CN110373021A - A kind of modified PA56 composite material and preparation method - Google Patents
A kind of modified PA56 composite material and preparation method Download PDFInfo
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Abstract
The present invention relates to technical field of polymer composite materials, more particularly to a kind of modified PA56 composite material and preparation method, modification PA56 composite material PA56 includes 1-2 parts of 5-10 parts of 3-6 parts of 3-5 parts of 4-8 parts of 6-12 parts of 9-15 parts of 7-13 parts of 10-18 parts of 65-75 parts of raw material PA56, glass fibre, organosilicon epoxy resin, plasticized modifier, filler, antioxidant, nucleating agent, coupling agent, composite synergist, the lubricant of following parts by weight.Modification PA56 composite material of the invention has good mechanical performance, anti-flammability and dimensional stability, high temperature resistance is good, it is not easy xanthochromia, use scope is wide, preparation method, convenient operation and control, high production efficiency, production cost is low, and A56 composite products quality obtained is stablized, with excellent comprehensive performance, industrialized production is utilized.
Description
Technical field
The present invention relates to technical field of polymer composite materials, and in particular to a kind of modified PA56 composite material and its preparation
Method.
Background technique
Biology base nylon PA56 is polymerized by biology base pentanediamine and petroleum base adipic acid, and pentanediamine, which derives from, relies ammonia
The product of acid decarboxylation, is homologue with hexamethylene diamine, is used to synthesising biological Geordie dragon 56 instead of hexamethylene diamine.Synthetic nylon is common at present
Raw material come from petroleum.The primary raw material hexamethylene diamine importation dependence of China's nylon66 fiber is high, and nylon cost fluctuation is big.Nylon 56 is
It is made by the product of China's independent research using 1,5- pentanediamine is obtained after L-lysine amino acid is engineered as polymerized monomer
The biology base nylon PA56 obtained.Ammonia in microorganism fungus kind was greatly improved using bioengineering in 2013 in Shanghai Kai Sai company
The efficiency of base acid decarboxylase has reached 100 times or so, therefore, microorganism can be effectively utilized saccharide converted into pentanediamine,
Successfully overcome in pentanediamine extraction process be easy cyclization problem, stabilize the extraction process of monomer, reduce product at
This, improves product quality.And biology base nylon PA56 successfully is made using 1, the 5- pentanediamine of bioconversion.
In the application in terms of long filament, PA56 wearability, dyeability etc. and PA66 are approximate, and in terms of intensity, PA56 is close
PA66, for pliability close to wool, density is low, makees clothes materials light weight, and wearability, service life are better than terylene.Nylon 56 is full
With water absorption rate 13% or more, it is higher than nylon66 fiber and nylon 6, is also much higher than terylene, high-hygroscopicity improves moisture absorbing and sweat releasing performance
And comfort level, reduce electrostatic, extends functionality.The glass transition temperature of nylon 56 is lower than nylon66 fiber and terylene, has excellent
Resistance to low temperature, materials light weight, wearability, service life are better than terylene.To sum up, in terms of long filament, the use of PA56
Too many differences are had no with PA66, in some aspects even better than PA66.
PA56 having many advantages in terms of long filament, but existing defects are applied in terms of engineering plastics, mainly have following
Several: 1. water absorption rate is high, and dimensional stability ratio PA66 is poor.2. crystallizing unstable, the form and size of crystallization are easy by temperature shadow
Sound changes, and work materials performance can change under high temperature environment for a long time.3. inoxidizability is poor, high-temperature baking is easily yellow
Become, doing light color material can change colour in drying use process.4. impact strength is lower, the impact that PA66 is not achieved after modification is strong
Degree.5. heat distortion temperature is low.And nylon is born more early as first of five large-engineering plastics, is widely used, yield is very big, kind
There are many class, and wherein PA6 and PA66 yield and consumption are maximum, occupy about 90% or more of entire nylon market.Therefore, improve
The performance deficiencies such as crystallization, water suction and the contraction of PA56 improve its mechanical performance, anti-flammability and dimensional stability, are allowed in automobile
Or PA66 can be partially or completely substituted in terms of electronic apparatus, it is widely used in engineering plastics, has a very important significance.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, it is multiple that the purpose of the present invention is to provide a kind of modified PA56
Condensation material, the PA56 composite material have good mechanical performance, anti-flammability and dimensional stability, inoxidizability and heat-resisting quantity
Can be good, it can be applied to engineering plastics.
Another object of the present invention is to provide a kind of preparation method of modified PA56 composite material, preparation method operations
Simply, easy to control, production cost, stable product quality are reduced, PA56 composite material obtained has good mechanicalness
Energy, anti-flammability and dimensional stability, inoxidizability and high temperature resistance are good, can be used for being mass produced.
