CN106398193B - Heat resistant polyamide 6T/11 composition and preparation method thereof - Google Patents
Heat resistant polyamide 6T/11 composition and preparation method thereof Download PDFInfo
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- CN106398193B CN106398193B CN201610855302.6A CN201610855302A CN106398193B CN 106398193 B CN106398193 B CN 106398193B CN 201610855302 A CN201610855302 A CN 201610855302A CN 106398193 B CN106398193 B CN 106398193B
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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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
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- 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
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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- 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
- C08G69/44—Polyester-amides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C08K2201/00—Specific properties of additives
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The present invention relates to a kind of heat resistant polyamide 6T/11 compositions and preparation method thereof, the heat resistant polyamide 6T/11 composition is prepared from the following materials: heat resistant polyamide 6T/11 resin prepolymer, heat resistant polyamide 6T/11 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.Heat resistant polyamide 6T/11 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 heat resistant polyamide 6T/11 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
CN 103333335A discloses a kind of high fluidity PA10T Amilan polyamide resin composition, is obtained by two kinds by solid phase
Different viscositys PA10T polyamide composition；Chinese patent CN 103360599A discloses a kind of high fluidity PA10T
Amilan polyamide resin composition is prepared by the PA10T resin prepolymer and PA10T resin alloy that are obtained by solid phase
It arrives；Chinese patent CN 103483809A 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 heat resistant polyamide 6T/11 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 heat resistant polyamide 6T/11 composition, the composition are prepared by the raw material of following parts by weight:
The intrinsic viscosity of the heat resistant polyamide 6T/11 resin prepolymer is 0.4~0.6dL/g；
The intrinsic viscosity of the heat resistant polyamide 6T/11 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, heat resistant polyamide 6T/11 composition is prepared by the raw material of following parts by weight:
In wherein some embodiments, heat resistant polyamide 6T/11 composition, further preferably by the original of following parts by weight
Material is prepared:
In wherein some embodiments, the intrinsic viscosity of the heat resistant polyamide 6T/11 resin prepolymer is 0.45~
0.55dL/g；The intrinsic viscosity of the heat resistant polyamide 6T/11 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 heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11
Resin is copolymerized by monomer 1 and polyesteramide, and the monomer 1 is the hexamethylene diamine that molar ratio is 1:1:0.45~0.55, to benzene
Dioctyl phthalate, 11- aminoundecanoic acid, the polyesteramide additional amount are the 1~8% of 1 total weight of monomer.
In wherein some embodiments, the heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11
Resin 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 heat resistant polyamide 6T/11 resin prepolymer is obtained；
(3) the heat resistant polyamide 6T/11 resin prepolymer for obtaining step (2) is persistently taken out at 310~320 DEG C
After vacuum 0.3~1 hour, the heat resistant polyamide 6T/11 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 heat resistant polyamide 6T/11 composition.
The preparation method of above-mentioned heat resistant polyamide 6T/11 composition, specific technical solution, comprising the following steps:
(1) by the heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin (PA6T/11)
80~100 DEG C, after 4~12 hours dry are placed in, cooling, by heat resistant polyamide 6T/11 resin prepolymer after cooling, resistance to height
Warm polyamide 6 T/11 resin and the toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline
(PBO), bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N, N'-, bis- (2,6- di-t-butyl -4- methyl
Phenyl) pentaerythritol diphosphate, anti-dripping agent and dimethicone be added in high-speed mixer and 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 heat resistant polyamide 6T/11 resin prepolymer and resistance in the step (1)
High temperature polyamide 6T/11 resin (PA6T/11) is placed in 90 DEG C, drying 4~6 hours；Technological parameter in the step (3) are as follows:
One 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, 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, eight area's temperature
Degree is 300~305 DEG C, and 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 heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11
Resin is copolymerized by monomer 1 and polyesteramide, and the monomer 1 is the hexamethylene diamine that molar ratio is 1:1:0.45~0.55, to benzene
Dioctyl phthalate, 11- aminoundecanoic acid, the polyesteramide additional amount are the 1~8% of 1 total weight of monomer.
