CN106633844A - High-heat-resistant high-fluidity copolyamide 6T composite material and preparation method thereof - Google Patents
High-heat-resistant high-fluidity copolyamide 6T composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/003—Additives being defined by their diameter
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- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention relates to a high-heat-resistant high-fluidity copolyamide 6T composite material and a preparation method thereof. The composite material is prepared from copolyamide 6T resin, toluene diisocynate, 2, 2'-(1, 3-phenylene)-bioxazoline, coupling agent, alkali-free glass fiber, N, N'-ethylene bistearic amide, N, N'-bis(2, 2, 6, 6-tetramethyk-4-piperidyl)-1, 3-phthalic diamide, bis(2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, anti-drop agent and dimethyl silicon oil. The high-heat-resistant high-fluidity copolyamide 6T composite material has the advantages of high heat resistance, high fluidity, high tensile strength and low water absorption rate and can be applied in the fields of electronic appliances, LEDs, automobiles, aerospace and military industry.
Description
Technical field
The present invention relates to Material Field, more particularly to a kind of high heat-resisting high flowing copolyamide 6T composites and its system
Preparation Method.
Background technology
Heat resistant polyamide is typically by aliphatic diamines and aromatic diacid, or aromatic diamines and fat
The diacid Jing polycondensations of race are prepared.Due to introducing phenyl ring on molecular backbone, heat resistant polyamide not only maintains fat
Mechanical property that polyamide has is good, acid and alkali-resistance and the advantages of self lubricity, also overcome that its water absorption rate is high, dimensional stability not
Good shortcoming so as in being particularly well-suited to auto industry, to replace automobile in part metals structural member, to realize light weight
Change, it is also possible to for manufacturing the insulating body of electronic device, or for surface mounting technique.
Industrialized high temperature resistant nylon mainly has nylon 6T (copolymer), nylon 9 T, nylon 10T etc..Nylon 6T resins
Fusing point is 370 DEG C or so, and it alreadys exceed decomposition temperature, actually can not carry out melt-processed, it is necessary to add the 3rd group
The monomer for dividing makes the melt temperature of polymer be down to less than 320 DEG C.But, the Third monomer for adding low content is not enough to improve it
Processing characteristics, and the range of work is too narrow, and add the Third monomer of high-load that the fusing point of copolymer resin can be made too low, up to not
To resistant to elevated temperatures requirement.
For above-mentioned problem, some researchs, such as Chinese patent CN are done to the modified of nylon in currently available technology
103333335A discloses a kind of high fluidity PA10T Amilan polyamide resin composition, and it is obtained by two kinds by solid phase
The PA10T polyamides composition of different viscositys；It is fire-retardant that Chinese patent CN 102604380A disclose a kind of high heat-resisting high CTI
Polyamide compoiste material, the wherein polyamide are polyhexamethylene adipamide/poly-paraphenylene terephthalamide's nonamethylene diamine copolymer or poly-
Paraphenylene terephthalamide's nonamethylene diamine；Chinese patent CN 103030972A disclose a kind of high heat-resisting low-warpage nylon 66 composites of dragon and
Its preparation method；Chinese patent CN 103012955A disclose a kind of high flowing fiberglass reinforced PP/PA composites and its preparation
Method；Chinese patent CN 103724979A disclose a kind of high flowing heatproof LED PPO/PA compositions and preparation method thereof.
The content 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-resisting, high fluidity, high stretching
The copolyamide 6T composites of degree and low water absorption, can serve as electrical/electronic components, automobile component, particularly can use
Make the molding substrate material of electronic unit.
To reach above-mentioned purpose, the present invention adopts below scheme：
A kind of high heat-resisting high flowing copolyamide 6T composites, the composite is by the raw material preparation of following weight portion
Into：
The copolyamide 6T resins are heat resistant polyamide 6T/66 resins (PA6T/66), heat resistant polyamide 6T/610
One kind in resin (PA6T/610), heat resistant polyamide 6T/612 resins (PA6T/612)；The copolyamide 6T resins
Intrinsic viscosity is 0.7～1.0dL/g.
The aliphatic polyamide resin is nylon 46 resin (PA46), polyhexamethylene adipamide resin
(PA66) at least one in.
The coupling agent be 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 in ethyl triethoxy silicane alkane.
The length of the alkali-free glass fibre be 2～4mm, a diameter of 9～11 μm.
The anti-dripping agent is fluoropolymer.
