CN106519663A - Flame-retardant and high temperature-resistant polyimide compound and preparation method thereof - Google Patents
Flame-retardant and high temperature-resistant polyimide compound and preparation method thereof Download PDFInfo
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- 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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C08K7/00—Use of ingredients characterised by shape
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention discloses a flame-retardant and high temperature-resistant polyimide compound and a preparation method thereof. The compound comprises, by weight, 40-70 parts of polyimide, 0.1-30 parts of polyol, 0-10 parts of an anti-impact modifier, 0-60 parts of a filler, 5-20 parts of a flame retardant, and 0.2-1 part of a heat stabilizer. The polyol and the polyimide are blended and modified, so the high temperature ageing resistance and the flame retardation performance are effectively improved; and the carbon formation ability of the polyimide is improved, so the burning time is shortened, and the flame retardation performance of the polyimide is improved. The use amount of the flame retardant is effectively reduced, so influences of the flame retardant on the the high temperature ageing resistance of the polyamide are reduced. The anti-impact modifier regulates the anti-impact strength of alloy and plays a great role in enhancement of the compatibility of polyester and polyamide. The compound is suitable for being applied to high-temperature and high-humidity application environment of precise electronic and electric parts and automobile engine compartments and the most advanced fields of aerospace.
Description
Technical field
The present invention relates to polymeric material field, more particularly to a kind of flame-resistant high-temperature-resistant polyamide compound and its preparation side
Method.
Background technology
Daiamid composition is due to excellent mechanical performance, chemical-resistant, machinability, hot-air aging resistance
Can, make them be usually used in the fields such as the electronic apparatus harsher to operating environment requirements, automobile, Aero-Space, electric tool,
It is wherein especially common with engine bonnet applications below.With Engine Downsizing development, turbocharging substitutes nature and inhales
The high air input of engine by air of air stripping, so as to improve the power and moment of torsion of electromotor, is that automobile lifting power makes full use of sending out for energy consumption
Exhibition trend.This high temperature resistant level for compeling the material for being used in electromotor periphery constantly must be upgraded, electromotor peripheral ring
Border temperature can reach more than 200 DEG C of operating temperature.At a temperature of common polyamide compositionss are usually used in the use, in long-time
Mechanical performance sharp-decay is caused due to thermo-oxidative ageing after exposure, or working of plastics and sheet metal component height after assembly
Warm storage process causes change in size beyond the margin of tolerance for allowing as the shrinkage factor of working of plastics is excessive, or is sending out
When motivation works, hot environment causes working of plastics stress deformation, and these factors all govern polyamide material in engine core zero
Part is moulding the development trend of Dai Gang.The new standard put into effect in some automobile main frame maker should to the polymeric material of electromotor periphery
With proposing more harsh requirement, including meet fire resistance simultaneously and after high temperature ageing fire resistance does not decline
Subtract, and mechanical performance has higher conservation rate.For example, General Motors standard GMW 16864 requires that polyamide possesses UL94V-
0, while experiencing 170 DEG C of high temperature ageings after 3000 hours, fire resistance still keeps UL94V-0 levels, in addition simultaneously will
The mechanical performance of material is asked to meet 170 DEG C of high temperature ageings, 1000 hours rates of property retention later more than 65%.Addition fire retardant leads to
Can often cause material property that decay occurs, and its thermal-oxidative aging property occurs significantly to reduce.For part fire retardant exists
The risk for separating out and losing is faced under hot conditionss so that high temperature ageing will meet above performance becomes extremely difficult.
The heatproof air aging performance that antioxidant can improve daiamid composition, including list are also referred to as by adding heat stabilizer
Solely addition or compounding addition mantoquita, hindered phenol, many aromatic amines, hindered amine, phosphite ester, thioesters etc. improves daiamid composition
Thermal-oxidative aging property.But it is rarely reported the heat resistant ability that Flame Retardancy energy is improved by adding antioxidant.
