CN104046000A - Alkali-free short glass fiber reinforced nylon material and preparation method - Google Patents
Alkali-free short glass fiber reinforced nylon material and preparation method Download PDFInfo
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- CN104046000A CN104046000A CN201310084298.4A CN201310084298A CN104046000A CN 104046000 A CN104046000 A CN 104046000A CN 201310084298 A CN201310084298 A CN 201310084298A CN 104046000 A CN104046000 A CN 104046000A
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- 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
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- 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
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- C08K2201/004—Additives being defined by their length
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Abstract
The invention belongs to the field of a composite high-molecular material and relates to an alkali-free short glass fiber reinforced nylon material and its preparation method. The alkali-free short glass fiber reinforced nylon material is prepared from the following components, by weight, 40-70 parts of nylon, 20-50 parts of alkali-free short glass fiber, 3-8 parts of a lubricant and 2-7 parts of an antioxidant. In comparison with the prior art, the preparation technology is simple; the material has advantages of low water absorption, superior stability and high thermal deformation temperature; the added alkali-free short glass fiber undergoes silane coupling agent surface treatment and has good caking property with a resin matrix; the length of the added glass fiber is short such that the glass fiber is uniformly dispersed in the resin matrix; and after injection moulding, the material is surface-brightening and there is no glass fiber flow liner or exposure.
Description
Technical field
The invention belongs to composite high-molecular material field, relate to a kind of alkali-free short glass fiber Reinforced Nylon material and preparation method thereof.
Technical background
Nylon (polymeric amide) is the outer most widely used a kind of thermoplastic engineering plastic of Present Domestic, it has the excellent specific properties such as tough wear-resisting, shock-resistant, antifatigue, corrosion-resistant, oil resistant, be widely used in the industries such as auto-parts, electronic apparatus, machinery, over 60 years, steady-state growth in the cut-throat competition of engineering plastics, its demand occupies the first place of five large-engineering plastics so far always.
At present, along with industrial develop rapidly, people are more and more higher to the requirement of engineering plastics, in order to make plastics further replace metal, expand its use range, require plastics improve primary characteristic and overcome some shortcoming.It is exactly that water-absorbent is large that general nylon is used disadvantage as engineering plastics, thereby affects dimension stability, time limit of service and relevant mechanical property.Therefore nylon products of a kind of good stability of the dimension excellent performance and preparation method thereof is badly in need of in this field.
Through the literature search of prior art is found, Chinese patent CN102344676A has announced a kind of glass reinforced nylon 6, although improved to a certain extent the performance of nylon 6, widened use field, but its enhancing process occurs in nylon building-up reactions, therefore its technique is comparatively loaded down with trivial details and restive, and it is only for nylon 6 single varieties simultaneously, and its use has certain limitation; Chinese patent CN102504529A has announced a kind of halogen-free flame-retardant long glass fiber reinforced nylon 6 and preparation method thereof, due to its use is roving glass fiber, therefore in the course of processing, glass add-on is inconvenient well controls, and is also unfavorable for that glass is uniformly dispersed in nylon simultaneously.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of alkali-free short glass fiber Reinforced Nylon material and preparation method thereof is provided.
The nylon reinforcements preparing by the present invention, water-absorbent is less, dimension stability is better, and its relevant mechanical property is also comparatively excellent simultaneously, and especially thermal deformation behavior is better, simultaneously, in its preparation process, only need through Screw Extrusion granulation, technique is very simple, due to what add, is alkali-free short glass fiber, therefore its dispersion in nylon resin is also comparatively even, and the consistency of short glass fiber and nylon resin is also comparatively desirable.
For achieving the above object, the present invention is by the following technical solutions:
An alkali-free short glass fiber Reinforced Nylon material, by the component that comprises following weight part content, made:
Nylon 40-70 part,
Alkali-free short glass fiber 20-50 part,
Lubricant 3-8 part,
Oxidation inhibitor 2-7 part.
Described nylon is formed by aliphatic dibasic acid, aliphatic diamine and aromatic acid polycondensation.