Wherein in some embodiments, high heat-resisting high flowing copolyamide 6T composites, by the raw material of following weight portion
It is prepared from：
Wherein in some embodiments, high heat-resisting high flowing copolyamide 6T composites, further preferably by following heavy
The raw material of amount part is prepared from：
Wherein in some embodiments, the intrinsic viscosity of the copolyamide 6T resins is 0.75～0.95dL/g；It is described
Aliphatic polyamide resin is polyhexamethylene adipamide resin (PA66), and its inherent viscosity is 1.22～1.84dL/g.
Wherein in some embodiments, the coupling agent is gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy
At least one in base silane；The anti-dripping agent is polytetrafluoroethylene (PTFE).
Wherein in some embodiments, the copolyamide 6T resins are formed by monomer 1 and polyesteramide copolymerization, the list
It is 1 that body 1 is mol ratio：0.5～0.6：0.4～0.5 hexamethylene diamine, terephthalic acid (TPA), aliphatic dibasic acid, and the hexamethylene diamine
With both terephthalic acid (TPA) and aliphatic dibasic acid consumption and mol ratio be 1, the aliphatic dibasic acid be adipic acid, the last of the ten Heavenly stems two
One kind in acid, dodecanedioic acid, the polyesteramide addition is the 1～8% of the gross weight of the monomer 1.
Wherein in some embodiments, the copolyamide 6T resins are obtained by following synthetic method：
(1) by vacuum drying after the monomer 1 be added in stirring-type polymer reactor, while adding the polyester acyl
Amine, and molecular weight regulator, antioxidant, water；Then 4～6min is vacuumized, leads to 4～6min of nitrogen, so circulated 5～7 times,
Reactant is set to be present in the lower environment of nitrogen protection, control in the stirring-type polymer reactor system pressure for 0.2～
0.3MPa；
(2) in 2～4 hours by the closed constant-speed heating of the 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
When 215 DEG C, 2.0MPa is deflated to, and maintains pressure in 2.0MPa, after reacting 1～2 hour, normal pressure is deflated to, while being warming up to
After continuing to react 1～2 hour at 310～320 DEG C, after constant temperature persistently vacuumizes 0.3～1 hour, the copolyamide 6T is obtained
Resin；
The molecular weight regulator is addition is the gross weight of the monomer 1 0.1～3% benzoic acid；The antioxygen
Agent is addition is the gross weight of the monomer 1 0.1～0.3% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,
3- benzene diamides；Appropriate amount of water.
It is a further object of the present invention to provide the preparation method of high heat-resisting high flowing copolyamide 6T composites.
The preparation method of the heat-resisting high flowing copolyamide 6T composites of above-mentioned height, specific technical scheme, including it is following
Step：
(1) the copolyamide 6T resins and aliphatic polyamide resin are placed in into 80～100 DEG C, are dried 4～12 hours
Afterwards, cool down, by copolyamide 6T resins, aliphatic polyamide resin after cooling, and the toluene di-isocyanate(TDI)
(TDI), 2,2'- (1,3- phenylenes)-bisoxazoline (PBO), N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzene of N'-
Diformamide, double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates, anti-dripping agent and dimethicone are added
Mixed in homogenizer；
(2) coupling agent, alkali-free glass fibre and N,N' ethylene bis stearmide are added into another high-speed stirring
Mix in machine and mixed；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (such as the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, granulates,
Technological parameter is as follows：One 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.
Wherein in some embodiments, by the copolyamide 6T resins and fatty polyamide tree in the step (1)
Fat is placed in 90 DEG C, is dried 4～6 hours；Technological parameter in the step (3) is：One area's temperature is 260～285 DEG C, two area's temperature
Spend for 290～300 DEG C, three area's temperature are 295～305 DEG C, four area's temperature are 300～305 DEG C, 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.
Wherein in 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 L/D of diameter D；The screw rod is provided with the gear block area of more than 1 (containing 1) and more than 1 (containing 1)
Left-hand thread area.
Wherein in some embodiments, the ratio L/D of the spiro rod length L and diameter D is 35～45；The screw rod is provided with
2 gear block areas and 1 left-hand thread area.
Wherein in some embodiments, the copolyamide 6T resins are formed by monomer 1 and polyesteramide copolymerization, the list
It is 1 that body 1 is mol ratio：0.5～0.6：0.4～0.5 hexamethylene diamine, terephthalic acid (TPA), aliphatic dibasic acid, and the hexamethylene diamine
With both terephthalic acid (TPA) and aliphatic dibasic acid consumption and mol ratio be 1, the aliphatic dibasic acid be adipic acid, the last of the ten Heavenly stems two
One kind in acid, dodecanedioic acid, the polyesteramide addition is the 1～8% of the gross weight of the monomer 1.
