CN106832916B - High heat conductive insulating copolyamide composite material and preparation method - Google Patents
High heat conductive insulating copolyamide composite material and preparation method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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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
- C08L77/12—Polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract
The present invention relates to a kind of high heat conductive insulating copolyamide composite material and preparation methods, the high heat conductive insulating copolyamide composite material is prepared from the following materials: copolyamide resin, aliphatic polyamide resin, toluene di-isocyanate(TDI), 2,2'- (1,3- phenylene)-bisoxazoline, coupling agent, boron nitride, aluminium oxide, silicon carbide, N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamide and bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates.The high heat conductive insulating copolyamide composite material has the characteristics that high thermal conductivity coefficient, high tensile, high fluidity, low water absorption and good insulation preformance, can be applied to electric, LED, automobile and other industries field.
Description
Technical field
The present invention relates to Material Fields, more particularly to a kind of high heat conductive insulating copolyamide composite material and its preparation side
Method.
Background technique
With the fast development of circuit board large scale integration and micro-packaging technology, electronic component volume constantly reduces,
Packing density is higher and higher, and power is increasing, and calorific value also increases therewith.Therefore, heat dissipation becomes one in electronics industry
A major issue.Metal, ceramics and carbon material with excellent heat conductivity performance, since electrical insulating property, machine-shaping property are poor,
Higher cost, it is difficult to adapt to the needs of present technology development.High molecular material have it is light, insulation, corrosion-resistant, processing performance is excellent
Advantage good, design freedom is big, but heating conduction is poor.Using high molecular material as matrix, conduction powder is filled, high score is passed through
Sub- material traditional molding methods can get heat conductive insulating composite material.Meanwhile the heat conductive insulating composite material also have it is corrosion-resistant
Property and preferable mechanical property can be used for heat exchanger material in Industrial Wastewater Treatment and Chemical Manufacture and powerful
The application fields such as the heat radiation lamp cup of LED light.
Heat resistant polyamide is usually by aliphatic diamines and aromatic diacid or aromatic diamines and fat
The diacid of race is prepared through polycondensation.Due to introducing phenyl ring on molecular backbone, heat resistant polyamide not only maintains fat
The mechanical property that polyamide has is good, acid and alkali-resistance and the advantages that self-lubrication, also overcome its water absorption rate is high, dimensional stability not
Good disadvantage, which are mainly applied to electric, LED, automobile and other industries.However, the thermal conductivity of heat resistant polyamide is smaller, from
And its application in some fields is limited, such as connector, motor, transformer, solenoid, wound around coil system, LED illumination
The application fields such as heat dissipation.
For above-mentioned problem, some researchs have been done to the heating conduction for improving polyamide in currently available technology, such as
Chinese patent CN 102070899A discloses a kind of insulating heat-conductive polyamide compoiste material, by polyamide (PA) resin, polyphenylene sulfide
Ether (PPS) resin, heat filling, glass fibre, coupling agent, antioxidant, processing aid are prepared；Chinese patent CN
105462241A discloses a kind of material and preparation method thereof for improving polyamide PA6 thermal conductivity of material；Chinese patent CN
105462252A discloses the technical solution and preparation method of a kind of short fine enhancing heat conductive insulating nylon 46 composite material；China
Patent CN 105504793A discloses a kind of halogen-free flameproof High-heat-conductiviinsulation insulation material and preparation method thereof, and the material is by nylon 6
Resin, modified aluminas, zinc oxide, magnesium hydroxide, toughener, halogen-free flame retardants, zinc stearate, antioxidant and coupling agent system
At.
Summary of the invention
The present invention be directed to the deficiencies in the prior art, it is therefore an objective to provide a kind of with high thermal conductivity coefficient, high tensile, height
The high heat conductive insulating copolyamide composite material of mobility, low water absorption and good insulation preformance, can be applied to electric, LED,
Automobile and other industries field.
In order to achieve the above objectives, the present invention uses following scheme:
A kind of high heat conductive insulating copolyamide composite material, the composite material are prepared by the raw material of following parts by weight:
The intrinsic viscosity of the copolyamide resin is 0.7~1.0dL/g.
The aliphatic polyamide resin is nylon 46 resin (PA46), polyhexamethylene adipamide resin
At least one of (PA66).
The coupling agent is gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-
Gamma-aminopropyl-triethoxy-silane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-ammonia third
Ylmethyl dimethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, aniline first
At least one of ethyl triethoxy silicane alkane.
In wherein some embodiments, the high heat conductive insulating copolyamide composite material, by the raw material of following parts by weight
It is prepared:
In wherein some embodiments, the high heat conductive insulating copolyamide composite material, further preferably by following heavy
The raw material of amount part is prepared:
In wherein some embodiments, the intrinsic viscosity of the copolyamide resin is 0.75~0.95dL/g；The rouge
Fat polyamide resin is polyhexamethylene adipamide resin (PA66), and inherent viscosity is 1.22~1.84dL/g.
In wherein some embodiments, the coupling agent is gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy
At least one of base silane；The shape of the boron nitride is sheet, and partial size is 5~150 μm；The partial size of the aluminium oxide is 5
~60 μm；The shape of the silicon carbide is crystal whisker-shaped, and diameter of whiskers is 0.05~2.5 μm, draw ratio >=20.
