CN106519665A - Flame-retardant reinforced polyamide composite material and preparation method thereof - Google Patents
Flame-retardant reinforced polyamide composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- 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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- 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
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Abstract
The invention relates to a flame-retardant reinforced polyamide composite material and a preparation method thereof. The flame-retardant reinforced polyamide composite material is prepared from polyamide 10T/11 resin, aliphatic polyamides, toluene diisocynate, 2,2'-(1,3-phenylene)-bisoxazoline, a coupling agent, phyllosilicate, alkylphosphinate, melamine pyrophosphate, zinc borate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,3-phthalic diamide and bis(2,6-tertiary butyl-4-methylphenyl)pentaerythritol diphosphate. The flame-retardant reinforced polyamide composite material has advantages of high flame retardation, high tensile strength, high fluidity and low water absorption rate and can be applied to fields of electronics, electrical appliances, LED, automobiles, aerospace, military industry and the like.
Description
Technical field
The present invention relates to Material Field, more particularly to a kind of flame retardancy reinforced polyamide composite material and preparation method thereof.
Background technology
Heat resistant polyamide is typically by aliphatic diamidogen and aromatic diacid, or aromatic diamidogen and fat
The diacid Jing polycondensations of race are prepared.As phenyl ring is introduced on molecular backbone, heat resistant polyamide not only maintains fat
Mechanical property that polyamide has is good, acid and alkali-resistance and the advantages of self lubricity, also overcome that its water absorption rate is high, dimensional stability not
Good shortcoming so as to be particularly well-suited in auto industry, to replace the part metals structural member in automobile, to realize light weight
Change, it is also possible to for manufacturing the insulating body of electronic device, or be used for surface mounting technique.
In heat resistant polyamide, the fusing point of PA10T resins is 320 DEG C or so, and which is more or less the same with decomposition temperature, processing
Temperature range is narrow, easily causes polymer decomposition in process.Therefore, in PA10T resin backbones, introducing the 3rd is single
Body expands which and uses field and improve its combination property improving its processing characteristics.But, add the Third monomer of low content not
Be enough to improve its processing characteristics, and add the Third monomer of high-load that the fusing point of copolymer resin can be made too low, do not reach resistance to
The requirement of high temperature.
Halogenated flame retardant was once the fire-retardant kind that polyamide is most frequently with, but most of halogenated flame retardant is given birth in burning
Into 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
The toxicity of combustion agent, raw cigarette and corrosivity are relatively low, with environmental requirement more and more higher, to the research of phosphorus flame retardant increasingly
Pay attention to.Phosphinates are the organic phosphorus flame retardant of new generation developed in recent years, environmentally friendly, heat stability and hydrolytic stability
It is good, do not cause polymer to decompose during processing, because of its excellent heat stability, be particularly well-suited to heat resistant polyamide halogen-free flameproof and change
Property.
For above-mentioned problem, some researchs, such as Chinese patent are done to the modified of polyamide in currently available technology
CN 103333335A disclose a kind of high fluidity PA10T Amilan polyamide resin composition, and which is obtained by solid phase by two kinds
Different viscositys PA10T polyamides composition；It is fire-retardant that Chinese patent CN102604380A discloses a kind of high heat-resisting high CTI
Polyamide compoiste material, the wherein polyamide are polyhexamethylene adipamide/poly-paraphenylene terephthalamide's nonamethylene diamine copolymer or poly-
Paraphenylene terephthalamide's nonamethylene diamine；Chinese patent CN 105038207A disclose it is a kind of with anti-flammability, high temperature resistant, high glaze lamp
The polyamide of decorating fittings strengthens formula, and the polyamide strengthens formula by PA6T, reinforcing filler, fire retardant, stabilizer, antioxygen
Agent and other processing aids are constituted；Chinese patent CN 102675865A disclose a kind of Amilan polyamide resin composition, resulting
Compositionss can meet UL94V-0 burning grades in 0.5mm and above thickness；Chinese patent CN 105176077A are disclosed
A kind of fire-retardant high-moduluss nylon material and its preparation method and application.
The content of the invention
The present invention be directed to the deficiencies in the prior art, it is therefore an objective to provide a kind of with high flame retardant, high tensile, Gao Liu
The polyamide compoiste material of dynamic property and low water absorption, can serve as electronic apparatus part, automobile component, is particularly useful as electricity
The sheathing material of sub- electrical equipment.
To reach above-mentioned purpose, the present invention adopts below scheme：
A kind of flame retardancy reinforced polyamide composite material, the composite are prepared from by the raw material of following weight portion：
The intrinsic viscosity of the polyamide 10T/11 resins is 0.7～1.0dL/g.
The aliphatic polyamide resin is nylon 46 resin (PA46), polyhexamethylene adipamide resin
(PA66) at least one in.