Wherein in some embodiments, the copolyamide 6T resins are obtained by following synthetic method：
(1) by vacuum drying after the monomer 1 be added in stirring-type polymer reactor, while adding the polyester acyl
Amine, and molecular weight regulator, antioxidant, water；Then 4～6min is vacuumized, leads to 4～6min of nitrogen, so circulated 5～7 times,
Reactant is set to be present in the lower environment of nitrogen protection, control in the stirring-type polymer reactor system pressure for 0.2～
0.3MPa；
(2) in 2～4 hours by the closed constant-speed heating of the 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
When 215 DEG C, 2.0MPa is deflated to, and maintains pressure in 2.0MPa, after reacting 1～2 hour, normal pressure is deflated to, while being warming up to
After continuing to react 1～2 hour at 310～320 DEG C, after constant temperature persistently vacuumizes 0.3～1 hour, the copolyamide 6T is obtained
Resin；
The molecular weight regulator is addition is the gross weight of the monomer 1 0.1～3% benzoic acid；The antioxygen
Agent is addition is the gross weight of the monomer 1 0.1～0.3% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,
3- benzene diamides；Appropriate amount of water.
The principle of the present invention is as follows：
For the not good defect of the processing temperature narrow limits and processing characteristics that solve copolyamide 6T resins, the present invention is adopted
Improve the processing characteristics of copolyamide 6T resins with aliphatic polyamide resin, this is because aliphatic polyamide resin possesses
Preferably mobile performance, and copolyamide 6T resins possess preferably mechanical property.Meanwhile, aliphatic polyamide resin and altogether
The end group of polyamide 6 T resins can respectively with toluene di-isocyanate(TDI) isocyanate groups, 2,2'- (1,3- phenylenes)-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- phenylenes)-bisoxazoline oxazoline group can also be with the idol on alkali-free glass fibre
Connection agent is reacted, and improves the interface binding power and compatibility of alkali-free glass fibre and above two polyamide, reduces floating
The probability that fibre occurs.
The coupling agent that the present invention is adopted, preferably gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane,
Contain amino, and anti-glass emergence on the surface agent N, N'- ethylenebisstearamides contain amide group, above-mentioned auxiliary agent can be with
The end group of above two polyamide reacts, so as to further improve alkali-free glass fibre and above two polyamide resin
The interface binding power and compatibility of fat, reduces the floating fine probability for occurring.
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 its 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 less, and tensile strength is higher, but its cost for preparing is higher, while single
Coupling agent needed for plane product is also more.Therefore, select the length and diameter of suitable alkali-free glass fibre excellent to processability
The high copolyamide 6T resin composite materials of different and cost performance are just particularly important.
The fusing point of double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N, N'- is 272 DEG C, boiling point is more than
360 DEG C, the better heat stability in copolyamide 6T resin composite materials Blending Processes, its amide group can be with above-mentioned two
The end group for planting polyamide reacts to improve compatibility, and hindered piperidine base can provide antioxidation and improve copolymer
Dyeability.
The fusing point of double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates is 239 DEG C, heat decomposition temperature surpasses
350 DEG C are crossed, can be offer in copolyamide 6T resin composite materials Blending Processes with good heat resistance and hydrolytic resistance
Superior colour stability and melt stability, while heat drop of the above two polyamide in pyroprocess can be prevented
Solution, and the hot oxygen discoloration caused due to 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 advantages that：
The present invention is led to for the not good defect of the processing temperature narrow limits and processing characteristics of existing copolyamide 6T resins
Cross using aliphatic polyamide resin to improve the processing characteristics of copolyamide 6T resins, at the same using toluene di-isocyanate(TDI) and
2,2'- (1,3- phenylene)-bisoxazolines are used as the compatilizer between both polyamides, and above two polyamides
Compatilizer between polyimide resin and alkali-free glass fibre, and add coupling agent and N, N'- ethylenebisstearamide to solve
Float fine problem, compounding use N, double (2,2,6,6- tetramethyl -4- piperidyls) -1, the 3- benzenedicarboxamides of N'- and double (2,6- bis-
The tert-butyl group -4- aminomethyl phenyls) pentaerythritol diphosphate to process Blending Processes in xanthochromia problem, preparation-obtained height is resistance to
The characteristics of hot high flowing copolyamide 6T composites have high heat-resisting, high fluidity, high tensile and low water absorption, can answer
For field of electronics, LED field, automotive field, Aero-Space and military industry field etc..
Description of the drawings
Fig. 1 show the preparation technology flow chart of high heat-resisting high flowing copolyamide 6T composites of the invention.
