CN106519665B - Flame retardancy reinforced polyamide composite material and preparation method thereof - Google Patents
Flame retardancy reinforced polyamide composite material and preparation method thereof Download PDFInfo
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- CN106519665B CN106519665B CN201610991142.8A CN201610991142A CN106519665B CN 106519665 B CN106519665 B CN 106519665B CN 201610991142 A CN201610991142 A CN 201610991142A CN 106519665 B CN106519665 B CN 106519665B
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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
- C08L77/12—Polyester-amides
-
- 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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- 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
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- 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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The present invention relates to a kind of flame retardancy reinforced polyamide composite materials and preparation method thereof, the flame retardancy reinforced polyamide composite material is prepared from the following materials: polyamide 10T/11 resin, aliphatic polyamide resin, toluene di-isocyanate(TDI), 2,2'- (1,3- phenylene)-bisoxazoline, coupling agent, phyllosilicate, alkyl phosphinate, melamine polyphosphate, zinc borate, 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.The flame retardancy reinforced polyamide composite material has the characteristics that high flame retardant, high tensile, high fluidity 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 flame retardancy reinforced polyamide composite material 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.
In heat resistant polyamide, the fusing point of PA10T resin is 320 DEG C or so, is not much different with decomposition temperature, is processed
Temperature range is narrow, be easy to cause polymer to decompose in process.Therefore, third list is introduced in PA10T resin backbone
Body improves its processing performance, expands it using field and improves its comprehensive performance.But the Third monomer of low content is added not
It is enough to improve its processing performance, and the Third monomer that high-content is added can make the fusing point of copolymer resin too low, be not achieved resistance to
The requirement of high temperature.
Halogenated flame retardant was once the commonly used fire-retardant kind of polyamide, but most of halogenated flame retardant is raw in burning
At toxic flue dust, corrosive gas, the secondary disaster is brought to production, application and environment.Compared with halogenated flame retardant, the resistance of phosphorus system
Toxicity, raw cigarette and the corrosivity for firing agent are lower, as environmental requirement is higher and higher, increasingly to the research of phosphorus flame retardant
Pay attention to.Phosphinates is the organic phosphorus flame retardant of new generation developed in recent years, environmentally friendly, thermal stability and hydrolytic stability
Well, do not cause polymer to decompose when processing, because of its excellent thermal stability, change especially suitable for heat resistant polyamide halogen-free flameproof
Property.
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；It is fire-retardant that Chinese patent CN102604380A discloses a kind of high CTI of high heat resistance
Polyamide compoiste material, wherein the polyamide is polyhexamethylene adipamide/poly-paraphenylene terephthalamide's nonamethylene diamine copolymer or gathers
Paraphenylene terephthalamide's nonamethylene diamine；Chinese patent CN 105038207A disclose it is a kind of with anti-flammability, high temperature resistant, high glaze lamp
The polyamide of decorating fittings enhances formula, and the polyamide enhancing formula is by PA6T, reinforcing filler, fire retardant, stabilizer, antioxygen
Agent and other processing aids form；Chinese patent CN 102675865A discloses a kind of Amilan polyamide resin composition, obtained
Composition can meet UL94V-0 combustion rating in 0.5mm and the above thickness；Chinese patent CN 105176077A is disclosed
A kind of fire-retardant high-modulus nylon material and its preparation method and application.
Summary of the invention
The present invention be directed to the deficiencies in the prior art, it is therefore an objective to provide a kind of with high flame retardant, high tensile, Gao Liu
The polyamide compoiste material of dynamic property and low water absorption, may be used as electronic apparatus component, automobile component, is particularly useful as electricity
The sheathing material of sub- electric appliance.
In order to achieve the above objectives, the present invention uses following scheme:
A kind of flame retardancy reinforced polyamide composite material, the composite material are prepared by the raw material of following parts by weight:
The intrinsic viscosity of the polyamide 10T/11 resin is 0.7~1.0dL/g.
The aliphatic polyamide resin is nylon 46 resin (PA46), polyhexamethylene adipamide resin
At least one of (PA66).
The coupling agent is gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-
Gamma-aminopropyl-triethoxy-silane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-ammonia third
Ylmethyl dimethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, aniline first
At least one of ethyl triethoxy silicane alkane.
Layered silicate is at least one of montmorillonite, kaolin, hydrotalcite, sepiolite.
The alkyl phosphinate is aluminum diethylphosphinate, diethyl phosphinic acids zinc, diethyl phosphinic acids calcium, diethyl
Phosphinic acids magnesium, dipropyl phosphinic acids aluminium, isobutylphosphinic aluminium, Methylethyl phosphinic acids aluminium, in aluminum phenylphosphinate at least
It is a kind of.