In wherein some embodiments, the copolyamide resin is copolymerized by monomer 1 and polyesteramide, the monomer
1 is the decamethylene diamine, terephthalic acid (TPA), aliphatic dibasic acid that molar ratio is 1:0.9~0.99:0.01~0.1, and described to benzene two
Both formic acid and aliphatic dibasic acid dosage and be 1 with the molar ratio of the decamethylene diamine, the aliphatic dibasic acid be adipic acid,
At least one of decanedioic acid, dodecanedioic acid, the polyesteramide additional amount are the 1~8% of 1 total weight of monomer.
In wherein some embodiments, the copolyamide resin is made by following synthetic method:
(1) monomer 1 after vacuum drying is added in stirring-type polymer reactor, while the polyester acyl is added
Amine and molecular weight regulator, antioxidant, water；Then 4~6min is vacuumized, 4~6min of nitrogen is led to, is so recycled 5~7 times,
Be present in reactant in the environment under nitrogen protection, control in the stirring-type polymer reactor system pressure be 0.2~
0.3MPa；
(2) in 2~4 hours by the closed constant-speed heating of stirring-type polymer reactor to 272~280 DEG C, adjust institute
The mixing speed for stating stirring-type polymer reactor is 30~50r/min, wherein when the stirring-type polymer reactor temperature reaches
At 215 DEG C, it is deflated to 2.0MPa, and maintains pressure after 2.0MPa, reaction 1~2 hour, normal pressure is deflated to, is warming up to simultaneously
After the reaction was continued at 310~320 DEG C 1~2 hour, after constant temperature persistently vacuumizes 0.3~1 hour, the copolyamide tree is obtained
Rouge；
The molecular weight regulator is 0.1~3% benzoic acid that additional amount is 1 total weight of monomer；The antioxygen
Agent is 0.1~0.3% N, the N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1 that additional amount is 1 total weight of monomer,
3- benzene diamides；Appropriate amount of water.
It is a further object of the present invention to provide the preparation methods of high heat conductive insulating copolyamide composite material.
The preparation method of above-mentioned high heat conductive insulating copolyamide composite material, specific technical solution, comprising the following steps:
(1) dry 4~12 under conditions of the copolyamide resin and aliphatic polyamide resin being placed in 80~100 DEG C
It is cooling after hour, by copolyamide resin after cooling, aliphatic polyamide resin and the toluene di-isocyanate(TDI), 2,
2'- (1,3- phenylene)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamides of N'- and double
(2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and is mixed；
(2) coupling agent, boron nitride, aluminium oxide and silicon carbide are added in another high-speed mixer and are mixed
It closes；
(3) mixture for mixing step (1) is added in parallel double-screw extruder through feeder, and in parallel double spiral shells
Lateral (such as the 4th area) of bar extruder (totally eight area) is added the mixture that step (2) mix and carries out melting extrusion, is granulated,
Technological parameter is as follows: area's temperature is 265~295 DEG C, and two area's temperature are 295~310 DEG C, and three area's temperature are 300~315 DEG C,
Four area's temperature are 305~315 DEG C, and five area's temperature are 305~315 DEG C, and six area's temperature are 305~315 DEG C, and seven area's temperature are 305
~315 DEG C, eight area's temperature are 305~315 DEG C, and die head temperature is 300~310 DEG C, and screw speed is 200~600rpm.
In wherein some embodiments, by the copolyamide resin and aliphatic polyamide resin in the step (1)
It is 4~6 hours dry under conditions of being placed in 90 DEG C；Technological parameter in the step (3) are as follows: area's temperature is 265~290 DEG C,
Two area's temperature are 295~305 DEG C, and three area's temperature are 300~310 DEG C, and four area's temperature are 305~310 DEG C, and five area's temperature are 305
~310 DEG C, six area's temperature are 305~310 DEG C, and seven area's temperature are 305~310 DEG C, and eight area's temperature are 305~310 DEG C, die head temperature
Degree is 300~305 DEG C, and screw speed is 200~400rpm.
In wherein some embodiments, the screw configuration of the parallel double-screw extruder is single thread；Spiro rod length L
It is 35~50 with the ratio between diameter D L/D；The screw rod be equipped with 1 or more (contain 1) gear block area and 1 or more (containing 1)
Left-hand thread area.
In wherein some embodiments, the ratio between the spiro rod length L and diameter D L/D are 35~45；The screw rod is equipped with
2 gear block areas and 1 left-hand thread area.
In wherein some embodiments, the copolyamide resin is copolymerized by monomer 1 and polyesteramide, the monomer
1 is the decamethylene diamine, terephthalic acid (TPA), aliphatic dibasic acid that molar ratio is 1:0.9~0.99:0.01~0.1, and described to benzene two
Both formic acid and aliphatic dibasic acid dosage and be 1 with the molar ratio of the decamethylene diamine, the aliphatic dibasic acid be adipic acid,
At least one of decanedioic acid, dodecanedioic acid, the polyesteramide additional amount are the 1~8% of 1 total weight of monomer.
In wherein some embodiments, the copolyamide resin is made by following synthetic method:
(1) monomer 1 after vacuum drying is added in stirring-type polymer reactor, while the polyester acyl is added
Amine and molecular weight regulator, antioxidant, water；Then 4~6min is vacuumized, 4~6min of nitrogen is led to, is so recycled 5~7 times,
Be present in reactant in the environment under nitrogen protection, control in the stirring-type polymer reactor system pressure be 0.2~
0.3MPa；
(2) in 2~4 hours by the closed constant-speed heating of stirring-type polymer reactor to 272~280 DEG C, adjust institute
The mixing speed for stating stirring-type polymer reactor is 30~50r/min, wherein when the stirring-type polymer reactor temperature reaches
At 215 DEG C, it is deflated to 2.0MPa, and maintains pressure after 2.0MPa, reaction 1~2 hour, normal pressure is deflated to, is warming up to simultaneously
After the reaction was continued at 310~320 DEG C 1~2 hour, after constant temperature persistently vacuumizes 0.3~1 hour, the copolyamide tree is obtained
Rouge；
The molecular weight regulator is 0.1~3% benzoic acid that additional amount is 1 total weight of monomer；The antioxygen
Agent is 0.1~0.3% N, the N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1 that additional amount is 1 total weight of monomer,
3- benzene diamides；Appropriate amount of water.