Specific embodiment
For feature, technological means and the specific purposes for being reached, the function of the present invention can be further appreciated that, this is parsed
Bright advantage and spirit, by following examples, the present invention is further elaborated.
The reaction mechanism of high heat-resisting high flowing copolyamide 6T composites of the invention as follows (ask for an interview by preparation technology flow chart
Fig. 1)：
Reaction mechanism
Can be with toluene two from the Amino End Group of above-mentioned reaction equation, aliphatic polyamide resin and copolyamide 6T resins
The isocyanate groups of isocyanates react, the Amino End Group of aliphatic polyamide resin and copolyamide 6T resins, end carboxylic
Base can react with the oxazoline group of 2,2'- (1,3- phenylene)-bisoxazoline, such that it is able to increase both polyamides
Compatibility between polyimide resin.
The raw material that the embodiment of the present invention is used is as follows：
Copolyamide 6T resins, self-control, 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 limited public affairs of the wide boundary new material in Shandong
Department, remaining auxiliary agent is selected from Chemical Reagent Co., Ltd., Sinopharm Group；
Polyhexamethylene adipamide resin (PA66), selected from China Shenma Group Co., Ltd., its inherent viscosity is respectively
1.22dL/g、1.66dL/g、1.84dL/g；
Toluene di-isocyanate(TDI), selected from Chemical Reagent Co., Ltd., Sinopharm Group；
2,2'- (1,3- phenylene)-bisoxazolines, selected from Chemical Reagent Co., Ltd., Sinopharm Group；
Coupling agent (gamma-aminopropyl-triethoxy-silane), selected from Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei；
Coupling agent (γ-aminopropyltrimethoxysilane), selected from Zhejiang boiling point Chemical Co., Ltd.；
Alkali-free glass fibre, selected from Chinese megalith limited company, length is 3mm, a diameter of 10 μm；
N, N'- ethylenebisstearamide, selected from Guangzhou Bo Han Chemical Co., Ltd.s；
Double (2,2,6,6- tetramethyl -4- piperidyls) -1, the 3- benzenedicarboxamides of N, N'-, have selected from such as Dong Jinkangtai chemistry
Limit company；
Double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates, it is limited selected from Shanghai point credit fine chemistry industry
Company；
Anti-dripping agent (polytetrafluoroethylene (PTFE)), selected from Minnesota ,USA mines and manufacturing industry company；
Dimethicone, selected from Dow corning company.
The present invention is described in detail below in conjunction with specific embodiment.
Copolyamide 6T resins in following examples are formed by monomer 1 and polyesteramide copolymerization, the monomer 1 for mole
Than for 1：0.5～0.6：0.4～0.5 hexamethylene diamine, terephthalic acid (TPA), aliphatic dibasic acid, and the hexamethylene diamine with to benzene two
The mol ratio of both formic acid and aliphatic dibasic acid consumption sum be 1, the aliphatic dibasic acid be adipic acid, decanedioic acid, 12
One kind in docosandioic acid, the polyesteramide addition is the 1～8% of the gross weight of the monomer 1, above-mentioned copolyamide 6T resins
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
Acid amides, it has such as Formula Il structure：
In Formula II, x=10～200, y=10～200, z=10～100.
The synthetic method of copolyamide 6T resins is as follows：
(1) by vacuum drying after the monomer 1 be added in stirring-type polymer reactor, while adding the polyester acyl
Amine, and molecular weight regulator, antioxidant, water；Then 4～6min is vacuumized, leads to 4～6min of nitrogen, so circulated 5～7 times,
Reactant is set to be present in the lower environment of nitrogen protection, control in the stirring-type polymer reactor system pressure for 0.2～
0.3MPa；
(2) in 2～4 hours by the closed constant-speed heating of the 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
When 215 DEG C, 2.0MPa is deflated to, and maintains pressure in 2.0MPa, after reacting 1～2 hour, normal pressure is deflated to, while being warming up to
After continuing to react 1～2 hour at 310～320 DEG C, after constant temperature persistently vacuumizes 0.3～1 hour, the copolyamide 6T is obtained
Resin；
The molecular weight regulator is addition is the gross weight of the monomer 1 0.1～3% benzoic acid；The antioxygen
Agent is addition is the gross weight of the monomer 1 0.1～0.3% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,
3- benzene diamides；Appropriate amount of water.
