CN1260277C - Method for preparing thermoplastic blended resin based composite material - Google Patents
Method for preparing thermoplastic blended resin based composite material Download PDFInfo
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- CN1260277C CN1260277C CN 200310101850 CN200310101850A CN1260277C CN 1260277 C CN1260277 C CN 1260277C CN 200310101850 CN200310101850 CN 200310101850 CN 200310101850 A CN200310101850 A CN 200310101850A CN 1260277 C CN1260277 C CN 1260277C
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 23
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 23
- 239000000805 composite resin Substances 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 title claims description 16
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 239000011199 continuous fiber reinforced thermoplastic Substances 0.000 claims abstract description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 4
- 238000004804 winding Methods 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 13
- 239000003063 flame retardant Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000011160 polymer matrix composite Substances 0.000 claims description 3
- 229920013657 polymer matrix composite Polymers 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 11
- 239000000843 powder Substances 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000000725 suspension Substances 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000004046 wet winding Methods 0.000 abstract 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 25
- 229920002530 polyetherether ketone Polymers 0.000 description 25
- 239000004927 clay Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000002041 carbon nanotube Substances 0.000 description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 description 11
- 239000011229 interlayer Substances 0.000 description 10
- 239000004697 Polyetherimide Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229920001601 polyetherimide Polymers 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 6
- 229910017083 AlN Inorganic materials 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 description 5
- 229920006258 high performance thermoplastic Polymers 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 230000002929 anti-fatigue Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002555 FeNi Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- Reinforced Plastic Materials (AREA)
Abstract
The present invention relates to a method for preparing a continuous fiber reinforced thermoplastic blending resin-based prepreg and a composite of the prepreg by a 'slurry process (wet process)'. In the method, a stable powder suspension solution (usually called 'slurry') is prepared from soluble thermoplastic resin as a carrier (a first component), non-soluble macromolecule particles (a second component) and/or other functional particles (a third component) as suspended particles; the continuous fiber prepreg is prepared by wet winding; then the thermoplastic blending resin-based composite is obtained by molding according to a conventional preparation process for a thermosetting composite. The composite of the present invention has universality and is suitable for the matching among various kinds of thermoplastic resin; the third component can also be introduced to functionally modify the base and the composite of the base, wherein the functions comprise separation, flame resistance, electric conduction, heat conduction, wave aspiration, etc., and a thermoplastic composite with integrated structure and functions is prepared; simultaneously, a structure with gradient components can also be prepared by the specific matching of particle size distribution of particles and a winding technology.
Description
Technical field
The present invention relates to the method that a kind of employing " slurry process " prepares continuous fiber reinforced thermoplastic blending resin base prepreg and matrix material thereof.
Background technology
High-performance thermoplastic resin base (as polyether-ether-ketone PEEK) matrix material possess high tenacity, high damage tolerance, anti-irradiation, moisture-proof heat and can repair, plurality of advantages such as Reshapable, in the aeronautical material system, occupy critical role.At present, the preparation method of high-performance thermoplastic prepreg mainly is a scorification, is about to surface and dipping that the fused thermoplastic resin is coated in fiber or fabric; Secondly also have electrostatic powder method (dry method) and slurry process (wet method) etc., both all are the surfaces that the particle of thermoplastic resin are dispersed in the fiber flexible fabric; Recently also develop and fiber shuffling method and mixed fiber yarn method etc., be characterized in thermoplastic resin is spun into silk, and then be combined into fibrous bundle with blending technology and fortifying fibre.
At polymeric material field, introduce second component carry out modification be improve that the material over-all properties is the most effective, one of most convenient, most economical method, be commonly called as " blend " modification.With the PEEK material is example, though its processing temperature is very high, but second-order transition temperature only is about 143 ℃, therefore its use temperature generally is not higher than 120 ℃, if can be by second component that adds high glass-transition temperature such as the temperature classification that liquid crystal polymer improves the PEEK material, this can be an attractive technological approaches undoubtedly.
Summary of the invention
The purpose of this invention is to provide a kind of continuous fiber reinforced thermoplastic blending resin base prepreg of low-cost preparation, and obtain the method for high-performance thermoplastic polymer matrix composites thus.Technical solution of the present invention is, does carrier with the solution of solubility thermoplastic resin, is suspension agent with insoluble second component, and it is again properties-correcting agent usually, with the thermoplastic composite prepreg of traditional " slurry process (wet method) " preparation blend base.Specific implementation method of the present invention is,
(1) the thermal plastic high polymer component (first component) with solubility is dissolved in the appropriate organic solvent in proportion, is mixed with the solution of low viscosity (as 3%wt).