The high temperature resistant thermal-oxidative aging property of polyamide material how is improved, the heat-resistant deforming temperature and high temperature ring of material is improved
The ability of external force effect is resisted under border, while improving the dimensional stability that material deposits generation in high temperature environments, is polyamide
Materials application is in the major consideration of engine high-temperature region parts.At the same time, higher fire-retardant rank is provided simultaneously with,
This kind of flame-resistant high-temperature-resistant polyamide material is rarely reported.
The content of the invention
The purpose of the present invention, is just to provide for a kind of flame-resistant high-temperature-resistant polyamide compound, and the complex has excellent
There are excellent mechanical performance, chemical-resistant, machinability while high temperature resistant thermal-oxidative aging property.
Another object of the present invention is also resided in and provides a kind of preparation method of flame-resistant high-temperature-resistant polyamide compound.
The object of the present invention is achieved like this：
A kind of flame-resistant high-temperature-resistant polyamide compound of the present invention includes following components and its weight portion：
In a kind of above-mentioned flame-resistant high-temperature-resistant polyamide compound, polyamide is by diamine and binary acid Step Condensation
Into, or formed by lactams ring-opening polymerisation, or formed by aminoacid Step Condensation, or by diamine, binary acid, lactams, ammonia
Component copolymerization in base acid is formed；Selected from PA46, PA66, PA6, PA11, PA12, PA610, PA612, PA1010, PA1012,
PA1212、PA4T、PA6T、PA9T、PA10T、PA6I、PAMXD6、PA6I/6T、PA66/6、PA6/66、PA6T/6I、PA6T/66
In one or more.Preferably, polyamide includes that mass ratio is 10：1～5：5 PA66 and semiaromatic polyamide composition, institute
The semiaromatic polyamide composition stated selected from PA4T, PA9T, PA10T, PA6I/6T, PA6T/6I, PA6T/66, PA10T/10I,
At least one in PA10T/66, PADT/DI；It is highly preferred that described semiaromatic polyamide composition is preferably PA10T, PA10T/
At least one in 10I, PA10T/66.
In a kind of above-mentioned flame-resistant high-temperature-resistant polyamide compound, polyhydric alcohol is dihydroxylic alcohols, trihydroxylic alcohol and hydroxyl quantity
More than or equal at least one in four polyhydric alcohol；Preferably, described dihydroxylic alcohols be 1，2-ethandiol, 1,3-PD, 2,
At least one of 3- butanediols, 1,5-PD and 2，2-dimethyl-1，3-propanediol and PTMEG apoplexy due to endogenous wind.Preferably, institute
The trihydroxylic alcohol stated be glycerol, trimethylolpropane, 2,3- bis- (2 '-ethoxy) hexamethylene -1- alcohol, 1,2,6- hexanetriols, 1,1,
Tri--(methylol) ethane of 1-, 3- (2 '-hydroxy ethoxy) propane -1,2- glycol, 3- (2 '-propoxyl) propane -1,2- glycol,
2- (2 '-hydroxy ethoxy) hexane -1,2- glycol, 6- (2 '-propoxyl) hexane -1,2- glycol, 1,1,1- tri- [(2 '-hydroxyl ethoxy
Base) methyl] ethane, 1,1,1- tri- [(2 '-propoxyl) methyl] propane, 1,1,1- tri- (4 '-hydroxyphenyl) ethane, 1,1,1- tri-
(hydroxyphenyl) propane, 1,1,3- tri- (dihydroxy -3- aminomethyl phenyls) propane, 1, Isosorbide-5-Nitrae-three (dihydroxy phenyl) butane, 1,1,5-
Three (hydroxyphenyl) -3- methylpentanes, two (trimethylolpropanes), trimethylolpropane ethoxylate, trimethylolpropane third
Epoxide compound and and trihydroxy polyethers (such as diethylene glycol, 2,2'-ethylenedioxybis(ethanol) .) at least one.Preferably, described polyhydric alcohol
For 1,1,3,3- tetra- (methoxyl group) propane, tetramethylolmethane, Bis(pentaerythritol), tripentaerythritol, and with certain degree of polymerization
At least one in polyvinyl alcohol, ethylene-vinyl alcohol copolymer.
