CN106633844B - High heat resistance height flows copolyamide 6T composite material and preparation method - Google Patents
High heat resistance height flows copolyamide 6T composite material and preparation method Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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Abstract
The present invention relates to a kind of high heat resistance height to flow copolyamide 6T composite material and preparation method, the high heat resistance height flowing copolyamide 6T composite material is prepared from the following materials: copolyamide 6T 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 6T 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 6T composite material and its system more particularly to a kind of high heat resistance height
Preparation 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.
Industrialized high temperature resistant nylon mainly has nylon 6T (copolymer), nylon 9 T, nylon 10T etc..Nylon 6T resin
Fusing point is 370 DEG C or so, alreadys exceed decomposition temperature, not can be carried out melt-processed actually, it is necessary to add third group
The monomer divided makes the melting temperature of polymer be down to 320 DEG C or less.But the Third monomer that low content is added is not enough to improve it
Processing performance, and the range of work is too narrow, and the Third monomer that high-content is added can make the fusing point of copolymer resin too low, up to not
To requirement resistant to high temperature.
For above-mentioned problem, some researchs, such as Chinese patent CN have been done to the modification of nylon in currently available technology
103333335A discloses a kind of high fluidity PA10T Amilan polyamide resin composition, is obtained by two kinds by solid phase
The PA10T polyamide of different viscositys forms；It is fire-retardant that Chinese patent CN 102604380A discloses a kind of high CTI of high heat resistance
Polyamide compoiste material, wherein the polyamide is polyhexamethylene adipamide/poly-paraphenylene terephthalamide's nonamethylene diamine copolymer or gathers
Paraphenylene terephthalamide's nonamethylene diamine；Chinese patent CN 103030972A disclose a kind of imperial 66 composite materials of high heat resistance low-warpage nylon and
Preparation method；Chinese patent CN 103012955A discloses 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 preparation method thereof.
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 6T composite material of degree and low water absorption, may be used as electrical/electronic components, automobile component, can especially use
Make 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 6T composite material, the composite material by the raw material preparation of following parts by weight and
At:
The copolyamide 6T resin is heat resistant polyamide 6T/66 resin (PA6T/66), heat resistant polyamide 6T/610
One of resin (PA6T/610), heat resistant polyamide 6T/612 resin (PA6T/612)；The copolyamide 6T resin
Intrinsic viscosity 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 6T composite material, by the raw material of following parts by weight
It is prepared:
In wherein some embodiments, high heat resistance height flows copolyamide 6T composite material, further preferably by following heavy
The raw material of amount part is prepared:
In wherein some embodiments, the intrinsic viscosity of the copolyamide 6T resin is 0.75~0.95dL/g；It is described
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 anti-dripping agent is polytetrafluoroethylene (PTFE).
In wherein some embodiments, the copolyamide 6T resin is copolymerized by monomer 1 and polyesteramide, the list
Body 1 is the hexamethylene diamine, terephthalic acid (TPA), aliphatic dibasic acid that molar ratio is 1:0.5~0.6:0.4~0.5, and the hexamethylene 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 6T 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 6T is obtained
Resin；
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 6T composite material.
The preparation method of above-mentioned high heat resistance height flowing copolyamide 6T composite material, specific technical solution, including it is following
Step:
(1) the copolyamide 6T resin and aliphatic polyamide resin are placed in 80~100 DEG C, drying 4~12 hours
Afterwards, cooling, by copolyamide 6T resin, aliphatic polyamide resin and the toluene di-isocyanate(TDI) after cooling
(TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzene of N'-
Diformamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-dripping agent and dimethicone are added
It is mixed into high-speed mixer；
(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 260~290 DEG C, and two area's temperature are 290~305 DEG C, and three area's temperature are 295~310 DEG C,
Four area's temperature are 300~310 DEG C, and five area's temperature are 300~310 DEG C, and six area's temperature are 300~310 DEG C, and seven area's temperature are 300
~310 DEG C, eight area's temperature are 300~310 DEG C, and die head temperature is 295~305 DEG C, and screw speed is 200~600rpm.