The purpose of the invention is achieved by the following technical solution: a kind of modified PA56 composite material, including following parts by weight
Raw material:
The present invention by by PA56 and glass fibre, plasticized modifier with organosilicon epoxy resin, composite synergist and
Other raw materials compounding makes modified PA56 composite material have good mechanical performance, anti-flammability and dimensional stability, inoxidizability
It is good with high temperature resistance, it can be applied to engineering plastics.
Further, the synthetic route of the PA56 is as follows:
Further, the glass fibre is alkali-free glass fibre.It is compound that the glass fibre of use is remarkably improved PA56
The mechanical performances such as bending modulus, intensity, the rigidity of material, and improve the weatherability of PA56 composite material, heatproof oxidation performance, fast light
Oxidisability and dimensional stability, meanwhile, the dosage of strict control glass fibre can be such that PA56 composite material has preferably tough
Property, if dosage is very few, the intensity of PA56 composite material, weatherability promotion are less, if dosage is excessive, it is compound to reduce PA56
The toughness of material, brittleness increase, are easily damaged.
Further, the preparation method of the organosilicon epoxy resin, comprising the following steps: by weight, take 1,2-
80-90 parts of epoxy group -4- vinyl cyclohexane, 0.8-1.2 parts of chloroplatinic acid, 4-5 parts of toluene are equal in mixing at a temperature of 80-90 DEG C
It after even, is added dropwise 3- (dimethylsilyl bis) -1,1,5,5- 50-55 parts of tetramethyl -3- phenyl trisiloxanes and dimethyl dichloro silicon
15-20 parts of alkane, time for adding 90-120min, 2-3h is reacted at being then 115-125 DEG C in temperature, is obtained after vacuum distillation
Organosilicon epoxy resin.The present invention through the above steps, makes organosilicon epoxy resin obtained have good adhesive property, can
It is matched with PA56, improves toughness and mechanical performance, the heat resistance and solvent resistance of composite epoxy resin.
Further, every part of plasticized modifier is composed of the following raw materials in parts by weight: hyperbranched epoxy resin 10-15
Part, 8-12 parts of ethylene-vinyl acetate copolymer and 8-12 parts of polyethylene；Wherein, the epoxy of the hyperbranched epoxy resin is worked as
Amount is 330~400g/eq, number-average molecular weight 4000-9000；Vinyl acetate in the ethylene-vinyl acetate copolymer
Content be 13-18wt%.Hyperbranched epoxy resin has good heat resistance, the processing performance of guarantee system, and can mention
The high compatibility with PA56, to increase toughness；By the selection to epoxide equivalent, can preferably improve hyperbranched resin with
The compatibility of PA56 and other raw materials, control toughening crosslink density；In the range of number-average molecular weight of hyperbranched epoxy resin,
Take into account flow processability, compatibility and heat resistance.Hyperbranched epoxy resin, ethylene-vinyl acetate copolymer and polyethylene group
At compound vinyl acetate monomer is introduced in strand, improve flexibility, impact resistance and each component intermiscibility.This
Invention passes through type, compounding and the weight proportion of strict control toughener, and the active force of molecule interchain between each component can be improved
And processing fluidity, and by the way that three's compounding is had synergistic effect, improve the performance of plasticized modifier.
Further, every part of composite synergist is composed of the following raw materials in parts by weight: 10-15 parts of magnesium sulfate crystal whisker,
10-15 parts of calcium chloride, 6-10 parts of zinc borate and 10-15 parts of polyphenylene oxide.
The present invention by using above-mentioned composite synergist, can significantly improve PA56 composite system ageing-resistant performance,
The performances such as anti-flammability, mechanical strength, dimensional stability；Wherein calcium chloride can by chelating reaction in conjunction with the amido bond of PA56,
It is allowed to that hydrogen bond can not be formed with water, water absorption rate is reduced, to improve the dimensional stability and mechanicalness of modified PA56 composite material
Energy；Composite synergist of the invention has good flame retardant effect, and Halogen, and good with PA56 compatibility will not be in use process
The appearance and mechanical performance of modified PA56 composite products can be improved in middle precipitation；The zinc borate of use can effectively improve
The flame retardant property of PA56 composite system, the generation of smog when reducing burning, and the chemistry that can improve composite system is steady
The performances such as qualitative, mechanical strength, prolong its service life；Polyphenylene oxide can be used as carbon forming agent, and anti-flammability is good, have from breath property,
It is matched with magnesium sulfate crystal whisker and calcium chloride, to further improve flame retardant effect and mechanical performance.
