CN101245185B - Continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material and method for manufacturing same - Google Patents
Continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material and method for manufacturing same Download PDFInfo
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Abstract
The invention discloses a long fiber enhanced polyamide/acrylonitrile-butadiene-styrene composite material and a preparation method thereof, and the composite material is prepared by mixing 10 to 80 percent weight of the long fiber enhanced polyamide resin master batch and 20 to 90 percent weight of the polyamide/acrylonitrile-butadiene-styrene alloy diluted resin. The composite material has excellent mechanical property, good heat resistance and chemical resistant, low moisture (water) absorption rate, fine creep resistance and good size stability. The long fiber enhanced polyamide/acrylonitrile-butadiene-styrene composite material is suitable for injection molding and can be used for manufacturing various ornamentations inside and outside automobiles, such as automobile meter panel stents, wind discharging defroster grids, automobile door components and the making materials of motorcycle baffles.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of continuous fiber reinforcing polyamide/acrylonitrile-butadiene-styrene resin matrix material and preparation method thereof.
Background technology
Polyamide resin (PA) not only mechanical property is excellent; But also have excellent chemical reagent-resistant performance, good self-lubricating property and snappiness; Therefore be widely used in every field, like various trolley parts, power tool shell, ecommerce equipment component, sports goods or the like.Yet also there is weak point in polymeric amide, and promptly low temperature and dry state shock strength are low, and water-absorbent and moisture absorption (water) rate, creep resistance are poor, density and materials processed cost are all higher, and therefore, this has limited its further application space again.
Improve constantly for what conformability required, prepare alloy material with other fluoropolymer resin blend and add fiber and filler material property is improved is two kinds of the most frequently used methods.
Wherein a kind of domestic method is with polymeric amide and other various thermoplastic resins, acrylonitrile-butadiene-styrene copolymer (ABS) resin for example, and blend forms polymer alloy material.This blend alloy material combines the common advantage of polymeric amide and other blending resins usually; Their original some shortcomings have been overcome simultaneously again; Therefore, the intermingling material that adopts this method to obtain not only can overcome some defect problems of above-mentioned polymeric amide, and; The excellent specific property of polymeric amide self can not receive very big influence yet, will obtain bigger application space.
It is good that acrylonitrile-butadiene-styrene copolymer (ABS) resin itself has a dimensional stability; The characteristics that the notch shock performance is high; Therefore; If polymeric amide and ABS resin are processed intermingling material, then possibly obtain a kind of so high notch shock performance, good dimensional stability, the equal excellent material of other each item performances.Yet ABS resin and polymeric amide are inconsistent basically in theory, will obtain above-mentioned desirable material for this reason, must adopt the technology of increase-volume.
For example Chinese publication CN1702116 discloses a kind of polyamide/acrylonitrile-butadiene-styrene resin composite materials and preparation method thereof, and prepared polyamide alloy material has high notched Izod impact strength, good dimensional stability and resistance toheat.
Improve other a kind of method of polyamide material performance; Be composite modified through adopting fiber, whisker, mineral filler etc. that polymeric amide is strengthened; Process the reinforced polyamide matrix material, can increase substantially the intensity, rigidity, anti-creep of polyamide material, performance such as heat-resisting like this.
Adopting conventional art to prepare fibre-reinforced polyamide/vinyl cyanide-butadiene-vinyl benzene composite material is with polyamide resin, acrylonitrile-butadiene-styrene resin and compatilizer, adopts the twin screw extruder melt blending to extrude and obtain.Though this technology of preparing can realize lightweight, reduce rate of moisture absorption and cost; But because this technology of preparing itself can be sheared very shortly continuous rove fiber or chopped strand (staple length is generally about 0.2～0.6mm); Mechanical property to material improves inadequately, can not obtain the reinforced polyamide/vinyl cyanide-butadiene-vinyl benzene composite material of superior.
To be that a kind of fortifying fibre is unidirectional arrange and enhancing thermoplastic resin that its length is identical with resin granular material length fiber reinforced thermoplastic resin.It strengthens thermoplastic resin with conventional staple fibre compares, and has excellent more mechanical property, dynamic fatigue resistance ability, creep-resistant property etc.; Particularly the shock resistance of material is very excellent.