In wherein some embodiments, by the copolyamide 6T resin and fatty polyamide tree in the step (1)
Rouge is placed in 90 DEG C, drying 4~6 hours；Technological parameter in the step (3) are as follows: area's temperature is 260~285 DEG C, two area's temperature
Degree is 290~300 DEG C, and three area's temperature are 295~305 DEG C, and four area's temperature are 300~305 DEG C, and five area's temperature are 300~305
DEG C, six area's temperature are 300~305 DEG C, and seven area's temperature are 300~305 DEG C, and eight area's temperature are 300~305 DEG C, and die head temperature is
295~300 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 6T resin is copolymerized by monomer 1 and polyesteramide, the list
Body 1 is the hexamethylene diamine, terephthalic acid (TPA), aliphatic dibasic acid that molar ratio is 1:0.5~0.6:0.4~0.5, and the hexamethylene 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 6T 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 6T is obtained
Resin；
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 6T resin, the present invention adopt
Improve the processing performance of copolyamide 6T resin with aliphatic polyamide resin, this is because aliphatic polyamide resin has
Preferable mobile performance and copolyamide 6T resin have preferable mechanical property.Meanwhile aliphatic polyamide resin and altogether
The end group of polyamide 6 T resin can respectively with the isocyanate groups of toluene di-isocyanate(TDI), 2,2'- (1,3- phenylene)-two
The oxazoline group of oxazoline reacts, and improves the compatibility of both polyamides.Meanwhile toluene di-isocyanate(TDI)
Isocyanate groups, 2,2'- (1,3- phenylene)-bisoxazoline oxazoline group can also be with the idol on alkali-free glass fibre
Connection agent is reacted, and the interface binding power and compatibility of alkali-free glass fibre and above two polyamide are improved, and is reduced floating
The probability that fibre occurs.
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 outer viewing of the length and diameter of alkali-free glass fibre to copolyamide 6T resin composite materials
Sound is larger.The length of alkali-free glass fibre is bigger, and the tensile property of resin composite materials is higher, while the possibility of glass emergence on the surface
Property 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 single
The required coupling agent of plane product is also more.Therefore, select the length and diameter of suitable alkali-free glass fibre excellent to processability
Different and high cost performance copolyamide 6T resin composite materials 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 6T resin composite materials Blending Processes, amide group can be with above-mentioned two
The end group of kind polyamide reacts to improve compatibility, and hindered piperidine base can provide antioxidation and improve copolymer
Dyeability.
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, can be to be provided in copolyamide 6T resin composite materials Blending Processes
Superior colour stability and melt stability, while the heat drop of above two polyamide in the high temperature process can be prevented
Solution, and the hot oxygen discoloration due to caused by long-time is inhibited, it also offers in nitrogen oxides (NOx) in the environment of gas
Colour 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 6T resin, leads to
Cross using aliphatic polyamide resin the processing performance for improving copolyamide 6T resin, at the same using toluene di-isocyanate(TDI) and
2,2'- (1,3- phenylene)-bisoxazolines are as the compatilizer and above two polyamides between both polyamides
Compatilizer between polyimide resin and alkali-free glass fibre, and coupling agent and N is added, N'- ethylenebisstearamide solve
Fine problem is floated, N, bis- (2,2,6,6- tetramethyl -4- piperidyl) -1, the 3- benzenedicarboxamides and bis- (2,6- bis- of N'- are used in compounding
Tert-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate handles the xanthochromia problem in Blending Processes, and preparation-obtained height is resistance to
Hot high flowing copolyamide 6T composite material has the characteristics that high heat resistance, high fluidity, high tensile and low water absorption, can answer
For 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 6T 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 for high heat resistance height of the present invention flowing copolyamide 6T composite material (preparation technology flow chart see
Fig. 1):
Reaction mechanism
By above-mentioned reaction equation it is found that the Amino End Group of aliphatic polyamide resin and copolyamide 6T resin can be with toluene two
The isocyanate groups of isocyanates react, Amino End Group, the end carboxylic of aliphatic polyamide resin and copolyamide 6T resin
Base can react with the oxazoline group of 2,2'- (1,3- phenylene)-bisoxazoline, so as to increase both polyamides
Compatibility between polyimide resin.
