CN106675012A - LDS polyamide composite material and preparation method thereof - Google Patents
LDS polyamide composite material and preparation method thereof Download PDFInfo
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- CN106675012A CN106675012A CN201611104604.6A CN201611104604A CN106675012A CN 106675012 A CN106675012 A CN 106675012A CN 201611104604 A CN201611104604 A CN 201611104604A CN 106675012 A CN106675012 A CN 106675012A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
-
- 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
-
- 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
- B29C2948/9258—Velocity
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention relates to an LDS polyamide composite material and a preparation method of the LDS polyamide composite material. The LDS polyamide composite material is prepared from the following raw materials: PA10T/11, aliphatic PA, TDI, PBO, a coupling agent, alkali-free glass fibers, an LDS additive, N,N'-bi-(2,2,6,6-tetramethyl-4-piperidyl)-1,3-phthalic diamide and bi(2,6-tert butyl-4-methyl phenyl)pentaerythritol diphosphate. The LDS polyamide composite material has the characteristics of greenness and environmental protection, high tensile strength, high fluidity, low water absorption rate and LDS, and can be applied to the industry fields of communications, automotive electronics, computers, electromechanical equipment, medical devices and the like.
Description
Technical field
The present invention relates to Material Field, more particularly to a kind of laser direct forming polyamide compoiste material and its preparation side
Method.
Background technology
Laser direct forming (LDS) is a kind of to integrate injection mo(u)lding, radium-shine processing and without electrochemical plating processing procedure three
The production technology of dimension molding interconnection element (3D-MID), the technology is applied to antenna for mobile phone, printed circuit board, sensor, microcomputer
The fine circuitry of the electronic devices such as electric system, global positioning system mobile terminal makes.LDS technology keys are will be to plastic substrate
A kind of laser direct forming additive of middle addition, laser direct forming additive destructurized, the copper in the presence of laser
Ion reduction is copper atom, is agglomerated into metallic particles, and this metallic particles is attached on the resin surface crossed by laser ablation, is formed
Metallic core, when subsequent chemistry is plated catalyst is played a part of, and promotes the metal ion in plating solution to be selectively deposited at
The region of laser scanning, forms metallic film.But, laser of the current LDS techniques mainly using Cu-Cr spinels is direct
Molding additive, wherein containing heavy metal Cr element, there is carcinogenecity to human body.
Heat resistant polyamide is typically by aliphatic diamidogen and aromatic diacid, or aromatic diamidogen and fat
The diacid Jing polycondensations of race are prepared.Due to introducing phenyl ring on molecular backbone, heat resistant polyamide not only maintains fat
Mechanical property that polyamide has is good, acid and alkali-resistance and the advantages of self lubricity, also overcome that its water absorption rate is high, dimensional stability not
Good shortcoming, therefore heat resistant polyamide is highly suitable as the substrate resin of LDS techniques.
For above-mentioned problem, some researchs have been done to the composite of LDS techniques in currently available technology, such as it is Chinese
Patent CN 103694704A discloses heat conductive insulating resin of a kind of laser direct forming and preparation method thereof, its substrate resin
For polyphenylene sulfide；Chinese patent CN 103450654A disclose it is a kind of can laser direct forming resin and preparation method thereof, its
Substrate resin is Merlon (PC) or PC/Abs (ABS) alloy；Chinese patent CN
106062040A discloses a kind of heat conduction polyamide compound, and the complex is comprising polyamide matrix, boron nitride and is scattered in
Laser direct forming additive in substrate, but do not announce the concrete composition of laser direct forming additive；Chinese patent
105492214A discloses a kind of flame-retardant thermoplastic compositions that can be used in laser direct forming method, and said composition includes heat
Plastic resin, laser direct forming additive and fire retardant.
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 tensile, high fluidity, low suction
Water rate and the laser direct forming polyamide compoiste material of environmental protection, can be applicable to communication, automotive electronics, computer, electromechanics
The industry fields such as equipment, medical apparatus and instruments.