The melamine polyphosphate is melamine poly aluminium phosphate, melamine polyphosphoric acid zinc, the poly- phosphorus of melamine
At least one of sour magnesium.
In wherein some embodiments, flame retardancy reinforced polyamide composite material is prepared by the raw material of following parts by weight:
In wherein some embodiments, flame retardancy reinforced polyamide composite material, further preferably by the original of following parts by weight
Material is prepared:
In wherein some embodiments, the intrinsic viscosity of the polyamide 10T/11 resin is 0.75~0.95dL/g；Institute
Stating aliphatic polyamide resin is polyhexamethylene adipamide resin (PA66), and inherent viscosity is 1.22~1.84dL/g.
In wherein some embodiments, the coupling agent is gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy
At least one of base silane；Layered silicate is montmorillonite；The alkyl phosphinate is aluminum diethylphosphinate；Institute
Stating melamine polyphosphate is melamine poly aluminium phosphate；The partial size of the zinc borate is 2~8 μm.
In wherein some embodiments, the polyamide 10T/11 resin is copolymerized by monomer 1 and polyesteramide, described
Monomer 1 is the decamethylene diamine, terephthalic acid (TPA), 11- aminoundecanoic acid that molar ratio is 1:1:0.01~0.1, and the polyesteramide adds
Enter 1~8% that amount is 1 total weight of monomer.
In wherein some embodiments, the polyamide 10T/11 resin is made by following synthetic method:
(1) monomer 1 after vacuum drying is added in stirring-type polymer reactor, while the polyester acyl is added
Amine and molecular weight regulator, antioxidant, water；Then 4~6min is vacuumized, 4~6min of nitrogen is led to, is so recycled 5~7 times,
Be present in reactant in the environment under nitrogen protection, control in the stirring-type polymer reactor system pressure be 0.2~
0.3MPa；
(2) in 2~4 hours by the closed constant-speed heating of stirring-type polymer reactor to 272~280 DEG C, adjust institute
The mixing speed for stating stirring-type polymer reactor is 30~50r/min, wherein when the stirring-type polymer reactor temperature reaches
At 215 DEG C, it is deflated to 2.0MPa, and maintains pressure after 2.0MPa, reaction 1~2 hour, normal pressure is deflated to, is warming up to simultaneously
After the reaction was continued at 310~320 DEG C 1~2 hour, after constant temperature persistently vacuumizes 0.3~1 hour, the polyamide 10T/ is obtained
11 resins；
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 flame retardancy reinforced polyamide composite material.
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, specific technical solution, comprising the following steps:
(1) the polyamide 10T/11 resin and aliphatic polyamide resin are placed in 80~100 DEG C, dry 4~12 is small
Shi Hou, it is cooling, by polyamide 10T/11 resin, aliphatic polyamide resin and the toluene di-isocyanate(TDI) after cooling,
2,2'- (1,3- phenylene)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and
Bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates are added in high-speed mixer and are mixed；
(2) coupling agent, phyllosilicate, alkyl phosphinate, melamine polyphosphate and zinc borate are added
It is mixed into another high-speed mixer；
(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 270~300 DEG C, and two area's temperature are 300~315 DEG C, and three area's temperature are 305~320 DEG C,
Four area's temperature are 310~320 DEG C, and five area's temperature are 310~320 DEG C, and six area's temperature are 310~320 DEG C, and seven area's temperature are 310
~320 DEG C, eight area's temperature are 310~320 DEG C, and die head temperature is 305~315 DEG C, and screw speed is 200~600rpm.
In wherein some embodiments, by the polyamide 10T/11 resin and fatty polyamide in the step (1)
Resin is placed in 90 DEG C, drying 4~6 hours；Technological parameter in the step (3) are as follows: area's temperature is 270~295 DEG C, 2nd area
Temperature is 300~310 DEG C, and three area's temperature are 305~315 DEG C, and four area's temperature are 310~315 DEG C, and five area's temperature are 310~315
DEG C, six area's temperature are 310~315 DEG C, and seven area's temperature are 310~315 DEG C, and eight area's temperature are 310~315 DEG C, and die head temperature is
305~310 DEG C, screw speed is 200~400rpm.
In wherein some embodiments, the screw configuration of the parallel double-screw extruder is single thread；Spiro rod length L
It is 35~50 with the ratio between diameter D L/D；The screw rod be equipped with 1 or more (contain 1) gear block area and 1 or more (containing 1)
Left-hand thread area.
In wherein some embodiments, the ratio between the spiro rod length L and diameter D L/D are 35~45；The screw rod is equipped with
2 gear block areas and 1 left-hand thread area.
