CN103589138A - Continuous-fiber-reinforced polyamide composite material prepreg tape and preparation method thereof - Google Patents
Continuous-fiber-reinforced polyamide composite material prepreg tape and preparation method thereof Download PDFInfo
- Publication number
- CN103589138A CN103589138A CN201210290728.3A CN201210290728A CN103589138A CN 103589138 A CN103589138 A CN 103589138A CN 201210290728 A CN201210290728 A CN 201210290728A CN 103589138 A CN103589138 A CN 103589138A
- Authority
- CN
- China
- Prior art keywords
- acid
- continuous
- star
- continuous fibre
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention relates to a continuous-fiber-reinforced polyamide composite material prepreg tape and a preparation method thereof. The prepreg tape comprises following raw materials by weight: 30-80 parts of a star-shaped polyamide substrate, 20-70 parts of continuous fiber and 0-30 parts of an additive. The preparation method includes steps of: plasticizing and fusing the star-shaped polyamide substrate and the additive through an extruder, after the star-shaped polyamide substrate and the additive are mixed, to obtain a melt of the star-shaped polyamide substrate; extruding steadily through double extrusion die heads and setting aside for further use; adding the continuous fiber into intersect double extrusion die heads, and pre-dipping the continuous fiber with the melt of the star-shaped polyamide substrate; adding the pre-dipped continuous fiber into a three-roller dipping device to allow that the continuous fiber is completely dipped by the melt of the star-shaped polyamide substrate; and cooling and shaping the obtained continuous fiber, thus obtaining the continuous-fiber-reinforced polyamide composite material prepreg tape. Compared with the prior art, the method can obtain the completely-dipped prepreg tap with uniformly dispersed fiber, the content of the resin in the prepreg tape is controllable, and the porosity is maintained to be not more than 0.2%.
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 as high tensile strength, flexural strength/modulus, high/low-temperature impact intensity etc., and there is the features such as relatively low density and recoverable, therefore obtained in recent years huge development, corresponding technology of preparing has also obtained important breakthrough.At present by the method for melt impregnation, prepare this material, require resin under molten state, to there is lower viscosity, and fiber has good wetting property.Therefore, the mobility of resin under molten state is better, is more conducive to obtain wetting property good, strengthens the high product of efficiency, can make high fibre content product surface performance and production efficiency be improved simultaneously.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
Object of the present invention is exactly to provide the content of resin in a kind of prepreg tape easy to control in order to overcome the defect of above-mentioned prior art existence, continuous fibre reinforced polyamide composite material prepreg that voidage is low and preparation method thereof.
Object of the present invention can be achieved through the following technical solutions: a kind of continuous fibre reinforced polyamide composite material prepreg, it is characterized in that, and the raw material of this prepreg tape is made by the component that comprises following weight part:
Star polyamide matrix 30-80 part,
Continuous fibre 20-70 part,
Additive 0-30 part.
Described star polyamide matrix is star polyamide and linear polyamidoamine (50-100: combination 50-0) in mass ratio; The polymer raw of described star polyamide at least comprises following three kinds of materials:
(I) dicarboxylic acid monomer and diamine monomer, or their salt 95-99.8mol%;
(II) comprise the polyfunctional monomer 0.05-1mol% of at least 3 X1 of functional group;
(III) the simple function group compound 0.15-4% that comprises the X2 of functional group;
Wherein, the X2 of the X1He of functional group functional group is carboxylic acid type functional group or the An Xing functional group that can react with dicarboxylic acid monomer and diamine monomer; ，X2Wei An type functional group during DangX1Wei carboxylic acid type functional group; The DangX1Wei An type Shi，X2Wei of functional group carboxylic acid type functional group.
The polymer raw of described star polyamide also comprises amino acid, lactan, as hexanolactam or hexosamine.
Described dicarboxylic acid monomer comprises aliphatics or the aromatic dicarboxylic acid with 4 to 12 carbon atoms; Described diamine monomer comprises aliphatics or the aromatic diamine with 4 to 12 carbon atoms; Described dicarboxylic acid monomer and the amount of substance of diamine monomer equate;
Described polyfunctional monomer has following general formula (a):
R-[-A-X1]
n (a)
Wherein, R represents to comprise at least two carbon atoms and can comprise the alkyl of one or more heteroatomic straight chains, ring-type, aromatics or aliphatic series, heteroatoms comprises O, S, N or P, the aliphatic alkyl that A represents covalent linkage or comprises 1-6 carbon atom, X1 represents primary amine or carboxylic acid functional, and n is the integer of 3-8;
Described simple function group compound is selected from n-hexadecyl amine, Octadecane base amine and dodecyl amine, acetic acid, lauric acid, benzylamine, phenylformic acid, propionic acid and 4-amino-2,2,6,6, one or more of-tetramethyl piperidine.
