CN1198453A - Polyether ether ketone compound material modified by thermotropic liquid crystal polymer - Google Patents
Polyether ether ketone compound material modified by thermotropic liquid crystal polymer Download PDFInfo
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- CN1198453A CN1198453A CN 97111710 CN97111710A CN1198453A CN 1198453 A CN1198453 A CN 1198453A CN 97111710 CN97111710 CN 97111710 CN 97111710 A CN97111710 A CN 97111710A CN 1198453 A CN1198453 A CN 1198453A
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Abstract
The present invention relates to a flock-reinforced polyether ether ketone composite material modified by thermotropic liquid crystal polymer, in which the thermotropic liquid crystal polymer (TLCP) is random total aromatics copolyester of backbone-type p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid or random copolyester of backbone-type p-hydroxybenzoic acid and diethyl terephthalate, and the described flock is surface-treated carbon fibre or glass fibre. The addition of TLCP not only can improve working property of said composite material, but also can raise the mechanical property of said composite material.
Description
The present invention relates to a kind of staple fibre enhanced thermoplastic material of using, specially refer to a kind of staple fibre reinforced polyether ether ketone matrix material with the TLCP modification.
Polyether-ether-ketone (PEEK) is a kind of special engineering plastics of excellent combination property, and it is with the forming process of thermotolerance, chemical stability and the thermoplastics of thermosetting resin.With staple fibre enhanced polyether-ether-ketone, compare with enhanced not, demonstrate higher intensity, modulus and thermotolerance.Polymer CompositesVol.17 P468 had reported short glass fiber and short carbon fiber enhanced polyether-ether-ketone composite material in 1996, and the mechanical property of this matrix material obviously is better than the polyether-ether-ketone matrix.Because the fusing point of polyether-ether-ketone is higher, melt viscosity is also bigger, and its melt fluidity is little to dependence on temperature, so polyether-ether-ketone is adding higher mold temperature (barrel temperature need be controlled at about 350～400 ℃) and the injection pressure of needs in man-hour.For staple fibre reinforced polyether ether ketone matrix material, owing to contain staple fibre thereby melt fluidity becomes poorer in the system, make processing difficulties.More disadvantageously, high-load fortifying fibre makes between fiber and the fiber, the friction between fiber and the equipment increases, and makes that fortifying fibre takes place acutely to fracture, and has reduced the reinforced effects of fortifying fibre.
The objective of the invention is to overcome staple fibre enhanced polyether-ether-ketone system melt fluidity poor, wearing and tearing, the staple fibre of equipment fractureed in a large number, and a kind of staple fibre reinforced polyether ether ketone matrix material with the TLCP modification is provided, this materials processing performance is good and mechanical property is high.
The raw material of polyether-ether-ketone composite material of the present invention is polyether-ether-ketone, staple fibre and TLCP, and the composition and the content of each raw material are as follows:
Component concentration (weight part)
Polyether-ether-ketone 40-80 (best 55-70)
TLCP 5-30
Staple fibre 10-40 (best 15-30)
Above-mentioned staple fibre is through surface-treated carbon fiber (CF) or glass fibre (GF).Fiberglass surfacing can be handled with coupling agent, grafting superpolymer.Carbon fiber can be used the surface oxidation method, or the method for galvanic deposit vinyl-acetic ester-maleic anhydride alternate copolymer or alternate styrene-maleic anhydride copolymer on the fiber surface deposition.Above-mentioned TLCP (TLCP) is the backbone chain type aromatic copolyesters, and fusion range is 190 ℃～350 ℃, is texture under polarizing microscope.The atactic polyester of P-hydroxybenzoic acid and ethylene glycol terephthalate for example, melting range is 250 ℃～350 ℃, structural formula is as follows:
TLCP can also be the random full aromatic copolyesters of P-hydroxybenzoic acid and 6-hydroxyl-2-naphthoic acid (HNB), and melting range is 270 ℃～350 ℃, and structural formula is as follows:
The method for making of polyether-ether-ketone composite material of the present invention is carried out according to the following steps:
With 10～20 parts of TLCP (TLCP), with 50～80 parts of matrix polyether-ether-ketones, and 10～40 parts on staple fibre, blend extruding pelletization, the injection moulding then in 370 ℃～400 ℃ by single screw rod or twin screw extruder.