In wherein some embodiments, the polyamide 10T/11 resin is copolymerized by monomer 1 and polyesteramide, described
Monomer 1 is the decamethylene diamine, terephthalic acid (TPA), 11- aminoundecanoic acid that molar ratio is 1:1:0.01~0.1, and the polyesteramide adds
Enter 1~8% that amount is 1 total weight of monomer.
In wherein some embodiments, the polyamide 10T/11 resin is made by following synthetic method:
(1) monomer 1 after vacuum drying is added in stirring-type polymer reactor, while the polyester acyl is added
Amine and molecular weight regulator, antioxidant, water；Then 4~6min is vacuumized, 4~6min of nitrogen is led to, is so recycled 5~7 times,
Be present in reactant in the environment under nitrogen protection, control in the stirring-type polymer reactor system pressure be 0.2~
0.3MPa；
(2) in 2~4 hours by the closed constant-speed heating of stirring-type polymer reactor to 272~280 DEG C, adjust institute
The mixing speed for stating stirring-type polymer reactor is 30~50r/min, wherein when the stirring-type polymer reactor temperature reaches
At 215 DEG C, it is deflated to 2.0MPa, and maintains pressure after 2.0MPa, reaction 1~2 hour, normal pressure is deflated to, is warming up to simultaneously
After the reaction was continued at 310~320 DEG C 1~2 hour, after constant temperature persistently vacuumizes 0.3~1 hour, the polyamide 10T/ is obtained
11 resins；
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 polyamide 10T/11 resin, the present invention
Improve the processing performance of polyamide 10T/11 resin using aliphatic polyamide resin, this is because aliphatic polyamide resin
Have preferable mobile performance and polyamide 10T/11 resin has preferable mechanical property.Meanwhile fatty polyamide tree
The end group of rouge and polyamide 10T/11 resin can (1,3- be sub- with the isocyanate groups of toluene di-isocyanate(TDI), 2,2'- respectively
Phenyl) the oxazoline group of-bisoxazoline reacts, improve the compatibility of both polyamides.Meanwhile toluene two is different
The isocyanate groups of cyanate, 2,2'- (1,3- phenylene)-bisoxazoline oxazoline group can also and phyllosilicate
Terminal hydroxy group react, and be attached to phyllosilicate, alkyl phosphinate, melamine polyphosphate and zinc borate
On coupling agent react, thus improve phyllosilicate, alkyl phosphinate, melamine polyphosphate and zinc borate with
The interface binding power and compatibility of above two polyamide reduce their shadows to polyamide compoiste material mechanical property
It rings.
The coupling agent that the present invention uses, preferably gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane,
Contain amino, above-mentioned auxiliary agent can react with the end group of above two polyamide, to further increase layer
The interface cohesion of shape silicate, alkyl phosphinate, melamine polyphosphate and zinc borate and above two polyamide
Power and compatibility reduce their influences to polyamide compoiste material mechanical property.
Fire retardant phyllosilicate, alkyl phosphinate, melamine polyphosphate and zinc borate can form mutually association
Same-action.Phyllosilicate and zinc borate can promote material surface at charcoal, increase charring layer, keep Char Residues Structure fine and close hard
Firmly, good barrier heat and gas effect have been played, they have the ability of capture free radical at high temperature, it is suppressed that polymer
The thermal degradation of matrix reduces the free radical generated when burning, reduces the degradation rate and heat release rate of polymer；Alkyl
Phosphonate primarily serves the effect that gas phase inhibits flame, while melamine polyphosphate then plays dilution fuel and solid phase phosphorous layer
Barrier action, therefore the phosphorus nitrogen collaboration enhancing flame retardant effect between them is obvious.
The fusing point of bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N, N'- is 272 DEG C, boiling point is greater than
360 DEG C, the better heat stability in polyamide resin composite material Blending Processes, amide group can gather with above two
The end group of amide resin reacts to improve compatibility, and hindered piperidine base can provide antioxidation and improve the dyeing of copolymer
Property.
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 superior to be provided in polyamide resin composite material Blending Processes
Colour stability and melt stability, while the thermal degradation of above two polyamide in the high temperature process can be prevented, and
The hot oxygen discoloration due to caused by long-time is inhibited, it also offers in nitrogen oxides (NOx) color in the environment of gas
Stability prevents gas from smoking discoloration.
