CN104725845A - Continuous-long-fiber-reinforced high-temperature-resistant nylon composite material and preparation method thereof - Google Patents
Continuous-long-fiber-reinforced high-temperature-resistant nylon composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a continuous-long-fiber-reinforced high-temperature-resistant nylon composite material which is prepared from the following components in percentage by weight: 25-45 wt% of high-temperature-resistant nylon resin, 4-8 wt% of maleic anhydride grafted high-temperature-resistant nylon, 15-35 wt% of continuous reinforcing fiber, 5-15 wt% of flame retardant, 1-5 wt% auxiliary flame retardant, 1-3 wt% of functional group grafted high-density polyethylene, 14-22.5 wt% of composite reinforced self-lubricating anti-wear agent and 0.5-1.0 wt% of processing assistant. The continuous-long-fiber-reinforced high-temperature-resistant nylon composite material with flame retardancy, high wear resistance and high self-lubricating property has sufficient wear resistance, self-lubricating property, mechanical properties, impact resistance, high temperature resistance and dimensional stability, and has favorable flame retardancy. The continuous-long-fiber-reinforced high-temperature-resistant nylon composite material is suitable for various high-temperature slide components and common structural parts with requirements for wear resistance, self-lubricating property and flame retardancy.
Description
Technical field
The invention belongs to high temperature resistant nylon composite material technical field, relate to one and there is flame retardant resistance, high-wearing feature and high self lubricity continuous fiber enhancing high temperature resistant nylon composite material and preparation method thereof.
Background technology
Semi-aromatic and aromatic series high temperature resistant nylon owing to having imported aromatic nucleus in main chain, and thermotolerance and mechanical property improve greatly, and water-intake rate declines, good stability of the dimension.Aromatic series and semi-aromatic high temperature resistant nylon have better wear resisting property in high temperature, very low temperature, high vacuum with under having the occasion of chemical mediator, be especially suitable for use as slide unit as manufactured the driving parts such as gear, turbine, cam, and bearing, lining, guide rail, piston etc. are wear-resisting, anti-friction part and general structural parts.But independent semi-aromatic and semi-aromatic high temperature resistant nylon resins fire retardant performance inadequate, intensity is not high, wear no resistance, in high-speed friction, abrasion loss is large, is difficult to meet the service requirements of the self-lubricating structural timber for a long time under high loads with surface abrasion resistance damage and low frictional properties matter.
Ultrahigh molecular weight polyethylene(UHMWPE) has relatively low frictional coefficient, excellent self-lubricating property and excellent impelling strength and chemical stability, thus weaving is widely used in, papermaking, chemical industry, the fields such as mine and machinery, utilize the snappiness of ultrahigh molecular weight polyethylene(UHMWPE) excellence, self lubricity is improving shock resistance, other performance of nylon can also be improved while reducing water-intake rate, material wear ability etc. is improved as reduced nylon frictional coefficient, in order to improve wear resistance and the self lubricity of high temperature resistant nylon composite material further, adopt the method for adding ultrahigh molecular weight polyethylene(UHMWPE) and the composite lubricated low friction compound of tetrafluoroethylene.Ultrahigh molecular weight polyethylene(UHMWPE) intensity is not high on the other hand, rigidity is less, while its modification of nylon, inevitably bring the reduction of intermingling material rigidity and intensity, in order to make material, there is excellent toughness, there is again high rigidity and intensity simultaneously, can be strengthened by inorganic nano-particle, whisker and fiber.In order to improve self lubricity and the wear resistance of high temperature resistant nylon further, also add tetrafluoroethylene, because tetrafluoroethylene is the polymkeric substance of difficult combustion, it reduces the addition of fire retardant while raising composite material self-lubricating and wear resistance.
Potassium titanate crystal whisker is good especially for the reinforced effects strengthening polymkeric substance, can be used for lightweight, high specific strength, the wear-resisting enhancing polymer composites of developing various novel high-level, and be applicable to making different shape complexity, thin-walled, showing bright and clean beautiful accurate reinforcing member.Nano silicon not only can improve the wear resistance of matrix material, and can improve the mechanical property of matrix material, especially can improve the shock strength of matrix material greatly.
Compared with extruding fiber reinforced high-temperature-resistant nylon composite materials with conventional twin screw, adopt the dipping coating equipment of continuous fiber reinforced thermoplastic material, in gained fiber reinforced high-temperature-resistant nylon composite materials particle, roving glass fiber is arranged in parallel with each other along composite material granular length direction, and length is identical with composite material granular length, matrix material has better mechanical property, thermotolerance and dimensional stability.
Patent CN 101134844 A provides a kind of nylon 66 composition that can be used for weaving without fiber shuttle, also ultrahigh molecular weight polyethylene(UHMWPE) has been used as anti-wear agent in its patent, but do not use potassium titanate crystal whisker and tetrafluoroethylene, its body material is also only PA66 and PA6, does not use high temperature resistant nylon; Patent CN 1607219 A provides a kind of high self-lubricating, wear-resisting, Reinforced Nylon engineering plastic alloy and manufacture method, although its patent has also used glass microballon, potassium titanate crystal whisker, tetrafluoroethylene and ultrahigh molecular weight polyethylene(UHMWPE), but it is not used continuous fibre and strengthens, do not adopt the dipping coating equipment of continuous fiber reinforced thermoplastic material to prepare matrix material yet; Patent CN 101134844 A provides a kind of flame-proof abrasion-resistant semi-fragrant polyamide composition, although used heat resistant polyamide in its patent, does not strengthen with continuous fiber, and anti-wear agent used is also different with self-lubricating agent.
Summary of the invention
The object of this invention is to provide one and there is flame retardant resistance, high-wearing feature and high self lubricity continuous fiber enhancing high temperature resistant nylon composite material and preparation method thereof.
In order to achieve the above object, the present invention adopts following technical scheme:
The invention provides a kind of continuous fiber and strengthen high temperature resistant nylon composite material, be made up of the component comprising following weight percentage:
It is semi-aromatic between 290 ~ 330 DEG C and one or more in all aromatic nylon that described high temperature resistant nylon resin is selected from fusing point; Wherein: described semi-aromatic high temperature resistant nylon is one or more in poly-paraphenylene terephthalamide's decamethylene diamine, poly-phthalyl nonamethylene diamine, poly-hexamethylene terephthalamide-co-hexamethylene adipamide multipolymer, poly-paraphenylene terephthalamide's nonamethylene diamine, poly-paraphenylene terephthalamide 12 carbon diamines or poly-phthalyl decamethylene diamine; Described all aromatic high temperature resistant nylon is one or both the composition in polyphthalamide or poly-terephthaloyl Ursol D.