The carbon fiber reinforced polyetheretherketonecomposite composite material of TLCP modification of using of the present invention is when melt-processed, TLCP and polyether-ether-ketone are melt, because TLCP has the rheological property of stronger shear shinning, thereby reduced the viscosity of melt, reduce the torque that adds the screw rod in man-hour and (seen Table I, characterize the rheological property of melt with HAAKE RC 90 torque rheometers, wherein balancing moment is proportional to viscosity, certain total torque constantly is proportional to the merit that is consumed until this moment blend), the wearing and tearing of material have been reduced to forcing machine and injection moulding machine, reduce staple fibre simultaneously and added the rate that fractures in man-hour, improve the average aspect ratio (see Table II) of staple fibre in matrix material, improved the mechanical property (seeing Table III) of polyether-ether-ketone composite material.
Table I is TLCP, carbon fiber and the polyether-ether-ketone composite material of the Different Weight ratio balancing moment M during blend in HAAKERC 90 torque rheometers
360 ℃Total torque during with 5 minutes (rotor speed is 40 rev/mins).
Table II is the number average length and the number average length-to-diameter ratio of TLCP, carbon fiber and the polyether-ether-ketone composite material carbon fiber in injection-molded item of Different Weight ratio.
Table III is the tensile mechanical properties of TLCP, carbon fiber and the polyether-ether-ketone composite material of Different Weight ratio.
Table I sample balancing moment M
360 ℃(Nm) total torque 5 minutes the time, (Nm-min) PEEK 5.8 31PEEK/CF 85,/15 9.8 49PEEK/CF/TLCP 70,/15,/15 8.8 44PEEK/CF 70,/30 13.8 68PEEK/CF/TLCP 55,/30,/15 9.5 51
From Table I as can be seen, with respect to the carbon fiber/polyetheretherketonecomposite system, the adding of TLCP has improved the processing characteristics of system.
Number average draw ratio PEEK/CF 85,/15 123.6 16.5PEEK/CF/TLCP 70,/15,/15 164.8 22.0PEEK/CF 70,/30 103.5 13.8PEEK/CF/TLCP 55,/30,/15 122.9 16.4 of the number average length of Table II sample carbon fiber (μ m) carbon fiber
From Table II as can be seen, with respect to the carbon fiber/polyetheretherketonecomposite system, the adding of TLCP, reduced carbon fiber extrude with injection moulding processing in the rate that fractures, improved the number average length-to-diameter ratio of carbon fiber.
Table III sample hot strength (MPa) stretch modulus (GPa) PEEK 91 2.9PEEK/CF 85,/15 141 5.2PEEK/CF/TLCP 70,/15,/15 154 5.6PEEK/CF 70/30 * * PEEK/CF/TLCP 55,/30,/15 183 8.8
Annotate: PEEK/CF 70/30 system can't moulding on the CS-183 injection moulding machine because viscosity is too big.
From Table III as can be seen, with respect to the carbon fiber/polyetheretherketonecomposite system, the adding of TLCP has improved the mechanical property of system.
Embodiment 1:
With 15 parts of PHB/HNB (73/27) TLCP, (limiting viscosity that records in concentrated sulfuric acid solution is [η]=0.83 dl/g, T for 15 parts of surface treated carbon fibers and 70 parts of polyether-ether-ketones
g=143 ℃, T
m=334 ℃) melt blending on the CS-194A forcing machine, temperature of rotor is 380 ℃, die temperature is 370 ℃.Extrude the granulation of bar cooling back, the gained pellet injects the square-section of ASTM standard on CS-183 MINI MAX injection moulding machine the dumbbell shape little batten that stretches, melt temperature is 380 ℃, the mould temperature is 150 ℃.Above-mentioned prescription is the balancing moment M during blend in HAAKE RC 90 torque rheometers
360 ℃Be 8.8 Nm, the total torque in the time of 5 minutes is 44 Nm-min.The tensile strength of above-mentioned tensile bars is 154 MPa, and tensile modulus is 5.6 GPa.The number average length-to-diameter ratio of carbon fiber is 22.0 in the gained injection stretch batten.Embodiment 2:
With 15 parts of PHB/HNB (73/27) TLCP, (limiting viscosity that records in concentrated sulfuric acid solution is [η]=0.83 dl/g, T for 30 parts of surface treated carbon fibers and 55 parts of polyether-ether-ketones
g=143 ℃, T
m=334 ℃), other condition is with embodiment 1.Above-mentioned prescription is the balancing moment M during blend in HAAKE RC 90 torque rheometers
360 ℃Be 9.5 Nm, the total torque in the time of 5 minutes is 51 Nm-min.The tensile strength of above-mentioned tensile bars is 183 MPa, and tensile modulus is 8.8 GPa.The number average length-to-diameter ratio of carbon fiber is 16.4 in the gained injection stretch batten.