Described dicarboxylic acid monomer is selected from one or more in hexanodioic acid, terephthalic acid, iso-phthalic acid, oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, pimelic acid, sebacic acid or dodecanedioic acid;
Described diamine monomer be selected from hexamethylene-diamine, m-xylene diamine, butanediamine, isophorone diamine, 3,3 ', one or more in 5-trimethylhexamethylenediamine or methyl pentamethylene diamine;
The preferred hexamethylene ketone group of R quaternary groups, 1 in described polyfunctional monomer general formula (a), 1,1,-tri-bases-propane, 1, one or more in the octavalence group of the quaternary groups of 2,3-, tri-bases-propane, phenyl trivalent group, benzyl, anthryl, xenyl, triphenyl, pyridine, indoles, furans, thiophene, purine, phenanthrene, diamino polymethylene, hexamethylene ketone group, hexamethylene ketone group and polyvalent alcohol and the resulting compound group of acrylonitrile reactor; One or more in the preferred methylene radical of A, ethylidene, propylidene, butylidene, polyoxyethylene thiazolinyl.
Described polyfunctional monomer preferably 2,2,6,6-tetra--(β-propyloic)-pimelinketone, 1,3,5 ,-benzenetricarboxylic acid, 2,4,6-tri--(amino caproyl)-1,3,5,-triazine, 3,5,3 ', 5 ' xenyl tetracarboxylic acid, 3,5,3 ', 5 ' benzophenone tetracarboxylic acid, Pyromellitic Acid, 4-aminoethyl-1,8-octamethylenediamine, nitrilo triethylamine, diethyl triamine, trientine, tetraethylenepentamine, trimeric cyanamide, 4-amino-ethyl-1, one or more of represented compound in 8 octamethylenediamines or following general formula (b);
R
1[A1-NH
2]
3 (b)
Wherein: R
1represent propane-1,1,1-, tri-bases or propane-1,2,3-, tri-basis set groups, A1 represents polyoxy ethylidene group.
The massfraction of described star polyamide matrix neutral line polymeric amide is 0-50%.
Described linear polyamidoamine is selected from one or more in PA6, PA66, PA12, PA46, PA610, PA612.
Described continuous fibre is selected from one or more in inorganic fibre, organic fibre, steel fiber; Described additive is selected from one or more in oxidation inhibitor, photostabilizer, fire retardant, static inhibitor.
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;
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-hydroxyl-benzophenone, 2-(2 '-hydroxyl-5 '-) benzotriazole, 2-(2 '-hydroxyl-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, tetramethylolmethane, eight bromo ether, triphenylphosphate, hexabromocyclododecane, zinc borate, encapsulated red phosphorus, TDE, two (2, the 3-dibromopropyl) ether 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, it is characterized in that, the method comprises the following steps: after star polyamide matrix, additive are mixed, pass through forcing machine plastifying fusion, obtain star polyamide matrix melt, and steadily extrude by two extrusion dies, stand-by; Continuous fibre is imported to 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 makes star polyamide matrix melt to continuous fibre complete wetting, and gained continuous fibre band cooling and shaping, obtains continuous fibre reinforced polyamide composite material prepreg; By regulating the rolling speed of material material proportioning, screw speed and continuous fibre, the weight fraction that makes star polyamide matrix in prepreg tape is that the weight fraction that the weight fraction of 30-80 part, additive is 0-30 part, fiber is 20-70 part.
The temperature of described forcing machine is set according to the melt temperature of star polyamide matrix and additive agent mixture, is generally 270-280 ℃.
Compared with prior art, the invention provides a kind of continuous fibre reinforced polyamide composite material prepreg and preparation method thereof, prepreg tape matrix resin is selected the polymeric amide that contains star structure, fluidity of molten is higher than conventional linear polymeric amide, more easily continuous fibre is flooded, employing is flooded continuous fibre with the impregnating equipment of staggered two extrusion dies, by special process, design, 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 completely and keeps porosity not higher than 0.2%.
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 moulding complexity.
Accompanying drawing explanation
Fig. 1 is the production technological process of continuous fibre reinforced polyamide composite material prepreg of the present invention.