Compared with prior art, the invention has the following advantages:
The present invention for existing polyamide 10T/11 resin anti-flammability is high, processing temperature narrow limits and processing performance
Bad defect improves the processing performance of polyamide 10T/11 resin by using aliphatic polyamide resin, uses simultaneously
Toluene di-isocyanate(TDI) and 2,2'- (1,3- phenylene)-bisoxazoline as the compatilizer between both polyamides,
And gather as above two polyamide with the phyllosilicate, alkyl phosphinate, melamine for being attached with coupling agent
Compatilizer between phosphate and zinc borate, and it is used in compounding phyllosilicate, alkyl phosphinate, melamine polyphosphoric acid
Salt and zinc borate improve the flame retardant property of this polyamide compoiste material, while phyllosilicate can also be improved this polyamides
The tensile strength and reduction water absorption rate, shrinking percentage of amine composite material, are finally used in compounding N, bis- (2,2,6, the 6- tetramethyl -4- of N'-
Piperidyl) -1,3- benzenedicarboxamide and bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates handle blending
Xanthochromia problem in the process, preparation-obtained flame retardancy reinforced polyamide composite material have high flame retardant, high tensile, height
The characteristics of mobility and low water absorption, can be applied to field of electronics, LED field, automotive field, aerospace and military project neck
Domain etc..
Detailed description of the invention
Fig. 1 show the preparation technology flow chart of flame retardancy reinforced polyamide composite material of the present invention.
Specific embodiment
To further understand the features of the present invention, technological means and specific purposes achieved, function, parse this hair
Bright advantage and spirit, by following embodiment, the present invention is further elaborated.
The reaction mechanism is as follows for flame retardancy reinforced polyamide composite material of the present invention (preparation technology flow chart is see Fig. 1):
By above-mentioned reaction equation it is found that the Amino End Group of aliphatic polyamide resin and polyamide 10T/11 resin can and toluene
The isocyanate groups of diisocyanate react, the Amino End Group of aliphatic polyamide resin and polyamide 10T/11 resin,
Carboxyl end group can react with the oxazoline group of 2,2'- (1,3- phenylene)-bisoxazoline, so as to increase both
Compatibility between polyamide.
Raw material used in the embodiment of the present invention is as follows:
Polyamide 10T/11 resin (PA10T/11) is made by oneself, and the decamethylene diamine in raw material is selected from Wuxi Yin and reaches the limited public affairs of nylon
Department, terephthalic acid (TPA) are selected from Beijing Yanshan Petrochemical Co., and 11- aminoundecanoic acid is selected from the limited public affairs of Taiyuan Zhong Lianze agrochemicals
Department, remaining auxiliary agent are selected from Sinopharm Chemical Reagent Co., Ltd.；
Polyhexamethylene adipamide resin (PA66), is selected from China Shenma Group Co., Ltd., and inherent viscosity is respectively
1.22dL/g,1.66dL/g,1.84dL/g；
Toluene di-isocyanate(TDI) is selected from Sinopharm Chemical Reagent Co., Ltd.；
2,2'- (1,3- phenylene)-bisoxazolines are selected from Sinopharm Chemical Reagent Co., Ltd.；
Coupling agent (gamma-aminopropyl-triethoxy-silane) is selected from Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei；
Coupling agent (γ-aminopropyltrimethoxysilane) is selected from Zhejiang boiling point Chemical Co., Ltd.；
Phyllosilicate (montmorillonite) is selected from Zhejiang Fenghong New Material Co., Ltd.；
Alkyl phosphinate (aluminum diethylphosphinate) is selected from Jiangsu Li Side new material Co., Ltd；
Melamine polyphosphate (melamine poly aluminium phosphate) is selected from Sichuan Fine Chemical Research and Design Inst.；
Zinc borate, is selected from 101 Chemical Co., Ltd. of Jining, and partial size is 2~8 μm；
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.
Below in conjunction with specific embodiment, the present invention will be described in detail.
Polyamide 10T/11 resin in following embodiment is copolymerized by monomer 1 and polyesteramide, and the monomer 1 is to rub
, than decamethylene diamine, terephthalic acid (TPA), 11- aminoundecanoic acid for 1:1:0.01~0.1, the polyesteramide additional amount is described for you
The 1~8% of 1 total weight of monomer, above-mentioned polyamide 10T/11 resin 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 polyamide 10T/11 resin is as follows:
(1) monomer 1 after vacuum drying is added in stirring-type polymer reactor, while the polyester acyl is added
Amine and molecular weight regulator, antioxidant, water；Then 4~6min is vacuumized, 4~6min of nitrogen is led to, is so recycled 5~7 times,
Be present in reactant in the environment under nitrogen protection, control in the stirring-type polymer reactor system pressure be 0.2~
0.3MPa；
(2) in 2~4 hours by the closed constant-speed heating of stirring-type polymer reactor to 272~280 DEG C, adjust institute
The mixing speed for stating stirring-type polymer reactor is 30~50r/min, wherein when the stirring-type polymer reactor temperature reaches
At 215 DEG C, it is deflated to 2.0MPa, and maintains pressure after 2.0MPa, reaction 1~2 hour, normal pressure is deflated to, is warming up to simultaneously
After the reaction was continued at 310~320 DEG C 1~2 hour, after constant temperature persistently vacuumizes 0.3~1 hour, the polyamide 10T/ is obtained
11 resins；
The molecular weight regulator is 0.1~3% benzoic acid that additional amount is 1 total weight of monomer；The antioxygen
Agent is 0.1~0.3% N, the N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1 that additional amount is 1 total weight of monomer,
3- benzene diamides；Appropriate amount of water.