Further, the magnesium sulfate crystal whisker is the magnesium sulfate crystal whisker that diameter is 500-800nm, draw ratio is 30-60.Institute
Stating magnesium sulfate crystal whisker is the magnesium sulfate crystal whisker handled by titanate coupling agent, and the additive amount of titanate coupling agent is that magnesium sulfate is brilliant
The 4-8% of palpus weight.Magnesium sulfate crystal whisker has preferable flame retardant property, and has both feature nontoxic, that smoke amount is small.Magnesium sulfate
Whisker is also used as reinforcing material in addition to as composite synergist synergist, and making PA56 composite material not only has preferably
Appearance, impact strength etc., while assigning its good dimensional stability and heat-resisting quantity.
Further, the filler by hollow glass micropearl, talcum powder, silicon powder and nano-titanium dioxide in mass ratio
(1-2): (1-2): (1-2): (0.5-1) is compounded.The present invention is can be uniformly dispersed by using above-mentioned filler in sealant
System in, and its powder structure can effectively facilitate the dispersed homogeneous degree of unclassified stores, and make modified PA56 composite wood obtained
Material mechanical property, mass change, volume change after liquid impregnates can keep very little change rate, while reduce modification
The production cost of PA56 composite material.
Further, the lubricant is in ethylene bis stearic acid amide, pentaerythritol stearate and polyethylene wax
It is at least one.The present invention can improve the internal lubrication and external lubricity of PA56 composite material by using above-mentioned lubricant,
Make it easier to extrusion molding, excellent processing performance.
Further, the coupling agent is vinyltriethoxysilane, gamma-aminopropyl-triethoxy-silane and phenylamino
At least one of methyltrimethoxysilane.The present invention can promote PA56, organosilicon epoxy tree by using above-mentioned coupling agent
The effect of the polymerization crosslinking of rouge and plasticized modifier, improves the mechanical strength of PA56 composite material, and improves material in reaction system
In wetability and dispersibility.
Further, the antioxidant is antioxidant 1010, irgasfos 168, antioxidant 1076, anti-oxidant DLTP, antioxygen
At least one of agent 126.The present invention can improve the inoxidizability of PA56 composite material by using above-mentioned antioxidant, solve
The problem of its easy xanthochromia, effectively inhibits the heat ageing degradation of PPA56 composite material, improves its stability.
Further, the nucleating agent is that graphene oxide, zinc oxide, ethylene-acrylic acid copolymer and sodium benzoate are pressed
Mass ratio 1:(1-2): (0.5-1.5): (0.5-1.5) is compounded.Further, the number of the ethylene-acrylic acid copolymer
Average molecular weight is 4000-6000.The content of acrylic acid is 14-25wt% in ethylene-acrylic acid copolymer.By be added it is above-mentioned at
Core agent, sodium benzoate and graphene oxide cooperate, and generate apparent collaboration activeness and quietness effect to PA56 matrix, are rising
It while humidification, is faster crystallized so that nylon is deposited in nucleating agent, the zinc oxide used can absorb micro for amphoteric oxide
Acid or alkaline matter, slow down the corrosion and aging of PPA56 composite material, improve its resistance to ag(e)ing, and can be total with ethylene-acrylic acid
Polymers combines, and the uniformity and fineness for improving the raising spherulitic crystal structure of modified PA56 composite material increase, to improve its physics
Performance and hydrophobicity reduce water imbibition.
Further, the preparation method of the graphene oxide includes the following steps: by weight, in 2-3 DEG C of temperature
Lower 1-2 parts of natural graphite powders, 0.5-1 parts of sodium nitrate are added to 18-22 parts of concentration is to add in the 97-99wt% concentrated sulfuric acid
2-3 parts of potassium permanganate, stir evenly, and after being then stirred to react 5-10min at a temperature of 14-18 DEG C, system temperature is risen to 30-
35 DEG C, 10-15 parts of deionized waters are added after stirring 20-30min in constant temperature；95-100 DEG C is then heated to, after keeping 15-20min
10-15 parts of deionized waters are added to be hydrolyzed, are eventually adding 6-8 parts of H2O2, mixed liquor is obtained, mixed liquor is filtered, washing to filter
Cake is in neutrality, and obtains graphene oxide.The present invention can be introduced a large amount of polarity on the surface of graphite oxide and be contained by the above method
Oxygen functional group (such as carboxyl, hydroxyl and epoxy group), graphene oxide obtained and zinc oxide, ethylene-acrylic acid copolymer and
Sodium benzoate link, the good dispersion of graphene oxide improve the crystalline stability of PA56 composite material, improve its tensile strength
And impact strength.