Raw material used in the embodiment of the present invention is as follows:
Copolyamide 6T resin is made by oneself, and the hexamethylene diamine in raw material is selected from Wuxi Yinda Nylon Co., Ltd., terephthalic acid (TPA)
Selected from Beijing Yanshan Petrochemical Co., adipic acid, decanedioic acid, dodecanedioic acid are selected from the wide limited public affairs of boundary new material in Shandong
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.；
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 6T resin in following embodiment is copolymerized by monomer 1 and polyesteramide, and the monomer 1 is mole
Than the hexamethylene diamine, terephthalic acid (TPA), aliphatic dibasic acid for 1:0.5~0.6:0.4~0.5, and the hexamethylene 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 6T resin
With such as following formula I structure:
In Formulas I, a=10~100, b=10~200, c=10~100, d=10~100, e=4 or 8 or 10, R are polyester
Amide has such as Formula Il structure:
In Formula II, x=10~200, y=10~200, z=10~100.
The synthetic method of copolyamide 6T 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 6T is obtained
Resin；
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 6T resin used in the present embodiment is constituted and synthesis step is as follows:
(1) monomer 1:1mol hexamethylene diamine, 0.6mol terephthalic acid (TPA), the 0.4mol decanedioic acid after vacuum drying are added to
In stirring-type polymer reactor, while 4% polyesteramide, 1.5% benzoic acid, 0.2% N of 1 total weight of monomer is added,
Medium of the 100mL water as mass-and heat-transfer is added in N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides；So
After vacuumize 5min, lead to nitrogen 5min, so circulation 6 times, be present in reactant in the environment under nitrogen protection, control stirring
System pressure is 0.3MPa in formula polymer reactor；
(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 6T resin is obtained；
The intrinsic viscosity of the above-mentioned copolyamide 6T resin (PA6T/610) being prepared is 0.86dL/g, melting temperature is
297℃。
A kind of high heat resistance height of the present embodiment flows copolyamide 6T composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide 6T composite material, comprising the following steps:
It is (1) cooling after the copolyamide 6T resin and polyhexamethylene adipamide resin being placed in 90 DEG C, drying 5 hours,
By copolyamide 6T resin after cooling, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) (TDI), 2,2'- (1,
3- phenylene)-bisoxazoline (PBO), N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'-, it is bis- (2,
6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
It is mixed in high-speed mixer；
(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 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 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 6T resin used in the present embodiment is constituted and synthesis step is as follows:
(1) monomer 1:1mol hexamethylene diamine, 0.6mol terephthalic acid (TPA), the 0.4mol dodecanedioic acid after vacuum drying are added
Enter into stirring-type polymer reactor, at the same be added 4% polyesteramide of 1 total weight of monomer, 1.5% benzoic acid, 0.2%
N, Jie of the 100mL water as mass-and heat-transfer is added in N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides
Matter；Then 5min is vacuumized, leads to nitrogen 5min, so circulation 6 times, is present in reactant in the environment under nitrogen protection, controls
System pressure is 0.3MPa in stirring-type polymer reactor processed；
(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 6T resin is obtained；
The intrinsic viscosity of the above-mentioned copolyamide 6T resin (PA6T/612) being prepared is 0.87dL/g, melting temperature is
296℃。
A kind of high heat resistance height of the present embodiment flows copolyamide 6T composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide 6T composite material, comprising the following steps:
It is (1) cooling after the copolyamide 6T resin and polyhexamethylene adipamide resin being placed in 90 DEG C, drying 5 hours,
By copolyamide 6T resin after cooling, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) (TDI), 2,2'- (1,
3- phenylene)-bisoxazoline (PBO), N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'-, it is bis- (2,
6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
It is mixed in high-speed mixer；
(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 260 DEG C, and two area's temperature are 290 DEG C, and three area's temperature are 295 DEG C, and four area's temperature are 300 DEG C, 5th area
Temperature is 300 DEG C, and six area's temperature are 300 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 295 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 6T resin used in the present embodiment is constituted and synthesis step is as follows:
(1) monomer 1:1mol hexamethylene diamine, 0.6mol terephthalic acid (TPA), the 0.4mol adipic acid after vacuum drying are added to
In stirring-type polymer reactor, while 4% polyesteramide, 1.5% benzoic acid, 0.2% N of 1 total weight of monomer is added,
Medium of the 100mL water as mass-and heat-transfer is added in N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides；So
After vacuumize 5min, lead to nitrogen 5min, so circulation 6 times, be present in reactant in the environment under nitrogen protection, control stirring
System pressure is 0.3MPa in formula polymer reactor；
(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 6T resin is obtained；
The intrinsic viscosity of the above-mentioned copolyamide 6T resin (PA6T/66) being prepared is 0.85dL/g, melting temperature is
299℃。
A kind of high heat resistance height of the present embodiment flows copolyamide 6T composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide 6T composite material, comprising the following steps:
It is (1) cooling after the copolyamide 6T resin and polyhexamethylene adipamide resin being placed in 90 DEG C, drying 5 hours,