The principle of the present invention is as follows:
Thermal conductivity in order to solve current copolyamide resin is smaller and processing temperature narrow limits and processing performance not
Good defect, the present invention improve the thermally conductive of copolyamide resin using thermal conducting agent boron nitride, aluminium oxide and the silicon carbide of compounding
Performance, while improving by aliphatic polyamide resin the processing performance of copolyamide resin, this is because aliphatic polyamides
Polyimide resin has preferable mobile performance and copolyamide resin has preferable mechanical property.Moreover, fatty polyamide
The end group of resin and copolyamide resin can respectively with the isocyanate groups of toluene di-isocyanate(TDI), the 2,2'- (Asia 1,3- benzene
Base) the oxazoline group of-bisoxazoline reacts, improve the compatibility of both polyamides.Also, toluene diisocyanate
The isocyanate groups of acid esters, 2,2'- (1,3- phenylene)-bisoxazoline oxazoline group can also be with boron nitride, oxidation
Coupling agent on aluminium, silicon carbide is reacted, to improve boron nitride, aluminium oxide, silicon carbide and above two polyamide
Interface binding power and compatibility, reduce their influences to polyamide compoiste material mechanical property.
The coupling agent that the present invention uses, preferably gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane,
Contain amino, above-mentioned auxiliary agent can react with the end group of above two polyamide, to further increase nitrogen
It is multiple to polyamide to reduce them for the interface binding power and compatibility for changing boron, aluminium oxide, silicon carbide and above two polyamide
The influence of condensation material mechanical property.
The present invention improves the heating conduction of copolyamide resin by being used in compounding boron nitride, aluminium oxide, silicon carbide,
Synergistic effect is obvious.Wherein, the boron nitride hardness of sheet is low, matter is soft, easily deforms and contacts with each other in the blending process,
To form mutually overlapped reticular structure, more phonon routes of transmission are created, the thermal conductivity of polyamide compoiste material is improved
Energy；Aluminium oxide has the characteristics that hardness is high, elevated temperature strength is big, antioxygenic property is good and cheap, can effectively improve poly-
The heating conduction of amide composite material；The silicon carbide draw ratio of crystal whisker-shaped is big, thermal conductivity is high, good insulation preformance, can rise well
It is acted on to bridge joint, doses advantageously form heat conduction network on a small quantity.
The fusing point of bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N, N'- is 272 DEG C, boiling point is greater than
360 DEG C, the better heat stability in polyamide resin composite material Blending Processes, amide group can gather with above two
The end group of amide resin reacts to improve compatibility, and hindered piperidine base can provide antioxidation and improve the dyeing of copolymer
Property.
The fusing point of bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates is 239 DEG C, thermal decomposition temperature is super
350 DEG C are crossed, there is good heat resistance and hydrolytic resistance, it can be superior to be provided in polyamide resin composite material Blending Processes
Colour stability and melt stability, while the thermal degradation of above two polyamide in the high temperature process can be prevented, and
The hot oxygen discoloration due to caused by long-time is inhibited, it also offers in nitrogen oxides (NOx) color in the environment of gas
Stability prevents gas from smoking discoloration.
Compared with prior art, the invention has the following advantages:
The present invention for current copolyamide resin thermal conductivity is smaller and processing temperature narrow limits and processing performance
Bad problem improves the heating conduction of copolyamide resin by compounding using boron nitride, aluminium oxide, silicon carbide, and
Improve the processing performance of copolyamide resin using aliphatic polyamide resin, while using toluene di-isocyanate(TDI) and 2,
2'- (1,3- phenylene)-bisoxazoline gathers as the compatilizer between both polyamides, and as above two
Compatilizer between amide resin and the boron nitride, aluminium oxide, silicon carbide that are attached with coupling agent, and it is used in compounding N, N'- is bis-
(2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamide and bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythrites
Bisphosphate handles the xanthochromia problem in Blending Processes, and preparation-obtained high heat conductive insulating copolyamide composite material has
The characteristics of high thermal conductivity coefficient, high tensile, high fluidity, low water absorption and good insulation preformance, can be applied to it is electric,
LED, automobile and other industries field.
Detailed description of the invention
Fig. 1 show the preparation technology flow chart of high heat conductive insulating copolyamide composite material of the present invention.
Specific embodiment
To further understand the features of the present invention, technological means and specific purposes achieved, function, parse this hair
Bright advantage and spirit, by following embodiment, the present invention is further elaborated.
The reaction mechanism is as follows that (preparation technology flow chart is see figure for high heat conductive insulating copolyamide composite material of the present invention
1):
Reaction mechanism
By above-mentioned reaction equation it is found that the Amino End Group of aliphatic polyamide resin and copolyamide resin can be different with toluene two
The isocyanate groups of cyanate react, and the Amino End Group of aliphatic polyamide resin and copolyamide resin, carboxyl end group can
It is reacted with the oxazoline group with 2,2'- (1,3- phenylene)-bisoxazoline, so as to increase both polyamide resins
Compatibility between rouge.