In a kind of above-mentioned flame-resistant high-temperature-resistant polyamide compound, filler is fibrous filler, Non-fibrous filling
At least one in agent, polymer-filled agent.The one kind of fibrous filler in glass fibre, carbon fiber, organic fiber
Or it is several；Non-fibrous filler is selected from aluminium oxide, white carbon black, clay, zirconium phosphate, Kaolin, Calcium Carbonate, copper, kieselguhr, stone
One or more in ink, Muscovitum, Silicon stone, titanium dioxide, zeolite, Talcum, wollastonite；Polymer-filled agent is selected from bead
And/or glass powder.
In a kind of above-mentioned flame-resistant high-temperature-resistant polyamide compound, anti-impact modifier is can to enter as elastomer matrix
The modified polymer of row and elastomer matrix pass through in the product formed by grafting or the special functional group of copolymerization at least one
Kind.Described can be polyethylene, polypropylene, polybutene, polyisoprene, second as the polymer that elastomer matrix is modified
Alkene-acrylic rubber (EPR), Ethylene-Propylene-Diene (EPDM) rubber, ethylene butylene rubber, ethylene-acrylate rubber, fourth
Butadiene-styrene rubber, butadiene-propylene acid esters rubber, Ethylene-octene rubber, acrylonitrile butadiene rubber, ethylene-propylene
Sour (EAA) product, ethane-acetic acid ethyenyl ester (EVA) product, ethylene-acrylate (EAE) product, acrylonitrile-butadiene-benzene
Ethylene (ABS) copolymer, styrene ethylene butadiene-styrene (SEBS) block copolymer, styrene-butadiene-benzene second
Alkene (SBS) copolymer, the core shell elastomer of metacrylate-butadiene-styrene (MBS) type, or more list to
The mixture of few two kinds of elastomers.The product formed by grafting or the special functional group of copolymerization by described elastomer matrix
Functional group is used to realize that elastomer matrix occurs certain effect with polyamide component that raising elastomer matrix to be compatible with polyamide
Property, including：Carboxylic acid, carboxylate, ester such as acrylate and methacrylate, ionomer, glycidyl such as ring
Oxygen groups, ethylene oxidic ester, acid anhydride such as maleic anhydride, oxazoline, maleimide, or its mixture.Specifically, it is described anti-
Impact modifying agent may be selected from：Ethylene-acrylate-glycidyl methacrylate trimer, Ethylene-butyl acrylate copolymerization
Thing, ethylene/n-butyl acrylate-glycidyl methacrylate copolymer, ethylene maleic acid anhydride copolymer, maleic anhydride
The ethylene-propylene-diene copolymer of grafting, the styrene-maleimide copolymer of maleic anhydride grafting, maleic anhydride change
Property styrene-ethylene-butylene-styrene copolymer, the SAN of maleic anhydride grafting, maleic anhydride connects
The acrylonitrile-butadiene-styrene copolymer of branch, and their hydrogenated form.
In a kind of above-mentioned flame-resistant high-temperature-resistant polyamide compound, fire retardant is bromide fire retardant, nitrogenated flame retardant, phosphorus
At least one in flame retardant, nitrogen phosphorus flame retardant and inorganic metal mineral flame retardants.Bromide fire retardant is brominated oxygen tree
At least one in fat, brominated Polystyrene, brominated polyphenylether and brominated polyphenylene alkane；The nitrogenated flame retardant be tripolycyanamide,
At least one in melamine cyanurate and polyurethane；The phosphorus flame retardant is inorganic phosphorus flame retardant and/or organic
Phosphorus flame retardant, the inorganic phosphorus flame retardant are at least one in a nanometer red phosphorus, phosphate and APP, described organic
Phosphorus flame retardant is at least one in dialkylphosphinic salts, phosphate ester, phosphite ester and phosphonate ester；The nitrogen phosphorous flame-retardant
Agent is melamine polyphosphate；The inorganic metal mineral flame retardants be magnesium hydroxide, aluminium hydroxide, magnesium aluminum-hydrotalcite, three
Aoxidize at least one in two antimony, Firebrake ZB and Zinc Oxide.