(2) with granularity less than the insoluble material component of 500 purposes (second component) in 〉=5% ,≤ratio of 50% weight fraction adds in the solution, adopt devices such as mechanical stirring and ultrasonic dispersing to stir, obtain stable aaerosol solution system, " slurry " that promptly is commonly called as.Proportionlity between each component is determined by the performance of composites target.
(3) adopt conventional slurry process (wet method) Technology and winding technology, the continuous tow of preparation solution preimpregnation.By adjusting solution and twining parameter, the amount of resin that the controlling fiber bundle is carried secretly and the distribution of each component in the preimpregnation bed of material.
(4) optionally, in above-mentioned (2) or process (3), can also add conduction, heat conduction, suction ripple, functional particles component such as fire-retardant.
(5) treat solvent evaporates, take off prepreg, and the processing sequence of same with thermosetting compound material prepreg routinely, cut out and cut, spread layer.Use conventional forming techniques such as autoclave, mold pressing, obtain the thermoplastic resin based composite material of blend base.
(6) according to the relation of blending resin matrix micro-structure and property, can additionally heat-treat matrix material.
The invention has the advantages that
(1) has versatility, be applicable to reasonably combined between the various high-performance thermoplastic resins, as polyether-ether-ketone (PEEK), polyimide (PI), polysulfones (PSF), polyethersulfone (PES), polyetherimide (PEI), polyphenylene sulfide (PPS) and macromolecular material of having a large capacity and a wide range etc.
(2) made full use of the prior art and the experience of thermosetting resin based composites, the equipment of preimpregnated material manufacture process is simple, and is easy to operate, and facility investment is few, low cost.
(3) slurry soln of co-mixing system has good film forming cohesiveness, and the prepreg that obtains promptly has certain mechanical strength after drying at room temperature, need not follow-up high-temperature fusion immersion system, and equipment is simple, and prepreg has good shop coating process.
(4) prepreg structure designability is strong.By adjusting processing parameters such as preimpregnation, winding, can control the concentration distribution of each component in the preimpregnation bed of material, obtain the prepreg of concentration uniform distribution and asymmetry Gradient distribution.
(5) by different formulating of recipe, can make prepreg have good fiber effect of impregnation may, improved the moulding process of thermoplastic composite, reduced porosity, can under lower temperature and pressure, carry out forming process.
(6) second components can be specific function phase particles, as nanometer powder, CNT (carbon nano-tube), conducting particles, heat conduction particle, fire-retardant particle, stealthy particle etc., and the thermoplastic resin based composite material of preparation structure-function integration.If second component is insoluble polymer particle, they also can be used as the 3rd component.
(7) can matrix material be heat-treated according to different needs, adjust microtexture and the mechanical property of optimizing the blending resin matrix, thus the physical chemistry quality of regulation and control matrix material.
Concrete enforcement
Embodiment 1: the thermoplastic composite that preparation has high heat-resisting function
To contain phenolphthalein lateral group polyarylether ketone (PEK-C, first component) and be dissolved in the tetrahydrofuran (THF) (THF), be mixed with the solution of 3wt%; (granularity is less than 500 orders with the PEEK powder, second component) and the clay (the 3rd component) that organises of nano lamellar add solution, stir into the heterogeneous aaerosol solution system of uniform PEEK/PEK-C/ clay (slurry), wherein, the weight fraction of PEK-C: PEEK=1: 1, nano lamellar clay content 1wt%.
On the wet method wrapping machine, twine, behind the devolatilization THF solvent, obtain the thermoplasticity prepreg.Prepreg is cut out and is cut the back by [0 °]
16Unidirectional shop layer adopts the mold pressing hot-forming method to prepare matrix material.Test shows, the pure PEEK polymer matrix composites performance that the mechanical property of this carbon fiber thermoplastic blends matrix composite and the PEEK/CF of reference (carbon fiber) fiber are total to the weave preparation is suitable, and second-order transition temperature is brought up to 200.9 ℃ (DMA) from 143 ℃, becomes high heat-stable thermoplastic resin based composite material.Wherein, the effect of nano lamellar clay the 3rd component is to promote gummosis, has improved condition of molding.
