, ethyl, n-propyl. KMnO is used as a catalyst so that the time for pre
iso-propyl. n-butyl, sec-butyl or iso-butyl: X is chloride ion 30 oxidization is shortened and the final properties of carbon
(Cl), bromide ion (Br), tetrafluoroborate (BF4) or hexafluo fibre are improved. CoCl2 and CoSO can also be used to
rohosphorate (PF6). catalytically improve the structure and properties of PAN.
The disubstituted imidazole-based ionic liquid is prefer BPO, succinic acid and the like can also be used as catalyst for
ably one or more selected from the group consisting of cyclization during the course of pre-oxidization of PAN.
1-ethyl-3-methyl imidazolium chloride (EMIMICl), 1-bu 35 These catalysts or their combination can reduce the activation
tyl-3-methyl imidazolium chloride (BMIMICl), 1-ethyl-3- energy of oxidization, slower heat release, and shorten the
methyl imidazolium bromide (EMIMBr), 1-ethyl-3-methyl time for pre-oxidization and lower the final temperature for
imidazolium tetrafluoroborate (EMIMBF), 1-butyl-3-me pre-oxidization and improve the mechanical properties of
thylimidazolium tetrafluoroborate (BMIMBF), 1-ethyl-3- carbon fibre.
methyl imidazolium hexafluorophophate (EMIMPF), and 40 The advantages of this embodiment are as follows:
1-butyl-3-methyl imidazolium hexafluorophophate (1) The skin-core structure is decreased and the compact
(BMIMPF). ness of pre-oxidized fibre is substantially increased.
The temperature for washing the drawn fibre in step c) is The increase of compactness of pre-oxidization is greatly
controlled in a range from 70° C. to 90° C. contributed by oxygen content, especially the radial distribu
In this embodiment, melt spinning is adopted to avoid the 45 tion of oxygen is related to the skin-core structure along the
use of a large amount of toxic or corrosive chemical solvent, cross-section of fibre. The key of pre-oxidization is elimina
without recovering and purifying the solvent used and three tion of skin-core structure of pre-oxidized fibre. Oxygen is
wastes treatment during manufacture, thereby saving not only blow through the melting section of twin-screw and diffuses
solvent but also recovery step and devices for solvent recov from surface to inside of the melt, substantially reducing the
ery and washing step, which can Substantially lower the 50 skin-core structure of pre-oxidized fibre;
manufacturing cost, and eliminate the serious environmental (2) Energy consumption is reduced, and therefore the cost
problems caused by solvent. The plasticizing effect of ionic of pre-oxidization is substantially lowered.
liquid is helpful for drawing PAN fibre. Unlike precursor fibre The pre-oxidization can be carried in a twin-screw and the
obtained by solution spinning, which has a large amount of melt can be uniformly oxidized under rotation of the twin
voids caused by double diffusion, the obtained PAN fibre 55 screw. Compared with the conventional pre-oxidization pro
hardly has voids and is compact, which is beneficial to the cess, the energy consumption of the process of the invention
increase of the strength of precursor fibre. is reduced so that the cost of pre-oxidization and further the
In an embodiment, the present invention provides a melt manufacturing cost of carbon fibres are lowered.
spinning process for producing a PAN-based pre-oxidized (3) Controllable pre-oxidization of PAN is realized.
fibre, comprising the following steps: 60 The temperature for pre-oxidization is 170° C.-220° C. and
a) dissolving a catalyst for pre-oxidation of PAN in anionic catalyst in certain ratio is added to facilitate the pre-oxidiza
liquid in a weight ratio from 1:100 to 0.01:100 followed by tion. The degree of oxidization of PAN is effectively con
adding PAN powder to obtain a mixture, wherein the weight trolled by difference retention time of melt in a twin-screw,
ratio of PAN powder to ionic liquid is between 1:1 and 1:0.25: temperature for pre-oxidization and catalyst content. The oxi
b) adding the mixture from step a) to hopper of twin-screw 65 dization is strictly controlled by adjusting the process param
spinning machine to conduct melting spinning while blowing eters, i.e. controllable pre-oxidization of PAN is realized by
an oxygen-containing gas into melting segment of the twin controlling the time, temperature and catalyst content used
 US 9,334,586 B2
7 8
for oxidization, pre-oxidization degree is improved and side In an embodiment, the present invention provides a process
reaction such as cross-linking is reduced. for producing a PAN based carbon fibre, comprising the fol
(4) The devices for process are simple and the process is lowing steps:
environmentally friendly. a) mixing PAN and a solvent in a solid-to-liquid ratio of
The pre-oxidization of the process is carried in a twin 5 0.1%-25% in a reactor, and heating and stirring the resulting
screw extruder which can realize a controllable pre-oxidiza mixture until the PAN is dissolved completely to obtain a
tion and sufficiently carry out the pre-oxidization, thereby Solution;
avoiding the use of existing expensive and complicated b) adding a catalyst KMnO, in an amount of 0.05 wt.%-0.1
devices for pre-oxidization. The melt spinning is used to wt.% based on the weight of the PAN to the solution from step
produce PAN pre-oxidized fibre in the process, and avoid the 10
a), followed by bubbling an oxygen-containing gas at 5
use of a large amount of toxic or corrosive chemical solvent, ml/min to obtain a spinning solution, then pre-oxidizing the
without recovering and purifying the solvent used and three spinning solution for 1-2.5 hrs at 90°C.-250° C.;
wastes treatment during manufacture. Not only solvent but c) spinning the spinning solution through a spinning
also recovery step and devices for solvent and washing step
are saved, therefore the manufacturing cost is Substantially 15 machine, followed by washing with water, drawing and ther
lowered, and the serious environmental problems caused by mosetting to obtain a pre-oxidized fibre with good pre-oxi
Solvent are eliminated. dization degree, which is subjected to a carbonization process
The tensile strength of carbon fibre obtained by carboniz to obtain a high-performance carbon fibre.
ing the pre-oxidized fibre from this embodiment is increased The solvent used in step a) is selected from the group
from 3.3-3.5 GPa to 4.0–4.6 GPa and has an advantage of consisting of 1-butyl-3-methylimidazolium chloride, 1-allyl
lower cost compared with the high strength carbon fibres 3-methylimidazolium chloride, dimethylformamide (DMF),
commercial available at present. dimethylacetamide (DMAc), dimethylsulfoxide (DMSO),
In an embodiment, the present invention provides a process sodium thiocyanate (NaSCN), nitric acid (HNO), and Zinc
for producing a high-strength carbon fibre, comprising the chloride (ZnCl2).
