CN108070253A - A kind of daiamid composition of high temperature heat-resistant oxygen aging and preparation method thereof - Google Patents
A kind of daiamid composition of high temperature heat-resistant oxygen aging and preparation method thereof Download PDFInfo
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- CN108070253A CN108070253A CN201711229949.9A CN201711229949A CN108070253A CN 108070253 A CN108070253 A CN 108070253A CN 201711229949 A CN201711229949 A CN 201711229949A CN 108070253 A CN108070253 A CN 108070253A
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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Abstract
The invention discloses a kind of daiamid compositions of high temperature heat-resistant oxygen aging and preparation method thereof, include the following raw material component by weight：100 parts of polyamide；10 ~ 60 parts of filler；0.1 ~ 5 part of heat stabilizer；0.15 ~ 5 part of polyalcohol；0.2 ~ 6 part of nanometer polyamide master batch；0.5 ~ 3 part of processing aid；Wherein, nanometer polyamide master batch is made products, and nanoparticle content scope is in 25%wt.The present invention selects suitable heat stabilizer, it is aided with polyalcohol and nano-particle, each component interaction, while adds in corresponding processing aid, a kind of daiamid composition of high temperature heat-resistant oxygen aging is obtained, there is excellent mechanical property, dimensional stability and high temperature resistant thermal-oxidative aging property.The sample surface function admirable of daiamid composition prepared by the present invention, surface without floating fine accumulation, under the high temperature conditions can property retention and dimensionally stable it is good, use field suitable for automobile engine periphery high temperature accessory and other heat-resisting materials.
Description
Technical field
The present invention relates to polymeric material field, the daiamid composition of more particularly to a kind of high temperature heat-resistant oxygen aging and its
Preparation method.
Background technology
PA6 and PA66 in polyamide (Polyamides, abbreviation PA) have intensity height, resistance to general chemical function admirable etc.
Feature is widely used in the fields such as household electrical appliances, automobile, electron and electrician as a kind of general engineering plastic.Common PA6 and PA66 can be with
Meet some occasions of less demanding to long-term Heat-resistant stable to use, but field is used at 150 DEG C or more in some long-term temperatures
Conjunction does not apply to then, such as automotive engine component, often at 150 DEG C or more, sometimes short-term local temperature may at 200 DEG C or more,
This requires PA materials to have good thermal stability.General copper salt kind stabilizer can form complex compound with polyamide, decompose hydrogen mistake
Oxide delays the high temperature ageing degradation speed of polyamide.It is reachable that mantoquita is used alone under the conditions of high temperature ageing below 150 DEG C
To good thermal stability result, but then effect is less desirable at a higher temperature, needs auxiliary with other components.Nano material is
Refer at least one-dimensional small-size effect for being in nano-scale, there is uniqueness in three dimensions, surface can only need to add greatly
A small amount of nano material can assign the excellent mechanical property of composite material, wear-resisting property, heat resistance and ageing-resistant performance etc..
Patent CN102791798A discloses a kind of heat aging-resistant polyamides, branching type polyamide, mantoquita and ferro element compound, but its
And cost higher to material requirements is higher.CN103890097A discloses a kind of heat-proof aging polyalcohol particle/polyamide compositions
Object is primarily upon the ageing-resistant effect of polyalcohol, less to then being paid close attention in terms of nanometer particle material.Patent CN105385152A is public
A kind of heat resistant polyamide has been opened, has only focused on 150 DEG C of performance, 200 DEG C or more of material aging performance is not closed then
Note.
It is usually at present 150 DEG C or so to the concern condition of the heat aging property of polyamide material, and its higher temperature
It is paid close attention to if condition such as 200 DEG C or more of ageing properties less.Therefore, in view of the above-mentioned problems, the present invention is using a kind of brand-new formula
Polyamide is modified, obtains a kind of daiamid composition of high temperature heat-resistant oxygen aging, there is good mechanical performance and resistance to
The features such as high temperature thermal oxidation ageing properties, excellent appearance and oil resistance, can be applied to automobile engine periphery high temperature and match somebody with somebody
The application fields such as part and other high temperature resistant electronic units.