Wherein aromatic acid is selected from terephthalic acid, m-phthalic acid, phthalic acid, 4, one or more in 4'-biphenyl dicarboxylic acid, naphthalic acid, preferably terephthalic acid;
Described aliphatic diamine is one or more in the aliphatic diamine that contains 4-13 carbon atom in molecular chain main chain, preferably hexanediamine;
Described aliphatic dibasic acid is one or more in the aliphatic dibasic acid that contains 4-13 carbon atom in molecular chain main chain, preferably has biological sebacic acid;
Described nylon is selected from one or more in NYLON610 T, 66T, nylon 66, NYLON610, nylon 1010, nylon 10T, preferably NYLON610 T;
Described alkali-free short glass fiber, through silane coupling agent, carry out surface treatment, preferred length is that 2-4mm(manufacturer is: Shenzhen Ya Taida Science and Technology Ltd., model ECS-13-3.0, fiberglass type: alkali-free, filament diameter (um): 13 ± 1, the short length (mm) of cutting: 3 ± 1, moisture content (%) :≤0.3, loss on ignition (%): 1 ± 0.2, the short rate (%) of cutting: >=90, the short rate basic oxide content (%) of cutting :≤0.8).
Described lubricant is ethylene acrylic acid co polymer (A-C540A);
Described oxidation inhibitor is Hinered phenols antioxidant and phosphite ester kind antioxidant is composite forms; preferred N; N'-pair-(3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (oxidation inhibitor 1098) and three [2.4-di-tert-butyl-phenyl] phosphorous acid esters (irgasfos 168) are composite, and the two mass ratio is 1:1.
A preparation method for above-mentioned alkali-free short glass fiber Reinforced Nylon material, comprises the following steps:
(1) by nylon dry 6-10 hour under 90-110 ℃ of condition, to remove wherein moisture;
(2) by said ratio, take the raw material of following weight part: dry nylon 40-70 part, oxidation inhibitor 2-7 part, lubricant 3-8 part in step (1), and fully mix;
(3) material step (2) being mixed is poured forcing machine hopper into, and takes 20-50 part short glass fiber and join side spout;
(4) start forcing machine, and open vacuum pump, through twin screw extruder extruding pelletization, obtain short glass fiber Reinforced Nylon pellet;
(5) by the dry 2-6 hour in 90-110 ℃ of baking oven of nylon pellet in step (4); Obtain alkali-free short glass fiber Reinforced Nylon material.
In described step (4), the screw slenderness ratio of twin screw extruder is 30-50, and extrusion temperature is 295～360 ℃ from 1st district to head scope, and rotating speed is 200-500r/min.
The present invention compared with the existing technology, has the following advantages:
(1) preparation technology is comparatively simple;
(2) resulting materials water-intake rate is low, and stability of material is superior, and heat-drawn wire is higher;
(3) add alkali-free short glass fiber through silane coupling agent surface-treated, the cementability of it and resin matrix is fine;
(4) Length of Glass Fiber adding is less, is convenient to it and is uniformly dispersed in resin matrix, and after injection moulding, surface-brightening is without glass flow liner or expose phenomenon.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.
In the following example, alkali-free short glass fiber used, manufacturer is: Shenzhen Ya Taida Science and Technology Ltd., model ECS-13-3.0.
In following embodiment, adopt following detection method:
Melt flow rate (MFR) (MFR) is pressed ASTM D1238-10, at 320 ℃, under 2.16kg condition, tests.
Tensile property is pressed ASTM D638-10 test, rate of extension 5mm/min.
Simply supported beam notched Izod impact strength is pressed ASTM D6110-10 test.
Flexural strength is pressed ASTM D790-10 test, presses down speed 1.25mm/min.
Heat-drawn wire is pressed ASTM D1525-09 test.
Water-absorbent test: under room temperature, sample is placed in moisture eliminator, a beaker that fills the saturated common salt aqueous solution is placed in moisture eliminator bottom, and maintaining relative humidity in moisture eliminator is 75%, and every 24h of mistake takes out sample and weighs, be designated as Gi, (i=1,2,3,4 ...), the sample after weighing is still put back in moisture eliminator.After 20 days, sample is put into drying in oven, and (7O ℃, 24h), is then placed in moisture eliminator and is cooled to room temperature weighing sample, is designated as G0.Press formula and calculate water content (Wi) % in sample, wherein the consistent water-intake rate that calculates (240h) after 10 days of the water-intake rate in the present invention:
Wi=(G
i-G0)／G
i×100％
Embodiment 1
A kind of alkali-free short glass fiber Reinforced Nylon material is provided, by following component, formed by weight: nylon resin 610T:70 part, alkali-free short glass fiber (length is 0.5cm): 20 parts, lubricant (ethylene acrylic acid co polymer A-C540A): 3 parts, oxidation inhibitor (oxidation inhibitor 1098: irgasfos 168 is composite=1:1): 7 parts, processing gross weight is 4kg.
