CN106433116B - High temperature resistant copolyamide 6T composition and preparation method thereof - Google Patents
High temperature resistant copolyamide 6T composition 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
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Abstract
The present invention relates to a kind of high temperature resistant copolyamide 6T compositions and preparation method thereof, the high temperature resistant copolyamide 6T composition is prepared from the following materials: high temperature resistant copolyamide 6T resin prepolymer, high temperature resistant copolyamide 6T 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.The high temperature resistant copolyamide 6T composition has the characteristics that 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, more particularly to a kind of high temperature resistant copolyamide 6T composition and preparation method thereof.
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 heat resistant polyamide mainly has polyamide 6 T (copolymer), polyamide 9T, polyamide 10T etc..Polyamides
The fusing point of amine 6T resin is 370 DEG C or so, alreadys exceed decomposition temperature, not can be carried out melt-processed actually, it is necessary to
The monomer of addition third component makes the melting temperature of polymer be down to 320 DEG C or less.But the Third monomer of low content is added not
It is enough to improve its processing performance, and the range of work is too narrow, and the Third monomer that high-content is added can make the molten of copolymer resin
Point is too low, and requirement resistant to high temperature is not achieved.
For above-mentioned problem, some researchs, such as Chinese patent have been done to the modification of polyamide in currently available technology
CN103333335A discloses a kind of high fluidity PA10T Amilan polyamide resin composition, is obtained by two kinds by solid phase
Different viscositys PA10T polyamide composition；It is poly- that Chinese patent CN103360599A discloses a kind of high fluidity PA10T
Amide resin composition is prepared by the PA10T resin prepolymer and PA10T resin alloy that are obtained by solid phase
It arrives；Chinese patent CN103483809A discloses a kind of high-fluidity polyamide base halogen-free flame-retarded heat-conducting composite material, by with
6 resin of high-fluidity nylon containing branched structure is matrix, while heat filling, halogen-free flame retardants, antioxidant and idol is added
The auxiliary agents such as connection agent are prepared for a kind of novel halogen-free flame-retarded heat-conducting composite material by double-screw melt blending technology；Chinese patent
CN103012955A discloses a kind of high flowing fiberglass reinforced PP/PA composite material and preparation method；Chinese patent
CN103724979A 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 which providing a kind of has high fluidity, high tensile and low
The high temperature resistant copolyamide 6T composition of water absorption rate, may be used as electrical/electronic components, automobile component, is particularly useful as
The molding substrate material of electronic component.
In order to achieve the above objectives, the present invention uses following scheme:
A kind of high temperature resistant copolyamide 6T composition, the composition are prepared by the raw material of following parts by weight:
The high temperature resistant copolyamide 6T resin prepolymer is heat resistant polyamide 6T/66 (PA6T/66) prepolymer, resistance to height
One of warm polyamide 6 T/610 (PA6T/610) prepolymer, heat resistant polyamide 6T/612 (PA6T/612) prepolymer；Institute
The intrinsic viscosity for stating high temperature resistant copolyamide 6T resin prepolymer is 0.4~0.6dL/g；
The high temperature resistant copolyamide 6T resin is heat resistant polyamide 6T/66 resin (PA6T/66), heat resistant polyamide
One of 6T/610 resin (PA6T/610), heat resistant polyamide 6T/612 resin (PA6T/612)；The high temperature resistant copolymerization
The intrinsic viscosity of amide 6T resin is 0.7~1.0dL/g；
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 temperature resistant copolyamide 6T composition is prepared by the raw material of following parts by weight:
In wherein some embodiments, high temperature resistant copolyamide 6T composition, further preferably by the original of following parts by weight
Material is prepared:
In wherein some embodiments, the intrinsic viscosity of the high temperature resistant copolyamide 6T resin prepolymer is 0.45~
0.55dL/g；The intrinsic viscosity of the high temperature resistant copolyamide 6T resin is 0.75~0.95dL/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 high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T tree
Rouge is copolymerized by monomer 1 and polyesteramide, and the monomer 1 is the hexamethylene diamine that molar ratio is 1:0.5~0.6:0.4~0.5, right
Phthalic acid, aliphatic dibasic acid, and the hexamethylene diamine and both terephthalic acid (TPA) and aliphatic dibasic acid dosage and mole
Than being 1, the aliphatic dibasic acid is one of adipic acid, decanedioic acid, dodecanedioic acid, and the polyesteramide additional amount is
The 1~8% of 1 total weight of monomer.
