CN108559256A - A kind of halogen-free flame-retardant polyamide resin combination and preparation method thereof - Google Patents
A kind of halogen-free flame-retardant polyamide resin combination and preparation method thereof Download PDFInfo
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- CN108559256A CN108559256A CN201810480297.4A CN201810480297A CN108559256A CN 108559256 A CN108559256 A CN 108559256A CN 201810480297 A CN201810480297 A CN 201810480297A CN 108559256 A CN108559256 A CN 108559256A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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 present invention relates to technical field of polymer materials, and in particular to a kind of halogen-free flame-retardant polyamide resin combination and preparation method thereof, which is prepared from the following materials：Polyamide, dissaving polymer, carbon fiber pipe, antioxidant, surface modifier, thixotropic agent, halogen-free flame retardants, fire retarding synergist；Wherein, the dissaving polymer is amine-terminated hyperbrancedization polyamide.The present invention is by using polyamide as resin matrix, coordinate a certain amount of dissaving polymer, carbon fiber pipe, halogen-free flame retardants, synergistic flame retardant, surface modifier and thixotropic agent, carbon fiber pipe, halogen-free flame retardants and synergistic flame retardant is set to be dispersed in polyamide, the halogen flame resistant polyamide resin composition of the present invention is made, with intensity height, good stability of the dimension, chemicals-resistant are good, superior electrical property, still keep outstanding physical property under the conditions of more severe temperature and humidity, there is high flame retardant simultaneously, reach UL94V0.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of halogen-free flame-retardant polyamide resin combination and its
Preparation method.
Background technology
Polyamide has excellent mechanical strength, heat resistance, chemical resistance, wear resistance and self lubricity,
And friction coefficient is low, includes electronic apparatus, automobile component, furniture, building materials and fiber, it has also become most important extensively using field
One of engineering plastics.
In general, flame-retardant additive used in existing daiamid composition be bromide fire retardant it is in the majority, bromide fire retardant because
Use is prohibited by numerous countries to be harmful to environment, the present invention is halogen-free flame-retardant polyamide resin combination, environmental protection
It is nontoxic.Object is closed for using red phosphorus or the polyamide of other inorganic fillers (such as magnesium hydroxide, hydrotalcite etc.) to hinder, is existed using red phosphorus
Will produce the noxious materials such as hydrogen phosphide in process and generate corrosiveness to electric equipment products can influence the service life of electricity consumption product,
And inorganic combustion inhibitor additive amount is big and not easy to be processed, and Amilan polyamide resin composition mechanical property can be caused not high.In the prior art,
Generally use fiber glass reinforced polyamide composition, the additive amount of general glass will reach 30% or more, and glass would generally when molding
Emerge influences appearance in product surface, in addition add glass fiber reinforced materials when, usual glass can when combinatorial injection molding is molded shape
Daiamid composition warpage, dimensional stability very sorrow are caused at orientation.
Invention content
In order to overcome shortcoming and defect existing in the prior art, it is poly- that the purpose of the present invention is to provide a kind of halogen-free flameproofs
Amide resin composition, with intensity height, good stability of the dimension, chemicals-resistant be good, superior electrical property, in more severe temperature and
Outstanding physical property is still kept under damp condition, while there is high flame retardant.
Another object of the present invention, which is taken notice of, provides a kind of preparation method of halogen-free flame-retardant polyamide resin combination, by adopting
With specific processing step and technological parameter, it is made that intensity height of the present invention, good stability of the dimension, chemicals-resistant is good, electrical property is excellent
More, outstanding physical property is still kept under the conditions of more severe temperature and humidity, while there is the Halogen of high flame retardant to hinder
Retardant polyamide resin composition.
The purpose of the invention is achieved by the following technical solution：A kind of halogen-free flame-retardant polyamide resin combination, by following
Raw material is prepared：
Wherein, the dissaving polymer is amine-terminated hyperbrancedization polyamide.
The polyamide of the present invention is used as resin matrix, with excellent mechanical strength, heat resistance, chemical resistance, resistance to
Abrasiveness and self lubricity, and friction coefficient is low；Dissaving polymer has three-dimensional structure, and molecular structure is more regular, phase
It is very narrow to molecular vibrational temperature, by adding a certain amount of dissaving polymer in polyamide, polyamide can be significantly reduced
Effective melt viscosity, and reduce processing temperature, improve the apparent property of Maranyl, and polyamide can be improved
Yield strength, stretch modulus, Notched Izod Impact Strength and bending strength, and then mechanical performance and processing performance are improved,
Meanwhile the dissaving polymer of selection is amine-terminated hyperbrancedization polyamide, contains a large amount of active function groups so that the carbon of addition
The dispersion and dipping of fibre pipe and halogen-free flame retardants and fire retarding synergist in polyamide substrate, increase carbon fiber pipe, Halogen
The compatibility of fire retardant and fire retarding synergist and polyamide matrix.
Carbon fiber pipe is seamless, the middle empty nanotube for having graphene sheet layer to crimp, and is typical monodimension nanometer material, has
The features such as density is small, intensity is high, good toughness, electrical and thermal conductivity performance are good, but since its large specific surface area, surface energy are done, have
Serious agglomeration, surface treated are unable to reach evenly dispersed effect, and if carbon fiber pipe not can be uniformly dispersed in
The effect of enhancing is not had in polymer then, therefore the present invention realizes carbon fiber by using surface modifier and dissaving polymer
It is fully dispersed in nylon resin to tie up pipe.
The halogen-free flame-retardant polyamide resin combination of the present invention, by using polyamide as resin matrix, cooperation is certain
Dissaving polymer, carbon fiber pipe, halogen-free flame retardants, synergistic flame retardant, surface modifier and the thixotropic agent of amount, make carbon fiber
Pipe, halogen-free flame retardants and synergistic flame retardant are dispersed in polyamide, and the halogen flame resistant polyamide resin combination of the present invention is made
Object, have good intensity height, good stability of the dimension, chemicals-resistant, superior electrical property, under the conditions of more severe temperature and humidity according to
Outstanding physical property is so kept, while there is high flame retardant, reaches UL94V0 (0.8mm).
Preferably, the polyamide is PA6/PA66/PA6T ternary polymerization materials, and the PA6/PA66/PA6T ternarys are total
Poly- material by caprolactam, adipic acid hexamethylene diamine salt and to benzoyl hexamethylene diamine melting copolymerization be made, wherein caprolactam, oneself
Diacid hexamethylene diamine salt and be 5-7 to the mass ratio of benzoyl hexamethylene diamine：2-4:1.
The present invention has that water imbibition is small, melt fluidity is big, power by selecting PA6/PA66/PA6T ternary polymerization materials
The effect of function admirable is learned, specific PA66's has good impact resistance and high intensity, can effectively make up the punching of PA6 notches
The problem of hit intensity difference, PA6T have the water imbibition told somebody what one's real intentions are and good melt fluidity, can effectively make up PA6 and PA66 by
The case where leading to product expansion, deformation in water suction, lead to mechanical characteristic reduction, change in size, the present invention is by rationally coordinating
The polymerized monomer of PA6, PA66 and PA6T so that PA6/PA66/PA6T ternary polymerization material melting points are low, and flexible bigger is conducive to
The movement and swing of molecule or segment, simultaneously because reducing the regularity of strand so that the crystallinity of polymer and crystallization
Rate reduces, and improves melt fluidity, reduces water imbibition, improves the mechanical stability of product.
Preferably, the carbon fiber pipe is modified multi wall carbon fiber pipe, the multi wall carbon fiber pipe caliber be 15-40nm,
Length is 0.2-2 μm, and specific modification procedure is：After multi wall carbon fiber pipe is passivated processing with the concentrated sulfuric acid, shone in gamma-rays
Penetrate it is lower tarine is grafted to multi wall carbon fiber pipe surface, obtain modified multi wall carbon fiber pipe.