Embodiment 1
The raw material of polyamide 10T/11 resin used in the present embodiment is constituted and synthesis step is as follows:
(1) by monomer 1:1mol decamethylene diamine, 1mol terephthalic acid (TPA), the 0.05mol 11- amino 11 after vacuum drying
Acid is added in stirring-type polymer reactor, at the same be added 4% polyesteramide of 1 total weight of monomer, 1.5% benzoic acid,
100mL water is added as mass-and heat-transfer in 0.2% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides
Medium；Then 5min is vacuumized, leads to nitrogen 5min, so circulation 6 times, reactant is made to be present in the environment under nitrogen protection
In, controlling system pressure in stirring-type polymer reactor is 0.3MPa；
(2) in 3 hours by the closed constant-speed heating of stirring-type polymer reactor to 275 DEG C, adjust stirring-type polymerization reaction
The mixing speed of device is 40r/min, wherein when stirring-type polymer reactor temperature reaches 215 DEG C, it is deflated to 2.0MPa, and
It maintains pressure in 2.0MPa, after reaction 1.5 hours, is deflated to normal pressure, while being warming up at 315 DEG C after the reaction was continued 1.5 hours,
After constant temperature persistently vacuumizes 0.5 hour, the polyamide 10T/11 resin is obtained；
The intrinsic viscosity of the above-mentioned polyamide 10T/11 resin being prepared is 0.85dL/g, melting temperature is 305 DEG C.
A kind of flame retardancy reinforced polyamide composite material of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprising the following steps:
(1) polyamide 10T/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
Polyamide 10T/11 resin, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) after cooling, 2,2'- (1,3- Asia benzene
Base)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) by coupling agent (γ-aminopropyltrimethoxysilane), montmorillonite, aluminum diethylphosphinate, the poly- phosphorus of melamine
Sour aluminium and zinc borate are added in another high-speed mixer and are 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 300 DEG C, and two area's temperature are 315 DEG C, and three area's temperature are 320 DEG C, and four area's temperature are 320 DEG C, 5th area
Temperature is 320 DEG C, and six area's temperature are 320 DEG C, and seven area's temperature are 320 DEG C, and eight area's temperature are 320 DEG C, and die head temperature is 315 DEG C,
Screw speed is 600rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 35,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Embodiment 2
The raw material of polyamide 10T/11 resin used in the present embodiment is constituted and synthesis step is the same as embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprising the following steps:
(1) polyamide 10T/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
Polyamide 10T/11 resin, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) after cooling, 2,2'- (1,3- Asia benzene
Base)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), montmorillonite, aluminum diethylphosphinate, the poly- phosphorus of melamine
Sour aluminium and zinc borate are added in another high-speed mixer and are 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 270 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 DEG C,
Screw speed is 200rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 50,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Embodiment 3
The raw material of polyamide 10T/11 resin used in the present embodiment is constituted and synthesis step is the same as embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprising the following steps:
(1) polyamide 10T/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
Polyamide 10T/11 resin, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) after cooling, 2,2'- (1,3- Asia benzene
Base)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), montmorillonite, aluminum diethylphosphinate, the poly- phosphorus of melamine
Sour aluminium and zinc borate are added in another high-speed mixer and are mixed；
(3) mixture for mixing step (1) is added in parallel double-screw extruder through feeder, and in parallel double spiral shells
Lateral (the 4th area) of bar extruder (totally eight area) is added the mixture that step (2) mix and carries out melting extrusion, is granulated, technique
Parameter is as follows: area's temperature is 295 DEG C, and two area's temperature are 310 DEG C, and three area's temperature are 315 DEG C, and four area's temperature are 315 DEG C, 5th area
Temperature is 315 DEG C, and six area's temperature are 315 DEG C, and seven area's temperature are 315 DEG C, and eight area's temperature are 315 DEG C, and die head temperature is 310 DEG C,
Screw speed is 400rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 45,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Embodiment 4
The raw material of polyamide 10T/11 resin used in the present embodiment is constituted and synthesis step is the same as embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprising the following steps:
(1) polyamide 10T/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
Polyamide 10T/11 resin, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) after cooling, 2,2'- (1,3- Asia benzene
Base)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), montmorillonite, aluminum diethylphosphinate, the poly- phosphorus of melamine
Sour aluminium and zinc borate are added in another high-speed mixer and are 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 315 DEG C, 5th area
Temperature is 315 DEG C, and six area's temperature are 315 DEG C, and seven area's temperature are 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Embodiment 5
The raw material of polyamide 10T/11 resin used in the present embodiment is constituted and synthesis step is the same as embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprising the following steps:
(1) polyamide 10T/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
Polyamide 10T/11 resin, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) after cooling, 2,2'- (1,3- Asia benzene
