CN103131170A - Continuous fiber reinforce polyamide composite material prepreg tape and preparation method thereof - Google Patents
Continuous fiber reinforce polyamide composite material prepreg tape and preparation method thereof Download PDFInfo
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- CN103131170A CN103131170A CN2011103863733A CN201110386373A CN103131170A CN 103131170 A CN103131170 A CN 103131170A CN 2011103863733 A CN2011103863733 A CN 2011103863733A CN 201110386373 A CN201110386373 A CN 201110386373A CN 103131170 A CN103131170 A CN 103131170A
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- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/242—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using metal fibres
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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Abstract
The invention discloses a continuous fiber reinforce polyamide composite material prepreg tape. The continuous fiber reinforce polyamide composite material prepreg tape is prepared by the following weight part components: 26-72 parts star-shaped polyamide matrix, 20-70 parts continuous fiber and 0-8 parts additive. The invention further discloses a preparation method of the continuous fiber reinforce polyamide composite material prepreg tape. Polyamide provided with a star-shaped structure is chosen by matrix resin of the prepreg tape, the liquidity of fondant is higher than the liquidity of traditional linear polyamide, dipping can be conducted easily to the continuous fiber, and dipping equipment with double intersect extrusion die heads is adopted to conduct the dipping to the continuous fiber. By means of special technology design, the continuous fiber reinforce polyamide composite material prepreg tape which is even in fiber distribution and is dipped completely is obtained, the resin content in the prepreg tape is easy to control, the fiber in the prepared continuous fiber reinforce polyamide composite material prepreg tape is guaranteed to be dipped completely, and the porosity rate is maintained not higher than 0.1%.
Description
Technical field
The present invention relates to technical field of polymer composite materials, relate in particular to a kind of continuous fibre reinforced polyamide composite material prepreg and preparation method thereof.
Background technology
Continuous fibre reinforced polyamide composite material prepreg has excellent mechanical property such as high tensile strength, flexural strength/modulus, high/low-temperature impact intensity etc., and have characteristics such as relatively low density and recoverable, therefore obtained in recent years huge development, corresponding technology of preparing has also obtained important breakthrough.Method by melt impregnation prepares this material at present, require resin to have lower viscosity under molten state, and fiber has wetting property preferably.Therefore, the mobility of resin under molten state is better, more is conducive to obtain wetting property good, strengthens the high product of efficient, simultaneously high fibre content product surface performance and production efficiency is improved.Chinese patent CN101474868A has related to the preparation of the prepreg tape of polymeric amide such as comprising PA6, PA66, but owing to adopting traditional linear polyamidoamine, its temperature flowing is limited, is unfavorable for the infiltration of Fiber In Composite Material and the further raising of fibre content.
Summary of the invention
The present invention provides a kind of continuous fibre reinforced polyamide composite material prepreg for the problem that solves above-mentioned prior art existence, and this composite material prepreg is to be prepared into by the high fluidity of molten polymeric amide and the continuous fibre that contain the star structure macromolecular chain.
Another object of the present invention is to provide the preparation method of above-mentioned continuous fibre reinforced polyamide composite material prepreg.
Purpose of the present invention is achieved through the following technical solutions:
A kind of continuous fibre reinforced polyamide composite material prepreg, made by the component that comprises following weight part:
Star polyamide matrix 26-72 part,
Continuous fibre 20-70 part,
Additive 0-8 part.
Preferably, described star polyamide matrix is the combination of the linear polyamidoamine of star polyamide and arbitrary proportion, and the polymer raw of described star polyamide comprises following two kinds of monomers at least:
(1) comprise the polyfunctional compound I of at least three same reaction functional groups;
(2) have general formula (IIa) or monomer II (IIb):
X-R
2-Y (IIa)
Wherein, R
2Expression comprises 2-20 carbon atom and can comprise heteroatomic replacement or unsubstituted aliphatic series, alicyclic or aromatic hydrocarbyl;
When X represented carboxylic acid functional, Y represented primary amine functional group, or when X represented primary amine functional group, Y represented carboxylic acid functional.
Preferably, the polymer raw of described star polyamide also comprises the monomer II I with following general formula (III), and described star polyamide is polymerized by polyfunctional compound I, monomer II and three kinds of starting monomers of monomer II I:
Z-R
3-Z (III)
Wherein, Z represents the functional group identical with the reactive functional groups of described polyfunctional compound I, R
3Expression comprises 2-20 carbon atom and can comprise heteroatomic replacement or unsubstituted aliphatic series, alicyclic or aromatic hydrocarbyl, and R
3With R
2Can be identical or different.
Preferably, described polyfunctional compound I has following general formula (I):
R
1-[-A-Z-]
m (I)
Wherein, R
1Expression comprises straight chain or the ring-type of at least two carbon atoms, and the alkyl of aromatics or aliphatic series, A represent covalent linkage or comprise the aliphatic alkyl of 1-6 carbon atom, and Z represents primary amine or carboxylic acid functional, and m is the integer of 3-8.