The content of the invention
It is an object of the invention in view of the above shortcomings of the prior art, provide a kind of high temperature resistant thermal-oxidative aging property it is good,
The daiamid composition for the high temperature heat-resistant oxygen aging that mechanical property is excellent and production cost is low, while invention further provides one kind
The preparation method of the polymer.
The technical solution used in the present invention is：A kind of daiamid composition of high temperature heat-resistant oxygen aging, by weight
Meter includes the following raw material component：
Wherein, the ratio between nano-particle in polyalcohol and nanometer polyamide master batch will be 0.1:1~100:It is high in the range of 1
In or less than this range material high temperature resistant thermal-oxidative aging property it is undesirable.
Specifically, polyamide high temperature resistant thermal-oxidative aging property is bad, so heat stabilizer, polyalcohol and nano-particle
Addition be even more important to the high temperature resistant thermal-oxidative aging property of composition.
As being further improved for said program, the content of the nano-particle in the nanometer polyamide master batch is 25%
Wt, the matrix resin of master batch is PA6 resins.
As being further improved for said program, the polyamide in PA66, PA6, PA610 at least one
Kind, relative viscosity is preferably 2.0-3.2.
As being further improved for said program, the nano-particle be magnesia, zinc oxide, aluminium oxide, zirconium oxide,
At least one of nano-particles such as iron oxide, between 15~100nm of particle size range, further preferred 30~85nm.
As being further improved for said program, the filler be E type glasses, fiber diameter range preferably 7~14 μ
m。
As being further improved for said program, the heat stabilizer for sodium bromide, cupric iodide, calcium bromide, calcium iodide,
At least one of magnesium bromide, magnesium iodide, potassium bromide, potassium iodide.
As being further improved for said program, the polyalcohol is pentaerythrite, bipentaerythrite, trihydroxy methyl second
At least one of alkane, tripentaerythritol.
Processing aid of the present invention is selected from least one of antioxidant, lubricant, weather resisting agent.Wherein, it is described anti-
Oxygen agent is selected from β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, four [β-(3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic acid] pentaerythritol ester, N, N'- be double-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine, it is double (2,
4- di-tert-butyl-phenyls) in pentaerythrite, 2,6- di-t-butyl -4-4 cresols and three (2,4- di-tert-butyl-phenyls) phosphite esters
At least one.The lubricant in OP waxes, rosin ester type waxes, calcium stearate, zinc stearate, aluminum stearate at least one
Kind.The weather resisting agent is selected from 2- (2 ˊ--5 ˊ of hydroxyl-aminomethyl phenyl) benzotriazole, poly- { [6- [(1,1,3,3- tetramethyl fourths
Base)-imino group] -1,3,5- triazine -2,4- diyls] [2- (2,2,6,6- tetramethyl-piperidyls)-amino]-hexylidene-[4- (2,
2,6,6- tetramethyl-piperidyls)-imino group], hexamethylphosphoramide, 2- (double (a, the a- dimethylbenzyls of 2'- hydroxyls -3', 5'
Base) phenyl) benzotriazole；2- (2- hydroxyls -3', 5'- dicumylphenyl) benzotriazole；2- (2- hydroxyls -3', 5'- dicumyl benzene
Base)-benzotriazole；2- (2'- hydroxyls -3', 5'- dicumylphenyl)-benzotriazole, 2'- (2'- hydroxyl -3'- tertiary butyls -5'-
Aminomethyl phenyl) -5- chlorobenzotriazoles, 2,4-DihydroxyBenzophenone, 4- benzoyloxys -2,2, in 6,6- tetramethyl piperidines
It is at least one.