High temperature resistant nylon matrix in described maleic anhydride graft high temperature resistant nylon is one or more in semi-aromatic or all aromatic nylon; Wherein: described semi-aromatic high temperature resistant nylon is one or more in poly-paraphenylene terephthalamide's decamethylene diamine, poly-phthalyl nonamethylene diamine, poly-hexamethylene terephthalamide-co-hexamethylene adipamide multipolymer, poly-paraphenylene terephthalamide's nonamethylene diamine, poly-paraphenylene terephthalamide 12 carbon diamines or poly-phthalyl decamethylene diamine; Described all aromatic high temperature resistant nylon is one or both the composition in polyphthalamide or poly-terephthaloyl Ursol D.
Described continuous fortifying fibre is one or more in continuous long glass fiber, continuous long basalt fibre, continuous long carbon fiber or continuous long aramid fiber, and Fibre diameter is 9 ~ 13 μm; Preferred continuous long basalt fibre.
Described fire retardant is one or more in phosphorus flame retardant or bromide fire retardant.
Described phosphorus flame retardant is one or more in hypo-aluminum orthophosphate, diethyl hypo-aluminum orthophosphate, phenyl hypo-aluminum orthophosphate, high temperature resistant red phosphorus combustion inhibitor master batch, polyphenylene phosphonic acids sulfobenzide ester, Melamine Polyphosphate or two caged phosphinate.
Described bromide fire retardant is one or more in brominated Polystyrene, ethylene two tetrabromophthalate imide, phenoxy group tetrabromobisphenol A carbonic ester oligopolymer or tribromophenoxy tetrabromobisphenol A carbonic ester oligopolymer.
The matrix resin of described high temperature resistant red phosphorus combustion inhibitor master batch is one or both the composition in poly-succinyl hexanediamine or poly-terephthaloyl Ursol D, and wherein red phosphorus content is 65wt%.
Described auxiliary flame retardant is one or more in antimonous oxide, zinc borate, sodium antimonate and lanthanum sesquioxide rare-earth oxide.
Described functional group grafted high density polyethylene is one or both the mixture in maleic anhydride graft high density polyethylene(HDPE) (HDPE-g-MAH) or glycidyl methacrylate graft high density polyethylene(HDPE) (HDPE-g-GMA).
Described weight percentage be 14 ~ 22.5% the agent of composite strengthening self-lubricating abrasion-resistant be the nano silicon (SiO of 1 ~ 3.5wt% by the weight percentage accounting for continuous fiber and strengthen the gross weight of high temperature resistant nylon composite material all components
2), account for potassium titanate crystal whisker that weight percentage that continuous fiber strengthens the gross weight of high temperature resistant nylon composite material all components is 3 ~ 5wt%, account for polytetrafluoroethylene (PTFE) that weight percentage that continuous fiber strengthens the gross weight of high temperature resistant nylon composite material all components is 4 ~ 6wt% and account for ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) composition that weight percentage that continuous fiber strengthens the gross weight of high temperature resistant nylon composite material all components is 6 ~ 8wt%.
The median size of described nano silicon is 30nm, and specific surface area is 600m
2/ g, loose density is 0.08g/cm
3, real density is 2.2g/cm
3.
The diameter of described potassium titanate crystal whisker is 0.1 ~ 0.5 μm, length is 3 ~ 15 μm.
The molecular weight of described ultrahigh molecular weight polyethylene(UHMWPE) is greater than 1,500,000.
Described weight percentage be 0.5 ~ 1% processing aid be the oxidation inhibitor of 0.25 ~ 0.5wt% and to account for weight percentage that continuous fiber strengthens the gross weight of high temperature resistant nylon composite material all components be that the lubricant of 0.25 ~ 0.5wt% forms by the weight percentage accounting for continuous fiber and strengthen the gross weight of high temperature resistant nylon composite material all components.
Described oxidation inhibitor is β-(3; 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester (antioxidant 1076) of propionic acid, N; one or more in N '-bis--(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (oxidation inhibitor 1098) or three [2.4-di-tert-butyl-phenyl] phosphorous acid ester (irgasfos 168s).
Described lubricant is one or both the composition in ultra-high molecular weight polysiloxane or pentaerythritol stearate.
Described continuous fiber strengthens high temperature resistant nylon composite material, and fiber is arranged in parallel with each other along composite material granular length direction, and length is identical with composite material granular length.
Present invention also offers the preparation method that a kind of above-mentioned continuous fiber strengthens high temperature resistant nylon composite material, comprise the following steps:
Be the high temperature resistant nylon resin of 25 ~ 45wt% by weight percentage, the weight percentage maleic anhydride graft high temperature resistant nylon that is 4 ~ 8wt%, the weight percentage fire retardant that is 5 ~ 15wt%, the weight percentage auxiliary flame retardant that is 1 ~ 5wt%, the weight percentage functional group's grafted high density polyethylene that is 1 ~ 3wt%, weight percentage be the composite strengthening self-lubricating abrasion-resistant agent of 14 ~ 22.5wt% and weight percentage be the processing aid of 0.5 ~ 1.0wt%, mix 5 ~ 15 minutes; The material mixed being added design temperature is that the twin screw extruder upstream addition mouth of 275 ~ 315 DEG C is mixing; Continuous fortifying fibre is added long fine coating machine die head, carry out infiltration coated, fibre content is adjusted to 15 ~ 35wt% by the engine speed of twin screw extruder and feeding frequency, is 11 ~ 13mm by adjust the pulling speed of dicing machine be the length that 4 ~ 6m/min controls pellet; Through cooling, traction, pelletizing, obtain continuous fiber and strengthen high temperature resistant nylon composite material.
The engine speed of described twin screw extruder is 200 ~ 300 turns/min, and feeding frequency is 10 ~ 20Hz.
Described high temperature resistant nylon resin need be in 100 DEG C of loft drier in temperature, dry 6h.
Described maleic anhydride graft high temperature resistant nylon, described fire retardant, described auxiliary flame retardant, described functional group grafted high density polyethylene, the agent of described composite strengthening self-lubricating abrasion-resistant need be in 80 DEG C of loft drier in temperature, dry 4h.
The present invention compared with the existing technology, has the following advantages and beneficial effect:
1, the present invention adopts and forms composite self-lubricating anti-wear agent by nano silicon, potassium titanate crystal whisker, tetrafluoroethylene and ultrahigh molecular weight polyethylene(UHMWPE), nano silicon and potassium titanate crystal whisker not only have enhancement but also have wear-resisting effect, make matrix material not sacrifice its mechanical property while having wear resistance; The wear resistance that tetrafluoroethylene and ultrahigh molecular weight polyethylene(UHMWPE) can increase matrix material can improve self lubricity again.
2, the present invention adopts maleic anhydride graft high temperature resistant nylon as the compatilizer of nylon and fiber, and improve the bonding force between nylon and fiber interface, nylon and fiber can bond together by compatilizer firmly, thus improve the mechanical property of matrix material.