Preferably, described R
1Preferred hexamethylene ketone group quaternary groups, 1,1,1,-three bases-propane, 1, one or more in the octavalence group of the quaternary groups of 2,3-, three bases-propane, phenyl trivalent group, diamino polymethylene, hexamethylene ketone group, hexamethylene ketone group and polyvalent alcohol and the resulting compound group of acrylonitrile reactor.
Preferably, one or more in described polyvalent alcohol preferred diol class, tetramethylolmethane, minashi sugar alcohol or N.F,USP MANNITOL.
Preferably, one or more in the preferred methylene radical of described A, polymethylene, polyoxyethylene thiazolinyl.
Preferably, one or more in the preferred ethylidene of described polymethylene, propylidene or butylidene.
Preferably, described polyfunctional compound I is preferred 2,2,6,6-four-(β-propyloic)-pimelinketone, 1,3,5 ,-benzenetricarboxylic acid, 2,4,6-three-(amino caproyl)-1,3,5 ,-triazine, 4-aminoethyl-1, one or more in the 8-octamethylenediamine.
Preferably, the preferred hexanolactam of described monomer II.
Preferably, one or more in the preferred succsinic acid of described monomer II I, hexanodioic acid, terephthalic acid, m-phthalic acid, sebacic acid, nonane diacid, dodecylic acid, lipid acid dimer, two (β-ethyl carboxyl) pimelinketone, hexamethylene-diamine, 5-making methylpentamethylenediamine diamine, an xylyene diamine, isophorone diamine, Isosorbide-5-Nitrae-dimethyl cyclohexane.
Preferably, described heteroatoms is nitrogen-atoms and/or Sauerstoffatom.
Preferably, the massfraction of described star polyamide matrix neutral line polymeric amide is 0-50%.
Preferably, described linear polyamidoamine is selected from one or more in PA6, PA66, PA12, PA46, PA610, PA612.
Preferably, described continuous fibre is selected from one or more in inorganic fibre, organic fibre, steel fiber.
Preferably, described inorganic fibre is selected from one or both in glass fibre, carbon fiber; Described organic fibre is selected from one or both in aromatic polyamide fibre, superhigh molecular weight polyethylene fibers; Described steel fiber is selected from Stainless Steel Fibre.
Preferably, described additive is selected from one or more in oxidation inhibitor, weather resisting agent, fire retardant, static inhibitor.
Preferably, described oxidation inhibitor is selected from one or more in oxidation inhibitor 1098, antioxidant 1010, irgasfos 168, oxidation inhibitor DLTDP, copper halide; Described weather resisting agent is selected from two (2,2,6,6-tetramethyl--4-piperidyl) sebate, 2, one or more in 4-dihydroxyl-benzophenone, 2-(2 '-hydroxyl-5 '-) benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 ' aminomethyl phenyl)-5-chlorinated benzotriazole; Described fire retardant is selected from one or more in weisspiessglanz, magnesium hydroxide, aluminium hydroxide, ammonium polyphosphate, eight bromo ether, triphenylphosphate, hexabromocyclododecane, zinc borate, encapsulated red phosphorus, TDE, two (2, the 3-dibromopropyl) ethers of tetrabromo-bisphenol, hexabromocyclododecane; Described static inhibitor is selected from one or both in carbon black, nano zine oxide.
A kind of preparation method of continuous fibre reinforced polyamide composite material prepreg comprises the following steps:
By the forcing machine plastifying fusion, obtain star polyamide matrix melt, and steadily extrude by two extrusion dies after star polyamide matrix, additive are mixed, stand-by; Continuous fibre is imported staggered two extrusion die, and star polyamide matrix melt carries out preimpregnation to continuous fibre; Continuous fibre band after preimpregnation imports three roller immersion systems and realizes that melt is to the complete wetting of fiber; Then with continuous fibre band cooling and shaping, namely obtain continuous fibre reinforced polyamide composite material prepreg; Be that 26-72 weight part, additive are that 0-8 weight part, fiber are the 20-70 weight part by star polyamide matrix in the rolling speed control prepreg tape of regulating material proportion, screw speed and continuous fibre.
The preparation method of described star polyamide matrix is referring to French Patent FR2743077 and FR2779730.
Prepreg tape of the present invention can be prepared into various automobile sheet materials, building board, communications and transportation pallet as required, and product that can the moulding complexity.
Compared with prior art, the present invention has following beneficial effect:
the invention provides a kind of continuous fibre reinforced polyamide composite material prepreg and preparation method thereof, the prepreg tape matrix resin is selected the polymeric amide that contains star structure, fluidity of molten is higher than the conventional linear polymeric amide, easier continuous fibre is flooded, employing is flooded continuous fibre with the impregnating equipment of staggered two extrusion dies, design by special process, can obtain all even dipping continuous fibre reinforced polyamide composite material prepregs completely of fiber dispersion, in prepreg tape, the content of resin can be easy to control, and guarantee that in the continuous fibre reinforced polyamide composite material prepreg of manufacturing, fiber infiltrates fully and keeps porosity not higher than 0.1%.
