CN107057341B - High heat conductive insulating polyamide compoiste material and preparation method thereof - Google Patents
High heat conductive insulating polyamide compoiste material and preparation method thereof Download PDFInfo
- Publication number
- CN107057341B CN107057341B CN201710012982.XA CN201710012982A CN107057341B CN 107057341 B CN107057341 B CN 107057341B CN 201710012982 A CN201710012982 A CN 201710012982A CN 107057341 B CN107057341 B CN 107057341B
- Authority
- CN
- China
- Prior art keywords
- area
- temperature
- polyamide
- resin
- heat conductive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyamides (AREA)
Abstract
The present invention relates to a kind of high heat conductive insulating polyamide compoiste materials and preparation method thereof, the high heat conductive insulating polyamide compoiste material is prepared from the following materials: polyamide 10T/11 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 polyamide compoiste 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 polyamide compoiste 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 polyamide compoiste material of mobility, low water absorption and good insulation preformance, can be applied to electric, LED, vapour
The industry fields such as vehicle.
In order to achieve the above objectives, the present invention uses following scheme:
A kind of high heat conductive insulating polyamide compoiste material, the composite material are prepared by the raw material of following parts by weight:
The intrinsic viscosity of the polyamide 10T/11 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 polyamide compoiste material, by the raw material system of following parts by weight
It is standby to form:
In wherein some embodiments, the high heat conductive insulating polyamide compoiste material, further preferably by following weight
The raw material of part is prepared:
In wherein some embodiments, the intrinsic viscosity of the polyamide 10T/11 resin is 0.75~0.95dL/g；Institute
Stating aliphatic 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 polyamide 10T/11 resin is copolymerized by monomer 1 and polyesteramide, described
Monomer 1 is the decamethylene diamine, terephthalic acid (TPA), 11- aminoundecanoic acid that molar ratio is 1:1:0.01~0.1, and the polyesteramide adds
Enter 1~8% that amount is 1 total weight of monomer.
In wherein some embodiments, the polyamide 10T/11 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 polyamide 10T/ is obtained
11 resins；
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 polyamide compoiste material.
The preparation method of above-mentioned high heat conductive insulating polyamide compoiste material, specific technical solution, comprising the following steps:
(1) dry 4 under conditions of the polyamide 10T/11 resin and aliphatic polyamide resin being placed in 80~100 DEG C
It is cooling after~12 hours, polyamide 10T/11 resin after cooling, aliphatic polyamide resin and the toluene two is different
Cyanate, 2,2'- (1,3- phenylene)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzene diformazans of N'-
Amide and bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates are added in high-speed mixer and are 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 270~300 DEG C, and two area's temperature are 300~315 DEG C, and three area's temperature are 305~320 DEG C,
Four area's temperature are 310~320 DEG C, and five area's temperature are 310~320 DEG C, and six area's temperature are 310~320 DEG C, and seven area's temperature are 310
~320 DEG C, eight area's temperature are 310~320 DEG C, and die head temperature is 305~315 DEG C, and screw speed is 200~600rpm.
In wherein some embodiments, by the polyamide 10T/11 resin and fatty polyamide in the step (1)
Resin 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 270~295
DEG C, two area's temperature are 300~310 DEG C, and three area's temperature are 305~315 DEG C, and four area's temperature are 310~315 DEG C, and five area's temperature are
310~315 DEG C, six area's temperature are 310~315 DEG C, and seven area's temperature are 310~315 DEG C, and eight area's temperature are 310~315 DEG C, mould
Head temperature is 305~310 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 polyamide 10T/11 resin is copolymerized by monomer 1 and polyesteramide, described
Monomer 1 is the decamethylene diamine, terephthalic acid (TPA), 11- aminoundecanoic acid that molar ratio is 1:1:0.01~0.1, and the polyesteramide adds
Enter 1~8% that amount is 1 total weight of monomer.