Embodiment 2: preparation has the structure-function integration thermoplastic composite of barriers function
The first component PEK-C that changes in the heterogeneous aaerosol solution system of PEEK/PEK-C/ clay (slurry) of above-mentioned example 1 is polyetherimide (PEI) or PES etc., can obtain the matrix material of similar mechanical property.For example, PEI is dissolved in the ethylene dichloride solvent, be mixed with the solution of 3wt%, (granularity is less than 500 orders with the PEEK powder, second component) and the nano lamellar clay add solution, stir into the heterogeneous suspension system of uniform PEEK/PEI/ nanoclay (slurry), wherein, heavily divide PEI: PEEK=1: 1, clay content 1% heavy part (1wt%).Then, on the wet method wrapping machine, twine devolatilization solvent, the prepreg that obtains having excellent in shape stability and spread coating process.Performance is suitable with example 1 in the face of this matrix material, but improves along liquid oxygen, the liquid hydrogen barrier property of bed thickness direction, and its reason is the distribution of nano lamellar clay at interlayer.
100 ℃ of aftertreatments 3 hours, the second-order transition temperature of matrix material improved 5-7% to the matrix material of moulding, and had eliminated the internal stress of matrix material.
Embodiment 3: preparation has structure-function integration matrix material of inhaling ripple, stealthy function
The 3rd component in above-mentioned example 1 and 2 is replaced into CNT (carbon nano-tube) (CNT), stirs into uniform PEEK/PEI or PEK-C/CNT three-phase suspension system (slurry), wherein, CNT (carbon nano-tube) content 1wt%.Press the method for example 1,2, the thermoplastic composite that obtains demonstrates than not adding the higher anti-interlayer cracking performance of CNT, higher impact injury impedance (higher CAI value), and bigger microwave absorbing effect.Its reason is the effect at the CNT of interlayer.
In like manner, also CNT can be replaced into FeNi nanometer powder, carbonyl iron dust etc., the thermoplastic composite that obtains also demonstrates than not adding the higher microwave absorbing effect of these powder, and its interlayer mechanical property does not have big change.
Embodiment 4: preparation has the thermoplastic composite of high heat conduction, antifatigue or conducting function
With reference to example 1 and 2, but the clay that changes wherein is aluminium nitride (AlN) ceramic particle of high heat conduction, the thermoplasticity prepreg of preparation PEEK/PEK-C/AlN heterogeneous system, wherein, AlN content 1wt%.Obtain the thermoplastic composite of high heat conduction, the reference matrix material that its anti-fatigue performance does not add the AlN powder improves a lot, and its interlayer mechanical property does not have big change.Believe that reason is heat conduction and the heat radiation that has improved resin at the AlN powder that interlayer distributes.
The same, changing the AlN ceramic particle is electroconductive particles such as carbon black particle or metallics, the thermoplasticity prepreg of preparation PEEK/PEK-C/ electroconductive particle heterogeneous system, wherein, electroconductive particle content 1wt%.The thermoplastic composite that obtains conducting electricity.Select the carbon fiber of conduction for use as fruit fiber, then the resistance of its thickness direction approaches zero; And if select non-conductive fibers such as glass fibre for use, then the electric conductivity of matrix material obtains bigger raising.Its reason is to be communicated with interlayer at the electroconductive particle that interlayer distributes, and has improved the electricity of resin and has led.
Embodiment 5: preparation has the thermoplastic composite of anti-flaming function
With reference to example 1 and 2, the nano lamellar clay that changes wherein is fire-retardant aluminium hydroxide, preparation PEEK/PEK-C/ aluminium hydroxide heterogeneous system thermoplasticity prepreg, wherein, aluminium hydroxide content 10wt%.Obtain fire-retardant thermoplastic composite.
Embodiment 6: the blend matrix thermoplastic composite that preparation particle compositional gradient distributes
With reference to example 1 and 2, remove the 3rd component clay, respectively with granularity 150 orders, 300 orders and 450 order PEEK powdered preparation prepregs, wherein, each 4 layers of 150 orders, 300 orders and 450 purpose PEEK/PEK-C prepregs are paved in proper order according to 150 orders/300 orders/450 orders.