Description of drawings
Fig. 1 is the production technological process of continuous fibre reinforced polyamide composite material prepreg.
Embodiment
Describe the present invention in detail below in conjunction with accompanying drawing.
Embodiment 1
Made by the component that comprises following weight parts based on continuous fibre reinforced polyamide composite material prepreg:
50.8 parts of continuous glass fibres (PPG company, 45882400tex continuous glass fibre),
49.2 parts of star polyamide matrix;
Wherein, star polyamide matrix, to prepare according to the method for describing in French Patent FR2743077, with 100 parts of hexanolactams (monomer II), 0.025 part 2,2,6,6-four-(β-propyloic)-pimelinketone (polyfunctional compound I) and 0.036 part of distilled water add copolymerization acquisition in autoclave.According to standard I S01133, the melt flow index of measuring under 275 ℃, 325 grams loads is 28g/10min.
(1) star polyamide matrix is passed through the forcing machine plastifying fusion, obtain star polyamide matrix melt, and steadily extrude by two extrusion dies, stand-by;
(2) continuous glass fibre volume 11 is arranged on the spindle 13 of creel 10 and draws the continuous tow 12 that is arranged in parallel, carefully continuous glass fibre bundle 12 after drawing, is passed through by creel 10 row's silk mouth 21 tension-adjusting gear 20, continuous glass fibre bundle 12 is on average arranged, avoid interfibrous mutual intersection and wearing and tearing, the continuous glass fibre bundle 12 of then on average arranging passes tensioning roller 22, and the preliminary dispersion that applies some tension assurance continuous glass fibre bundle 12 to continuous glass fibre bundle 12 namely forms the continuous fibre band; Again the continuous fibre band is eliminated through static eraser 30 static that produces, then the continuous fibre band is preheating to 260 ℃ through the infrared baking oven 40 that preheats; Die head 61 and die head 62 that continuous fibre band after preheating imports in pair extrusion dies 60 through tension-adjusting gear 50, star polyamide matrix melt carries out preimpregnation to the continuous fibre band, adopt single screw extrusion machine, extrusion die 61 and die head 62 temperature are arranged on 240 ℃, guarantee that the star polyamide resin has lower viscosity;
(3) with in step (2) through the continuous fibre band of preimpregnation, import three roller immersion systems 70, wherein the temperature of stack 71, stack 72, stack 73 all is arranged on 240 ℃, make the star polyamide resin have lower viscosity and mobility preferably, realize that molten resin is to the complete wetting of fiber.The continuous fibre band of complete wetting enters cooling roller pressure device 80 and carries out coolingly, and wherein cooling and shaping roller 81 and cooling and shaping roller 82 are connected with water of condensation, and the gap adjustment of two cooling and shaping rollers is to 0.5mm.The continuous fibre band obtains thickness after cooling and shaping be 0.5mm, and ganoid continuous fibre strengthens the star polyamide prepreg tape.Be 49.2 weight parts by star polyamide matrix in the rolling speed control prepreg tape of adjusting screw(rod) rotating speed or rate of feeding and continuous fibre, glass fibre is 50.8 weight parts.Enter traction wind2 90 coiling and moldings, packing after the prepreg tape cool to room temperature, can obtain fiber dispersion evenly, flood completely that continuous glass fibre strengthens the star polyamide prepreg tape, technological process is as shown in Figure 1.The performance test results of this material sees Table 1.
Comparative Examples
Except not adding 2,2,6,6-four-(β-propyloic)-pimelinketone in the preparation process of star polyamide matrix, implement according to the condition in embodiment 1 and step.The performance test results of this material sees Table 1.
Embodiment 2
Made by the component that comprises following weight parts based on continuous fibre reinforced polyamide composite material prepreg:
53.2 parts of continuous carbon fibres (eastern beautiful fiber research institute, T700 24K continuous carbon fibre),
46.8 parts of star polyamide matrix;
Wherein, star polyamide matrix, it is the method for describing according in French Patent FR2743077, with 100 parts of hexanolactams (monomer II), 0.031 part 2,2,6,6-four-(β-propyloic)-pimelinketone (polyfunctional compound I) and 0.036 part of distilled water add copolymerization acquisition in autoclave.According to standard ISO 1133, the melt flow index of measuring under 275 ℃, 325 grams loads is 47g/10min.