In wherein some embodiments, the polyamide 10T/11 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 polyamide 10T/ is obtained
11 resins；
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 polyamide 10T/11 resin is smaller and processing temperature narrow limits and processability
The bad defect of energy, the present invention improve polyamide 10T/11 tree using thermal conducting agent boron nitride, aluminium oxide and the silicon carbide of compounding
The heating conduction of rouge, while improving by aliphatic polyamide resin the processing performance of polyamide 10T/11 resin, this be because
Have preferable mobile performance for aliphatic polyamide resin and polyamide 10T/11 resin has preferable mechanical property.
Moreover, the end group of aliphatic polyamide resin and polyamide 10T/11 resin can respectively with the isocyanic acid of toluene di-isocyanate(TDI)
Ester group, 2,2'- (1,3- phenylene)-bisoxazoline oxazoline group react, improve both polyamides
Compatibility.Also, the oxazoline group of the isocyanate groups of toluene di-isocyanate(TDI), 2,2'- (1,3- phenylene)-bisoxazoline
Group can also be reacted with the coupling agent on boron nitride, aluminium oxide, silicon carbide, to improve boron nitride, aluminium oxide, silicon carbide
With the interface binding power and compatibility of above two polyamide, their shadows to polyamide compoiste material mechanical property are reduced
It rings.
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 thermal conductivity of polyamide 10T/11 resin by being used in compounding boron nitride, aluminium oxide, silicon carbide
Can, synergistic effect is obvious.Wherein, the boron nitride hardness of sheet is low, matter is soft, easily deforms in the blending process and mutual
Contact creates more phonon routes of transmission, improves leading for polyamide compoiste material to form mutually overlapped reticular structure
Hot property；Aluminium oxide has the characteristics that hardness is high, elevated temperature strength is big, antioxygenic property is good and cheap, can effectively mention
The heating conduction of super polyamide composite material；The silicon carbide draw ratio of crystal whisker-shaped is big, thermal conductivity is high, good insulation preformance, can be very well
Ground plays the role of 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 polyamide 10T/11 resin thermal conductivity is smaller and processing temperature narrow limits and processing
The bad problem of performance improves the thermal conductivity of polyamide 10T/11 resin by compounding using boron nitride, aluminium oxide, silicon carbide
Can, and improve using aliphatic polyamide resin the processing performance of polyamide 10T/11 resin, while use toluene two is different
Cyanate and 2,2'- (1,3- phenylene)-bisoxazoline as between both polyamides compatilizer and conduct
Compatilizer between above two polyamide and the boron nitride, aluminium oxide, silicon carbide that are attached with coupling agent, and compounding makes
With N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (2,6- di-t-butyl -4- methylbenzenes
Base) pentaerythritol diphosphate handles the xanthochromia problem in Blending Processes, and preparation-obtained high heat conductive insulating polyamide is multiple
Condensation 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.
Detailed description of the invention
Fig. 1 show the preparation technology flow chart of high heat conductive insulating polyamide compoiste 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 (preparation technology flow chart is see Fig. 1) for high heat conductive insulating polyamide compoiste material of the present invention:
By above-mentioned reaction equation it is found that the Amino End Group of aliphatic polyamide resin and polyamide 10T/11 resin can and toluene
The isocyanate groups of diisocyanate react, the Amino End Group of aliphatic polyamide resin and polyamide 10T/11 resin,
Carboxyl end group can react with the oxazoline group of 2,2'- (1,3- phenylene)-bisoxazoline, so as to increase both
Compatibility between polyamide.
Raw material used in the embodiment of the present invention is as follows:
Polyamide 10T/11 resin (PA10T/11) is made by oneself, and the decamethylene diamine in raw material is selected from Wuxi Yin and reaches the limited public affairs of nylon
Department, terephthalic acid (TPA) are selected from Beijing Yanshan Petrochemical Co., and 11- aminoundecanoic acid is selected from the limited public affairs of Taiyuan Zhong Lianze agrochemicals
Department, remaining auxiliary agent are 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.