Base)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), montmorillonite, aluminum diethylphosphinate, the poly- phosphorus of melamine
Sour aluminium and zinc borate are added in another high-speed mixer and are 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 315 DEG C, 5th area
Temperature is 315 DEG C, and six area's temperature are 315 DEG C, and seven area's temperature are 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Embodiment 6
The raw material of polyamide 10T/11 resin used in the present embodiment is constituted and synthesis step is the same as embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprising the following steps:
(1) polyamide 10T/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
Polyamide 10T/11 resin, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) after cooling, 2,2'- (1,3- Asia benzene
Base)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), montmorillonite, aluminum diethylphosphinate, the poly- phosphorus of melamine
Sour aluminium and zinc borate are added in another high-speed mixer and are 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 315 DEG C, 5th area
Temperature is 315 DEG C, and six area's temperature are 315 DEG C, and seven area's temperature are 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 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 polyamide 10T/11 resin used in this comparative example is constituted and synthesis step is the same as embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprising the following steps:
(1) polyamide 10T/11 resin is placed in 90 DEG C, after 5 hours dry, cooling, by polyamide 10T/11 after cooling
Resin and N, bis- (2,2,6,6- tetramethyl -4- piperidyl) -1, the 3- benzenedicarboxamides of N'- and bis- (2,6- di-t-butyl -4-
Aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), montmorillonite, aluminum diethylphosphinate, the poly- phosphorus of melamine
Sour aluminium and zinc borate are added in another high-speed mixer and are 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 315 DEG C, 5th area
Temperature is 315 DEG C, and six area's temperature are 315 DEG C, and seven area's temperature are 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Comparative example 2
The raw material of polyamide 10T/11 resin used in this comparative example is constituted and synthesis step is the same as embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprising the following steps:
(1) polyamide 10T/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
Polyamide 10T/11 resin, polyhexamethylene adipamide resin and bis- (2,2,6, the 6- tetramethyl -4- piperidines of N, N'- after cooling
Base) -1,3- benzenedicarboxamide and bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates are added to high-speed stirred
It is mixed in machine；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), montmorillonite, aluminum diethylphosphinate, the poly- phosphorus of melamine
Sour aluminium and zinc borate are added in another high-speed mixer and are 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 315 DEG C, 5th area
Temperature is 315 DEG C, and six area's temperature are 315 DEG C, and seven area's temperature are 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is equipped with 2 gear block areas and 1 left-hand thread area.
Comparative example 3
The raw material of polyamide 10T/11 resin used in this comparative example is constituted and synthesis step is the same as embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprising the following steps:
(1) polyamide 10T/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
Polyamide 10T/11 resin, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) after cooling, 2,2'- (1,3- Asia benzene
Base)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), aluminum diethylphosphinate, melamine poly aluminium phosphate and
Zinc borate 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 315 DEG C, 5th area
Temperature is 315 DEG C, and six area's temperature are 315 DEG C, and seven area's temperature are 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 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 4
The raw material of polyamide 10T/11 resin used in this comparative example is constituted and synthesis step is the same as embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprising the following steps:
(1) polyamide 10T/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after 5 hours dry, cooling will
Polyamide 10T/11 resin, polyhexamethylene adipamide resin and toluene di-isocyanate(TDI) after cooling, 2,2'- (1,3- Asia benzene
Base)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), montmorillonite and aluminum diethylphosphinate are added to another
It is mixed in high-speed mixer；
(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 315 DEG C, 5th area
Temperature is 315 DEG C, and six area's temperature are 315 DEG C, and seven area's temperature are 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 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'- and
Bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates are respectively 0.15 part, 0.15 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):
Flame retardant property: press UL 94-2006 standard testing, 1/8 inch of thickness of sample (i.e. 3.2mm)；
Tensile property: GB/T 1040.1-2006 standard testing, rate of extension 10mm/min are pressed；
Mobile performance: press GB/T 3682-2000 standard testing, 309 DEG C of test temperature, load 1.2kg；
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 montmorillonite, aluminum diethylphosphinate, melamine poly aluminium phosphate and zinc borate from Examples 1 to 6
Additional amount it is more, the flame retardant property of polyamide 10T/11 resin composite materials is better, at the same with the content of montmorillonite increase,
The tensile strength of polyamide 10T/11 resin composite materials is bigger；Aliphatic polyamide resin (polyhexamethylene adipamide resin)
Additional amount is more, and the melt index of polyamide 10T/11 resin composite materials is bigger, and processing performance is better；The water suction of each embodiment
Rate variation is little.In summary the comprehensive performance of factor, embodiment 6 is best.