The present invention is by selecting modified carbon fiber pipe so that the compatibility of carbon fiber pipe and polyamide is more preferable, greatly improves
The comprehensive performance of the halogen-free flame-retardant polyamide resin combination of the present invention, specific concentrated sulfuric acid passivation can open what is said or talked about nanotube
Port is formed it into the hydroxyl or carboxyl of activation, is then generated free radicals using radiation condition, and then causes tarine list
The polymerisation of body improves grafting rate, in addition, skeleton of the carbon fiber pipe as composition, close by the raw material components of composition
Be combined together, play a good role to the structural stability of composition.
Preferably, the amine-terminated hyperbrancedization polyamide is reacted using amine monomers and esters monomer and is made in methyl alcohol, institute
State amine monomers, the molar ratio of esters monomer is 1:2-4.5, the quality of the gross mass and methanol of the amine monomers and esters monomer it
Than being 1:2.5-9, the amine monomers are polyamino amine, and the polyamino amine is ammonia, ethylenediamine, hexamethylene diamine, diethylenetriamines
One or more of, the esters monomer is methyl acrylate and/or methyl methacrylate.
The present invention is by selecting the above amine-terminated hyperbrancedization polyamide, this ultrabranching polyamide molecule outer layer to contain largely
Active function groups, and melt viscosity is told somebody what one's real intentions are, and is added in polyamide, and effective melt of polyamide can be significantly reduced
Viscosity reduces processing temperature and thermal degradation, and can further increase carbon fiber pipe, halogen-free flame retardants and synergistic flame retardant with
The compatibility of polyamide, makes them be dispersed in polyamide, further increases the mechanical property and flame retardant property of the present invention.
Preferably, the halogen-free flame retardants is liquid phosphonium flame retardant, and the liquid phosphonium flame retardant is phosphate trimethylbenzene
Ester, phosphate toluene diphenyl ester, tricresyl phosphate (dimethylbenzene) ester, bisphenol-A-bis- (diphenyl phosphoesters) and the bis- (diphenyl of resorcinol
Phosphate) one or more；The fire retarding synergist is melamine salt, phosphazene compound, boehmite, oxalic acid aluminium, zeolite
One or more of molecular sieve, organic nano imvite, anhydrous zinc borate.
The present invention does not contain halogen by using the above liquid phosphonium flame retardant, has better flame retarding efficiency, and hold
Easily adhere to the surface of polyamide, realizes the flame-retardant modified of polyamide, while by the adjustment effect of ultrabranching polyamide, making liquid
The compatibility of state phosphonium flame retardant and polyamide is more preferable so that liquid phosphonium flame retardant is evenly distributed in polyamide.The present invention
By using the above fire retarding synergist, coordinate liquid phosphonium flame retardant, there is better flame retardant effect.More preferably, liquid
It according to mass ratio is 2-3 that phosphonium flame retardant, which is tricresyl phosphate and bisphenol-A-bis- (diphenyl phosphoesters),:1 compounds, resistance
Combustion synergist is one or more combinations in phosphazene compound, zeolite molecular sieve, anhydrous zinc borate, more preferably, fire-retardant
It according to mass ratio is 1 that synergist, which is phosphazene compound, zeolite molecular sieve, anhydrous zinc borate,:2-3:0.8-1 is compounded, liquid
The mass ratio of phosphonium flame retardant and fire retarding synergist is preferably 8-12:1, phosphazene compound will not cause the deterioration of physical property and
It can play the role of toughening, zeolite molecular sieve has suction-operated, the gas and injection moulding process that absorbable composition burning generates
Middle absorption small-molecule substance, play the role of reduce mold deposit, anhydrous zinc borate specific surface area is small, be it is nontoxic, tasteless, corrosion-free and
Irritating inorganic combustion inhibitor, can it is fire-retardant and eliminate smoke, go out electric arc.
Preferably, the antioxidant is Hinered phenols antioxidant and/or phosphite ester kind antioxidant；The thixotropic agent is gas
One or more of aerosil, blanc fixe, polyamide wax and anti-sagging agent；The surface modifier is that silane is even
Join agent and/or surfactant；The silane coupling agent is gamma-aminopropyl-triethoxy-silane, γ-(the third oxygen of 2,3- epoxies) third
The one or more of base trimethoxy silane and γ-methacryloxypropyl trimethoxy silane；The surfactant
According to mass ratio it is 1 for nonionic surface active agent and anionic surfactant:8-10 is compounded.
The present invention is used to improve the sintering character of PA6/PA66/PA6T ternary polymerization materials by using the above antioxidant,
It is anti-oxidant to carry, whole part performance is improved, and can delay or inhibit the progress of material oxidation process to prevent to make
The aging of part simultaneously extends its service life, and the specific antioxidant is that Hinered phenols antioxidant and phosphite ester kind antioxidant are pressed
It is 2-3 according to mass ratio：1 compounds, the preferred antioxidant 1010 of the Hinered phenols antioxidant, antioxidant 1098, phosphite ester
The preferred irgasfos 168 of kind antioxidant, antioxidant 2921；The present invention by using the above thixotropic agent increase polyamide melting when
Mobility, the more preferably described thixotropic agent are Degussa A200, A300, moral mountain QS-30, Cabot LM-150, intelligent space LA-
One or more of 150；The present invention handles liquid phosphonium flame retardant and carbon fiber pipe by using the above silane coupling agent,
Make carbon fiber pipe be easy to be combined with polyamide so that liquid phosphonium flame retardant is easy effectively to adhere in polyamide surface, and uniformly divides
It dissipates, realize reinforced polyamide anti-flammability and enhances the purpose of performance；The present invention is by selecting the above surfactant that can improve
The dispersion effect of carbon fiber pipe and liquid phosphonium flame retardant in the solution, increases its resting period, convenient for subsequent step when long
Between operate under, carbon fiber pipe and liquid phosphonium flame retardant still can disperse in organic solvent, contain convenient for carbon fiber pipe and liquid
Phosphorus fire retardant is dispersed in polyamide；The more preferably described anion surfactant is neopelex,
The nonionic surfactant is polyoxyethylene nonylphenol ether, and the surface modifier of the specific present invention is silane coupling agent and surface-active
Agent is 1 according to mass ratio:2-3 is compounded.
Another object of the present invention is achieved through the following technical solutions：A kind of system of halogen-free flame-retardant polyamide resin combination
Preparation Method includes the following steps：
(1) surface modifier of carbon fiber pipe and 2/3rds mass is added in organic solvent, and at 50-65 DEG C
At a temperature of carry out ultrasonic disperse 6-8h, obtain carbon fiber pipe dispersion liquid；
(2) the carbon fiber pipe dispersion liquid of the step (1) is added in polyamide and antioxidant, and added a certain amount of organic
Solvent is warming up to 150-180 DEG C under conditions of 0-20MPa pressure, is stirred to react 60-120min under inert gas protection,
Mixing speed is 700-900r/min, is cooled to room temperature after reaction, isolates solid product, and reinforced polyamide is made；
(3) dissaving polymer of half quality and the reinforced polyamide of step (2) are uniformly mixed, extruding pelletization；
(4) halogen-free flame retardants and fire retarding synergist are scattered in 70-100 DEG C of water, and residual surface modifying agent are added,
Stirring, obtains halogen-free flameproof liquid；
(5) product of the step (3) is immersed in 10-30min in the halogen-free flameproof liquid of the step (4), then existed
It is dried at a temperature of 80-120 DEG C, obtains once impregnating halogen-free flame-retardant polyamide；
(6) the primary immersion halogen-free anti-inflaming polyurethane in the step (5) is uniformly mixed with remaining dissaving polymer,
Extruding pelletization；
(7) product of the step (6) is immersed in 10-30min in the halogen-free flameproof liquid of the step (4), then existed
It is dried at a temperature of 80-120 DEG C, obtains secondary immersion halogen-free flame-retardant polyamide；
(8) by thixotropic agent and secondary immersion halogen-free flame-retardant polyamide extruding pelletization, the halogen-free flame-retardant polyamide tree is obtained
Oil/fat composition.
