CN103571183A - Continuous glass fiber reinforced nylon 6 prepreg tape and preparation method thereof - Google Patents

Continuous glass fiber reinforced nylon 6 prepreg tape and preparation method thereof Download PDF

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Publication number
CN103571183A
CN103571183A CN201210269495.9A CN201210269495A CN103571183A CN 103571183 A CN103571183 A CN 103571183A CN 201210269495 A CN201210269495 A CN 201210269495A CN 103571183 A CN103571183 A CN 103571183A
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China
Prior art keywords
continuous glass
glass fibre
prepreg tape
nylon
reinforced nylon
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CN201210269495.9A
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Chinese (zh)
Inventor
李东英
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LIAONING LIAOJIE TECHNOLOGY Co Ltd
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LIAONING LIAOJIE TECHNOLOGY Co Ltd
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Priority to CN201210269495.9A priority Critical patent/CN103571183A/en
Publication of CN103571183A publication Critical patent/CN103571183A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28Shaping operations therefor
    • B29C70/40Shaping or impregnating by compression not applied
    • B29C70/50Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter

Abstract

The invention belongs to the field of high molecular materials and forming thereof, and in particular relates to a continuous glass fiber reinforced nylon 6 prepreg tape and a preparation method thereof. The continuous glass fiber reinforced nylon 6 prepreg tape consists of the following components in parts by weight: 100 parts of nylon 6, 65-150 parts of continuous glass fiber, 2-10 parts of a compatilizer and 0.2-1 part of antioxidant. The continuous glass fiber reinforced nylon 6 prepreg tape, compared with the prior art, is free from a solvent in a production process, thus relieving pollution on environment and harm on health of production workers, and further reducing the corrosion of equipment.

Description

A kind of continuous glass fibre reinforced nylon 6 prepreg tape and preparation method thereof
Technical field
The invention belongs to macromolecular material and forming process field thereof, particularly a kind of continuous glass fibre reinforced nylon 6 prepreg tape and preparation method thereof.
Background technology
Nylon 6 is polyamide resins, one of maximum engineering plastics of application at present, in its structure, contain a large amount of polarity amide groups, can form well-set hydrogen bond, therefore, nylon 6 has higher fusing point, good physical and mechanical property, wear resistance and self lubricity, and these Comprehensive Characteristics are Other Engineering plastics, as not available in PP, PE.Meanwhile, the polarity of amide group, very easily absorbs water nylon 6, causes its rigidity to decline to a great extent, and poor dimensional stability, thereby has limited the application of nylon 6.Therefore, researcher has started the research composite modified to nylon 6 both at home and abroad.And at present, the most generally and the most effectively improve the method for nylon 6 material comprehensive physical mechanical property and use glass fiber reinforced nylon 6.
And in glass fiber-reinforced nylon 6 composite material, glass fibre is divided into staple fibre, macrofiber and three kinds of states of continuous fibre conventionally.During short glass fiber Reinforced Nylon matrix material, need fiber is mixing with resin in forcing machine, due to the shearing action between screw rod and machine barrel, fiber can sustain damage, and length falls sharply, and can not obviously improve the mechanical property of strongthener.Long fiber reinforced Nylon 6 matrix materials, though than short glass fiber reinforced nylon 6 composite materials property, make moderate progress, its intensity still can not meet the requirement that mechanical property is higher.Continuous glass-fiber reinforced nylon 6 matrix material arises at the historic moment, and the principal element that affects continuous glass-fiber reinforced nylon 6 material physical property has two kinds: 1, the wetting property of nylon 6 and glass fibre; 2, the mobility of nylon resin melt.Poor because of the mobility of nylon resin, conventional prepreg tape production method has solution dipping method and molten resin method at present.Though solution dipping method can reach certain dipping effect, the use of solvent, not only to environment, and works the mischief safely to direct labor's health.
Summary of the invention
The object of the invention is to provide a kind of continuous glass fibre reinforced nylon 6 prepreg tape, to solve glass fiber reinforced nylon 6 prepreg tape of the prior art, generally adopt solution dipping method to produce, and the solvent using in production process is not only to environment, and the technical matters that direct labor's health is worked the mischief safely.
Another object of the present invention is to provide a kind of preparation method of continuous glass fibre reinforced nylon 6 prepreg tape, to solve glass fiber reinforced nylon 6 prepreg tape of the prior art, generally adopt solution dipping method to produce, and the solvent using in production process is not only to environment, and the technical matters that direct labor's health is worked the mischief safely.