(1) star polyamide matrix is passed through the forcing machine plastifying fusion, obtain star polyamide matrix melt, and steadily extrude by two extrusion dies, stand-by;
(2) continuous carbon fibre volume 11 is arranged on the spindle 13 of creel 10 and draws the continuous tow 12 that is arranged in parallel, carefully continuous carbon fibre bundle 12 after drawing, is passed through by creel 10 row's silk mouth 21 tension-adjusting gear 20, continuous carbon fibre bundle 12 is on average arranged, avoid interfibrous mutual intersection and wearing and tearing, the continuous carbon fibre bundle 12 of then on average arranging passes tensioning roller 22, and the preliminary dispersion of applying some tension assurance continuous carbon fibre bundle 12 for continuous carbon fibre bundle 12 namely forms the continuous fibre band; Again the continuous fibre band is eliminated through static eraser 30 static that produces, then the continuous fibre band is preheating to 270 ℃ through the infrared baking oven 40 that preheats; Die head 61 and die head 62 that continuous fibre band after preheating imports in pair extrusion dies 60 through tension-adjusting gear 50, star polyamide matrix melt carries out preimpregnation to the continuous fibre band, adopt single screw extrusion machine, extrusion die 61 and die head 62 temperature are arranged on 240 ℃, guarantee that the star polyamide resin has lower viscosity;
(3) with in step (2) through the continuous fibre band of preimpregnation, import three roller immersion systems 70, wherein the temperature of stack 71, stack 72, stack 73 all is arranged on 230 ℃, make the star polyamide resin have lower viscosity and mobility preferably, realize that molten resin is to the complete wetting of fiber.The continuous fibre band of complete wetting enters cooling roller pressure device 80 and carries out coolingly, and wherein cooling and shaping roller 81 and cooling and shaping roller 82 are connected with water of condensation, and the gap adjustment of two cooling and shaping rollers is to 0.5mm.The continuous fibre band obtains thickness after cooling and shaping be 0.5mm, ganoid continuous fibre strengthens the star polyamide prepreg tape, is that 46.8 weight parts, carbon fiber are 53.2 weight parts by star polyamide matrix in the rolling speed control prepreg tape of adjusting screw(rod) rotating speed or rate of feeding and continuous fibre.Enter traction wind2 90 coiling and moldings, packing after the prepreg tape cool to room temperature, can obtain flooding the star polyamide of continuous carbon fibre enhancing completely prepreg tape, technological process as shown in Figure 1.The performance test results of this material sees Table 1.
Embodiment 3
Made by the component that comprises following weight parts based on continuous fibre reinforced polyamide composite material prepreg:
70 parts of continuous glass fibres (PPG company, 4588 2400tex continuous glass fibres),
26 parts of star polyamide matrix,
3.5 parts of magnesium hydroxides,
1,098 0.25 parts, oxidation inhibitor,
Irgasfos 168,0.25 part;
Wherein the preparation method of star polyamide matrix, component and content are with embodiment 1.
As shown in Figure 1, (1) passes through the blend of forcing machine plastifying fusion with star polyamide matrix and additive, obtains star polyamide matrix melt, and steadily extrudes by two extrusion dies, and is stand-by;
(2) continuous glass fibre volume 11 is arranged on the spindle 13 of creel 10 and draws the continuous tow 12 that is arranged in parallel, carefully continuous glass fibre bundle 12 after drawing, is passed through by creel 10 row's silk mouth 21 tension-adjusting gear 20, continuous glass fibre bundle 12 is on average arranged, avoid interfibrous mutual intersection and wearing and tearing, the continuous glass fibre bundle 12 of then on average arranging passes tensioning roller 22, and the preliminary dispersion that applies some tension assurance continuous glass fibre bundle 12 to continuous glass fibre bundle 12 namely forms the continuous fibre band; Again the continuous fibre band is eliminated through static eraser 30 static that produces, then the continuous fibre band is preheating to 250 ℃ through pre-electrically heated baking oven 40; Die head 61 and die head 62 that continuous fibre band after preheating imports in pair extrusion dies 60 through tension-adjusting gear 50, star polyamide matrix melt carries out preimpregnation to the continuous fibre band, adopt single screw extrusion machine, extrusion die 61 and die head 62 temperature are arranged on 240 ℃, guarantee that the star polyamide resin has lower viscosity;
(3) with in step (2) through the continuous fibre band of preimpregnation, import three roller immersion systems 70, wherein the temperature of stack 71, stack 72, stack 73 all is arranged on 235 ℃, make the star polyamide resin have lower viscosity and mobility preferably, realize that molten resin is to the complete wetting of fiber.The continuous fibre band of complete wetting enters cooling roller pressure device 80 and carries out coolingly, and wherein cooling and shaping roller 81 and cooling and shaping roller 82 are connected with water of condensation, and the gap adjustment of two cooling and shaping rollers is to 0.5mm.The continuous fibre band obtains thickness after cooling and shaping be 0.5mm, ganoid continuous fibre strengthens the star polyamide prepreg tape, controls the weight of star polyamide matrix, additive and fiber in prepreg tape by the rolling speed of regulating material proportion, screw speed and continuous fibre.Enter traction wind2 90 coiling and moldings, packing after the prepreg tape cool to room temperature, can obtaining flooding completely, continuous glass fibre strengthens the star polyamide prepreg tape.The performance test results of this material sees Table 1.