It is a further object of the present invention to provide a kind of high temperature heat-resistant oxygen simple for process, condition is easily-controllable, production cost is relatively low
The preparation method of the daiamid composition of aging：Each raw material components are weighed by weight, it will be dried using homogenizer
Polyamide, nanometer polyamide master batch, heat stabilizer, polyalcohol and processing aid be uniformly mixed, from double screw extruder
Main mouth of feeding adds in, and filler is fed through side and added in, temperature be 230~290 DEG C, vacuum degree is -0.05~-0.08MPa, rotating speed is
Pass through double screw extruder melting extrusion, granulation, acquisition graininess high temperature heat-resistant oxygen under the process conditions of 300~500rp/min
The daiamid composition finished product of aging.
Wherein, the preparation method of nanometer polyamide master batch comprises the following steps：Each material component is included polyamide, nanometer
Particle, silane coupling agent, lubricant, antioxidant and other auxiliary agents are added in high mixing device, control temperature in 80~160 DEG C,
3~15min, 500~2000RP/min of rotating speed are stirred, feeding the material mixed to mouth through twin-screw extrusion owner adds in, in temperature
Pass through twin-screw extrusion under 210-280 DEG C of degree, vacuum degree -0.05~-0.08MPa, the process conditions of rotating speed 300-500RP/min
Machine melting extrusion is granulated, and obtains graininess nanometer polyamide master batch.
The beneficial effects of the invention are as follows：
1st, the amide group being connected on polyamide molecule main chain with methylene is under the high temperature conditions easily by oxidative degradation, this hair
Bright preferably suitable heat stabilizer, selects special polyalcohol and Nanocomposites system, is hindered by polyalcohol surface into carbon
The degradation that effect reduces polyamide molecule chain is limited every effect and nano-particle, composition is made to obtain excellent mechanical property and resistance to
Thermal-oxidative aging property.
2nd, the present invention passes through special polyalcohol and Nanocomposites system, the polyalcohol lubricant body special as one
System, and nano-particle can promote the scattered in polyamide of glass, the compound interaction of the two obtains a kind of surface colour
The daiamid composition of damp good, without floating fine accumulation high temperature heat-resistant oxygen aging.
3rd, the present invention squeezes polyamide resin, nanometer polyamide master batch, heat stabilizer, polyalcohol and processing aid through melting
Go out to be granulated, it is not high to equipment requirement, it is simple for process easily-controllable, it is of low cost, it is suitable for mass production.
The sample surface function admirable of daiamid composition prepared by the present invention, surface is without floating fine accumulation, in hot conditions
Lower property retention rate is high and dimensionally stable is good, suitable for automobile engine periphery high temperature accessory and other high temperature resistant electronic units.
Specific embodiment
The present invention is specifically described with reference to embodiment, in order to technical field personnel to the present invention
Understand.It is necessary to it is emphasized that embodiment is only intended to, the present invention will be further described herein, it is impossible to be interpreted as to this
The limitation of invention protection domain, fields person skilled in the art, the non-intrinsically safe made according to foregoing invention content to the present invention
The modifications and adaptations of property, should still fall within protection scope of the present invention.Mentioned raw materials following simultaneously are unspecified, are
Commercial product；The processing step or preparation method not referred in detail be processing step known to a person skilled in the art or
Preparation method.
1st, the preparation of nanometer polyamide master batch：Nanometer polyamide master batch in the embodiment of the present invention 1~5 is made products,
Each material component is included polyamide, nano-particle, silane coupling agent, lubricant, antioxidant and high mix of other auxiliary agents addition to set
In standby, control temperature stirs 3~15min, 500~2000RP/min of rotating speed in 80~160 DEG C, and the material mixed is passed through
Twin-screw extrusion owner feeds mouth and adds in, in 210-280 DEG C of temperature, vacuum in -0.05~-0.08MPa, rotating speed 300-500RP/
Under the process conditions of min by double screw extruder melting extrusion, be granulated, obtain graininess nanometer polyamide master batch.