The object of the invention is achieved through the following technical solutions:
A reinforced nylon 6 prepreg tape, by the component that comprises following weight part, made:
6 100 parts of nylon;
65 ~ 150 parts of continuous glass fibres;
2 ~ 10 parts of compatilizers;
0.2 ~ 1 part, oxidation inhibitor.
Preferably, described nylon 6 is high fusion index nylon, its melting index >50g/10min.
Preferably, described continuous glass fibre is continuous roving, and its fiber type is E glass or S glass, and its fibre single thread diameter is 1200Tex ~ 2400Tex.
Preferably, described continuous glass fibre is for infiltrating the continuous glass fibre of processing through coupling agent.
Preferably, described coupling agent is selected from one or more in 3-aminopropyl triethoxysilane, γ-ammonia oxygen propyl-triethoxysilicane or γ-(methacryloxy) propyl trimethoxy silicane.
Preferably, described compatilizer is selected from a kind of in calcium maleate grafting POE, calcium maleate grafting PE or calcium maleate grafting EPDM, and wherein, maleic anhydride grafting ratio is all greater than 0.8.
Preferably, described oxidation inhibitor is selected from one or more in oxidation inhibitor 1098, oxidation inhibitor 944, irgasfos 168, oxidation inhibitor 327, oxidation inhibitor 1790 or antioxidant 1010.
A preparation method for continuous glass fibre reinforced nylon 6 prepreg tape, comprises the following steps:
(1) take by weight 6,2 ~ 10 parts of compatilizers of 100 parts of nylon, 0.2 ~ 1 part of oxidation inhibitor joins in high mixer, fully mix;
(2) mixture step (1) being obtained joins in single screw extrusion machine, and melt blending is extruded and carried out film by die head;
(3) continuous glass fibre of 65 ~ 150 weight parts is drawn by creel unit, after tension-adjusting gear, exhibition silk device, primary heater unit, nylon 6 films of extruding with die head flood in recombiner unit, rolling after flattening unit, traction unit, obtains continuous glass fibre reinforced nylon 6 prepreg tape.
Preferably, in described step (2), single screw extrusion machine temperature is established 8 sections altogether, and first paragraph and second segment extrusion temperature are at 210 ~ 230 ℃, and other 6 sections of extrusion temperatures are at 230 ~ 290 ℃; It is 10 ~ 20Hz that extruder main unit frequency is controlled.
Preferably, the primary heater unit in described step (3) is infrared heating device, and Heating temperature is 160 ~ 230 ℃; The thickness of the continuous glass fibre reinforced nylon 6 prepreg tape making in described step (3) is 0.18 ~ 0.30mm, and width is 635 ± 5mm.
Compared with prior art, the present invention has the following advantages:
1, glass fiber reinforced nylon 6 prepreg tape of the present invention does not need to use solvent in process of production, thereby reduces the harm to the pollution of environment and direct labor's health, also can reduce the corrosion to equipment;
2, the mobility properties-correcting agent using is at present in the course of processing, can react with the oxidation inhibitor generation radical termination in system, consume in a large number and do not have the effect improving liquidity, also can cause constant product quality poor, also produce in process of production irritating smell simultaneously; And the present invention uses high fusion index nylon, melting index is high can guarantee the good mobility of mixed system, increases the dipping effect of nylon and glass fibre, without adding mobility properties-correcting agent;
3, the lubricant using is at present volatile under higher processing temperature, thereby causes the foaming phenomenon of product external surfaces, directly affects product surface quality; And the present invention is when the mobility of mixed system improves, lubricant effect is also improved, without making with lubricator, do not need to add the mobility properties-correcting agent of peroxide yet, can effectively prevent that it from reacting with oxidation inhibitor generation radical termination in system, thereby improve product surface smooth finish, and be conducive to reduce production costs;
4, glass fiber reinforced nylon 6 prepreg tape of the present invention adopts the nylon of commercialization high fusion index to make raw material, can avoid adding unsaturated carboxylic acid or its acid anhydrides etc., thereby simplifies technique, reduces costs;
5, directly to adding in mixed system coupling agent easily to damage existing system balance, and can there is faint reaction with other compositions in system in coupling agent, affects product stability; And the continuous glass fibre that the present invention adopts coupling agent treatment to cross infiltrates processing to the continuous glass fibre on creel with coupling agent in advance, make coupling agent and glass fibre there is good bonding force.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, and in embodiment, each component, except specified otherwise, is weight part.