In wherein some embodiments, the high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T tree
Rouge is made by following synthetic method:
(1) monomer 1 after vacuum drying is added in stirring-type polymer reactor, while the polyamide is added
Ester 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, the high temperature resistant copolyamide 6T resin prepolymer is obtained；
(3) the high temperature resistant copolyamide 6T resin prepolymer for obtaining step (2) is persistently taken out at 310~320 DEG C
After vacuum 0.3~1 hour, the high temperature resistant copolyamide 6T resin is obtained；
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 temperature resistant copolyamide 6T composition.
The preparation method of above-mentioned high temperature resistant copolyamide 6T composition, specific technical solution, comprising the following steps:
(1) the high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T resin are placed in 80~100
DEG C, it is cooling after 4~12 hours dry, by high temperature resistant copolyamide 6T resin prepolymer after cooling, high temperature resistant copolyamide 6T
Resin and the toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, N'- it is bis- (2,2,
6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythrite diphosphonic acid
Ester, anti-dripping agent and dimethicone, which are added in high-speed mixer, to be mixed；
(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 high temperature resistant copolyamide 6T resin prepolymer and resistance in the step (1)
High temperature copolyamide 6T resin 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 be 290~300 DEG C, three area's temperature be 295~305 DEG C, four area's temperature be 300~305 DEG C, five
Area's temperature be 300~305 DEG C, six area's temperature be 300~305 DEG C, seven area's temperature be 300~305 DEG C, eight area's temperature be 300~
305 DEG C, die head temperature is 295~300 DEG C, and screw speed is 200~400rpm.
In wherein some embodiments, the screw configuration of the parallel double-screw extruder is single thread；Spiro rod length L
It is 35~50 with the ratio between diameter D L/D；The screw rod be equipped with 1 or more (contain 1) gear block area and 1 or more (containing 1)
Left-hand thread area.
In wherein some embodiments, the ratio between the spiro rod length L and diameter D L/D are 35~45；The screw rod is equipped with
2 gear block areas and 1 left-hand thread area.
In wherein some embodiments, the high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T tree
Rouge is copolymerized by monomer 1 and polyesteramide, and the monomer 1 is the hexamethylene diamine that molar ratio is 1:0.5~0.6:0.4~0.5, right
Phthalic acid, aliphatic dibasic acid, and the hexamethylene diamine and both terephthalic acid (TPA) and aliphatic dibasic acid dosage and mole
Than being 1, the aliphatic dibasic acid is one of adipic acid, decanedioic acid, dodecanedioic acid, and the polyesteramide additional amount is
The 1~8% of 1 total weight of monomer.