Embodiment 1
The raw material of the copolyamide 6T resins used in the present embodiment is constituted and synthesis step is as follows：
(1) by the monomer 1 after vacuum drying：1mol hexamethylene diamines, 0.6mol terephthalic acid (TPA)s, 0.4mol decanedioic acid are added to
In stirring-type polymer reactor, while the 4% of the gross weight of monomer 1 polyesteramide, 1.5% benzoic acid, 0.2% N is added,
The medium of N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides, addition 100mL water as mass-and heat-transfer；So
After vacuumize 5min, lead to nitrogen 5min, so circulation 6 times makes reactant be present in the lower environment of nitrogen protection, and control is stirred
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 polymerisation
The mixing speed of device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 215 DEG C, 2.0MPa is deflated to, and
Maintain pressure in 2.0MPa, after reacting 1.5 hours, be deflated to normal pressure, while after continuing to react 1.5 hours at being warming up to 315 DEG C,
After constant temperature persistently vacuumizes 0.5 hour, the copolyamide 6T resins are obtained；
The intrinsic viscosity of above-mentioned copolyamide 6T resins (PA6T/610) for preparing is 0.86dL/g, melt temperature is
297℃。
A kind of high heat-resisting high flowing copolyamide 6T composites of the present embodiment, are prepared from by the following raw material：
The preparation method of the heat-resisting high flowing copolyamide 6T composites of above-mentioned height, comprises the following steps：
(1) the copolyamide 6T resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling,
By copolyamide 6T resins, polyhexamethylene adipamide resin after cooling, and toluene di-isocyanate(TDI) (TDI), 2,2'- (1,
3- phenylenes)-bisoxazoline (PBO), N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'-, it is double (2,
6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
Mixed in homogenizer；
(2) by coupling agent (γ-aminopropyltrimethoxysilane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another homogenizer and is mixed；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, granulates, technique
Parameter is as follows：One 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 35 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 2
The raw material of the copolyamide 6T resins used in the present embodiment is constituted and synthesis step is as follows：
(1) by the monomer 1 after vacuum drying：1mol hexamethylene diamines, 0.6mol terephthalic acid (TPA)s, 0.4mol dodecanedioic acids add
Enter in stirring-type polymer reactor, at the same add the gross weight of monomer 1 4% polyesteramide, 1.5% benzoic acid, 0.2%
N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides, add 100mL water as mass-and heat-transfer Jie
Matter；Then 5min is vacuumized, leads to nitrogen 5min, so circulation 6 times in making the environment that reactant is present under nitrogen protection, is controlled
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 polymerisation
The mixing speed of device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 215 DEG C, 2.0MPa is deflated to, and
Maintain pressure in 2.0MPa, after reacting 1.5 hours, be deflated to normal pressure, while after continuing to react 1.5 hours at being warming up to 315 DEG C,
After constant temperature persistently vacuumizes 0.5 hour, the copolyamide 6T resins are obtained；
The intrinsic viscosity of above-mentioned copolyamide 6T resins (PA6T/612) for preparing is 0.87dL/g, melt temperature is
296℃。
A kind of high heat-resisting high flowing copolyamide 6T composites of the present embodiment, are prepared from by the following raw material：
The preparation method of the heat-resisting high flowing copolyamide 6T composites of above-mentioned height, comprises the following steps：
(1) the copolyamide 6T resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling,
By copolyamide 6T resins, polyhexamethylene adipamide resin after cooling, and toluene di-isocyanate(TDI) (TDI), 2,2'- (1,
3- phenylenes)-bisoxazoline (PBO), N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'-, it is double (2,
6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
Mixed in homogenizer；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another homogenizer and is mixed；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, granulates, technique
Parameter is as follows：One 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 50 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 3
The raw material of the copolyamide 6T resins used in the present embodiment is constituted and synthesis step is as follows：
(1) by the monomer 1 after vacuum drying：1mol hexamethylene diamines, 0.6mol terephthalic acid (TPA)s, 0.4mol adipic acids are added to
In stirring-type polymer reactor, while the 4% of the gross weight of monomer 1 polyesteramide, 1.5% benzoic acid, 0.2% N is added,
The medium of N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides, addition 100mL water as mass-and heat-transfer；So
After vacuumize 5min, lead to nitrogen 5min, so circulation 6 times makes reactant be present in the lower environment of nitrogen protection, and control is stirred
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 polymerisation
The mixing speed of device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 215 DEG C, 2.0MPa is deflated to, and
Maintain pressure in 2.0MPa, after reacting 1.5 hours, be deflated to normal pressure, while after continuing to react 1.5 hours at being warming up to 315 DEG C,
After constant temperature persistently vacuumizes 0.5 hour, the copolyamide 6T resins are obtained；
The intrinsic viscosity of above-mentioned copolyamide 6T resins (PA6T/66) for preparing is 0.85dL/g, melt temperature is
299℃。
A kind of high heat-resisting high flowing copolyamide 6T composites of the present embodiment, are prepared from by the following raw material：
The preparation method of the heat-resisting high flowing copolyamide 6T composites of above-mentioned height, comprises the following steps：
(1) the copolyamide 6T resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling,
By copolyamide 6T resins, polyhexamethylene adipamide resin after cooling, and toluene di-isocyanate(TDI) (TDI), 2,2'- (1,
3- phenylenes)-bisoxazoline (PBO), N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'-, it is double (2,
6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
Mixed in homogenizer；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another homogenizer and is mixed；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, granulates, technique
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 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 45 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 4
The raw material of the copolyamide 6T resins used in the present embodiment is constituted and synthesis step is with embodiment 3.