(1) nylon resin is dried to 10 hours fully to remove wherein moisture under 90 ℃ of conditions,
(2) then the components such as nylon, oxidation inhibitor, lubricant are fully mixed;
(3) pour forcing machine hopper into, the alkali-free short glass fiber after processing is joined to side spout simultaneously;
(4) start forcing machine, and unlatching vacuum pump, through twin screw extruder extruding pelletization, extruder screw length-to-diameter ratio is 40, extrusion temperature is respectively 295 ℃, 305 ℃, 315 ℃, 325 ℃, 330 ℃, 335 ℃, 340 ℃ from 1st district to head, rotating speed is 400r/min, obtains alkali-free short glass fiber Reinforced Nylon pellet.
Alkali-free short glass fiber Reinforced Nylon pellet is dried to 6 hours in 90 ℃ of baking ovens.Last alkali-free short glass fiber Reinforced Nylon pellet injection moulding on injection moulding machine, injection temperature interval is 310 ℃, 320 ℃, 315 ℃, obtains the batten for correlated performance test, detailed performance is in Table 1.
Embodiment 2
A kind of alkali-free short glass fiber Reinforced Nylon material is provided, by following component, formed by weight: nylon resin 66T:65 part, alkali-free short glass fiber (length is 0.7cm): 25 parts, lubricant (ethylene acrylic acid co polymer A-C540A): 6 parts, oxidation inhibitor (oxidation inhibitor 1098: irgasfos 168 is composite=1:1): 4 parts, processing gross weight is 4kg.
(1) nylon resin is dried to 9 hours fully to remove wherein moisture under 95 ℃ of conditions,
(2) then the components such as nylon, oxidation inhibitor, lubricant are fully mixed;
(3) pour forcing machine hopper into, the alkali-free short glass fiber after processing is joined to side spout simultaneously;
(4) start forcing machine, and unlatching vacuum pump, through twin screw extruder extruding pelletization, extruder screw length-to-diameter ratio is 35, extrusion temperature is respectively 310 ℃, 320 ℃, 325 ℃, 335 ℃, 330 ℃, 335 ℃, 335 ℃ from 1st district to head, rotating speed is 300r/min, obtains alkali-free short glass fiber Reinforced Nylon pellet.
Alkali-free short glass fiber Reinforced Nylon pellet is dried to 4 hours in 100 ℃ of baking ovens.Last alkali-free short glass fiber Reinforced Nylon pellet injection moulding on injection moulding machine, injection temperature interval is 310 ℃, 320 ℃, 315 ℃, obtains the batten for correlated performance test, detailed performance is in Table 1.
Embodiment 3
A kind of alkali-free short glass fiber Reinforced Nylon material is provided, by following component, formed by weight: nylon resin 66:60 part, alkali-free short glass fiber (length is 1.2cm): 30 parts, lubricant (ethylene acrylic acid co polymer A-C540A): 5 parts, oxidation inhibitor (oxidation inhibitor 1098: irgasfos 168 is composite=1:1): 5 parts, processing gross weight is 4kg.
(1) nylon resin is dried to 8 hours fully to remove wherein moisture under 100 ℃ of conditions,
(2) then the components such as nylon, oxidation inhibitor, lubricant are fully mixed;
(3) pour forcing machine hopper into, the alkali-free short glass fiber after processing is joined to side spout simultaneously;
(4) start forcing machine, and unlatching vacuum pump, through twin screw extruder extruding pelletization, extruder screw length-to-diameter ratio is 50, extrusion temperature is respectively 300 ℃, 310 ℃, 320 ℃, 330 ℃, 335 ℃, 340 ℃, 345 ℃ from 1st district to head, rotating speed is 500r/min, obtains alkali-free short glass fiber Reinforced Nylon pellet.