Embodiment 3:
With 20 parts of PHB/HNB (73/27) TLCP, (limiting viscosity that records in concentrated sulfuric acid solution is [η]=0.83 dl/g, T for 40 parts of surface treated carbon fibers and 40 parts of polyether-ether-ketones
g=143 ℃, T
m=334 ℃) melt blending on the CS-194A forcing machine, temperature of rotor is 380 ℃, die temperature is 370 ℃.Extrude bar cooling back granulation, obtain short carbon fiber enhanced polyether-ether-ketone composite material with the TLCP modification.Embodiment 4:
With 10 parts of PHB/HNB (73/27) TLCP, (limiting viscosity that records in concentrated sulfuric acid solution is [η]=0.83 dl/g, T for 10 parts of surface treated carbon fibers and 80 parts of polyether-ether-ketones
g=143 ℃, T
m=334 ℃) melt blending on the CS-194A forcing machine, temperature of rotor is 380 ℃, die temperature is 370 ℃.Extrude bar cooling back granulation, obtain short carbon fiber enhanced polyether-ether-ketone composite material with the TLCP modification.Comparative Examples 1:
Strengthen 85 parts of polyether-ether-ketones with 15 parts of carbon fibers, other condition is with embodiment 1.Above-mentioned prescription is the balancing moment M during blend in HAAKERC 90 torque rheometers
360 ℃Be 9.8 Nm, the total torque in the time of 5 minutes is 49Nm-min.The tensile strength of above-mentioned tensile bars is 141 MPa, and tensile modulus is 5.2 GPa.The number average length-to-diameter ratio of carbon fiber is 16.5 in the gained injection stretch batten.Comparative Examples 2:
Strengthen 70 parts of polyether-ether-ketones with 30 parts of carbon fibers, other condition is with embodiment 1.Above-mentioned prescription is the balancing moment M during blend in HAAKERC 90 torque rheometers
360 ℃Be 13.8 Nm, the total torque in the time of 5 minutes is 68Nm-min.Because the viscosity of this system is too big, to such an extent as to can't be at CS-183 MINI MAX injection moulding machine in injection molding.The number average length-to-diameter ratio that gained is extruded carbon fiber in the bar is 13.8.
Claims (10)
1, a kind of polyether-ether-ketone composite material of modification comprises polyether-ether-ketone, staple fibre, it is characterized in that described matrix material also comprises TLCP, and its component and content (weight part) are as follows:
Component concentration
Polyether-ether-ketone 40-80
TLCP 5-30
Staple fibre 10-40
2, a kind of polyether-ether-ketone composite material according to claim 1 is characterized in that described polyether-ether-ketone content is 55-70 by weight.
3, a kind of polyether-ether-ketone composite material according to claim 1 is characterized in that the content of described staple fibre is 15-30 by weight.
4, a kind of polyether-ether-ketone composite material according to claim 1 is characterized in that described TLCP is the backbone chain type TLCP.
5, a kind of polyether-ether-ketone composite material according to claim 4 is characterized in that described backbone chain type TLCP is the backbone chain type aromatic copolyesters.
6, a kind of polyether-ether-ketone composite material according to claim 1 is characterized in that described staple fibre is short glass fiber or short carbon fiber.
7,, it is characterized in that described backbone chain type aromatic copolyesters is the atactic polyester of P-hydroxybenzoic acid and 6-hydroxyl-2-naphthoic acid according to any one polyether-ether-ketone composite material in the claim 5.