Summary of the invention
The purpose of this invention is to provide a kind of continuous fiber reinforcing polyamide/acrylonitrile-butadiene-styrene resin matrix material, strengthen the PA/ABS matrix material to overcome the mechanical property that prior art exists macrofiber not high, that a kind of low cost, various stable performances are provided.
Another object of the present invention provides the preparation method of above-mentioned matrix material, and this preparation method controls simply, cost is low.
The object of the invention can be achieved through following technical scheme.
A kind of continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material is formed by the polyamide/acrylonitrile-butadiene-styrene alloy letdown resin blending of the continuous fiber reinforcing polyamide masterbatch resin and 20%～90% (weight) of 10%～80% (weight).
Wherein, the continuous fiber reinforcing polyamide masterbatch resin is made up of the macrofiber of the polyamide resin and 30%～60% (weight) of 40%～70% (weight);
Polyamide/acrylonitrile-butadiene-styrene alloy letdown resin is made up of the expanding material of the acrylonitrile-butadiene-styrene resin and 5%～15% (weight) of the polyamide resin, 20%～55% (weight) of 30%～75% (weight); Expanding material is vinylbenzene-copolymer-maleic anhydride or vinylbenzene-N-phenylmaleimide multipolymer.
In whole continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material, the content of continuous fiber is 5%～35% (weight).
The purpose of this invention is to provide a kind of continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material with higher notch shock performance, good heat resistance ability, chemical resistance and dimensional stability.
Above-mentioned polyamide resin can be one or more in polyamide 6 (PA6), polyamide 66 (PA66), polymeric amide 11 (PA11), polymeric amide 12 (PA12), polyamide 6 10 (PA610), the polyamide 6 12 (PA612), preferred polyamide 6 and polyamide 66 resin.
The preparation method of above-mentioned continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material comprises the steps:
(1) adopt the pultrude process method to process the continuous fiber reinforcing polyamide master batch by proportioning macrofiber and polyamide resin, processing temperature is at 260 ℃-280 ℃; Macrofiber is arranged in parallel with each other along master batch particle length direction, and length is identical with the master batch particle;
(2) with polyamide resin, acrylonitrile-butadiene-styrene resin and vinylbenzene-copolymer-maleic anhydride or vinylbenzene-N-phenylmaleimide multipolymer; By the melt kneading method blend that proportioning adopts screw rod to extrude, obtain polyamide/acrylonitrile-butadiene-styrene alloy letdown resin;
(3) continuous fiber reinforcing polyamide master batch and polyamide/acrylonitrile-butadiene-styrene alloy letdown resin are processed continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material by the proportioning blending.
Above-mentioned steps (1) said " pultrude process (Pultrusion) " moulding process knows altogether for the technology of this area that at present described in DE2448217: a branch of macrofiber is introduced in the impregnation chamber through the continuous fibre access road; Advance along broken line after this bundle macrofiber is alternately walked around tensioning roller in groups, the macrofiber behind the dipping along the outlet the center through forming the fiber reinforced thermoplastic resin of predetermined shape; At last, fiber reinforced thermoplastic resin being become length through cooling, pelletizing is the fiber reinforced thermoplastic resin particle of 6～18mm.In this resin particle, macrofiber is arranged in parallel with each other, and its length is identical with particle length.
Continuous fiber reinforcing polyamide/the vinyl cyanide-butadiene-vinyl benzene composite material that makes through the present invention is applicable to injection moulding, and macrofiber is uniformly dispersed in goods, and product surface does not have " revealing fine " phenomenon fully; And this matrix material has splendid mechanical property, and like tensile strength, flexural strength, especially resistance to impact shock is very excellent; And good thermotolerance, chemical resistant properties, low moisture absorption (water) rate, good creep resistance are arranged, and good dimensional stability.This type continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material can be used for making various inner and outer decorative parts of automobile, like the automobile instrument disc carrier, and air exhausting grille, defroster grille and door assembly, and the manufacturing materials of motorcycle plate washer etc.