Embodiment 1 ~ 5
Continuous glass fibre reinforced nylon 6 prepreg tape in embodiment 1 ~ 5, by the component in table 1, made respectively:
Table 1
Embodiment Nylon 6 Continuous glass fibre Compatilizer Oxidation inhibitor
Embodiment 1 100 65 3 0.6
Embodiment 2 100 80 5 0.9
Embodiment 3 100 100 8 0.9
Embodiment 4 100 120 2 0.2
Embodiment 5 100 150 10 1.0
Wherein, in embodiment 1, nylon 6 melting index are 50g/10min; Compatilizer is calcium maleate grafting POE, and maleic anhydride grafting ratio is 0.9; Continuous glass fibre is that 3-aminopropyl triethoxysilane coupling agent infiltrates the continuous roving of processing, and fiber type is s glass, and fibre single thread diameter is 1200Tex, and oxidation inhibitor is 0.2 part of antioxidant 1010 and 0.4 part of irgasfos 168; Continuous glass fibre reinforced nylon 6 prepreg tape thickness is 0.25 ± 0.02mm, and width is 635 ± 5mm.
In embodiment 2, nylon 6 melting index are 60g/10min; Compatilizer is calcium maleate grafting PE, and maleic anhydride grafting ratio is 1; Continuous glass fibre is that γ-ammonia oxygen propyl-triethoxysilicane coupling agent infiltrates the continuous roving of processing, and fiber type is E glass, and fibre single thread diameter is 1200Tex, and oxidation inhibitor is 0.3 part of antioxidant 1010 and 0.6 part of irgasfos 168; Continuous glass fibre reinforced nylon 6 prepreg tape thickness is 0.22 ± 0.02mm, and width is 635 ± 5mm.
In embodiment 3, nylon 6 melting index are 60g/10min; Compatilizer is calcium maleate grafting EPDM, and maleic anhydride grafting ratio is 1.1; Continuous glass fibre is that γ-(methacryloxy) propyl trimethoxy silicane coupling agent infiltrates the continuous roving of processing, fiber type is E glass, fibre single thread diameter is 1200Tex, and oxidation inhibitor is 0.3 part of antioxidant 1010 and 0.6 part of irgasfos 168; Continuous glass fibre reinforced nylon 6 prepreg tape thickness is 0.24 ± 0.02mm, and width is 635 ± 5mm.
In embodiment 4, nylon 6 melting index are 65g/10min; Compatilizer is calcium maleate grafting POE, and maleic anhydride grafting ratio is 0.85; Continuous glass fibre is for being E glass, and fibre single thread diameter is 1800Tex, and oxidation inhibitor is 0.2 part of oxidation inhibitor 1790; Continuous glass fibre reinforced nylon 6 prepreg tape thickness is 0.20 ± 0.02mm, and width is 635 ± 5mm.
In embodiment 5, nylon 6 melting index are 70g/10min; Compatilizer is calcium maleate grafting EPDM, and maleic anhydride grafting ratio is 1.1; Continuous glass fibre is that γ-(methacryloxy) propyl trimethoxy silicane coupling agent infiltrates the continuous roving of processing, fiber type is S glass, fibre single thread diameter is 2400Tex, and oxidation inhibitor is 0.8 part of oxidation inhibitor 944 and 0.2 part of oxidation inhibitor 327; Continuous glass fibre reinforced nylon 6 prepreg tape thickness is 0.28 ± 0.02mm, and width is 635 ± 5mm.
The preparation method of the prepreg tape in embodiment 1 ~ 5 is as follows:
(1) in the ratio in table 1, take nylon 6, compatilizer, oxidation inhibitor and join in high mixer, fully mix;
(2) mixture step (1) being obtained joins in single screw extrusion machine, and melt blending is extruded and carried out film by die head;
(3) continuous glass fibre is drawn by creel unit, after tension-adjusting gear, exhibition silk device, primary heater unit, nylon 6 films of extruding with die head flood in recombiner unit, through flattening unit, traction unit, last rolling, obtains continuous glass fibre reinforced nylon 6 prepreg tape.
Wherein, in step in embodiment 1 (2), extruder barrel temperature is followed successively by 210 ℃, 210 ℃, 260 ℃, 260 ℃, 260 ℃, 260 ℃, 260 ℃, 260 ℃, extruder main unit frequency is 16Hz, and in step (3), primary heater unit is infrared heating device, and Heating temperature is 190 ℃.
In step in embodiment 2 (2), extruder barrel temperature is followed successively by 220 ℃, 220 ℃, 280 ℃, 280 ℃, 280 ℃, 280 ℃, 280 ℃, 280 ℃, extruder main unit frequency is 12Hz, in step (3), primary heater unit is infrared heating device, and Heating temperature is 190 ℃.