Polyamide 10T/11 resin in following embodiment is copolymerized by monomer 1 and polyesteramide, and the monomer 1 is to rub
, than decamethylene diamine, terephthalic acid (TPA), 11- aminoundecanoic acid for 1:1:0.01~0.1, the polyesteramide additional amount is described for you
The 1~8% of 1 total weight of monomer, above-mentioned polyamide 10T/11 resin have such as following formula I structure:
In Formulas I, a=10~200, b=10~200, c=10~100, R are polyesteramide, have such as Formula Il knot
Structure:
In Formula II, x=10~200, y=10~200, z=10~100.
The synthetic method of polyamide 10T/11 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 polyamide 10T/ is obtained
11 resins；
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
The raw material of polyamide 10T/11 resin used in the present embodiment is constituted and synthesis step is as follows:
(1) by monomer 1:1mol decamethylene diamine, 1mol terephthalic acid (TPA), the 0.05mol 11- amino 11 after vacuum drying
Acid is 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 polyamide 10T/11 resin is obtained；
The intrinsic viscosity of the above-mentioned polyamide 10T/11 resin being prepared is 0.85dL/g, melting temperature is 305 DEG C.
A kind of high heat conductive insulating polyamide compoiste 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 polyamide compoiste material, comprising the following steps:
(1) under conditions of polyamide 10T/11 resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours,
It is cooling, by polyamide 10T/11 resin after cooling, polyhexamethylene adipamide resin and 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 (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 300 DEG C, and two area's temperature are 315 DEG C, and three area's temperature are 320 DEG C, and four area's temperature are 320 DEG C, 5th area
Temperature is 320 DEG C, and six area's temperature are 320 DEG C, and seven area's temperature are 320 DEG C, and eight area's temperature are 320 DEG C, and die head temperature is 315 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
The raw material of polyamide 10T/11 resin used in the present embodiment is constituted and synthesis step is the same as embodiment 1.
A kind of high heat conductive insulating polyamide compoiste 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 polyamide compoiste material, comprising the following steps:
(1) under conditions of polyamide 10T/11 resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours,
It is cooling, by polyamide 10T/11 resin after cooling, polyhexamethylene adipamide resin and 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 (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 270 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 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 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
The raw material of polyamide 10T/11 resin used in the present embodiment is constituted and synthesis step is the same as embodiment 1.
A kind of high heat conductive insulating polyamide compoiste 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 polyamide compoiste material, comprising the following steps:
(1) under conditions of polyamide 10T/11 resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours,
It is cooling, by polyamide 10T/11 resin after cooling, polyhexamethylene adipamide resin and 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 (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 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 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 polyamide 10T/11 resin used in the present embodiment is constituted and synthesis step is the same as embodiment 1.
A kind of high heat conductive insulating polyamide compoiste 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 polyamide compoiste material, comprising the following steps:
(1) under conditions of polyamide 10T/11 resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours,
It is cooling, by polyamide 10T/11 resin after cooling, polyhexamethylene adipamide resin and 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 (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 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 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 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 polyamide 10T/11 resin used in the present embodiment is constituted and synthesis step is the same as embodiment 1.
A kind of high heat conductive insulating polyamide compoiste 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 polyamide compoiste material, comprising the following steps:
(1) under conditions of polyamide 10T/11 resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours,
It is cooling, by polyamide 10T/11 resin after cooling, polyhexamethylene adipamide resin and 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 (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 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 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 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 polyamide 10T/11 resin used in the present embodiment is constituted and synthesis step is the same as embodiment 1.
A kind of high heat conductive insulating polyamide compoiste 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 polyamide compoiste material, comprising the following steps:
(1) under conditions of polyamide 10T/11 resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours,
It is cooling, by polyamide 10T/11 resin after cooling, polyhexamethylene adipamide resin and 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 (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 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 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 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 polyamide 10T/11 resin used in this comparative example is constituted and synthesis step is the same as embodiment 1.
A kind of high heat conductive insulating polyamide compoiste 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 polyamide compoiste material, comprising the following steps:
(1) cooling under conditions of polyamide 10T/11 resin being placed in 90 DEG C after drying 5 hours, by polyamides after cooling
Amine 10T/11 resin and N, bis- (2,2,6,6- tetramethyl -4- piperidyl) -1, the 3- benzenedicarboxamides of N'- and bis- (2,6- bis- uncles
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 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 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 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 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 polyamide 10T/11 resin used in this comparative example is constituted and synthesis step is the same as embodiment 1.