2nd, the preparation method of the daiamid composition of high temperature heat-resistant oxygen aging：Each raw material components are weighed by weight, are made
Dried polyamide, nanometer polyamide master batch, heat stabilizer, polyalcohol and processing aid are mixed with homogenizer
It is even, from twin-screw extrusion owner feed mouth add in, filler through side feed add in, temperature be 230~290 DEG C, vacuum degree be -0.05
Pass through double screw extruder melting extrusion, granulation, acquisition under~-0.08MPa, the process conditions that rotating speed is 300~500rp/min
The daiamid composition of graininess high temperature heat-resistant oxygen aging.
Embodiment 1
A kind of daiamid composition object of high temperature heat-resistant oxygen aging includes the following raw material component by weight：
Wherein, polyamide PA6；In nanometer polyamide master batch the content of nano-particle be 25%wt, nano-particle
Species is magnesia；Filler be E type glasses, a diameter of 7 μm of glass；Heat stabilizer is cupric iodide；Polyalcohol is double Ji Wusi
Alcohol；Processing aid includes N, N'- couples-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine, three (bis- uncles of 2,4-
Butyl phenyl) phosphite mixture and 2,4-DihydroxyBenzophenone, each component weight ratio is 1:1:1 mixture.
Embodiment 2
A kind of daiamid composition object of high temperature heat-resistant oxygen aging includes the following raw material component by weight：
Wherein, polyamide PA66/PA6；In nanometer polyamide master batch the content of nano-particle be 25%wt, nanometer
Particle kind is zinc oxide；Filler be E type glasses, a diameter of 10 μm of glass；Heat stabilizer is potassium iodide；Polyalcohol is three hydroxyls
Methyl ethane；Processing aid includes N, N'- is double-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine, three (2,
4- di-tert-butyl-phenyls) phosphite mixture and zinc stearate, each component weight ratio is 1:1:2 mixture.
Embodiment 3
A kind of daiamid composition object of high temperature heat-resistant oxygen aging includes the following raw material component by weight：
Wherein, polyamide PA66；In nanometer polyamide master batch the content of nano-particle be 25%wt, nano-particle
Species is magnesia and zinc oxide weight ratio is 1:1 mixture；Filler be E type glasses, a diameter of 10 μm of glass；It is hot steady
Determine that agent is cupric iodide and calcium bromide weight ratio is 1:1 mixture；Polyalcohol is tripentaerythritol；Processing aid includes N,
N'- pairs-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine, three (2,4- di-tert-butyl-phenyls) phosphite esters
Mixture, rosin ester type waxes and calcium stearate, each component weight ratio are 1:1:2:1 mixture.
Embodiment 4
A kind of daiamid composition object of high temperature heat-resistant oxygen aging includes the following raw material component by weight：
Wherein, polyamide PA610；In nanometer polyamide master batch the content of nano-particle be 25%wt, nanoparticle
Subcategory is zirconium oxide and iron oxide weight ratio is 1:2 mixture；Filler be E type glasses, a diameter of 14 μm of glass；Heat
Stabilizer is cupric iodide and calcium bromide weight ratio is 3:1 mixture；Polyalcohol is bipentaerythrite and trimethylolethane
Weight ratio is 1:1 mixture；Processing aid includes four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythrites
Ester, three (2,4- di-tert-butyl-phenyl) phosphite mixtures, OP waxes and aluminum stearate, each component weight ratio are 1:1:3:1
Mixture.
Embodiment 5
A kind of daiamid composition object of high temperature heat-resistant oxygen aging includes the following raw material component by weight：
Wherein, polyamide PA66/PA6；In nanometer polyamide master batch the content of nano-particle be 25%wt, nanometer
Particle kind is iron oxide and iron zinc oxide weight ratio is 1:3 mixture；Filler be E type glasses, a diameter of 10 μ of glass
m；Heat stabilizer is cupric iodide and calcium bromide and potassium iodide weight ratio is 3:1:1 mixture；Polyalcohol is bipentaerythrite
It is 1 with trimethylolethane:2 mixture；Processing aid includes N, and N'- is double-(3- (3,5- di-tert-butyl-hydroxy phenyls)
Propiono) hexamethylene diamine, three (2,4- di-tert-butyl-phenyl) phosphite mixtures, OP waxes, calcium stearate and zinc stearate, respectively
Composition weight ratio is 1:1:3:1:1 mixture.