It is compared with embodiment 6, comparative example 1 is to be not added with aliphatic polyamide resin (polyhexamethylene adipamide resin)
Polyamide 10T/11 resin composite materials, melt index is only 5g/10min (309 DEG C of test temperature, load 1.2kg), is added
Work performance is bad；Comparative example 2 is to be not added with toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO)
Polyamide 10T/11 resin composite materials, aliphatic polyamide resin (polyhexamethylene adipamide resin) and polyamide 10T/11
Resin compatible is bad, to cause undesirable influence to the tensile property of polyamide 10T/11 resin composite materials；Comparison
Example 3 is the polyamide 10T/11 resin composite materials for being not added with montmorillonite, and tensile property is bad；Parallel double spiral shells of comparative example 4
The screw configuration of bar extruder is double thread, and the ratio between spiro rod length L and diameter D L/D are 30, and parallel double spiral shells of embodiment 6
The screw configuration of bar extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40, while comparative example 4 is not added with three
Poly cyanamid poly aluminium phosphate and zinc borate, by comparison it can be found that using parallel double-screw extruder described in embodiment 6 spiral shell
Bar parameter and melamine poly aluminium phosphate, zinc borate, the polyamide 10T/11 resin composite materials being prepared it is fire-retardant
Performance, tensile property, processing performance and water absorbing properties are greatly improved, and obtain high flame retardant, high tensile, high fluidity
With the beneficial effect of the polyamide 10T/11 resin composite materials of low water absorption.
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 flame retardancy reinforced polyamide composite material, which is characterized in that be prepared by the raw material of following parts by weight:
The polyamide 10T resin is copolymerized by monomer 1 and polyesteramide, the monomer 1 be molar ratio be 1:1:0.01~
0.1 decamethylene diamine, terephthalic acid (TPA), 11- aminoundecanoic acid, the polyesteramide additional amount be 1 total weight of monomer 1~
8%；
The intrinsic viscosity of the polyamide 10T resin is 0.7~1.0dL/g；
The aliphatic polyamide resin is at least one of nylon 46 resin, polyhexamethylene adipamide resin；
The coupling agent is gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-γ-
Aminopropyl triethoxysilane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-aminopropyl
Methyl dimethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, anilinomethyl
At least one of triethoxysilane；
Layered silicate is at least one of montmorillonite, kaolin, hydrotalcite, sepiolite；
The alkyl phosphinate is aluminum diethylphosphinate, diethyl phosphinic acids zinc, diethyl phosphinic acids calcium, diethyl time phosphine
At least one of sour magnesium, dipropyl phosphinic acids aluminium, isobutylphosphinic aluminium, Methylethyl phosphinic acids aluminium, aluminum phenylphosphinate；
The melamine polyphosphate is melamine poly aluminium phosphate, melamine polyphosphoric acid zinc, melamine polyphosphoric acid magnesium
At least one of；
The polyesteramide has such as Formula Il structure:
In Formula II, x=10~200, y=10~200, z=10~100；
In the preparation of the flame retardancy reinforced polyamide composite material, the screw configuration of used parallel double-screw extruder is single
Line screw thread；The ratio between spiro rod length L and diameter D L/D are 35~50.
2. flame retardancy reinforced polyamide composite material according to claim 1, which is characterized in that by the raw material of following parts by weight
It is prepared:
3. flame retardancy reinforced polyamide composite material according to claim 1 or 2, which is characterized in that the polyamide 10T tree
The intrinsic viscosity of rouge is 0.75~0.95dL/g；The aliphatic polyamide resin is polyhexamethylene adipamide resin, characteristic
Viscosity is 1.22~1.84dL/g.