3, the present invention adopts the dipping coating equipment of continuous fiber reinforced thermoplastic material, obtained flame retardant resistance, high self lubricity and wear resistance and have in the high temperature resistant nylon composite material particle of high strength and thermotolerance, roving glass fiber is arranged in parallel with each other along composite material granular length direction, and length is identical with composite material granular length, impart the better mechanical property of matrix material, thermotolerance and dimensional stability.
What 4, prepared by the present invention have flame retardant resistance, high-wearing feature and high self lubricity continuous fiber strengthens high temperature resistant nylon composite material and has enough wear resistancies, self lubricity, mechanical property, shock-resistance, high thermal resistance and dimensional stability, has good flame retardant resistance simultaneously; Be applicable to various high temperature and have the slide unit of requirement and general structural parts to wear resistance, self lubricity and flame retardant resistance.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.
Be below the embodiment with high-wearing feature and high self lubricity continuous fiber enhancing high temperature resistant nylon composite material and preparation method thereof of the present invention, but therefore do not limit protection scope of the present invention.
The fusing point of high temperature resistant nylon resin used is below 290 ~ 330 DEG C.
The Fibre diameter of continuous fortifying fibre used is below 9 ~ 13 μm.
The red phosphorus content of high temperature resistant red phosphorus combustion inhibitor used is below 65wt%.
The median size of nano silicon used is below 30nm, and specific surface area is 600m
2/ g, loose density is 0.08g/cm
3, real density is 2.2g/cm
3.
The diameter of potassium titanate crystal whisker used is below 0.1 ~ 0.5 μm, length is 3 ~ 15 μm.
The molecular weight of ultrahigh molecular weight polyethylene(UHMWPE) used is below greater than 1,500,000.
Embodiment 1
(1) poly-paraphenylene terephthalamide's decamethylene diamine being placed in temperature is 100 DEG C of loft drier, dry 6h; Maleic anhydride graft is gathered paraphenylene terephthalamide's decamethylene diamine, diethyl hypo-aluminum orthophosphate, lanthanum sesquioxide, HDPE-g-MAH, nano silicon, tetrafluoroethylene and ultrahigh molecular weight polyethylene(UHMWPE) agent and be placed in 80 DEG C of loft drier respectively, dry 4h;
(2) 35wt% is gathered paraphenylene terephthalamide's decamethylene diamine, 5wt% maleic anhydride graft gathers paraphenylene terephthalamide's decamethylene diamine, 12wt% diethyl hypo-aluminum orthophosphate, 3wt% lanthanum sesquioxide, 2wt%HDPE-g-MAH, 2.25wt% nano silicon, 4wt% potassium titanate crystal whisker, 1098 oxidation inhibitor of 5wt%PTFE, 7wt%UHMWPE, 0.25wt%, 0.25wt%168 oxidation inhibitor, 0.25wt% ultra-high molecular weight polysiloxane emollient join in high-speed mixer successively and mix, mixing time is 12 minutes;
(3) material will mixed in (2), adds and is set as that the twin screw extruder upstream addition mouth of 275-315 DEG C is mixing; Continuous long basalt fibre is added long fine coating machine die head, carry out infiltration coated, basalt fibre content is adjusted to 24wt% by the engine speed of twin screw extruder and feeding frequency, and wherein the engine speed of twin screw extruder is 250 turns/min, and feeding frequency is 16Hz.The length being controlled pellet by the pulling speed 5m/min adjusting dicing machine is 12mm; Through cooling, traction, pelletizing, obtain that there is the continuous long basalt fibre of flame retardant resistance, high-wearing feature and high self lubricity and strengthen poly-paraphenylene terephthalamide's decamethylene diamine matrix material.The prepared continuous long basalt fibre of flame retardant resistance, high-wearing feature and high self lubricity that has strengthens poly-paraphenylene terephthalamide's decamethylene diamine matrix material, and fiber is arranged in parallel with each other along composite material granular length direction, and length is identical with composite material granular length.
Embodiment 2
(1) poly-hexamethylene terephthalamide-co-hexamethylene adipamide multipolymer being placed in temperature is 100 DEG C of loft drier, dry 6h; Maleic anhydride graft is gathered hexamethylene terephthalamide-co-hexamethylene adipamide multipolymer, phenyl hypo-aluminum orthophosphate, lanthanum sesquioxide, HDPE-g-MAH, nano silicon, tetrafluoroethylene and ultrahigh molecular weight polyethylene(UHMWPE) agent and be placed in 80 DEG C of loft drier respectively, dry 4h;
(2) 35wt% is gathered hexamethylene terephthalamide-co-hexamethylene adipamide multipolymer, 5wt% maleic anhydride graft gathers hexamethylene terephthalamide-co-hexamethylene adipamide multipolymer, 12wt% phenyl hypo-aluminum orthophosphate, 3wt% lanthanum sesquioxide, 2wt%HDPE-g-MAH, 2.25wt% nano silicon, 4wt% potassium titanate crystal whisker, 1098 oxidation inhibitor of 5wt%PTFE, 7wt%UHMWPE, 0.25wt%, 0.25wt%168 oxidation inhibitor, 0.25wt% ultra-high molecular weight polysiloxane emollient join in high-speed mixer successively and mix, mixing time is 12 minutes;
(3) material will mixed in (2), adds and is set as that the twin screw extruder upstream addition mouth of 275-315 DEG C is mixing; Continuous long basalt fibre is added long fine coating machine die head, carry out infiltration coated, basalt fibre content is adjusted to 24wt% by the engine speed of twin screw extruder and feeding frequency, and wherein the engine speed of twin screw extruder is 250 turns/min, and feeding frequency is 16Hz.The length being controlled pellet by the pulling speed 5m/min adjusting dicing machine is 12mm; Through cooling, traction, pelletizing, obtain that there is the continuous long basalt fibre of flame retardant resistance, high-wearing feature and high self lubricity and strengthen poly-hexamethylene terephthalamide-co-hexamethylene adipamide copolymer composite.The prepared continuous long basalt fibre of flame retardant resistance, high-wearing feature and high self lubricity that has strengthens poly-hexamethylene terephthalamide-co-hexamethylene adipamide copolymer composite, fiber is arranged in parallel with each other along composite material granular length direction, and length is identical with composite material granular length.
