CN106519664B - High heat resistance height flows copolyamide composite material and preparation method - Google Patents
High heat resistance height flows copolyamide composite material and preparation method Download PDFInfo
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- 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
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Abstract
The present invention relates to a kind of high heat resistance height to flow copolyamide composite material and preparation method, the high heat resistance height flowing 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, alkali-free glass fibre, N, N'- ethylenebisstearamide, N, N'- bis- (2, 2, 6, 6- tetramethyl -4- piperidyl) -1, 3- benzenedicarboxamide, bis- (2, 6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent, dimethicone.High heat resistance height flowing copolyamide composite material has the characteristics that high heat resistance, high fluidity, high tensile and low water absorption, can be applied to field of electronics, LED field, automotive field, aerospace and military industry field etc..
Description
Technical field
The present invention relates to Material Fields, flow copolyamide composite material and its preparation more particularly to a kind of high heat resistance height
Method.
Background technique
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, makes it particularly suited in auto industry, to replace the part metals structural member in automobile, to realize light weight
Change, can also be used to the insulating body of manufacture electronic device, or be used for surface mounting technique.
In heat resistant polyamide, the fusing point of PA10T resin is 320 DEG C or so, is not much different with decomposition temperature, is processed
Temperature range is narrow, be easy to cause polymer to decompose in process.Therefore, third list is introduced in PA10T resin backbone
Body improves its processing performance, expands it using field and improves its comprehensive performance.But the Third monomer of low content is added not
It is enough to improve its processing performance, and the Third monomer that high-content is added can make the fusing point of copolymer resin too low, be not achieved resistance to
The requirement of high temperature.
For above-mentioned problem, some researchs, such as Chinese patent have been done to the modification of polyamide in currently available technology
CN 103333335A discloses a kind of high fluidity PA10T Amilan polyamide resin composition, is obtained by two kinds by solid phase
Different viscositys PA10T polyamide composition；Chinese patent CN 102604380A discloses a kind of high CTI resistance of high heat resistance
Copolyamide composite material is fired, wherein the polyamide is polyhexamethylene adipamide/poly-paraphenylene terephthalamide's nonamethylene diamine copolymer
Or poly-paraphenylene terephthalamide's nonamethylene diamine；Chinese patent CN 103030972A discloses a kind of imperial 66 composite woods of high heat resistance low-warpage nylon
Material and preparation method thereof；Chinese patent CN 103012955A disclose a kind of high flowing fiberglass reinforced PP/PA composite material and its
Preparation method；Chinese patent CN 103724979A discloses a kind of high flowing heatproof LED PPO/PA composition and its preparation side
Method.
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 strong with high heat resistance, high fluidity, high stretching
The copolyamide composite material of degree and low water absorption, may be used as electrical/electronic components, automobile component, is particularly useful as
The molding substrate material of electronic component.
In order to achieve the above objectives, the present invention uses following scheme:
A kind of high heat resistance height flows copolyamide composite material, the composite material by the raw material preparation of following parts by weight and
At:
The copolyamide resin is heat resistant polyamide 10T/106 resin (PA10T/106), heat resistant polyamide 10T/
One of 1010 resins (PA10T/1010), heat resistant polyamide 10T/1012 resin (PA10T/1012)；The copolymerization acyl
The intrinsic viscosity of polyimide 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.
The length of the alkali-free glass fibre is 2~4mm, and diameter is 9~11 μm.
The anti-dripping agent is fluoropolymer.
In wherein some embodiments, high heat resistance height flows copolyamide composite material, by the raw material system of following parts by weight
It is standby to form:
In wherein some embodiments, high heat resistance height flows copolyamide composite material, further preferably by following weight
The raw material of 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 anti-dripping agent is polytetrafluoroethylene (PTFE).
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 the decamethylene diamine
With both terephthalic acid (TPA) and aliphatic dibasic acid dosage and molar ratio be 1, the aliphatic dibasic acid be adipic acid, the last of the ten Heavenly stems two
One of 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 resistance height flowing copolyamide composite material.