A kind of high heat conductive insulating polyamide compoiste 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 polyamide compoiste material, comprising the following steps:
(1) under conditions of polyamide 10T/11 resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours,
It is cooling, by polyamide 10T/11 resin after cooling, polyhexamethylene adipamide resin and bis- (2,2,6, the 6- tetramethyls of N, N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide and bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates addition
It is mixed into high-speed mixer；
(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 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 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 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 polyamide 10T/11 resin used in this comparative example is constituted and synthesis step is the same as embodiment 1.
A kind of high heat conductive insulating polyamide compoiste 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 polyamide compoiste material, comprising the following steps:
(1) under conditions of polyamide 10T/11 resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours,
It is cooling, by polyamide 10T/11 resin after cooling, polyhexamethylene adipamide resin and 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) 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 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 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 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 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 polyamide 10T/11 resin used in this comparative example is constituted and synthesis step is the same as embodiment 1.
A kind of high heat conductive insulating polyamide compoiste 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 polyamide compoiste material, comprising the following steps:
(1) under conditions of polyamide 10T/11 resin and polyhexamethylene adipamide resin being placed in 90 DEG C after drying 5 hours,
It is cooling, by polyamide 10T/11 resin after cooling, polyhexamethylene adipamide resin and 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 (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 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 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 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, polyamide 10T/11
Parallel thermal conductivity and tensile strength are bigger in the face of resin composite materials；Aliphatic polyamide resin (polyhexamethylene adipamide
Resin) additional amount it is more, the melt index of polyamide 10T/11 resin composite materials is bigger, and processing performance is better；It is each to implement
Water absorption rate and the surface resistivity variation of example are little.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)
Polyamide 10T/11 resin composite materials, melt index is only 5g/10min (309 DEG C of test temperature, load 1.2kg), is added
Work performance is bad；Comparative example 2 is to be not added with toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO)
Polyamide 10T/11 resin composite materials, aliphatic polyamide resin (polyhexamethylene adipamide resin) and polyamide 10T/11
Resin compatible is bad, so that the tensile property to polyamide 10T/11 resin composite materials is caused with thermal conductivity parallel in face
Undesirable influence；Comparative example 3 is the polyamide 10T/11 resin composite materials for being not added with coupling agent, boron nitride, aluminium oxide and carbon
SiClx and above two polyamide compatibility are bad, thus to the tensile properties of polyamide 10T/11 resin composite materials and
Parallel thermal conductivity causes undesirable influence in face；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 are 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 are 40, by comparison it can be found that being squeezed out using parallel double-screw described in embodiment 6
The Screw Parameters of machine, parallel thermal conductivity in the face for the polyamide 10T/11 resin composite materials being prepared, tensile property plus
Work performance is greatly improved, and obtains high thermal conductivity coefficient, high tensile, high fluidity, low water absorption and good insulation preformance
The beneficial effect of high heat conductive insulating polyamide compoiste material.
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 polyamide compoiste material, which is characterized in that be prepared by the raw material of following parts by weight:
The intrinsic viscosity of the polyamide 10T/11 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 polyamide 10T/11 resin is copolymerized by monomer 1 and polyesteramide, and it is 1:1:0.01 that the monomer 1, which is molar ratio,
~0.1 decamethylene diamine, terephthalic acid (TPA), 11- aminoundecanoic acid, the polyesteramide additional amount are the 1 of 1 total weight of monomer
~8%；
The polyesteramide has such as Formula Il structure:
In Formula II, x=10~200, y=10~200, z=10~100；
In the preparation of the high heat conductive insulating polyamide compoiste material, the screw configuration of used parallel double-screw extruder is
Single thread；The ratio between spiro rod length L and diameter D L/D are 35~50.