Embodiment 3
(1) poly-paraphenylene terephthalamide's nonamethylene diamine being placed in temperature is 100 DEG C of loft drier, dry 6h; Maleic anhydride graft is gathered paraphenylene terephthalamide's nonamethylene diamine, brominated Polystyrene, antimonous oxide, nano silicon, HDPE-g-MAH, nano silicon, tetrafluoroethylene and ultrahigh molecular weight polyethylene(UHMWPE) agent and be placed in 80 DEG C of loft drier respectively, dry 4h;
(2) 35wt% is gathered paraphenylene terephthalamide's nonamethylene diamine, 6wt% maleic anhydride graft gathers paraphenylene terephthalamide's nonamethylene diamine, 10wt% brominated Polystyrene, 3wt% antimonous oxide, 2wt%HDPE-g-MAH, 2.25wt% nano silicon, 4wt% potassium titanate crystal whisker, 1076 oxidation inhibitor of 5wt%PTFE, 7wt%UHMWPE, 0.25wt%, 0.25wt%168 oxidation inhibitor, 0.25wt% pentaerythritol stearate lubricant join in high-speed mixer successively and mix, mixing time is 10 minutes;
(3) material will mixed in (2), adds and is set as that the twin screw extruder upstream addition mouth of 275-315 DEG C is mixing; Continuous long basalt fibre is added long fine coating machine die head, carry out infiltration coated, basalt fibre content is adjusted to 25wt% by the engine speed of twin screw extruder and feeding frequency, and wherein the engine speed of twin screw extruder is 250 turns/min, and feeding frequency is 15Hz.The length being controlled pellet by the pulling speed 5m/min adjusting dicing machine is 12mm; Through cooling, traction, pelletizing, obtain that there is the continuous long basalt fibre of flame retardant resistance, high-wearing feature and high self lubricity and strengthen poly-paraphenylene terephthalamide's nonamethylene diamine matrix material.The prepared continuous long basalt fibre of flame retardant resistance, high-wearing feature and high self lubricity that has strengthens poly-paraphenylene terephthalamide's nonamethylene diamine matrix material, and fiber is arranged in parallel with each other along composite material granular length direction, and length is identical with composite material granular length.
Embodiment 4
(1) polyphthalamide being placed in temperature is 100 DEG C of loft drier, dry 6h; Maleic anhydride graft polyphthalamide, tribromophenoxy tetrabromobisphenol A carbonic ester oligopolymer, zinc borate, HDPE-g-MAH, nano silicon, tetrafluoroethylene and ultrahigh molecular weight polyethylene(UHMWPE) agent are placed in 80 DEG C of loft drier respectively, dry 4h;
(2) 1076 oxidation inhibitor of 35wt% polyphthalamide, 6wt% maleic anhydride graft polyphthalamide, 10wt% tribromophenoxy tetrabromobisphenol A carbonic ester oligopolymer, 3wt% zinc borate, 2wt%HDPE-g-MAH, 2.25wt% nano silicon, 4wt% potassium titanate crystal whisker, 5wt%PTFE, 7wt%UHMWPE, 0.25wt%, 0.125wt%168 oxidation inhibitor, 0.25wt% pentaerythritol stearate and 0.125wt% ultra-high molecular weight polysiloxane emollient are joined in high-speed mixer successively and mix, mixing time is 10 minutes;
(3) material will mixed in (2), adds and is set as that the twin screw extruder upstream addition mouth of 275-315 DEG C is mixing; Continuous long basalt fibre is added long fine coating machine die head, carry out infiltration coated, basalt fibre content is adjusted to 25wt% by the engine speed of twin screw extruder and feeding frequency, and wherein the engine speed of twin screw extruder is 250 turns/min, and feeding frequency is 15Hz.The length being controlled pellet by the pulling speed 5m/min adjusting dicing machine is 12mm; Through cooling, traction, pelletizing, obtain that there is the continuous long basalt fibre of flame retardant resistance, high-wearing feature and high self lubricity and strengthen polyphthalamide composite material.The prepared continuous long basalt fibre of flame retardant resistance, high-wearing feature and high self lubricity that has strengthens polyphthalamide composite material, and fiber is arranged in parallel with each other along composite material granular length direction, and length is identical with composite material granular length.
Embodiment 5
(1) poly-paraphenylene terephthalamide 12 carbon diamines being placed in temperature is 100 DEG C of loft drier, dry 6h; Maleic anhydride graft is gathered paraphenylene terephthalamide 12 carbon diamines, high temperature resistant red phosphorus combustion inhibitor master batch, tribromophenoxy tetrabromobisphenol A carbonic ester oligopolymer, sodium antimonate, HDPE-g-GMA, nano silicon, tetrafluoroethylene and ultrahigh molecular weight polyethylene(UHMWPE) agent and be placed in 80 DEG C of loft drier respectively, dry 4h;
(2) 45wt% is gathered paraphenylene terephthalamide 12 carbon diamines, 4wt% maleic anhydride graft gathers paraphenylene terephthalamide 12 carbon diamines, 5wt% is high temperature resistant red phosphorus combustion inhibitor master batch (matrix resin of high temperature resistant red phosphorus combustion inhibitor master batch is poly-succinyl hexanediamine), 10wt% tribromophenoxy tetrabromobisphenol A carbonic ester oligopolymer, 5wt% sodium antimonate, 1wt%HDPE-g-GMA, 1wt% nano silicon, 3wt% potassium titanate crystal whisker, 4wt%PTFE, 6wt%UHMWPE, 1076 oxidation inhibitor of 0.25wt%, 0.25wt%168 oxidation inhibitor and 0.5wt% pentaerythritol stearate lubricant join in high-speed mixer successively and mix, mixing time is 15 minutes,
(3) material will mixed in (2), adds and is set as that the twin screw extruder upstream addition mouth of 275-315 DEG C is mixing; Continuous long carbon fiber is added long fine coating machine die head, carry out infiltration coated, carbon fiber content is adjusted to 15wt% by the engine speed of twin screw extruder and feeding frequency, and wherein the engine speed of twin screw extruder is 300 turns/min, and feeding frequency is 20Hz.The length being controlled pellet by the pulling speed 4m/min adjusting dicing machine is 13mm; Through cooling, traction, pelletizing, obtain that there is flame retardant resistance, high-wearing feature and high self lubricity continuous long carbon fiber and strengthen poly-paraphenylene terephthalamide 12 carbon diamines matrix material.Prepared have flame retardant resistance, high-wearing feature and high self lubricity continuous long carbon fiber strengthen poly-paraphenylene terephthalamide 12 carbon diamines matrix material, and fiber is arranged in parallel with each other along composite material granular length direction, and length is identical with composite material granular length.