In wherein some embodiments, the high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T tree
Rouge is made by following synthetic method:
(1) monomer 1 after vacuum drying is added in stirring-type polymer reactor, while the polyamide is added
Ester 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, the high temperature resistant copolyamide 6T resin prepolymer is obtained；
(3) the high temperature resistant copolyamide 6T resin prepolymer for obtaining step (2) is persistently taken out at 310~320 DEG C
After vacuum 0.3~1 hour, the high temperature resistant copolyamide 6T resin is obtained；
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 high temperature resistant copolyamide 6T resin, this
Invention improves the processing performance of high temperature resistant copolyamide 6T resin using high temperature resistant copolyamide 6T resin prepolymer, this be because
Have a preferable mobile performance for high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T resin have compared with
Good mechanical property.Meanwhile (characteristic is glutinous for the strand of the lower intrinsic viscosity in part of high temperature resistant copolyamide 6T resin prepolymer
Spend it is lower, activity it is higher) end group can respectively with the isocyanate groups of toluene di-isocyanate(TDI), 2,2'- (1,3- Asia benzene
Base) chain extending reaction occurs for the oxazoline group of-bisoxazoline, the intrinsic viscosity of such prepolymer is improved to zone of reasonableness, thus
Reduce influence of such prepolymer to high temperature resistant copolyamide 6T resin mechanical property, and the isocyanic acid of toluene di-isocyanate(TDI)
Ester group, 2,2'- (1,3- phenylene)-bisoxazoline oxazoline group can also with the coupling agent on alkali-free glass fibre into
Row reaction, improves the interface binding power and compatibility of alkali-free glass fibre and high temperature resistant copolyamide 6T resin, reduces floating fine hair
Raw probability.
The coupling agent that the present invention uses, preferably gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane,
Contain amino, and anti-glass emergence on the surface agent N, N'- ethylenebisstearamide contains amide group, above-mentioned auxiliary agent can be with
The end group of high temperature resistant copolyamide 6T resin reacts, to further increase alkali-free glass fibre and high temperature resistant copolyamide
The interface binding power and compatibility of 6T resin reduce the floating fine probability occurred.
Mechanical property and appearance effects of the length and diameter of alkali-free glass fibre to high temperature resistant copolyamide 6T resin
It is larger.The length of alkali-free glass fibre is bigger, and the tensile property of resin composite materials is higher, while a possibility that glass emergence on the surface
It is consequently increased；The diameter of alkali-free glass fibre is smaller, and tensile strength is higher, but the cost of its preparation is higher, while unit
Coupling agent needed for area is also more.Therefore, select the length and diameter of suitable alkali-free glass fibre excellent to processability
And the high high temperature resistant copolyamide 6T resin combination of cost performance is 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, better heat stability during high temperature resistant copolyamide 6T resin alloy, amide group can be total with high temperature resistant
The end group of polyamide 6 T resin 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, it can be excellent to be provided during high temperature resistant copolyamide 6T resin alloy
Colour stability and melt stability more, while the heat drop of high temperature resistant copolyamide 6T resin 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 is bad for the processing temperature narrow limits and processing performance of existing high temperature resistant copolyamide 6T resin
Defect improves the processing performance of high temperature resistant copolyamide 6T resin by using high temperature resistant copolyamide 6T resin prepolymer,
Part high temperature resistant copolyamide 6T is solved using toluene di-isocyanate(TDI) and 2,2'- (1,3- phenylene)-bisoxazoline simultaneously
The defect that resin prepolymer keeps the mechanical properties decrease of high temperature resistant copolyamide 6T resin excessive, and coupling agent and N is added,
N'- ethylenebisstearamide is floating fine to solve the problems, such as, is used in compounding N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -
1,3- benzenedicarboxamide and bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates are handled in Blending Processes
Xanthochromia problem, preparation-obtained high temperature resistant copolyamide 6T composition have high fluidity, high tensile and low water absorption
The characteristics of, it can be applied to field of electronics, LED field, automotive field, aerospace and military industry field etc..
Detailed description of the invention
Fig. 1 show the preparation technology flow chart of high temperature resistant copolyamide 6T composition of the present invention.
Specific embodiment
To further understand the features of the present invention, technological means and specific purposes achieved, function, parse this hair
Bright advantage and spirit, by following embodiment, the present invention is further elaborated.