Embodiment 4
Made by the component that comprises following weight parts based on continuous fibre reinforced polyamide composite material prepreg:
20 parts, carbon fiber (eastern beautiful fiber research institute, T70024K continuous carbon fibre),
72 parts of star polyamide matrix,
7.5 parts of weisspiessglanzs,
0.25 part of antioxidant 1010,
0.25 part of irgasfos 168;
Wherein the preparation method of star polyamide matrix, component and content are with embodiment 1.
As shown in Figure 1, (1) passes through the blend of forcing machine plastifying fusion with star polyamide matrix and additive, obtains star polyamide matrix melt, and steadily extrudes by two extrusion dies, and is stand-by;
(2) continuous carbon fibre volume 11 is arranged on the spindle 13 of creel 10 and draws the continuous tow 12 that is arranged in parallel, carefully continuous carbon fibre bundle 12 after drawing, is passed through by creel 10 row's silk mouth 21 tension-adjusting gear 20, continuous carbon fibre bundle 12 is on average arranged, avoid interfibrous mutual intersection and wearing and tearing, the continuous carbon fibre bundle 12 of then on average arranging passes tensioning roller 22, and the preliminary dispersion of applying some tension assurance continuous carbon fibre bundle 12 for continuous carbon fibre bundle 12 namely forms the continuous fibre band; Again the continuous fibre band is eliminated through static eraser 30 static that produces, then the continuous fibre band is preheating to 240 ℃ through pre-infrared heating oven 40; Die head 61 and die head 62 that continuous fibre band after preheating imports in pair extrusion dies 60 through tension-adjusting gear 50, star polyamide matrix melt carries out preimpregnation to the continuous fibre band, adopt twin screw extruder, extrusion die 61 and die head 62 temperature are arranged on 240 ℃, guarantee that the star polyamide resin has lower viscosity;
(3) with in step (2) through the continuous fibre band of preimpregnation, import three roller immersion systems 70, wherein the temperature of stack 71, stack 72, stack 73 all is arranged on 225 ℃, make the star polyamide resin have lower viscosity and mobility preferably, realize that molten resin is to the complete wetting of fiber.The continuous fibre band of complete wetting enters cooling roller pressure device 80 and carries out coolingly, and wherein cooling and shaping roller 81 and cooling and shaping roller 82 are connected with water of condensation, and the gap adjustment of two cooling and shaping rollers is to 0.5mm.The continuous fibre band obtains thickness after cooling and shaping be 0.5mm, ganoid continuous fibre strengthens the star polyamide prepreg tape, controls the weight of star polyamide matrix, additive and fiber in prepreg tape by the rolling speed of regulating material proportion, screw speed and continuous fibre.Enter traction wind2 90 coiling and moldings, packing after the prepreg tape cool to room temperature, can obtaining flooding completely, continuous carbon fibre strengthens the star polyamide prepreg tape.The performance test results of this material sees Table 1.
Embodiment 5
Continuous fibre reinforced polyamide composite material prepreg is made by the component that comprises following weight parts:
47 parts of star polyamide matrix,
Superhigh molecular weight polyethylene fibers is 50 parts continuously,
Weather resisting agent 2,1 part of 4-dihydroxyl-benzophenone,
2 parts of ammonium polyphosphate flame retardants;
Wherein, star polyamide matrix is the composition of 30 parts of star polyamide and 17 parts of linear polyamidoamine PA66.Star polyamide is to prepare according to the method for describing in French Patent FR2743077, with 100 parts of hexanolactams (monomer II), 0.02 part 1,3,5 ,-benzenetricarboxylic acid (polyfunctional compound I), 0.018 part of terephthalic acid (monomer II I) and 0.036 part of distilled water add copolymerization acquisition in autoclave.According to standard ISO 1133, the melt flow index of measuring under 275 ℃, 325 grams loads is 30g/10min.
(1) star polyamide matrix and additive are passed through the blend of forcing machine plastifying fusion, obtain star polyamide matrix melt, and steadily extrude by two extrusion dies, stand-by;
(2) continuous superhigh molecular weight polyethylene fibers is imported staggered two extrusion die, star polyamide matrix melt carries out preimpregnation to continuous fibre;
(3) the continuous fibre band through preimpregnation imports three roller immersion systems, realizes that molten resin is to the complete wetting of fiber.The continuous fibre band of complete wetting enters the cooling roller pressure device and carries out cooling and shaping, can obtain fiber dispersion evenly, flood completely that continuous fibre strengthens the star polyamide prepreg tape.Control the weight of star polyamide matrix, additive and fiber in prepreg tape by the rolling speed of regulating material proportion, screw speed and continuous fibre.The performance test results of this material sees Table 1.