Embodiment 6
(1) poly-phthalyl decamethylene diamine being placed in temperature is 100 DEG C of loft drier, dry 6h; Maleic anhydride graft is gathered phthalyl decamethylene diamine, the two tetrabromophthalate imide of ethylene, zinc borate, HDPE-g-GMA, nano silicon, tetrafluoroethylene and ultrahigh molecular weight polyethylene(UHMWPE) agent and be placed in 80 DEG C of loft drier respectively, dry 4h;
(2) 25wt% is gathered phthalyl decamethylene diamine, 8wt% maleic anhydride graft gathers phthalyl decamethylene diamine, the two tetrabromophthalate imide of 5wt% ethylene, 1wt% zinc borate, 3wt%HDPE-g-GMA, 3.5wt% nano silicon, 5wt% potassium titanate crystal whisker, 1098 oxidation inhibitor of 6wt%PTFE, 8wt%UHMWPE, 0.15wt%, 0.1wt%168 oxidation inhibitor and 0.25wt% ultra-high molecular weight polysiloxane emollient join in high-speed mixer successively and mix, mixing time is 5 minutes;
(3) material will mixed in (2), adds and is set as that the twin screw extruder upstream addition mouth of 275-315 DEG C is mixing; Continuous long glass fiber is added long fine coating machine die head, carry out infiltration coated, content of glass fiber is adjusted to 35wt% by the engine speed of twin screw extruder and feeding frequency, and wherein the engine speed of twin screw extruder is 200 turns/min, and feeding frequency is 15Hz.The length being controlled pellet by the pulling speed 6m/min adjusting dicing machine is 11mm; Through cooling, traction, pelletizing, obtain that there is flame retardant resistance, high-wearing feature and high self lubricity continuous long glass fiber and strengthen poly-phthalyl decamethylene diamine matrix material.Prepared have flame retardant resistance, high-wearing feature and high self lubricity continuous long glass fiber strengthen poly-phthalyl decamethylene diamine matrix material, and fiber is arranged in parallel with each other along composite material granular length direction, and length is identical with composite material granular length.
Embodiment 7
(1) poly-phthalyl hexanediamine-co-hexamethylene adipamide multipolymer being placed in temperature is 100 DEG C of loft drier, dry 6h; Maleic anhydride graft is gathered phthalyl hexanediamine-co-hexamethylene adipamide multipolymer, two caged phosphinate, lanthanum sesquioxide, HDPE-g-MAH, nano silicon, tetrafluoroethylene and ultrahigh molecular weight polyethylene(UHMWPE) agent and be placed in 80 DEG C of loft drier respectively, dry 4h;
(2) 35wt% is gathered phthalyl hexanediamine-co-hexamethylene adipamide multipolymer, 6wt% maleic anhydride graft gathers phthalyl hexanediamine-co-hexamethylene adipamide multipolymer, the two caged phosphinate of 9wt%, 2wt% lanthanum sesquioxide, 2wt%HDPE-g-MAH, 2.25wt% nano silicon, 3wt% potassium titanate crystal whisker, 1098 oxidation inhibitor of 4wt%PTFE, 6wt%UHMWPE, 0.25wt%, 0.25wt%168 oxidation inhibitor and 0.25wt% ultra-high molecular weight polysiloxane emollient join in high-speed mixer successively and mix, mixing time is 8 minutes;
(3) material will mixed in (2), adds and is set as that the twin screw extruder upstream addition mouth of 275-315 DEG C is mixing; Continuous long basalt fibre is added long fine coating machine die head, carry out infiltration coated, basalt fibre content is adjusted to 30wt% by the engine speed of twin screw extruder and feeding frequency, and wherein the engine speed of twin screw extruder is 200 turns/min, and feeding frequency is 12Hz.The length being controlled pellet by the pulling speed 5m/min adjusting dicing machine is 12mm; Through cooling, traction, pelletizing, obtain that there is the continuous long basalt fibre of flame retardant resistance, high-wearing feature and high self lubricity and strengthen poly-phthalyl hexanediamine-co-hexamethylene adipamide copolymer composite.The prepared continuous long basalt fibre of flame retardant resistance, high-wearing feature and high self lubricity that has strengthens poly-phthalyl hexanediamine-co-hexamethylene adipamide copolymer composite, fiber is arranged in parallel with each other along composite material granular length direction, and length is identical with composite material granular length.
Embodiment 8
(1) poly-terephthaloyl Ursol D being placed in temperature is 100 DEG C of loft drier, dry 6h; Maleic anhydride graft is gathered terephthaloyl Ursol D, phenoxy group tetrabromobisphenol A carbonic ester oligopolymer, zinc borate, HDPE-g-MAH, nano silicon, tetrafluoroethylene and ultrahigh molecular weight polyethylene(UHMWPE) agent and be placed in 80 DEG C of loft drier respectively, dry 4h;
(2) 45wt% is gathered terephthaloyl Ursol D, 4wt% maleic anhydride graft gathers terephthaloyl Ursol D, 15wt% phenoxy group tetrabromobisphenol A carbonic ester oligopolymer, 5wt% zinc borate, 1wt%HDPE-g-MAH, 1wt% nano silicon, 3wt% potassium titanate crystal whisker, 1098 oxidation inhibitor of 4wt%PTFE, 6wt%UHMWPE, 0.25wt%, 0.25wt%168 oxidation inhibitor and 0.5wt% pentaerythritol stearate lubricant join in high-speed mixer successively and mix, mixing time is 15 minutes;
(3) material will mixed in (2), adds and is set as that the twin screw extruder upstream addition mouth of 275-315 DEG C is mixing; Continuous long aramid fiber is added long fine coating machine die head, carry out infiltration coated, aramid fiber content is adjusted to 15wt% by the engine speed of twin screw extruder and feeding frequency, and wherein the engine speed of twin screw extruder is 300 turns/min, and feeding frequency is 20Hz.The length being controlled pellet by the pulling speed 6m/min adjusting dicing machine is 11mm; Through cooling, traction, pelletizing, obtain that there is the continuous long aramid fiber of flame retardant resistance, high-wearing feature and high self lubricity and strengthen poly-terephthaloyl Ursol D matrix material.The prepared continuous long aramid fiber of flame retardant resistance, high-wearing feature and high self lubricity that has strengthens poly-terephthaloyl Ursol D matrix material, and fiber is arranged in parallel with each other along composite material granular length direction, and length is identical with composite material granular length.
Embodiment 9
(1) poly-phthalyl nonamethylene diamine being placed in temperature is 100 DEG C of loft drier, dry 6h; Maleic anhydride graft is gathered phthalyl nonamethylene diamine, polyphenylene phosphonic acids sulfobenzide ester, lanthanum sesquioxide, HDPE-g-MAH, nano silicon, tetrafluoroethylene and ultrahigh molecular weight polyethylene(UHMWPE) agent and be placed in 80 DEG C of loft drier respectively, dry 4h;
(2) 35wt% is gathered phthalyl nonamethylene diamine, 6wt% maleic anhydride graft gathers phthalyl nonamethylene diamine, 9wt% polyphenylene phosphonic acids sulfobenzide ester, 2wt% lanthanum sesquioxide, 2wt%HDPE-g-MAH, 2.25wt% nano silicon, 3wt% potassium titanate crystal whisker, 1098 oxidation inhibitor of 4wt%PTFE, 6wt%UHMWPE, 0.25wt%, 0.25wt%168 oxidation inhibitor and 0.25wt% ultra-high molecular weight polysiloxane emollient join in high-speed mixer successively and mix, mixing time is 8 minutes;
(3) material will mixed in (2), adds and is set as that the twin screw extruder upstream addition mouth of 275-315 DEG C is mixing; Continuous long basalt fibre is added long fine coating machine die head, carry out infiltration coated, basalt fibre content is adjusted to 30wt% by the engine speed of twin screw extruder and feeding frequency, and wherein the engine speed of twin screw extruder is 250 turns/min, and feeding frequency is 10Hz.The length being controlled pellet by the pulling speed 4m/min adjusting dicing machine is 13mm; Through cooling, traction, pelletizing, obtain that there is the continuous long basalt fibre of flame retardant resistance, high-wearing feature and high self lubricity and strengthen poly-phthalyl nonamethylene diamine matrix material.The prepared continuous long basalt fibre of flame retardant resistance, high-wearing feature and high self lubricity that has strengthens poly-phthalyl nonamethylene diamine matrix material, and fiber is arranged in parallel with each other along composite material granular length direction, and length is identical with composite material granular length.