Raw material used in the embodiment of the present invention is as follows:
Copolyamide resin is made by oneself, and the decamethylene diamine in raw material is selected from Wuxi Yinda Nylon Co., Ltd., terephthalic acid (TPA) choosing
From Beijing Yanshan Petrochemical Co., adipic acid, decanedioic acid, dodecanedioic acid are selected from Shandong Guang Yin new material Co., Ltd,
Remaining auxiliary agent is selected from Sinopharm Chemical Reagent Co., Ltd.；
Polyhexamethylene adipamide resin (PA66), is selected from China Shenma Group Co., Ltd., and inherent viscosity is respectively
1.22dL/g,1.66dL/g,1.84dL/g；
Toluene di-isocyanate(TDI) is selected from Sinopharm Chemical Reagent Co., Ltd.；
2,2'- (1,3- phenylene)-bisoxazolines are selected from Sinopharm Chemical Reagent Co., Ltd.；
Coupling agent (gamma-aminopropyl-triethoxy-silane) is selected from Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei；
Coupling agent (γ-aminopropyltrimethoxysilane) is selected from Zhejiang boiling point Chemical Co., Ltd.；
Boron nitride, sheet, partial size are 5~150 μm, abundant up to special cermacis Co., Ltd selected from Shandong Zibo；
Aluminium oxide, partial size are 5~60 μm, are selected from Zibo Nuo Da Chemical Co., Ltd.；
Silicon carbide, crystal whisker-shaped, diameter of whiskers are 0.05~2.5 μm, draw ratio >=20, selected from Xuzhou victory innovative material science and technology
Co., Ltd；
Bis- (2,2,6,6- tetramethyl -4- piperidyl) -1, the 3- benzenedicarboxamides of N, N'-, have selected from such as Dong Jinkangtai chemistry
Limit company；
Bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, it is limited selected from Shanghai point credit fine chemistry industry
Company.
Below in conjunction with specific embodiment, the present invention will be described in detail.
Copolyamide resin in following embodiment is copolymerized by monomer 1 and polyesteramide, and the monomer 1 is molar ratio
For the decamethylene diamine, terephthalic acid (TPA), aliphatic dibasic acid of 1:0.9~0.99:0.01~0.1, and the terephthalic acid (TPA) and rouge
Both fat race binary acid dosage and be 1 with the molar ratio of the decamethylene diamine, the aliphatic dibasic acid be adipic acid, decanedioic acid,
At least one of dodecanedioic acid, the polyesteramide additional amount are the 1~8% of 1 total weight of monomer, above-mentioned copolymerization acyl
Polyimide resin has such as following formula I structure:
In Formulas I, a=10~100, b=10~200, c=10~100, d=10~100, e=4 or 8 or 10, R are polyester
Amide has such as Formula Il structure:
In Formula II, x=10~200, y=10~200, z=10~100.
The synthetic method of copolyamide resin is as follows:
(1) monomer 1 after vacuum drying is added in stirring-type polymer reactor, while the polyester acyl is added
Amine and molecular weight regulator, antioxidant, water；Then 4~6min is vacuumized, 4~6min of nitrogen is led to, is so recycled 5~7 times,
Be present in reactant in the environment under nitrogen protection, control in the stirring-type polymer reactor system pressure be 0.2~
0.3MPa；
(2) in 2~4 hours by the closed constant-speed heating of stirring-type polymer reactor to 272~280 DEG C, adjust institute
The mixing speed for stating stirring-type polymer reactor is 30~50r/min, wherein when the stirring-type polymer reactor temperature reaches
At 215 DEG C, it is deflated to 2.0MPa, and maintains pressure after 2.0MPa, reaction 1~2 hour, normal pressure is deflated to, is warming up to simultaneously
After the reaction was continued at 310~320 DEG C 1~2 hour, after constant temperature persistently vacuumizes 0.3~1 hour, the copolyamide tree is obtained
Rouge；
The molecular weight regulator is 0.1~3% benzoic acid that additional amount is 1 total weight of monomer；The antioxygen
Agent is 0.1~0.3% N, the N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1 that additional amount is 1 total weight of monomer,
3- benzene diamides；Appropriate amount of water.