The preparation method of above-mentioned high heat resistance height flowing copolyamide composite material, specific technical solution, including following step
It is rapid:
(1) the copolyamide resin and aliphatic polyamide resin are placed in 80~100 DEG C, after 4~12 hours dry,
It is cooling, by copolyamide resin after cooling, aliphatic polyamide resin and the toluene di-isocyanate(TDI) (TDI), 2,
2'- (1,3- phenylene)-bisoxazoline (PBO), N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- phenyl-diformyls of N'-
Amine, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent and dimethicones are added to high speed
It is mixed in blender；
(2) coupling agent, alkali-free glass fibre and N,N' ethylene bis stearmide are added to another high-speed stirring
It mixes in machine and is mixed；
(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)
90 DEG C are placed in, drying 4~6 hours；Technological parameter in the step (3) are as follows: area's temperature is 265~290 DEG C, two area's temperature
It is 295~305 DEG C, 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 300
~305 DEG C, 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 the decamethylene diamine
With both terephthalic acid (TPA) and aliphatic dibasic acid dosage and molar ratio be 1, the aliphatic dibasic acid be adipic acid, the last of the ten Heavenly stems two
One of 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:
The bad defect of processing temperature narrow limits and processing performance in order to solve copolyamide resin, the present invention use
Aliphatic polyamide resin improves the processing performance of copolyamide resin, this is because aliphatic polyamide resin has preferably
Mobile performance and copolyamide resin have preferable mechanical property.Meanwhile aliphatic polyamide resin and copolyamide
The end group of resin can respectively with the isocyanate groups of toluene di-isocyanate(TDI), 2,2'- (1,3- phenylene)-bisoxazoline
Oxazoline group reacts, and improves the compatibility of both polyamides.Meanwhile the isocyanates of toluene di-isocyanate(TDI)
Group, 2,2'- (1,3- phenylene)-bisoxazoline oxazoline group can also be carried out with the coupling agent on alkali-free glass fibre
Reaction improves the interface binding power and compatibility of alkali-free glass fibre and above two polyamide, reduces what floating fibre occurred
Probability.
The coupling agent that the present invention uses, preferably gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane,
Contain amino, and anti-glass emergence on the surface agent N, N'- ethylenebisstearamide contains amide group, above-mentioned auxiliary agent can be with
The end group of above two polyamide reacts, to further increase alkali-free glass fibre and above two polyamide resin
The interface binding power and compatibility of rouge reduce the floating fine probability occurred.
Mechanical property and appearance effects of the length and diameter of alkali-free glass fibre to copolyamide resin composite materials
It is larger.The length of alkali-free glass fibre is bigger, and the tensile property of resin composite materials is higher, while a possibility that glass emergence on the surface
It is consequently increased；The diameter of alkali-free glass fibre is smaller, and tensile strength is higher, but the cost of its preparation is higher, while unit
Coupling agent needed for area is also more.Therefore, select the length and diameter of suitable alkali-free glass fibre excellent to processability
And the high copolyamide resin composite materials of cost performance are just particularly important.
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 copolyamide resin composite materials Blending Processes, amide group can with it is above two
The end group of polyamide reacts to improve compatibility, and hindered piperidine base can provide antioxidation and improve the dye of copolymer
Color.
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 excellent to be provided in copolyamide resin composite materials Blending Processes
Colour stability and melt stability more, 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) face in the environment of gas
Color stability prevents gas from smoking discoloration.
Compared with prior art, the invention has the following advantages:
The present invention defect bad for the processing temperature narrow limits and processing performance of existing copolyamide resin, passes through
Improve the processing performance of copolyamide resin using aliphatic polyamide resin, while using toluene di-isocyanate(TDI) and 2,
2'- (1,3- phenylene)-bisoxazoline is as the compatilizer and above two polyamide between both polyamides
Compatilizer between resin and alkali-free glass fibre, and coupling agent and N is added, N'- ethylenebisstearamide solve to float
Fine problem, is used in compounding 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 handles the xanthochromia problem in Blending Processes, preparation-obtained high heat resistance
Height flowing copolyamide composite material has the characteristics that high heat resistance, high fluidity, high tensile and low water absorption, can be applied to
Field of electronics, LED field, automotive field, aerospace and military industry field etc..