Embodiment 10
(1) poly-paraphenylene terephthalamide's decamethylene diamine and polyphthalamide being placed in temperature is 100 DEG C of loft drier, dry 6h; Maleic anhydride graft polyphthalamide, maleic anhydride graft polyphthalamide, hypo-aluminum orthophosphate, Melamine Polyphosphate, lanthanum sesquioxide, HDPE-g-MAH, HDPE-g-GMA, nano silicon, tetrafluoroethylene and ultrahigh molecular weight polyethylene(UHMWPE) agent are placed in 80 DEG C of loft drier respectively, dry 4h;
(2) 20wt% is gathered paraphenylene terephthalamide's decamethylene diamine, 20wt% polyphthalamide, 3wt% maleic anhydride graft gathers paraphenylene terephthalamide's decamethylene diamine, 3wt% maleic anhydride graft polyphthalamide, 8wt% hypo-aluminum orthophosphate, 5wt% Melamine Polyphosphate, 3wt% lanthanum sesquioxide, 1wt%HDPE-g-MAH, 1wt%HDPE-g-GMA, 2.25wt% nano silicon, 3wt% potassium titanate crystal whisker, 4wt%PTFE, 6wt%UHMWPE, 1098 oxidation inhibitor of 0.25wt%, 0.25wt%168 oxidation inhibitor and 0.25wt% ultra-high molecular weight polysiloxane emollient join in high-speed mixer successively and mix, mixing time is 15 minutes,
(3) material will mixed in (2), adds and is set as that the twin screw extruder upstream addition mouth of 275-315 DEG C is mixing; Continuous long basalt fibre is added long fine coating machine die head, carry out infiltration coated, basalt fibre content is adjusted to 20wt% by the engine speed of twin screw extruder and feeding frequency, and wherein the engine speed of twin screw extruder is 300 turns/min, and feeding frequency is 15Hz.The length being controlled pellet by the pulling speed 6m/min adjusting dicing machine is 11mm; Through cooling, traction, pelletizing, obtain that there is the continuous long basalt fibre of flame retardant resistance, high-wearing feature and high self lubricity and strengthen poly-paraphenylene terephthalamide's decamethylene diamine/polyphthalamide composite material.The prepared continuous long basalt fibre of flame retardant resistance, high-wearing feature and high self lubricity that has strengthens poly-paraphenylene terephthalamide's decamethylene diamine/polyphthalamide composite material, fiber is arranged in parallel with each other along composite material granular length direction, and length is identical with composite material granular length.
Comparative example 1
(1) poly-paraphenylene terephthalamide's decamethylene diamine being placed in temperature is 100 DEG C of loft drier, dry 6h; Maleic anhydride graft is gathered paraphenylene terephthalamide's decamethylene diamine, diethyl hypo-aluminum orthophosphate, lanthanum sesquioxide be placed in 80 DEG C of loft drier, dry 4h respectively;
(2) 55.25wt% is gathered paraphenylene terephthalamide's decamethylene diamine, 5wt% maleic anhydride graft gathers paraphenylene terephthalamide's decamethylene diamine, 12wt% diethyl hypo-aluminum orthophosphate, 3wt% lanthanum sesquioxide, 0.25wt% 1098,0.25wt%168 oxidation inhibitor, 0.25wt% ultra-high molecular weight polysiloxane emollient join in high-speed mixer successively and mix, mixing time is 12 minutes;
(3) material will mixed in (2), adds and is set as that the twin screw extruder upstream addition mouth of 275-315 DEG C is mixing; Continuous long basalt fibre is added long fine coating machine die head, carry out infiltration coated, basalt fibre content is adjusted to 24wt% by the engine speed of twin screw extruder and feeding frequency, and wherein the engine speed of twin screw extruder is 250 turns/min, and feeding frequency is 16Hz.The length being controlled pellet by the pulling speed 5m/min adjusting dicing machine is 12mm; Through cooling, traction, pelletizing, obtain continuous long basalt fibre and strengthen poly-paraphenylene terephthalamide's decamethylene diamine matrix material.Prepared continuous long basalt fibre strengthens poly-paraphenylene terephthalamide's decamethylene diamine matrix material, and fiber is arranged in parallel with each other along composite material granular length direction, and length is identical with composite material granular length.
Comparative example 2
(1) poly-hexamethylene terephthalamide-co-hexamethylene adipamide multipolymer being placed in temperature is 100 DEG C of loft drier, dry 6h; Maleic anhydride graft is gathered hexamethylene terephthalamide-co-hexamethylene adipamide multipolymer, phenyl hypo-aluminum orthophosphate, lanthanum sesquioxide, HDPE-g-MAH, nano silicon, tetrafluoroethylene and ultrahigh molecular weight polyethylene(UHMWPE) agent and be placed in 80 DEG C of loft drier respectively, dry 4h;
(2) 35wt% is gathered hexamethylene terephthalamide-co-hexamethylene adipamide multipolymer, 5wt% maleic anhydride graft gathers hexamethylene terephthalamide-co-hexamethylene adipamide multipolymer, 12wt% phenyl hypo-aluminum orthophosphate, 3wt% lanthanum sesquioxide, 2wt%HDPE-g-MAH, 2.25wt% nano silicon, 4wt% potassium titanate crystal whisker, 1098 oxidation inhibitor of 5wt%PTFE, 7wt%UHMWPE, 0.25wt%, 0.25wt%168 oxidation inhibitor, 0.25wt% ultra-high molecular weight polysiloxane emollient join in high-speed mixer successively and mix, mixing time is 12 minutes;
(3) material will mixed in (2), adds and is set as that the twin screw extruder upstream addition mouth of 275-315 DEG C is mixing; Added by long basalt fibre and introduce twin screw extruder downstream macrofiber charging opening, the amount controlling basalt fibre is 24wt%, and wherein the engine speed of twin screw extruder is 250 turns/min, and feeding frequency is 13Hz; Through extruding check rod, namely granulation obtains matrix material.