following steps: 25 The catalyst used in stepb) is one or more selected from the
a) mixing 0.01-2 parts by weight of a carbon nanotube and group consisting of potassium permanganate (KMnO4),
100 parts by weight of a solvent, and ultrasonic processing for cobalt dichloride (CoCl2), cobalt sulphate (CoSO), benzoyl
1.5-3 hrs with an ultrasonic cell disrupter at 300 w-600 w to peroxide (BPO), succinic acid, hydrogen peroxide (HO),
obtain a mixture; ammonia, and low molecular weight amine.
b) adding 0.01-5 parts by weight of a polymer thickener to 30 The time required for pre-oxidization is shortened and the
the mixture from step a) followed by ultrasonic processing for final properties of carbon fibre are improved by using KMnO,
1-2 hrs with an ultrasonic cell disrupter at 300 w-600 w to as a catalyst. CoCl2 and CoSO can also be used to catalyti
obtain another mixture; cally improve the structure and properties of PAN. BPO and
c) forming a coating of 100-300 nm on pre-oxidized fibre Succinic acid can also be used as a catalyst for cyclization
with the mixture obtained from step b), followed by carbon 35 during pre-oxidization of PAN. The catalyst mentioned above
izing, to obtain the high-strength carbon fibre. may be used either alone or in combination to reduce the
The carbon nanotube used in step a) is a carboxylated activation energy of oxidization, slow heat release, shorten
multi-walled carbon nanotube. the time for pre-oxidization and lower the temperature for
The solvent used in step b) is selected from the group pre-oxidization, thereby improving the mechanical proper
consisting of dimethyl sulfoxide, N,N-dimethylformamide, 40 ties of carbon fibre.
dimethylacetamide, and distilled water. The oxygen-containing gas used in step b) is oxygen or air.
The polymer thickener used in step b) is selected from the After oxidization of stepb), the structure and properties of
group consisting of polyacrylonitrile, polyvinyl alcohol, and oxidized product is characterized by Fourier Transform Infra
C-cyanoacrylate. The thickener is selected depending on the red Spectroscopy (FTIR), thermogravimetry (TG), differen
Solvent used. 45 tial scanning calorimetry (DSC) and NMR, for better deter
The coating in step c) is formed by immersing the pre mination of the property of the spinning Solution.
oxidized fibre in the mixture obtained from step b) in a solid The structure and properties of the pre-oxidized fibre from
to-liquid ratio of 1:3-1:2 and standing for 1-2 hrs. step c) is related to the selection of temperature and time for
The coating in step c) is formed by electrostatic spraying pre-oxidization. Temperature for pre-oxidization of 60°
the mixture obtained from stepb) onto the surface of the fibre 50 C.-160° C. and time for pre-oxidization of 1 hr-1.5 hrs are
with a voltage of 80 kV-120 kV, a spray distance of 25 cm-40 conditions for relatively low pre-oxidization degree, and the
cm, and a rotation speed of spray gun of 2800 r/min-3000 fibre obtained can be used in civil application.
r/min. Temperature for pre-oxidization of 165° C.-250° C. and
The advantages of this embodiment are as follows: time for pre-oxidization of 1.5 hrs-2 hrs are conditions for
(1) The defects on the surface of fibres are decreased by 55 relatively high pre-oxidization degree, and the fibre obtained
repairing the Surface, and therefore stress concentration can can be used in industrial application.
be effectively eliminated, resulting in an increase of 15%- The spinning process used in step c) is wet spinning, dry
30% and 30% in tensile strength and toughness of carbon wet spinning, gel spinning, liquid crystal spinning or jelly
fibre, respectively; spinning
(2) The process time is short, and the process can be used in 60 The tensile strength of carbon fibres obtained according to
combination with the online equipment, therefore investment this embodiment is 4.0–4.6 Gpa.
on equipments and the cost for process are low; The advantages of this embodiment are as follows:
(3) The ratio of carbon nanotube to solvent and the winding (1) Fibres can be uniformly oxidized and the skin-core
speed can be adjusted depending on the degree of defect of structure is reduced.
carbon fibres to obtain a better strengthening effect; 65 Oxygen is uniformly diffused from surface to inside of
(4) The process effect is good and yield is high; fibre in the reactor with stirring. The colour gets deeper as the
(5) It is easily to handle and readily to be industrialized. pre-oxidization proceeds, and the pre-oxidization degree in
 US 9,334,586 B2
10
fibre is uniform, which is different from the prior art wherein FIG. 7-2 shows another SEM photograph of the cross
non-uniformly oxidization is occurred and skin-core struc section of PAN fibre obtained when PAN/BMIMICl is 1.2:1
ture is caused. after washed with water;
(2) Energy consumption and therefore the cost are reduced. FIG. 8 is a curve diagram illustrating the relationship
The pre-oxidization can be carried out in a reactor. When between Tg and PAN content of the fibres obtained from
the temperature of pre-oxidization is 160° C.-220°C., a good PAN/IBMIMIC system before washed with water;
pre-oxidization can be reached in a pre-oxidization time of 2 FIG.9 shows a SEM photograph of the cross section of the
hrs. In addition, pre-oxidization can be fully completed with fibre obtained when PAN/IBMIMICl is 1:1 and KMnO/
stirring. Compared with the conventional pre-oxidization BMIMICl is 0.01:100 after washed with water;
10 FIG. 10 shows a SEM photograph of the cross section of
process, energy consumption is reduced and so does the cost
of pre-oxidization, and therefore cost of carbon fibres is the fibre obtained when PAN/IBMIMICl is 1:1 and KMnO/
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/
15
tion conditions, i.e. controllable pre-oxidization of PAN is BMIMICl is 0.01:100 after washed with water;
realized by controlling the time, temperature and catalyst FIG. 12 shows a SEM photograph of the cross section of
content used for oxidization, thereby improving pre-oxidiza the fibre obtained when PAN/BMIMICl is 1:1 and BPO/
tion degree and reducing side reaction Such as cross-linking BMIMICl is 0.1:100 after washed with water;
FIG. 13 shows the infrared spectra of fibres obtained when
(4) The devices for process are simple. PAN/BMIMICl is 1:1 and KMnO/IBMIMICl is 0.1:100:
The pre-oxidization is carried out in a reactor, which is FIG. 14 shows the infrared spectra of fibres obtained when
beneficial for realization of a controllable and sufficiently PAN/BMIMICl is 1:1 and BPO/IBMIMICl is 0.1:100:
completed pre-oxidization, so that expensive and compli FIG. 15 shows a filed emission SEM photograph at 10000x
cated devices of prior art are avoided. magnification for carbon fibres treated with polyacrylonitrile:
By modification on the prior carbon fibres producing line, 25 multi-walled carbon nanotube: dimethylsulfoxide–0.05:0.5:
the complicated process of pre-oxidization is simplified. The 100 by weight;
pre-oxidization can be carried directly in a reactor, and spin FIG.16 shows a filed emission SEM photograph at 10000x
ning is carried. The skin-core structure of carbon fibre magnification for carbon fibres treated with polyvinyl alco
obtained according to the present process is reduced, which hol: multi-walled carbon nanotube: N,N-dimethylforma
30 mide=0.05:0.5:100 by weight;
improves the tensile strength of fibres from 3.3-3.5 GPa to
4.0-4.6 GPa and has an advantage of lower cost compared FIG. 17 shows a filed emission SEM photograph at 10000x
with the high strength carbon fibres commercial available at magnification for carbon fibres treated with polyvinyl alco
present. hol: multi-walled carbon nanotube: water 5:0.05:100 by
weight;
35
BRIEF DESCRIPTION OF THE DRAWING FIG. 18 shows a filed emission SEM photograph at 10000x
magnification for carbon fibres treated with C-cyanoacrylate:
The present invention will be further described in details in multi-walled carbon nanotube: water 5:0.05:100 by weight;
connection with certain preferred embodiments with refer FIG. 19-1 is a flow diagram showing a process of produc
ence to the accompanying drawings, in which ing PAN based carbon fibres in prior art;
FIG. 1 shows a SEM photograph of the cross-section of
40 FIG. 19-2 is a flow diagram showing an improved process
carbon fibre precursor based precursor fibre spun from a of producing PAN based carbon fibres;
spinning Solution containing 2 wt.% gelling agent based on FIG. 20-1 shows the infrared spectra of PAN/IL pre-oxi
dized at 170° C. for different times, 1: not pre-oxidized; 2: 20
the total weight of the solution; min: 3: 40 min: 4: 60 min; 5: 90 min;
FIG. 2 shows a SEM photograph of the cross-section of 45 FIG. 20-2 shows the infrared spectra of PAN/IL pre-oxi
carbon fibre precursor based precursor fibre spun from a dized at 160° C. for different times, 1: 20 min:2:40 min: 3: 60
spinning Solution containing 3 wt.% gelling agent based on min: 4: 90 min; 5: 120 min; 6: 150 min:
the total weight of the solution; FIG. 21 shows the infrared spectra of PAN/DMSO pre
FIG. 3 shows a SEM photograph of the cross-section of oxidized at 175°C. for different times, 1: 4 hrs: 2: 5 hrs: 3: not
carbon fibre precursor based precursor fibre spun from a 50 pre-oxidized;
spinning Solution containing 4 wt.% gelling agent based on FIG.22 shows the infrared spectra of PAN precursor fibre
the total weight of the solution; pre-oxidized in oxidization furnace, 1: pre-oxidized at 250°
FIG. 4 shows a SEM photograph of the cross-section of C.; 2: not pre-oxidized.
carbon fibre precursor based precursor fibre spun from a
spinning Solution containing 5 wt.% gelling agent based on 55 EXAMPLES
the total weight of the solution;
FIG. 5-1 shows a SEM photograph of the cross-section of For a better understanding of embodiments of the present
PAN fibre obtained when PAN/BMIMICl is 1:1 afterwashed invention, together with the technical means, the characteris
with water; tics and the purposes as well as effects thereof, reference is
FIG. 5-2 shows another SEM photograph of the cross 60 made to the following embodiments.
section of PAN fibre obtained when PAN/BMIMICl is 1:1
after washed with water; Example 1
FIG. 6 is a DMA curve diagram of the PAN fibre obtained
when PAN/IBMIMICl is 1:1; First, 5 g anhydrous PAN powder and 95 g DMSO solvent
FIG. 7-1 shows a SEM photograph of the cross-section of 65 are uniformly mixed in a three-neck flask, while heated in an
PAN fibre obtained when PAN/BMIMICl is 1.2:1 after oil bath maintained at a temperature of 70° C., and stirred to
washed with water; completely dissolve PAN powder. After the PAN powder is
 US 9,334,586 B2
11 12
dissolved, 2 g distilled water is added. Upon mechanical SEM photograph (magnification factor of which being
stirred for one hour, the slurry is transferred to a spinning 15,000) of PAN based precursor fibre spun from a spinning
machine for spinning, and the PAN based precursor fibre Solution containing 5 wt.% gelling agent based on the total
obtained by the gel spinning (in which the spinning tempera weight of the solution. It can be seen from FIG. 4 that the
ture is 60°C., the coagulation bath temperature is 10-20°C., cross-section of the obtained PAN based precursor fibre is
the primary washing temperature is 75° C., the secondary uniform nearly without skin-core structure and Voids, and the
temperature is 100° C.) has a tensile strength of 4.31 GPa. precursor fibre is structural compact. Therefore, the tensile
FIG. 1 shows a SEM photograph (magnification factor of strength of the PAN based precursor fibre for carbon fibre is
which is 15,000) of PAN based precursor fibre spun from a 10
Substantially increased.
spinning Solution containing 2 wt.% gelling agent based on
the total weight of the solution. It can be seen from FIG. 1 that Example 5
the cross-section of the obtained PAN based precursor fibre is
circle nearly without Voids across the section and the precur First, 5 g anhydrous PAN powder and 95 g ZnCl2 solvent
sor fibre is structural compact. Therefore, the tensile strength 15
are uniformly mixed in a three-neck flask, while heated in an
of the PAN based precursor fibre for carbon fibre is substan oil bath maintained at a temperature of 100° C., and stirred to
tially increased. completely dissolve the PAN powder. After the PAN powder
is dissolved, 2 g thiourea is added. Upon mechanical stirred
Example 2 for one hour, the slurry is transferred to a spinning machine
for spinning, and the PAN based precursor fibre obtained by
First, 10 g anhydrous PAN powder and 90 g DMF solvent the gel spinning (the spinning condition is the same as those
are uniformly mixed in a three-neck flask, while heated in an in example 1) has a tensile strength of 4.51 GPa.