The coupling agent be gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-
Gamma-aminopropyl-triethoxy-silane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-ammonia third
Ylmethyl dimethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, aniline first
At least one in ethyl triethoxy silicane alkane.
Layered silicate is montmorillonite, Kaolin, brucite, at least one in meerschaum.
The alkyl phosphinate is aluminum diethylphosphinate, diethyl phosphinic acid zinc, diethyl phosphinic acid calcium, diethyl
In phosphinic acid magnesium, dipropyl phosphinic acid aluminum, isobutylphosphinic aluminum, Methylethyl phosphinic acid aluminum, aluminum phenylphosphinate at least
It is a kind of.
The melamine polyphosphate is tripolycyanamide poly aluminium phosphate, tripolycyanamide polyphosphoric acid zinc, the poly- phosphorus of tripolycyanamide
At least one in sour magnesium.
Wherein in some embodiments, flame retardancy reinforced polyamide composite material is prepared from by the raw material of following weight portion：
Wherein in some embodiments, flame retardancy reinforced polyamide composite material, further preferably by the original of following weight portion
Material is prepared from：
Wherein in some embodiments, the intrinsic viscosity of the polyamide 10T/11 resins is 0.75～0.95dL/g；Institute
It is polyhexamethylene adipamide resin (PA66) to state aliphatic polyamide resin, and its intrinsic viscosity is 1.22～1.84dL/g.
Wherein in some embodiments, the coupling agent is gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy
At least one in base silane；Layered silicate is montmorillonite；The alkyl phosphinate is aluminum diethylphosphinate；Institute
Melamine polyphosphate is stated for tripolycyanamide poly aluminium phosphate；The particle diameter of the Firebrake ZB is 2～8 μm.
Wherein in some embodiments, the polyamide 10T/11 resins are formed by monomer 1 and polyesteramide copolymerization, described
It is 1 that monomer 1 is mol ratio：1：0.01～0.1 decamethylene diamine, p-phthalic acid, 11- aminoundecanoic acids, the polyesteramide add
Enter that amount is 1 gross weight of the monomer 1～8%.
Wherein in some embodiments, the polyamide 10T/11 resins are obtained by following synthetic method：
(1) by vacuum drying after the monomer 1 be added in stirring-type polymer reactor, while adding the polyester acyl
Amine, and molecular weight regulator, antioxidant, water；Then 4～6min of evacuation, leads to 4～6min of nitrogen, so circulates 5～7 times,
Reactant is made to be present in the lower environment of nitrogen protection, control in the stirring-type polymer reactor system pressure for 0.2～
0.3MPa；
(2) in 2～4 hours by the stirring-type polymer reactor closed constant-speed heating to 272～280 DEG C, adjust institute
The mixing speed for stating stirring-type polymer reactor is 30～50r/min, wherein, when the stirring-type polymer reactor temperature reaches
When 215 DEG C, 2.0MPa is deflated to, and maintains pressure in 2.0MPa, after reacting 1～2 hour, be deflated to normal pressure, while being warming up to
After continuing reaction at 310～320 DEG C 1～2 hour, constant temperature continued evacuation after 0.3～1 hour, obtained the polyamide 10T/
11 resins；
The molecular weight regulator is addition is 1 gross weight of the monomer 0.1～3% benzoic acid；The antioxygen
Agent is addition is 1 gross weight of the monomer 0.1～0.3% N, bis- (2,2,6,6- tetramethyl -4- piperidyls) -1 of N'-,
3- benzene diamides；Appropriate amount of water.
It is a further object of the present invention to provide the preparation method of flame retardancy reinforced polyamide composite material.
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, specific technical scheme, comprises the following steps：
(1) the polyamide 10T/11 resins and aliphatic polyamide resin are placed in into 80～100 DEG C, are dried 4～12 little
Shi Hou, cooling, by the polyamide 10T/11 resins after cooling, aliphatic polyamide resin, and the toluene di-isocyanate(TDI),
2,2'- (1,3- phenylenes)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and
Double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates are mixed in being added to homogenizer；
(2) coupling agent, phyllosilicate, alkyl phosphinate, melamine polyphosphate and Firebrake ZB are added
Mixed in another homogenizer；
(3) during the compound Jing feeders for mixing step (1) add parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (such as the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, pelletize,
Technological parameter is as follows：One 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.
Wherein in some embodiments, by the polyamide 10T/11 resins and fatty polyamide in the step (1)
Resin is placed in 90 DEG C, is dried 4～6 hours；Technological parameter in the step (3) is：One 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.
Wherein in some embodiments, the screw configuration of the parallel double-screw extruder is single thread；Spiro rod length L
Ratio L/D with diameter D is 35～50；The screw rod is provided with the gear block area of more than 1 (containing 1) and more than 1 (containing 1)
Left-hand thread area.
Wherein in some embodiments, the ratio L/D of the spiro rod length L and diameter D is 35～45；The screw rod is provided with
2 gear block areas and 1 left-hand thread area.