In the step (1) of the present invention, first carbon fiber pipe under the action of surface modifier and is ultrasonically treated and is made
Its is evenly dispersed in organic solvent, then in step (2), polyamide is added into carbon fiber pipe dispersion also, is precipitated
Method prepares reinforced polyamide, and then polyamide is coated on carbon fiber pipe surface during crystallizing precipitation, realizes carbon fiber pipe
It is evenly dispersed in polyamide, so that the performance of polyamide is enhanced, when 150-180 DEG C of selection can be too low to avoid temperature
Polyamides amine solvent is insufficient, and temperature is excessively high to cause polyamide oxidation to influence its performance；By portion in the step (3) of the present invention
Dissaving polymer is divided to be granulated with reinforced polyamide technology, dissaving polymer has a large amount of active function groups, then step (4)
(5) it in, will be immersed in halogen-free flameproof liquid through the modified polyamide of dissaving polymer so that halogen-free flameproof also can be more preferable
Be adsorbed on polyamide surface, be granulated using in step (6), so that halogen-free flame retardants is dispersed in polyamide, step (7)
It repeats to impregnate, increases the utilization rate of approximately fire retardant, finally carry out an extruding pelletization again, obtain the halogen-free flameproof of the present invention
Amilan polyamide resin composition.
Preferably, in the step (1), it according to volume ratio is 6-8 that the organic solvent, which is methanol, ethyl alcohol and acetone,:1-
3:1 compounds；The gross mass of organic solvent and the mass ratio of the polyamide are 5- in the step (1) and step (2)
20:1；The rate of temperature fall for being cooled to room temperature of the step (2) is 2-3 DEG C/5min, mixing speed 500-600r/min.
Preferably, first the reinforced polyamide of the dissaving polymer of half quality and step (2) is existed in the step (3)
It is uniformly mixed again after 5-7h is dried in a vacuum at 30-40 DEG C, mixing velocity 1000-1200r/min, incorporation time is
5-8min is squeezed out using double screw extruder, and double screw extruder has 6 temperature control areas, the temperature of each temperature control area to be
160-180 DEG C, head temperature is 160-180 DEG C；In the step (6), halogen-free anti-inflaming polyurethane and residue first will be once impregnated
Dissaving polymer is dried in a vacuum after 5-7h at 30-40 DEG C and is uniformly mixed again, mixing velocity 1000-1200r/
Min, incorporation time 5-8min, is squeezed out using double screw extruder, and double screw extruder has 6 temperature control areas, each temperature control
The temperature in area is 160-180 DEG C, and head temperature is 160-180 DEG C.
In the present invention, it is 160-180 DEG C by the control of the extrusion temperature of step (3) and step (6), that is, can guarantee that polyamide fills
Divide melting, and temperature can be prevented excessively high, causes polyamide to be aoxidized, influence its performance.
Preferably, it in the step (8), is squeezed out using double screw extruder, screw diameter 65mm, the draw ratio of screw rod
It is 40:1, double screw extruder has 6 temperature control areas, the first 140-160 DEG C of area, the second 230-240 DEG C of area, third area 250-260
DEG C, the 4th 260-270 DEG C of area, the 5th 270-280 DEG C of area, the 6th 250-270 DEG C of area, 265-275 DEG C of head temperature.
The preparation method of the present invention can be uniform by carbon fiber pipe by using specific processing step and technological parameter
It is dispersed in polyamide, and will approximately fire retardant preferably be mixed with polyamide, other than the sub- polyamide surface of absorption, also
It can penetrate into polyamide, greatly enhance the intensity and anti-flammability for polyamide.
The beneficial effects of the present invention are：The halogen-free flame-retardant polyamide resin combination of the present invention, by using polyamide
As resin matrix, a certain amount of dissaving polymer, carbon fiber pipe, halogen-free flame retardants, synergistic flame retardant, surface is coordinated to be modified
Agent and thixotropic agent make carbon fiber pipe, halogen-free flame retardants and synergistic flame retardant be dispersed in polyamide, and the halogen of the present invention is made
Flame resistant polyamide resin composition has good intensity height, good stability of the dimension, chemicals-resistant, superior electrical property, more severe
Outstanding physical property is still kept under the conditions of temperature and humidity, while there is high flame retardant, reaches UL94V0 (0.8mm).
The polyamide of the present invention is used as resin matrix, with excellent mechanical strength, heat resistance, chemical resistance, resistance to
Abrasiveness and self lubricity, and friction coefficient is low；Dissaving polymer has three-dimensional structure, and molecular structure is more regular, phase
It is very narrow to molecular vibrational temperature, by adding a certain amount of dissaving polymer in polyamide, polyamide can be significantly reduced
Effective melt viscosity, and reduce processing temperature, improve the apparent property of Maranyl, and polyamide can be improved
Yield strength, stretch modulus, Notched Izod Impact Strength and bending strength, and then mechanical performance and processing performance are improved,
Meanwhile the dissaving polymer of selection is amine-terminated hyperbrancedization polyamide, contains a large amount of active function groups so that the carbon of addition
The dispersion and dipping of fibre pipe and halogen-free flame retardants and fire retarding synergist in polyamide substrate, increase carbon fiber pipe, Halogen
The compatibility of fire retardant and fire retarding synergist and polyamide matrix.
The preparation method of the present invention can be uniform by carbon fiber pipe by using specific processing step and technological parameter
It is dispersed in polyamide, and will approximately fire retardant preferably be mixed with polyamide, other than being adsorbed on polyamide surface, moreover it is possible to
It penetrates into polyamide, greatly enhances the intensity and anti-flammability for polyamide.
Specific implementation mode
For the ease of the understanding of those skilled in the art, with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of halogen-free flame-retardant polyamide resin combination, is prepared from the following materials：
Wherein, the dissaving polymer is amine-terminated hyperbrancedization polyamide.
The polyamide is PA6/PA66/PA6T ternary polymerization materials, and the PA6/PA66/PA6T ternary polymerizations material is logical
Cross caprolactam, adipic acid hexamethylene diamine salt and to benzoyl hexamethylene diamine melting copolymerization be made, wherein caprolactam, adipic acid oneself two
Amine salt and be 5 to the mass ratio of benzoyl hexamethylene diamine：2:1.
The carbon fiber pipe is modified multi wall carbon fiber pipe, and the multi wall carbon fiber pipe caliber is 15-40nm, length is
0.2-2 μm, specific modification procedure is：It, will under gamma-rays irradiation after multi wall carbon fiber pipe is passivated processing with the concentrated sulfuric acid
Tarine is grafted to multi wall carbon fiber pipe surface, obtains modified multi wall carbon fiber pipe.
The amine-terminated hyperbrancedization polyamide is reacted in methyl alcohol using amine monomers and esters monomer to be made, the amine list
Body, esters monomer molar ratio be 1:2, the mass ratio of the gross mass and methanol of the amine monomers and esters monomer is 1:2.5
The amine monomers are polyamino amine, and the polyamino amine is ethylenediamine, and the esters monomer is methyl acrylate.
The halogen-free flame retardants is liquid phosphonium flame retardant, and the liquid phosphonium flame retardant is tricresyl phosphate；It is described
Fire retarding synergist is melamine salt.
The antioxidant is Hinered phenols antioxidant；The thixotropic agent is aerosil；The surface modifier is
Silane coupling agent and surfactant；The silane coupling agent is gamma-aminopropyl-triethoxy-silane；The surfactant is
Nonionic surface active agent and anionic surfactant are 1 according to mass ratio:8 compound.