The reaction mechanism is as follows that (preparation technology flow chart is see figure for high temperature resistant copolyamide 6T resin combination of the present invention
1):
Reaction mechanism
By upper reaction equation it is found that the end ammonia of high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T resin
Base can react with the isocyanate groups of toluene di-isocyanate(TDI), high temperature resistant copolyamide 6T resin prepolymer and resistance to height
The Amino End Group of warm copolyamide 6T resin, carboxyl end group can be sent out with the oxazoline group of 2,2'- (1,3- phenylene)-bisoxazoline
Raw reaction.The intrinsic viscosity of high temperature resistant copolyamide 6T resin is lower, and activity is higher, therefore, high temperature resistant copolyamide 6T tree
The end group of the strand of the lower intrinsic viscosity in the part of rouge prepolymer can respectively preferentially with the isocyanic acid of toluene di-isocyanate(TDI)
The oxazoline group generation chain extending reaction of ester group, 2,2'- (1,3- phenylene)-bisoxazoline, improves the spy of such prepolymer
Property viscosity is to zone of reasonableness, to reduce such prepolymer to the shadow of high temperature resistant copolyamide 6T resin combination mechanical property
It rings, while can use the processing performance that such prepolymer improves resin combination again, to prepare with high fluidity, height
The high temperature resistant copolyamide 6T composition of tensile strength and low water absorption.
Raw material used in the embodiment of the present invention is as follows:
High temperature resistant copolyamide 6T resin prepolymer (copolymerization PA6T prepolymer) and (copolymerization of high temperature resistant copolyamide 6T resin
PA6T), make by oneself, the hexamethylene diamine in raw material is selected from Wuxi Yinda Nylon Co., Ltd., and terephthalic acid (TPA) is selected from Beijing Yanshan Mountain petroleum
Chemical company, adipic acid, decanedioic acid, dodecanedioic acid are selected from Shandong Guang Yin new material Co., Ltd, remaining auxiliary agent is selected from state
Chemical reagent Co., Ltd, medicine group；
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.
High temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T resin in following embodiment is by monomer 1
Be copolymerized with polyesteramide, the monomer 1 be the hexamethylene diamine, terephthalic acid (TPA) that molar ratio is 1:0.5~0.6:0.4~0.5,
Aliphatic dibasic acid, and the hexamethylene diamine and both terephthalic acid (TPA) and aliphatic dibasic acid dosage and molar ratio be 1, it is described
Aliphatic dibasic acid is one of adipic acid, decanedioic acid, dodecanedioic acid, and the polyesteramide additional amount is the monomer 1
The 1~8% of total weight has such as following formula I structure:
In Formulas I, a=10~100, b=10~200, c=10~100, d=10~100, e=4 or 8 or 10, R are polyester
Amide has such as Formula Il structure:
In Formula II, x=10~200, y=10~200, z=10~100.
The synthetic method of high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T resin is as follows:
(1) monomer 1 after vacuum drying is added in stirring-type polymer reactor, while the polyamide is added
Ester 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, the high temperature resistant copolyamide 6T resin prepolymer is obtained；
(3) the high temperature resistant copolyamide 6T resin prepolymer for obtaining step (2) is persistently taken out at 310~320 DEG C
After vacuum 0.3~1 hour, the high temperature resistant copolyamide 6T resin is obtained；
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
High temperature resistant copolyamide 6T resin prepolymer used in the present embodiment and high temperature resistant copolyamide 6T resin
Raw material 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,
Obtain high temperature resistant copolyamide 6T resin prepolymer；
(3) that the high temperature resistant copolyamide 6T resin prepolymer that step (2) obtains persistently is vacuumized 0.5 at 315 DEG C is small
Shi Hou obtains high temperature resistant copolyamide 6T resin；
The intrinsic viscosity of the above-mentioned high temperature resistant copolyamide 6T resin prepolymer (PA6T/610 prepolymer) being prepared is
0.51dL/g, melting temperature are 288 DEG C, the intrinsic viscosity of high temperature resistant copolyamide 6T resin (PA6T/610) be 0.86dL/g,
Melting temperature is 297 DEG C.