Wherein in some embodiments, the polyamide 10T/11 resins are formed by monomer 1 and polyesteramide copolymerization, described
It is 1 that monomer 1 is mol ratio：1：0.01～0.1 decamethylene diamine, p-phthalic acid, 11- aminoundecanoic acids, the polyesteramide add
Enter that amount is 1 gross weight of the monomer 1～8%.
Wherein in some embodiments, the polyamide 10T/11 resins are obtained by following synthetic method：
(1) by vacuum drying after the monomer 1 be added in stirring-type polymer reactor, while adding the polyester acyl
Amine, and molecular weight regulator, antioxidant, water；Then 4～6min of evacuation, leads to 4～6min of nitrogen, so circulates 5～7 times,
Reactant is made to be present in the lower environment of nitrogen protection, control in the stirring-type polymer reactor system pressure for 0.2～
0.3MPa；
(2) in 2～4 hours by the stirring-type polymer reactor closed constant-speed heating to 272～280 DEG C, adjust institute
The mixing speed for stating stirring-type polymer reactor is 30～50r/min, wherein, when the stirring-type polymer reactor temperature reaches
When 215 DEG C, 2.0MPa is deflated to, and maintains pressure in 2.0MPa, after reacting 1～2 hour, be deflated to normal pressure, while being warming up to
After continuing reaction at 310～320 DEG C 1～2 hour, constant temperature continued evacuation after 0.3～1 hour, obtained the polyamide 10T/
11 resins；
The molecular weight regulator is addition is 1 gross weight of the monomer 0.1～3% benzoic acid；The antioxygen
Agent is addition is 1 gross weight of the monomer 0.1～0.3% N, bis- (2,2,6,6- tetramethyl -4- piperidyls) -1 of N'-,
3- benzene diamides；Appropriate amount of water.
The principle of the present invention is as follows：
For the not good defect of the processing temperature narrow limits and processing characteristics that solve polyamide 10T/11 resins, the present invention
Improve the processing characteristics of polyamide 10T/11 resins using aliphatic polyamide resin, this is because aliphatic polyamide resin
Possess preferably mobile performance, and polyamide 10T/11 resins possess preferably mechanical property.Meanwhile, fatty polyamide tree
The end group of fat and polyamide 10T/11 resins can respectively with toluene di-isocyanate(TDI) isocyanate groups, (1,3- is sub- for 2,2'-
Phenyl) the oxazoline group of-bisoxazoline reacts, and improves the compatibility of both polyamides.Meanwhile, toluene two is different
The isocyanate groups of cyanate, the oxazoline group of 2,2'- (1,3- phenylenes)-bisoxazoline can also and phyllosilicate
Terminal hydroxy group react, and be attached to phyllosilicate, alkyl phosphinate, melamine polyphosphate and Firebrake ZB
On coupling agent react, so as to improve phyllosilicate, alkyl phosphinate, melamine polyphosphate and Firebrake ZB with
The interface binding power of above two polyamide and the compatibility, reduce their shadows to polyamide compoiste material mechanical property
Ring.
The coupling agent that the present invention is adopted, preferably gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane,
Contain amino, above-mentioned auxiliary agent can react with the end group of above two polyamide, so as to further improve layer
The interface cohesion of shape silicate, alkyl phosphinate, melamine polyphosphate and Firebrake ZB and above two polyamide
Power and the compatibility, reduce their impacts to polyamide compoiste material mechanical property.
Fire retardant phyllosilicate, alkyl phosphinate, melamine polyphosphate and Firebrake ZB can form mutually association
Same-action.Phyllosilicate and Firebrake ZB can promote material surface into charcoal, increased charring layer, make Char Residues Structure fine and close hard
Firmly, good obstruct 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 produced during burning, reduces the degradation rate and HRR of polymer；Alkyl
Phosphonate primarily serves the effect that gas phase suppresses 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 double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N, N'- is 272 DEG C, boiling point is more than
360 DEG C, the better heat stability in polyamide resin composite material Blending Processes, its amide group can be poly- with above two
The end group of amide resin reacts to improve the compatibility, and hindered piperidine base can provide antioxidation and improve the dyeing of copolymer
Property.