oil bath maintained at a temperature of 90°C., and stirred to
completely dissolve the PAN powder. After the PAN powder Example 6
is dissolved, 3 g ethylene glycol is added. Upon mechanical
stirred for one hour, the slurry is transferred to a spinning 25 First, PAN powder and BMIMBF4 are uniformly mixed
machine for spinning, and the PAN based precursor fibre in a mass ratio of 1:1 in a high speed mixer. Then the mixture
obtained by the gel spinning (the spinning condition is the is transferred to a twin-screw spinning machine for melt
same as those in example 1) has a tensile strength of 4.4 GPa. spinning (in which screw speed is 50 r/min, the temperatures
FIG. 2 shows a SEM photograph (magnification factor of for feeding section, plasticizing section and melting section
which is 15,000) of PAN based precursor fibre spun from a 30 are set at 185°C., 190° C. and 185°C., respectively, the aspect
spinning Solution containing 3 wt.% gelling agent based on ratio of the spinneret is 1:3 and the orifices in the spinneret is
the total weight of the solution. It can be seen from FIG. 2 that 0.5 mm in diameter). The spun fibre is subjected to a primary
the cross-section of the obtained PAN based precursor fibre is dry-heat drawing, a secondary dry-heat drawing, washing
circle nearly without Voids across the section, and the precur with water, oiling and thermosetting (in which the drawing
35 ratio is 2-10 times, the drawing temperature is 90°C.-120° C.
sor fibre is structural compact and skin-core structure is not
observed. and the washing temperature is 25°C.-40°C.) to give PAN
fibre. The obtained PAN fibre has a tensile strength of 2.8
Example 3 cN/dtex and an elongation at break of 19.0%.
First, 10g anhydrous PAN powder and 90 g DMAc solvent 40 Example 7
are uniformly mixed in a three-neck flask, while heated in a
sandbath maintained at a temperature of 90°C., and stirred to First, PAN powder and BMIMBF4 are uniformly mixed
completely dissolve the PAN powder. After the PAN powder in a mass ratio of 1.2:1 in a high speed mixer. Then the
is dissolved, 4 g ethylene glycol is added. Upon mechanical mixture is transferred to a twin-screw spinning machine for
stirred for one hour, the slurry is transferred to a spinning 45 melt spinning in which the screw speed is adjusted to 75
machine for spinning, and the PAN based precursor fibre r/min, the temperatures for feeding section, plasticizing sec
obtained by the gel spinning (the spinning condition is the tion and melting section are set at 180° C., 185°C. and 180°
same as those in example 1) has a tensile strength of 4.2 GPa. C., respectively, the aspect ratio of the spinneret is 1:3 and the
FIG. 3 shows a SEM photograph (magnification factor of orifices in the spinneret is 0.5 mm in diameter. The spun fibre
which is 25,000) of PAN based precursor fibre spun from a 50 is Subjected to a primary dry-heat drawing, a secondary dry
spinning Solution containing 4 wt.% gelling agent based on heat drawing, washing with water, oiling and thermosetting to
the total weight of the solution. It can be seen from FIG.3 that give PAN fibre. The obtained PAN fibre has a tensile strength
the cross-section of the obtained PAN based precursor fibre is of 3.6 cn/dtex and an elongation at break of 8.9%.
circle nearly without Voids across the section and the precur
sor fibre is structural compact. 55 Example 8
Example 4 First, PAN powder and BMIMBF4 are uniformly mixed
in a mass ratio of 1:1 in a high speed mixer. Then the mixture
First, 5g anhydrous PAN powder and 95 g NaSCN solvent is transferred to a twin-screw spinning machine for melt
are uniformly mixed in a three-neck flask, while heated in an 60 spinning in which the screw speed is adjusted to 70 r/min, the
oil bath maintained at a temperature of 100° C., and stirred to temperatures for feeding section, plasticizing section and
completely dissolve the PAN powder. After the PAN powder melting section are set at 185° C., 190° C. and 190° C.,
is dissolved, 5 g urea is added. Upon mechanical stirred for respectively, the aspect ratio of the spinneret is 1:3 and the
one hour, the slurry is transferred to a spinning machine for orifices in the spinneret is 0.5 mm in diameter. The spun fibre
spinning, and the PAN based precursor fibre obtained by the 65 is Subjected to a primary dry-heat drawing, a secondary dry
gel spinning (the spinning condition is the same as those in heat drawing, washing with water, oiling and thermosetting to
example 1) has a tensile strength of 4.5 GPa. FIG. 4 shows a give PAN fibres. The obtained PAN fibre has a tensile strength
 US 9,334,586 B2
13 14
of 4.0 cM/dtex and an elongation at break of 16.9%. FIG. 5 blowing oxygen through the melting section of the twin
shows a SEM photograph of the cross-section of PAN fibre screw spinning machine, wherein the oxygen flow is 5
after washed with water. It can be concluded from the SEM ml/min, the screw speed is 120 r/min, the temperatures for the
photograph that the cross section of the fibre is circle without feeding section, plasticizing section and melting section are
skin-core structure. FIG. 6 is the DMA curve diagram of the 185°C., 220° C. and 220° C., respectively, the aspect ratio of
PAN fibre obtained with PAN/BMIMICl of 1:1. It can be the spinneret is 1:3 and the orifices in the spinneret is 0.5 mm
deduced from FIG. 6 that the glass transition temperature of in diameter. The spun fibre is directly subjected to dry-heat
PAN is decreased upon the addition of plasticizer and it is drawing (wherein the drawing temperature is 140°C., the
beneficial to drawing of macromolecule chain. total drawing ratio is 6 times). The drawn fibre is washed with
10
water at 90° C., followed by thermoset in dry and hot air at
Example 9 150° C. to give PAN pre-oxidization fibre with a pre-oxidiza
tion degree of 31%.