In figure: creel 10, continuous glass fibre volume 11, continuous tow 12, spindle 13, tension-adjusting gear 20, row's silk mouthfuls 21, tensioning roller 22, static eraser 30, preheat baking oven 40, tension-adjusting gear 50, two extrusion die 60, die head 61, die head 62, three roller immersion systems 70, stack 71, stack 72, stack 73, cooling roller pressure device 80, cooling and shaping roller 81, cooling and shaping roller 82, traction wind2 90.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Based on continuous fibre reinforced polyamide composite material prepreg, by the component that comprises following weight parts, made:
50.8 parts of continuous glass fibres (PPG company, 4588 2400tex continuous glass fibres),
49.2 parts of star polyamide matrix;
Wherein, star polyamide matrix, to prepare according to the method for describing in the patent CN101421336A of French Rhodia management company, by 99mol%N salt (waiting mole hexanodioic acid and hexamethylene-diamine), 0.25mol%2,2,6,6-tetra--(β-propyloic)-pimelinketone and 0.75mol% phenylformic acid add autoclave.Under whipped state, mixture is heated to the temperature of 280 ℃ under 7.5 normal atmosphere, keeps 2 hours at this temperature, reduces subsequently pressure, then uses nitrogen purging autoclave one and a half hours, and keep temperature is 280 ℃ simultaneously.Subsequently system is placed in to 0.5 atmospheric pressure vacuum condition lower 1 hour.Molten polymer is extruded subsequently granulation and obtains star-like polyamide matrix.According to standard ISO 1133, the melt flow index of measuring under 275 ℃, 325 grams loads is 60g/10min.
(1) star polyamide matrix is passed through to 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 being arranged in parallel, carefully continuous glass fibre bundle 12 from drawing, is passed through by creel 10 to row's silk mouth 21 in 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 is through tensioning roller 22, and the preliminary dispersion that applies some tension assurance continuous glass fibre bundle 12 to continuous glass fibre bundle 12 forms continuous fibre band; Again continuous fibre band is eliminated to the static producing through static eraser 30, then continuous fibre band is preheating to 280 ℃ through the infrared baking oven 40 that preheats; Continuous fibre band after preheating imports die head 61 and the die head 62 in two extrusion dies 60 through tension-adjusting gear 50, star polyamide matrix melt carries out preimpregnation to continuous fibre band, adopt single screw extrusion machine, extrusion die 61 and die head 62 temperature are arranged on 280 ℃, guarantee that star polyamide resin has lower viscosity;
(3) by 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 is all arranged on 270 ℃, make star polyamide resin there is lower viscosity and good mobility, realize the complete wetting of molten resin to 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.It is that 0.5mm, ganoid continuous fibre strengthen star polyamide prepreg tape that continuous fibre band obtains thickness after cooling and shaping.By adjusting screw(rod) rotating speed or rate of feeding and prepreg tape winding speed, making star polyamide matrix in prepreg tape is 49.2 weight parts, and glass fibre is 50.8 weight parts.After prepreg tape cool to room temperature, enter traction wind2 90 coiling and moldings, packing, can obtain fiber dispersion evenly, flood continuous glass fibre completely and strengthen star polyamide prepreg tape, technological process is as shown in Figure 1.The performance test results of this material is in Table 1.
Comparative example
Except not adding 2,2,6,6-tetra--(β-propyloic)-pimelinketone and phenylformic acid in the preparation process of star polyamide matrix, according to the condition in embodiment 1 and step, implement.The performance test results of this material is in Table 1.
Embodiment 2
Based on continuous fibre reinforced polyamide composite material prepreg, by the component that comprises following weight parts, made:
20 parts of continuous carbon fibres (eastern beautiful fiber research institute, T700 24K continuous carbon fibre),
80 parts of star polyamide matrix;
Wherein, star-like polyamide matrix is to obtain by following steps, by 95mol%N salt (waiting mole hexanodioic acid and hexamethylene-diamine), and 1mol%2,2,6,6-tetra--(β-propyloic)-pimelinketone and 4mol% propionic acid add autoclave.Other preparation technology is identical with example 1, and according to standard ISO 1133, the melt flow index of measuring under 275 ℃, 325 grams loads is 48g/10min.
(1) star polyamide matrix is passed through to 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 being arranged in parallel, carefully continuous carbon fibre bundle 12 from drawing, is passed through by creel 10 to row's silk mouth 21 in 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 is through tensioning roller 22, and the preliminary dispersion of applying some tension assurance continuous carbon fibre bundle 12 to continuous carbon fibre bundle 12 forms continuous fibre band; Again continuous fibre band is eliminated to the static producing through static eraser 30, then continuous fibre band is preheating to 280 ℃ through the infrared baking oven 40 that preheats; Continuous fibre band after preheating imports die head 61 and the die head 62 in two extrusion dies 60 through tension-adjusting gear 50, star polyamide matrix melt carries out preimpregnation to continuous fibre band, adopt single screw extrusion machine, extrusion die 61 and die head 62 temperature are arranged on 280 ℃, guarantee that star polyamide resin has lower viscosity;
(3) by 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 is all arranged on 270 ℃, make star polyamide resin there is lower viscosity and good mobility, realize the complete wetting of molten resin to 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.It is 0.5mm that continuous fibre band obtains thickness after cooling and shaping, ganoid continuous fibre strengthens star polyamide prepreg tape, by adjusting screw(rod) rotating speed or rate of feeding and prepreg tape winding speed, making star polyamide matrix in prepreg tape is that 80 weight parts, carbon fiber are 20 weight parts.After prepreg tape cool to room temperature, enter traction wind2 90 coiling and moldings, packing, can obtain flooding continuous carbon fibre completely and strengthen star polyamide prepreg tape, technological process as shown in Figure 1.The performance test results of this material is in Table 1.
