CN103804683B - A kind of polyamide resin and consisting of daiamid composition - Google Patents
A kind of polyamide resin and consisting of daiamid composition Download PDFInfo
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- CN103804683B CN103804683B CN201310721601.7A CN201310721601A CN103804683B CN 103804683 B CN103804683 B CN 103804683B CN 201310721601 A CN201310721601 A CN 201310721601A CN 103804683 B CN103804683 B CN 103804683B
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- polyamide resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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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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Abstract
The present invention discloses a kind of polyamide resin, is made up of following component: the decamethylene diamine of component A:40-48mol% and the hexanediamine of 2-10mol%; The terephthalic acid of B component: 40-48mol% and the hexanodioic acid of 2-10mol%; Comprise a daiamid composition for described polyamide resin, by weight percentage, comprise following component: polyamide resin 30 ~ 99.9%; Reinforcing filler 0 ~ 60%; Fire retardant 0 ~ 50%; Other auxiliary agents 0.1 ~ 10%; Polyamide resin of the present invention and consisting of daiamid composition, there is higher brightness, can be applied to and product color is required higher occasion; Thermotolerance is strong, can be applied to if reflow soldering temperature is more than 270oThe occasion of C.
Description
Technical field
The present invention relates to polymeric material field, in particular to a kind of polyamide resin and consisting of daiamid composition.
Background technology
Polymeric amide is because having good over-all properties, comprise mechanical property, thermotolerance, wearability, chemical proofing and self lubricity, and frictional coefficient is low, there is certain flame retardant resistance, it is easy to processing etc., it is extensively suitable for by glass fibre and other filler filling enhancing modified, it is to increase the aspects such as performance and broadened application scope. In recent years semiaromatic polyamide composition due to its resistance toheat and mechanical property more excellent and by focus development.
A well known fact is, polymeric amide produces to decompose under being easy to oxidized or high temperature, causes color of resin to shade, seriously affects its quality. Therefore the improvement of polymeric amide brightness becomes an important research topic.
Summary of the invention
In order to overcome the shortcoming of prior art and deficiency, the primary and foremost purpose of the present invention is to provide the polyamide resin of a kind of high brightness and high heat resistance.
A kind of polyamide resin, by mole meter, is made up of following component:
The decamethylene diamine of component A:40-48mol% and the hexanediamine of 2-10mol%;
The terephthalic acid of B component: 40-48mol% and the hexanodioic acid of 2-10mol%.
The fusing point of described polyamide resin is higher than 270oC, it is preferable to 280oC~320oC; Melting point resin is too low, and under the pyroprocessing of reflow soldering, goods are easily out of shape; Melting point resin is too high, causes its processing characteristics to decline; Further, fusing point is too high close to decomposition temperature, it is easy to goods various aspects of performance is all declined.
The brightness value L obtaining colour table after the injection moulding of described polyamide resin is greater than 75.0, it is preferable to be greater than 76.0; Resin brightness value is too low, causes its goods to shade, affects final utilization.
Comprise a daiamid composition for described polyamide resin, by weight percentage, comprise following component:
Polyamide resin 30 ~ 99.9%;
Reinforcing filler 0 ~ 60%;
Fire retardant 0 ~ 50%;
Other auxiliary agents 0 ~ 10%;
The content of described reinforcing filler is preferably 15-50%; Filler content is too low, causes daiamid composition mechanical property poor; Filler content is too high, and daiamid composition product surface is floating fine serious, affects product appearance.
The shape of described reinforcing filler is threadiness, and its mean length is 0.01 ~ 20mm, it is preferable to 0.1 ~ 6mm; Its length-to-diameter ratio is 5 ~ 2000:1, it is preferable to 30 ~ 600:1, and when fibrous reinforcing filler content is in above-mentioned scope, the high temperature rigid that daiamid composition will show high heat distortion temperature and increase, fiber measurement is obtained by above-mentioned size by milscale.
Described reinforcing filler is inorganic reinforcing filler or organic reinforcing fillers;
Described inorganic reinforcing filler is selected from one or more of glass fibre, potassium titanate fiber, the glass fibre of clad, ceramic fiber, wollastonite fibre, metallic carbide fibres, metal-cured fiber, fibrous magnesium silicate, sapphire whisker, silicon carbide fiber, gypsum fiber or boron fibre, it is preferable to glass fibre; Use glass fibre not only can improve the mouldability of daiamid composition, and mechanical property such as tensile strength, flexural strength and modulus in flexure can be improved, and heat-drawn wire when improving thermotolerance such as thermoplastic resin composition carries out molding.