The preparation method of the halogen-free flame-retardant polyamide resin combination, includes the following steps：
(1) surface modifier of carbon fiber pipe and 2/3rds mass is added in organic solvent, and in 50 DEG C of temperature
Degree is lower to carry out ultrasonic disperse 8h, obtains carbon fiber pipe dispersion liquid；
(2) the carbon fiber pipe dispersion liquid of the step (1) is added in polyamide and antioxidant, and added a certain amount of organic
Solvent is warming up to 150 DEG C under conditions of 0MPa pressure, is stirred to react 60min, mixing speed is under inert gas protection
900r/min is cooled to room temperature after reaction, isolates solid product, and reinforced polyamide is made；
(3) dissaving polymer of half quality and the reinforced polyamide of step (2) are uniformly mixed, extruding pelletization；
(4) halogen-free flame retardants and fire retarding synergist are scattered in 70 DEG C of water, obtain halogen-free flameproof liquid；
(5) product of residual surface modifying agent and the step (3) is immersed in the halogen-free flameproof liquid of the step (4)
Then 30min is dried at a temperature of 80 DEG C, obtain once impregnating halogen-free flame-retardant polyamide；
(6) the primary immersion halogen-free anti-inflaming polyurethane in the step (5) is uniformly mixed with remaining dissaving polymer,
Extruding pelletization；
(7) product of the step (6) is immersed in 30min in the halogen-free flameproof liquid of the step (4), then at 80 DEG C
At a temperature of dry, obtain secondary immersion halogen-free flame-retardant polyamide；
(8) by thixotropic agent and secondary immersion halogen-free flame-retardant polyamide extruding pelletization, the halogen-free flame-retardant polyamide tree is obtained
Oil/fat composition.
In the step (1), it according to volume ratio is 6 that the organic solvent, which is methanol, ethyl alcohol and acetone,:1:1 compounds；
The gross mass of organic solvent and the mass ratio of the polyamide are 5 in the step (1) and step (2):1；The step (2)
The rate of temperature fall for being cooled to room temperature be 2 DEG C/5min, mixing speed 600r/min.
First by the dissaving polymer of half quality and the reinforced polyamide of step (2) at 30 DEG C in the step (3)
It is uniformly mixed again after 7h is dried in a vacuum, mixing velocity 1000r/min, incorporation time 8min uses twin-screw
Extruder is squeezed out, and double screw extruder has 6 temperature control areas, and the temperature of each temperature control area is 160 DEG C, and head temperature is
160℃；In the step (6), first will once impregnate halogen-free anti-inflaming polyurethane with remaining dissaving polymer at 30 DEG C true
It is uniformly mixed again after aerial dry 7h, mixing velocity 1000r/min, incorporation time 5-8min are squeezed using twin-screw
Go out machine to be squeezed out, double screw extruder there are 6 temperature control areas, and the temperature of each temperature control area is 160 DEG C, and head temperature is 160 DEG C.
It in the step (8), is squeezed out using double screw extruder, screw diameter 65mm, the draw ratio of screw rod is 40:1,
Double screw extruder has 6 temperature control areas, the first 140 DEG C of area, the second 230 DEG C of area, 250 DEG C of third area, the 4th 260 DEG C of area, and the 5th
270 DEG C of area, the 6th 250 DEG C of area, 265 DEG C of head temperature.
Embodiment 2
A kind of halogen-free flame-retardant polyamide resin combination, is prepared from the following materials：
Wherein, the dissaving polymer is amine-terminated hyperbrancedization polyamide.
The polyamide is PA6/PA66/PA6T ternary polymerization materials, and the PA6/PA66/PA6T ternary polymerizations material is logical
Cross caprolactam, adipic acid hexamethylene diamine salt and to benzoyl hexamethylene diamine melting copolymerization be made, wherein caprolactam, adipic acid oneself two
Amine salt and be 7 to the mass ratio of benzoyl hexamethylene diamine：4:1.
The carbon fiber pipe is modified multi wall carbon fiber pipe, and the multi wall carbon fiber pipe caliber is 15-40nm, length is
0.2-2 μm, specific modification procedure is：It, will under gamma-rays irradiation after multi wall carbon fiber pipe is passivated processing with the concentrated sulfuric acid
Tarine is grafted to multi wall carbon fiber pipe surface, obtains modified multi wall carbon fiber pipe.
The amine-terminated hyperbrancedization polyamide is reacted in methyl alcohol using amine monomers and esters monomer to be made, the amine list
Body, esters monomer molar ratio be 1:4.5, the mass ratio of the gross mass and methanol of the amine monomers and esters monomer is 1:9,
The amine monomers are polyamino amine, and the polyamino amine is hexamethylene diamine, and the esters monomer is methyl methacrylate.
The halogen-free flame retardants is liquid phosphonium flame retardant, and the liquid phosphonium flame retardant is the bis- (diphenylphosphines of bisphenol-A-
Acid esters)；The fire retarding synergist is zeolite molecular sieve.
The antioxidant is phosphite ester kind antioxidant；The thixotropic agent is blanc fixe；The surface modifier is
Surfactant；The surfactant is nonionic surface active agent and anionic surfactant is according to mass ratio
1:9 compound.
The preparation method of the halogen-free flame-retardant polyamide resin combination, includes the following steps：
(1) surface modifier of carbon fiber pipe and 2/3rds mass is added in organic solvent, and in 65 DEG C of temperature
Degree is lower to carry out ultrasonic disperse 6h, obtains carbon fiber pipe dispersion liquid；
(2) the carbon fiber pipe dispersion liquid of the step (1) is added in polyamide and antioxidant, and added a certain amount of organic
Solvent is warming up to 180 DEG C under conditions of 20MPa pressure, is stirred to react 60min, mixing speed is under inert gas protection
900r/min is cooled to room temperature after reaction, isolates solid product, and reinforced polyamide is made；
(3) dissaving polymer of half quality and the reinforced polyamide of step (2) are uniformly mixed, extruding pelletization；
(4) halogen-free flame retardants and fire retarding synergist are scattered in 100 DEG C of water, obtain halogen-free flameproof liquid；
(5) product of residual surface modifying agent and the step (3) is immersed in the halogen-free flameproof liquid of the step (4)
Then 10min is dried at a temperature of 120 DEG C, obtain once impregnating halogen-free flame-retardant polyamide；
(6) the primary immersion halogen-free anti-inflaming polyurethane in the step (5) is uniformly mixed with remaining dissaving polymer,
Extruding pelletization；
(7) product of the step (6) is immersed in 10min in the halogen-free flameproof liquid of the step (4), then 120
It is dried at a temperature of DEG C, obtains secondary immersion halogen-free flame-retardant polyamide；
(8) by thixotropic agent and secondary immersion halogen-free flame-retardant polyamide extruding pelletization, the halogen-free flame-retardant polyamide tree is obtained
Oil/fat composition.
Preferably, in the step (1), it according to volume ratio is 8 that the organic solvent, which is methanol, ethyl alcohol and acetone,:3:1 is multiple
With into；The gross mass of organic solvent and the mass ratio of the polyamide are 20 in the step (1) and step (2):1；Institute
The rate of temperature fall for being cooled to room temperature for stating step (2) is 3 DEG C/5min, mixing speed 600r/min.
First by the dissaving polymer of half quality and the reinforced polyamide of step (2) at 40 DEG C in the step (3)
It is uniformly mixed again after 5h is dried in a vacuum, mixing velocity 1200r/min, incorporation time 5min uses twin-screw
Extruder is squeezed out, and double screw extruder has 6 temperature control areas, and the temperature of each temperature control area is 180 DEG C, and head temperature is
180℃；In the step (6), first will once impregnate halogen-free anti-inflaming polyurethane with remaining dissaving polymer at 40 DEG C true
It is uniformly mixed again after aerial dry 5h, mixing velocity 1200r/min, incorporation time 5min use twin-screw extrusion
Machine is squeezed out, and double screw extruder has 6 temperature control areas, and the temperature of each temperature control area is 180 DEG C, and head temperature is 180 DEG C.