Embodiment 1
Copolyamide resin used in the present embodiment is polyamide 10T/106 resin (PA10T/106), raw material structure
At and synthesis step it is as follows:
(1) monomer 1:1mol decamethylene diamine, 0.95mol terephthalic acid (TPA), the 0.05mol adipic acid after vacuum drying are added
Into stirring-type polymer reactor, at the same be added 4% polyesteramide of 1 total weight of monomer, 1.5% benzoic acid, 0.2%
Medium of the 100mL water as mass-and heat-transfer is added in N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides；
Then 5min is vacuumized, leads to nitrogen 5min, so circulation 6 times, is present in reactant in the environment under nitrogen protection, control is stirred
Mixing system pressure in formula polymer reactor is 0.3MPa；
(2) in 3 hours by the closed constant-speed heating of stirring-type polymer reactor to 275 DEG C, adjust stirring-type polymerization reaction
The mixing speed of device is 40r/min, wherein when stirring-type polymer reactor temperature reaches 215 DEG C, it is deflated to 2.0MPa, and
It maintains pressure in 2.0MPa, after reaction 1.5 hours, is deflated to normal pressure, while being warming up at 315 DEG C after the reaction was continued 1.5 hours,
After constant temperature persistently vacuumizes 0.5 hour, the copolyamide resin is obtained；
The intrinsic viscosity of the above-mentioned copolyamide resin (PA10T/106) being prepared is 0.85dL/g, melting temperature is
301℃。
A kind of high heat conductive insulating copolyamide composite material of the present embodiment, is prepared by the raw material of following parts by weight:
The preparation method of above-mentioned high heat conductive insulating copolyamide composite material, comprising the following steps:
(1) cold under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours
But, by copolyamide resin after cooling, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI), 2,2'-, (1,3- is sub-
Phenyl)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) coupling agent (γ-aminopropyltrimethoxysilane), boron nitride, aluminium oxide and silicon carbide are added to another
It is mixed in high-speed mixer；
(3) mixture for mixing step (1) is added in parallel double-screw extruder through feeder, and in parallel double spiral shells
Lateral (the 4th area) of bar extruder (totally eight area) is added the mixture that step (2) mix and carries out melting extrusion, is granulated, technique
Parameter is as follows: area's temperature is 295 DEG C, and two area's temperature are 310 DEG C, and three area's temperature are 315 DEG C, and four area's temperature are 315 DEG C, 5th area
Temperature is 315 DEG C, and six area's temperature are 315 DEG C, and seven area's temperature are 315 DEG C, and eight area's temperature are 315 DEG C, and die head temperature is 310 DEG C,
Screw speed is 600rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 35,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Embodiment 2
Copolyamide resin used in the present embodiment is polyamide 10T/1012 resin (PA10T/1012), raw material
It constitutes and synthesis step is as follows:
(1) by monomer 1:1mol decamethylene diamine, 0.95mol terephthalic acid (TPA), the 0.05mol dodecanedioic acid after vacuum drying
Be added in stirring-type polymer reactor, at the same be added 4% polyesteramide of 1 total weight of monomer, 1.5% benzoic acid,
100mL water is added as mass-and heat-transfer in 0.2% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides
Medium；Then 5min is vacuumized, leads to nitrogen 5min, so circulation 6 times, reactant is made to be present in the environment under nitrogen protection
In, controlling system pressure in stirring-type polymer reactor is 0.3MPa；
(2) in 3 hours by the closed constant-speed heating of stirring-type polymer reactor to 275 DEG C, adjust stirring-type polymerization reaction
The mixing speed of device is 40r/min, wherein when stirring-type polymer reactor temperature reaches 215 DEG C, it is deflated to 2.0MPa, and
It maintains pressure in 2.0MPa, after reaction 1.5 hours, is deflated to normal pressure, while being warming up at 315 DEG C after the reaction was continued 1.5 hours,
After constant temperature persistently vacuumizes 0.5 hour, the copolyamide resin is obtained；
The intrinsic viscosity of the above-mentioned copolyamide resin (PA10T/1012) being prepared is 0.88dL/g, melting temperature is
297℃。
A kind of high heat conductive insulating copolyamide composite material of the present embodiment, is prepared by the raw material of following parts by weight:
The preparation method of above-mentioned high heat conductive insulating copolyamide composite material, comprising the following steps:
(1) cold under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours
But, by copolyamide resin after cooling, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI), 2,2'-, (1,3- is sub-
Phenyl)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), boron nitride, aluminium oxide and silicon carbide are added to another
It is mixed in high-speed mixer；
(3) mixture for mixing step (1) is added in parallel double-screw extruder through feeder, and in parallel double spiral shells
Lateral (the 4th area) of bar extruder (totally eight area) is added the mixture that step (2) mix and carries out melting extrusion, is granulated, technique
Parameter is as follows: area's temperature is 265 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 300 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 200rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 50,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Embodiment 3
Copolyamide resin used in the present embodiment is polyamide 10T/1010 resin (PA10T/1010), raw material
It constitutes and synthesis step is as follows:
(1) monomer 1:1mol decamethylene diamine, 0.95mol terephthalic acid (TPA), the 0.05mol decanedioic acid after vacuum drying are added
Into stirring-type polymer reactor, at the same be added 4% polyesteramide of 1 total weight of monomer, 1.5% benzoic acid, 0.2%
Medium of the 100mL water as mass-and heat-transfer is added in N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides；
Then 5min is vacuumized, leads to nitrogen 5min, so circulation 6 times, is present in reactant in the environment under nitrogen protection, control is stirred
Mixing system pressure in formula polymer reactor is 0.3MPa；
(2) in 3 hours by the closed constant-speed heating of stirring-type polymer reactor to 275 DEG C, adjust stirring-type polymerization reaction
The mixing speed of device is 40r/min, wherein when stirring-type polymer reactor temperature reaches 215 DEG C, it is deflated to 2.0MPa, and
It maintains pressure in 2.0MPa, after reaction 1.5 hours, is deflated to normal pressure, while being warming up at 315 DEG C after the reaction was continued 1.5 hours,
After constant temperature persistently vacuumizes 0.5 hour, the copolyamide resin is obtained；
The intrinsic viscosity of the above-mentioned copolyamide resin (PA10T/1010) being prepared is 0.86dL/g, melting temperature is
299℃。
A kind of high heat conductive insulating copolyamide composite material of the present embodiment, is prepared by the raw material of following parts by weight:
The preparation method of above-mentioned high heat conductive insulating copolyamide composite material, comprising the following steps:
(1) cold under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours
But, by copolyamide resin after cooling, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI), 2,2'-, (1,3- is sub-
Phenyl)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), boron nitride, aluminium oxide and silicon carbide are added to another
It is mixed in high-speed mixer；
(3) mixture for mixing step (1) is added in parallel double-screw extruder through feeder, and in parallel double spiral shells
Lateral (the 4th area) of bar extruder (totally eight area) is added the mixture that step (2) mix and carries out melting extrusion, is granulated, technique
Parameter is as follows: area's temperature is 290 DEG C, and two area's temperature are 305 DEG C, and three area's temperature are 310 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 DEG C,
Screw speed is 400rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 45,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Embodiment 4
The raw material of copolyamide resin used in the present embodiment is constituted and synthesis step is the same as embodiment 3.