The present invention also provides a kind of preparation methods of above-mentioned modification PA56 composite material, include the following steps:
(1) it is weighed according to parts by weight and is previously dried PA56 of the moisture content less than 0.2% and organosilicon epoxy resin, increases
Tough modifying agent, coupling agent, nucleating agent and filler mixing dispersion, stir evenly under the conditions of temperature is 210-230 DEG C, are made
Material A；
(2) antioxidant, composite synergist and lubricant and material A are mixed into dispersion, is 230-250 DEG C of condition in temperature
Under stir evenly, be made material B；
(3) material B is added in extrusion equipment from main spout, while glass fibre is added to extrusion from side spout
It in equipment, is kneaded, squeezed out and is granulated, obtain modified PA56 composite material.
Further, each area's temperature of the extrusion equipment is respectively as follows: one Qu Wendu: 210-220 DEG C, two area's temperature:
225-235 DEG C, three Qu Wendu: 240-255 DEG C, four Qu Wendu: 260-275 DEG C, five Qu Wendu: 285-295 DEG C, six Qu Wendu:
260-270 DEG C, seven area's temperature: 250-260 DEG C, eight area's temperature: 240-250 DEG C, nine Qu Wendu: 250-260 DEG C, revolving speed 100-
150RPM, the side spout are located between 5th area and 6th area.Glass fibre selects suitable opportunity to be added, and improves glass fibers
Dimension and the adhesion strength of PA56, improve impact strength, and glass fibre is prevented to be easy to be extruded machine and cut because the time is added too early
Qie get Tai is broken, and humidification is caused to reduce；And cause mixing uneven when preventing from being added too late, it is influenced to composite material entirety
Reinforcing effect.
The present invention passes through each area's temperature of strict control extrusion process, and PA56 composite material can be made to squeeze out and stablized, mouldability
Well, phenomena such as being less prone to cracking has the property such as preferable intensity, toughness, shock resistance, property dimensional stability and heat-resisting quantity
Energy.
The beneficial effects of the present invention are: the present invention by by PA56 and glass fibre, plasticized modifier with organosilicon ring
Oxygen resin, composite synergist and other raw materials compounding, and by way of addition nucleating agent directional induction crystallization, make crystalline
State is stablized, to keep composite material more stable, heat distortion temperature is also promoted therewith；Modified PA56 composite material has good
Mechanical performance, anti-flammability and dimensional stability, inoxidizability and high temperature resistance are good, can be applied to engineering plastics, use scope
Extensively.
The preparation method of modification PA56 composite material of the invention, convenient operation and control, high production efficiency, production cost
Low, stable product quality, PA56 composite material obtained has good mechanical performance, anti-flammability and dimensional stability, antioxygen
The property changed and high temperature resistance are good, are conducive to industrialized production.
Specific embodiment
For the ease of the understanding of those skilled in the art, below 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
In the present embodiment, a kind of modified PA56 composite material, the raw material including following parts by weight: 70 parts of PA56, glass fibers
15 parts of dimension, 9 parts of organosilicon epoxy resin, 12 parts of plasticized modifier, 8 parts of filler, 6 parts of antioxidant, 4 parts of nucleating agent, coupling
4 parts of agent, 6 parts of composite synergist, 2 parts of lubricant.
Further, the glass fibre is alkali-free glass fibre.
Further, the preparation method of the organosilicon epoxy resin, comprising the following steps: by weight, take 1,2-
85 parts of epoxy group -4- vinyl cyclohexane, 1 part of epoxychloropropane chloroplatinic acid, 4.5 parts of toluene at a temperature of 85 DEG C in being uniformly mixed
Afterwards, 3- (dimethylsilyl bis) -1 is added dropwise, 1,5,5- 52 parts of tetramethyl -3- phenyl trisiloxanes and dimethyldichlorosilane 18
Part, time for adding 100min reacts 2.5 at being then 120 DEG C in temperature, obtains organosilicon epoxy resin after vacuum distillation.
Further, every part of plasticized modifier is composed of the following raw materials in parts by weight: 12 parts of hyperbranched epoxy resin,
10 parts and 9 parts of polyethylene of ethylene-vinyl acetate copolymer；Wherein, the epoxide equivalent of the hyperbranched epoxy resin is 340g/
Eq, number-average molecular weight 4500；The content of vinyl acetate is 14wt% in the ethylene-vinyl acetate copolymer.