By copolyamide 6T resin after cooling, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) (TDI), 2,2'- (1,
3- phenylene)-bisoxazoline (PBO), N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'-, it is bis- (2,
6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
It is mixed in high-speed mixer；
(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 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 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 6T 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 6T composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide 6T composite material, comprising the following steps:
It is (1) cooling after the copolyamide 6T resin and polyhexamethylene adipamide resin being placed in 90 DEG C, drying 5 hours,
By copolyamide 6T resin after cooling, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) (TDI), 2,2'- (1,
3- phenylene)-bisoxazoline (PBO), N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'-, it is bis- (2,
6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
It is mixed in high-speed mixer；
(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 280 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 300 DEG C, and eight area's temperature are 300 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 6T 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 6T composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide 6T composite material, comprising the following steps:
It is (1) cooling after the copolyamide 6T resin and polyhexamethylene adipamide resin being placed in 90 DEG C, drying 5 hours,
By copolyamide 6T resin after cooling, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) (TDI), 2,2'- (1,
3- phenylene)-bisoxazoline (PBO), N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'-, it is bis- (2,
6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
It is mixed in high-speed mixer；
(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 280 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 300 DEG C, and eight area's temperature are 300 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 6T 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 6T composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide 6T composite material, comprising the following steps:
It is (1) cooling after the copolyamide 6T resin and polyhexamethylene adipamide resin being placed in 90 DEG C, drying 5 hours,
By copolyamide 6T resin after cooling, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) (TDI), 2,2'- (1,
3- phenylene)-bisoxazoline (PBO), N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'-, it is bis- (2,
6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
It is mixed in high-speed mixer；
(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 280 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 300 DEG C, and eight area's temperature are 300 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 6T 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 6T composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide 6T composite material, comprising the following steps:
(1) the copolyamide 6T resin is placed in 90 DEG C, after 5 hours dry, cooling, by copolyamide 6T after cooling
Resin and N, bis- (2,2,6,6- tetramethyl -4- piperidyl) -1, the 3- benzenedicarboxamides of N'-, bis- (2,6- di-t-butyl -4- first
Base phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added in high-speed mixer into
Row 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 280 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 300 DEG C, and eight area's temperature are 300 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 6T 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 6T composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide 6T composite material, comprising the following steps:
It is (1) cooling after the copolyamide 6T resin and polyhexamethylene adipamide resin being placed in 90 DEG C, drying 5 hours,
By copolyamide 6T resin after cooling, polyhexamethylene adipamide resin and bis- (2,2,6, the 6- tetramethyl -4- piperidines of N, N'-
Base) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-dripping agent (poly- four
Vinyl fluoride) 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 280 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 300 DEG C, and eight area's temperature are 300 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 6T 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 6T composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide 6T composite material, comprising the following steps:
It is (1) cooling after the copolyamide 6T resin and polyhexamethylene adipamide resin being placed in 90 DEG C, drying 5 hours,
By copolyamide 6T resin after cooling, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) (TDI), 2,2'- (1,
3- phenylene)-bisoxazoline (PBO), N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'-, it is bis- (2,
6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
It is mixed in high-speed mixer；
(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 280 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, and five area's temperature are 305
DEG C, six area's temperature are 305 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 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 6T 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 6T composite material, is prepared from the following raw materials:
The preparation method of above-mentioned high heat resistance height flowing copolyamide 6T composite material, comprising the following steps:
It is (1) cooling after the copolyamide 6T resin and polyhexamethylene adipamide resin being placed in 90 DEG C, drying 5 hours,
By copolyamide 6T resin after cooling, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) (TDI), 2,2'- (1,
3- phenylene)-bisoxazoline (PBO), N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'-, it is bis- (2,