Described organic reinforcing fillers is selected from Kevlar and/or carbon fiber.
The shape of described reinforcing filler is Non-fibrous, such as powder shape, particulate state, tabular, needle-like, fabric or felted, its median size is 0.001��10 ��m, it is preferable to 0.01��5 ��m, will cause the melt processable of polyamide resin difference when the median size of reinforcing filler is less than 0.001 ��m, when the median size of reinforcing filler is greater than 10 ��m, bad injection moulding product appearance will be caused. the median size of above-mentioned reinforcing filler is measured by absorption method, it can be selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, agalmatolite, wilkinite, polynite, lithium montmorillonite, synthetic mica, asbestos, silico-aluminate, aluminum oxide, silicon oxide, magnesium oxide, zirconium white, titanium oxide, ferric oxide, calcium carbonate, magnesiumcarbonate, rhombspar, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, granulated glass sphere, ceramic bead, boron nitride, one or more of silicon carbide or silicon-dioxide. these reinforcing fillers can be hollow, in addition, for swelling property layered silicates such as wilkinite, polynite, lithium montmorillonite, synthetic micas, it is possible to use the organic montmorillonoid after adopting organic ammonium salt that interlayer ion carries out cationic exchange.
In order to make daiamid composition obtain more excellent mechanical property, can adopting coupling agent that inorganic reinforcing filler is carried out functional processing, wherein coupling agent is selected from isocyanic ester based compound, organosilane based compound, organic titanate based compound, organo-borane based compound, epoxy compounds; It is preferably organosilane based compound;
Wherein, described organosilane based compound be selected from the alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group(ing), the alkoxysilane compound containing trialkylsilyl group in molecular structure containing sulfydryl, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing isocyanate group, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing amino, alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing carbon-carbon unsaturated group, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group one or more.
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group(ing) be selected from ��-glycidoxypropyltrime,hoxysilane, ��-glycidoxy propyl-triethoxysilicane, ��-(the own base of 3,4-oxirane ring) ethyl trimethoxy silane one or more;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing sulfydryl is selected from �� mercaptopropyitrimethoxy silane and/or ��-Mercaptopropyltriethoxysilane;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups be selected from ��-ureidopropyltriethoxysilane, ��-ureido-propyl Trimethoxy silane, ��-(2-urea groups ethyl) TSL 8330 one or more;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing isocyanate group be selected from ��-isocyanate group propyl-triethoxysilicane, ��-isocyanate group propyl trimethoxy silicane, ��-isocyanate group propyl group methyl dimethoxysilane, ��-isocyanate group propyl group methyldiethoxysilane, ��-isocyanate group propyl group ethyldimethoxysilane, ��-isocyanate group propyl group ethyl diethoxy silane, ��-isocyanate group propyltrichlorosilan one or more;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing amino be selected from ��-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, ��-(2-amino-ethyl) TSL 8330, gamma-amino propyl trimethoxy silicane one or more;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl is selected from ��-hydroxypropyl Trimethoxy silane and/or ��-hydroxypropyl triethoxyl silane;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing carbon-carbon unsaturated group be selected from ��-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, N-��-(N-vinylbenzylaminoethyl)-gamma-amino propyl trimethoxy silicane hydrochloride one or more;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group is selected from 3-trimethoxy-silylpropyl succinyl oxide;
Described organosilane based compound is preferably ��-methacryloxypropyl trimethoxy silane, ��-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, ��-(2-amino-ethyl) TSL 8330, gamma-amino propyl trimethoxy silicane or 3-trimethoxy-silylpropyl succinyl oxide.
Can conventionally adopt above-mentioned organosilane based compound that inorganic reinforcing filler is carried out surface treatment, and then itself and polyamide resin are carried out melting mixing, to prepare described daiamid composition; Directly while inorganic reinforcing filler and polyamide resin melting mixing, organosilane based compound can also be added and carries out in-situ blending;
Wherein, the consumption of described coupling agent is 0.05 ~ 10wt% relative to inorganic reinforcing filler weight, it is preferable to 0.1 ~ 5wt%; When the consumption of coupling agent is less than 0.05wt%, it does not reach the effect of obvious improved mechanical properties; When the consumption of coupling agent is greater than 10wt%, inorganic reinforcing filler easily condenses, and disperses bad risk in polyamide resin, finally causes mechanical property to decline.
Described fire retardant is fire retardant or the composition of fire retardant and fire-retardant assistance agent, and its content is preferably 10 ~ 40wt%; Flame retardant agent content is too low causes flame retardant effect to be deteriorated, and flame retardant agent content is too high causes material property to decline.