Further, every part of composite synergist is composed of the following raw materials in parts by weight: 12 parts of magnesium sulfate crystal whisker, chlorination
13 parts of calcium, 8 parts of zinc borate and 11 parts of polyphenylene oxide.
Further, the magnesium sulfate crystal whisker is the magnesium sulfate crystal whisker that diameter is 600nm, draw ratio is 40.The sulfuric acid
Magnesium whisker is to handle by (dioctyl phosphoryl) titanate esters of isopropyl three, and the additive amount of titanate coupling agent is magnesium sulfate crystal whisker
The 5% of weight.
Further, the filler by hollow glass micropearl, talcum powder, silicon powder and nano-titanium dioxide in mass ratio
1.5:1.8:1.5:0.7 is compounded.
Further, the lubricant is that ethylene bis stearic acid amide and pentaerythritol stearate 1:1 in mass ratio are multiple
With forming.The coupling agent is vinyltriethoxysilane.The antioxidant is that antioxidant 1010 and anti-oxidant DLTP press matter
Amount is compounded than 1:2.
Further, the nucleating agent is that graphene oxide, zinc oxide, ethylene-acrylic acid copolymer and sodium benzoate are pressed
Mass ratio 1:1.5:1.2:1.2 is compounded.The number-average molecular weight of the ethylene-acrylic acid copolymer is 5300.Ethylene-propylene
The content of acrylic acid is 16wt% in acid copolymer.
Further, the preparation method of the graphene oxide includes the following steps: by weight, at a temperature of 2 DEG C
It is to add 2.5 parts of permanganic acid in the 98wt% concentrated sulfuric acid that 1.5 parts of natural graphite powders, 0.7 part of sodium nitrate, which are added to 20 parts of concentration,
Potassium stirs evenly, and after being then stirred to react 7min at a temperature of 15 DEG C, system temperature is risen to 32 DEG C, after constant temperature stirs 25min
12 parts of deionized waters are added；98 DEG C are then heated to, keeps 12 parts of deionized waters of addition after 18min to be hydrolyzed, is eventually adding 7
Part H2O2, mixed liquor is obtained, mixed liquor is filtered, washing is in neutrality to filter cake, obtains graphene oxide.
A kind of preparation method of above-mentioned modification PA56 composite material, includes the following steps:
(1) it is weighed according to parts by weight and is previously dried PA56 of the moisture content less than 0.2% and organosilicon epoxy resin, increases
Tough modifying agent, coupling agent, nucleating agent and filler mixing dispersion, stir evenly under the conditions of temperature is 220 DEG C, material are made
A；
(2) antioxidant, composite synergist and lubricant and material A are mixed into dispersion, is stirred under the conditions of temperature is 240 DEG C
It mixes uniformly, material B is made；
(3) material B is added in extrusion equipment from main spout, while glass fibre is added to extrusion from side spout
It in equipment, is kneaded, squeezed out and is granulated, obtain modified PA56 composite material.
Further, each area's temperature of the extrusion equipment is respectively as follows: one Qu Wendu: 215 DEG C, two area's temperature: 230 DEG C,
Three Qu Wendu: 245 DEG C, four Qu Wendu: 265 DEG C, five Qu Wendu: 290 DEG C, six Qu Wendu: 265 DEG C, seven area's temperature: 255 DEG C, eight
Area's temperature: 245 DEG C, nine Qu Wendu: 255 DEG C, revolving speed 120RPM, the side spout is located between 5th area and 6th area.
Embodiment 2
In the present embodiment, a kind of modified PA56 composite material, the raw material including following parts by weight: 65 parts of PA56, glass fibers
Tie up 10 parts, 7 parts of organosilicon epoxy resin, 9 parts of plasticized modifier, 6 parts of filler, 4 parts of antioxidant, 3 parts of nucleating agent, coupling agent
3 parts, 5 parts of composite synergist, 1.5 parts of lubricant.
Further, the preparation method of the organosilicon epoxy resin, comprising the following steps: by weight, take 1,2-
80 parts of epoxy group -4- vinyl cyclohexane, 0.8 part of chloroplatinic acid, 4 parts of toluene are in after mixing, being added dropwise 3- at a temperature of 80 DEG C
(dimethylsilyl bis) -1,1,5,5- 50 parts of tetramethyl -3- phenyl trisiloxanes and 15 parts of dimethyldichlorosilane, time for adding
For 90min, 3h is reacted at being then 115 DEG C in temperature, obtains organosilicon epoxy resin after vacuum distillation.