In wherein some embodiments, the heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11
Resin 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 heat resistant polyamide 6T/11 resin prepolymer is obtained；
(3) the heat resistant polyamide 6T/11 resin prepolymer for obtaining step (2) is persistently taken out at 310~320 DEG C
After vacuum 0.3~1 hour, the heat resistant polyamide 6T/11 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 heat resistant polyamide 6T/11 resin,
The present invention improves the processing performance of heat resistant polyamide 6T/11 resin using heat resistant polyamide 6T/11 resin prepolymer, this
It is because heat resistant polyamide 6T/11 resin prepolymer has preferable mobile performance and heat resistant polyamide 6T/11 resin
Has preferable mechanical property.Meanwhile the strand of the lower intrinsic viscosity in part of heat resistant polyamide 6T/11 resin prepolymer
The end group of (intrinsic viscosity is lower, activity higher) can respectively with the isocyanate groups of toluene di-isocyanate(TDI), 2,2'- (1,
3- phenylene) chain extending reaction occurs for the oxazoline group of-bisoxazoline, the intrinsic viscosity of such prepolymer is improved to reasonable model
It encloses, to reduce influence of such prepolymer to heat resistant polyamide 6T/11 resin mechanical property, and toluene di-isocyanate(TDI)
Isocyanate groups, 2,2'- (1,3- phenylene)-bisoxazoline oxazoline group can also on alkali-free glass fibre
Coupling agent is reacted, and the interface binding power and compatibility of alkali-free glass fibre and heat resistant polyamide 6T/11 resin, drop are improved
The low floating fine probability occurred.
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 heat resistant polyamide 6T/11 resin reacts, to further increase alkali-free glass fibre and heat resistant polyamide
The interface binding power and compatibility of 6T/11 resin reduce the floating fine probability occurred.
Mechanical property and appearance effects of the length and diameter of alkali-free glass fibre to heat resistant polyamide 6T/11 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 heat resistant polyamide 6T/11 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 heat resistant polyamide 6T/11 resin alloy, amide group can be with high temperature resistant
The end group of polyamide 6 T/11 resin reacts to improve compatibility, and hindered piperidine base can provide antioxidation and improve copolymerization
The dyeability of object.
The fusing point of bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates is 239 DEG C, thermal decomposition temperature is super
350 DEG C are crossed, there is good heat resistance and hydrolytic resistance, can be provided in the process for heat resistant polyamide 6T/11 resin alloy
Superior colour stability and melt stability, while the heat of heat resistant polyamide 6T/11 resin in the high temperature process can be prevented
Degradation, 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, prevent 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 heat resistant polyamide 6T/11 resin
Defect improves the processability of heat resistant polyamide 6T/11 resin by using heat resistant polyamide 6T/11 resin prepolymer
Can, while toluene di-isocyanate(TDI) and 2 are used, 2'- (1,3- phenylene)-bisoxazoline solves part heat resistant polyamide
The defect that 6T/11 resin prepolymer keeps the mechanical properties decrease of heat resistant polyamide 6T/11 resin excessive, and coupling agent is added
And N, N'- ethylenebisstearamide are floating fine to solve the problems, such as, are used in compounding N, bis- (2,2,6, the 6- tetramethyl -4- piperidines of N'-
Base) -1,3- benzenedicarboxamide and bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates handle Blending Processes
In xanthochromia problem, preparation-obtained heat resistant polyamide 6T/11 composition have high fluidity, high tensile and low suction
The characteristics of water rate, 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 heat resistant polyamide 6T/11 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 (preparation technology flow chart is see Fig. 1) for heat resistant polyamide 6T/11 resin combination of the present invention:
Reaction mechanism
By upper reaction equation it is found that the end of heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin
Amino can react with the isocyanate groups of toluene di-isocyanate(TDI), heat resistant polyamide 6T/11 resin prepolymer and
The Amino End Group of heat resistant polyamide 6T/11 resin, carboxyl end group can be with the oxazolines of 2,2'- (1,3- phenylene)-bisoxazoline
Group reacts.The intrinsic viscosity of heat resistant polyamide 6T/11 resin is lower, and activity is higher, therefore, heat resistant polyamide
The end group of the strand of the lower intrinsic viscosity in the part of 6T/11 resin prepolymer can respectively preferentially with toluene di-isocyanate(TDI)
The oxazoline group generation chain extending reaction of isocyanate groups, 2,2'- (1,3- phenylene)-bisoxazoline, improves such pre-polymerization
The intrinsic viscosity of object is to zone of reasonableness, to reduce such prepolymer to heat resistant polyamide 6T/11 resin combination mechanical property
The influence of energy, while can use such prepolymer again and improving the processing performance of resin combination, so that preparing has high stream
The heat resistant polyamide 6T/11 composition of dynamic property, high tensile and low water absorption.