In a kind of above-mentioned flame-resistant high-temperature-resistant polyamide compound heat stabilizer be mantoquita heat stabilizer, Hinered phenols resist
At least one in oxygen agent, phosphite ester kind antioxidant, thioether kind antioxidant and many aromatic amine antioxidant.Hindered phenol is 1,1,
3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane (CAS：1843-03-4), 1,3,5- tri- (3,5- di-t-butyl -4-
Hydroxybenzyl) isocyanuric acid (CAS：27676-62-6), double (6- tert-butyl-m-cresols) (CAS of 4,4'- butylidenes：85-60-9),
β-positive octadecanol ester (the CAS of (3,5- di-tert-butyl-hydroxy phenyls) propanoic acid：2082-79-3), four [β-(3,5- bis- tertiary fourths
Base -4- hydroxy phenyls) propanoic acid] pentaerythritol ester (CAS：6683-19-8), 3,9- pair [1,1- dimethyl -2- [(the 3- tert-butyl groups -
4- hydroxy-5-methyl base phenyl) propionyloxy] ethyl] -2,4,8,10- four oxaspiros [5.5] hendecane (CAS：90498-90-1)
With 1,3,5- trimethyls -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene (CAS：In 1709-70-2) at least one
Kind.Phosphite ester is distearyl pentaerythritol diphosphite (CAS：3806-34-6), double (2,6- di-t-butyl -4- first
Base phenyl) pentaerythritol diphosphate (CAS：80693-00-1), 2-2 '-di-2-ethylhexylphosphine oxide (4,6- dibutyl-benzyl) -2- ethyls
Hexyl phosphite ester (CAS:126050-54-2), phosphorous acid three (2,4- di-tert-butyl-phenyl) ester (CAS:31570-04-4), it is sub-
Tricresyl phosphate nonyl phenyl ester (CAS：26523-78-4) with the split isopropyl diphenyl base C12-15- alcohol phosphite ester (CAS of 4,4'-:
At least one in 96152-48-6).It is preferred that thioesters is tetramethylolmethane four (3- lauryl thiopropionates) (CAS:29598-
76-3).It is preferred that many aromatic amines are 4,4'- bis- (propyloxy phenyl base) diphenylamines (CAS:10081-67-1).
Fire retardant, nucleator, foaming agent, antistatic are included in a kind of above-mentioned flame-resistant high-temperature-resistant polyamide compound also
At least one in agent, lubricant, releasing agent, ultraviolet absorber, hindered amine as light stabilizer and coloring agent.Nucleator is granule
Particle diameter is less than at least one in 1 μm of inorganic nucleator and organic nucleating agent；The inorganic nucleator is Pulvis Talci, montmorillonite
With at least one in Calcium Carbonate；The organic nucleating agent be sodium benzoate, Sorbitol dibenzyl ester and carboxylic acid sodium salt at least
It is a kind of.
The present invention also provides a kind of flame-resistant high-temperature-resistant polyamide compound preparation method, including following preparation process：
(1) prepare raw material according to following components and weight portion content：
(2) mass content of the polyamide drying to moisture in above-mentioned raw materials is less than into 0.05%；
(3) by above-mentioned polyamide, polyhydric alcohol, anti-impact modifier, filler, fire retardant, germanium dioxide, heat stabilizer
Melting extrusion during double screw extruder is put into after mixing gathers through cooling down the flame-resistant high-temperature-resistant for obtaining the present invention with pelletize simultaneously
Amide complex, each area's temperature of double screw extruder are 280～320 DEG C；400 revs/min of engine speed.
There is the advantage of several aspects compared with prior art in the present invention：
The flame-resistant high-temperature-resistant polyamide compound of the present invention is made to be provided simultaneously with excellent fire resistance, and fire resistance and machine
Tool performance has high-temperature aging resisting characteristic, and deep fades do not occur with high temperature ageing causes part application to be failed, and meets automobile primary
Material requirements of the machine factory to electromotor periphery.
The present invention carries out blending and modifying using polyhydric alcohol and polyamide, it is found that polyhydric alcohol effectively can improve high temperature resistant simultaneously
Ageing properties and fire resistance, by improving polyamide into the ability of carbon, reduce burning time, improve the anti-flammability of polyamide
Energy.The usage amount to fire retardant can be effectively reduced, so as to reduce the impact to polyamide heat resistant performance of fire retardant.