Further, every part of plasticized modifier is composed of the following raw materials in parts by weight: 10 parts of hyperbranched epoxy resin,
8 parts and 8 parts of polyethylene of ethylene-vinyl acetate copolymer；Wherein, the epoxide equivalent of the hyperbranched epoxy resin is 370g/
Eq, number-average molecular weight 6000；The content of vinyl acetate is 18wt% in the ethylene-vinyl acetate copolymer.
Further, every part of composite synergist is composed of the following raw materials in parts by weight: 10 parts of magnesium sulfate crystal whisker, chlorination
10 parts of calcium, 6 parts of zinc borate and 10 parts of polyphenylene oxide.
Further, the magnesium sulfate crystal whisker is the magnesium sulfate crystal whisker that diameter is 500nm, draw ratio is 70.The sulfuric acid
Magnesium whisker is to handle by titanate, and the additive amount of titanate coupling agent is the 4% of magnesium sulfate crystal whisker weight.
Further, the filler by hollow glass micropearl, talcum powder, silicon powder and nano-titanium dioxide in mass ratio
1:1.5:1:0.5 is compounded.
Further, the lubricant is ethylene bis stearic acid amide.The coupling agent is phenylaminomethyl trimethoxy
Silane.The antioxidant is that irgasfos 168 and antioxidant 1076 1:0.5 in mass ratio are compounded.
Further, the nucleating agent is that graphene oxide, zinc oxide, ethylene-acrylic acid copolymer and sodium benzoate are pressed
Mass ratio 1:1:0.5:0.5 is compounded.The number-average molecular weight of the ethylene-acrylic acid copolymer is 4800.Ethylene-acrylic acid
The content of acrylic acid is 18wt% in copolymer.
Further, the preparation method of the graphene oxide includes the following steps: by weight, at a temperature of 3 DEG C
It is to add 2 parts of potassium permanganate in the 98wt% concentrated sulfuric acid that 1 part of natural graphite powder, 0.5 part of sodium nitrate, which are added to 18 parts of concentration,
It stirs evenly, after being then stirred to react 5min at a temperature of 14 DEG C, system temperature is risen to 30- DEG C, constant temperature adds after stirring 20min
Enter 10 parts of deionized waters；95 DEG C are then heated to, keeps 15 parts of deionized waters of addition after 20min to be hydrolyzed, is eventually adding 68
Part H2O2, mixed liquor is obtained, mixed liquor is filtered, washing is in neutrality to filter cake, obtains graphene oxide.
A kind of preparation method of above-mentioned modification PA56 composite material, includes the following steps:
(1) it is weighed according to parts by weight and is previously dried PA56 of the moisture content less than 0.2% and organosilicon epoxy resin, increases
Tough modifying agent, coupling agent, nucleating agent and filler mixing dispersion, stir evenly under the conditions of temperature is 210 DEG C, material are made
A；
(2) antioxidant, composite synergist and lubricant and material A are mixed into dispersion, is stirred under the conditions of temperature is 230
Uniformly, material B is made；
(3) material B is added in extrusion equipment from main spout, while glass fibre is added to extrusion from side spout
It in equipment, is kneaded, squeezed out and is granulated, obtain modified PA56 composite material.
Further, each area's temperature of the extrusion equipment is respectively as follows: one Qu Wendu: 210 DEG C, two area's temperature: 225 DEG C,
Three Qu Wendu: 240 DEG C, four Qu Wendu: 260 DEG C, five Qu Wendu: 285 DEG C, six Qu Wendu: 260 DEG C, seven area's temperature: 250 DEG C, eight
Area's temperature: 240 DEG C, nine Qu Wendu: 250 DEG C, revolving speed 100RPM, the side spout is located between 5th area and 6th area.
Remaining content of the present embodiment is same as Example 1, and which is not described herein again.
Embodiment 3
In the present embodiment, a kind of modified PA56 composite material, the raw material including following parts by weight: 75 parts of PA56, glass fibers
18 parts of dimension, 13 parts of organosilicon epoxy resin, 15 parts of plasticized modifier, 12 parts of filler, 8 parts of antioxidant, 5 parts of nucleating agent, idol
Join 6 parts of agent, 10 parts of composite synergist, 2.5 parts of lubricant.
Further, the preparation method of the organosilicon epoxy resin, comprising the following steps: by weight, take 1,2-
90 parts of epoxy group -4- vinyl cyclohexane, 1.2 parts of chloroplatinic acid, 5 parts of toluene are in after mixing, being added dropwise 3- at a temperature of 90 DEG C
(dimethylsilyl bis) -1,1,5,5- 55 parts of tetramethyl -3- phenyl trisiloxanes and 20 parts of dimethyldichlorosilane, time for adding
For 120min, 2h is reacted at being then 125 DEG C in temperature, obtains organosilicon epoxy resin after vacuum distillation.