In step in embodiment 3 (2), extruder barrel temperature is followed successively by 225 ℃, 225 ℃, 275 ℃, 275 ℃, 275 ℃, 275 ℃, 275 ℃, 275 ℃, extruder main unit frequency is 14Hz, in step (3), primary heater unit is infrared heating device, and Heating temperature is 190 ℃.
In step in embodiment 4 (2), extruder barrel temperature is followed successively by 210 ℃, 220 ℃, 230 ℃, 245 ℃, 260 ℃, 275 ℃, 280 ℃, 290 ℃, extruder main unit frequency is 10Hz, in step (3), primary heater unit is infrared heating device, and Heating temperature is 230 ℃.
In step in embodiment 5 (2), extruder barrel temperature is followed successively by 210 ℃, 210 ℃, 230 ℃, 230 ℃, 240 ℃, 240 ℃, 250 ℃, 260 ℃, extruder main unit frequency is 20Hz, in step (3), primary heater unit is infrared heating device, and Heating temperature is 160 ℃.
To the continuous glass fibre reinforced nylon 6 prepreg tape making in embodiment 1 ~ 5, by 0 °/90 ° layings, be pressed into 3mm sheet material, its mechanical property to be tested, test result is as table 2:
Table 2
Figure BDA00001953736900051
Figure BDA00001953736900061
Glass fiber reinforced nylon 6 prepreg tape of the present invention does not need to use solvent in process of production, thereby reduces the harm to the pollution of environment and direct labor's health, also can reduce the corrosion to equipment.Glass fiber reinforced nylon 6 prepreg tape of the present invention adopts the nylon of commercialization high fusion index to make raw material, can avoid adding unsaturated carboxylic acid or its acid anhydrides etc., thereby simplifies technique, reduces costs.
The mobility properties-correcting agent using is at present in the course of processing, can react with the oxidation inhibitor generation radical termination in system, consume in a large number and do not have the effect improving liquidity, also can cause constant product quality poor, also produce in process of production irritating smell simultaneously; And the present invention uses high fusion index nylon, melting index is high can guarantee the good mobility of mixed system, increases the dipping effect of nylon and glass fibre, without adding mobility properties-correcting agent.
The lubricant using is at present volatile under higher processing temperature, thereby causes the foaming phenomenon of product external surfaces, directly affects product surface quality; And the present invention is when the mobility of mixed system improves, lubricant effect is also improved, without making with lubricator, do not need to add the mobility properties-correcting agent of peroxide yet, can effectively prevent that it from reacting with oxidation inhibitor generation radical termination in system, thereby improve product surface smooth finish, and be conducive to reduce production costs.
Directly to adding in mixed system coupling agent easily to damage existing system balance, and can there is faint reaction with other compositions in system in coupling agent, affects product stability; And the continuous glass fibre that the present invention adopts coupling agent treatment to cross infiltrates processing to the continuous glass fibre on creel with coupling agent in advance, make coupling agent and glass fibre there is good bonding force.
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 glass fibre reinforced nylon 6 prepreg tape, is characterized in that, by the component that comprises following weight part, is made:
6 100 parts of nylon;
65 ~ 150 parts of continuous glass fibres;
2 ~ 10 parts of compatilizers;
0.2 ~ 1 part, oxidation inhibitor.
2. continuous glass fibre reinforced nylon 6 prepreg tape as claimed in claim 1, is characterized in that, described nylon 6 is high fusion index nylon, its melting index >50g/10min.
3. continuous glass fibre reinforced nylon 6 prepreg tape as claimed in claim 1, is characterized in that, described continuous glass fibre is continuous roving, and its fiber type is E glass or S glass, and its fibre single thread diameter is 1200Tex ~ 2400Tex.
4. continuous glass fibre reinforced nylon 6 prepreg tape as claimed in claim 1, is characterized in that, described continuous glass fibre is for infiltrating the continuous glass fibre of processing through coupling agent.
5. continuous glass fibre reinforced nylon 6 prepreg tape as claimed in claim 4, it is characterized in that, described coupling agent is selected from one or more in 3-aminopropyl triethoxysilane, γ-ammonia oxygen propyl-triethoxysilicane or γ-(methacryloxy) propyl trimethoxy silicane.
6. continuous glass fibre reinforced nylon 6 prepreg tape as claimed in claim 1, it is characterized in that, described compatilizer is selected from a kind of in calcium maleate grafting POE, calcium maleate grafting PE or calcium maleate grafting EPDM, and wherein, maleic anhydride grafting ratio is all greater than 0.8.