Embodiment
Raw materials used among the embodiment:
Polyamide 6 resin 1 (PA6-1): relative viscosity 2.4, number-average molecular weight is about 13,000, Ube chemical industrial company product;
Polyamide 6 resin 2 (PA6-2): relative viscosity 3.0, number-average molecular weight is about 24,000, German BASF AG product;
ABS-1: the divinyl percentage composition is about 20%, and Qi Mei company in Taiwan produces, Polylac747;
ABS-2: the divinyl percentage composition is about 40%, and Korea S LG chemical company produces;
ABS-3: the divinyl percentage composition is about 60%, and Lanzhou general petrochemicals factory produces;
Vinylbenzene-N-phenylmaleimide multipolymer (SMI): NEC chemistry, MS-NC;
Styrene-maleic anhydride copolymer (SMA): Nova chemical company product, maleic anhydride percentage composition are 28%;
Spun glass: Johns Manville Company products, PR4402400858;
Thomel: toray chemical company product.
The product performance testing method:
Tensile property: press ASTM D638 method, draw speed 50 mm/min.
Bending property: press ASTM D790 method, trial speed 2 mm/min.
Izod notched Izod impact strength: press ASTM D256 method, the sample of 3.2 mm thick.
Heat-drawn wire: press ASTM D648 method, 120 ℃/hour of temperature rise rates, 1.82MPa is test down.
Water-intake rate: press the ISO62 method,, measure under the 50%RH equilibrium conditions at 23 ℃.
Embodiment 1
With the polyamide resin PA6-1 of 50kg and the continuous glass fibre of 50kg, under 270 ℃ dipping processing temperature, adopt pultrusion method to process the continuous fiber reinforcing polyamide master batch; The weight percentage of spun glass is 50%, and is arranged in parallel with each other along master batch particle length direction, and length is identical with the master batch particle.
Simultaneously; Vinylbenzene-N-phenylmaleimide multipolymer SMI with 75kg polyamide resin PA6-2,20kg acrylonitrile-butadiene-styrene resin ABS-1 and 5kg; The melt kneading method blend of adopting screw rod to extrude obtains polyamide/acrylonitrile-butadiene-styrene alloy PA/ABS letdown resin;
Then; Polyamide/acrylonitrile-butadiene-styrene alloy letdown resin blending with continuous fiber reinforcing polyamide master batch and the 90kg of 10kg; Said product is injection molded into standard batten with plastic-injection moulding machine in 85 ℃ of dryings after 4 hours in convection oven, 270 ℃ of injection temperatures.The batten of injection formed is put into the glass moisture eliminator immediately and after room temperature is placed at least 24 hours, is carried out performance test.Test result is seen table 1.
In continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material of finally processing, the weight percentage of spun glass is 5%.
Embodiment 2
With embodiment 1, adopting pultrusion method to process the spun glass weight percentage is 50% continuous fiber reinforcing polyamide master batch.
Simultaneously; Vinylbenzene-N-phenylmaleimide multipolymer SMI with 60kg polyamide resin PA6-2,30kg acrylonitrile-butadiene-styrene resin ABS-2 and 10kg; The melt kneading method blend of adopting screw rod to extrude obtains polyamide/acrylonitrile-butadiene-styrene alloy letdown resin;
Then, with the polyamide/acrylonitrile-butadiene-styrene alloy letdown resin blending of continuous fiber reinforcing polyamide master batch and the 70kg of 30kg, and be injection molded into the test of standard mechanics test bars, test result is seen table 1.
In continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material of finally processing, the weight percentage of spun glass is 15%.
Embodiment 3
With embodiment 1, adopting pultrusion method to process the spun glass weight percentage is 50% continuous fiber reinforcing polyamide master batch.
Simultaneously; Vinylbenzene-N-phenylmaleimide multipolymer SMI with 40kg polyamide resin PA6-2,45kg acrylonitrile-butadiene-styrene resin ABS-3 and 15kg; The melt kneading method blend of adopting screw rod to extrude obtains polyamide/acrylonitrile-butadiene-styrene alloy letdown resin;
Then, with the polyamide/acrylonitrile-butadiene-styrene alloy letdown resin blending of continuous fiber reinforcing polyamide master batch and the 40kg of 60kg, and be injection molded into the test of standard mechanics test bars, test result is seen table 1.
In continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material of finally processing, the weight percentage of spun glass is 30%.
Embodiment 4
With the polyamide resin PA6-2 of 60kg and the continuous glass fibre of 40kg, under 270 ℃ dipping processing temperature, adopt pultrusion method to process the continuous fiber reinforcing polyamide master batch; The weight percentage of spun glass is 40%, and is arranged in parallel with each other along master batch particle length direction, and length is identical with the master batch particle.
Simultaneously; Vinylbenzene-N-phenylmaleimide multipolymer SMI with 30kg polyamide resin PA6-2,55kg acrylonitrile-butadiene-styrene resin ABS-2 and 15kg; The melt kneading method blend of adopting screw rod to extrude obtains polyamide/acrylonitrile-butadiene-styrene alloy letdown resin;
Then, with the polyamide/acrylonitrile-butadiene-styrene alloy letdown resin blending of continuous fiber reinforcing polyamide master batch and the 20kg of 80kg, and be injection molded into the test of standard mechanics test bars, test result is seen table 1.
In continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material of finally processing, the weight percentage of spun glass is 32%.
Comparative example 1
With embodiment 1, adopting pultrusion method to process the spun glass weight percentage is 50% continuous fiber reinforcing polyamide master batch.
Then, with the polymeric amide letdown resin PA6-2 blending of continuous fiber reinforcing polyamide master batch and the 70kg of 30kg, and be injection molded into the test of standard mechanics test bars, test result is seen table 1.
In the continuous fiber reinforcing polyamide material of finally processing, the weight percentage of spun glass is 15%.
Table 1 macrofiber strengthens the composition and the performance of PA/ABS matrix material
Can find out from the test result of last table comparative example and embodiment 2; Compare with the continuous fiber reinforcing polyamide material; Continuous fiber reinforcing polyamide/the vinyl cyanide-butadiene-vinyl benzene composite material that makes through the present invention is keeping excellent mechanical property; In the time of like tensile strength, flexural strength, resistance to impact shock and good thermotolerance, chemical-resistant, reduce the water-intake rate of material, increased performance and size stability.
Embodiment 5
With the polyamide resin PA6-1 of 70kg and the continuous glass fibre of 30kg, under 270 ℃ dipping processing temperature, adopt pultrusion method to process the continuous fiber reinforcing polyamide master batch; The weight percentage of spun glass is 30%, and is arranged in parallel with each other along master batch particle length direction, and length is identical with the master batch particle.
Simultaneously; Vinylbenzene-copolymer-maleic anhydride SMA with 40kg polyamide resin PA6-2,50kg acrylonitrile-butadiene-styrene resin ABS-2 and 10kg; The melt kneading method blend of adopting screw rod to extrude obtains polyamide/acrylonitrile-butadiene-styrene (PA/ABS) alloy letdown resin;
Then, with the polyamide/acrylonitrile-butadiene-styrene alloy letdown resin blending of continuous fiber reinforcing polyamide master batch and the 30kg of 70kg, and be injection molded into the test of standard mechanics test bars, test result is seen table 2.
In continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material of finally processing, the weight percentage of spun glass is 21%.
Embodiment 6
With the polyamide resin PA6-1 of 60kg and the continuous glass fibre of 40kg, under 270 ℃ dipping processing temperature, adopt pultrusion method to process the continuous fiber reinforcing polyamide master batch; The weight percentage of spun glass is 40%, and is arranged in parallel with each other along master batch particle length direction, and length is identical with the master batch particle.
Simultaneously; Vinylbenzene-copolymer-maleic anhydride SMA with 40kg polyamide resin PA6-2,50kg acrylonitrile-butadiene-styrene resin ABS-2 and 10kg; The melt kneading method blend of adopting screw rod to extrude obtains polyamide/acrylonitrile-butadiene-styrene alloy letdown resin;
Then, with the polyamide/acrylonitrile-butadiene-styrene alloy letdown resin blending of continuous fiber reinforcing polyamide master batch and the 50kg of 50kg, and be injection molded into the test of standard mechanics test bars, test result is seen table 2.
In continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material of finally processing, the weight percentage of spun glass is 20%.
Embodiment 7
With the polyamide resin PA6-1 of 40kg and the continuous glass fibre of 60kg, under 270 ℃ dipping processing temperature, adopt pultrusion method to process the continuous fiber reinforcing polyamide master batch; The weight percentage of spun glass is 60%, and is arranged in parallel with each other along master batch particle length direction, and length is identical with the master batch particle.
Simultaneously; Vinylbenzene-N-phenylmaleimide multipolymer SMI with 40kg polyamide resin PA6-1,50kg acrylonitrile-butadiene-styrene resin ABS-2 and 10kg; The melt kneading method blend of adopting screw rod to extrude obtains polyamide/acrylonitrile-butadiene-styrene alloy letdown resin;
Then, with the polyamide/acrylonitrile-butadiene-styrene alloy letdown resin blending of continuous fiber reinforcing polyamide master batch and the 67kg of 33kg, and be injection molded into the test of standard mechanics test bars, test result is seen table 2.
In continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material of finally processing, the weight percentage of spun glass is 19.8%.
Embodiment 8
With the polyamide resin PA6-1 of 50kg and the continuous carbon fibre of 50kg, under 270 ℃ dipping processing temperature, adopt pultrusion method to process the continuous fiber reinforcing polyamide master batch; The weight percentage of thomel is 50%, and is arranged in parallel with each other along master batch particle length direction, and length is identical with the master batch particle.
Simultaneously; Vinylbenzene-N-phenylmaleimide multipolymer SMI with 40kg polyamide resin PA6-1,50kg acrylonitrile-butadiene-styrene resin ABS-2 and 10kg; The melt kneading method blend of adopting screw rod to extrude obtains polyamide/acrylonitrile-butadiene-styrene alloy letdown resin;
Then, with the polyamide/acrylonitrile-butadiene-styrene alloy letdown resin blending of continuous fiber reinforcing polyamide master batch and the 60kg of 40kg, and be injection molded into the test of standard mechanics test bars, test result is seen table 2.
In continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material of finally processing, the weight percentage of thomel is 20%.
Comparative example 2
Behind vinylbenzene-copolymer-maleic anhydride SMA proportional mixing with 50kg polyamide resin PA6-2,25kg acrylonitrile-butadiene-styrene resin ABS-2 and 5kg; Resin is added twin screw extruder (screw diameter 35mm continuously equably from the forcing machine casing drum; Length-to-diameter ratio L/D=36) in the main barrel, then the 20kg spun glass is introduced main barrel from stage casing, the downstream charging opening of main barrel.Each section of main barrel temperature (from charging opening to head) is respectively 230 ℃, 250 ℃, 260 ℃, 260 ℃, 250 ℃, and screw speed is 300 rev/mins.The extruded stock bar obtains staple fibre reinforced polyamide/vinyl cyanide-butadiene-vinyl benzene composite material through tank cooling back pelletizing.Said product is injection molded into standard batten with plastic-injection moulding machine in 85 ℃ of dryings after 5 hours in convection oven, 270 ℃ of injection temperatures.The batten of injection formed is put into the glass moisture eliminator immediately and after room temperature is placed at least 24 hours, is carried out performance test.Test result is seen table 2.
Proportion of composing by above-mentioned comparative example and embodiment has prepared macrofiber enhancing PA/ABS resin combination, and performance test is as shown in table 2.
Table 2 macrofiber strengthens the composition and the performance of PA/ABS matrix material
Can find out from the test result of the foregoing description and comparative example; Adopt the fibre-reinforced polyamide/vinyl cyanide-butadiene-vinyl benzene composite material of traditional double screw rod extruding technology preparation; Though can realize reducing rate of moisture absorption and the purpose that partly improves the mechanical property of material; But because this technology of preparing can be sheared continuous fibre very short, thereby can not obtain the reinforced polyamide/vinyl cyanide-butadiene-vinyl benzene composite material of superior.