4. flame retardancy reinforced polyamide composite material according to claim 1 or 2, which is characterized in that the coupling agent is γ-
At least one of aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane；Layered silicate is montmorillonite；
The alkyl phosphinate is aluminum diethylphosphinate；The melamine polyphosphate is melamine poly aluminium phosphate；It is described
The partial size of zinc borate is 2~8 μm.
5. flame retardancy reinforced polyamide composite material according to claim 1, which is characterized in that the polyamide 10T resin
It is made by following synthetic method:
(1) monomer 1 after vacuum drying is added in stirring-type polymer reactor, while the polyesteramide is added,
And molecular weight regulator, antioxidant, water；Then 4~6min is vacuumized, 4~6min of nitrogen is led to, so recycles 5~7 times, makes
Reactant is present in the environment under nitrogen protection, control in the stirring-type polymer reactor system pressure be 0.2~
0.3MPa；
(2) in 2~4 hours by the closed constant-speed heating of stirring-type polymer reactor to 272~280 DEG C, stirred described in adjusting
The mixing speed for mixing formula polymer reactor is 30~50r/min, wherein when the stirring-type polymer reactor temperature reaches 215
DEG C when, be deflated to 2.0MPa, and maintain pressure in 2.0MPa, after reaction 1~2 hour, be deflated to normal pressure, while being warming up to 310
After the reaction was continued at~320 DEG C 1~2 hour, after constant temperature persistently vacuumizes 0.3~1 hour, the polyamide 10T 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 flame retardancy reinforced polyamide composite materials of claim 1-5, which is characterized in that
The following steps are included:
(1) cold after the polyamide 10T resin and aliphatic polyamide resin being placed in 80~100 DEG C, drying 4~12 hours
But, by polyamide 10T resin, aliphatic polyamide resin and the toluene di-isocyanate(TDI) after cooling, 2,2'- (1,3-
Phenylene)-bisoxazoline, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N'- and bis- (bis- uncles of 2,6-
Butyl -4- aminomethyl phenyl) pentaerythritol diphosphate is added in high-speed mixer and mixed；
(2) coupling agent, phyllosilicate, alkyl phosphinate, melamine polyphosphate and zinc borate are added to separately
It is mixed in one high-speed mixer；
(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
270~300 DEG C, two area's temperature be 300~315 DEG C, three area's temperature be 305~320 DEG C, four area's temperature be 310~320 DEG C, five
Area's temperature be 310~320 DEG C, six area's temperature be 310~320 DEG C, seven area's temperature be 310~320 DEG C, eight area's temperature be 310~
320 DEG C, die head temperature is 305~315 DEG C, and screw speed is 200~600rpm.
7. preparation method according to claim 6, which is characterized in that by the polyamide 10T resin in the step (1)
90 DEG C are placed in aliphatic polyamide resin, drying 4~6 hours；Technological parameter in the step (3) are as follows: area's temperature is
270~295 DEG C, two area's temperature be 300~310 DEG C, three area's temperature be 305~315 DEG C, four area's temperature be 310~315 DEG C, five
Area's temperature be 310~315 DEG C, six area's temperature be 310~315 DEG C, seven area's temperature be 310~315 DEG C, eight area's temperature be 310~
315 DEG C, die head temperature is 305~310 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610991142.8A CN106519665B (en) | 2016-11-08 | 2016-11-08 | Flame retardancy reinforced polyamide composite material and preparation method thereof |
Applications Claiming Priority (1)
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| US11401416B2 (en) | 2017-10-17 | 2022-08-02 | Celanese Sales Germany Gmbh | Flame retardant polyamide composition |
| CN109438976B (en) * | 2018-09-29 | 2021-06-08 | 辰东意普万新材料(广东)有限公司 | Copolymerized nylon product and preparation method thereof |
| CN110591332B (en) * | 2019-10-21 | 2022-03-25 | 广东圆融新材料有限公司 | Polyphenylene ether/polyamide 66 composition and method for making same |
| CN110724374B (en) * | 2019-10-24 | 2022-03-25 | 广东圆融新材料有限公司 | Flame-retardant polyphenyl ether/polyamide 66 composition and preparation method thereof |
| CN110628202B (en) * | 2019-11-08 | 2022-03-25 | 广东圆融新材料有限公司 | High dielectric constant polyphenylene ether/polyamide 66 composition and preparation method thereof |
| CN110643175B (en) * | 2019-11-11 | 2022-04-15 | 广东圆融新材料有限公司 | High dielectric constant polyamide 6/polyphenyl ether composition and preparation method thereof |
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| US11981812B2 (en) | 2022-07-20 | 2024-05-14 | Celanese Sales Germany Gmbh | Flame retardant polyamide composition |
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