A kind of high heat conductive insulating copolyamide composite material of the present embodiment, is prepared by the raw material of following parts by weight:
The preparation method of above-mentioned high heat conductive insulating copolyamide composite material, comprising the following steps:
(1) cold under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours
But, by copolyamide resin after cooling, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI), 2,2'-, (1,3- is sub-
Phenyl)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), boron nitride, aluminium oxide and silicon carbide are added to another
It is mixed in high-speed mixer；
(3) mixture for mixing step (1) is added in parallel double-screw extruder through feeder, and in parallel double spiral shells
Lateral (the 4th area) of bar extruder (totally eight area) is added the mixture that step (2) mix and carries out melting extrusion, is granulated, technique
Parameter is as follows: area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Embodiment 5
The raw material of copolyamide resin used in the present embodiment is constituted and synthesis step is the same as embodiment 3.
A kind of high heat conductive insulating copolyamide composite material of the present embodiment, is prepared by the raw material of following parts by weight:
The preparation method of above-mentioned high heat conductive insulating copolyamide composite material, comprising the following steps:
(1) cold under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours
But, by copolyamide resin after cooling, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI), 2,2'-, (1,3- is sub-
Phenyl)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), boron nitride, aluminium oxide and silicon carbide are added to another
It is mixed in high-speed mixer；
(3) mixture for mixing step (1) is added in parallel double-screw extruder through feeder, and in parallel double spiral shells
Lateral (the 4th area) of bar extruder (totally eight area) is added the mixture that step (2) mix and carries out melting extrusion, is granulated, technique
Parameter is as follows: area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Embodiment 6
The raw material of copolyamide resin used in the present embodiment is constituted and synthesis step is the same as embodiment 3.
A kind of high heat conductive insulating copolyamide composite material of the present embodiment, is prepared by the raw material of following parts by weight:
The preparation method of above-mentioned high heat conductive insulating copolyamide composite material, comprising the following steps:
(1) cold under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours
But, by copolyamide resin after cooling, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI), 2,2'-, (1,3- is sub-
Phenyl)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), boron nitride, aluminium oxide and silicon carbide are added to another
It is mixed in high-speed mixer；
(3) mixture for mixing step (1) is added in parallel double-screw extruder through feeder, and in parallel double spiral shells
Lateral (the 4th area) of bar extruder (totally eight area) is added the mixture that step (2) mix and carries out melting extrusion, is granulated, technique
Parameter is as follows: area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Comparative example 1
The raw material of copolyamide resin used in this comparative example is constituted and synthesis step is the same as embodiment 3.
A kind of high heat conductive insulating copolyamide composite material of this comparative example, is prepared by the raw material of following parts by weight:
The preparation method of above-mentioned high heat conductive insulating copolyamide composite material, comprising the following steps:
(1) cooling under conditions of copolyamide resin being placed in 90 DEG C after drying 5 hours, by copolyamide after cooling
Resin and N, bis- (2,2,6,6- tetramethyl -4- piperidyl) -1, the 3- benzenedicarboxamides of N'- and bis- (2,6- di-t-butyl -4-
Aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), boron nitride, aluminium oxide and silicon carbide are added to another
It is mixed in high-speed mixer；
(3) mixture for mixing step (1) is added in parallel double-screw extruder through feeder, and in parallel double spiral shells
Lateral (the 4th area) of bar extruder (totally eight area) is added the mixture that step (2) mix and carries out melting extrusion, is granulated, technique
Parameter is as follows: area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Comparative example 2
The raw material of copolyamide resin used in this comparative example is constituted and synthesis step is the same as embodiment 3.
A kind of high heat conductive insulating copolyamide composite material of this comparative example, is prepared by the raw material of following parts by weight:
The preparation method of above-mentioned high heat conductive insulating copolyamide composite material, comprising the following steps:
(1) cold under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours
But, by copolyamide resin after cooling, polyhexamethylene adipamide resin and bis- (2,2,6, the 6- tetramethyl -4- piperazines of N, N'-
Piperidinyl) -1,3- benzenedicarboxamide and bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates are added to high-speed stirring
It mixes in machine and is mixed；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), boron nitride, aluminium oxide and silicon carbide are added to another
It is mixed in high-speed mixer；
(3) mixture for mixing step (1) is added in parallel double-screw extruder through feeder, and in parallel double spiral shells
Lateral (the 4th area) of bar extruder (totally eight area) is added the mixture that step (2) mix and carries out melting extrusion, is granulated, technique
Parameter is as follows: area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Comparative example 3
The raw material of copolyamide resin used in this comparative example is constituted and synthesis step is the same as embodiment 3.
A kind of high heat conductive insulating copolyamide composite material of this comparative example, is prepared by the raw material of following parts by weight:
The preparation method of above-mentioned high heat conductive insulating copolyamide composite material, comprising the following steps:
(1) cold under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours
But, by copolyamide resin after cooling, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI), 2,2'-, (1,3- is sub-
Phenyl)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) boron nitride, aluminium oxide and silicon carbide are added in another high-speed mixer and are mixed；
(3) mixture for mixing step (1) is added in parallel double-screw extruder through feeder, and in parallel double spiral shells
Lateral (the 4th area) of bar extruder (totally eight area) is added the mixture that step (2) mix and carries out melting extrusion, is granulated, technique
Parameter is as follows: area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Comparative example 4
The raw material of copolyamide resin used in this comparative example is constituted and synthesis step is the same as embodiment 3.