Alkali-free short glass fiber Reinforced Nylon pellet is dried to 2 hours in 110 ℃ of baking ovens.Last alkali-free short glass fiber Reinforced Nylon pellet injection moulding on injection moulding machine, injection temperature interval is 310 ℃, 320 ℃, 315 ℃, obtains the batten for correlated performance test, detailed performance is in Table 1.
Embodiment 4
A kind of alkali-free short glass fiber Reinforced Nylon material is provided, by following component, formed by weight: nylon resin 610:55 part, alkali-free short glass fiber (length is 1.0cm): 35 parts, lubricant (ethylene acrylic acid co polymer A-C540A): 7 parts, oxidation inhibitor (oxidation inhibitor 1098: irgasfos 168 is composite=1:1): 3 parts, processing gross weight is 4kg.
(1) nylon resin is dried to 6 hours fully to remove wherein moisture under 110 ℃ of conditions,
(2) then the components such as nylon, oxidation inhibitor, lubricant are fully mixed;
(3) pour forcing machine hopper into, the alkali-free short glass fiber after processing is joined to side spout simultaneously;
(4) start forcing machine, and unlatching vacuum pump, through twin screw extruder extruding pelletization, extruder screw length-to-diameter ratio is 40, extrusion temperature is respectively 305 ℃, 315 ℃, 325 ℃, 335 ℃, 335 ℃, 340 ℃, 345 ℃ from 1st district to head, rotating speed is 350r/min, obtains alkali-free short glass fiber Reinforced Nylon pellet.
Alkali-free short glass fiber Reinforced Nylon pellet is dried to 6 hours in 95 ℃ of baking ovens.Last alkali-free short glass fiber Reinforced Nylon pellet injection moulding on injection moulding machine, injection temperature interval is 310 ℃, 320 ℃, 315 ℃, obtains the batten for correlated performance test, detailed performance is in Table 1.
Embodiment 5
A kind of alkali-free short glass fiber Reinforced Nylon material is provided, by following component, formed by weight: nylon resin 1010:50 part, alkali-free short glass fiber (length is 1.3cm): 40 parts, lubricant (ethylene acrylic acid co polymer A-C540A): 4 parts, oxidation inhibitor (oxidation inhibitor 1098: irgasfos 168 is composite=1:1): 6 parts, processing gross weight is 4kg.
(1) nylon resin is dried to 7 hours fully to remove wherein moisture under 105 ℃ of conditions,
(2) then the components such as nylon, oxidation inhibitor, lubricant are fully mixed;
(3) pour forcing machine hopper into, the alkali-free short glass fiber after processing is joined to side spout simultaneously;
(4) start forcing machine, and unlatching vacuum pump, through twin screw extruder extruding pelletization, extruder screw length-to-diameter ratio is 30, extrusion temperature is respectively 310 ℃, 320 ℃, 325 ℃, 335 ℃, 330 ℃, 335 ℃, 335 ℃ from 1st district to head, rotating speed is 200r/min, obtains alkali-free short glass fiber Reinforced Nylon pellet.
Alkali-free short glass fiber Reinforced Nylon pellet is dried to 3 hours in 110 ℃ of baking ovens.Last alkali-free short glass fiber Reinforced Nylon pellet injection moulding on injection moulding machine, injection temperature interval is 310 ℃, 320 ℃, 315 ℃, obtains the batten for correlated performance test, detailed performance is in Table 1.
Embodiment 6
A kind of alkali-free short glass fiber Reinforced Nylon material is provided, by following component, formed by weight: nylon resin 10T:45 part, alkali-free short glass fiber (length is 0.7cm): 45 parts, lubricant (ethylene acrylic acid co polymer A-C540A): 6 parts, oxidation inhibitor (oxidation inhibitor 1098: irgasfos 168 is composite=1:1): 4 parts, processing gross weight is 4kg.