It in the step (8), is squeezed out using double screw extruder, screw diameter 65mm, the draw ratio of screw rod is 40:1,
Double screw extruder has 6 temperature control areas, the first 160 DEG C of area, the second 240 DEG C of area, 260 DEG C of third area, the 4th 270 DEG C of area, and the 5th
280 DEG C of area, the 6th 270 DEG C of area, 275 DEG C of head temperature.
Embodiment 3
A kind of halogen-free flame-retardant polyamide resin combination, is prepared from the following materials：
Wherein, the dissaving polymer is amine-terminated hyperbrancedization polyamide.
The polyamide is PA6/PA66/PA6T ternary polymerization materials, and the PA6/PA66/PA6T ternary polymerizations material is logical
Cross caprolactam, adipic acid hexamethylene diamine salt and to benzoyl hexamethylene diamine melting copolymerization be made, wherein caprolactam, adipic acid oneself two
Amine salt and be 6 to the mass ratio of benzoyl hexamethylene diamine：3:1.
The carbon fiber pipe is modified multi wall carbon fiber pipe, and the multi wall carbon fiber pipe caliber is 15-40nm, length is
0.2-2 μm, specific modification procedure is：It, will under gamma-rays irradiation after multi wall carbon fiber pipe is passivated processing with the concentrated sulfuric acid
Tarine is grafted to multi wall carbon fiber pipe surface, obtains modified multi wall carbon fiber pipe.
The amine-terminated hyperbrancedization polyamide is reacted in methyl alcohol using amine monomers and esters monomer to be made, the amine list
Body, esters monomer molar ratio be 1:3, the mass ratio of the gross mass and methanol of the amine monomers and esters monomer is 1:4, institute
It is polyamino amine to state amine monomers, and the polyamino amine is diethylenetriamines, and the esters monomer is methyl acrylate.
It is liquid phosphonium flame retardant to state halogen-free flame retardants, and the liquid phosphonium flame retardant is tricresyl phosphate, phosphoric acid first
Benzene diphenyl ester, tricresyl phosphate (dimethylbenzene) ester (TXP) are 1 according to mass ratio:1:1 compounds；The fire retarding synergist is trimerization
Cyanamide salt, zeolite molecular sieve are 1 according to mass ratio:2 compound.
It according to mass ratio is 2 that the antioxidant, which is Hinered phenols antioxidant and phosphite ester kind antioxidant,:1 compounds；
The thixotropic agent is polyamide wax；The surface modifier is silane coupling agent；The silane coupling agent is three second of γ-aminopropyl
Oxysilane, γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy silicanes and γ-methacryloxypropyl trimethoxy silane
It is 1 according to mass ratio:1:1 compounds.
The preparation method of the halogen-free flame-retardant polyamide resin combination, includes the following steps：
(1) surface modifier of carbon fiber pipe and 2/3rds mass is added in organic solvent, and in 55 DEG C of temperature
Degree is lower to carry out ultrasonic disperse 7h, obtains carbon fiber pipe dispersion liquid；
(2) the carbon fiber pipe dispersion liquid of the step (1) is added in polyamide and antioxidant, and added a certain amount of organic
Solvent is warming up to 160 DEG C under conditions of 10MPa pressure, is stirred to react 80min, mixing speed is under inert gas protection
700-900r/min is cooled to room temperature after reaction, isolates solid product, and reinforced polyamide is made；
(3) dissaving polymer of half quality and the reinforced polyamide of step (2) are uniformly mixed, extruding pelletization；
(4) halogen-free flame retardants and fire retarding synergist are scattered in 80 DEG C of water, obtain halogen-free flameproof liquid；
(5) product of residual surface modifying agent and the step (3) is immersed in the halogen-free flameproof liquid of the step (4)
Then 20min is dried at a temperature of 100 DEG C, obtain once impregnating halogen-free flame-retardant polyamide；
(6) the primary immersion halogen-free anti-inflaming polyurethane in the step (5) is uniformly mixed with remaining dissaving polymer,
Extruding pelletization；
(7) product of the step (6) is immersed in 15min in the halogen-free flameproof liquid of the step (4), then 100
It is dried at a temperature of DEG C, obtains secondary immersion halogen-free flame-retardant polyamide；
(8) by thixotropic agent and secondary immersion halogen-free flame-retardant polyamide extruding pelletization, the halogen-free flame-retardant polyamide tree is obtained
Oil/fat composition.
In the step (1), it according to volume ratio is 7 that the organic solvent, which is methanol, ethyl alcohol and acetone,:2:1 compounds；
The gross mass of organic solvent and the mass ratio of the polyamide are 10 in the step (1) and step (2):1；The step
(2) the rate of temperature fall for being cooled to room temperature is 2 DEG C/5min, mixing speed 550r/min.
First by the dissaving polymer of half quality and the reinforced polyamide of step (2) at 35 DEG C in the step (3)
It is uniformly mixed again after 6h is dried in a vacuum, mixing velocity 1050r/min, incorporation time 6min uses twin-screw
Extruder is squeezed out, and double screw extruder has 6 temperature control areas, and the temperature of each temperature control area is 170 DEG C, and head temperature is
160℃；In the step (6), first will once impregnate halogen-free anti-inflaming polyurethane with remaining dissaving polymer at 35 DEG C true
It is uniformly mixed again after aerial dry 6h, mixing velocity 1050r/min, incorporation time 5-8min are squeezed using twin-screw
Go out machine to be squeezed out, double screw extruder there are 6 temperature control areas, and the temperature of each temperature control area is 170 DEG C, and head temperature is 170 DEG C.
It in the step (8), is squeezed out using double screw extruder, screw diameter 65mm, the draw ratio of screw rod is 40:1,
Double screw extruder has 6 temperature control areas, the first 150 DEG C of area, the second 235 DEG C of area, 255 DEG C of third area, the 4th 265 DEG C of area, and the 5th
275 DEG C of area, the 6th 265 DEG C of area, 270 DEG C of head temperature.
Embodiment 4
A kind of halogen-free flame-retardant polyamide resin combination, is prepared from the following materials：
Wherein, the dissaving polymer is amine-terminated hyperbrancedization polyamide.
The polyamide is PA6/PA66/PA6T ternary polymerization materials, and the PA6/PA66/PA6T ternary polymerizations material is logical
Cross caprolactam, adipic acid hexamethylene diamine salt and to benzoyl hexamethylene diamine melting copolymerization be made, wherein caprolactam, adipic acid oneself two
Amine salt and be 5 to the mass ratio of benzoyl hexamethylene diamine：3:1.
The carbon fiber pipe is modified multi wall carbon fiber pipe, and the multi wall carbon fiber pipe caliber is 15-40nm, length is
0.2-2 μm, specific modification procedure is：It, will under gamma-rays irradiation after multi wall carbon fiber pipe is passivated processing with the concentrated sulfuric acid
Tarine is grafted to multi wall carbon fiber pipe surface, obtains modified multi wall carbon fiber pipe.
The amine-terminated hyperbrancedization polyamide is reacted in methyl alcohol using amine monomers and esters monomer to be made, the amine list
Body, esters monomer molar ratio be 1:4, the mass ratio of the gross mass and methanol of the amine monomers and esters monomer is 1:6, institute
It is polyamino amine to state amine monomers, and the polyamino amine is ethylenediamine and hexamethylene diamine according to molar ratio 1:1 compounds, the esters
Monomer is methyl acrylate.