Described fire retardant is halogenated flame retardant or halogen-free flame retardants;
Described halogenated flame retardant is selected from one or more of brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, decabromodiphynly oxide, decabromodiphenyl, brominated polycarbonate, full bromine three cyclopentadecane or brominated aromatic cross-linked polymer, it is preferable to preferably brominated Polystyrene;
Described halogen-free flame retardants is selected from one or more of the fire retardant of nitrogenous flame ratardant, phosphonium flame retardant or nitrogenous and phosphorus; It is preferably phosphonium flame retardant.
Described phosphonium flame retardant is selected from one or more of monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene system phosphoric acid ester, butylbenzene system phosphoric acid ester or hypophosphite; It is preferably hypophosphite;
Described hypophosphite has the hypophosphite of following structure formula I:
In formula, R1, R2Identical or different, represent for straight chain or containing the alkyl of 1 ~ 6 carbon atom of side chain and/or aryl or phenyl; The nitrogenous base that M is Mg, Ca, Al, Zn, Bi, Mn, Na, K or has been protonated; M is 1 ~ 3.
Other auxiliary agents described are selected from one or more of softening agent, thickening material, antistatic agent, releasing agent, toner, staining agent or nucleator.
The present invention compared with prior art, has following useful effect:
1) polyamide resin of the present invention is prepared by specific repeating unit, and the brightness value L obtaining colour table after injection moulding is greater than 75.0, has higher brightness, can be applied to and product color is required higher occasion;
2) fusing point of the polyamide resin of the present invention is higher than 270oC, thermotolerance is strong, can be applied to if reflow soldering temperature is more than 270oThe occasion of C;
3) daiamid composition preparing gained by the polyamide resin of the present invention also has high brightness and strong thermotolerance, it is possible to be applied to product color, occasion that heat resistant requirements is higher.
Embodiment
Below by embodiment, the present invention being described further, following examples are that the present invention preferably implements mode, but embodiments of the present invention are not by the restriction of following embodiment.
The testing method of gained polymeric amide relative viscosity: with reference to GB12006.1-89, polymeric amide sticky number measuring method; Concrete testing method is: 25 �� 0.01oC98% the vitriol oil in measure the relative viscosity �� r that concentration is the polymeric amide of 0.25g/dl;
The testing method of the fusing point of polymeric amide: with reference to ASTMD3418-2003, StandardTestMethodforTransitionTemperaturesofPolymersByD ifferentialScanningCalorimetry; Concrete testing method is: the fusing point adopting PerkinElmerDimondDSC analyser test sample; Nitrogen atmosphere, flow velocity is 40mL/min; First with 10 during testoC/min is warming up to 340oC, 340oCKeep 2min, then with 10oC/min is cooled to 50oC, then with 10oC/min is warming up to 340oC, is set to fusing point T by endotherm peak temperature nowm;
The testing method of gained polymeric amide terminal amino group content: with autopotentiometric titrator titration sample end amino content; Getting 0.5g polymkeric substance, add phenol 45mL and anhydrous methanol 3mL, reflux, observation sample is chilled to room temperature after dissolving completely, with the hydrochloric acid standard solution titration terminal amino group content demarcated;
The testing method of gained polymeric amide content of carboxyl end group: with autopotentiometric titrator titration sample end carboxyl-content; Getting 0.5g polymkeric substance, add ortho-cresol 50mL, backflow is dissolved, and adds rapidly 400 �� L formaldehyde solutions after letting cool, with the KOH-ethanolic soln titration content of carboxyl end group demarcated;
The testing method of gained polyamide resin lightness l value: use Standard colour board mould, gets after 3000g polymer particle carries out injection moulding, obtains the colour table of one-sided smooth. This colour table is placed on the precious Color-Eye7000A Computer color testing instrument of reason and obtains brightness value L value.
Embodiment 1 ~ 4 and comparative example 1 ~ 13
The autoclave pressure being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth adds reaction raw materials in the ratio in form; Add phenylformic acid, sodium hypophosphite and deionized water again; Phenylformic acid amount of substance is the 2.5% of the total amount of substance of diamines, diacid, lactan and amino acid, and sodium hypophosphite weight is the 0.1% of deionizing water other charged material weight outer, and deionized water weight is the 30% of total charged material weight; Vacuumize and it is filled with high pure nitrogen as protection gas, under agitation 2 hours, be warmed up to 220oC, by reaction mixture 220oC stirs 1 hour, then under agitation makes the temperature of reactant be elevated to 230oC; Reaction is 230oProceeding 2 hours under the constant temperature of C and the constant voltage of 2.2MPa, remove the water formed and keep constant pressure by moving, reacted rear discharging, prepolymer is in 80oUnder C, vacuum-drying 24 hours, obtain prepolymer product, and described prepolymer product is 250oUnder C, 50Pa vacuum condition, solid-phase tack producing 10 hours, obtain polymeric amide. The relative viscosity of polymeric amide, fusing point and lightness l value arrange in table 1.