To reach above-mentioned purpose, the present invention adopts below scheme：
A kind of laser direct forming polyamide compoiste material, the composite is 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.
The length of the alkali-free glass fibre be 2~4mm, a diameter of 9~11 μm.
The laser direct forming additive is at least one in alkali formula cupric phosphate, cupric phosphate, copper sulfate.
Wherein in some embodiments, laser direct forming polyamide compoiste material is prepared by the raw material of following weight portion
Form：
Wherein in some embodiments, laser direct forming polyamide compoiste material, further preferably by following weight portion
Raw material be 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；The laser direct forming additive is alkali formula cupric phosphate.
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 adds
Enter that amount is the gross weight of the monomer 1 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 set to be present in the lower environment of nitrogen protection, control in the stirring-type polymer reactor system pressure for 0.2~
0.3MPa；
(2) in 2~4 hours by the closed constant-speed heating of the stirring-type polymer reactor to 272~280 DEG C, adjust institute
The mixing speed for stating stirring-type polymer reactor is 30~50r/min, wherein, when the stirring-type polymer reactor temperature reaches
When 215 DEG C, 2.0MPa is deflated to, and maintains pressure in 2.0MPa, after reacting 1~2 hour, normal pressure is deflated to, while being warming up to
After continuing to react 1~2 hour at 310~320 DEG C, constant temperature continued evacuation after 0.3~1 hour, obtained the polyamide 10T/
11 resins；
The molecular weight regulator is addition is the gross weight of the monomer 1 0.1~3% benzoic acid；The antioxygen
Agent is addition is the gross weight of the monomer 1 0.1~0.3% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,
3- benzene diamides；Appropriate amount of water.
It is a further object of the present invention to provide the preparation method of laser direct forming polyamide compoiste material.
The preparation method of above-mentioned laser direct forming polyamide compoiste material, specific technical scheme is comprised 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 polyamide 10T/11 resins, aliphatic polyamide resin after cooling, 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 added in homogenizer and are mixed；
(2) coupling agent, alkali-free glass fibre and laser direct forming additive are added to into another high-speed stirred
Mixed in machine；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (such as the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, 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
It is 35~50 with the ratio L/D of diameter D；The screw rod is provided with the gear block area of more than 1 (containing 1) and more than 1 (containing 1)
Left-hand thread area.
Wherein in some embodiments, the ratio L/D of the spiro rod length L and diameter D is 35~45；The screw rod is provided with
2 gear block areas and 1 left-hand thread area.
Wherein in some embodiments, the 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 adds
Enter that amount is the gross weight of the monomer 1 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 set to be present in the lower environment of nitrogen protection, control in the stirring-type polymer reactor system pressure for 0.2~
0.3MPa；
(2) in 2~4 hours by the closed constant-speed heating of the stirring-type polymer reactor to 272~280 DEG C, adjust institute
The mixing speed for stating stirring-type polymer reactor is 30~50r/min, wherein, when the stirring-type polymer reactor temperature reaches
When 215 DEG C, 2.0MPa is deflated to, and maintains pressure in 2.0MPa, after reacting 1~2 hour, normal pressure is deflated to, while being warming up to
After continuing to react 1~2 hour at 310~320 DEG C, constant temperature continued evacuation after 0.3~1 hour, obtained the polyamide 10T/
11 resins；
The molecular weight regulator is addition is the gross weight of the monomer 1 0.1~3% benzoic acid；The antioxygen
Agent is addition is the gross weight of the monomer 1 0.1~0.3% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,
3- benzene diamides；Appropriate amount of water.