Comparative example 1
A kind of daiamid composition object of high temperature heat-resistant oxygen aging includes the following raw material component by weight：
Wherein, polyamide PA66；In nanometer polyamide master batch the content of nano-particle be 25%wt, nano-particle
Species is magnesia and zinc oxide weight ratio is 1:1 mixture；Filler be E type glasses, a diameter of 10 μm of glass；It is hot steady
Determine that agent is cupric iodide and calcium bromide weight ratio is 1:1 mixture；Polyalcohol is tripentaerythritol；Processing aid includes N,
N'- pairs-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine, three (2,4- di-tert-butyl-phenyls) phosphite esters
Mixture, rosin ester type waxes and calcium stearate, each component weight ratio are 1:1:2:1 mixture.
Comparative example 2
A kind of daiamid composition object of high temperature heat-resistant oxygen aging includes the following raw material component by weight：
Wherein, polyamide PA66；In nanometer polyamide master batch the content of nano-particle be 25%wt, nano-particle
Species is magnesia and zinc oxide weight ratio is 1:1 mixture；Filler be E type glasses, a diameter of 10 μm of glass；It is hot steady
Determine that agent is cupric iodide and calcium bromide weight ratio is 1:1 mixture；Polyalcohol is tripentaerythritol；Processing aid includes N,
N'- pairs-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine, three (2,4- di-tert-butyl-phenyls) phosphite esters
Mixture, rosin ester type waxes and calcium stearate, each component weight ratio are 1:1:2:1 mixture.
Raw material used in the present invention, but following raw material is not limited only to, while following mentioned raw materials are unspecified,
It is commercial product：
Polyamide, such as YH800 are purchased from Hunan Yue Hua chemical inc；EPR27, table mountain god horse are public
Department, PA610 are purchased from Bada companies of Germany etc.；
Heat stabilizer, Brueggemann company etc.；
Polyalcohol, Guangzhou Gong Xin chemical companies etc.；
Nano-particle, Haitai Nano Material Co., Ltd., Nanjing etc..
Every test mode is as follows：
Mechanics Performance Testing：Tensile strength is with reference to ISO 527-2 standard testings, and bending strength is with bending modulus with reference to ISO
178 standard testings, impact strength is with reference to 180 standard testings of ISO.
Relative viscosity is tested：Relative viscosity test reference standard GB/T1632-1993 test, using Ubbelohde viscometer,
25 DEG C of constant temperature 15min record flow time, are computed that viscosity can be obtained.
Ageing properties are tested：After placing 1500h at 230 DEG C, with reference to ISO 527-2 standard testing tensile properties.
Examples 1 to 5 and the prepared sample obtained of comparative example 1~2 are subjected to properties test, test result respectively
It is as shown in table 1 below.
The component proportion (parts by weight) and the performance test results of 1 Examples 1 to 5 of table and comparative example 1~2
With reference to upper table, as can be seen that the daiamid composition shows good mechanical property and height from embodiment 1-5
Heatproof air aging performance under the conditions of temperature, the ratio of polyalcohol and nano-particle is not limiting scope in comparative example, shows heat-resisting
Oxygen aging poor-performing.The Mechanical Properties of Products of material production prepared by the present invention is good, high temperature resistant thermal-oxidative aging property and table
Good result of the face without floating fibre.
Embodiment described above is only that the preferred embodiment of the present invention is described, and is set not departing from the present invention
On the premise of meter spirit, various modifications and improvement that those of ordinary skill in the art make technical scheme should all
It falls into the protection domain that claims of the present invention determines.
Claims (10)
1. a kind of daiamid composition of high temperature heat-resistant oxygen aging, which is characterized in that by weight including the following raw material component：
100 parts of polyamide；
10 ~ 60 parts of filler；
0.1 ~ 5 part of heat stabilizer；
0.15 ~ 5 part of polyalcohol；
0.2 ~ 6 part of nanometer polyamide master batch；
0.5 ~ 3 part of processing aid；
Wherein, the ratio between nano-particle in polyalcohol and nanometer polyamide master batch is 0.1:1~100:1.