A kind of high heat conductive insulating copolyamide composite material of this comparative example, is prepared by the raw material of following parts by weight:
The preparation method of above-mentioned high heat conductive insulating copolyamide composite material, comprising the following steps:
(1) cold under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours
But, by copolyamide resin after cooling, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI), 2,2'-, (1,3- is sub-
Phenyl)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), boron nitride, aluminium oxide and silicon carbide are added to another
It is mixed in high-speed mixer；
(3) mixture for mixing step (1) is added in parallel double-screw extruder through feeder, and in parallel double spiral shells
Lateral (the 4th area) of bar extruder (totally eight area) is added the mixture that step (2) mix and carries out melting extrusion, is granulated, technique
Parameter is as follows: area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is double thread, and the ratio between spiro rod length L and diameter D L/D are 30,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
The following are embodiments and comparative example list (table 1):
1 embodiment of table and comparative example raw material form parts by weight list
Bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of the N of above embodiments and comparative example, N'- and
Bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates are respectively 0.15 part, 0.15 part.
The various embodiments described above and the made plastic part sample of comparative example are subjected to following performance test (the results are shown in Table 2):
Parallel thermal conductivity in face: ASTM E1461 standard testing is pressed；
Tensile property: GB/T 1040.1-2006 standard testing, rate of extension 10mm/min are pressed；
Mobile performance: press GB/T 3682-2000 standard testing, 309 DEG C of test temperature, load 1.2kg；
Water absorbing properties: GB/T 1034-2008 standard testing is pressed, the testing time is for 24 hours；
Surface resistivity: 60093 standard testing of IEC is pressed.
2 embodiment of table and comparative example performance list
As can be seen that the additive amount of boron nitride, aluminium oxide and silicon carbide is more from Examples 1 to 6, copolyamide resin
Parallel thermal conductivity and tensile strength are bigger in the face of composite material；Aliphatic polyamide resin (polyhexamethylene adipamide resin)
Additional amount it is more, the melt index of copolyamide resin composite materials is bigger, and processing performance is better；The water absorption rate of each embodiment
It is little with surface resistivity variation.In summary the comprehensive performance of factor, embodiment 6 is best.
It is compared with embodiment 6, comparative example 1 is to be not added with aliphatic polyamide resin (polyhexamethylene adipamide resin)
Copolyamide resin composite materials, melt index is only 6g/10min (309 DEG C of test temperature, load 1.2kg), processability
It can be bad；Comparative example 2 be not added with toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO) is total to
Polyamide resin composite material, polyamide compatibility is not together for aliphatic polyamide resin (polyhexamethylene adipamide resin)
It is good, to cause undesirable influence to the tensile property of copolyamide resin composite materials with thermal conductivity parallel in face；Comparison
Example 3 is the copolyamide resin composite materials for being not added with coupling agent, boron nitride, aluminium oxide and silicon carbide and above two polyamide
Resin compatible is bad, to cause to the tensile properties of copolyamide resin composite materials with thermal conductivity parallel in face bad
Influence；The screw configuration of the parallel double-screw extruder of comparative example 4 is double thread, the ratio between spiro rod length L and diameter D L/D
It is 30, and the screw configuration of the parallel double-screw extruder of embodiment 6 is single thread, the ratio between spiro rod length L and diameter D L/D
Be 40, by comparison it can be found that using parallel double-screw extruder described in embodiment 6 Screw Parameters, be prepared
Copolyamide resin composite materials face in parallel thermal conductivity, tensile property, processing performance be greatly improved, obtain height and lead
Hot coefficient, high tensile, high fluidity, low water absorption and good insulation preformance high heat conductive insulating copolyamide composite material
Beneficial effect.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (9)
1. a kind of high heat conductive insulating copolyamide composite material, which is characterized in that be prepared by the raw material of following parts by weight:
The intrinsic viscosity of the copolyamide resin is 0.7~1.0dL/g；
The aliphatic polyamide resin is at least one of nylon 46 resin, polyhexamethylene adipamide resin；
The coupling agent is gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-γ-
Aminopropyl triethoxysilane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-aminopropyl
Methyl dimethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, anilinomethyl
At least one of triethoxysilane；
The copolyamide resin is copolymerized by monomer 1 and polyesteramide, and it is 1:0.9~0.99 that the monomer 1, which is molar ratio:
0.01~0.1 decamethylene diamine, terephthalic acid (TPA), aliphatic dibasic acid, and both the terephthalic acid (TPA) and aliphatic dibasic acid
Dosage and be 1 with the molar ratio of the decamethylene diamine, the aliphatic dibasic acid are adipic acid, decanedioic acid, in dodecanedioic acid
At least one, the polyesteramide additional amount are the 1~8% of 1 total weight of monomer；
The polyesteramide has such as Formula Il structure:
In Formula II, x=10~200, y=10~200, z=10~100；
The screw configuration of parallel double-screw extruder used in the preparation of the heat conductive insulating copolyamide composite material is
Single thread；The ratio between spiro rod length L and diameter D L/D are 35~50.