The principle of the present invention is as follows：
Using the carcinogenic laser direct forming additive containing heavy metal Cr element in order to solve current LDS techniques
Problem, and the not good defect of processing temperature narrow limits and processing characteristics of polyamide 10T/11 resins, the present invention is not using
The effect of laser direct forming is reached containing chromium and with the laser direct forming additive of LDS functions, while passing through fat
Fat polyamide resin improving the processing characteristics of polyamide 10T/11 resins, this is because aliphatic polyamide resin possess compared with
Good mobile performance, and polyamide 10T/11 resins possess preferably mechanical property.And, aliphatic polyamide resin and poly-
The end group of amide 10T/11 resins can respectively with toluene di-isocyanate(TDI) isocyanate groups, 2,2'- (1,3- phenylenes)-
The oxazoline group of bisoxazoline reacts, and improves the compatibility of both polyamides.Also, toluene di-isocyanate(TDI)
Isocyanate groups, 2,2'- (1,3- phenylenes)-bisoxazoline oxazoline group can also with alkali-free glass fibre, swash
Coupling agent on light straight forming additive is reacted, so as to improve alkali-free glass fibre, laser direct forming additive with
The interface binding power of above two polyamide and the compatibility, reduce the floating fine probability for occurring and they are compound to polyamide
The impact of material mechanical performance.
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 alkali-free glass
Glass fiber, the interface binding power of laser direct forming additive and above two polyamide and the compatibility, reduce them right
The impact of polyamide compoiste material mechanical property.
The length and diameter of alkali-free glass fibre to the mechanical property and appearance effects of polyamide resin composite material compared with
Greatly.The length of alkali-free glass fibre is bigger, and the tensile property of its resin composite materials is higher, while the probability of glass emergence on the surface
Increase therewith；The diameter of alkali-free glass fibre is less, and tensile strength is higher, but its cost for preparing is higher, while unit plane
Coupling agent needed for product is also more.Therefore, select the length and diameter of suitable alkali-free glass fibre excellent to processability and
The high polyamide resin composite material of cost performance is just particularly important.
The fusing point of double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N, N'- is 272 DEG C, boiling point is more than
360 DEG C, the better heat stability in 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, can be to provide superior in polyamide resin composite material Blending Processes with good thermostability and hydrolytic resistance
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 is for adopting the carcinogenic laser direct forming additive containing heavy metal Cr element in existing LDS techniques
Problem, by being added using environmental protection, the laser direct forming with LDS functions that heat decomposition temperature is high, heat stability is good
Plus agent is reaching the effect of laser direct forming, and the processing temperature narrow limits for existing polyamide 10T/11 resins and
The not good defect of processing characteristics, by the processing characteristics for improving polyamide 10T/11 resins using aliphatic polyamide resin,
It is used as between both polyamides using toluene di-isocyanate(TDI) and 2,2'- (1,3- phenylenes)-bisoxazoline simultaneously
Compatilizer, and as above two polyamide and the alkali-free glass fibre, the laser direct forming that are attached with coupling agent
Compatilizer between additive, and compounding use N, double (2,2,6,6- tetramethyl -4- piperidyls) -1, the 3- phenyl-diformyls of N'-
Amine and double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates to process Blending Processes in xanthochromia problem, institute
The laser direct forming polyamide compoiste material for preparing has environmental protection, high tensile, high fluidity, low water absorption
And the characteristics of laser direct forming, can be applicable to the industries such as communication, automotive electronics, computer, electromechanical equipment, medical apparatus and instruments neck
Domain.
Description of the drawings
Fig. 1 show the preparation technology flow chart of laser direct forming polyamide compoiste material of the present invention.
Specific embodiment
For feature, technological means and the specific purposes for being reached, the function of the present invention can be further appreciated that, this is parsed
Bright advantage and spirit, by following examples, the present invention is further elaborated.