Embodiment 3
Based on continuous fibre reinforced polyamide composite material prepreg, by the component that comprises following weight parts, made:
70 parts of continuous glass fibres (PPG company, 4588 2400tex continuous glass fibres),
30 parts of star polyamide matrix,
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 by star polyamide matrix and additive, obtains star polyamide matrix melt, and steadily extrudes 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 being arranged in parallel, carefully continuous glass fibre bundle 12 from drawing, is passed through by creel 10 to row's silk mouth 21 in 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 is through tensioning roller 22, and the preliminary dispersion that applies some tension assurance continuous glass fibre bundle 12 to continuous glass fibre bundle 12 forms continuous fibre band; Again continuous fibre band is eliminated to the static producing through static eraser 30, then continuous fibre band is preheating to 280 ℃ through pre-electrically heated baking oven 40; Continuous fibre band after preheating imports die head 61 and the die head 62 in two extrusion dies 60 through tension-adjusting gear 50, star polyamide matrix melt carries out preimpregnation to continuous fibre band, adopt single screw extrusion machine, extrusion die 61 and die head 62 temperature are arranged on 280 ℃, guarantee that star polyamide resin has lower viscosity;
(3) by 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 is all arranged on 270 ℃, make star polyamide resin there is lower viscosity and good mobility, realize the complete wetting of molten resin to 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.It is 0.5mm that continuous fibre band obtains thickness after cooling and shaping, ganoid continuous fibre strengthens star polyamide prepreg tape, by regulating material proportion, the rolling speed of screw speed and continuous fibre is controlled the weight of star polyamide matrix, additive and fiber in prepreg tape.After prepreg tape cool to room temperature, enter traction wind2 90 coiling and moldings, packing, can obtain flooding continuous glass fibre completely and strengthen star polyamide prepreg tape.The performance test results of this material is in Table 1.
Embodiment 4
Based on continuous fibre reinforced polyamide composite material prepreg, by the component that comprises following weight parts, made:
20 parts, carbon fiber (eastern beautiful fiber research institute, T700 24K continuous carbon fibre),
50 parts of star polyamide matrix,
22 parts of TDE,
7 parts of weisspiessglanzs,
0.25 part of antioxidant 1010,
0.75 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 by star polyamide matrix and additive, obtains star polyamide matrix melt, and steadily extrudes 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 being arranged in parallel, carefully continuous carbon fibre bundle 12 from drawing, is passed through by creel 10 to row's silk mouth 21 in 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 is through tensioning roller 22, and the preliminary dispersion of applying some tension assurance continuous carbon fibre bundle 12 to continuous carbon fibre bundle 12 forms continuous fibre band; Again continuous fibre band is eliminated to the static producing through static eraser 30, then continuous fibre band is preheating to 280 ℃ through pre-infrared heating oven 40; Continuous fibre band after preheating imports die head 61 and the die head 62 in two extrusion dies 60 through tension-adjusting gear 50, star polyamide matrix melt carries out preimpregnation to continuous fibre band, adopt twin screw extruder, extrusion die 61 and die head 62 temperature are arranged on 280 ℃, guarantee that star polyamide resin has lower viscosity;
(3) by 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 is all arranged on 270 ℃, make star polyamide resin there is lower viscosity and good mobility, realize the complete wetting of molten resin to 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.It is 0.5mm that continuous fibre band obtains thickness after cooling and shaping, ganoid continuous fibre strengthens star polyamide prepreg tape, by regulating material proportion, the rolling speed of screw speed and continuous fibre is controlled the weight of star polyamide matrix, additive and fiber in prepreg tape.After prepreg tape cool to room temperature, enter traction wind2 90 coiling and moldings, packing, can obtain flooding continuous carbon fibre completely and strengthen star polyamide prepreg tape.The performance test results of this material is in Table 1.
Embodiment 5
Continuous fibre reinforced polyamide composite material prepreg is made by the component that comprises following weight parts:
40 parts of star polyamide matrix,
Superhigh molecular weight polyethylene fibers is 40 parts continuously,
15 parts of ammonium polyphosphate flame retardants,
4.5 parts of fire retardant tetramethylolmethanes
Weather resisting agent 2,0.5 part of 4-dihydroxyl-benzophenone,
Wherein, star polyamide matrix, is the composition of 30 parts of star polyamide and 10 parts of linear polyamidoamine PA66.Wherein star-like polymeric amide is by 99.8mol%N salt (waiting mole hexanodioic acid and hexamethylene-diamine), 0.05mol%1,3,5,-benzenetricarboxylic acid and 0.15mol% n-hexadecyl amine and 40 parts of defoamers add autoclave, follow-up other steps are identical with embodiment 1, and according to standard ISO 1133, the melt flow index of measuring under 275 ℃, 325 grams loads is 50g/10min.