Embodiment 6
Continuous fibre reinforced polyamide composite material prepreg is made by the component that comprises following weight parts:
60 parts of star polyamide matrix,
Stainless Steel Fibre is 35 parts continuously,
2 parts of oxidation inhibitor DLTDP,
2 parts, fire retardant aluminium hydroxide,
1 part of fire retardant triphenylphosphate;
Wherein, star polyamide matrix is the composition of 45 parts of star polyamide and 15 parts of linear polyamidoamine PA6.Star polyamide is to prepare according to the method for describing in French Patent FR2743077, with 100 parts of hexanolactams (monomer II), 0.035 part 2,4,6-three-(amino caproyl)-1,3,5,-triazine (polyfunctional compound I), 0.015 part of lipid acid dimer (monomer II I) and 0.036 part of distilled water add copolymerization acquisition in autoclave.According to standard ISO 1133, the melt flow index of measuring under 275 ℃, 325 grams loads is 35g/10min.
(1) star polyamide matrix and additive are passed through the blend of forcing machine plastifying fusion, obtain star polyamide matrix melt, and steadily extrude by two extrusion dies, stand-by;
(2) continuous Stainless Steel Fibre is imported staggered two extrusion die, star polyamide matrix melt carries out preimpregnation to continuous fibre;
(3) the continuous fibre band through preimpregnation imports three roller immersion systems, realizes that molten resin is to the complete wetting of fiber.The continuous fibre band of complete wetting enters the cooling roller pressure device and carries out cooling and shaping, can obtain fiber dispersion evenly, flood completely that continuous fibre strengthens the star polyamide prepreg tape.Control the weight of star polyamide matrix, additive and fiber in prepreg tape by the rolling speed of regulating material proportion, screw speed and continuous fibre.The performance test results of this material sees Table 1.
Embodiment 7
Continuous fibre reinforced polyamide composite material prepreg is made by the component that comprises following weight parts:
65 parts of star polyamide matrix,
Aromatic polyamide fibre is 28 parts continuously,
3 parts of weather resisting agent 2-(2 '-hydroxyl-5 '-) benzotriazoles,
2 parts of TDE,
2 parts of static inhibitor nano zine oxides;
Wherein, star polyamide matrix is the composition of 32.5 parts of star polyamide and 32.5 parts of linear polyamidoamine PA12.Star polyamide is to prepare according to the method for describing in French Patent FR2743077, with 100 parts of hexanolactams (monomer II), 0.025 part 4-aminoethyl-1,8-octamethylenediamine (polyfunctional compound I), 0.015 part of hexamethylene-diamine (monomer II I) and 0.036 part of distilled water add copolymerization acquisition in autoclave.According to standard ISO 1133, the melt flow index of measuring under 275 ℃, 325 grams loads is 38g/10min.
(1) star polyamide matrix and additive are passed through the blend of forcing machine plastifying fusion, obtain star polyamide matrix melt, and steadily extrude by two extrusion dies, stand-by;
(2) continuous aromatic polyamide fibre is imported staggered two extrusion die, star polyamide matrix melt carries out preimpregnation to continuous fibre;
(3) the continuous fibre band through preimpregnation imports three roller immersion systems, realizes that molten resin is to the complete wetting of fiber.The continuous fibre band of complete wetting enters the cooling roller pressure device and carries out cooling and shaping, can obtain fiber dispersion evenly, flood completely that continuous fibre strengthens the star polyamide prepreg tape.Control the weight of star polyamide matrix, additive and fiber in prepreg tape by the rolling speed of regulating material proportion, screw speed and continuous fibre.The performance test results of this material sees Table 1.
The tensile strength testing standard is GB/T 1447-2005; The flexural strength testing standard is GB/T1449-2005; The shock strength testing standard is GB/T 1451-2005; Fibre content utilizes densimetry to test, and its testing method is as follows:
Utilize the air-discharging method to test respectively fibre density and be ρ
Fiber, resin density is ρ
Polyamide matrix, prepreg tape density is ρ
Prepreg tape, utilize formula C=(ρ
Polyamide matrix-ρ
Prepreg tape)/(ρ
Polyamide matrix-ρ
Fiber), calculate fibre content.
Table 1
Can illustrate by table 1 adopts star polyamide matrix can prepare high fibre content polyamide compoiste material prepreg tape in conjunction with the wetting method with staggered two extrusion die heads of uniqueness, and effect of impregnation may is obvious, is conducive to the performance raising of polyamide compoiste material and the further reduction of production cost.
Above disclosed be only several specific embodiments of the application, but the application is not limited thereto, the changes that any person skilled in the art can think of all should drop in the application's protection domain.