Adopt 12 layers of quasi-isotropic matrix material of mold pressing hot-forming method preparation.The result shows that the PEEK particle of 150 orders shop layer one side is evenly distributed on the interior and interlayer of layer of carbon fiber, and the PEEK particle of 450 order layers, one side nearly all is distributed in the surface and the interlayer of carbon fiber, and the distribution of PEEK powder presents gradient-structure in the whole matrix material.
Embodiment 7: the thermoplastic composite for preparing low-cost blend matrix
With reference to example 1, the PEEK/PEK-C/ clay three-phase that changes wherein is PPS/PA (nylon) two phase system, and wherein, PPS is second component, heavily divides PES: PA=1: 1.Obtain the thermoplastic composite of PPS/PA matrix.This example shows that universal polymer-Polymer Systems also can adopt this method to be prepared into the thermoplastic composite of blend base.
Claims (4)
1, the preparation method of a kind of employing " slurry process " preparation continuous fiber reinforced thermoplastic thermoplastic blends matrix composite is characterized in that,
(1) the thermal plastic high polymer component with solubility is dissolved in the appropriate organic solvent in proportion, and preparation is into about the solution of 3wt%.
(2) with granularity less than the insoluble polymer particle of 500 purposes component in 〉=5% ,≤ratio of 50% weight fraction adds in the solution, adopts mechanical stirring and ultrasonic dispersing device to stir, and obtains stable aaerosol solution system.
(3) adopt conventional slurry process to twine dipping technique, preimpregnation continuous tow; Adjust component, solution and winding dip parameters, obtaining high molecular component is that external phase, corpus fibrosum divide 45%～65% prepreg.
(4) treat the solvent devolatilization after, the processing sequence of same with thermosetting compound material prepreg is routinely cut out and is cut, spreads layer, uses autoclave, mold pressing routine techniques, moulding obtains the thermoplastic resin based composite material of blend base.
2. the preparation method of thermoplasticity thermoplastic blends matrix composite according to claim 1, it is characterized in that, in the process of insoluble component being sneaked into soluble component solution or afterwards, the functional particle component that adds conduction, heat conduction, suction ripple or fire-retardant class forms insoluble second phase composition that is scattered in the blending resin system.
3. the preparation method of thermoplasticity thermoplastic blends matrix composite according to claim 1 is characterized in that, by the varigrained insoluble component particle of dipping in the layer of difference shop, presses globule size order shop layer, will obtain the matrix material of granularity Gradient distribution.
4. the preparation method of its mixed polymer matrix composites of thermoplasticity according to claim 1 is characterized in that, according to the relation of the micro-structure and property of blending resin matrix itself, can heat-treat matrix material.
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| CN 200310101850 CN1260277C (en) | 2003-10-21 | 2003-10-21 | Method for preparing thermoplastic blended resin based composite material |
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| CN 200310101850 CN1260277C (en) | 2003-10-21 | 2003-10-21 | Method for preparing thermoplastic blended resin based composite material |
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| CN1260277C true CN1260277C (en) | 2006-06-21 |
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| CN101402256B (en) * | 2008-09-05 | 2012-08-15 | 中国船舶重工集团公司第七二五研究所 | Compression moulding forming method with wet-process for wave-suction composite material |
| CN102139263B (en) * | 2011-01-19 | 2013-07-03 | 金发科技股份有限公司 | Method for applying polyether-ether-ketone heat-conducting insulating coating |
| CN102936370B (en) * | 2011-08-15 | 2016-07-27 | 辽宁辽杰科技有限公司 | A kind of continuous fiber reinforced thermoplastic resin prepreg tape and preparation method thereof |
| CN104527175A (en) * | 2014-12-15 | 2015-04-22 | 沈阳航空航天大学 | Method for functionally modifying composite material laminated board by using nano wave absorbing membrane |
| CN114133606A (en) * | 2021-12-29 | 2022-03-04 | 中国航空制造技术研究院 | Preparation method and system of high-toughness thermosetting resin-based prepreg |
| CN115011073A (en) * | 2022-07-07 | 2022-09-06 | Oppo广东移动通信有限公司 | Fiber reinforced plastic, preparation method thereof, electronic equipment structural member and electronic equipment |
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| CX01 | Expiry of patent term |
Granted publication date: 20060621 |