Continuous fiber reinforcing polyamide/the vinyl cyanide-butadiene-vinyl benzene composite material that makes through the present invention has splendid mechanical property, and like tensile strength, flexural strength, especially resistance to impact shock is very excellent; And good thermotolerance, chemical resistant properties, low moisture absorption (water) rate, good creep resistance are arranged, and good dimensional stability.This continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material can be used for making various inner and outer decorative parts of automobile, like the automobile instrument disc carrier, and air exhausting grille, defroster grille and door assembly, and the manufacturing materials of motorcycle plate washer etc.
Claims (2)
1. a continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material is characterized in that, is made up of following raw materials by weight percent:
Continuous fiber reinforcing polyamide masterbatch resin 10%～80%;
Polyamide/acrylonitrile-butadiene-styrene alloy letdown resin 20%～90%;
Described continuous fiber reinforcing polyamide masterbatch resin is made up of following raw materials by weight percent:
Polyamide resin 40%～70%;
Macrofiber 30%～60%;
Said macrofiber is the inorganic fibre of one or more formations in spun glass or the thomel;
Said polyamide resin is a number-average molecular weight 10000～25000, and the relative viscosity index is at 2.0～3.0 polyamide 6;
The composition and the weight percent of described polyamide/acrylonitrile-butadiene-styrene alloy letdown resin are:
Polyamide resin 30%～75%;
Acrylonitrile-butadiene-styrene resin 20%～55%;
Expanding material 5%～15%;
The divinyl weight percentage is 20%～60% in the said acrylonitrile-butadiene-styrene resin;
Said expanding material is a kind of in styrene-maleic anhydride copolymer or the vinylbenzene-N-phenylmaleimide multipolymer;
In whole continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material, the content of continuous fiber is 5%～35%.
2. the preparation method of continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material according to claim 1 is characterized in that, comprises the steps:
(1) with macrofiber and polyamide resin, adopt pultrusion method to process the continuous fiber reinforcing polyamide masterbatch resin, macrofiber is arranged in parallel with each other along master batch particle length direction, and length is identical with the master batch particle;
(2) with polyamide resin, acrylonitrile-butadiene-styrene resin and expanding material, the melt kneading method blend of adopting screw rod to extrude obtains polyamide/acrylonitrile-butadiene-styrene alloy letdown resin;
(3) continuous fiber reinforcing polyamide master batch and the blending of polyamide/acrylonitrile-butadiene-styrene alloy letdown resin are processed continuous fiber reinforcing polyamide/vinyl cyanide-butadiene-vinyl benzene composite material;
Said macrofiber is the inorganic fibre of one or more formations in spun glass or the thomel;
Said expanding material is a kind of in styrene-maleic anhydride copolymer or the vinylbenzene-N-phenylmaleimide multipolymer;
Said polyamide resin is selected from a kind of or more than one mixtures in polyamide 6, polyamide 66, polymeric amide 11, polymeric amide 12, polyamide 6 10, the polyamide 6 12.
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| WO2015132628A1 (en) * | 2014-03-03 | 2015-09-11 | Trinseo Europe Gmbh | Styrenic composition containing long fibers |
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| CN102051045B (en) * | 2009-10-30 | 2013-03-27 | 上海普利特复合材料股份有限公司 | High-rigidity glass fiber reinforced PA6/ABS composite material |
| CN103173007A (en) * | 2011-12-21 | 2013-06-26 | 上海杰事杰新材料(集团)股份有限公司 | High-performance long-fiber-reinforced nylon composite material and preparation method thereof |
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| CN107043534A (en) * | 2017-04-07 | 2017-08-15 | 北京隆轩橡塑有限公司 | A kind of polyamide 66 composite material of high-strength toughness reinforcing and preparation method thereof |
| CN107739505A (en) * | 2017-11-10 | 2018-02-27 | 南京立汉化学有限公司 | A kind of thermally resistant fiber glass reinforced nylon 6 12 and preparation method thereof |
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| CN109722018A (en) * | 2018-12-21 | 2019-05-07 | 金旸（厦门）新材料科技有限公司 | A kind of high rigidity low water absorbable PA/ABS alloy material and preparation method thereof |
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