A kind of high heat-resisting high flowing copolyamide 6T composites of the present embodiment, are prepared from by the following raw material：
The preparation method of the heat-resisting high flowing copolyamide 6T composites of above-mentioned height, comprises the following steps：
(1) the copolyamide 6T resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling,
By copolyamide 6T resins, polyhexamethylene adipamide resin after cooling, and toluene di-isocyanate(TDI) (TDI), 2,2'- (1,
3- phenylenes)-bisoxazoline (PBO), N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'-, it is double (2,
6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
Mixed in homogenizer；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another homogenizer and is mixed；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, granulates, technique
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, 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 40 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 5
The raw material of the copolyamide 6T resins used in the present embodiment is constituted and synthesis step is with embodiment 3.
A kind of high heat-resisting high flowing copolyamide 6T composites of the present embodiment, are prepared from by the following raw material：
The preparation method of the heat-resisting high flowing copolyamide 6T composites of above-mentioned height, comprises the following steps：
(1) the copolyamide 6T resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling,
By copolyamide 6T resins, polyhexamethylene adipamide resin after cooling, and toluene di-isocyanate(TDI) (TDI), 2,2'- (1,
3- phenylenes)-bisoxazoline (PBO), N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'-, it is double (2,
6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
Mixed in homogenizer；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another homogenizer and is mixed；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, granulates, technique
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, 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 40 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 6
The raw material of the copolyamide 6T resins used in the present embodiment is constituted and synthesis step is with embodiment 3.
A kind of high heat-resisting high flowing copolyamide 6T composites of the present embodiment, are prepared from by the following raw material：
The preparation method of the heat-resisting high flowing copolyamide 6T composites of above-mentioned height, comprises the following steps：
(1) the copolyamide 6T resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling,
By copolyamide 6T resins, polyhexamethylene adipamide resin after cooling, and toluene di-isocyanate(TDI) (TDI), 2,2'- (1,
3- phenylenes)-bisoxazoline (PBO), N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'-, it is double (2,
6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
Mixed in homogenizer；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another homogenizer and is mixed；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, granulates, technique
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, 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 40 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 1
The raw material of the copolyamide 6T resins used in this comparative example is constituted and synthesis step is with embodiment 3.
A kind of high heat-resisting high flowing copolyamide 6T composites of this comparative example, are prepared from by the following raw material：
The preparation method of the heat-resisting high flowing copolyamide 6T composites of above-mentioned height, comprises the following steps：
(1) the copolyamide 6T resins are placed in into 90 DEG C, after being dried 5 hours, cooling, by the copolyamide 6T after cooling
Resin, and N, N'- double (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides, double (2,6- di-t-butyl -4- first
Base phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added in homogenizer
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 homogenizer and is mixed；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, granulates, technique
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, 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 40 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 2
The raw material of the copolyamide 6T resins used in this comparative example is constituted and synthesis step is with embodiment 3.
A kind of high heat-resisting high flowing copolyamide 6T composites of this comparative example, are prepared from by the following raw material：
The preparation method of the heat-resisting high flowing copolyamide 6T composites of above-mentioned height, comprises the following steps：
(1) the copolyamide 6T resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling,
By copolyamide 6T resins, polyhexamethylene adipamide resin after cooling, and double (2,2,6, the 6- tetramethyl -4- piperidines of N, N'-
Base) -1,3- benzenedicarboxamides, double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates, anti-dripping agent (poly- four
PVF) and dimethicone be added in homogenizer 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 homogenizer and is mixed；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, granulates, technique
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, 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 40 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 3
The raw material of the copolyamide 6T resins used in this comparative example is constituted and synthesis step is with embodiment 3.