Raw material used in the embodiment of the present invention is as follows:
Heat resistant polyamide 6T/11 resin prepolymer (PA6T/11 prepolymer) and heat resistant polyamide 6T/11 resin
(PA6T/11), it makes 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
Petrochemical corporation (complex), 11- aminoundecanoic acid are selected from Taiyuan Zhong Lianze agrochemicals Co., Ltd, remaining auxiliary agent is selected from Chinese medicines group
Learn reagent Co., Ltd；
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.
Heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin in following embodiment is by list
Body 1 and polyesteramide are copolymerized, the monomer 1 be the hexamethylene diamine, terephthalic acid (TPA) that molar ratio is 1:1:0.45~0.55,
11- aminoundecanoic acid, the polyesteramide additional amount are the 1~8% of 1 total weight of monomer, have such as following formula I structure:
In Formulas I, a=10~200, b=10~200, c=10~100, R are polyesteramide, have such as Formula Il knot
Structure:
In Formula II, x=10~200, y=10~200, z=10~100.
The synthetic method of heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 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, heat resistant polyamide 6T/11 resin prepolymer is obtained；
(3) the heat resistant polyamide 6T/11 resin prepolymer that step (2) obtains persistently is vacuumized at 310~320 DEG C
After 0.3~1 hour, heat resistant polyamide 6T/11 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
Heat resistant polyamide 6T/11 resin prepolymer used in the present embodiment and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step it is as follows:
(1) by monomer 1:1mol hexamethylene diamine, 1mol terephthalic acid (TPA), the 0.5mol 11- aminoundecanoic acid after vacuum drying
Be added in stirring-type polymer reactor, at the same be added 4% polyesteramide of 1 total weight of monomer, 1.5% benzoic acid,
100mL water is added as mass-and heat-transfer in 0.2% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides
Medium；Then 5min is vacuumized, leads to nitrogen 5min, so circulation 6 times, reactant is made to be present in the environment under nitrogen protection
In, controlling system pressure in stirring-type polymer reactor is 0.3MPa；
(2) in 3 hours by the closed constant-speed heating of stirring-type polymer reactor to 275 DEG C, adjust stirring-type polymerization reaction
The mixing speed of device is 40r/min, wherein when stirring-type polymer reactor temperature reaches 215 DEG C, it is deflated to 2.0MPa, and
It maintains pressure in 2.0MPa, after reaction 1.5 hours, is deflated to normal pressure, while being warming up at 315 DEG C after the reaction was continued 1.5 hours,
Obtain heat resistant polyamide 6T/11 resin prepolymer；
(3) that the heat resistant polyamide 6T/11 resin prepolymer that step (2) obtains persistently is vacuumized 0.5 at 315 DEG C is small
Shi Hou obtains heat resistant polyamide 6T/11 resin；
The intrinsic viscosity of the above-mentioned heat resistant polyamide 6T/11 resin prepolymer being prepared is 0.51dL/g, melting is warm
Degree is 290 DEG C, and the intrinsic viscosity of heat resistant polyamide 6T/11 resin is 0.86dL/g, melting temperature is 299 DEG C.
A kind of heat resistant polyamide 6T/11 composition of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned heat resistant polyamide 6T/11 composition, comprising the following steps:
(1) the heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
It is cooling after dry 5 hours, by heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, bis- (the 2,2,6,6- tetramethyls of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-drop
It falls agent (polytetrafluoroethylene (PTFE)) and dimethicone is added in high-speed mixer and is 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
Heat resistant polyamide 6T/11 resin prepolymer used in the present embodiment and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step with embodiment 1.
A kind of heat resistant polyamide 6T/11 composition of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned heat resistant polyamide 6T/11 composition, comprising the following steps:
(1) the heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
It is cooling after dry 5 hours, by heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, bis- (the 2,2,6,6- tetramethyls of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-drop
It falls agent (polytetrafluoroethylene (PTFE)) and dimethicone is added in high-speed mixer and is 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
Heat resistant polyamide 6T/11 resin prepolymer used in the present embodiment and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step with embodiment 1.