Claims (19)
1. a continuous fibre reinforced polyamide composite material prepreg, is characterized in that, made by the component that comprises following weight part:
Star polyamide matrix 26-72 part,
Continuous fibre 20-70 part,
Additive 0-8 part.
2. continuous fibre reinforced polyamide composite material prepreg as claimed in claim 1, it is characterized in that, described star polyamide matrix is the combination of the linear polyamidoamine of star polyamide and arbitrary proportion, and the polymer raw of described star polyamide comprises following two kinds of monomers at least:
(1) comprise the polyfunctional compound I of at least three same reaction functional groups;
(2) have general formula (IIa) or monomer II (IIb):
X-R
2-Y (IIa)
Wherein, R
2Expression comprises 2-20 carbon atom and can comprise heteroatomic replacement or unsubstituted aliphatic series, alicyclic or aromatic hydrocarbyl;
When X represented carboxylic acid functional, Y represented primary amine functional group, or when X represented primary amine functional group, Y represented carboxylic acid functional.
3. continuous fibre reinforced polyamide composite material prepreg as claimed in claim 2, it is characterized in that, the polymer raw of described star polyamide also comprises the monomer II I with following general formula (III), and described star polyamide is polymerized by polyfunctional compound I, monomer II and three kinds of starting monomers of monomer II I:
Z-R
3-Z (III)
Wherein, Z represents the functional group identical with the reactive functional groups of described polyfunctional compound I, R
3Expression comprises 2-20 carbon atom and can comprise heteroatomic replacement or unsubstituted aliphatic series, alicyclic or aromatic hydrocarbyl, and R
3With R
2Can be identical or different.
4. continuous fibre reinforced polyamide composite material prepreg as claimed in claim 2 or claim 3, is characterized in that, described polyfunctional compound I has following general formula (I):
R
1-[-A-Z-]
m (I)
Wherein, R
1Expression comprises straight chain or the ring-type of at least two carbon atoms, and the alkyl of aromatics or aliphatic series, A represent covalent linkage or comprise the aliphatic alkyl of 1-6 carbon atom, and Z represents primary amine or carboxylic acid functional, and m is the integer of 3-8.
5. continuous fibre reinforced polyamide composite material prepreg as claimed in claim 4, is characterized in that described R
1Preferred hexamethylene ketone group quaternary groups, 1,1,1,-three bases-propane, 1, one or more in the octavalence group of the quaternary groups of 2,3-, three bases-propane, phenyl trivalent group, diamino polymethylene, hexamethylene ketone group, hexamethylene ketone group and polyvalent alcohol and the resulting compound group of acrylonitrile reactor.
6. continuous fibre reinforced polyamide composite material prepreg as claimed in claim 5, is characterized in that, one or more in described polyvalent alcohol preferred diol class, tetramethylolmethane, minashi sugar alcohol or N.F,USP MANNITOL.
7. continuous fibre reinforced polyamide composite material prepreg as claimed in claim 4, is characterized in that, one or more in the preferred methylene radical of described A, polymethylene, polyoxyethylene thiazolinyl.
8. continuous fibre reinforced polyamide composite material prepreg as claimed in claim 7, is characterized in that, one or more in the preferred ethylidene of described polymethylene, propylidene or butylidene.
9. continuous fibre reinforced polyamide composite material prepreg as claimed in claim 4, is characterized in that, described polyfunctional compound I preferred 2,2,6,6-four-(β-propyloic)-pimelinketone, 1,3,5 ,-benzenetricarboxylic acid, 2,4,6-three-(amino caproyl)-1,3,5,-triazine, 4-aminoethyl-1, one or more in the 8-octamethylenediamine.
10. continuous fibre reinforced polyamide composite material prepreg as claimed in claim 2 or claim 3, is characterized in that the preferred hexanolactam of described monomer II.
11. continuous fibre reinforced polyamide composite material prepreg as claimed in claim 3, it is characterized in that, one or more in the preferred succsinic acid of described monomer II I, hexanodioic acid, terephthalic acid, m-phthalic acid, sebacic acid, nonane diacid, dodecylic acid, lipid acid dimer, two (β-ethyl carboxyl) pimelinketone, hexamethylene-diamine, 5-making methylpentamethylenediamine diamine, an xylyene diamine, isophorone diamine, Isosorbide-5-Nitrae-dimethyl cyclohexane.
12. continuous fibre reinforced polyamide composite material prepreg, is characterized in that as claimed in claim 2 or claim 3, described heteroatoms is nitrogen-atoms and/or Sauerstoffatom.
13. continuous fibre reinforced polyamide composite material prepreg, is characterized in that as claimed in claim 2 or claim 3, the massfraction of described star polyamide matrix neutral line polymeric amide is 0-50%.
14. continuous fibre reinforced polyamide composite material prepreg, is characterized in that as claimed in claim 2 or claim 3, described linear polyamidoamine is selected from one or more in PA6, PA66, PA12, PA46, PA610, PA612.