First, PAN powder and BMIMICl are uniformly mixed in
a mass ratio of 1.2:1 in a high speed mixer. Then the mixture Example 12
is transferred to a twin-screw spinning machine for melt 15
spinning in which the screw speed is adjusted to 60 r/min, the First, potassium permanganate particles and BMIMIC1
temperatures for feeding section, plasticizing section and are uniformly mixed in a three-neck flaskin a weight ratio of
melting section are set at 180° C., 185° C. and 185° C., 0.01:100. After the potassium permanganate is completely
respectively, the aspect ratio of the spinneret is 1:3 and the dissolved, the dried PAN powder and BMIMICl are uni
orifices in the spinneret is 0.5 mm in diameter. The spun fibre formly mixed in a high speed mixer in a weight ratio of 1:1,
is subjected to a primary dry-heat drawing, a secondary dry followed by transferred to a twin-screw spinning machine for
heat drawing, washing with water, oiling and thermosetting to melt spinning while blowing oxygen through the melting
give PAN fibres. The obtained PAN fibre has a tensile strength section of the twin-screw spinning machine, wherein the oxy
of 4.0 cM/dtex and an elongation at break of 14.3%. FIG. 7 gen flow is 2 ml/min, the screw speed is 50 r/min, the tem
shows a SEM photograph of the cross-section of PAN fibre 25 peratures for the feeding section, plasticizing section and
after washed with water. It can be seen from the SEM photo melting section are 185°C., 190° C. and 185°C., respectively,
graph that the cross section of the fibre is nearly circle and the the aspect ratio of the spinneret is 1:3 and the orifices in the
core is relatively structural compact resulting in the PAN spinneret is 0.5 mm in diameter. The spun fibre is subjected to
based precursor fibre with relatively excellent physical and dry-heat drawing (wherein the drawing temperature is 120°
mechanical properties. FIG. 8 is a curve diagram illustrating 30 C., the total drawing ratio is 45 times). The drawn fibre is
the relationship between Tg and PAN content of the fibres washed with water at 80°C., followed by thermoset in dry and
obtained from PAN/BMIMIC1 system before washed with hot air at 120-150° C. to give PAN pre-oxidization fibre with
water. It can be deduced from FIG. 8 that the glass transition a pre-oxidization degree of 31%. FIG. 9 shows a SEM pho
temperature of PAN decreases with the decrease of the PAN tograph of the cross section of the fibre obtained when PAN/
content, i.e. BMIMICl functions as a plasticizer during the 35 BMIMICl is 1:1 and KMnO4/BMIMICl is 0.01:100 after
melt spinning, the higher the BMIMICl content, the lower washed with water. It can be seen from FIG. 9 that the cross
the glass transition of the melt, and the more beneficial to section of the pre-oxidized fibre is very compact in structure
drawing of the fibre during Subsequent procedure. and nearly circle in shape, and that there is nearly no voids in
the core, the density is increased and the pre-oxidized fibre
Example 10 40 has relatively excellent physical and mechanical properties.
First, Cobalt dichloride, a catalyst of PAN pre-oxidization Example 13
is dissolved in an ionic liquid (1-butyl-3 methyl-imidazolium
chloride) in a weight ratio of 1:100. Then anhydrous PAN First, potassium permanganate particles and BMIMIC1
powder is added with the weight ratio of PAN powder to ionic 45 are uniformly mixed in a three-neck flaskin a weight ratio of
liquid being 1:1. The obtained mixture is feed into a twin 0.1:100. After the potassium permanganate is completely
screw spinning machine for melt spinning while blowing air dissolved, the dried PAN powder and BMIMICl are uni
through the melting section of the twin-screw spinning formly mixed in a high speed mixer in a weight ratio of 1:1,
machine, wherein the air flow is 1 ml/min, the screw speed is followed by transferred to a twin-screw spinning machine for
40 r/min, the temperatures for the feeding section, plasticiz 50 melt spinning while blowing oxygen through the melting
ing section and melting section are 170° C., 185°C. and 185° section of the twin-screw spinning machine, wherein the oxy
C., respectively, the aspect ratio of the spinneret is 1:3 and the gen flow is 2 ml/min, the screw speed is 50 r/min, the tem
orifices in the spinneret is 0.5 mm in diameter. The spun fibre peratures for the feeding section, plasticizing section and
is directly subjected to dry-heat drawing (wherein the draw melting section are 185°C., 190° C. and 185°C., respectively,
ing temperature is 110°C., the total drawing ratio is 4 times). 55 the aspect ratio of the spinneret is 1:3 and the orifices in the
The drawn fibre is washed with water at 70° C., followed by spinneret is 0.5 mm in diameter. The spun fibre is subjected to
thermoset in dry and hot air at 150° C. to give PAN pre dry-heat drawing (wherein the drawing temperature is 120°
oxidization fibre with a pre-oxidization degree of 31%. C., the total drawing ratio is 45 times). The drawn fibres is
washed with water at 80°C., followed by thermoset in dry and
Example 11 60 hot air at 150° C. to give PAN pre-oxidization fibre with a
pre-oxidization degree of 67%. FIG. 10 shows a SEM photo
First, cobalt sulphate, a catalyst of PAN pre-oxidization is graph of part of the cross section of the fibre obtained when
dissolved in an ionic liquid (1-butyl-3-methyl imidazolium PAN/BMIMICl is 1:1 and KMnO4/BMIMICl is 0.1:100
tetrafluoroborate) in a weight ratio of 0.01:100. Then anhy after washed with water. FIG. 13 shows the infrared spectra of
drous PAN powder is added with the weight ratio of PAN 65 fibres obtained when PAN/BMIMICl is 1:1 and KMnO4/
powder to ionic liquid being 1:1. The obtained mixture is feed BMIMICl is 0.1:100, wherein curve 1 is for pre-oxidized
into a twin-screw spinning machine for melt spinning while fibre and curve 2 is for precursor fibre. It can be concluded
 US 9,334,586 B2
15 16
from FIG. 13 that the absorption peak of cyano group (2240 pre-oxidized fibre and curve 2 is for precursor fibre. It can be
cm-1) upon oxidization decreases while the absorption peak concluded from FIG. 14 that the absorption peak of cyano
of —C—N (1630 cm-1) increases, indicating that part of group (2240 cm-1) upon oxidization decreases while the
cyano groups are converted to —C=N upon pre-oxidization, absorption peak of—C—N (1630 cm-1) increases, indicat
facilitating the formation of intramolecular ring. It can be ing that part of cyano groups are converted to —C=N upon
seen from FIG. 10 that the cross section of the pre-oxidized pre-oxidization, facilitating the formation of intramolecular
fibre is very compact in structure and there is no skin-core r1ng.