A kind of heat resistant polyamide 6T/11 composition of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned heat resistant polyamide 6T/11 composition, comprising the following steps:
(1) the heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
It is cooling after dry 5 hours, by heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, bis- (the 2,2,6,6- tetramethyls of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-drop
It falls agent (polytetrafluoroethylene (PTFE)) and dimethicone is added in high-speed mixer and is 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
Heat resistant polyamide 6T/11 resin prepolymer used in the present embodiment and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step with embodiment 1.
A kind of heat resistant polyamide 6T/11 composition of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned heat resistant polyamide 6T/11 composition, comprising the following steps:
(1) the heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
It is cooling after dry 5 hours, by heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, bis- (the 2,2,6,6- tetramethyls of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-drop
It falls agent (polytetrafluoroethylene (PTFE)) and dimethicone is added in high-speed mixer and is 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
Heat resistant polyamide 6T/11 resin prepolymer used in the present embodiment and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step with embodiment 1.
A kind of heat resistant polyamide 6T/11 composition of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned heat resistant polyamide 6T/11 composition, comprising the following steps:
(1) the heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
It is cooling after dry 5 hours, by heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, bis- (the 2,2,6,6- tetramethyls of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-drop
It falls agent (polytetrafluoroethylene (PTFE)) and dimethicone is added in high-speed mixer and is 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
Heat resistant polyamide 6T/11 resin prepolymer used in the present embodiment and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step with embodiment 1.
A kind of heat resistant polyamide 6T/11 composition of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned heat resistant polyamide 6T/11 composition, comprising the following steps:
(1) the heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
It is cooling after dry 5 hours, by heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, bis- (the 2,2,6,6- tetramethyls of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-drop
It falls agent (polytetrafluoroethylene (PTFE)) and dimethicone is added in high-speed mixer and is 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 heat resistant polyamide 6T/11 resin used in this comparative example constitutes and the same embodiment of synthesis step
1。
A kind of heat resistant polyamide 6T/11 composition of this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned heat resistant polyamide 6T/11 composition, comprising the following steps:
(1) the heat resistant polyamide 6T/11 resin is placed in 90 DEG C, after 5 hours dry, cooling will be after cooling resistance to
High temperature polyamide 6T/11 resin and N, bis- (2,2,6,6- tetramethyl -4- piperidyl) -1, the 3- benzenedicarboxamides of N'-, it is bis- (2,
6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added to
It is mixed in high-speed mixer；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another high-speed mixer and is mixed；
(3) mixture for mixing step (1) is added in parallel double-screw extruder through feeder, and in parallel double spiral shells
Lateral (the 4th area) of bar extruder (totally eight area) is added the mixture that step (2) mix and carries out melting extrusion, is granulated, technique
Parameter is as follows: area's temperature is 280 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 300 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Comparative example 2
Heat resistant polyamide 6T/11 resin prepolymer used in this comparative example and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step with embodiment 1.
A kind of heat resistant polyamide 6T/11 composition of this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned heat resistant polyamide 6T/11 composition, comprising the following steps:
(1) the heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
It is cooling after dry 5 hours, by heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N, N'-, bis- (2,6- di-t-butyl -4- methylbenzenes
Base) pentaerythritol diphosphate, anti-dripping agent (polytetrafluoroethylene (PTFE)) and dimethicone be added in high-speed mixer and mixed
It closes；
(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
Heat resistant polyamide 6T/11 resin prepolymer used in this comparative example and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step with embodiment 1.
A kind of heat resistant polyamide 6T/11 composition of this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned heat resistant polyamide 6T/11 composition, comprising the following steps:
(1) the heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
It is cooling after dry 5 hours, by heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, bis- (the 2,2,6,6- tetramethyls of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-drop
It falls agent (polytetrafluoroethylene (PTFE)) and dimethicone is added in high-speed mixer and is 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
Heat resistant polyamide 6T/11 resin prepolymer used in this comparative example and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step with embodiment 1.
A kind of heat resistant polyamide 6T/11 composition of this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned heat resistant polyamide 6T/11 composition, comprising the following steps:
(1) the heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
It is cooling after dry 5 hours, by heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, bis- (the 2,2,6,6- tetramethyls of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-drop
It falls agent (polytetrafluoroethylene (PTFE)) and dimethicone is added in high-speed mixer and is 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 heat resistant polyamide 6T/11 resin prepolymer is more from Examples 1 to 6, resistance to height
The melt index of warm polyamide 6 T/11 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 its heat resistant polyamide 6T/11 resin combination are bigger, but generate a possibility that floating fine simultaneously
It is bigger；The water absorption rate variation of each embodiment is little.In summary the comprehensive performance of factor, embodiment 6 is best.