2. high heat conductive insulating copolyamide composite material according to claim 1, which is characterized in that by following parts by weight
Raw material is prepared:
3. high heat conductive insulating copolyamide composite material according to claim 1 or 2, which is characterized in that the copolymerization acyl
The intrinsic viscosity of polyimide resin is 0.75~0.95dL/g；The aliphatic polyamide resin is polyhexamethylene adipamide resin,
Inherent viscosity is 1.22~1.84dL/g.
4. high heat conductive insulating copolyamide composite material according to claim 1 or 2, which is characterized in that the coupling agent
For at least one of gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane；The shape of the boron nitride is
Sheet, partial size are 5~150 μm；The partial size of the aluminium oxide is 5~60 μm；The shape of the silicon carbide is crystal whisker-shaped, and whisker is straight
Diameter is 0.05~2.5 μm, draw ratio >=20.
5. high heat conductive insulating copolyamide composite material according to claim 1 or 2, which is characterized in that the copolymerization acyl
Polyimide resin is made by following synthetic method:
(1) monomer 1 after vacuum drying is added in stirring-type polymer reactor, while the polyesteramide is added,
And molecular weight regulator, antioxidant, water；Then 4~6min is vacuumized, 4~6min of nitrogen is led to, so recycles 5~7 times, makes
Reactant is present in the environment under nitrogen protection, control in the stirring-type polymer reactor system pressure be 0.2~
0.3MPa；
(2) in 2~4 hours by the closed constant-speed heating of stirring-type polymer reactor to 272~280 DEG C, stirred described in adjusting
The mixing speed for mixing formula polymer reactor is 30~50r/min, wherein when the stirring-type polymer reactor temperature reaches 215
DEG C when, be deflated to 2.0MPa, and maintain pressure in 2.0MPa, after reaction 1~2 hour, be deflated to normal pressure, while being warming up to 310
After the reaction was continued at~320 DEG C 1~2 hour, after constant temperature persistently vacuumizes 0.3~1 hour, the copolyamide resin is obtained；
The molecular weight regulator is 0.1~3% benzoic acid that additional amount is 1 total weight of monomer；The antioxidant is
Additional amount is 0.1~0.3% N of 1 total weight of monomer, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene
Diamides；Appropriate amount of water.
6. a kind of preparation method of the described in any item high heat conductive insulating copolyamide composite materials of claim 1-5, feature
It is, comprising the following steps:
(1) 4~12 hours dry under conditions of the copolyamide resin and aliphatic polyamide resin being placed in 80~100 DEG C
Afterwards, cooling, by copolyamide resin after cooling, aliphatic polyamide resin and the toluene di-isocyanate(TDI), 2,2'-
(1,3- phenylene)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and it is bis- (2,
6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) coupling agent, boron nitride, aluminium oxide and silicon carbide are added in another high-speed mixer and are mixed；
(3) mixture for mixing step (1) is added in parallel double-screw extruder through feeder, and squeezes in parallel double-screw
The mixture that the lateral addition step (2) of machine mixes out carries out melting extrusion, is granulated, and technological parameter is as follows: area's temperature is
265~295 DEG C, two area's temperature be 295~310 DEG C, three area's temperature be 300~315 DEG C, four area's temperature be 305~315 DEG C, five
Area's temperature be 305~315 DEG C, six area's temperature be 305~315 DEG C, seven area's temperature be 305~315 DEG C, eight area's temperature be 305~
315 DEG C, die head temperature is 300~310 DEG C, and screw speed is 200~600rpm.
7. preparation method according to claim 6, which is characterized in that by the copolyamide resin in the step (1)
It is 4~6 hours dry under conditions of being placed in 90 DEG C with aliphatic polyamide resin；Technological parameter in the step (3) an are as follows: area
Temperature is 265~290 DEG C, and two area's temperature are 295~305 DEG C, and three area's temperature are 300~310 DEG C, and four area's temperature are 305~310
DEG C, five area's temperature are 305~310 DEG C, and six area's temperature are 305~310 DEG C, and seven area's temperature are 305~310 DEG C, and eight area's temperature are
305~310 DEG C, die head temperature is 300~305 DEG C, and screw speed is 200~400rpm.
8. preparation method according to claim 6 or 7, which is characterized in that the screw shaped of the parallel double-screw extruder
Shape is single thread；The ratio between spiro rod length L and diameter D L/D are 35~50；The screw rod is equipped with 1 or more gear block area
With 1 or more left-hand thread area.
9. preparation method according to claim 8, which is characterized in that the ratio between described spiro rod length L and diameter D L/D is 35
~45；The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
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| CN108129834A (en) * | 2017-12-28 | 2018-06-08 | 许飞扬 | A kind of flame-resistant insulation composite nylon material |
| CN111334042A (en) * | 2020-04-14 | 2020-06-26 | 广东圆融新材料有限公司 | Low-dielectric-constant polyphenylene sulfide composition and preparation method thereof |
| CN111849164A (en) * | 2020-08-14 | 2020-10-30 | 广东圆融新材料有限公司 | Low-linear expansion coefficient polyphenylene sulfide/polyamide 66 composition and preparation method thereof |
| CN111875963A (en) * | 2020-08-18 | 2020-11-03 | 广东圆融新材料有限公司 | Low-linear expansion coefficient polyphenylene sulfide/nylon 6 composite material and preparation method thereof |
| CN111978719A (en) * | 2020-08-28 | 2020-11-24 | 广东圆融新材料有限公司 | Polyamide 66 composite material and preparation method thereof |
| CN111944308A (en) * | 2020-08-31 | 2020-11-17 | 广东圆融新材料有限公司 | Nylon 6 composite material with low linear expansion coefficient and preparation method thereof |
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