A kind of high heat-resisting high flowing copolyamide 6T composites of this comparative example, are prepared from by the following raw material：
The preparation method of the heat-resisting high flowing copolyamide 6T composites of above-mentioned height, comprises the following steps：
(1) the copolyamide 6T resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling,
By copolyamide 6T resins, polyhexamethylene adipamide resin after cooling, and toluene di-isocyanate(TDI) (TDI), 2,2'- (1,
3- phenylenes)-bisoxazoline (PBO), N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'-, it is double (2,
6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
Mixed in homogenizer；
(2) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds alkali-free glass fibre to carry out melting extrusion, granulates, 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 40 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 4
The raw material of the copolyamide 6T resins used in this comparative example is constituted and synthesis step is with embodiment 3.
A kind of high heat-resisting high flowing copolyamide 6T composites of this comparative example, are prepared from by the following raw material：
The preparation method of the heat-resisting high flowing copolyamide 6T composites of above-mentioned height, comprises the following steps：
(1) the copolyamide 6T resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling,
By copolyamide 6T resins, polyhexamethylene adipamide resin after cooling, and toluene di-isocyanate(TDI) (TDI), 2,2'- (1,
3- phenylenes)-bisoxazoline (PBO), N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'-, it is double (2,
6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
Mixed in homogenizer；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another homogenizer and is mixed；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, granulates, technique
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, 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 30 for the ratio L/D of double thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
It is below embodiment and comparative example list (table 1)：
The embodiment of table 1 constitutes weight portion list with comparative example raw material
Double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of the N of above example and comparative example, N'-,
Double (2,6- di-t-butyl -4- aminomethyl phenyls) 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 working of plastics sample of comparative example are carried out into following performance test (result is as shown in table 2)：
Mobile performance：By GB/T 3682-2000 standard testings, 309 DEG C of test temperature, load 1.2kg；
Tensile property：By GB/T 1040.1-2006 standard testings, rate of extension 10mm/min；
Heat resistance：By GB/T 1634.1-2004 standard testings, bending stress 0.45MPa；
Water absorbing properties：By GB/T 1034-2008 standard testings, testing time 24h.
The embodiment of table 2 and comparative example performance list
As can be seen that the addition of aliphatic polyamide resin (polyhexamethylene adipamide resin) is got over from embodiment 1～6
Many, the melt index of its copolyamide 6T resin composite materials is bigger, and processing characteristics is better；The addition of alkali-free glass fibre is got over
Many, the tensile strength and heat distortion temperature of its copolyamide 6T resin composite materials is bigger, but floats fine possibility while producing
It is bigger；The water absorption rate change of each embodiment is little.Comprehensive factors above, the combination property of embodiment 6 is optimal.
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, its melt index is only 5g/10min (309 DEG C of test temperature, load 1.2kg), processing
Performance is not good；Comparative example 2 is to be not added with toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylenes)-bisoxazoline (PBO)
Copolyamide 6T resin composite materials, aliphatic polyamide resin (polyhexamethylene adipamide resin) polyamide 6 T resins phase together
Capacitive is not good, so as to cause bad impact to the tensile property of copolyamide 6T resin composite materials；Comparative example 3 is not add
Plus coupling agent, N, the copolyamide 6T resin composite materials of N'- ethylenebisstearamides, its copolyamide 6T resin compounded materials
The floating fine phenomenon on material surface increases, and resin composite materials are not good with alkali-free glass fibre compatibility, so as to resin composite materials
Tensile property cause bad impact；The screw configuration of the parallel double-screw extruder of comparative example 4 be double thread, screw rod
The ratio L/D of length L and diameter D be 30, and the screw configuration of the parallel double-screw extruder of embodiment 6 be single thread, screw rod
The ratio L/D of length L and diameter D is 40, by contrast it is found that using the parallel double-screw extruder described in embodiment 6
Screw Parameters, the processing characteristics of the copolyamide 6T resin composite materials that it is prepared, tensile property, heat resistance and water suction
Performance is greatly improved, and obtains the copolyamide 6T resin compoundeds of high heat-resisting, high fluidity, high tensile and low water absorption
The beneficial effect of material.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply 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, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed, but and
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that for one of ordinary skill in the art comes
Say, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (10)
1. a kind of high heat-resisting high flowing copolyamide 6T composites, it is characterised in that prepared by the raw material of following weight portion and
Into：
The copolyamide 6T resins are heat resistant polyamide 6T/66 resins, heat resistant polyamide 6T/610 resins, high temperature resistant are gathered
One kind in acid amides 6T/612 resins；The intrinsic viscosity of the copolyamide 6T resins is 0.7～1.0dL/g；
The aliphatic polyamide resin is at least one in nylon 46 resin, polyhexamethylene adipamide resin；
The coupling agent be 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 in triethoxysilane；
The length of the alkali-free glass fibre be 2～4mm, a diameter of 9～11 μm；
The anti-dripping agent is fluoropolymer.