2. a kind of daiamid composition of high temperature heat-resistant oxygen aging according to claim 1, it is characterised in that：Described receives
The content of nano-particle in rice polyamide master batch is 25%wt, and the matrix resin of master batch is PA6 resins.
3. a kind of daiamid composition of high temperature heat-resistant oxygen aging according to claim 1, it is characterised in that：Described is poly-
Amide resin is selected from least one of PA66, PA6, PA610, relative viscosity 2.0-3.2.
4. a kind of daiamid composition of high temperature heat-resistant oxygen aging according to claim 1, it is characterised in that：The nanometer
Nano-particle in polyamide master batch is magnesia, zinc oxide, aluminium oxide, zirconium oxide, at least one in ferric oxide nano particles
Kind.
5. a kind of daiamid composition of high temperature heat-resistant oxygen aging according to claim 1, it is characterised in that：Described fills out
Agent is filled for E type glasses, 7 ~ 14 μm of fiber diameter range.
6. a kind of daiamid composition of high temperature heat-resistant oxygen aging according to claim 1, it is characterised in that：The heat
Stabilizer is at least one of sodium bromide, cupric iodide, calcium bromide, calcium iodide, magnesium bromide, magnesium iodide, potassium bromide, potassium iodide.
7. a kind of daiamid composition of high temperature heat-resistant oxygen aging according to claim 1, it is characterised in that：Described is more
First alcohol is at least one of pentaerythrite, bipentaerythrite, trimethylolethane, tripentaerythritol.
8. a kind of daiamid composition of high temperature heat-resistant oxygen aging according to claim 1, it is characterised in that：Described adds
Work auxiliary agent is selected from least one of antioxidant, lubricant, weather resisting agent.
9. a kind of preparation method of the daiamid composition of high temperature heat-resistant oxygen aging of claim 1 ~ 8 any one of them is prepared,
It is characterized in that：Each raw material components are weighed by weight, are gathered dried polyamide, nanometer using homogenizer
Amide master batch, heat stabilizer, polyalcohol and processing aid are uniformly mixed, and feeding mouth from twin-screw extrusion owner adds in, filler warp
Side, which is fed, to be added in, in the technique item that temperature is 230 ~ 290 DEG C, vacuum degree is -0.05 ~ -0.08MPa, rotating speed is 300 ~ 500rp/min
Pass through double screw extruder melting extrusion, granulation, the daiamid composition of acquisition graininess high temperature heat-resistant oxygen aging under part.
10. a kind of preparation method of the daiamid composition of high temperature heat-resistant oxygen aging according to claim 9, feature exist
In the preparation method of nanometer polyamide master batch comprises the following steps：Each material component is included polyamide, nano-particle, silane
Coupling agent, lubricant, antioxidant and other auxiliary agents are added in high mixing device, control temperature in 80 ~ 160 DEG C, and stirring 3 ~
15min, 500 ~ 2000RP/min of rotating speed feed the material mixed to mouth through twin-screw extrusion owner and add in, in temperature 210-280
DEG C, vacuum -0.05 ~ -0.08MPa, rotating speed 300-500 RP/min process conditions under by double screw extruder melt squeeze
Go out, be granulated, obtain graininess nanometer polyamide master batch.
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| CN116875045A (en) * | 2023-05-12 | 2023-10-13 | 江苏金发科技新材料有限公司 | Glass fiber reinforced nylon material and preparation method thereof |
| CN116751452A (en) * | 2023-07-31 | 2023-09-15 | 安徽优泰新材料有限公司 | Aging-resistant polyamide heat insulation strip material and preparation process thereof |
| CN116751452B (en) * | 2023-07-31 | 2024-01-16 | 安徽优泰新材料有限公司 | Aging-resistant polyamide heat insulation strip material and preparation process thereof |
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