A kind of high temperature resistant copolyamide 6T composition of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned high temperature resistant copolyamide 6T composition, comprising the following steps:
(1) the high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T resin are placed in 90 DEG C, done
It is cooling after dry 5 hours, by high temperature resistant copolyamide 6T resin prepolymer after cooling, high temperature resistant copolyamide 6T resin, and
Toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, the bis- (2,2,6,6- tetramethyl -4- of N'-
Piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-dripping agent
(polytetrafluoroethylene (PTFE)) and dimethicone, which are added in high-speed mixer, to be mixed；
(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
High temperature resistant copolyamide 6T resin prepolymer used in the present embodiment and high temperature resistant copolyamide 6T resin
Raw material 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,
Obtain high temperature resistant copolyamide 6T resin prepolymer；
(3) that the high temperature resistant copolyamide 6T resin prepolymer that step (2) obtains persistently is vacuumized 0.5 at 315 DEG C is small
Shi Hou obtains high temperature resistant copolyamide 6T resin；
The intrinsic viscosity of the above-mentioned high temperature resistant copolyamide 6T resin prepolymer (PA6T/612 prepolymer) being prepared is
0.52dL/g, melting temperature are 288 DEG C, the intrinsic viscosity of high temperature resistant copolyamide 6T resin (PA6T/612) be 0.87dL/g,
Melting temperature is 296 DEG C.
A kind of high temperature resistant copolyamide 6T composition of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned high temperature resistant copolyamide 6T composition, comprising the following steps:
(1) the high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T resin are placed in 90 DEG C, done
It is cooling after dry 5 hours, by high temperature resistant copolyamide 6T resin prepolymer after cooling, high temperature resistant copolyamide 6T resin, and
Toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, the bis- (2,2,6,6- tetramethyl -4- of N'-
Piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-dripping agent
(polytetrafluoroethylene (PTFE)) and dimethicone, which are added in high-speed mixer, to be 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 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
High temperature resistant copolyamide 6T resin prepolymer used in the present embodiment and high temperature resistant copolyamide 6T resin
Raw material 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,
Obtain high temperature resistant copolyamide 6T resin prepolymer；
(3) that the high temperature resistant copolyamide 6T resin prepolymer that step (2) obtains persistently is vacuumized 0.5 at 315 DEG C is small
Shi Hou obtains high temperature resistant copolyamide 6T resin；
The intrinsic viscosity of the above-mentioned high temperature resistant copolyamide 6T resin prepolymer (PA6T/66 prepolymer) being prepared is
0.50dL/g, melting temperature are 289 DEG C, and the intrinsic viscosity of high temperature resistant copolyamide 6T resin (PA6T/66) is 0.85dL/g, melts
Melting temperature is 299 DEG C.
A kind of high temperature resistant copolyamide 6T composition of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned high temperature resistant copolyamide 6T composition, comprising the following steps:
(1) the high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T resin are placed in 90 DEG C, done
It is cooling after dry 5 hours, by high temperature resistant copolyamide 6T resin prepolymer after cooling, high temperature resistant copolyamide 6T resin, and
Toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, the bis- (2,2,6,6- tetramethyl -4- of N'-
Piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-dripping agent
(polytetrafluoroethylene (PTFE)) and dimethicone, which are added in high-speed mixer, to be mixed；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another high-speed mixer and is mixed；
(3) mixture for mixing step (1) is added in parallel double-screw extruder through feeder, and in parallel double spiral shells
Lateral (the 4th area) of bar extruder (totally eight area) is added the mixture that step (2) mix and carries out melting extrusion, is granulated, technique
Parameter is as follows: area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 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
High temperature resistant copolyamide 6T resin prepolymer used in the present embodiment and high temperature resistant copolyamide 6T resin
Raw material is constituted and synthesis step is the same as embodiment 3.