Detailed description of the invention
Fig. 1 show the preparation technology flow chart of high heat resistance height flowing 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 resistance height of the present invention flowing copolyamide composite material
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.；
Alkali-free glass fibre, selected from Chinese megalith limited liability company, length 3mm, diameter is 10 μm；
N, N'- ethylenebisstearamide are selected from Guangzhou Bo Han Chemical 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；
Anti-dripping agent (polytetrafluoroethylene (PTFE)) is selected from Minnesota ,USA mines and manufacturing industry company；
Dimethicone is selected from Dow corning 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 decamethylene diamine with to benzene two
The molar ratio of both formic acid and aliphatic dibasic acid dosage sum is 1, and the aliphatic dibasic acid is adipic acid, decanedioic acid, 12
One of docosandioic acid, the polyesteramide additional amount are the 1~8% of 1 total weight of monomer, above-mentioned copolyamide resin tool
Just like 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
The raw material of copolyamide resin used in the present embodiment is constituted and synthesis step 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 resistance height of the present embodiment flows copolyamide composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide composite material, comprising the following steps:
(1) the copolyamide resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
(1,3- is sub- by copolyamide resin, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) (TDI) after cooling, 2,2'-
Phenyl)-bisoxazoline (PBO), N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamides, bis- (2,6- bis-
Tert-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to high speed
It is mixed in blender；
(2) by coupling agent (γ-aminopropyltrimethoxysilane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another high-speed mixer and is 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 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
The raw material of copolyamide resin used in the present embodiment is constituted 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 resistance height of the present embodiment flows copolyamide composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide composite material, comprising the following steps:
(1) the copolyamide resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
(1,3- is sub- by copolyamide resin, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) (TDI) after cooling, 2,2'-
Phenyl)-bisoxazoline (PBO), N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamides, bis- (2,6- bis-
Tert-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to high speed
It is mixed in blender；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another high-speed mixer and is 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 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
The raw material of copolyamide resin used in the present embodiment is constituted 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 resistance height of the present embodiment flows copolyamide composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide composite material, comprising the following steps:
(1) the copolyamide resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
(1,3- is sub- by copolyamide resin, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) (TDI) after cooling, 2,2'-
Phenyl)-bisoxazoline (PBO), N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamides, bis- (2,6- bis-
Tert-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to high speed
It is mixed in blender；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another high-speed mixer and is 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 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 resistance height of the present embodiment flows copolyamide composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide composite material, comprising the following steps:
(1) the copolyamide resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
(1,3- is sub- by copolyamide resin, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) (TDI) after cooling, 2,2'-
Phenyl)-bisoxazoline (PBO), N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamides, bis- (2,6- bis-
Tert-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to high speed
It is mixed in blender；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another high-speed mixer and is 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.
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 resistance height of the present embodiment flows copolyamide composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide composite material, comprising the following steps:
(1) the copolyamide resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
(1,3- is sub- by copolyamide resin, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) (TDI) after cooling, 2,2'-
Phenyl)-bisoxazoline (PBO), N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamides, bis- (2,6- bis-
Tert-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to high speed
It is mixed in blender；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another high-speed mixer and is 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.
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 resistance height of the present embodiment flows copolyamide composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide composite material, comprising the following steps:
(1) the copolyamide resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
(1,3- is sub- by copolyamide resin, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) (TDI) after cooling, 2,2'-
Phenyl)-bisoxazoline (PBO), N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamides, bis- (2,6- bis-
Tert-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to high speed
It is mixed in blender；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another high-speed mixer and is 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 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 resistance height of this comparative example flows copolyamide composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide composite material, comprising the following steps:
(1) the copolyamide resin is placed in 90 DEG C, after 5 hours dry, cooling, by copolyamide tree after cooling
Rouge and N, bis- (2,2,6,6- tetramethyl -4- piperidyl) -1, the 3- benzenedicarboxamides of N'-, bis- (2,6- di-t-butyl -4- methyl
Phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added in high-speed mixer and carry out
Mixing；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another high-speed mixer and is 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 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 resistance height of this comparative example flows copolyamide composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide composite material, comprising the following steps:
(1) the copolyamide resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
Copolyamide resin after cooling, polyhexamethylene adipamide resin and N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -
1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-dripping agent (polytetrafluoroethyl-ne
Alkene) and dimethicone be added in high-speed mixer and mixed；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another high-speed mixer and is 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 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 resistance height of this comparative example flows copolyamide composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide composite material, comprising the following steps:
(1) the copolyamide resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
(1,3- is sub- by copolyamide resin, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) (TDI) after cooling, 2,2'-
Phenyl)-bisoxazoline (PBO), N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamides, bis- (2,6- bis-
Tert-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to high speed
It is mixed in blender；
(2) 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 alkali-free glass fibre and carries out melting extrusion, is granulated, and technological parameter is as follows:
One 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, and five area's temperature are 310
DEG C, 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, and 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 resistance height of this comparative example flows copolyamide composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide composite material, comprising the following steps:
(1) the copolyamide resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
(1,3- is sub- by copolyamide resin, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) (TDI) after cooling, 2,2'-
Phenyl)-bisoxazoline (PBO), N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamides, bis- (2,6- bis-
Tert-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to high speed
It is mixed in blender；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another high-speed mixer and is 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 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'-,
Bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicones
Respectively 0.15 part, 0.15 part, 1 part, 0.2 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):
Mobile performance: press GB/T 3682-2000 standard testing, 309 DEG C of test temperature, load 1.2kg；
Tensile property: GB/T 1040.1-2006 standard testing, rate of extension 10mm/min are pressed；
Heat resistance: GB/T 1634.1-2004 standard testing, bending stress 0.45MPa are pressed；
Water absorbing properties: GB/T 1034-2008 standard testing is pressed, the testing time is for 24 hours.