Further, every part of plasticized modifier is composed of the following raw materials in parts by weight: 15 parts of hyperbranched epoxy resin,
12 parts and 12 parts of polyethylene of ethylene-vinyl acetate copolymer；Wherein, the epoxide equivalent of the hyperbranched epoxy resin is
390g/eq, number-average molecular weight 7400；The content of vinyl acetate is 16wt% in the ethylene-vinyl acetate copolymer.
Further, every part of composite synergist is composed of the following raw materials in parts by weight: 15 parts of magnesium sulfate crystal whisker, chlorination
15 parts of calcium, 10 parts of zinc borate and 15 parts of polyphenylene oxide.
Further, the magnesium sulfate crystal whisker is the magnesium sulfate crystal whisker that diameter is 800nm, draw ratio is 50.The sulfuric acid
Magnesium whisker is by the magnesium sulfate crystal whisker of three stearic ester group isopropyl titanate processing, and the additive amount of titanate coupling agent is magnesium sulfate
The 8% of whisker weight.
Further, the lubricant is polyethylene wax.The coupling agent is gamma-aminopropyl-triethoxy-silane.It is described
Antioxidant is that antioxidant 1010 and antioxidant 126 are formed according to mass ratio 1:2.
Further, the nucleating agent is that graphene oxide, zinc oxide, ethylene-acrylic acid copolymer and sodium benzoate are pressed
Mass ratio 1:2:1.5 is compounded.The number-average molecular weight of the ethylene-acrylic acid copolymer is 5700.Ethylene-acrylic acid copolymer
The content of acrylic acid is 21wt% in object.
Further, the preparation method of the graphene oxide includes the following steps: by weight, at a temperature of 2 DEG C
It is to add 3 parts of potassium permanganate in the 98wt% concentrated sulfuric acid, stir that 2 parts of natural graphite powders, 1 part of sodium nitrate, which are added to 22 parts of concentration,
It mixes uniformly, after being then stirred to react 5min at a temperature of 18 DEG C, system temperature is risen to 35 DEG C, is added after constant temperature stirring 20min
15 parts of deionized waters；100 DEG C are then heated to, keeps 10 parts of deionized waters of addition after 15min to be hydrolyzed, is eventually adding 8 parts
H2O2, mixed liquor is obtained, mixed liquor is filtered, washing is in neutrality to filter cake, obtains graphene oxide.
A kind of preparation method of above-mentioned modification PA56 composite material, includes the following steps:
(1) it is weighed according to parts by weight and is previously dried PA56 of the moisture content less than 0.2% and organosilicon epoxy resin, increases
Tough modifying agent, coupling agent, nucleating agent and filler mixing dispersion, stir evenly under the conditions of temperature is 230 DEG C, material are made
A；
(2) antioxidant, composite synergist and lubricant and material A are mixed into dispersion, is stirred under the conditions of temperature is 250 DEG C
It mixes uniformly, material B is made；
(3) material B is added in extrusion equipment from main spout, while glass fibre is added to extrusion from side spout
It in equipment, is kneaded, squeezed out and is granulated, obtain modified PA56 composite material.
Further, each area's temperature of the extrusion equipment is respectively as follows: one Qu Wendu: 220 DEG C, two area's temperature: 35 DEG C, three
Area's temperature: 255 DEG C, four Qu Wendu: 275 DEG C, five Qu Wendu: 295 DEG C, six Qu Wendu: 270 DEG C, seven area's temperature: 260 DEG C, 8th area
Temperature: 250 DEG C, nine Qu Wendu: 260 DEG C, revolving speed 150RPM, the side spout is located between 5th area and 6th area.
Remaining content of the present embodiment is same as Example 1, and which is not described herein again.
Embodiment 4
In the present embodiment, a kind of modified PA56 composite material, the raw material including following parts by weight: 68 parts of PA56, glass fibers
16 parts of dimension, 9 parts of organosilicon epoxy resin, 11 parts of plasticized modifier, 7 parts of filler, 5 parts of antioxidant, 4 parts of nucleating agent, coupling
4 parts of agent, 8 parts of composite synergist, 1.8 parts of lubricant.
Further, every part of plasticized modifier is composed of the following raw materials in parts by weight: 12 parts of hyperbranched epoxy resin,
9 parts and 11 parts of polyethylene of ethylene-vinyl acetate copolymer；Wherein, the epoxide equivalent of the hyperbranched epoxy resin is 360g/
Eq, number-average molecular weight 8200；The content of vinyl acetate is 18wt% in the ethylene-vinyl acetate copolymer.