7. continuous glass fibre reinforced nylon 6 prepreg tape as claimed in claim 1, is characterized in that, described oxidation inhibitor is selected from one or more in oxidation inhibitor 1098, oxidation inhibitor 944, irgasfos 168, oxidation inhibitor 327, oxidation inhibitor 1790 or antioxidant 1010.
8. a preparation method for the continuous glass fibre reinforced nylon 6 prepreg tape as described in any one in claim 1 ~ 7, is characterized in that, comprises the following steps:
(1) take by weight 6,2 ~ 10 parts of compatilizers of 100 parts of nylon, 0.2 ~ 1 part of oxidation inhibitor joins in high mixer, fully mix;
(2) mixture step (1) being obtained joins in single screw extrusion machine, and melt blending is extruded and carried out film by die head;
(3) continuous glass fibre of 65 ~ 150 weight parts is drawn by creel unit, after tension-adjusting gear, exhibition silk device, primary heater unit, nylon 6 films of extruding with die head flood in recombiner unit, rolling after flattening unit, traction unit, obtains continuous glass fibre reinforced nylon 6 prepreg tape.
9. the preparation method of continuous glass fibre reinforced nylon 6 prepreg tape as claimed in claim 8, it is characterized in that, in described step (2), single screw extrusion machine temperature is established 8 sections altogether, and first paragraph and second segment extrusion temperature are at 210 ~ 230 ℃, and other 6 sections of extrusion temperatures are at 230 ~ 290 ℃; It is 10 ~ 20Hz that extruder main unit frequency is controlled.
10. the preparation method of continuous glass fibre reinforced nylon 6 prepreg tape as claimed in claim 8, is characterized in that, the primary heater unit in described step (3) is infrared heating device, and Heating temperature is 160 ~ 230 ℃; The thickness of the continuous glass fibre reinforced nylon 6 prepreg tape making in described step (3) is 0.18 ~ 0.30mm, and width is 635 ± 5mm.
CN201210269495.9A 2012-07-31 2012-07-31 Continuous glass fiber reinforced nylon 6 prepreg tape and preparation method thereof Pending CN103571183A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106273556A (en) * 2015-05-26 2017-01-04 句容市百事特复合材料有限公司 The preparation technology of the thermoplastic profiles of GFRTP material strip and chopped fiber composite strengthening
CN108192201A (en) * 2017-12-25 2018-06-22 中广核俊尔新材料有限公司 A kind of continuous fiber reinforced thermoplastic resin composite material quant blade and preparation method thereof
CN109651804A (en) * 2018-11-23 2019-04-19 中广核俊尔新材料有限公司 A kind of continuous glass fibre enhancing nylon composite board and preparation method thereof and preparing the application in automobile brake pedal

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1827671A (en) * 2006-02-17 2006-09-06 常州市兴柏化工有限公司 Continuous fiber reinforced composite materials, its production method and special equipment therefor
CN102295792A (en) * 2010-06-28 2011-12-28 辽宁杰事杰新材料有限公司 Continuous fiber enhanced thermoplastic antiflaming presoaking belt composite material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1827671A (en) * 2006-02-17 2006-09-06 常州市兴柏化工有限公司 Continuous fiber reinforced composite materials, its production method and special equipment therefor
CN102295792A (en) * 2010-06-28 2011-12-28 辽宁杰事杰新材料有限公司 Continuous fiber enhanced thermoplastic antiflaming presoaking belt composite material and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106273556A (en) * 2015-05-26 2017-01-04 句容市百事特复合材料有限公司 The preparation technology of the thermoplastic profiles of GFRTP material strip and chopped fiber composite strengthening
CN106273556B (en) * 2015-05-26 2019-04-09 句容市百事特复合材料有限公司 The preparation process of GFRTP material strip and the thermoplastic profiles of staple fiber composite strengthening
CN108192201A (en) * 2017-12-25 2018-06-22 中广核俊尔新材料有限公司 A kind of continuous fiber reinforced thermoplastic resin composite material quant blade and preparation method thereof
CN108192201B (en) * 2017-12-25 2021-04-09 中广核俊尔新材料有限公司 Continuous fiber reinforced thermoplastic resin composite material paddle blade and preparation method thereof
CN109651804A (en) * 2018-11-23 2019-04-19 中广核俊尔新材料有限公司 A kind of continuous glass fibre enhancing nylon composite board and preparation method thereof and preparing the application in automobile brake pedal
CN109651804B (en) * 2018-11-23 2021-03-23 中广核俊尔新材料有限公司 Continuous glass fiber reinforced nylon composite board, preparation method thereof and application thereof in preparation of automobile brake pedal

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Application publication date: 20140212