Table 1
Continued 1
From the comparison of embodiment 1 ~ 4 and comparative example 1 ~ 13 it may be seen that the lightness l value of embodiment gained 10T resin of the present invention is all more than 78, and the lightness l value of comparative example 6T resinoid is all about 70, and its lightness l value is far below embodiment resin. And in comparative example 10T/66,66 content are when more than 30mol%, the fusing point of polyamide resin is reduced to 250oBelow C, this just means the decline of its thermotolerance, cannot be used for the place that heat resistant requirements is higher, if reflow soldering temperature is more than 270oThe occasion of C.
Embodiment 5 ~ 8 and comparative example 14 ~ 20
By the formula of table 2 by polyamide resin, fire retardant, other auxiliary agents high-speed mixer and mixing evenly after, adding in twin screw extruder by main spout, reinforcing filler is fed by feeding scale side, side, extrudes, crossing water cooling, granulation also obtains described daiamid composition after drying. Wherein, extrusion temperature is 330oC��
In table 2 following table, formula is weight part
As can be seen from the comparison of the embodiment 5 ~ 8 of table 2 and comparative example 14 ~ 20, the composition that the embodiment of the present application prepares has more outstanding lightness l value than the composition that comparative example prepares, its brightness value is better than comparative example, can be applied to and product color is required higher occasion.
Claims (18)
1. a polyamide resin, it is characterised in that, by mole meter, it is made up of following component:
The decamethylene diamine of component A:40-48mol% and the hexanediamine of 2-10mol%;
The terephthalic acid of B component: 40-48mol% and the hexanodioic acid of 2-10mol%.
2. polyamide resin according to claim 1, it is characterised in that, the fusing point of described polyamide resin is higher than 270oC��
3. polyamide resin according to claim 2, it is characterised in that, the fusing point of described polyamide resin is 280-330oC��
4. polyamide resin according to claim 1, it is characterised in that, the brightness value L obtaining colour table after the injection moulding of described polyamide resin is greater than 75.0.
5. polyamide resin according to claim 4, it is characterised in that, the lightness l value obtaining colour table after the injection moulding of described polyamide resin is greater than 76.0.
6. comprise a daiamid composition for the polyamide resin described in the arbitrary item of claim 1 ~ 5, percentage, comprise following component:
Polyamide resin 30 ~ 99.9%;
Reinforcing filler 0 ~ 60%;
Fire retardant 0 ~ 50%;
Other auxiliary agents 0.1 ~ 10%.
7. daiamid composition according to claim 6, it is characterised in that, the shape of described reinforcing filler is threadiness, and its mean length is 0.01-20mm; Its length-to-diameter ratio is 5 ~ 2000:1; The content of described reinforcing filler is 10 ~ 50wt%.
8. daiamid composition according to claim 7, it is characterised in that, the mean length of described reinforcing filler is 0.1 ~ 6mm.
9. daiamid composition according to claim 7, it is characterised in that, the length-to-diameter ratio of described reinforcing filler is 30 ~ 600:1.
10. daiamid composition according to the arbitrary item of claim 7-9, it is characterized in that, described reinforcing filler is inorganic reinforcing filler or organic reinforcing fillers, and described inorganic reinforcing filler is selected from one or more of glass fibre, potassium titanate fiber, the glass fibre of clad, ceramic fiber, wollastonite fibre, metallic carbide fibres, metal-cured fiber, fibrous magnesium silicate, sapphire whisker, silicon carbide fiber, gypsum fiber or boron fibre; Described organic reinforcing fillers is selected from Kevlar and/or carbon fiber.
11. daiamid compositions according to claim 10, it is characterised in that, described inorganic reinforcing filler is glass fibre.
12. daiamid compositions according to claim 6, it is characterized in that, the shape of described reinforcing filler is Non-fibrous, its median size is 0.001��10 ��m, it is selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, agalmatolite, wilkinite, polynite, lithium montmorillonite, synthetic mica, asbestos, silico-aluminate, aluminum oxide, silicon oxide, magnesium oxide, zirconium white, titanium oxide, ferric oxide, calcium carbonate, magnesiumcarbonate, rhombspar, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, granulated glass sphere, ceramic bead, boron nitride, one or more of silicon carbide or silicon-dioxide.