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 to 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 to 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 the complete wetting of molten resin to fiber.The continuous fibre band of complete wetting enters cooling roller pressure device and carries out cooling and shaping, can obtain fiber dispersion evenly, flood continuous fibre completely and strengthen star polyamide prepreg tape.By regulating material proportion, the rolling speed of screw speed and continuous fibre is controlled the weight of star polyamide matrix, additive and fiber in prepreg tape.
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 39 parts continuously,
0.5 part of oxidation inhibitor DLTDP,
0.5 part of weather resisting agent 2-(2 '-hydroxyl-5 '-) benzotriazole,
Wherein, star polyamide matrix, is the composition of 45 parts of star polyamide and 15 parts of linear polyamidoamine PA6.Wherein star-like polymeric amide is by 87mol%N salt (waiting mole hexanodioic acid and hexamethylene-diamine), 10mol% hexanolactam, 0.6mol%2,4,6-tri--(amino caproyl)-1,3,5 ,-triazine and 2.4mol% dodecyl amine add autoclave.Subsequent step is with example 1; According to standard ISO 1133, the melt flow index of measuring under 275 ℃, 325 grams loads is 45g/10min.
(1) star polyamide matrix and additive are passed through to 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 to 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 the complete wetting of molten resin to fiber.The continuous fibre band of complete wetting enters cooling roller pressure device and carries out cooling and shaping, can obtain fiber dispersion evenly, flood continuous fibre completely and strengthen star polyamide prepreg tape.By regulating material proportion, the rolling speed control speed of screw speed and continuous fibre, makes the weight of star polyamide matrix, additive and fiber in prepreg tape.
Embodiment 7
Continuous fibre reinforced polyamide composite material prepreg is made by the component that comprises following weight parts:
57 parts of star polyamide matrix,
Aromatic polyamide fibre is 28 parts continuously,
9 parts of fire retardant eight bromo ethers,
4 parts of fire retardant zinc borates,
2 parts of static inhibitor nano zine oxides;
Wherein, star polyamide matrix, is the composition of 28.5 parts of star polyamide and 28.5 parts of linear polyamidoamine PA66.Wherein star-like polymeric amide is by 91mol%N salt (waiting mole hexanodioic acid and hexamethylene-diamine), 0.8mol%, and 5mol% six hexosamines, 4-aminoethyl-1,8-octamethylenediamine and 3.2mol% phenylformic acid add autoclave.Subsequent step is with example 1, and 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 to 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 to 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 the complete wetting of molten resin to fiber.The continuous fibre band of complete wetting enters cooling roller pressure device and carries out cooling and shaping, can obtain fiber dispersion evenly, flood continuous fibre completely and strengthen star polyamide prepreg tape.By regulating material proportion, the rolling speed of screw speed and continuous fibre is controlled the weight of star polyamide matrix, additive and fiber in prepreg tape.
Table 1
Wherein, tensile strength testing standard is that GB/T 1447-2005 flexural strength testing standard is GB/T1449-2005; Shock strength testing standard is GB/T 1451-2005; Fibre content utilizes densimetry to test, and its testing method is as follows: utilize air-discharging method to test respectively fibre density for 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.
By table 1, can illustrate and adopt 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 is obvious, be conducive to the performance raising of polyamide compoiste material and the further reduction of production cost.
Disclosed is above only several specific embodiments of the application, but the application is not limited thereto, and the changes that any person skilled in the art can think of, all should drop in the application's protection domain.
Claims (10)
1. a continuous fibre reinforced polyamide composite material prepreg, is characterized in that, the raw material of this prepreg tape is made by the component that comprises following weight part:
Star polyamide matrix 30-80 part,
Continuous fibre 20-70 part,
Additive 0-30 part.
2. a kind of continuous fibre reinforced polyamide composite material prepreg according to claim 1, is characterized in that, described star polyamide matrix is star polyamide and linear polyamidoamine (50-100: combination 50-0) in mass ratio; The polymer raw of described star polyamide at least comprises following three kinds of materials:
(I) dicarboxylic acid monomer and diamine monomer, or their salt 95-99.8mol%;
(II) comprise the polyfunctional monomer 0.05-1mol% of at least 3 X1 of functional group;
(III) the simple function group compound 0.15-4mol% that comprises the X2 of functional group;
Wherein, the X2 of the X1He of functional group functional group is carboxylic acid type functional group or the An Xing functional group that can react with dicarboxylic acid monomer and diamine monomer; ，X2Wei An type functional group during DangX1Wei carboxylic acid type functional group; The DangX1Wei An type Shi，X2Wei of functional group carboxylic acid type functional group;
The polymer raw of described star polyamide also comprises amino acid and lactan.