The reaction mechanism of laser direct forming polyamide compoiste material of the present invention is following, and (preparation technology flow chart asks for an interview figure
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 that the embodiment of the present invention is used is as follows：
Polyamide 10T/11 resins (PA10T/11), self-control, the decamethylene diamine in raw material reaches the limited public affairs of nylon selected from Wuxi Yin
Department, p-phthalic acid is 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 is 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)-bisoxazolines, selected from Chemical Reagent Co., Ltd., Sinopharm Group；
Coupling agent (gamma-aminopropyl-triethoxy-silane), selected from Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei；
Coupling agent (γ-aminopropyltrimethoxysilane), selected from Zhejiang boiling point Chemical Co., Ltd.；
Alkali-free glass fibre, selected from Chinese megalith limited company, length is 3mm, a diameter of 10 μm；
Laser direct forming additive (alkali formula cupric phosphate), selected from Shandong West Asia chemical industry company limited；
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 is described
The 1~8% of the gross weight of monomer 1, 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 is polyesteramide, and it has 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 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 set to be present in the lower environment of nitrogen protection, control in the stirring-type polymer reactor system pressure for 0.2~
0.3MPa；
(2) in 2~4 hours by the closed constant-speed heating of the stirring-type polymer reactor to 272~280 DEG C, adjust institute
The mixing speed for stating stirring-type polymer reactor is 30~50r/min, wherein, when the stirring-type polymer reactor temperature reaches
When 215 DEG C, 2.0MPa is deflated to, and maintains pressure in 2.0MPa, after reacting 1~2 hour, normal pressure is deflated to, while being warming up to
After continuing to react 1~2 hour at 310~320 DEG C, constant temperature continued evacuation after 0.3~1 hour, obtained the polyamide 10T/
11 resins；
The molecular weight regulator is addition is the gross weight of the monomer 1 0.1~3% benzoic acid；The antioxygen
Agent is addition is the gross weight of the monomer 1 0.1~0.3% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,
3- benzene diamides；Appropriate amount of water.
Embodiment 1
The raw material of the 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 the gross weight of monomer 1 4% polyesteramide, 1.5% benzoic acid,
0.2% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides, addition 100mL water are used as mass-and heat-transfer
Medium；Then evacuation 5min, leads to nitrogen 5min, and so circulation 6 times makes reactant be present in the environment under nitrogen protection
In, it is 0.3MPa to control system pressure in stirring-type polymer reactor；
(2) in 3 hours by the closed constant-speed heating of stirring-type polymer reactor 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
Maintain pressure in 2.0MPa, after reacting 1.5 hours, be deflated to normal pressure, while after continuing to react 1.5 hours at being warming up to 315 DEG C,
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 laser direct forming polyamide compoiste material of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned laser direct forming polyamide compoiste 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 (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate is added in homogenizer and mixed；
(2) coupling agent (γ-aminopropyltrimethoxysilane), alkali-free glass fibre and alkali formula cupric phosphate are added to another
Mixed in platform homogenizer；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, 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 laser direct forming polyamide compoiste material of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned laser direct forming polyamide compoiste 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 (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate is added in homogenizer and mixed；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and alkali formula cupric phosphate are added to another
Mixed in platform homogenizer；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, 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 laser direct forming polyamide compoiste material of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned laser direct forming polyamide compoiste 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 (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate is added in homogenizer and mixed；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and alkali formula cupric phosphate are added to another
Mixed in platform homogenizer；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, 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 laser direct forming polyamide compoiste material of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned laser direct forming polyamide compoiste 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 (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate is added in homogenizer and mixed；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and alkali formula cupric phosphate are added to another