2. high heat conductive insulating polyamide compoiste material according to claim 1, which is characterized in that by the original of following parts by weight
Material is prepared:
3. high heat conductive insulating polyamide compoiste material according to claim 1 or 2, which is characterized in that the polyamide
The intrinsic viscosity of 10T/11 resin is 0.75~0.95dL/g；The aliphatic polyamide resin is polyhexamethylene adipamide tree
Rouge, inherent viscosity are 1.22~1.84dL/g.
4. high heat conductive insulating polyamide compoiste material according to claim 1 or 2, which is characterized in that the coupling agent is
At least one of gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane；The shape of the boron nitride is piece
Shape, 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, diameter of whiskers
It is 0.05~2.5 μm, draw ratio >=20.
5. high heat conductive insulating polyamide compoiste material according to claim 1, which is characterized in that the polyamide 10T/11
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 polyamide 10T/11 tree is obtained
Rouge；
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 polyamide compoiste materials of claim 1-5, feature exist
In, comprising the following steps:
(1) dry 4~12 under conditions of the polyamide 10T/11 resin and aliphatic polyamide resin being placed in 80~100 DEG C
It is cooling after hour, by polyamide 10T/11 resin, aliphatic polyamide resin and the toluene diisocynate after cooling
Ester, 2,2'- (1,3- phenylene)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'-
It is added in high-speed mixer and is mixed with bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates；
(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
270~300 DEG C, two area's temperature be 300~315 DEG C, three area's temperature be 305~320 DEG C, four area's temperature be 310~320 DEG C, five
Area's temperature be 310~320 DEG C, six area's temperature be 310~320 DEG C, seven area's temperature be 310~320 DEG C, eight area's temperature be 310~
320 DEG C, die head temperature is 305~315 DEG C, and screw speed is 200~600rpm.
7. preparation method according to claim 6, which is characterized in that by the polyamide 10T/11 in the step (1)
Resin and aliphatic polyamide resin are 4~6 hours dry under conditions of being placed in 90 DEG C；Technological parameter in the step (3) are as follows:
One area's temperature is 270~295 DEG C, and two area's temperature are 300~310 DEG C, and three area's temperature are 305~315 DEG C, and four area's temperature are 310
~315 DEG C, five area's temperature are 310~315 DEG C, and six area's temperature are 310~315 DEG C, and seven area's temperature are 310~315 DEG C, eight area's temperature
Degree is 310~315 DEG C, and die head temperature is 305~310 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710012982.XA CN107057341B (en) | 2017-01-09 | 2017-01-09 | High heat conductive insulating polyamide compoiste material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710012982.XA CN107057341B (en) | 2017-01-09 | 2017-01-09 | High heat conductive insulating polyamide compoiste material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107057341A CN107057341A (en) | 2017-08-18 |
| CN107057341B true CN107057341B (en) | 2019-07-19 |
Family
ID=59623370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710012982.XA Active CN107057341B (en) | 2017-01-09 | 2017-01-09 | High heat conductive insulating polyamide compoiste material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107057341B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403924B (en) * | 2022-09-19 | 2024-02-20 | 会通新材料股份有限公司 | Heat-absorbing polyamide composition and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585491A (en) * | 2012-01-09 | 2012-07-18 | 金发科技股份有限公司 | Reinforced polyamide composition with high liquidity and low warpage and preparation method and application thereof |
| CN102719099A (en) * | 2012-06-08 | 2012-10-10 | 金发科技股份有限公司 | Thermal conductive molding compound and preparation method thereof |
| CN103044904A (en) * | 2012-12-27 | 2013-04-17 | 安徽科聚新材料有限公司 | Special heat-conducting and insulating material for LED (light-emitting diode) lamp holder and preparation method thereof |
| CN103937192A (en) * | 2014-05-12 | 2014-07-23 | 东莞市信诺橡塑工业有限公司 | PC/PA 11 (polycarbonate/polyamide 11) composition and preparation method thereof |