(1) nylon resin is dried to 8 hours fully to remove wherein moisture under 100 ℃ of conditions,
(2) then the components such as nylon, oxidation inhibitor, lubricant are fully mixed;
(3) pour forcing machine hopper into, the alkali-free short glass fiber after processing is joined to side spout simultaneously;
(4) start forcing machine, and unlatching vacuum pump, through twin screw extruder extruding pelletization, extruder screw length-to-diameter ratio is 40, extrusion temperature is respectively 315 ℃, 325 ℃, 335 ℃, 345 ℃, 345 ℃, 350 ℃, 355 ℃ from 1st district to head, rotating speed is 400r/min, obtains alkali-free short glass fiber Reinforced Nylon pellet.
Alkali-free short glass fiber Reinforced Nylon pellet is dried to 4 hours in 105 ℃ of baking ovens.Last alkali-free short glass fiber Reinforced Nylon pellet injection moulding on injection moulding machine, injection temperature interval is 310 ℃, 320 ℃, 315 ℃, obtains the batten for correlated performance test, detailed performance is in Table 1.
Embodiment 7
A kind of alkali-free short glass fiber Reinforced Nylon material is provided, by following component, formed by weight: nylon resin 610T:40 part, alkali-free short glass fiber (length is 1.5cm): 50 parts, lubricant (ethylene acrylic acid co polymer A-C540A): 8 parts, oxidation inhibitor (oxidation inhibitor 1098: irgasfos 168 is composite=1:1): 2 parts, processing gross weight is 4kg.
(1) nylon resin is dried to 7 hours fully to remove wherein moisture under 105 ℃ of conditions,
(2) then the components such as nylon, oxidation inhibitor, lubricant are fully mixed;
(3) pour forcing machine hopper into, the alkali-free short glass fiber after processing is joined to side spout simultaneously;
(4) start forcing machine, and unlatching vacuum pump, through twin screw extruder extruding pelletization, extruder screw length-to-diameter ratio is 50, extrusion temperature is respectively 320 ℃, 325 ℃, 335 ℃, 340 ℃, 345 ℃, 355 ℃, 360 ℃ from 1st district to head, rotating speed is 500r/min, obtains alkali-free short glass fiber Reinforced Nylon pellet.
Alkali-free short glass fiber Reinforced Nylon pellet is dried to 6 hours in 95 ℃ of baking ovens.Last alkali-free short glass fiber Reinforced Nylon pellet injection moulding on injection moulding machine, injection temperature interval is 310 ℃, 320 ℃, 315 ℃, obtains the batten for correlated performance test, detailed performance is in Table 1.
Comparative example:
Take 3kg and be dried 8 hours fully to remove wherein moisture under 100 ℃ of conditions, then by nylon, oxidation inhibitor 150g(5%), lubricant 150g(5%) etc. component fully mix, finally in injection moulding machine injection moulding, injection temperature interval is 290,300,295, obtain the batten for correlated performance test, and contrast with embodiment 1-7, detailed performance is in Table 1.
Through experimental test, the performance test results of material is as table 1:
Table 1
From the product test of the embodiment shown in table 1 and comparative example, relatively can find out, product tensile strength prepared by the present invention, shock strength, flexural strength, heat-drawn wire etc. all obtain obviously significantly promoting.Illustrate that glass has played obvious reinforced effects, also proved to a certain extent that the consistency of resin and glass is better simultaneously; From data, it can also be seen that, short fiber Reinforced Nylon material water-intake rate obviously reduces, water resistance significantly promotes, be conducive to keep good dimensional stability in environment is used, from melting index, can know simultaneously, the molten finger of short fiber Reinforced Nylon material is not very low, has certain fluidity, is convenient to forming process.
By implementation process and the detected result of each embodiment, the known matrix material obtaining in nylon resin that the short glass fiber of 20-50 part is added to by preparation method of the present invention, guaranteeing that system is easily under the prerequisite of forming process, there is desirable mechanical property and water tolerance, after injection moulding simultaneously, surface-brightening is without glass flow liner or expose phenomenon, therefore has wider application prospect.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (9)
1. an alkali-free short glass fiber Reinforced Nylon material, is characterized in that: by the component that comprises following weight part content, made:
Nylon 40-70 part,
Alkali-free short glass fiber 20-50 part,
Lubricant 3-8 part,
Oxidation inhibitor 2-7 part.