structure and no voids, the pre-oxidized fibre is structural
uniform from Surface to inside, and without skin-core struc Examples 16-20
ture as obtained by wet spinning 10
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 flaskin a weight ratio of 0.01:100. After 15
TABLE 1
the benzoyl peroxide is completely dissolved, the dried PAN
powder and BMIMICl are uniformly mixed in a high speed The catalyst for PAN pre-oxidization and ionic liquids as well as the
mixer in a weight ratio of 1:1, followed by transferred to a pre-oxidization degree of the obtained fibres
twin-screw spinning machine for melt spinning while blow Catalyst for PAN Pre-oxidization
ing oxygen through the melting section of the twin-screw No. preoxidization Ionic liquid degree(%)
spinning machine, wherein the oxygen flow is 2 ml/min, the
screw speed is 50 r/min, the temperatures for the feeding Example 16 K2S2O8 (EMIMIC| 50
Example 17 Succinic acid BMIMBr 63
section, plasticizing section and melting section are 185°C., Example 18 Hydrogen peroxide (EMIMIBF4 82
190° C. and 185° C., respectively, the aspect ratio of the Example 19 Ammonia (EMIMIBF6 68
spinneret is 1:3 and the orifices in the spinneret is 0.5 mm in 25 Example 20 Hydroxylamine
hydrochloride
BMIMIBF4 79
diameter. The spun fibre is subjected to dry-heat drawing
(wherein the drawing temperature is 120° C., the total draw
ingratio is 45 times). The drawn fibres is washed with water
at 80°C., followed by thermoset in dry and hot air at 150° C. Example 21
to give PAN pre-oxidization fibre with a pre-oxidization 30
degree of 47%. FIG. 11 shows a SEM photograph of the cross 0.05 parts by weight of carboxylated multi-walled carbon
section of the fibre obtained when PAN/BMIMICl is 1:1 and nanotube (available from Chengdu Institute of Organic
BPO/IBMIMICl is 0.01:100 after washed with water. It can Chemistry of Chinese Academy of Sciences, with length of
be seen from FIG. 11 that the cross section of the pre-oxidized 10-30 Lum, inner diameter of 10-20 nm, outer diameter of 5-10
fibre is nearly circle in shape and is relatively compact in core 35 nm) and 100 parts by weight of dimethylsulfoxide solvent are
and, and the pre-oxidized fibre has relatively excellent physi mixed, ultrasonic processed for 3 hrs in an ultrasonic cell
cal and mechanical properties. disrupter operating at 300 w; to the resulting solution is added
0.05 parts by weight of polymer thickener PAN (with poly
Example 15 merization degree of 88,000 and particle size of 230 nm-250
40 nm) and ultrasonic processed for 2 hrs in an ultrasonic cell
First, benzoyl peroxide and BMIMICl are uniformly disrupter operating at 300 w. The oxidized PAN pre-oxidized
mixed in a three-neck flask in a weight ratio of 0.1:100. After fibre is dipped into the obtained solution in a solid-to-liquid
the benzoyl peroxide is completely dissolved, the dried PAN ratio of 1:3 for 1 hr., and a coating of 200 nm is formed on the
powder and BMIMICl are uniformly mixed in a high speed surface of the oxidized PAN pre-oxidized fibre. The oxidized
mixer in a weight ratio of 1:1, followed by transferred to a 45 PAN pre-oxidized fibre is carbonized at 1000°C. to give high
twin-screw spinning machine for melt spinning while blow strength carbon fibre. FIG. 15 shows a filed emission SEM
ing oxygen through the melting section of the twin-screw photograph (magnification factor of which is 10,000) of car
spinning machine, wherein the oxygen flow is 2 ml/min, the bon fibres treated with PAN: multi-walled carbon nanotube:
screw speed is 50 r/min, the temperatures for the feeding dimethylsulfoxide=0.05:0.05:100 by weight. It can be seen
section, plasticizing section and melting section are 185°C., 50 from FIG. 15 that carbon nanotubes are uniformly attached to
190° C. and 185° C., respectively, the aspect ratio of the the surface of fibres and can repair voids on the surface of
spinneret is 1:3 and the orifices in the spinneret is 0.5 mm in fibre so that the tensile strength of carbon fibre can be effec
diameter. The spun fibre is subjected to dry-heat drawing tively increased.
(wherein the drawing temperature is 120° C., the total draw
ingratio is 45 times). The drawn fibres is washed with water 55 Example 22
at 80°C., followed by thermoset in dry and hot air at 150° C.
to give PAN pre-oxidization fibre with a pre-oxidization 0.5 parts by weight of carboxylated multi-walled carbon
degree of 73%. FIG. 12 shows a SEM photograph of part of nanotube (available from Chengdu Institute of Organic
the cross section of the fibre obtained when PAN/BMIMIC1 Chemistry of Chinese Academy of Sciences, with length of
is 1:1 and BPO/IBMIMICl is 0.1:100 after washed with 60 10-30 Lum, inner diameter of 10-20 nm, outer diameter of 5-10
water. It can be seen from FIG. 12 that the cross section of the nm) and 100 parts by weight of N,N-dimethylformamide
pre-oxidized fibre is very compact in structure and there is no Solvent are mixed, ultrasonic processed for 1.5 hrs in an
skin-core structure and no voids, the pre-oxidized fibre is ultrasonic cell disrupter operating at 600 w. To the resulting
structural uniform from Surface to inside, and without skin solution is added 0.05 parts by weight of polymer thickener
core structure as obtained by wet spinning FIG. 14 shows 65 polyvinyl alcohol (with polymerization degree of 88,000 and
infrared spectra of fibres obtained when PAN/IBMIMICl is particle size of 230 nm-250 nm) and ultrasonic processed for
1:1 and BPO/BMIMICl is 0.1:100, wherein curve 1 is for 1 hrs in an ultrasonic cell disrupter operating at 600 w. The
 US 9,334,586 B2
17 18
oxidized PAN pre-oxidized fibre is dipped into the obtained Chemistry of Chinese Academy of Sciences, with length of
Solution in a solid-to-liquid ratio of 1:2 for 2 hrs; a coating of 10-30 Lum, inner diameter of 10-20 nm, outer diameter of 5-10
200 nm is formed on the surface of the oxidized PAN pre nm) and 100 parts by weight of water solvent are mixed,
oxidized fibre. The oxidized PAN pre-oxidized fibre is car ultrasonic processed for 1.5 hrs in an ultrasonic cell disrupter
bonized at 1000°C. to give high strength carbon fibre. FIG.16 operating at 500 w. To the resulting solution is added 0.01
shows a filed emission SEM photograph (magnification fac parts by weight of polymer thickener C-cyanoacrylate and
tor of which is 10,000) of carbon fibres treated with polyvinyl ultrasonic processed for 1 hr in an ultrasonic cell disrupter
alcohol: multi-walled carbon nanotube: N,N-dimethylforma operating at 500 w. The obtained solution is electrostatically
mide=0.05:0.5:100 by weight. It can be seen from FIG. 16 sprayed onto the surface of the oxidized PAN pre-oxidized
that multi-walled carbon nanotubes are uniformly attached to 10
the surface of carbon fibre and repair voids on the surface of fibre with a voltage of 100 kV, a spray distance of 30 cm and
carbon fibre, which is beneficial to increase of the tensile a rotation speed of spray gun of 2900 r/min to form a coating
strength of carbon fibres. of 100 nm thereon. The oxidized PAN pre-oxidized fibre is
carbonized at 1000° C. to give high strength carbon fibre.