| CN105348520A (en) * | 2015-12-07 | 2016-02-24 | 中北大学 | Semi-aromatic polyamide and synthesis method thereof |
-
2017
- 2017-01-09 CN CN201710012982.XA patent/CN107057341B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585491A (en) * | 2012-01-09 | 2012-07-18 | 金发科技股份有限公司 | Reinforced polyamide composition with high liquidity and low warpage and preparation method and application thereof |
| CN102719099A (en) * | 2012-06-08 | 2012-10-10 | 金发科技股份有限公司 | Thermal conductive molding compound and preparation method thereof |
| CN103044904A (en) * | 2012-12-27 | 2013-04-17 | 安徽科聚新材料有限公司 | Special heat-conducting and insulating material for LED (light-emitting diode) lamp holder and preparation method thereof |
| CN103937192A (en) * | 2014-05-12 | 2014-07-23 | 东莞市信诺橡塑工业有限公司 | PC/PA 11 (polycarbonate/polyamide 11) composition and preparation method thereof |
| CN105348520A (en) * | 2015-12-07 | 2016-02-24 | 中北大学 | Semi-aromatic polyamide and synthesis method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 扩链反应在高分子材料合成中的应用;汪朝阳 等;《化学推进剂与高分子材料》;20031225;第1卷(第6期);第23-26页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107057341A (en) | 2017-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106832916B (en) | High heat conductive insulating copolyamide composite material and preparation method | |
| CN106519654B (en) | Halogen-free fire-retarding reinforced polyamide composite material and preparation method | |
| CN106479174B (en) | Fire-retardant enhancing copolyamide 6T composite material and preparation method | |
| CN106832915B (en) | High heat conductive insulating polyamide 6 T composite material and preparation method | |
| CN106497043B (en) | Fire-retardant enhancing copolyamide composite material and preparation method | |
| CN106519665B (en) | Flame retardancy reinforced polyamide composite material and preparation method thereof | |
| CN109265986A (en) | A kind of high thermal conductivity nylon composite materials | |
| CN111004501A (en) | Modified bio-based nylon 56 material and preparation method and application thereof | |
| CN109679341A (en) | A kind of high intensity, high glaze, apperance performance fiberglass reinforced high-temperature nylon material and preparation method thereof | |
| CN106751807B (en) | High heat conductive insulating copolyamide 6T composite material and preparation method | |
| CN102796366B (en) | Non-antimony flame-retardant polyamide composite material and preparation method and application thereof | |
| CN104212170A (en) | High thermal conductive wear resistant polyphenylene sulfide composite material and preparation method thereof | |
| CN107057341B (en) | High heat conductive insulating polyamide compoiste material and preparation method thereof | |
| CN106751800B (en) | Laser direct forming copolyamide 6T composite material and preparation method | |
| KR20130078154A (en) | Thermal conductive polyphenylene sulfide resin composition having a good surface gloss and article using the same | |
| CN106366657B (en) | High heat resistance height flows nylon composite materials and preparation method thereof | |
| CN106398193B (en) | Heat resistant polyamide 6T/11 composition and preparation method thereof | |
| CN106433116B (en) | High temperature resistant copolyamide 6T composition and preparation method thereof | |
| CN106675020B (en) | Laser direct forming polyamide 6 T composite material and preparation method | |
| CN106519652B (en) | High heat resistance height flows polyamide compoiste material and preparation method thereof | |
| CN115260755B (en) | Polyamide composite material and preparation method and application thereof | |
| CN106633844B (en) | High heat resistance height flows copolyamide 6T composite material and preparation method | |
| CN106336653B (en) | High temperature resistant co-polyamide composition and preparation method thereof | |
| CN106675012B (en) | Laser direct forming polyamide compoiste material and preparation method thereof | |
| CN106433119B (en) | Heat resistant polyamide 10T/11 composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 523850 Baibugao Avenue, Wushajiang, Chang'an Town, Dongguan City, Guangdong Province, 355 Patentee after: Guangdong Sinoplast New Materials Co.,Ltd. Address before: 523850 Baibugao Avenue, Wushajiang, Chang'an Town, Dongguan City, Guangdong Province, 355 Patentee before: GUANGDONG SINOPLAST ADVANCED MATERIAL CO.,LTD. |