The fusing point of double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates is 239 DEG C, heat decomposition temperature surpasses
350 DEG C are crossed, with good thermostability and hydrolytic resistance, can be to provide superior in polyamide resin composite material Blending Processes
Colour stability and melt stability, while thermal degradation of the above two polyamide in pyroprocess can be prevented, and
The hot oxygen discoloration caused due to long-time is inhibited, be 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 advantages that：
The present invention for existing polyamide 10T/11 resins anti-flammability is high, processing temperature narrow limits and processing characteristics
Not good defect, improves the processing characteristics of polyamide 10T/11 resins by using aliphatic polyamide resin, while adopting
Toluene di-isocyanate(TDI) and 2,2'- (1,3- phenylene)-bisoxazoline are used as the compatilizer between both polyamides,
And gather with the phyllosilicate of coupling agent, alkyl phosphinate, tripolycyanamide is attached with as above two polyamide
Compatilizer between phosphate and Firebrake ZB, and compounding use phyllosilicate, alkyl phosphinate, tripolycyanamide polyphosphoric acid
Salt and Firebrake ZB improving the fire resistance of this polyamide compoiste material, while phyllosilicate can also improve this polyamides
The tensile strength of amine composite and reduction water absorption rate, shrinkage factor, last compounding use N, double (2,2,6, the 6- tetramethyl -4- of N'-
Piperidyl) -1,3- benzenedicarboxamides and double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates to be processing blending
During xanthochromia problem, preparation-obtained flame retardancy reinforced polyamide composite material has high flame retardant, high tensile, height
The characteristics of mobility and low water absorption, can be applicable to field of electronics, LED field, automotive field, Aero-Space and military project neck
Domain etc..
Description of the drawings
Fig. 1 show the preparation technology flow chart of flame retardancy reinforced polyamide composite material of the present invention.
Specific embodiment
Feature, technological means and the specific purposes for reaching, function by further appreciating that the present invention, parses this
Bright advantage and spirit, by following examples, the present invention is further elaborated.
The reaction mechanism of flame retardancy reinforced polyamide composite material of the present invention is following (preparation technology flow chart asks for an interview Fig. 1)：
From above-mentioned reaction equation, aliphatic polyamide resin and polyamide 10T/11 resins Amino End Group can and toluene
The isocyanate groups of diisocyanate react, the Amino End Group of aliphatic polyamide resin and polyamide 10T/11 resins,
End carboxyl can react with the oxazoline group of 2,2'- (1,3- phenylene)-bisoxazoline, such that it is able to increase both
The compatibility between polyamide.
The raw material used by the embodiment of the present invention is as follows：
Polyamide 10T/11 resins (PA10T/11), self-control, the decamethylene diamine in raw material reach the limited public affairs of nylon selected from Wuxi Yin
Department, p-phthalic acid are selected from Beijing Yanshan Petrochemical Co., and 11- aminoundecanoic acids are selected from the limited public affairs of Taiyuan Zhong Lianze agrochemicals
Department, remaining auxiliary agent are selected from Chemical Reagent Co., Ltd., Sinopharm Group；
Polyhexamethylene adipamide resin (PA66), selected from China Shenma Group Co., Ltd., its intrinsic viscosity is respectively
1.22dL/g、1.66dL/g、1.84dL/g；
Toluene di-isocyanate(TDI), selected from Chemical Reagent Co., Ltd., Sinopharm Group；
2,2'- (1,3- phenylene)-bisoxazoline, selected from Chemical Reagent Co., Ltd., Sinopharm Group；
Coupling agent (gamma-aminopropyl-triethoxy-silane), selected from Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei；
Coupling agent (γ-aminopropyltrimethoxysilane), selected from Zhejiang boiling point Chemical Co., Ltd.；
Phyllosilicate (montmorillonite), selected from Zhejiang Fenghong New Material Co., Ltd.；
Alkyl phosphinate (aluminum diethylphosphinate), selected from Jiangsu Li Side new materials company limited；
Melamine polyphosphate (tripolycyanamide poly aluminium phosphate), selected from Sichuan Fine Chemical Research and Design Inst.；
Firebrake ZB, selected from 101 Chemical Co., Ltd. of Jining, particle diameter is 2～8 μm；
Double (2,2,6,6- tetramethyl -4- piperidyls) -1, the 3- benzenedicarboxamides of N, N'-, have selected from such as Dong Jinkangtai chemistry
Limit company；
Double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates, it is limited selected from Shanghai point credit fine chemistry industry
Company.
The present invention is described in detail below in conjunction with specific embodiment.
Polyamide 10T/11 resins in following examples are formed by monomer 1 and polyesteramide copolymerization, and the monomer 1 is to rub
You are than being 1：1：0.01～0.1 decamethylene diamine, p-phthalic acid, 11- aminoundecanoic acids, the polyesteramide addition are described
The 1～8% of 1 gross weight of monomer, above-mentioned polyamide 10T/11 resins have such as following formula I structure：
In Formulas I, a=10～200, b=10～200, c=10～100, R are polyesteramide, and there is Formula Il such as to tie for which
Structure：
In Formula II, x=10～200, y=10～200, z=10～100.