3. a kind of continuous fibre reinforced polyamide composite material prepreg according to claim 2, is characterized in that, described dicarboxylic acid monomer comprises aliphatics or the aromatic dicarboxylic acid with 4 to 12 carbon atoms; Described diamine monomer comprises aliphatics or the aromatic diamine with 4 to 12 carbon atoms; Described dicarboxylic acid monomer and the amount of substance of diamine monomer equate;
Described polyfunctional monomer has following general formula:
R-[-A-X1]
n (a)
Wherein, R represents to comprise at least two carbon atoms and can comprise the alkyl of one or more heteroatomic straight chains, ring-type, aromatics or aliphatic series, heteroatoms comprises O, S, N or P, the aliphatic alkyl that A represents covalent linkage or comprises 1-6 carbon atom, X1 represents primary amine or carboxylic acid functional, and n is the integer of 3-8;
Described simple function group compound is selected from n-hexadecyl amine, Octadecane base amine and dodecyl amine, acetic acid, lauric acid, benzylamine, phenylformic acid, propionic acid and 4-amino-2,2,6,6, one or more of-tetramethyl piperidine.
4. according to a kind of continuous fibre reinforced polyamide composite material prepreg described in claim 2 or 3, it is characterized in that, described dicarboxylic acid monomer is selected from one or more in hexanodioic acid, terephthalic acid, iso-phthalic acid, oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, pimelic acid, sebacic acid or dodecanedioic acid;
Described diamine monomer is selected from hexamethylene-diamine, m-xylene diamine, butanediamine, isophorone diamine, 3,3, one or more in 5-trimethylhexamethylenediamine or methyl pentamethylene diamine;
The preferred hexamethylene ketone group of R quaternary groups, 1 in described polyfunctional monomer general formula (a), 1,1,-tri-bases-propane, 1, one or more in the octavalence group of the quaternary groups of 2,3-, tri-bases-propane, phenyl trivalent group, benzyl, anthryl, xenyl, triphenyl, pyridine, indoles, furans, thiophene, purine, phenanthrene, diamino polymethylene, hexamethylene ketone group, hexamethylene ketone group and polyvalent alcohol and the resulting compound group of acrylonitrile reactor; One or more in the preferred methylene radical of A, ethylidene, propylidene, butylidene, polyoxyethylene thiazolinyl.
5. a kind of continuous fibre reinforced polyamide composite material prepreg according to claim 4, it is characterized in that described polyfunctional monomer preferably 2, 2, 6, 6-tetra--(β-propyloic)-pimelinketone, 1, 3, 5,-benzenetricarboxylic acid, 2, 4, 6-tri--(amino caproyl)-1, 3, 5,-triazine, 3, 5, 3 ', 5 ' xenyl tetracarboxylic acid, 3, 5, 3 ', 5 ' benzophenone tetracarboxylic acid, Pyromellitic Acid, 4-aminoethyl-1, 8-octamethylenediamine, nitrilo triethylamine, diethyl triamine, trientine, tetraethylenepentamine, trimeric cyanamide, 4-amino-ethyl-1, one or more of represented compound in 8 octamethylenediamines or following general formula (b),
R
1[A1-NH
2]
3 (b)
Wherein: R
1represent propane-1,1,1-, tri-bases or propane-1,2,3-, tri-basis set groups, A1 represents polyoxy ethylidene group.
6. a kind of continuous fibre reinforced polyamide composite material prepreg according to claim 2, is characterized in that, the massfraction of described star polyamide matrix neutral line polymeric amide is 0-50%.
7. according to a kind of continuous fibre reinforced polyamide composite material prepreg described in claim 2 or 6, it is characterized in that, described linear polyamidoamine is selected from one or more in PA6, PA66, PA12, PA46, PA610, PA612.
8. a kind of continuous fibre reinforced polyamide composite material prepreg according to claim 1, is characterized in that, described continuous fibre is selected from one or more in inorganic fibre, organic fibre, steel fiber; Described additive is selected from one or more in oxidation inhibitor, photostabilizer, fire retardant, static inhibitor.
9. a kind of continuous fibre reinforced polyamide composite material prepreg according to claim 8, 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;
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-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, tetramethylolmethane, eight bromo ether, triphenylphosphate, hexabromocyclododecane, zinc borate, encapsulated red phosphorus, TDE, two (2, the 3-dibromopropyl) ether of tetrabromo-bisphenol, hexabromocyclododecane; Described static inhibitor is selected from one or both in carbon black, nano zine oxide.