A kind of high temperature resistant copolyamide 6T composition of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned high temperature resistant copolyamide 6T composition, comprising the following steps:
(1) the high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T resin are placed in 90 DEG C, done
It is cooling after dry 5 hours, by high temperature resistant copolyamide 6T resin prepolymer after cooling, high temperature resistant copolyamide 6T resin, and
Toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, the bis- (2,2,6,6- tetramethyl -4- of N'-
Piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-dripping agent
(polytetrafluoroethylene (PTFE)) and dimethicone, which are added in high-speed mixer, to be 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.
Embodiment 5
High temperature resistant copolyamide 6T resin prepolymer used in the present embodiment and high temperature resistant copolyamide 6T resin
Raw material is constituted and synthesis step is the same as embodiment 3.
A kind of high temperature resistant copolyamide 6T composition of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned high temperature resistant copolyamide 6T composition, comprising the following steps:
(1) the high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T resin are placed in 90 DEG C, done
It is cooling after dry 5 hours, by high temperature resistant copolyamide 6T resin prepolymer after cooling, high temperature resistant copolyamide 6T resin, and
Toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, the bis- (2,2,6,6- tetramethyl -4- of N'-
Piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-dripping agent
(polytetrafluoroethylene (PTFE)) and dimethicone, which are added in high-speed mixer, to be 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.
Embodiment 6
High temperature resistant copolyamide 6T resin prepolymer used in the present embodiment and high temperature resistant copolyamide 6T resin
Raw material is constituted and synthesis step is the same as embodiment 3.
A kind of high temperature resistant copolyamide 6T composition of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned high temperature resistant copolyamide 6T composition, comprising the following steps:
(1) the high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T resin are placed in 90 DEG C, done
It is cooling after dry 5 hours, by high temperature resistant copolyamide 6T resin prepolymer after cooling, high temperature resistant copolyamide 6T resin, and
Toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, the bis- (2,2,6,6- tetramethyl -4- of N'-
Piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-dripping agent
(polytetrafluoroethylene (PTFE)) and dimethicone, which are added in high-speed mixer, to be 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 1
The raw material of high temperature resistant copolyamide 6T resin used in this comparative example constitutes and the same embodiment of synthesis step
3。
A kind of high temperature resistant copolyamide 6T composition of this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned high temperature resistant copolyamide 6T composition, comprising the following steps:
(1) the high temperature resistant copolyamide 6T resin is placed in 90 DEG C, after 5 hours dry, cooling, by resistance to height after cooling
Warm copolyamide 6T resin and N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamides, bis- (2,6-
Di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to height
It is mixed in fast blender；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another high-speed mixer and is mixed；
(3) mixture for mixing step (1) is added in parallel double-screw extruder through feeder, and in parallel double spiral shells
Lateral (the 4th area) of bar extruder (totally eight area) is added the mixture that step (2) mix and carries out melting extrusion, is granulated, technique
Parameter is as follows: area's temperature is 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
High temperature resistant copolyamide 6T resin prepolymer used in this comparative example and high temperature resistant copolyamide 6T resin
Raw material is constituted and synthesis step is the same as embodiment 3.
A kind of high temperature resistant copolyamide 6T composition of this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned high temperature resistant copolyamide 6T composition, comprising the following steps:
(1) the high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T resin are placed in 90 DEG C, done
It is cooling after dry 5 hours, by high temperature resistant copolyamide 6T resin prepolymer after cooling, high temperature resistant copolyamide 6T resin, and
Bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N, N'-, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) seasons
Penta tetrol bisphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone are added in high-speed mixer and are 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
High temperature resistant copolyamide 6T resin prepolymer used in this comparative example and high temperature resistant copolyamide 6T resin
Raw material is constituted and synthesis step is the same as embodiment 3.