The synthetic method of polyamide 10T/11 resins is as follows：
(1) by vacuum drying after the monomer 1 be added in stirring-type polymer reactor, while adding the polyester acyl
Amine, and molecular weight regulator, antioxidant, water；Then 4～6min of evacuation, leads to 4～6min of nitrogen, so circulates 5～7 times,
Reactant is made to be present in the lower environment of nitrogen protection, control in the stirring-type polymer reactor system pressure for 0.2～
0.3MPa；
(2) in 2～4 hours by the stirring-type polymer reactor closed constant-speed heating to 272～280 DEG C, adjust institute
The mixing speed for stating stirring-type polymer reactor is 30～50r/min, wherein, when the stirring-type polymer reactor temperature reaches
When 215 DEG C, 2.0MPa is deflated to, and maintains pressure in 2.0MPa, after reacting 1～2 hour, be deflated to normal pressure, while being warming up to
After continuing reaction at 310～320 DEG C 1～2 hour, constant temperature continued evacuation after 0.3～1 hour, obtained the polyamide 10T/
11 resins；
The molecular weight regulator is addition is 1 gross weight of the monomer 0.1～3% benzoic acid；The antioxygen
Agent is addition is 1 gross weight of the monomer 0.1～0.3% N, bis- (2,2,6,6- tetramethyl -4- piperidyls) -1 of N'-,
3- benzene diamides；Appropriate amount of water.
Embodiment 1
The raw material of the polyamide 10T/11 resins used in the present embodiment is constituted and synthesis step is as follows：
(1) by the monomer 1 after vacuum drying：1mol decamethylene diamines, 1mol p-phthalic acids, 0.05mol 11- amino 11
Acid is added in stirring-type polymer reactor, at the same add 1 gross weight of monomer 4% polyesteramide, 1.5% benzoic acid,
0.2% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides, addition 100mL water are used as mass-and heat-transfer
Medium；Then evacuation 5min, leads to nitrogen 5min, so circulation 6 times, the environment for making reactant be present under nitrogen protection
In, it is 0.3MPa to control system pressure in stirring-type polymer reactor；
(2) in 3 hours by stirring-type polymer reactor closed constant-speed heating to 275 DEG C, adjust stirring-type polyreaction
The mixing speed of device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 215 DEG C, 2.0MPa is deflated to, and
Pressure is maintained in 2.0MPa, after reaction 1.5 hours, normal pressure is deflated to, while after being warming up at 315 DEG C and continuing reaction 1.5 hours,
Constant temperature continued evacuation after 0.5 hour, obtained the polyamide 10T/11 resins；
The intrinsic viscosity of the above-mentioned polyamide 10T/11 resins for preparing is 0.85dL/g, melt temperature is 305 DEG C.
A kind of flame retardancy reinforced polyamide composite material of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprises the following steps：
(1) polyamide 10T/11 resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling will
Polyamide 10T/11 resins after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI), 2,2'- (1,3- sub- benzene
Base)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and double (bis- tertiary fourths of 2,6-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) by coupling agent (γ-aminopropyltrimethoxysilane), montmorillonite, aluminum diethylphosphinate, the poly- phosphorus of tripolycyanamide
Sour aluminum and Firebrake ZB are mixed in being added to another homogenizer；
(3) during the compound Jing feeders for mixing step (1) add parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, pelletize, technique
Parameter is as follows：One 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 35 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 2
The raw material of the polyamide 10T/11 resins used in the present embodiment is constituted and synthesis step is with embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprises the following steps：
(1) polyamide 10T/11 resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling will
Polyamide 10T/11 resins after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI), 2,2'- (1,3- sub- benzene
Base)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and double (bis- tertiary fourths of 2,6-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), montmorillonite, aluminum diethylphosphinate, the poly- phosphorus of tripolycyanamide
Sour aluminum and Firebrake ZB are mixed in being added to another homogenizer；
(3) during the compound Jing feeders for mixing step (1) add parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, pelletize, technique
Parameter is as follows：One 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 50 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 3
The raw material of the polyamide 10T/11 resins used in the present embodiment is constituted and synthesis step is with embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprises the following steps：
(1) polyamide 10T/11 resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling will
Polyamide 10T/11 resins after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI), 2,2'- (1,3- sub- benzene
Base)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and double (bis- tertiary fourths of 2,6-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), montmorillonite, aluminum diethylphosphinate, the poly- phosphorus of tripolycyanamide
Sour aluminum and Firebrake ZB are mixed in being added to another homogenizer；
(3) during the compound Jing feeders for mixing step (1) add parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, pelletize, technique
Parameter is as follows：One 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 45 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 4
The raw material of the polyamide 10T/11 resins used in the present embodiment is constituted and synthesis step is with embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprises the following steps：
(1) polyamide 10T/11 resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling will
Polyamide 10T/11 resins after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI), 2,2'- (1,3- sub- benzene
Base)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and double (bis- tertiary fourths of 2,6-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), montmorillonite, aluminum diethylphosphinate, the poly- phosphorus of tripolycyanamide
Sour aluminum and Firebrake ZB are mixed in being added to another homogenizer；
(3) during the compound Jing feeders for mixing step (1) add parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, pelletize, technique