The embodiment with high-wearing feature and high self lubricity continuous fiber enhancing high temperature resistant nylon composite material obtained by this invention and comparative example performance see the following form 1:
Table 1
Drawn the following conclusions by the test data of table 1: by upper table performance, (1) can find out that the properties of embodiment is best, for most preferred embodiment, the continuous fiber of preparation strengthens high temperature resistant nylon composite material mechanical property and heat-drawn wire is high, abrasion of rolling are little; (2) agent of composite strengthening self-lubricating abrasion-resistant is not added in the matrix material prepared by comparative example 1, add the properties of the embodiment 1 of composite strengthening self-lubricating abrasion-resistant agent all higher than comparative example 1, especially: both rolling wear index are with the biggest gap, illustrate that the agent of composite strengthening self-lubricating abrasion-resistant not only has the effect reducing abrasion of rolling, the mechanical property of matrix material can also be kept; The vertical combustion of embodiment 1 is FV-0 level, and the vertical combustion of comparative example 1 does not pass through, and the agent of composite strengthening self-lubricating abrasion-resistant is described, also has the effect reducing amount of flame-retardant agent; (3) method of matrix material prepared by comparative example 2 is traditional twin screw extrusion by melting; Embodiment 2 is the dipping coating equipment adopting continuous fiber reinforced thermoplastic material, flame retardant resistance, high self lubricity and wear resistance obtained by embodiment 2 and have in the high temperature resistant nylon composite material particle of high strength and thermotolerance, roving glass fiber is arranged in parallel with each other along composite material granular length direction, and length is identical with composite material granular length, the properties of embodiment 2 is all high than comparative example 2 a lot.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (16)
1. continuous fiber strengthens a high temperature resistant nylon composite material, it is characterized in that: be made up of the component comprising following weight percentage:
2. continuous fiber according to claim 1 strengthens high temperature resistant nylon composite material, it is characterized in that: it is semi-aromatic between 290 ~ 330 DEG C and one or more in all aromatic nylon that described high temperature resistant nylon resin is selected from fusing point; Wherein: described semi-aromatic high temperature resistant nylon is one or more in poly-paraphenylene terephthalamide's decamethylene diamine, poly-phthalyl nonamethylene diamine, poly-hexamethylene terephthalamide-co-hexamethylene adipamide multipolymer, poly-paraphenylene terephthalamide's nonamethylene diamine, poly-paraphenylene terephthalamide 12 carbon diamines or poly-phthalyl decamethylene diamine; Described all aromatic high temperature resistant nylon is one or both the composition in polyphthalamide or poly-terephthaloyl Ursol D.
3. continuous fiber according to claim 1 strengthens high temperature resistant nylon composite material, it is characterized in that: the high temperature resistant nylon matrix in described maleic anhydride graft high temperature resistant nylon is one or more in semi-aromatic or all aromatic nylon; Wherein: described semi-aromatic high temperature resistant nylon is one or more in poly-paraphenylene terephthalamide's decamethylene diamine, poly-phthalyl nonamethylene diamine, poly-hexamethylene terephthalamide-co-hexamethylene adipamide multipolymer, poly-paraphenylene terephthalamide's nonamethylene diamine, poly-paraphenylene terephthalamide 12 carbon diamines or poly-phthalyl decamethylene diamine; Described all aromatic high temperature resistant nylon is one or both the composition in polyphthalamide or poly-terephthaloyl Ursol D.
4. continuous fiber according to claim 1 strengthens high temperature resistant nylon composite material, it is characterized in that: described continuous fortifying fibre is one or more in continuous long glass fiber, continuous long basalt fibre, continuous long carbon fiber or continuous long aramid fiber, and Fibre diameter is 9 ~ 13 μm; Preferred continuous long basalt fibre.
5. continuous fiber according to claim 1 strengthens high temperature resistant nylon composite material, it is characterized in that: described fire retardant is one or more in phosphorus flame retardant or bromide fire retardant.
6. continuous fiber according to claim 5 strengthens high temperature resistant nylon composite material, it is characterized in that: described phosphorus flame retardant is one or more in hypo-aluminum orthophosphate, diethyl hypo-aluminum orthophosphate, phenyl hypo-aluminum orthophosphate, high temperature resistant red phosphorus combustion inhibitor master batch, polyphenylene phosphonic acids sulfobenzide ester, Melamine Polyphosphate or two caged phosphinate;
Or described bromide fire retardant is one or more in brominated Polystyrene, ethylene two tetrabromophthalate imide, phenoxy group tetrabromobisphenol A carbonic ester oligopolymer or tribromophenoxy tetrabromobisphenol A carbonic ester oligopolymer.
7. continuous fiber according to claim 6 strengthens high temperature resistant nylon composite material, it is characterized in that: the matrix resin of described high temperature resistant red phosphorus combustion inhibitor master batch is one or both the composition in poly-succinyl hexanediamine or poly-terephthaloyl Ursol D, and wherein red phosphorus content is 65wt%.
8. continuous fiber according to claim 1 strengthens high temperature resistant nylon composite material, it is characterized in that: described auxiliary flame retardant is one or more in antimonous oxide, zinc borate, sodium antimonate and lanthanum sesquioxide rare-earth oxide.
9. continuous fiber according to claim 1 strengthens high temperature resistant nylon composite material, it is characterized in that: described functional group grafted high density polyethylene is one or both the mixture in maleic anhydride graft high density polyethylene(HDPE) or glycidyl methacrylate graft high density polyethylene(HDPE).
10. continuous fiber according to claim 1 strengthens high temperature resistant nylon composite material, it is characterized in that: the agent of described composite strengthening self-lubricating abrasion-resistant is the nano silicon of 1 ~ 3.5wt% by the weight percentage accounting for continuous fiber and strengthen the gross weight of high temperature resistant nylon composite material all components, the weight percentage accounting for the gross weight of continuous fiber enhancing high temperature resistant nylon composite material all components is the potassium titanate crystal whisker of 3 ~ 5wt%, account for tetrafluoroethylene that weight percentage that continuous fiber strengthens the gross weight of high temperature resistant nylon composite material all components is 4 ~ 6wt% and account for the ultrahigh molecular weight polyethylene(UHMWPE) composition that weight percentage that continuous fiber strengthens the gross weight of high temperature resistant nylon composite material all components is 6 ~ 8wt%.
11. continuous fibers according to claim 10 strengthen high temperature resistant nylon composite material, it is characterized in that: the median size of described nano silicon is 30nm, and specific surface area is 600m
2/ g, loose density is 0.08g/cm
3, real density is 2.2g/cm
3;
Or the diameter of described potassium titanate crystal whisker be 0.1 ~ 0.5 μm, length is 3 ~ 15 μm;
Or the molecular weight of described ultrahigh molecular weight polyethylene(UHMWPE) is greater than 1,500,000.