6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
It is mixed in high-speed mixer；
(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 280 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 300 DEG C, and eight area's temperature are 300 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 6T 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 6T resin composite materials are bigger, but generate a possibility that floating fine simultaneously
It is bigger；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 6T resin composite materials, melt index is only 5g/10min (309 DEG C of test temperature, load 1.2kg), processing
Performance is bad；Comparative example 2 is to be not added with toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO)
Copolyamide 6T resin composite materials, aliphatic polyamide resin (polyhexamethylene adipamide resin) polyamide 6 T resin phase together
Capacitive is bad, to cause undesirable influence to the tensile property of copolyamide 6T resin composite materials；Comparative example 3 is not add
Add coupling agent, N, the copolyamide 6T resin composite materials of N'- ethylenebisstearamide, copolyamide 6T resin compounded material
Expect that the floating fine phenomenon on surface increases, resin composite materials and alkali-free glass fibre compatibility are bad, thus to resin composite materials
Tensile property cause undesirable influence；The screw configuration of the parallel double-screw extruder of comparative example 4 is double thread, screw rod
The ratio between 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, screw rod
The ratio between length L and diameter D L/D are 40, by comparing 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 suction of the copolyamide 6T resin composite materials being prepared
Performance is greatly improved, and obtains high heat resistance, high fluidity, the copolyamide 6T resin compounded of high tensile and low water absorption
The beneficial effect of 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 resistance height flows copolyamide 6T composite material, which is characterized in that by the raw material preparation of following parts by weight
At:
The intrinsic viscosity of the copolyamide 6T resin is 0.7~1.0dL/g；
The copolyamide 6T resin is copolymerized by monomer 1 and polyesteramide, the monomer 1 be molar ratio be 1:0.5~
Hexamethylene diamine, terephthalic acid (TPA), the aliphatic dibasic acid of 0.6:0.4~0.5, and the hexamethylene diamine and terephthalic acid (TPA) and aliphatic
The molar ratio of both binary acid dosage sum is 1, and the aliphatic dibasic acid is adipic acid, decanedioic acid, one in dodecanedioic acid
Kind, the polyesteramide additional amount is the 1~8% of 1 total weight of monomer；
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.
2. high heat resistance height according to claim 1 flows copolyamide 6T composite material, which is characterized in that by following weight
The raw material of part is prepared:
3. high heat resistance height according to claim 1 or 2 flows copolyamide 6T composite material, which is characterized in that described total
The inherent viscosity of polyamide 6 T resin is 0.75~0.95dL/g；The aliphatic polyamide resin is polyhexamethylene adipamide
Resin, inherent viscosity are 1.22~1.84dL/g.
4. high heat resistance height according to claim 1 or 2 flows copolyamide 6T composite material, which is characterized in that the idol
Connection agent is at least one of gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane；The anti-dripping agent is
Polytetrafluoroethylene (PTFE).
5. high heat resistance height according to claim 1 flows copolyamide 6T composite material, which is characterized in that the copolymerization acyl
Amine 6T 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 6T 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 resistance height flowing copolyamide 6T composite materials of claim 1-5,
It is characterized in that, comprising the following steps:
(1) cold after the copolyamide 6T resin and aliphatic polyamide resin being placed in 80~100 DEG C, drying 4~12 hours
But, by copolyamide 6T resin, aliphatic polyamide resin and the toluene di-isocyanate(TDI) after cooling, 2,2'- (1,
3- phenylene)-bisoxazoline, 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 and dimethicone be added in high-speed mixer and carry out
Mixing；
(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
260~290 DEG C, two area's temperature be 290~305 DEG C, three area's temperature be 295~310 DEG C, four area's temperature be 300~310 DEG C, five
Area's temperature be 300~310 DEG C, six area's temperature be 300~310 DEG C, seven area's temperature be 300~310 DEG C, eight area's temperature be 300~
310 DEG C, die head temperature is 295~305 DEG C, and screw speed is 200~600rpm.
7. preparation method according to claim 6, which is characterized in that by the copolyamide 6T tree in the step (1)
Rouge and aliphatic polyamide resin are placed in 90 DEG C, drying 4~6 hours；Technological parameter in the step (3) are as follows: area's temperature
It is 260~285 DEG C, two area's temperature are 290~300 DEG C, and three area's temperature are 295~305 DEG C, and four area's temperature are 300~305 DEG C,
Five area's temperature are 300~305 DEG C, and six area's temperature are 300~305 DEG C, and seven area's temperature are 300~305 DEG C, and eight area's temperature are 300
~305 DEG C, die head temperature is 295~300 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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| 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 |
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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 |
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| Title |
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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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