2 embodiment of table and comparative example performance list
As can be seen that the additional amount of aliphatic polyamide resin (polyhexamethylene adipamide resin) is got over from Examples 1 to 6
More, the melt index of copolyamide resin composite materials is bigger, and processing performance is better；The additional amount of alkali-free glass fibre is got over
More, the tensile strength and heat distortion temperature of copolyamide resin composite materials are bigger, but generate a possibility that floating fibre simultaneously and get over
Greatly；The water absorption rate variation of each embodiment is 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)
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；Comparative example 3 is to be not added with coupling
Agent, N, the copolyamide resin composite materials of N'- ethylenebisstearamide, copolyamide resin composite materials surface are floated
Fine phenomenon increases, and resin composite materials and alkali-free glass fibre compatibility are bad, thus to the tensile property of resin composite materials
Cause undesirable influence；The screw configuration of the parallel double-screw extruder of comparative example 4 is double thread, spiro rod length L and straight
The ratio between diameter D L/D is 30, and the screw configuration of the parallel double-screw extruder of embodiment 6 is single thread, spiro rod length L and straight
The ratio between diameter D L/D be 40, by comparison it can be found that using parallel double-screw extruder described in embodiment 6 Screw Parameters,
Processing performance, tensile property, heat resistance and the water absorbing properties of its copolyamide resin composite materials being prepared obtain very
It is big to improve, obtain the beneficial effect of the copolyamide resin composite materials of high heat resistance, high fluidity, high tensile and low water absorption
Fruit.
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 resistance height flows 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 length of the alkali-free glass fibre is 2~4mm, and diameter is 9~11 μm；
The anti-dripping agent is fluoropolymer；
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 the decamethylene diamine and terephthalic acid (TPA) and aliphatic two
The molar ratio of both first acid dosage sum is 1, and the aliphatic dibasic acid is one of adipic acid, decanedioic acid, dodecanedioic acid,
The polyesteramide additional amount is 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；
In the preparation of the high heat resistance height flowing copolyamide composite material, the screw shaped of used parallel double-screw extruder
Shape is single thread；The ratio between spiro rod length L and diameter D L/D are 35~50.
2. high heat resistance height according to claim 1 flows copolyamide composite material, which is characterized in that by following parts by weight
Raw material be prepared:
3. high heat resistance height according to claim 1 or 2 flows copolyamide composite material, which is characterized in that the copolymerization
The intrinsic viscosity of amide resin is 0.75~0.95dL/g；The aliphatic polyamide resin is polyhexamethylene adipamide resin,
Its inherent viscosity is 1.22~1.84dL/g.
4. high heat resistance height according to claim 1 or 2 flows copolyamide composite material, which is characterized in that the coupling
Agent is at least one of gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane；The anti-dripping agent is poly-
Tetrafluoroethene.
5. high heat resistance height according to claim 1 flows copolyamide composite material, which is characterized in that the copolyamide
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 resistance height flowing copolyamide composite materials of claim 1-5, special
Sign is, comprising the following steps:
(1) cold after the copolyamide resin and aliphatic polyamide resin being placed in 80~100 DEG C, drying 4~12 hours
But, 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'-, bis- (bis- uncles of 2,6-
Butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent and dimethicone be added in high-speed mixer and mixed
It closes；
(2) coupling agent, alkali-free glass fibre and N,N' ethylene bis stearmide are added to another high-speed mixer
In 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)
90 DEG C are placed in aliphatic polyamide resin, drying 4~6 hours；Technological parameter in the step (3) are as follows: area's temperature is
265~290 DEG C, two area's temperature be 295~305 DEG C, three area's temperature be 300~310 DEG C, four area's temperature be 305~310 DEG C, five
Area's temperature be 305~310 DEG C, six area's temperature be 305~310 DEG C, seven area's temperature be 305~310 DEG C, eight area's temperature be 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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Citations (3)
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|---|---|---|---|---|
| CN102206411A (en) * | 2010-03-30 | 2011-10-05 | E.I.内穆尔杜邦公司 | Flame-retardant polyamide resin composition and products containing same |
| CN103534313A (en) * | 2011-05-13 | 2014-01-22 | 帝斯曼知识产权资产管理有限公司 | Flame retardant semi-aromatic polyamide composition and moulded products made therefrom |
| CN105504789A (en) * | 2014-10-10 | 2016-04-20 | Ems专利股份公司 | Reinforced polyamide moulding compositions and injection mouldings produced therefrom |
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2016
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206411A (en) * | 2010-03-30 | 2011-10-05 | E.I.内穆尔杜邦公司 | Flame-retardant polyamide resin composition and products containing same |
| CN103534313A (en) * | 2011-05-13 | 2014-01-22 | 帝斯曼知识产权资产管理有限公司 | Flame retardant semi-aromatic polyamide composition and moulded products made therefrom |
| CN105504789A (en) * | 2014-10-10 | 2016-04-20 | Ems专利股份公司 | Reinforced polyamide moulding compositions and injection mouldings produced therefrom |
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| 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》;20031231;第1卷(第6期);第23-26页 |
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