The halogen-free flame retardants is liquid phosphonium flame retardant, and the liquid phosphonium flame retardant is tricresyl phosphate, bis-phenol
A- bis- (diphenyl phosphoesters) and resorcinol bis- (diphenyl phosphoesters) are 2 according to quality:2：1 compounds；The resistance
It according to mass ratio is 3 that combustion synergist, which is zeolite molecular sieve and organic nano imvite,:2 compound.
It according to mass ratio is 3 that the antioxidant, which is Hinered phenols antioxidant and phosphite ester kind antioxidant,:1 compounds；
The thixotropic agent is aerosil, blanc fixe, polyamide wax and is 3 according to mass ratio:1:2 compound；It is described
Surface modifier is silane coupling agent and surfactant；The silane coupling agent is γ-(the third oxygen of 2,3- epoxies) propyl front three
Oxysilane；It according to mass ratio is 1 that the surfactant, which is nonionic surface active agent and anionic surfactant,:
10 compound.
The preparation method of the halogen-free flame-retardant polyamide resin combination, includes the following steps：
(1) surface modifier of carbon fiber pipe and 2/3rds mass is added in organic solvent, and in 60 DEG C of temperature
Degree is lower to carry out ultrasonic disperse 7h, obtains carbon fiber pipe dispersion liquid；
(2) the carbon fiber pipe dispersion liquid of the step (1) is added in polyamide and antioxidant, and added a certain amount of organic
Solvent is warming up to 160 DEG C under conditions of 5MPa pressure, is stirred to react 100min, mixing speed is under inert gas protection
800r/min is cooled to room temperature after reaction, isolates solid product, and reinforced polyamide is made；
(3) dissaving polymer of half quality and the reinforced polyamide of step (2) are uniformly mixed, extruding pelletization；
(4) halogen-free flame retardants and fire retarding synergist are scattered in 90 DEG C of water, obtain halogen-free flameproof liquid；
(5) product of residual surface modifying agent and the step (3) is immersed in the halogen-free flameproof liquid of the step (4)
Then 25min is dried at a temperature of 110 DEG C, obtain once impregnating halogen-free flame-retardant polyamide；
(6) the primary immersion halogen-free anti-inflaming polyurethane in the step (5) is uniformly mixed with remaining dissaving polymer,
Extruding pelletization；
(7) product of the step (6) is immersed in 25min in the halogen-free flameproof liquid of the step (4), then 110
It is dried at a temperature of DEG C, obtains secondary immersion halogen-free flame-retardant polyamide；
(8) by thixotropic agent and secondary immersion halogen-free flame-retardant polyamide extruding pelletization, the halogen-free flame-retardant polyamide tree is obtained
Oil/fat composition.
In the step (1), it according to volume ratio is 8 that the organic solvent, which is methanol, ethyl alcohol and acetone,:2:1 compounds；
The gross mass of organic solvent and the mass ratio of the polyamide are 15 in the step (1) and step (2):1；The step
(2) the rate of temperature fall for being cooled to room temperature is 3 DEG C/5min, mixing speed 600r/min.
First by the dissaving polymer of half quality and the reinforced polyamide of step (2) at 40 DEG C in the step (3)
It is uniformly mixed again after 5h is dried in a vacuum, mixing velocity 1200r/min, incorporation time 5min uses twin-screw
Extruder is squeezed out, and double screw extruder has 6 temperature control areas, and the temperature of each temperature control area is 175 DEG C, and head temperature is
175℃；In the step (6), first will once impregnate halogen-free anti-inflaming polyurethane with remaining dissaving polymer at 40 DEG C true
It is uniformly mixed again after aerial dry 5h, mixing velocity 1200r/min, incorporation time 5min use twin-screw extrusion
Machine is squeezed out, and double screw extruder has 6 temperature control areas, and the temperature of each temperature control area is 175 DEG C, and head temperature is 175 DEG C.
It in the step (8), is squeezed out using double screw extruder, screw diameter 65mm, the draw ratio of screw rod is 40:1,
Double screw extruder has 6 temperature control areas, the first 145 DEG C of area, the second 235 DEG C of area, 255 DEG C of third area, the 4th 265 DEG C of area, and the 5th
275 DEG C of area, the 6th 260 DEG C of area, 270 DEG C of head temperature.
Embodiment 5
A kind of halogen-free flame-retardant polyamide resin combination, is prepared from the following materials：
Wherein, the dissaving polymer is amine-terminated hyperbrancedization polyamide.
The polyamide is PA6/PA66/PA6T ternary polymerization materials, and the PA6/PA66/PA6T ternary polymerizations material is logical
Cross caprolactam, adipic acid hexamethylene diamine salt and to benzoyl hexamethylene diamine melting copolymerization be made, wherein caprolactam, adipic acid oneself two
Amine salt and be 6 to the mass ratio of benzoyl hexamethylene diamine：2:1.
The carbon fiber pipe is modified multi wall carbon fiber pipe, and the multi wall carbon fiber pipe caliber is 15-40nm, length is
0.2-2 μm, specific modification procedure is：It, will under gamma-rays irradiation after multi wall carbon fiber pipe is passivated processing with the concentrated sulfuric acid
Tarine is grafted to multi wall carbon fiber pipe surface, obtains modified multi wall carbon fiber pipe.
The amine-terminated hyperbrancedization polyamide is reacted in methyl alcohol using amine monomers and esters monomer to be made, the amine list
Body, esters monomer molar ratio be 1:3.5, the mass ratio of the gross mass and methanol of the amine monomers and esters monomer is 1:8,
The amine monomers are polyamino amine, and the polyamino amine is diethylenetriamines, and the esters monomer is methyl acrylate and first
Base methyl acrylate is 1 according to molar ratio：1 compounds.
The halogen-free flame retardants is liquid phosphonium flame retardant, and the liquid phosphonium flame retardant is phosphate toluene diphenyl ester；Institute
It is anhydrous zinc borate to state fire retarding synergist.
It according to mass ratio is 2.5 that the antioxidant, which is Hinered phenols antioxidant and phosphite ester kind antioxidant,:1 compounding and
At；The thixotropic agent is aerosil；The surface modifier is silane coupling agent and surfactant；The silane is even
Connection agent is gamma-aminopropyl-triethoxy-silane；The surfactant is nonionic surface active agent and anionic surface
Activating agent is 1 according to mass ratio:9 compound.
The preparation method of the halogen-free flame-retardant polyamide resin combination, includes the following steps：
(1) surface modifier of carbon fiber pipe and 2/3rds mass is added in organic solvent, and in 60 DEG C of temperature
Degree is lower to carry out ultrasonic disperse 6h, obtains carbon fiber pipe dispersion liquid；
(2) the carbon fiber pipe dispersion liquid of the step (1) is added in polyamide and antioxidant, and added a certain amount of organic
Solvent is warming up to 155 DEG C under conditions of 18MPa pressure, is stirred to react 100min, mixing speed under inert gas protection
For 800r/min, it is cooled to room temperature after reaction, isolates solid product, reinforced polyamide is made；
(3) dissaving polymer of half quality and the reinforced polyamide of step (2) are uniformly mixed, extruding pelletization；
(4) halogen-free flame retardants and fire retarding synergist are scattered in 90 DEG C of water, obtain halogen-free flameproof liquid；
(5) product of residual surface modifying agent and the step (3) is immersed in the halogen-free flameproof liquid of the step (4)
Then 12min is dried at a temperature of 120 DEG C, obtain once impregnating halogen-free flame-retardant polyamide；
(6) the primary immersion halogen-free anti-inflaming polyurethane in the step (5) is uniformly mixed with remaining dissaving polymer,
Extruding pelletization；
(7) product of the step (6) is immersed in 12min in the halogen-free flameproof liquid of the step (4), then 120
It is dried at a temperature of DEG C, obtains secondary immersion halogen-free flame-retardant polyamide；
(8) by thixotropic agent and secondary immersion halogen-free flame-retardant polyamide extruding pelletization, the halogen-free flame-retardant polyamide tree is obtained
Oil/fat composition.