2. heat-resisting high flowing copolyamide 6T composites of height according to claim 1, it is characterised in that by following weight
The raw material of part is prepared from：
3. heat-resisting high flowing copolyamide 6T composites of height according to claim 1 and 2, it is characterised in that described common
The intrinsic viscosity of polyamide 6 T resins is 0.75～0.95dL/g；The aliphatic polyamide resin is polyhexamethylene adipamide tree
Fat, its inherent viscosity is 1.22～1.84dL/g.
4. heat-resisting high flowing copolyamide 6T composites of height according to claim 1 and 2, it is characterised in that the idol
Connection agent is at least one in gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane；The anti-dripping agent is
Polytetrafluoroethylene (PTFE).
5. heat-resisting high flowing copolyamide 6T composites of height according to claim 1 and 2, it is characterised in that described common
Polyamide 6 T resins are formed by monomer 1 and polyesteramide copolymerization, and it is 1 that the monomer 1 is mol ratio：0.5～0.6：0.4～0.5
Hexamethylene diamine, terephthalic acid (TPA), aliphatic dibasic acid, and the hexamethylene diamine and both terephthalic acid (TPA) and aliphatic dibasic acid use
The mol ratio of amount sum is 1, and the aliphatic dibasic acid is the one kind in adipic acid, decanedioic acid, dodecanedioic acid, the polyester acyl
Amine addition is the 1～8% of the gross weight of the monomer 1.
6. heat-resisting high flowing copolyamide 6T composites of height according to claim 5, it is characterised in that the copolymerization acyl
Amine 6T resins are obtained by following synthetic method：
(1) by vacuum drying after the monomer 1 be added in stirring-type polymer reactor, while add the polyesteramide,
And molecular weight regulator, antioxidant, water；Then 4～6min is vacuumized, leads to 4～6min of nitrogen, so circulated 5～7 times, made
Reactant is present in the lower environment of nitrogen protection, control in the stirring-type polymer reactor system pressure for 0.2～
0.3MPa；
(2) in 2～4 hours by the closed constant-speed heating of the stirring-type polymer reactor to 272～280 DEG C, adjust described in stir
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, normal pressure is deflated to, while being warming up to 310
After continuing to react 1～2 hour at～320 DEG C, after constant temperature persistently vacuumizes 0.3～1 hour, the copolyamide 6T trees are obtained
Fat；
The molecular weight regulator is addition is the gross weight of the monomer 1 0.1～3% benzoic acid；The antioxidant is
Addition is the N of the 0.1～0.3% of the gross weight of the monomer 1, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene
Diamides；Appropriate amount of water.
7. the preparation method of the high heat-resisting high flowing copolyamide 6T composites described in a kind of any one of claim 1-6, its
It is characterised by, comprises the following steps：
(1) the copolyamide 6T resins and aliphatic polyamide resin are placed in into 80～100 DEG C, it is cold after being dried 4～12 hours
But, by copolyamide 6T resins, the aliphatic polyamide resin after cooling, and the toluene di-isocyanate(TDI), 2,2'- (1,
3- phenylenes)-bisoxazoline, N, N'- double (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides, double (2,6- bis-
The tert-butyl group -4- aminomethyl phenyls) pentaerythritol diphosphate, anti-dripping agent and dimethicone be added in homogenizer and carry out
Mixing；
(2) coupling agent, alkali-free glass fibre and N,N' ethylene bis stearmide are added into another homogenizer
In mixed；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and are squeezed in parallel double-screw
Going out the mixture that the lateral addition step (2) of machine mixes carries out melting extrusion, granulates, and technological parameter is as follows：One 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.
8. preparation method according to claim 7, it is characterised in that by the copolyamide 6T trees in the step (1)
Fat and aliphatic polyamide resin are placed in 90 DEG C, are dried 4～6 hours；Technological parameter in the step (3) is：One area's temperature
For 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.
9. the preparation method according to claim 7 or 8, it is characterised in that the screw shaped of the parallel double-screw extruder
Shape is single thread；The ratio L/D of spiro rod length L and diameter D is 35～50；The screw rod is provided with the gear block area of more than 1
Left-hand thread area with more than 1.
10. preparation method according to claim 9, it is characterised in that the ratio L/D of the spiro rod length L and diameter D is 35
～45；The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
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