The impact strength of composite is adjusted by anti-impact modifier, while preferred anti-impact modifier is to strengthening
Polyester is played an important role with the compatibility of polyamide, provides more excellent mechanical performance for the exotic material, and can
To meet requirement of the automobile main frame maker to material.Electronic apparatus part, the automobile engine nacelle for being particularly suitable for application to precision is high
The leading-edge fields such as the applied environment and Aero-Space of warm high humidity.
Specific embodiment
Below in conjunction with embodiment, the invention will be further described.
The material manufacturer and model that table 1 is adopted by the embodiment of the present invention and comparative example is as follows：
1 comparative example of table and the used raw material of embodiment
Embodiment 1～3 and comparative example 1～5：
Polyamide, polyester, filler, fire retardant, anti-impact modifier, heat stabilizer are measured by 2 formula of table, by above-mentioned original
The mass content of polyamide, polyester drying to moisture in material is less than 0.05%, by above-mentioned polyamide, polyester, filler, phase
Hold agent, melting extrusion in double screw extruder put into after antioxidant mixing, obtain the present embodiment and right through cooling and pelletize
Than the product of embodiment, each area's temperature of double screw extruder is 280-320 DEG C；400 revs/min of engine speed.
2 embodiment 1～5 of table and comparative example 1～4 (weight portion)
The composite material test method for preparing gained is as follows：
According to ISO527-2/1A, by the 4mm thickness test bars, the width 10mm, test speed 5mm/ that are molded preparation
Min, 23 DEG C of tensile strengths in atmosphere of test, be designated as TS (23 DEG C) (at least 5 same compositions and shaped samples test result
Meansigma methodss)；Unit is MPa.
According to the temperature that ISO75-2 A methods test materials are deformed upon in the case where 1.8MPa load is received, HDT, unit are designated as：
℃。
According to UL-94, each embodiment and the composite mold in reference examples are made into the thick test strip of 0.8mm.Then exist
Test strip is adjusted under 23 DEG C and 50% relative humidity and test within 48 hours its UL-94 flammability rating afterwards.According to ISO 188
In the UL-94 grades of 180 DEG C of test materials after aging 3000 hours.
Thermo-oxidative ageing is tested according to ISO 527-2/1A, by the 4mm thickness test bars, the width 10mm that are molded preparation,
Test speed 5mm/min, aerial aging front and aging after-drawing intensity (TS) (at least 5 same compositions of 23 DEG C of test
With the meansigma methodss of shaped samples test result).Hot air aging uses thermal aging oven, and adjusting temperature is carried out for 180 DEG C, is being reached
After ageing time 1000h, sample is taken out from ageing oven, is heated seal with aluminium foil bag after being cooled to room temperature, prevents from evaluating mechanical property
Any dampness is absorbed before.Compare with aging front corresponding mechanical property, calculate the conservation rate of tensile strength, and with percentage ratio
Represent, be designated as aging rear TS conservation rates.
The embodiment of the present invention 1～5 and 1～4 test result of comparative example are as shown in table 3：
3 embodiment 1～5 of table and comparative example 1～4 can test results
The data from table, comparative example 1 and comparative example 3, comparative example 2 compare discovery, the increase of amount of flame-retardant agent with comparative example 4
Cause conservation rate dramatic decrease of the mechanical performance after high temperature ageing.42% and 41% is decayed to from 54%, 50% respectively.But
The reduction of fire retardant component, such as comparative example 3, comparative example 4 its fire resistance but accordingly there occurs deterioration.Using the technology of the present invention
The embodiment 1 and embodiment 2 of scheme reduces the consumption (consistent with comparative example 3,4 flame retardant agent content of comparative example respectively) of fire retardant
But still UL94V-0 ranks can be obtained, as fire retardant is reduced, cost further can be reduced.Which is fire-retardant after high temperature ageing
Rank and mechanical performance conservation rate significantly increase, and can meet automobile main frame maker while to Flame Retardancy energy, mechanicalness
The requirement of energy and their high-temperature aging resisting characteristics.Add anti-impact modifier on the basis of embodiment 1,2 so that tensile strength
Further improve, the conservation rate after mechanical performance is aging has the increase of slight amplitude.