2. alkali-free short glass fiber Reinforced Nylon material according to claim 1, is characterized in that: described nylon is formed by aliphatic dibasic acid, aliphatic diamine and aromatic acid polycondensation;
Wherein aromatic acid is selected from terephthalic acid, m-phthalic acid, phthalic acid, 4, one or more in 4'-biphenyl dicarboxylic acid, naphthalic acid, preferably terephthalic acid;
Described aliphatic diamine is one or more in the aliphatic diamine that contains 4-13 carbon atom in molecular chain main chain, preferably hexanediamine;
Described aliphatic dibasic acid is one or more in the aliphatic dibasic acid that contains 4-13 carbon atom in molecular chain main chain, preferably has biological sebacic acid.
3. alkali-free short glass fiber Reinforced Nylon material according to claim 1, is characterized in that: described nylon is selected from one or more in NYLON610 T, 66T, nylon 66, NYLON610, nylon 1010, nylon 10T, preferably NYLON610 T.
4. alkali-free short glass fiber Reinforced Nylon material according to claim 1, is characterized in that: described alkali-free short glass fiber, through silane coupling agent, carry out surface treatment, and length is 2-4mm.
5. alkali-free short glass fiber Reinforced Nylon material according to claim 1, is characterized in that: described lubricant is ethylene acrylic acid co polymer.
6. alkali-free short glass fiber Reinforced Nylon material according to claim 1, is characterized in that: described oxidation inhibitor is Hinered phenols antioxidant and phosphite ester kind antioxidant is composite forms.
7. alkali-free short glass fiber Reinforced Nylon material according to claim 6; it is characterized in that: described oxidation inhibitor is N; N'-pair-(3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (oxidation inhibitor 1098) and three [2.4-di-tert-butyl-phenyl] phosphorous acid esters (irgasfos 168) are composite, and the two mass ratio is 1:1.
8. a preparation method for arbitrary described alkali-free short glass fiber Reinforced Nylon material in claim 1-7, is characterized in that: comprise the following steps:
(1) by nylon dry 6-10 hour under 90-110 ℃ of condition, to remove wherein moisture;
(2) by proportioning claimed in claim 1, take the raw material of following weight part: dry nylon 40-70 part, oxidation inhibitor 2-7 part, lubricant 3-8 part in step (1), and fully mix;
(3) material step (2) being mixed is poured forcing machine hopper into, and takes 20-50 part short glass fiber and join side spout;
(4) start forcing machine, and open vacuum pump, through twin screw extruder extruding pelletization, obtain short glass fiber Reinforced Nylon pellet;
(5) by the dry 2-6 hour in 90-110 ℃ of baking oven of nylon pellet in step (4); Obtain alkali-free short glass fiber Reinforced Nylon material.
9. preparation method according to claim 8, is characterized in that: in described step (4), the screw slenderness ratio of twin screw extruder is 30-50, and extrusion temperature is 295～360 ℃ from 1st district to head scope, and rotating speed is 200-500r/min.
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| CN104448795A (en) * | 2014-11-28 | 2015-03-25 | 安徽丹凤电子材料股份有限公司 | Glass-fiber-reinforced nylon manufacturing process |
| CN105385152A (en) * | 2015-12-22 | 2016-03-09 | 上海金发科技发展有限公司 | Low-emission high-heat-resistant polyamide composite material and preparation method thereof |
| CN105778492A (en) * | 2014-12-19 | 2016-07-20 | 上海杰事杰新材料(集团)股份有限公司 | Heatproof wear-resistant alkali-free short glass fiber-reinforced nylon PA610T composition and preparation method thereof |
| CN106398202A (en) * | 2016-08-31 | 2017-02-15 | 合肥会通新材料有限公司 | Polyamide engineering plastic, and preparation method thereof |
| CN106566168A (en) * | 2015-10-13 | 2017-04-19 | 上海杰事杰新材料(集团)股份有限公司 | Heat-resistant semi-aromatic nylon/polyphenyl ether alloy material and preparation method thereof |
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| CN111621151A (en) * | 2020-07-09 | 2020-09-04 | 东莞市奥能工程塑料有限公司 | High-rigidity high-bonding-strength nylon reinforced material and preparation method thereof |
| CN113061329A (en) * | 2021-04-14 | 2021-07-02 | 长虹美菱股份有限公司 | Plastic hinge and refrigerator |
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