In the step (1), it according to volume ratio is 6 that the organic solvent, which is methanol, ethyl alcohol and acetone,:3:1 compounds；
The gross mass of organic solvent and the mass ratio of the polyamide are 18 in the step (1) and step (2):1；The step
(2) the rate of temperature fall for being cooled to room temperature is 3 DEG C/5min, mixing speed 600r/min.
First by the dissaving polymer of half quality and the reinforced polyamide of step (2) at 30 DEG C in the step (3)
It is uniformly mixed again after 7h is dried in a vacuum, mixing velocity 1000r/min, incorporation time 8min uses twin-screw
Extruder is squeezed out, and double screw extruder has 6 temperature control areas, and the temperature of each temperature control area is 180 DEG C, and head temperature is
180℃；In the step (6), first will once impregnate halogen-free anti-inflaming polyurethane with remaining dissaving polymer at 30 DEG C true
It is uniformly mixed again after aerial dry 7h, mixing velocity 1000r/min, incorporation time 8min use twin-screw extrusion
Machine is squeezed out, and double screw extruder has 6 temperature control areas, and the temperature of each temperature control area is 180 DEG C, and head temperature is 180 DEG C.
It in the step (8), is squeezed out using double screw extruder, screw diameter 65mm, the draw ratio of screw rod is 40:1,
Double screw extruder has 6 temperature control areas, the first 160 DEG C of area, the second 230 DEG C of area, 250 DEG C of third area, the 4th 260 DEG C of area, and the 5th
270 DEG C of area, the 6th 250 DEG C of area, 265 DEG C of head temperature.
Embodiment 6
A kind of halogen-free flame-retardant polyamide resin combination, is prepared from the following materials：
Wherein, the dissaving polymer is amine-terminated hyperbrancedization polyamide.
The polyamide is PA6/PA66/PA6T ternary polymerization materials, and the PA6/PA66/PA6T ternary polymerizations material is logical
Cross caprolactam, adipic acid hexamethylene diamine salt and to benzoyl hexamethylene diamine melting copolymerization be made, wherein caprolactam, adipic acid oneself two
Amine salt and be 7 to the mass ratio of benzoyl hexamethylene diamine：3:1.
The carbon fiber pipe is modified multi wall carbon fiber pipe, and the multi wall carbon fiber pipe caliber is 15-40nm, length is
0.2-2 μm, specific modification procedure is：It, will under gamma-rays irradiation after multi wall carbon fiber pipe is passivated processing with the concentrated sulfuric acid
Tarine is grafted to multi wall carbon fiber pipe surface, obtains modified multi wall carbon fiber pipe.
The amine-terminated hyperbrancedization polyamide is reacted in methyl alcohol using amine monomers and esters monomer to be made, the amine list
Body, esters monomer molar ratio be 1:4, the mass ratio of the gross mass and methanol of the amine monomers and esters monomer is 1:9, institute
It is polyamino amine to state amine monomers, and the polyamino amine is ethylenediamine, and the esters monomer is methyl acrylate.
The halogen-free flame retardants is liquid phosphonium flame retardant, and the liquid phosphonium flame retardant is tricresyl phosphate, bis-phenol
A- bis- (diphenyl phosphoesters) is 2 according to mass ratio:1 compounds；The fire retarding synergist is oxalic acid aluminium.
It according to mass ratio is 3 that the antioxidant, which is Hinered phenols antioxidant and phosphite ester kind antioxidant,:1 compounds；
The thixotropic agent is anti-sagging agent；The surface modifier is silane coupling agent and surfactant；The silane coupling agent is
γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy silicane；The surfactant is nonionic surface active agent and anion
Type surfactant is 1 according to mass ratio:8 compound.
The preparation method of the halogen-free flame-retardant polyamide resin combination, includes the following steps：
(1) surface modifier of carbon fiber pipe and 2/3rds mass is added in organic solvent, and in 65 DEG C of temperature
Degree is lower to carry out ultrasonic disperse 6h, obtains carbon fiber pipe dispersion liquid；
(2) the carbon fiber pipe dispersion liquid of the step (1) is added in polyamide and antioxidant, and added a certain amount of organic
Solvent is warming up to 180 DEG C under conditions of 20MPa pressure, is stirred to react 120min, mixing speed under inert gas protection
For 900r/min, it is cooled to room temperature after reaction, isolates solid product, reinforced polyamide is made；
(3) dissaving polymer of half quality and the reinforced polyamide of step (2) are uniformly mixed, extruding pelletization；
(4) halogen-free flame retardants and fire retarding synergist are scattered in 70 DEG C of water, obtain halogen-free flameproof liquid；
(5) product of residual surface modifying agent and the step (3) is immersed in the halogen-free flameproof liquid of the step (4)
Then 30min is dried at a temperature of 100 DEG C, obtain once impregnating halogen-free flame-retardant polyamide；
(6) the primary immersion halogen-free anti-inflaming polyurethane in the step (5) is uniformly mixed with remaining dissaving polymer,
Extruding pelletization；
(7) product of the step (6) is immersed in 30min in the halogen-free flameproof liquid of the step (4), then 100
It is dried at a temperature of DEG C, obtains secondary immersion halogen-free flame-retardant polyamide；
(8) by thixotropic agent and secondary immersion halogen-free flame-retardant polyamide extruding pelletization, the halogen-free flame-retardant polyamide tree is obtained
Oil/fat composition.
In the step (1), it according to volume ratio is 8 that the organic solvent, which is methanol, ethyl alcohol and acetone,:1:1 compounds；
The gross mass of organic solvent and the mass ratio of the polyamide are 20 in the step (1) and step (2):1；The step
(2) the rate of temperature fall for being cooled to room temperature is 3 DEG C/5min, mixing speed 600r/min.
First by the dissaving polymer of half quality and the reinforced polyamide of step (2) at 40 DEG C in the step (3)
It is uniformly mixed again after 5h is dried in a vacuum, mixing velocity 1200r/min, incorporation time 5min uses twin-screw
Extruder is squeezed out, and double screw extruder has 6 temperature control areas, and the temperature of each temperature control area is 160 DEG C, and head temperature is
160℃；In the step (6), first will once impregnate halogen-free anti-inflaming polyurethane with remaining dissaving polymer at 40 DEG C true
It is uniformly mixed again after aerial dry 5h, mixing velocity 1200r/min, incorporation time 5min use twin-screw extrusion
Machine is squeezed out, and double screw extruder has 6 temperature control areas, and the temperature of each temperature control area is 160 DEG C, and head temperature is 160 DEG C.
It in the step (8), is squeezed out using double screw extruder, screw diameter 65mm, the draw ratio of screw rod is 40:1,
Double screw extruder has 6 temperature control areas, the first 160 DEG C of area, the second 240 DEG C of area, 260 DEG C of third area, the 4th 270 DEG C of area, and the 5th
280 DEG C of area, the 6th 270 DEG C of area, 275 DEG C of head temperature.
The test performance such as following table of the halogen-free flame-retardant polyamide resin combination of 1-6 of the embodiment of the present invention：
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Cantilever beam notch goes out intensity KJ/M2 | 9 | 8.8 | 9.1 | 8.6 | 9.2 | 8.7 |
| Tensile strength (MPa) | 151 | 150 | 154 | 152 | 150 | 148 |
| Bending strength (MPa) | 210 | 215 | 213 | 213 | 210 | 209 |
| UL94 flame retardant ratings (0.8mm) | V0 | V0 | V0 | V0 | V0 | V0 |
| Electric trace index (CTI) V | 600 | 600 | 600 | 600 | 600 | 600 |
| Surface gloss | It is good | It is good | It is good | It is good | It is good | It is good |
| Dimensional stability | It is good | It is good | It is good | It is good | It is good | It is good |
| It is molded 1500 mold deposits (range estimation) | Unobvious | Unobvious | Unobvious | Unobvious | Unobvious | Unobvious |
There is the polyamide of the present invention good cantilever beam notch to go out intensity, tensile strength, bending strength and UL94 resistances
Fire grade, and after machine-shaping have excellent surface gloss and dimensional stability, after Multi-step injection molding, mold deposit compared with
It is few, almost without having very strong use value.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other manner,
Any obvious replacement is not departed under the premise of present inventive concept within protection scope of the present invention.