Above example is used for illustrative purposes only, rather than limitation of the present invention, about the technology people of technical field
Member, without departing from the spirit and scope of the present invention, can also make various conversion or modification, therefore all equivalents
Technical scheme should also belong to scope of the invention, should be limited by each claim.
Claims (9)
1. a kind of flame-resistant high-temperature-resistant polyamide compound, it is characterised in that including following components and its weight portion：
2. a kind of flame-resistant high-temperature-resistant polyamide compound as claimed in claim 1, it is characterised in that described polyamide is by two
First amine and binary acid Step Condensation are formed, or are formed by lactams ring-opening polymerisation, or are formed by aminoacid Step Condensation, or by two
Component copolymerization in first amine, binary acid, lactams, aminoacid is formed.
3. a kind of flame-resistant high-temperature-resistant polyamide compound as claimed in claim 1, it is characterised in that described polyhydric alcohol is two
First alcohol, trihydroxylic alcohol and hydroxyl quantity are more than or equal at least one in four polyhydric alcohol.
4. a kind of flame-resistant high-temperature-resistant polyamide compound as claimed in claim 1, it is characterised in that described filler is fibre
Dimension shape filler, Non-fibrous filler, at least one in polymer-filled agent.
5. a kind of flame-resistant high-temperature-resistant polyamide compound as claimed in claim 1, it is characterised in that described impact modification
Agent is the polymer and elastomer matrix that can be modified as elastomer matrix by grafting or the special functional group of copolymerization
At least one in the product for being formed.
6. a kind of flame-resistant high-temperature-resistant polyamide compound as claimed in claim 1, it is characterised in that described fire retardant is bromine
At least one in flame retardant, nitrogenated flame retardant, phosphorus flame retardant, nitrogen phosphorus flame retardant and inorganic metal mineral flame retardants.
7. a kind of flame-resistant high-temperature-resistant polyamide compound as claimed in claim 1, it is characterised in that described heat stabilizer is
In mantoquita heat stabilizer, Hinered phenols antioxidant, phosphite ester kind antioxidant, thioether kind antioxidant and many aromatic amine antioxidant
At least one.
8. a kind of flame-resistant high-temperature-resistant polyamide compound as claimed in claim 1, it is characterised in that also bag nucleator, anti-quiet
At least one in electric agent, foaming agent, lubricant, releasing agent, ultraviolet absorber, hindered amine as light stabilizer and coloring agent.
9. flame-resistant high-temperature-resistant polyamide compound preparation method as claimed in claim 1, it is characterised in that including following preparation
Step：
(1) prepare raw material according to following components and weight portion content：
(2) mass content of the polyamide drying to moisture in above-mentioned raw materials is less than into 0.05%；
(3) will be input after the mixing of above-mentioned polyamide, polyhydric alcohol, anti-impact modifier, filler, fire retardant and heat stabilizer double
Melting extrusion in screw extruder, obtains the flame-resistant high-temperature-resistant polyamide compound of the present invention, double spiral shells through cooling and pelletize
The each area's temperature of bar extruder is 280 DEG C to 320 DEG C；400 revs/min of engine speed.