Mixed in platform homogenizer；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, 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 laser direct forming polyamide compoiste material of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned laser direct forming polyamide compoiste 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 (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate is added in homogenizer and mixed；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and alkali formula cupric phosphate are added to another
Mixed in platform homogenizer；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, 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 laser direct forming polyamide compoiste material of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned laser direct forming polyamide compoiste 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 (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate is added in homogenizer and mixed；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and alkali formula cupric phosphate are added to another
Mixed in platform homogenizer；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, 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 laser direct forming polyamide compoiste material of this comparative example, is prepared from by the following raw material：
The preparation method of above-mentioned laser direct forming polyamide compoiste 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 is added in homogenizer and mixed；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and alkali formula cupric phosphate are added to another
Mixed in platform homogenizer；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, 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 laser direct forming polyamide compoiste material of this comparative example, is prepared from by the following raw material：
The preparation method of above-mentioned laser direct forming polyamide compoiste 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) coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and alkali formula cupric phosphate are added to another
Mixed in platform homogenizer；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, 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 laser direct forming polyamide compoiste material of this comparative example, is prepared from by the following raw material：
The preparation method of above-mentioned laser direct forming polyamide compoiste 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 (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate is added in homogenizer and mixed；
(2) alkali-free glass fibre and alkali formula cupric phosphate are added in another homogenizer and are mixed；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, 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 laser direct forming polyamide compoiste material of this comparative example, is prepared from by the following raw material：
The preparation method of above-mentioned laser direct forming polyamide compoiste 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 (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate is added in homogenizer and mixed；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and alkali formula cupric phosphate are added to another
Mixed in platform homogenizer；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) is mixed to carry out melting extrusion, 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)：
The embodiment of table 1 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)：
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；
Plastic part surface coat of metal adhesive force tests (test of hundred lattice)：It is specific as follows by ASTM D3359 standard testings,
In 23 ± 2 DEG C of room temperature, under conditions of relative humidity 50 ± 5%, with sharp cutter (knife edge angle is 15 °~30 °) in test specimens
Draw 10 × 10 1mm × 1mm small grids, each line depth and coating bottom in product surface；Hairbrush cleans down test zone；With
3M600 adhesive tapes firmly cling tested small grid, and firmly wipe adhesive tape with erasing rubber, to increase adhesive tape with tested region
Contact area and dynamics；Adhesive tape one end is held, gummed paper is shut down rapidly with 60 ° of angles in vertical direction, same position carries out 2
Secondary same test.Result judgement：Require during adhesive force >=4B to be qualified；5B- scribing edges are smooth, in the edge of line and friendship
Without peeling paint at crunode；4B- has the peeling paint of small pieces, and the gross area that comes off less than 5% in the intersection of line；
3B- has a peeling paint of small pieces at the edge and intersection of line, and comes off the gross area between 5%~15%；2B- exists
There is a sheet of peeling paint at the edge and intersection of line, and comes off the gross area between 15%~35%；1B- is in line
Edge and intersection have a sheet of peeling paint, and come off the gross area between 35%~65%；0B- is on the side of line
Edge and intersection have sheet of peeling paint, and the gross area that comes off more than 65%.
The embodiment of table 2 and comparative example performance catalog
As can be seen that the addition of alkali-free glass fibre is more from embodiment 1~6, polyamide 10T/11 resin compoundeds
The tensile strength of material is bigger；The addition of aliphatic polyamide resin (polyhexamethylene adipamide resin) is more, polyamide
The melt index of 10T/11 resin composite materials is bigger, and processing characteristics is better；The water absorption rate change of each embodiment is little, while golden
Category coating adhesion is satisfied by requiring.Comprehensive factors above, the combination property of embodiment 6 is optimal.