12. continuous fibers according to claim 1 strengthen high temperature resistant nylon composite materials, it is characterized in that: described processing aid is the oxidation inhibitor of 0.25 ~ 0.5wt% and to account for weight percentage that continuous fiber strengthens the gross weight of high temperature resistant nylon composite material all components be that the lubricant of 0.25 ~ 0.5wt% forms by the weight percentage accounting for continuous fiber and strengthen the gross weight of high temperature resistant nylon composite material all components.
13. continuous fibers according to claim 12 strengthen high temperature resistant nylon composite material, it is characterized in that: described oxidation inhibitor is β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, N, one or more in N '-bis--(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine or three [2.4-di-tert-butyl-phenyl] phosphorous acid ester;
Or described lubricant is one or both the composition in ultra-high molecular weight polysiloxane or pentaerythritol stearate.
14. continuous fibers according to claim 1 strengthen high temperature resistant nylon composite material, it is characterized in that: described continuous fiber strengthens high temperature resistant nylon composite material, fiber is arranged in parallel with each other along composite material granular length direction, and length is identical with composite material granular length.
15. 1 kinds of arbitrary described continuous fibers of claim 1 to 14 strengthen the preparation method of high temperature resistant nylon composite material, it is characterized in that: comprise the following steps:
Be the high temperature resistant nylon resin of 25 ~ 45wt% by weight percentage, the weight percentage maleic anhydride graft high temperature resistant nylon that is 4 ~ 8wt%, the weight percentage fire retardant that is 5 ~ 15wt%, the weight percentage auxiliary flame retardant that is 1 ~ 5wt%, the weight percentage functional group's grafted high density polyethylene that is 1 ~ 3wt%, weight percentage be the composite strengthening self-lubricating abrasion-resistant agent of 14 ~ 22.5wt% and weight percentage be the processing aid of 0.5 ~ 1.0wt%, mix 5 ~ 15 minutes; The material mixed being added design temperature is that the twin screw extruder upstream addition mouth of 275 ~ 315 DEG C is mixing; Continuous fortifying fibre is added long fine coating machine die head, carry out infiltration coated, fibre content is adjusted to 15 ~ 35wt% by the engine speed of twin screw extruder and feeding frequency, is 11 ~ 13mm by adjust the pulling speed of dicing machine be the length that 4 ~ 6m/min controls pellet; Through cooling, traction, pelletizing, obtain continuous fiber and strengthen high temperature resistant nylon composite material.
16. continuous fibers according to claim 15 strengthen the preparation method of high temperature resistant nylon composite material, it is characterized in that: the engine speed of described twin screw extruder is 200 ~ 300 turns/min, and feeding frequency is 10 ~ 20Hz;
Or described high temperature resistant nylon resin need be in 100 DEG C of loft drier in temperature, dry 6h;
Or described maleic anhydride graft high temperature resistant nylon, described fire retardant, described auxiliary flame retardant, described functional group grafted high density polyethylene, the agent of described composite strengthening self-lubricating abrasion-resistant need be in 80 DEG C of loft drier in temperature, dry 4h.
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| CN109294226A (en) * | 2018-09-07 | 2019-02-01 | 惠州市沃特新材料有限公司 | A kind of fire-retardant PA composite material and preparation method of enhancing |
| CN109929246A (en) * | 2019-03-13 | 2019-06-25 | 金旸（厦门）新材料科技有限公司 | A kind of nylon material and its preparation method and application |
| CN112029280A (en) * | 2020-11-06 | 2020-12-04 | 江苏金发科技新材料有限公司 | Halogen-free flame-retardant polyamide composite material and preparation method thereof |
| CN114437538A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Long glass fiber reinforced nylon composite material and preparation method and application thereof |
| CN115926447A (en) * | 2022-12-13 | 2023-04-07 | 上海和达汽车配件有限公司 | Carbon fiber reinforced nylon material and preparation method and application thereof |
| CN117659691A (en) * | 2023-12-11 | 2024-03-08 | 宁波合裕新材料科技有限公司 | High CTI flame-retardant high-temperature-resistant nylon composite material and preparation method and application thereof |
| CN118006122A (en) * | 2024-01-31 | 2024-05-10 | 金发科技股份有限公司 | Lightweight polyamide composition and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1607219A (en) * | 2003-10-14 | 2005-04-20 | 林安良 | High self-lubricating, high wear resisting, reinforced nylon engineering plastic alloy and method for making same |
| EP1988113A1 (en) * | 2007-05-03 | 2008-11-05 | Ems-Patent Ag | Partially aromatic polyamide moulding masses and their applications |
| CN102120879A (en) * | 2011-02-19 | 2011-07-13 | 本松工程塑料（杭州）有限公司 | High-temperature resistant and high-CTI (Comparative Tracing Index) flame-retardant polyamide composite material and preparation method thereof |
| CN102408708A (en) * | 2011-09-30 | 2012-04-11 | 中山市纳普工程塑料有限公司 | Production method of polyphthalamide long fiber coated reinforced material |
| CN103059406A (en) * | 2011-10-19 | 2013-04-24 | 辽宁辽杰科技有限公司 | Bidirectional continuous basalt fiber reinforced thermoplastic resin composite sheet material and preparation method thereof |
-
2013
- 2013-12-24 CN CN201310724299.0A patent/CN104725845A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1607219A (en) * | 2003-10-14 | 2005-04-20 | 林安良 | High self-lubricating, high wear resisting, reinforced nylon engineering plastic alloy and method for making same |
| EP1988113A1 (en) * | 2007-05-03 | 2008-11-05 | Ems-Patent Ag | Partially aromatic polyamide moulding masses and their applications |
| CN102120879A (en) * | 2011-02-19 | 2011-07-13 | 本松工程塑料（杭州）有限公司 | High-temperature resistant and high-CTI (Comparative Tracing Index) flame-retardant polyamide composite material and preparation method thereof |
| CN102408708A (en) * | 2011-09-30 | 2012-04-11 | 中山市纳普工程塑料有限公司 | Production method of polyphthalamide long fiber coated reinforced material |
| CN103059406A (en) * | 2011-10-19 | 2013-04-24 | 辽宁辽杰科技有限公司 | Bidirectional continuous basalt fiber reinforced thermoplastic resin composite sheet material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 周静 等: "《近代材料科学研究技术进展》", 31 December 2012, 武汉理工大学出版社 * |
| 杨伟 等: "《聚碳酸酯合金技术与应用》", 30 September 2008, 机械工业出版社 * |
| 顾国芳 等: "《化学建材用助剂原理与应用》", 28 February 2003, 化学工业出版社 * |
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| CN114437538A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Long glass fiber reinforced nylon composite material and preparation method and application thereof |
| CN112029280A (en) * | 2020-11-06 | 2020-12-04 | 江苏金发科技新材料有限公司 | Halogen-free flame-retardant polyamide composite material and preparation method thereof |
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| CN118006122A (en) * | 2024-01-31 | 2024-05-10 | 金发科技股份有限公司 | Lightweight polyamide composition and preparation method and application thereof |
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