Priority Applications (1)
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573683A (en) * | 2017-08-29 | 2018-01-12 | 合肥会通新材料有限公司 | A kind of low-k fiber glass reinforced polyamide material and preparation method thereof |
| CN110819105A (en) * | 2019-10-08 | 2020-02-21 | 江苏沃特新材料科技有限公司 | Nylon composite material and preparation method and application thereof |
| CN111253734A (en) * | 2020-01-23 | 2020-06-09 | 上海锦湖日丽塑料有限公司 | High-damping heat-aging-resistant polyamide composition and preparation method thereof |
| CN111849157A (en) * | 2020-07-30 | 2020-10-30 | 宁波耀众模塑科技有限公司 | Flame-retardant polyamide mixture for polyurethane foamed product |
| CN112708267A (en) * | 2020-12-07 | 2021-04-27 | 金发科技股份有限公司 | Polyamide composition for circuit breaker and preparation method and application thereof |
| CN114507441A (en) * | 2021-12-24 | 2022-05-17 | 金发科技股份有限公司 | Polyamide composite material and preparation method and application thereof |
| CN116396608A (en) * | 2023-04-13 | 2023-07-07 | 清远市一丞阻燃材料有限公司 | Fiber-reinforced halogen-free flame-retardant nylon composition and preparation method thereof |
| CN116731512A (en) * | 2023-08-02 | 2023-09-12 | 巴斯夫新材料有限公司 | Thermoplastic polyamide composition, method for producing same and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464881A (en) * | 2010-11-10 | 2012-05-23 | 杜邦公司 | Halogen-free flame-retardant polyamide composition |
| CN103890097A (en) * | 2011-08-31 | 2014-06-25 | 英威达技术有限公司 | Compositions of polyhydric alcohols and polyamides |
| CN105283510A (en) * | 2013-03-25 | 2016-01-27 | 纳幕尔杜邦公司 | Heat resistant polyamide compositions |
-
2016
- 2016-11-21 CN CN201611039555.2A patent/CN106519663A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464881A (en) * | 2010-11-10 | 2012-05-23 | 杜邦公司 | Halogen-free flame-retardant polyamide composition |
| CN103890097A (en) * | 2011-08-31 | 2014-06-25 | 英威达技术有限公司 | Compositions of polyhydric alcohols and polyamides |
| CN105283510A (en) * | 2013-03-25 | 2016-01-27 | 纳幕尔杜邦公司 | Heat resistant polyamide compositions |
Non-Patent Citations (1)
| Title |
|---|
| 彭治汉 等: "《塑料工业手册 聚酰胺》", 30 November 2001, 化学工业出版社 * |
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| CN107573683B (en) * | 2017-08-29 | 2021-02-12 | 会通新材料股份有限公司 | Low-dielectric-constant glass fiber reinforced polyamide material and preparation method thereof |
| CN107573683A (en) * | 2017-08-29 | 2018-01-12 | 合肥会通新材料有限公司 | A kind of low-k fiber glass reinforced polyamide material and preparation method thereof |
| CN110819105B (en) * | 2019-10-08 | 2022-05-20 | 江苏沃特新材料科技有限公司 | Nylon composite material and preparation method and application thereof |
| CN110819105A (en) * | 2019-10-08 | 2020-02-21 | 江苏沃特新材料科技有限公司 | Nylon composite material and preparation method and application thereof |
| CN111253734A (en) * | 2020-01-23 | 2020-06-09 | 上海锦湖日丽塑料有限公司 | High-damping heat-aging-resistant polyamide composition and preparation method thereof |
| CN111253734B (en) * | 2020-01-23 | 2022-08-05 | 上海锦湖日丽塑料有限公司 | High-damping heat-aging-resistant polyamide composition and preparation method thereof |
| CN111849157A (en) * | 2020-07-30 | 2020-10-30 | 宁波耀众模塑科技有限公司 | Flame-retardant polyamide mixture for polyurethane foamed product |
| CN112708267B (en) * | 2020-12-07 | 2022-12-06 | 金发科技股份有限公司 | Polyamide composition for circuit breaker and preparation method and application thereof |
| CN112708267A (en) * | 2020-12-07 | 2021-04-27 | 金发科技股份有限公司 | Polyamide composition for circuit breaker and preparation method and application thereof |
| CN114507441A (en) * | 2021-12-24 | 2022-05-17 | 金发科技股份有限公司 | Polyamide composite material and preparation method and application thereof |
| CN116396608A (en) * | 2023-04-13 | 2023-07-07 | 清远市一丞阻燃材料有限公司 | Fiber-reinforced halogen-free flame-retardant nylon composition and preparation method thereof |
| CN116731512A (en) * | 2023-08-02 | 2023-09-12 | 巴斯夫新材料有限公司 | Thermoplastic polyamide composition, method for producing same and use thereof |
| CN116731512B (en) * | 2023-08-02 | 2023-10-31 | 巴斯夫新材料有限公司 | Thermoplastic polyamide composition, method for producing same and use thereof |
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