It is compared with embodiment 6, comparative example 1 is to be not added with aliphatic polyamide resin (polyhexamethylene adipamide resin)
Polyamide 10T/11 resin composite materials, its melt index is only 6g/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
Example 3 is to be not added with the polyamide 10T/11 resin composite materials of coupling agent, alkali-free glass fibre, laser direct forming additive with
The above two polyamide compatibility is not good, so as to tensile property and metal-plated to polyamide 10T/11 resin composite materials
Layer adhesive force causes bad impact；The screw configuration of the parallel double-screw extruder of comparative example 4 is double thread, and screw rod is long
The ratio L/D of degree L and diameter D is 30, and the screw configuration of the parallel double-screw extruder of embodiment 6 is single thread, and screw rod is long
The ratio L/D of degree L and diameter D is 40, by contrast it is found that using the spiral shell of the parallel double-screw extruder described in embodiment 6
Bar parameter, the tensile property of the polyamide 10T/11 resin composite materials that it is prepared, processing characteristics, water absorbing properties and metal
Coating adhesion is greatly improved, and obtains environmental protection, high tensile, high fluidity, low water absorption and laser straight and is connected into
The beneficial effect of the polyamide 10T/11 resin composite materials of type.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed, but and
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that for one of ordinary skill in the art comes
Say, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (10)
1. a kind of laser direct forming polyamide compoiste 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 at least one in nylon 46 resin, polyhexamethylene adipamide resin；
The coupling agent be gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-γ-
Aminopropyl triethoxysilane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-aminopropyl
Methyl dimethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, anilinomethyl
At least one in triethoxysilane；
The length of the alkali-free glass fibre be 2~4mm, a diameter of 9~11 μm；
The laser direct forming additive is at least one in alkali formula cupric phosphate, cupric phosphate, copper sulfate.
2. laser direct forming polyamide compoiste material according to claim 1, it is characterised in that by following weight portion
Raw material is prepared from：
3. laser direct forming polyamide compoiste material according to claim 1 and 2, it is characterised in that the polyamide
The intrinsic viscosity of 10T/11 resins is 0.75~0.95dL/g；The aliphatic polyamide resin is polyhexamethylene adipamide tree
Fat, its intrinsic viscosity is 1.22~1.84dL/g.
4. laser direct forming polyamide compoiste material according to claim 1 and 2, it is characterised in that the coupling agent
For at least one in gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane；The laser direct forming adds
Plus agent is alkali formula cupric phosphate.
5. laser direct forming polyamide compoiste 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,
P-phthalic acid, 11- aminoundecanoic acids, the polyesteramide addition is the 1~8% of the gross weight of the monomer 1.
6. laser direct forming polyamide compoiste material according to claim 5, it is characterised in that 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 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 closed constant-speed heating of the stirring-type polymer reactor to 272~280 DEG C, adjust described in stir
The mixing speed for mixing formula polymer reactor is 30~50r/min, wherein, when the stirring-type polymer reactor temperature reaches 215
DEG C when, be deflated to 2.0MPa, and maintain pressure in 2.0MPa, after reaction 1~2 hour, normal pressure is deflated to, while being warming up to 310
After continuing to react 1~2 hour at~320 DEG C, constant temperature continued evacuation after 0.3~1 hour, obtained the polyamide 10T/11 trees
Fat；
The molecular weight regulator is addition is the gross weight of the monomer 1 0.1~3% benzoic acid；The antioxidant is
Addition is the N of the 0.1~0.3% of the gross weight of the monomer 1, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene
Diamides；Appropriate amount of water.
7. the preparation method of the laser direct forming polyamide compoiste material described in a kind of any one of claim 1-6, its feature
It is to 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 polyamide 10T/11 resins, aliphatic polyamide resin after cooling, 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 is added in homogenizer and mixed；
(2) coupling agent, alkali-free glass fibre and laser direct forming additive are added in another homogenizer
Mixed；
(3) the compound Jing feeders for mixing step (1) are added in parallel double-screw extruder, and are squeezed in parallel double-screw
Going out the mixture that the lateral addition step (2) of machine mixes carries out melting extrusion, and pelletize, technological parameter is 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
Left-hand thread area with more than 1.
10. preparation method according to claim 9, it is characterised in that the ratio L/D of the spiro rod length L and diameter D is 35
~45；The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611104604.6A CN106675012B (en) | 2016-12-05 | 2016-12-05 | Laser direct forming polyamide compoiste material and preparation method thereof |
Applications Claiming Priority (1)
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