13. daiamid compositions according to claim 12, it is characterised in that, the median size of described reinforcing filler is 0.01��5 ��m.
14. daiamid compositions according to claim 6, it is characterized in that, described fire retardant is halogenated flame retardant or halogen-free flame retardants, and described halogenated flame retardant is selected from one or more of brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, decabromodiphynly oxide, decabromodiphenyl, brominated polycarbonate, full bromine three cyclopentadecane or brominated aromatic cross-linked polymer; Described halogen-free flame retardants is selected from one or more of the fire retardant of nitrogenous flame ratardant, phosphonium flame retardant or nitrogenous and phosphorus; The content of described fire retardant is 10 ~ 40wt%.
15. daiamid compositions according to claim 14, it is characterised in that, described halogenated flame retardant is brominated Polystyrene.
16. daiamid compositions according to claim 14, it is characterised in that, described halogen-free flame retardants is phosphonium flame retardant.
17. daiamid compositions according to claim 16, it is characterized in that, described phosphonium flame retardant be selected from monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene system phosphoric acid ester, butylbenzene system phosphoric acid ester, hypophosphite one or more.
18. daiamid compositions according to claim 17, it is characterised in that, described phosphonium flame retardant is the hypophosphite with following structure formula I:
In formula, R1, R2Identical or different, represent for straight chain or containing the alkyl of 1 ~ 6 carbon atom of side chain and/or aryl or phenyl; The nitrogenous base that M is Mg, Ca, Al, Zn, Bi, Mn, Na, K or has been protonated; M is 1 ~ 3.
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| CN201310721601.7A CN103804683B (en) | 2013-05-20 | 2013-12-24 | A kind of polyamide resin and consisting of daiamid composition |
| PCT/CN2014/070041 WO2014187153A1 (en) | 2013-05-20 | 2014-01-02 | Polyamide resin and polyamide combination formed of same |
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| CN2013101862487 | 2013-05-20 | ||
| CN201310721601.7A CN103804683B (en) | 2013-05-20 | 2013-12-24 | A kind of polyamide resin and consisting of daiamid composition |
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| CN103254424A (en) * | 2013-05-20 | 2013-08-21 | 金发科技股份有限公司 | Polyamide resin and polyamide composition composed thereof |
| FR3019825B1 (en) | 2014-04-15 | 2017-10-27 | Arkema France | THERMOPLASTIC COMPOSITE MATERIAL BASED ON SEMI-CRYSTALLINE POLYAMIDE AND PROCESS FOR PRODUCING THE SAME |
| CN104017204B (en) * | 2014-05-20 | 2017-11-17 | 珠海万通化工有限公司 | A kind of polyamide and the daiamid composition being made from it |
| CN104098900A (en) * | 2014-07-08 | 2014-10-15 | 安徽宁国市高新管业有限公司 | Flame-retardant heat-resisting ageing-resistant cable sheath material |
| CN104262619B (en) * | 2014-09-15 | 2016-07-13 | 浙江理工大学 | A kind of phosphor-containing flame-proof polyamide and preparation method thereof and application |
| CN104262952B (en) * | 2014-09-19 | 2016-03-30 | 金发科技股份有限公司 | A kind of low potential of hydrogen polyamide moulding composition |
| CN105385118B (en) * | 2015-11-18 | 2016-11-09 | 南通开普乐工程塑料有限公司 | A kind of high CTI value fire-retardant reinforced PBT composite material |
| CN112745497A (en) * | 2020-12-29 | 2021-05-04 | 南京开创新材料科技有限公司 | Semi-aromatic polyamide resin and preparation method and application thereof |
| CN113604144B (en) * | 2021-08-09 | 2022-04-05 | 红旗集团江西铜业有限公司 | Hot-melt self-adhesive paint and application thereof in enameled wire |
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2013
- 2013-05-20 CN CN2013101862487A patent/CN103254424A/en active Pending
- 2013-12-24 CN CN201310721601.7A patent/CN103804683B/en active Active
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2014
- 2014-01-02 WO PCT/CN2014/070041 patent/WO2014187153A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735609A (en) * | 2009-12-18 | 2010-06-16 | 金发科技股份有限公司 | Halogen-free fire-retarding reinforced polyamide composition and molded product prepared by using same |
| CN102040830A (en) * | 2010-12-20 | 2011-05-04 | 金发科技股份有限公司 | Polyamide composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103804683A (en) | 2014-05-21 |
| WO2014187153A1 (en) | 2014-11-27 |
| CN103254424A (en) | 2013-08-21 |
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