Parameter is as follows：One area's temperature is 290 DEG C, and two area's temperature are 305 DEG C, and three area's temperature are 310 DEG C, and four area's temperature are 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 40 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 5
The raw material of the polyamide 10T/11 resins used in the present embodiment is constituted and synthesis step is with embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprises the following steps：
(1) polyamide 10T/11 resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling will
Polyamide 10T/11 resins after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI), 2,2'- (1,3- sub- benzene
Base)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and double (bis- tertiary fourths of 2,6-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), montmorillonite, aluminum diethylphosphinate, the poly- phosphorus of tripolycyanamide
Sour aluminum and Firebrake ZB are mixed in being added to another homogenizer；
(3) during the compound Jing feeders for mixing step (1) add parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, pelletize, technique
Parameter is as follows：One area's temperature is 290 DEG C, and two area's temperature are 305 DEG C, and three area's temperature are 310 DEG C, and four area's temperature are 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 40 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 6
The raw material of the polyamide 10T/11 resins used in the present embodiment is constituted and synthesis step is with embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprises the following steps：
(1) polyamide 10T/11 resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling will
Polyamide 10T/11 resins after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI), 2,2'- (1,3- sub- benzene
Base)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and double (bis- tertiary fourths of 2,6-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), montmorillonite, aluminum diethylphosphinate, the poly- phosphorus of tripolycyanamide
Sour aluminum and Firebrake ZB are mixed in being added to another homogenizer；
(3) during the compound Jing feeders for mixing step (1) add parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, pelletize, technique
Parameter is as follows：One area's temperature is 290 DEG C, and two area's temperature are 305 DEG C, and three area's temperature are 310 DEG C, and four area's temperature are 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 40 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 1
The raw material of the polyamide 10T/11 resins used in this comparative example is constituted and synthesis step is with embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of this comparative example, is prepared from by the following raw material：
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprises the following steps：
(1) polyamide 10T/11 resins are placed in into 90 DEG C, after being dried 5 hours, cooling, by the polyamide 10T/11 after cooling
Resin, and double (2,2,6,6- tetramethyl -4- piperidyls) -1, the 3- benzenedicarboxamides of N, N'- and double (2,6- di-t-butyl -4-
Aminomethyl phenyl) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), montmorillonite, aluminum diethylphosphinate, the poly- phosphorus of tripolycyanamide
Sour aluminum and Firebrake ZB are mixed in being added to another homogenizer；
(3) during the compound Jing feeders for mixing step (1) add parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, pelletize, technique
Parameter is as follows：One area's temperature is 290 DEG C, and two area's temperature are 305 DEG C, and three area's temperature are 310 DEG C, and four area's temperature are 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 40 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 2
The raw material of the polyamide 10T/11 resins used in this comparative example is constituted and synthesis step is with embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of this comparative example, is prepared from by the following raw material：
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprises the following steps：
(1) polyamide 10T/11 resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling will
Polyamide 10T/11 resins after cooling, polyhexamethylene adipamide resin, and double (2,2,6, the 6- tetramethyl -4- piperidines of N, N'-
Base) -1,3- benzenedicarboxamides and double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates are added to high-speed stirred
Mixed in machine；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), montmorillonite, aluminum diethylphosphinate, the poly- phosphorus of tripolycyanamide
Sour aluminum and Firebrake ZB are mixed in being added to another homogenizer；
(3) during the compound Jing feeders for mixing step (1) add parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, pelletize, technique
Parameter is as follows：One area's temperature is 290 DEG C, and two area's temperature are 305 DEG C, and three area's temperature are 310 DEG C, and four area's temperature are 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 40 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 3
The raw material of the polyamide 10T/11 resins used in this comparative example is constituted and synthesis step is with embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of this comparative example, is prepared from by the following raw material：
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprises the following steps：
(1) polyamide 10T/11 resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling will
Polyamide 10T/11 resins after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI), 2,2'- (1,3- sub- benzene
Base)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and double (bis- tertiary fourths of 2,6-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), aluminum diethylphosphinate, tripolycyanamide poly aluminium phosphate and
Firebrake ZB is mixed in being added to another homogenizer；
(3) during the compound Jing feeders for mixing step (1) add parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, pelletize, technique
Parameter is as follows：One area's temperature is 290 DEG C, and two area's temperature are 305 DEG C, and three area's temperature are 310 DEG C, and four area's temperature are 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 40 for the ratio L/D of single thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 4
The raw material of the polyamide 10T/11 resins used in this comparative example is constituted and synthesis step is with embodiment 1.