8,, it is characterized in that described backbone chain type aromatic copolyesters is the atactic polyester of P-hydroxybenzoic acid and ethylene glycol terephthalate according to any one polyether-ether-ketone composite material in the claim 5.
9, require described short glass fiber according to right 6, it is characterized in that it is the glass fibre that handled with coupling agent or graft copolymer on the surface.
10, short carbon fiber according to claim 6 is characterized in that it is that oxidation style is used on the surface, or the carbon fiber handled of Means of Electrodeposition.
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| Application Number | Priority Date | Filing Date | Title |
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| CN97111710A CN1073601C (en) | 1997-05-05 | 1997-05-05 | Polyether ether ketone compound material modified by thermotropic liquid crystal polymer |
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| CN97111710A CN1073601C (en) | 1997-05-05 | 1997-05-05 | Polyether ether ketone compound material modified by thermotropic liquid crystal polymer |
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| CN1073601C CN1073601C (en) | 2001-10-24 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101151322B (en) * | 2005-04-06 | 2010-10-13 | 威格斯制造有限公司 | Polymeric material |
| CN103374197A (en) * | 2012-04-19 | 2013-10-30 | 黑龙江鑫达企业集团有限公司 | High-strength carbon fiber reinforced polyether-ether-ketone composite material and preparation method thereof |
| CN105713343A (en) * | 2014-12-05 | 2016-06-29 | 黑龙江鑫达企业集团有限公司 | High-mobility TLCP/PES/PEEK composite material and preparation method thereof |
| CN109608863A (en) * | 2018-11-29 | 2019-04-12 | 山东凯盛新材料股份有限公司 | Polyether ketone ketone composite material and preparation method for nanometer injection molding |
| CN110343361A (en) * | 2019-06-21 | 2019-10-18 | 军事科学院系统工程研究院后勤科学与技术研究所 | A kind of personnel's neck extension Sign Board modified PE EK material |
| CN113308084A (en) * | 2021-06-25 | 2021-08-27 | 重庆沃特智成新材料科技有限公司 | Polyether ketone composite material and preparation method thereof |
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| US11352480B2 (en) | 2016-03-18 | 2022-06-07 | Ticona Llc | Polyaryletherketone composition |
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Family Cites Families (4)
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| JPH0774301B2 (en) * | 1987-12-25 | 1995-08-09 | 東レ株式会社 | Resin composition and molded articles, films and fibers thereof |
| CN1055710C (en) * | 1996-05-06 | 2000-08-23 | 中国科学院化学研究所 | Composite containing carbon fibre and liquid crystal polymer |
| JP3047861B2 (en) * | 1997-07-08 | 2000-06-05 | 日本電気株式会社 | Working / standby system uninterruptible switching device for ATM communication equipment |
| JP4225054B2 (en) * | 2002-12-24 | 2009-02-18 | パナソニック電工株式会社 | Manufacturing method of photoelectric composite wiring board |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101151322B (en) * | 2005-04-06 | 2010-10-13 | 威格斯制造有限公司 | Polymeric material |
| CN103374197A (en) * | 2012-04-19 | 2013-10-30 | 黑龙江鑫达企业集团有限公司 | High-strength carbon fiber reinforced polyether-ether-ketone composite material and preparation method thereof |
| CN103374197B (en) * | 2012-04-19 | 2016-06-22 | 黑龙江鑫达企业集团有限公司 | A kind of high-strength carbon fiber reinforced polyether ether ketone composite and preparation method thereof |
| CN105713343A (en) * | 2014-12-05 | 2016-06-29 | 黑龙江鑫达企业集团有限公司 | High-mobility TLCP/PES/PEEK composite material and preparation method thereof |
| CN109608863A (en) * | 2018-11-29 | 2019-04-12 | 山东凯盛新材料股份有限公司 | Polyether ketone ketone composite material and preparation method for nanometer injection molding |
| CN110343361A (en) * | 2019-06-21 | 2019-10-18 | 军事科学院系统工程研究院后勤科学与技术研究所 | A kind of personnel's neck extension Sign Board modified PE EK material |
| CN113308084A (en) * | 2021-06-25 | 2021-08-27 | 重庆沃特智成新材料科技有限公司 | Polyether ketone composite material and preparation method thereof |
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| CN1073601C (en) | 2001-10-24 |
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