10. the preparation method of a continuous fibre reinforced polyamide composite material prepreg as claimed in claim 1, it is characterized in that, the method comprises the following steps: after star polyamide matrix, additive are mixed, pass through forcing machine plastifying fusion, obtain star polyamide matrix melt, and steadily extrude by two extrusion dies, stand-by; Continuous fibre is imported to 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 makes star polyamide matrix melt to continuous fibre complete wetting, and gained continuous fibre band cooling and shaping, obtains continuous fibre reinforced polyamide composite material prepreg; By regulating the rolling speed of material material proportioning, screw speed and continuous fibre, the weight fraction that makes star polyamide matrix in prepreg tape is that the weight fraction that the weight fraction of 30-80 part, additive is 0-30 part, fiber is 20-70 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210290728.3A CN103589138A (en) | 2012-08-15 | 2012-08-15 | Continuous-fiber-reinforced polyamide composite material prepreg tape and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210290728.3A CN103589138A (en) | 2012-08-15 | 2012-08-15 | Continuous-fiber-reinforced polyamide composite material prepreg tape and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103589138A true CN103589138A (en) | 2014-02-19 |
Family
ID=50079472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210290728.3A Pending CN103589138A (en) | 2012-08-15 | 2012-08-15 | Continuous-fiber-reinforced polyamide composite material prepreg tape and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103589138A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107735434A (en) * | 2015-06-24 | 2018-02-23 | 阿科玛法国公司 | The method that fibre-reinforced semicrystalline polyamides groundmass composite material is manufactured by the die sinking of prepolymer reactive precursor composition |
| CN107985160A (en) * | 2016-10-27 | 2018-05-04 | 上海杰事杰新材料(集团)股份有限公司 | Lorry compartment floor and preparation method thereof |
| CN109438979A (en) * | 2018-11-22 | 2019-03-08 | 浙江华谊胜德材料科技有限公司 | A kind of high smooth engineering plastic alloy and preparation method thereof |
| CN109517380A (en) * | 2018-11-29 | 2019-03-26 | 上海金发科技发展有限公司 | A kind of halogen-free flame-retardant reinforced nylon composite material that wet and heat ageing resistant is precipitated |
| CN110643172A (en) * | 2018-06-26 | 2020-01-03 | 泰兴汤臣压克力有限公司 | Preparation method of nylon alloy material in acrylic line plate |
| CN113400691A (en) * | 2021-05-24 | 2021-09-17 | 上海化工研究院有限公司 | High-performance ultrahigh molecular weight polyethylene strip and preparation method thereof |
| CN115011114A (en) * | 2022-07-02 | 2022-09-06 | 厦门市嘉能科技有限公司 | High-fluidity nylon and preparation method thereof |
| CN116462964A (en) * | 2023-05-09 | 2023-07-21 | 浙江新力新材料股份有限公司 | Flame-retardant reinforced high-temperature nylon material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1777633A (en) * | 2003-03-11 | 2006-05-24 | 罗狄亚工程塑料有限责任公司 | Polyamide piece reinforced with long fibres |
| WO2007036929A2 (en) * | 2005-09-29 | 2007-04-05 | Nilit Ltd. | Modified polyamides, uses thereof and process for their preparation |
| CN101421336A (en) * | 2006-03-31 | 2009-04-29 | 罗地亚管理公司 | High-fluidity polyamide |
| CN101474868A (en) * | 2008-10-15 | 2009-07-08 | 上海杰事杰新材料股份有限公司 | Equipment for preparing continuous fiber reinforced thermoplastic resin composite material presoaked belt and use thereof |
| CN102477155A (en) * | 2010-11-29 | 2012-05-30 | 上海杰事杰新材料(集团)股份有限公司 | Preparation method of multi-arm star polyamide polymer |
-
2012
- 2012-08-15 CN CN201210290728.3A patent/CN103589138A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1777633A (en) * | 2003-03-11 | 2006-05-24 | 罗狄亚工程塑料有限责任公司 | Polyamide piece reinforced with long fibres |
| WO2007036929A2 (en) * | 2005-09-29 | 2007-04-05 | Nilit Ltd. | Modified polyamides, uses thereof and process for their preparation |
| CN101421336A (en) * | 2006-03-31 | 2009-04-29 | 罗地亚管理公司 | High-fluidity polyamide |
| CN101474868A (en) * | 2008-10-15 | 2009-07-08 | 上海杰事杰新材料股份有限公司 | Equipment for preparing continuous fiber reinforced thermoplastic resin composite material presoaked belt and use thereof |
| CN102477155A (en) * | 2010-11-29 | 2012-05-30 | 上海杰事杰新材料(集团)股份有限公司 | Preparation method of multi-arm star polyamide polymer |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107735434A (en) * | 2015-06-24 | 2018-02-23 | 阿科玛法国公司 | The method that fibre-reinforced semicrystalline polyamides groundmass composite material is manufactured by the die sinking of prepolymer reactive precursor composition |