A kind of flame retardancy reinforced polyamide composite material of this comparative example, is prepared from by the following raw material：
The preparation method of above-mentioned flame retardancy reinforced polyamide composite material, comprises the following steps：
(1) polyamide 10T/11 resins and polyhexamethylene adipamide resin are placed in into 90 DEG C, after being dried 5 hours, cooling will
Polyamide 10T/11 resins after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI), 2,2'- (1,3- sub- benzene
Base)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and double (bis- tertiary fourths of 2,6-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), montmorillonite and aluminum diethylphosphinate are added to into another
Mixed in homogenizer；
(3) during the compound Jing feeders for mixing step (1) add parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, pelletize, technique
Parameter is as follows：One area's temperature is 290 DEG C, and two area's temperature are 305 DEG C, and three area's temperature are 310 DEG C, and four area's temperature are 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 30 for the ratio L/D of double thread, spiro rod length L and diameter D,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
It is below embodiment and comparative example catalog (table 1)：
1 embodiment of table constitutes weight portion catalog with comparative example raw material
Double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of the N of above example and comparative example, N'- and
Double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates are respectively 0.15 part, 0.15 part.
The various embodiments described above and the made working of plastics sample of comparative example are carried out into following performance test (result is as shown in table 2)：
Fire resistance：By UL 94-2006 standard testings, 1/8 inch of thickness of sample (i.e. 3.2mm)；
Tensile property：By GB/T 1040.1-2006 standard testings, rate of extension 10mm/min；
Mobile performance：By GB/T 3682-2000 standard testings, 309 DEG C of test temperature, load 1.2kg；
Water absorbing properties：By GB/T 1034-2008 standard testings, testing time 24h.
2 embodiment of table and comparative example performance catalog
As can be seen that montmorillonite, aluminum diethylphosphinate, tripolycyanamide poly aluminium phosphate and Firebrake ZB from embodiment 1～6
Addition it is more, the fire resistance of polyamide 10T/11 resin composite materials is better, at the same with montmorillonite content increase,
The tensile strength of polyamide 10T/11 resin composite materials is bigger；Aliphatic polyamide resin (polyhexamethylene adipamide resin)
Addition is more, and the melt index of polyamide 10T/11 resin composite materials is bigger, and processing characteristics is better；The water suction of each embodiment
Rate change is little.Comprehensive factors above, the combination property of embodiment 6 are optimal.
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, its melt index be only 5g/10min (309 DEG C of test temperature, load 1.2kg), plus
Work performance is not good；Comparative example 2 is to be not added with toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylenes)-bisoxazoline (PBO)
Polyamide 10T/11 resin composite materials, aliphatic polyamide resin (polyhexamethylene adipamide resin) and polyamide 10T/11
Resin compatible is not good, so as to cause bad impact to the tensile property of polyamide 10T/11 resin composite materials；Contrast
, to be not added with the polyamide 10T/11 resin composite materials of montmorillonite, its tensile property is not good for example 3；Parallel pair of spiral shell of comparative example 4
The screw configuration of bar extruder is 30 for the ratio L/D of double thread, spiro rod length L and diameter D, and parallel pair of spiral shell of embodiment 6
The screw configuration of bar extruder is 40 for the ratio L/D of single thread, spiro rod length L and diameter D, while comparative example 4 is not added with three
Poly cyanamid poly aluminium phosphate and Firebrake ZB, by contrast it is found that using the spiral shell of the parallel double-screw extruder described in embodiment 6
Bar parameter and tripolycyanamide poly aluminium phosphate, Firebrake ZB, the polyamide 10T/11 resin composite materials which prepares it is fire-retardant
Performance, tensile property, processing characteristics 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 arbitrarily can be combined, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed, but and
Therefore can not be construed as limiting the scope of the patent.It should be pointed out that for one of ordinary skill in the art comes
Say, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (10)
1. a kind of flame retardancy reinforced polyamide composite material, it is characterised in that be prepared from by the raw material of following weight portion：
The intrinsic viscosity of the polyamide 10T/11 resins is 0.7～1.0dL/g；
The aliphatic polyamide resin is nylon 46 resin, at least one in polyhexamethylene adipamide resin；
The coupling agent be gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-γ-
Aminopropyl triethoxysilane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-aminopropyl
Methyl dimethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, anilinomethyl
At least one in triethoxysilane；
Layered silicate is montmorillonite, Kaolin, brucite, at least one in meerschaum；
The alkyl phosphinate is aluminum diethylphosphinate, diethyl phosphinic acid zinc, diethyl phosphinic acid calcium, diethyl time phosphine
At least one in sour magnesium, dipropyl phosphinic acid aluminum, isobutylphosphinic aluminum, Methylethyl phosphinic acid aluminum, aluminum phenylphosphinate；
The melamine polyphosphate is tripolycyanamide poly aluminium phosphate, tripolycyanamide polyphosphoric acid zinc, tripolycyanamide polyphosphoric acid magnesium
In at least one.