Claims (10)
1. a kind of halogen-free flame-retardant polyamide resin combination, which is characterized in that be prepared from the following materials：
Wherein, the dissaving polymer is amine-terminated hyperbrancedization polyamide.
2. halogen-free flame-retardant polyamide resin combination according to claim 1, it is characterised in that：The polyamide is PA6/
PA66/PA6T ternary polymerization materials, the PA6/PA66/PA6T ternary polymerizations material pass through caprolactam, hexamethylene diamine adipate
Salt and the melting copolymerization of benzoyl hexamethylene diamine is made, wherein caprolactam, adipic acid hexamethylene diamine salt and to benzoyl hexamethylene diamine
Mass ratio is 5-7：2-4:1.
3. halogen-free flame-retardant polyamide resin combination according to claim 1, it is characterised in that：The carbon fiber pipe is to change
Property multi wall carbon fiber pipe, the multi wall carbon fiber pipe caliber is 15-40nm, length is 0.2-2 μm, and specific modification procedure is：It will
After multi wall carbon fiber pipe is passivated processing with the concentrated sulfuric acid, tarine is grafted to multi wall carbon fiber under gamma-rays irradiation
Pipe surface obtains modified multi wall carbon fiber pipe.
4. halogen-free flame-retardant polyamide resin combination according to claim 1, it is characterised in that：Amine-terminated hyperbrancedization
Polyamide react in methyl alcohol using amine monomers and esters monomer to be made, the amine monomers, esters monomer molar ratio be 1:2-
4.5, the mass ratio of the gross mass and methanol of the amine monomers and esters monomer is 1:2.5-9 the amine monomers are polyamino
Amine, the polyamino amine are one or more of ammonia, ethylenediamine, hexamethylene diamine, diethylenetriamines, and the esters monomer is third
E pioic acid methyl ester and/or methyl methacrylate.
5. halogen-free flame-retardant polyamide resin combination according to claim 1, it is characterised in that：The halogen-free flame retardants is
Liquid phosphonium flame retardant, the liquid phosphonium flame retardant are tricresyl phosphate, phosphate toluene diphenyl ester, tricresyl phosphate (dimethylbenzene)
The one or more of ester, bisphenol-A-bis- (diphenyl phosphoesters) and resorcinol bis- (diphenyl phosphoesters)；The fire-retardant synergistic
Agent is melamine salt, phosphazene compound, boehmite, oxalic acid aluminium, zeolite molecular sieve, organic nano imvite, anhydrous zinc borate
One or more of.
6. halogen-free flame-retardant polyamide resin combination according to claim 1, it is characterised in that：The antioxidant is to be obstructed
Phenolic antioxidant and/or phosphite ester kind antioxidant；The thixotropic agent is aerosil, blanc fixe, polyamide wax
One or more of with anti-sagging agent；The surface modifier is silane coupling agent and/or surfactant；The silane is even
Connection agent is gamma-aminopropyl-triethoxy-silane, γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy silicanes and γ-methacryl
The one or more of oxygroup propyl trimethoxy silicane；The surfactant is nonionic surface active agent and anionic
Surfactant is 1 according to mass ratio:8-10 is compounded.
7. a kind of preparation method of halogen-free flame-retardant polyamide resin combination as claimed in any one of claims 1 to 6, feature
It is, includes the following steps：
(1) surface modifier of carbon fiber pipe and 2/3rds mass is added in organic solvent, and in 50-65 DEG C of temperature
Lower progress ultrasonic disperse 6-8h, obtains carbon fiber pipe dispersion liquid；
(2) the carbon fiber pipe dispersion liquid of the step (1) is added in polyamide and antioxidant, and added a certain amount of organic molten
Agent is warming up to 150-180 DEG C under conditions of 0-20MPa pressure, is stirred to react 60-120min, stirs under inert gas protection
It is 700-900r/min to mix speed, is cooled to room temperature after reaction, isolates solid product, and reinforced polyamide is made；
(3) dissaving polymer of half quality and the reinforced polyamide of step (2) are uniformly mixed, extruding pelletization；
(4) halogen-free flame retardants and fire retarding synergist are scattered in 70-100 DEG C of water, and residual surface modifying agent is added, stirred
It mixes, obtains halogen-free flameproof liquid；
(5) product of the step (3) is immersed in 10-30min in the halogen-free flameproof liquid of the step (4), then in 80-
It is dried at a temperature of 120 DEG C, obtains once impregnating halogen-free flame-retardant polyamide；
(6) the primary immersion halogen-free anti-inflaming polyurethane in the step (5) is uniformly mixed with remaining dissaving polymer, is squeezed out
It is granulated；
(7) product of the step (6) is immersed in 10-30min in the halogen-free flameproof liquid of the step (4), then in 80-
It is dried at a temperature of 120 DEG C, obtains secondary immersion halogen-free flame-retardant polyamide；
(8) by thixotropic agent and secondary immersion halogen-free flame-retardant polyamide extruding pelletization, the halogen-free flame-retardant polyamide resin group is obtained
Close object.
8. the preparation method of halogen-free flame-retardant polyamide resin combination according to claim 7, it is characterised in that：The step
Suddenly in (1), it according to volume ratio is 6-8 that the organic solvent, which is methanol, ethyl alcohol and acetone,:1-3:1 compounds；The step
(1) and in step (2) gross mass of organic solvent and the mass ratio of the polyamide are 5-20:1；The drop of the step (2)
The rate of temperature fall of temperature to room temperature is 2-3 DEG C/5min, mixing speed 500-600r/min.
9. the preparation method of halogen-free flame-retardant polyamide resin combination according to claim 7, it is characterised in that：The step
Suddenly first the dissaving polymer of half quality and the reinforced polyamide of step (2) are dried in a vacuum at 30-40 DEG C in (3)
It is uniformly mixed again after 5-7h, mixing velocity 1000-1200r/min, incorporation time 5-8min uses twin-screw extrusion
Machine is squeezed out, and double screw extruder has 6 temperature control areas, and the temperature of each temperature control area is 160-180 DEG C, and head temperature is
160-180℃；In the step (6), halogen-free anti-inflaming polyurethane first will be once impregnated with remaining dissaving polymer at 30-40 DEG C
Under 5-7h is dried in a vacuum after be uniformly mixed again, mixing velocity 1000-1200r/min, incorporation time 5-8min,
It being squeezed out using double screw extruder, double screw extruder has 6 temperature control areas, and the temperature of each temperature control area is 160-180 DEG C,
Head temperature is 160-180 DEG C.
10. the preparation method of halogen-free flame-retardant polyamide resin combination according to claim 7, it is characterised in that：It is described
It in step (8), is squeezed out using double screw extruder, screw diameter 65mm, the draw ratio of screw rod is 40:1, double screw extruder
There are 6 temperature control areas, the first 140-160 DEG C of area, the second 230-240 DEG C of area, 250-260 DEG C of third area, the 4th 260-270 DEG C of area,
5th 270-280 DEG C of area, the 6th 250-270 DEG C of area, 265-275 DEG C of head temperature.
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