It is compared with embodiment 6, comparative example 1 is to be not added with the high temperature resistant of heat resistant polyamide 6T/11 resin prepolymer
Polyamide 6 T/11 resin combination, melt index are only 6g/10min (309 DEG C of test temperature, load 1.2kg), processability
It can be bad；Comparative example 2 be not added with toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO) it is resistance to
High temperature polyamide 6T/11 resin combination, the heat resistant polyamide 6T/11 resin prepolymer of the lower intrinsic viscosity in part is to resistance to
The tensile property and bending property of high temperature polyamide 6T/11 resin combination cause undesirable influence；Comparative example 3 is to be not added with
Coupling agent, N, the heat resistant polyamide 6T/11 resin combination of N'- ethylenebisstearamide, heat resistant polyamide 6T/11
The floating fine phenomenon on resin combination surface increases, and resin combination and alkali-free glass fibre compatibility are bad, thus to resin group
The tensile property and bending property for closing object cause undesirable influence；The screw configuration of the parallel double-screw extruder of comparative example 4
For double thread, the ratio between spiro rod length L and diameter D L/D are 30, and the screw configuration of the parallel double-screw extruder of embodiment 6
For single thread, the ratio between spiro rod length L and diameter D L/D are 40, by comparing it can be found that using parallel described in embodiment 6
The Screw Parameters of double screw extruder, the processing performance for the heat resistant polyamide 6T/11 resin combination being prepared stretch
Performance, bending property and water absorbing properties are greatly improved, and obtain high fluidity, the high temperature resistant of high tensile and low water absorption
The beneficial effect of polyamide 6 T/11 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 heat resistant polyamide 6T/11 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 heat resistant polyamide 6T/11 resin prepolymer is 0.4~0.6dL/g；
The intrinsic viscosity of the heat resistant polyamide 6T/11 resin is 0.7~1.0dL/g；
The heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are total to by monomer 1 and polyesteramide
Poly- to form, the monomer 1 is the hexamethylene diamine, terephthalic acid (TPA), 11- aminoundecanoic acid that molar ratio is 1:1:0.45~0.55, institute
State 1~8% that polyesteramide additional amount is 1 total weight of monomer；
The polyesteramide has such as Formula Il structure:
In Formula II, x=10~200, y=10~200, z=10~100；
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. heat resistant polyamide 6T/11 composition according to claim 1, which is characterized in that by the original of following parts by weight
Material is prepared:
3. heat resistant polyamide 6T/11 composition according to claim 1 or 2, which is characterized in that the high temperature resistant polyamides
The intrinsic viscosity of amine 6T/11 resin prepolymer is 0.45~0.55dL/g；The characteristic of the heat resistant polyamide 6T/11 resin is glutinous
Degree is 0.75~0.95dL/g.
4. heat resistant polyamide 6T/11 composition according to claim 1 or 2, which is characterized in that the coupling agent is
At least one of gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane；The anti-dripping agent is polytetrafluoro
Ethylene.
5. heat resistant polyamide 6T/11 composition according to claim 1, which is characterized in that the heat resistant polyamide
6T/11 resin prepolymer and heat resistant polyamide 6T/11 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 heat resistant polyamide 6T/11 resin prepolymer is obtained；
(3) the heat resistant polyamide 6T/11 resin prepolymer for obtaining step (2) persistently vacuumizes at 310~320 DEG C
After 0.3~1 hour, the heat resistant polyamide 6T/11 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 heat resistant polyamide 6T/11 compositions of claim 1-5, feature exist
In, comprising the following steps:
(1) the heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 80~100 DEG C,
It is cooling after 4~12 hours dry, by heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11
Resin and the toluene di-isocyanate(TDI), 2,2'- (1,3- phenylene)-bisoxazoline, N, bis- (2,2,6, the 6- tetramethyls of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates, anti-drop
It falls agent and dimethicone 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 by the heat resistant polyamide in the step (1)
6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C, drying 4~6 hours；Work in the step (3)
Skill 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, 4th area
Temperature 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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| US7179855B2 (en) * | 1998-05-14 | 2007-02-20 | Ems - Chemie Ag | Polyamide molding compositions containing prepolymeric polyamides, a method for the preparation thereof and the use thereof |
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