2. flame retardancy reinforced polyamide composite material according to claim 1, it is characterised in that by the raw material of following weight portion
It is prepared from：
3. flame retardancy reinforced polyamide composite material according to claim 1 and 2, it is characterised in that the polyamide 10T/
The intrinsic viscosity of 11 resins is 0.75～0.95dL/g；The aliphatic polyamide resin is polyhexamethylene adipamide resin, its
Intrinsic viscosity is 1.22～1.84dL/g.
4. flame retardancy reinforced polyamide composite material according to claim 1 and 2, it is characterised in that the coupling agent be γ-
At least one in aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane；Layered silicate is montmorillonite；
The alkyl phosphinate is aluminum diethylphosphinate；The melamine polyphosphate is tripolycyanamide poly aluminium phosphate；It is described
The particle diameter of Firebrake ZB is 2～8 μm.
5. flame retardancy reinforced polyamide composite material according to claim 1 and 2, it is characterised in that the polyamide 10T/
11 resins are formed by monomer 1 and polyesteramide copolymerization, and it is 1 that the monomer 1 is mol ratio：1：0.01～0.1 decamethylene diamine, to benzene
Dioctyl phthalate, 11- aminoundecanoic acids, the polyesteramide addition are the 1～8% of 1 gross weight of the monomer.
6. flame retardancy reinforced polyamide composite material according to claim 5, it is characterised in that the polyamide 10T/11 trees
Fat is obtained by following synthetic method：
(1) by vacuum drying after the monomer 1 be added in stirring-type polymer reactor, while add the polyesteramide,
And molecular weight regulator, antioxidant, water；Then 4～6min of evacuation, leads to 4～6min of nitrogen, so circulates 5～7 times, makes
Reactant is present in the lower environment of nitrogen protection, control in the stirring-type polymer reactor system pressure for 0.2～
0.3MPa；
(2) in 2～4 hours by the stirring-type polymer reactor closed constant-speed heating to 272～280 DEG C, adjust described in stir
The mixing speed for mixing formula polymer reactor is 30～50r/min, wherein, when the stirring-type polymer reactor temperature reaches 215
DEG C when, be deflated to 2.0MPa, and maintain pressure in 2.0MPa, after reaction 1～2 hour, be deflated to normal pressure, while being warming up to 310
After continuing reaction at～320 DEG C 1～2 hour, constant temperature continued evacuation after 0.3～1 hour, obtained the polyamide 10T/11 trees
Fat；
The molecular weight regulator is addition is 1 gross weight of the monomer 0.1～3% benzoic acid；The antioxidant is
Addition is the N of the 0.1～0.3% of 1 gross weight of the monomer, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene
Diamides；Appropriate amount of water.
7. the preparation method of the flame retardancy reinforced polyamide composite material described in a kind of any one of claim 1-6, it is characterised in that
Comprise the following steps：
(1) the polyamide 10T/11 resins and aliphatic polyamide resin are placed in into 80～100 DEG C, after being dried 4～12 hours,
Cooling, by the polyamide 10T/11 resins after cooling, aliphatic polyamide resin, and the toluene di-isocyanate(TDI), 2,2'-
(1,3- phenylenes)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and it is double (2,
6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) coupling agent, phyllosilicate, alkyl phosphinate, melamine polyphosphate and Firebrake ZB are added to separately
Mixed in one homogenizer；
(3) during the compound Jing feeders for mixing step (1) add parallel double-screw extruder, and squeeze in parallel double-screw
Going out the mixture that the lateral addition step (2) of machine mixes carries out melting extrusion, and pelletize, technological parameter are as follows：One 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.
8. preparation method according to claim 7, it is characterised in that by the polyamide 10T/11 in the step (1)
Resin and aliphatic polyamide resin are placed in 90 DEG C, are dried 4～6 hours；Technological parameter in the step (3) is：One area's temperature
Spend for 270～295 DEG C, two area's temperature are 300～310 DEG C, three area's temperature are 305～315 DEG C, four area's temperature are 310～315
DEG C, five area's temperature are 310～315 DEG C, and 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, die head temperature is 305～310 DEG C, and screw speed is 200～400rpm.
9. the preparation method according to claim 7 or 8, it is characterised in that the screw shaped of the parallel double-screw extruder
Shape is single thread；The ratio L/D of spiro rod length L and diameter D is 35～50；The screw rod is provided with the gear block area of more than 1
With the left-hand thread area of more than 1.
10. preparation method according to claim 9, it is characterised in that the ratio L/D of the spiro rod length L and diameter D is 35
～45；The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
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| US11401416B2 (en) | 2017-10-17 | 2022-08-02 | Celanese Sales Germany Gmbh | Flame retardant polyamide composition |
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| CN110628202A (en) * | 2019-11-08 | 2019-12-31 | 广东圆融新材料有限公司 | High dielectric constant polyphenylene 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 |
| CN110643175A (en) * | 2019-11-11 | 2020-01-03 | 广东圆融新材料有限公司 | High dielectric constant polyamide 6/polyphenyl ether 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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