A kind of high temperature resistant copolyamide 6T composition of this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned high temperature resistant copolyamide 6T composition, comprising the following steps:
(1) the high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T resin are placed in 90 DEG C, done
It is cooling after dry 5 hours, by high temperature resistant copolyamide 6T resin prepolymer after cooling, high temperature resistant copolyamide 6T resin, and
Toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, the bis- (2,2,6,6- tetramethyl -4- of N'-
Piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-dripping agent
(polytetrafluoroethylene (PTFE)) and dimethicone, which are added in high-speed mixer, to be mixed；
(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 290 DEG C, and two area's temperature are 305 DEG C, and three area's temperature are 310 DEG C, and four area's temperature are 315 DEG C, and five area's temperature are 315
DEG C, six area's temperature are 315 DEG C, and seven area's temperature are 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 DEG C, 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
High temperature resistant copolyamide 6T resin prepolymer used in this comparative example and high temperature resistant copolyamide 6T resin
Raw material is constituted and synthesis step is the same as embodiment 3.
A kind of high temperature resistant copolyamide 6T composition of this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned high temperature resistant copolyamide 6T composition, comprising the following steps:
(1) the high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T resin are placed in 90 DEG C, done
It is cooling after dry 5 hours, by high temperature resistant copolyamide 6T resin prepolymer after cooling, high temperature resistant copolyamide 6T resin, and
Toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, the bis- (2,2,6,6- tetramethyl -4- of N'-
Piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-dripping agent
(polytetrafluoroethylene (PTFE)) and dimethicone, which are added in high-speed mixer, to be 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 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；
Bending property: pressing GB/T 9341-2008 standard testing, is bent rate 10mm/min；
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 high temperature resistant copolyamide 6T resin prepolymer is more from Examples 1 to 6, resistance to height
The melt index of warm copolyamide 6T resin combination is bigger, and processing performance is better；The additional amount of alkali-free glass fibre is more,
The tensile strength and bending strength of high temperature resistant copolyamide 6T resin combination are bigger, but generate a possibility that floating fibre simultaneously and get over
Greatly；The water absorption rate variation of each embodiment is little.In summary the comprehensive performance of factor, embodiment 6 is best.
Be compared with embodiment 6, comparative example 1 be not added with high temperature resistant copolyamide 6T resin prepolymer high temperature resistant it is total
Polyamide 6 T resin combination, melt index are only 6g/10min (309 DEG C of test temperature, load 1.2kg), and processing performance is not
It is good；Comparative example 2 is to be not added with the high temperature resistant of toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO)
The high temperature resistant copolyamide 6T resin prepolymer of copolyamide 6T resin combination, the lower intrinsic viscosity in part is total to high temperature resistant
The tensile property and bending property of polyamide 6 T resin combination cause undesirable influence；Comparative example 3 be not added with coupling agent,
The high temperature resistant copolyamide 6T resin combination of N, N'- ethylenebisstearamide, high temperature resistant copolyamide 6T resin combination
The floating fine phenomenon on object surface increases, and resin combination and alkali-free glass fibre compatibility are bad, thus the drawing to resin combination
It stretches performance and bending property causes undesirable influence；The screw configuration of the parallel double-screw extruder of comparative example 4 is two-wire spiral shell
Line, the ratio between spiro rod length L and diameter D L/D are 30, and the screw configuration of the parallel double-screw extruder of embodiment 6 is single line spiral shell
Line, the ratio between spiro rod length L and diameter D L/D are 40, by comparison it can be found that being squeezed using parallel double-screw described in embodiment 6
The Screw Parameters of machine out, the processing performance for the high temperature resistant copolyamide 6T resin combination being prepared, tensile property, bending
Performance and water absorbing properties are greatly improved, and obtain the high temperature resistant copolyamide of high fluidity, high tensile and low water absorption
The beneficial effect of 6T resin combination.