| CN107985160A (en) * | 2016-10-27 | 2018-05-04 | 上海杰事杰新材料(集团)股份有限公司 | Lorry compartment floor and preparation method thereof |
| CN110643172A (en) * | 2018-06-26 | 2020-01-03 | 泰兴汤臣压克力有限公司 | Preparation method of nylon alloy material in acrylic line plate |
| CN109438979A (en) * | 2018-11-22 | 2019-03-08 | 浙江华谊胜德材料科技有限公司 | A kind of high smooth engineering plastic alloy and preparation method thereof |
| CN109517380A (en) * | 2018-11-29 | 2019-03-26 | 上海金发科技发展有限公司 | A kind of halogen-free flame-retardant reinforced nylon composite material that wet and heat ageing resistant is precipitated |
| CN113400691A (en) * | 2021-05-24 | 2021-09-17 | 上海化工研究院有限公司 | High-performance ultrahigh molecular weight polyethylene strip and preparation method thereof |
| CN115011114A (en) * | 2022-07-02 | 2022-09-06 | 厦门市嘉能科技有限公司 | High-fluidity nylon and preparation method thereof |
| CN115011114B (en) * | 2022-07-02 | 2023-05-26 | 厦门市嘉能科技有限公司 | High-fluidity nylon and preparation method thereof |
| CN116462964A (en) * | 2023-05-09 | 2023-07-21 | 浙江新力新材料股份有限公司 | Flame-retardant reinforced high-temperature nylon material and preparation method and application thereof |
| CN116462964B (en) * | 2023-05-09 | 2024-03-22 | 浙江新力新材料股份有限公司 | Flame-retardant reinforced high-temperature nylon material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103589138A (en) | Continuous-fiber-reinforced polyamide composite material prepreg tape and preparation method thereof | |
| CN103131170A (en) | Continuous fiber reinforce polyamide composite material prepreg tape and preparation method thereof | |
| CN101707929B (en) | Composite polyamide article | |
| CN101474868B (en) | Equipment for preparing continuous fiber reinforced thermoplastic resin composite material presoaked belt and use thereof | |
| EP1741540B1 (en) | Use of a polyamide moulding composition with high melt rigidity for coextruding with a polymer melting at a high temperature | |
| CN102850816A (en) | Thermoplastic resin composite material and preparation method and application thereof | |
| CN103387709A (en) | Thermoplastic composite material, and preparation method and application thereof | |
| CN100381498C (en) | Method for preparing polycondensation reaction type reinforced thermoplastic resin in long fibres | |
| CN102555238A (en) | Manufacturing method of fiber cloth reinforced thermoplastic resin composite material | |
| CN103509354A (en) | Basalt fiber reinforced thermoplastic polyphenylene sulfide composite material and preparation method thereof | |
| CN110229415B (en) | Flame-retardant-grade continuous glass fiber reinforced polypropylene prepreg tape material and preparation method thereof | |
| WO2022252661A1 (en) | Continuous long fiber-reinforced thermoplastic composite board, and preparation method therefor and use thereof | |
| CN103554906A (en) | Nylon 66 impregnated ingredient and method of producing long glass fiber reinforced nylon 66 aggregate by utilizing ingredient | |
| CN107501924A (en) | A kind of graphene, continuous glass-fiber collaboration reinforced polyamide composite and preparation method thereof | |
| CN204604939U (en) | A kind of manufacturing equipment of continuous fiber reinforced thermoplastic composite material | |
| CN104672893A (en) | Polyamide continuous fiber composite material prepreg tape as well as preparation method and application thereof | |
| CN107760024A (en) | A kind of nylon based composites of 3D printing neck protector and preparation method thereof | |
| CN107501925A (en) | Fine collaboration reinforced polyamide composite of a kind of graphene, continuous carbon and preparation method thereof | |
| CN104669636A (en) | Preparation method of hybrid fiber reinforced polypropylene high-intensity composite material | |
| CN105949773A (en) | Organosilicon thermoplastic film and preparation method thereof | |
| US20240052115A1 (en) | Long-carbon-chain polyamide resin composition and continuous fiber reinforced long-carbon-chain polyamide composite material | |
| CN107969122A (en) | For the method by the thermoplastic polymer continuous producing composite material profile sections with high fluidity | |
| KR20220034161A (en) | Method of making impregnated fibrous material by reactive drawing | |
| CN109651804B (en) | Continuous glass fiber reinforced nylon composite board, preparation method thereof and application thereof in preparation of automobile brake pedal | |
| CN217553378U (en) | Bio-based polyamide composite board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140219 |
|
| RJ01 | Rejection of invention patent application after publication |