15. continuous fibre reinforced polyamide composite material prepreg as claimed in claim 1 is characterized in that described continuous fibre is selected from one or more in inorganic fibre, organic fibre, steel fiber.
16. continuous fibre reinforced polyamide composite material prepreg as claimed in claim 15 is characterized in that described inorganic fibre is selected from one or both in glass fibre, carbon fiber; Described organic fibre is selected from one or both in aromatic polyamide fibre, superhigh molecular weight polyethylene fibers; Described steel fiber is selected from Stainless Steel Fibre.
17. continuous fibre reinforced polyamide composite material prepreg as claimed in claim 1 is characterized in that described additive is selected from one or more in oxidation inhibitor, weather resisting agent, fire retardant, static inhibitor.
18. continuous fibre reinforced polyamide composite material prepreg as claimed in claim 17 is characterized in that described oxidation inhibitor is selected from one or more in oxidation inhibitor 1098, antioxidant 1010, irgasfos 168, oxidation inhibitor DLTDP, copper halide; Described weather resisting agent is selected from two (2,2,6,6-tetramethyl--4-piperidyl) sebate, 2, one or more in 4-dihydroxyl-benzophenone, 2-(2 '-hydroxyl-5 '-) benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 ' aminomethyl phenyl)-5-chlorinated benzotriazole; Described fire retardant is selected from one or more in weisspiessglanz, magnesium hydroxide, aluminium hydroxide, ammonium polyphosphate, eight bromo ether, triphenylphosphate, hexabromocyclododecane, zinc borate, encapsulated red phosphorus, TDE, two (2, the 3-dibromopropyl) ethers of tetrabromo-bisphenol, hexabromocyclododecane; Described static inhibitor is selected from one or both in carbon black, nano zine oxide.
19. the preparation method of a continuous fibre reinforced polyamide composite material prepreg as claimed in claim 1 is characterized in that, comprises the following steps:
By the forcing machine plastifying fusion, obtain star polyamide matrix melt, and steadily extrude by two extrusion dies after star polyamide matrix, additive are mixed, stand-by; Continuous fibre is imported staggered two extrusion die, and star polyamide matrix melt carries out preimpregnation to continuous fibre; Continuous fibre band after preimpregnation imports three roller immersion systems and realizes that melt is to the complete wetting of fiber; Then with continuous fibre band cooling and shaping, namely obtain continuous fibre reinforced polyamide composite material prepreg; Be that 26-72 weight part, additive are that 0-8 weight part, fiber are the 20-70 weight part by star polyamide matrix in the rolling speed control prepreg tape of regulating material proportion, screw speed and continuous fibre.
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| CN105017795A (en) * | 2014-04-25 | 2015-11-04 | 句容市百事特复合材料有限公司 | Thin belt-shaped reinforcing material and application thereof |
| CN105086436A (en) * | 2015-09-14 | 2015-11-25 | 长沙五犇新材料科技有限公司 | Continuous glass fiber reinforced flame-retardant nylon composite board and production process thereof |
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| CN115260753A (en) * | 2021-04-30 | 2022-11-01 | 上海凯赛生物技术股份有限公司 | Long carbon chain polyamide resin composition and continuous fiber reinforced long carbon chain polyamide composite material |
| CN115785659A (en) * | 2021-09-10 | 2023-03-14 | 上海凯赛生物技术股份有限公司 | Long fiber reinforced wear-resistant self-lubricating bio-based polyamide composite material and preparation method thereof |
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| CN105017795A (en) * | 2014-04-25 | 2015-11-04 | 句容市百事特复合材料有限公司 | Thin belt-shaped reinforcing material and application thereof |
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| CN106182494A (en) * | 2016-09-07 | 2016-12-07 | 东华大学 | A kind of preparation technology of continuous fiber reinforced thermoplastic prepreg tape |
| CN106182494B (en) * | 2016-09-07 | 2018-10-23 | 东华大学 | A kind of preparation process of continuous fiber reinforced thermoplastic prepreg tape |
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| CN110204896A (en) * | 2019-06-19 | 2019-09-06 | 广州华新科智造技术有限公司 | Polyamide compoiste material and preparation method thereof |
| CN115260753A (en) * | 2021-04-30 | 2022-11-01 | 上海凯赛生物技术股份有限公司 | Long carbon chain polyamide resin composition and continuous fiber reinforced long carbon chain polyamide composite material |
| CN115260753B (en) * | 2021-04-30 | 2024-02-09 | 上海凯赛生物技术股份有限公司 | Long carbon chain polyamide resin composition and continuous fiber reinforced long carbon chain polyamide composite material |
| CN115785659A (en) * | 2021-09-10 | 2023-03-14 | 上海凯赛生物技术股份有限公司 | Long fiber reinforced wear-resistant self-lubricating bio-based polyamide composite material and preparation method thereof |
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Application publication date: 20130605 |