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 temperature resistant copolyamide 6T composition, which is characterized in that pass through parallel double-screw by the raw material of following parts by weight
Extruder is prepared:
The intrinsic viscosity of the high temperature resistant copolyamide 6T resin prepolymer is 0.4~0.6dL/g；The high temperature resistant copolyamide
The intrinsic viscosity of 6T resin is 0.7~1.0dL/g；
The high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T resin are copolymerized by monomer 1 and polyesteramide
It forming, the monomer 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 and both terephthalic acid (TPA) and aliphatic dibasic acid dosage and molar ratio be 1, the aliphatic dibasic acid
For one of adipic acid, decanedioic acid, dodecanedioic acid, the polyesteramide additional amount be 1 total weight of monomer 1~
8%；
The polyesteramide has such as Formula Il structure:
In Formula II, x=10~200, y=10~200, z=10~100；
The coupling agent is gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-γ-
Aminopropyl triethoxysilane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-aminopropyl
Methyl dimethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, anilinomethyl
At least one of triethoxysilane；
The length of the alkali-free glass fibre is 2~4mm, and diameter is 9~11 μm；
The anti-dripping agent is fluoropolymer；
The screw configuration of the parallel double-screw extruder is single thread；The ratio between spiro rod length L and diameter D L/D are 35~50.
2. high temperature resistant copolyamide 6T composition according to claim 1, which is characterized in that by the raw material of following parts by weight
It is prepared:
3. high temperature resistant copolyamide 6T composition according to claim 1 or 2, which is characterized in that the high temperature resistant copolymerization
The intrinsic viscosity of amide 6T resin prepolymer is 0.45~0.55dL/g；The intrinsic viscosity of the high temperature resistant copolyamide 6T resin
For 0.75~0.95dL/g.
4. high temperature resistant copolyamide 6T composition according to claim 1 or 2, which is characterized in that the coupling agent is γ-
At least one of aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane；The anti-dripping agent is polytetrafluoroethyl-ne
Alkene.
5. high temperature resistant copolyamide 6T composition according to claim 1, which is characterized in that the high temperature resistant copolyamide
6T resin prepolymer and high temperature resistant copolyamide 6T resin are 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, the high temperature resistant copolyamide 6T resin prepolymer is obtained；
(3) the high temperature resistant copolyamide 6T resin prepolymer for obtaining step (2) persistently vacuumizes at 310~320 DEG C
After 0.3~1 hour, the high temperature resistant copolyamide 6T resin is obtained；
The molecular weight regulator is 0.1~3% benzoic acid that additional amount is 1 total weight of monomer；The antioxidant is
Additional amount is 0.1~0.3% N of 1 total weight of monomer, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene
Diamides；Appropriate amount of water.
6. a kind of preparation method of the described in any item high temperature resistant copolyamide 6T compositions of claim 1-5, which is characterized in that
The following steps are included:
(1) the high temperature resistant copolyamide 6T resin prepolymer and high temperature resistant copolyamide 6T resin are placed in 80~100 DEG C, done
It is cooling after dry 4~12 hours, by high temperature resistant copolyamide 6T resin prepolymer after cooling, high temperature resistant copolyamide 6T resin,
And the toluene di-isocyanate(TDI), 2,2'- (1,3- phenylene)-bisoxazoline, N, the bis- (2,2,6,6- tetramethyl -4- piperazines of N'-
Piperidinyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-dripping agent and two
Methyl-silicone oil is added in high-speed mixer and is mixed；
(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 the high temperature resistant is copolymerized acyl in the step (1)
Amine 6T resin prepolymer and high temperature resistant copolyamide 6T resin are placed in 90 DEG C, drying 4~6 hours；Technique in the step (3)
Parameter are as follows: area's temperature is 260~285 DEG C, and two area's temperature are 290~300 DEG C, and three area's temperature are 295~305 DEG C, four Qu Wen
Degree is 300~305 DEG C, and 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, eight area's temperature are 300~305 DEG C, and 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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| CN113150542B (en) * | 2021-04-12 | 2023-03-03 | 河南华盈新材料有限公司 | Self-plasticizing PA6T |
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