Example 23
15 Example 26
0.05 parts by weight of carboxylated multi-walled carbon
nanotube (available from Chengdu Institute of Organic 2 parts by weight of carboxylated multi-walled carbon
Chemistry of Chinese Academy of Sciences, with length of nanotube (available from Chengdu Institute of Organic
10-30 Lum, inner diameter of 10-20 nm, outer diameter of 5-10 Chemistry of Chinese Academy of Sciences, with length of
nm) and 100 parts by weight of water solvent are mixed, 10-30 um, inner diameter of 10-20 nm, and outer diameter of
ultrasonic processed for 2 hrs in an ultrasonic cell disrupter 5-10 nm) and 100 parts by weight of dimethylacetamide
operating at 500 w. To the resulting solution is added 5 parts Solvent are mixed, ultrasonic processed for 1.5 hrs in an
by weight of polymer thickener polyvinyl alcohol (with poly ultrasonic cell disrupter operating at 500 w. To the resulting
merization degree of 88,000 and particle size of 230 nm-250 solution is added 2 parts by weight of polymer thickener
nm) and ultrasonic processed for 1.5 hrs in an ultrasonic cell 25 C-cyanoacrylate and ultrasonic processed for 1 hr in an ultra
disrupter operating at 600 w. The obtained solution is elec sonic cell disrupter operating at 500w. The obtained solution
trostatically sprayed onto the surface of the oxidized PAN is electrostatically sprayed onto the surface of the oxidized
pre-oxidized fibre with a voltage of 80 kV, a spray distance of PAN pre-oxidized fibre with a voltage of 120 kV, a spray
25cm and a rotation speed of spraygun of 2800 r/minto form distance of 30 cm and a rotation speed of spray gun of 2900
a coating of 300 nm thereon. The oxidized PAN pre-oxidized 30 r/min to form a coating of 100 nm thereon. The oxidized PAN
fibre is carbonized at 1000° C. to give high strength carbon pre-oxidized fibre is carbonized at 1000° C. to give high
fibre. FIG. 17 shows a filed emission SEM photograph (mag strength carbon fibre. The mechanical properties of carbon
nification factor of which is 10,000) of carbon fibres treated fibres obtained from Examples 21-26 are shown in table 2.
with polyvinyl alcohol: multi-walled carbon nanotube:
water=5:0.05:100 by weight. 35 TABLE 2

Example 24 Mechanical properties of carbon fibres obtained

Mechanical properties
0.05 parts by weight of carboxylated multi-walled carbon
nanotube (available from Chengdu Institute of Organic 40 Tensile strength Elongation at break
Chemistry of Chinese Academy of Sciences, with length of Strength? Variation Elongation Variation
10-30 Lum, inner diameter of 10-20 nm, outer diameter of 5-10 GPa. range (%) (%) range %
nm) and 100 parts by weight of water solvent are mixed,
ultrasonic processed for 1.5 hrs in an ultrasonic cell disrupter Contrast (untreated) 3.18 8.90
Example 21 3.80 +22.64 13.5 +51.6
operating at 500 w. To the resulting solution is added 5 parts 45
Example 22 4.35 -36.79 14.3 +60.6
by weight of polymer thickener C-cyanoacrylate (with Example 23 4.40 +38.36. 1S.O --68.5
molecular weight of 400-800, available from Shanghai Tailuo Example 24 4.67 --46.85 16.3 +83.1
Company Ltd.) and ultrasonic processed for 1 hr in an ultra Example 25 4.78 --SO3O 16.9 --89.8
Example 26 4.71 +48.11 16.0 79.7
sonic cell disrupter operating at 500w. The obtained solution
is electrostatically sprayed onto the surface of the oxidized 50
PAN pre-oxidized fibre with a voltage of 120 kV, a spray
distance of 40 cm and a rotation speed of spray gun of 3000 Example 27
r/min to form a coating of 100 nm thereon. The oxidized PAN
pre-oxidized fibre is carbonized at 1000° C. to give high 1-butyl-3-methylimidazolium chloride ionic liquid and
strength carbon fibre. FIG. 18 shows a filed emission SEM 55 PAN powder are added in a reactor with mechanical stirrer.
photograph (magnification factor of which is 10,000) of car Upon the polymer is completely dissolved, a catalyst KMnO4
bon fibres treated with C.-cyanoacrylate: multi-walled carbon is added to facilitate cyclization of PAN. The weight percent
nanotube: water 5:0.05:100 by weight. It can be seen from of the above material areas follows: PAN, 5%; solvent, 95%.
FIG. 18 that multi-walled carbon nanotubes are uniformly KMnO, is added at 0.05 wt.% of PAN. The mixture is stirred
attached to the surface of carbon fibres and repair voids on the 60 at 170° C., oxygen is blown into the reactor at certain flow
surface of carbon fibres, which is beneficial to increase of the rate. The temperature and time of pre-oxidization is con
tensile strength of carbon fibre. trolled and samples are collected when the reaction time is 20
min, 40 min, 60 min and 90 min, respectively, to get PAN
Example 25 spinning solutions with different pre-oxidization degree.
65 FIG. 19-2 shows an improved process of producing PAN
0.01 parts by weight of carboxylated Multi-walled Carbon based carbon fibre used in this example. FIG. 20-1 shows
nanotube (available from Chengdu Institute of Organic infrared spectra of PAN/IL pre-oxidized at 170° C. for differ
 US 9,334,586 B2
19 20
ent time. It can be seen from the spectra that as the pre the oxidization degree of comparative example 1 is compara
oxidization time increases, the intensity of the absorption tive with that of Examples 27, 28 and 29, however the oxi
peak of—C=N group decreases and that of—C=N group dization effect of examples 27, 28 and 29 is better and the
increases, and the intramolecular cyclization degree process is simpler, therefore the cost of the Subsequent carbon
increases. fibres manufacturing can be decreased.
The basic principle, main characteristics and advantages of
Example 28 the invention are illustrated and described above. It should be
understood by the skilled in the art that the examples and
1-butyl-3-methylimidazolium chloride ionic liquid and description are used to illustrate the principle of the invention
10 and should not be taken as limiting the scope of the invention,
PAN are added in a reactor with mechanical stirrer. Upon the and there will be various changes and modifications without
polymer is completely dissolved, a catalyst KMnO4 is added departing the sprit and scope of the invention and those
to facilitate cyclization of PAN. The weight percent of the changes and modifications fall within the scope of the inven
above material are as follows: PAN, 5%; solvent, 95%. tion. The scope of the invention is defined by the accompa
KMnO, is added at 0.05 wt.% of PAN. The mixture is stirred 15 nying claims and equivalents thereof.
at 160° C., oxygen is blown into the reactor at 5 ml/min. The The invention claimed is:
temperature and time of pre-oxidization is controlled and 1. A melt spinning process for producing a PAN-based
samples are collected when the reaction time is 20 min, 40 pre-oxidized fibre, comprising the following steps:
min, 60 min, 90 min, 120 minand 150 min, respectively, to get a) dissolving a catalyst for pre-oxidation of PAN in anionic
PAN spinning solutions with different pre-oxidization liquid in a weight ratio from 1:100 to 0.01:100 followed
degree. FIG. 20-2 shows infrared spectra of PAN/IL pre by adding PAN powder to obtain a mixture, wherein the
oxidized at 160° C. for different time. It can be seen from the
spectra that as the pre-oxidization time increases, the inten weight ratio of PAN powder to ionic liquid is between
sity of the absorption peak of—C=N group decreases and 1:1 and 1:0.25:
b) adding the mixture from step a) to a hopper of twin
that of —C=N group increases, and the intramolecular Screw spinning machine to conduct melting spinning
cyclization degree increases. However, the cyclization degree 25
while blowing an oxygen-containing gas into a melting
at 160° C. is lower than that at 170° C.
segment of the twin-screw spinning machine, wherein
Example 29 the flow rate of the oxygen-containing gas is between 1
ml/min and 5 ml/min, and the rotational velocity of
DMSO and PAN are added in a reactor with mechanical 30 screw is between 40 and 120 r/min, and the temperature
stirrer. Upon the polymer is completely dissolved, a catalyst at a feed segment is between 170° C. and 185°C., and the
KMnO4 is added to facilitate cyclization of PAN. The weight temperature for plasticizing is between 185°C. and 220
percent of the above material are as follows: PAN, 10%: C., and the temperature for melting is between 185°C.
DMSO, 90%. KMnO is added at 0.05 wt.% of PAN. The and 220° C.;
mixture is stirred at 175°C., oxygen-containing gas is blown 35 c) dry-heat drawing the spun fibre directly under a tem
into the reactor at a rate of 5 ml/min. The temperature and perature between 110 and 140°C. with a total draw ratio
time of pre-oxidization is controlled, and pre-oxidization is between 4 and 6, then washing the drawn fibre with
proceeded for about 4-5 hrs to get PAN spinning solution. water at 70-90° C., followed by thermosetting in dry hot
FIG. 21 shows infrared spectra of PAN/DMSO pre-oxidized air at 120-150° C. to give the PAN based pre-oxidized
fibre.
at 175° C. for different time. It can be seen from the spectra 40
2. The melting spinning process according to claim 1,
that as the pre-oxidization time increases, the intensity of the characterised in that the catalyst for pre-oxidation of PAN
absorption peak of —C=N group decreases and that of used in step a) is one or more selected from the group con
—C=N group increases, and the intramolecular cyclization sisting of potassium permanganate, cobalt dichloride, cobalt
degree increases. Sulphate, potassium persulfate, benzoyl peroxide, Succinic
45
Comparative Example 1 acid, hydrogen peroxide, Ammonia, and hydroxylamine
hydrochloride.
First, a PAN/DMSO spinning solution is wet spun by con 3. The melting spinning process according to claim 1,
ventional process. Then PAN precursor fibres are obtained characterised in that the ionic liquid used in step a) is disub
after a series of post-treatments. PAN precursor fibre is pre 50 stituted imidazole-based ionic liquid.
oxidized in a pre-oxidization furnace with 6 heating sections 4. The melting spinning process according to claim 3,
characterised in that the disubstituted imidazole-based ionic
with the onset temperature of 170° C., the temperature is liquid is one or more selected from the group consisting of
warmed up 10° C./10 min, while samples of pre-oxidized
fibres are collected at different temperature, and finally main 1-ethyl-3-methyl imidazolium chloride (EMIMICl), 1-bu
tained at 260° C. for 0.5 hr. The samples of pre-oxidized fibres 55 tyl-3-methyl imidazolium chloride (BMIMICl), 1-ethyl-3-
are Subjected to infrared analysis and compared with that methyl imidazolium bromide (EMIMBr), 1-ethyl-3-methyl
obtained from the above two systems in terms of pre-oxidiza imidazolium tetrafluoroborate (EMIMIBF), 1-butyl-3-me
tion degree. It has been found that the new process of spinning thylimidazolium tetrafluoroborate (BMIMBF), 1-ethyl-3-
after the spinning Solution being pre-oxidized can reach the methyl imidazolium hexafluorophophate (EMIMPF) and
same pre-oxidization degree as that obtained from conven 60
1-butyl-3-methyl imidazolium hexafluorophophate
tional process, however, the pre-oxidization cost of the new (BMIMPF).
process can be substantially decreased, and therefore the 5. The melting spinning process according to claim 1,
manufacturing cost of carbon fibres is decreased. FIG. 22 characterised in that the oxygen-containing gas used in stepb)
shows infrared spectra of PAN precursor fibre pre-oxidized in is oxygen or air.
oxidization furnace. Compared with Examples 27, 28 and 29.