Further, every part of composite synergist is composed of the following raw materials in parts by weight: 13 parts of magnesium sulfate crystal whisker, chlorination
13 parts of calcium, 7 parts of zinc borate and 14 parts of polyphenylene oxide.
Further, the filler by hollow glass micropearl, talcum powder, silicon powder and nano-titanium dioxide in mass ratio
1.2:1.2:1.8:0.6 is compounded.
Further, the lubricant is that ethylene bis stearic acid amide and pentaerythritol stearate 1:2 in mass ratio are multiple
With forming.The coupling agent is that gamma-aminopropyl-triethoxy-silane and phenylaminomethyl trimethoxy silicon 1:1 in mass ratio are compounded
It forms.The antioxidant is antioxidant 126.
Further, the nucleating agent is that graphene oxide, zinc oxide, ethylene-acrylic acid copolymer and sodium benzoate are pressed
Mass ratio 1:1.4:0.8:0.8 is compounded.The number-average molecular weight of the ethylene-acrylic acid copolymer is 4600.
Remaining content of the present embodiment is same as Example 1, and which is not described herein again.
Comparative example 1
The present embodiment and comparative example 1 the difference is that:
A kind of modified PA56 composite material, the raw material including following parts by weight: 70 parts of PA56,15 parts of glass fibre, filling
8 parts of agent, 6 parts of antioxidant, 4 parts of nucleating agent, 12 parts of composite synergist, 4 parts of coupling agent, 6 parts of composite synergist, 2 parts of lubricant.
Comparative example 2
In the present embodiment, a kind of modified PA56 composite material, the raw material including following parts by weight: 70 parts of PA56, glass fibers
15 parts of dimension, 9 parts of organosilicon epoxy resin, 12 parts of plasticized modifier, 8 parts of filler, 6 parts of antioxidant, 4 parts of coupling agent, lubrication
2 parts of agent.
Comparative example 3
In the present embodiment, a kind of modified PA56 composite material, the raw material including following parts by weight: 70 parts of PA56, glass fibers
15 parts of dimension, 9 parts of organosilicon epoxy resin, 12 parts of plasticized modifier, 8 parts of filler, 6 parts of antioxidant, 4 parts of nucleating agent, coupling
4 parts of agent, 2 parts of lubricant.
Respectively to the every physical progress of modified PA56 composite material obtained in specific embodiment 1-4 and comparative example 1-3
Detection, the results are shown in Table 1:
Wherein, the test of tensile strength, elongation at break is according to ISO527, bending strength, bending modulus measurement according to
ISO178, the strong measurement of Izod notched impact is according to ISO179, and the measurement of heat distortion temperature is according to ISO75-2.
Therefore, modification PA56 composite material of the invention has good mechanical performance, anti-flammability and dimensional stability, resistance to
High-temperature behavior is good, is not easy xanthochromia, can be applied to engineering plastics, and use scope is wide.Preparation method, convenient operation and control, production
High-efficient, production cost is low, and PA56 composite products quality obtained is stablized, and has excellent comprehensive performance, utilizes industry
Metaplasia produces.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. a kind of modified PA56 composite material, it is characterised in that: the raw material including following parts by weight:
2. a kind of modified PA56 composite material according to claim 1, it is characterised in that: every part of plasticized modifier by
The raw material composition of following parts by weight: 10-15 parts of hyperbranched epoxy resin, 8-12 parts of ethylene-vinyl acetate copolymer and poly- second
8-12 parts of alkene；The content of vinyl acetate is 13-18wt% in the ethylene-vinyl acetate copolymer.
3. a kind of modified PA56 composite material according to claim 1, it is characterised in that: every part of composite synergist by
The raw material composition of following parts by weight: 10-15 parts of magnesium sulfate crystal whisker, 10-15 parts of calcium chloride, 6-10 parts of zinc borate and polyphenylene oxide 10-
15 parts.
4. a kind of modified PA56 composite material according to claim 1, it is characterised in that: the filler is by hollow glass
Microballon, talcum powder, silicon powder and nano-titanium dioxide (1-2) in mass ratio: (1-2): (1-2): (0.5-1) is compounded.
5. a kind of modified PA56 composite material according to claim 1, it is characterised in that: the antioxidant is antioxidant
1010, at least one of irgasfos 168, antioxidant 1076, anti-oxidant DLTP, antioxidant 126.
6. a kind of modified PA56 composite material according to claim 1, it is characterised in that: the lubricant is that ethylene is double hard
At least one of resin acid amide, pentaerythritol stearate and polyethylene wax.
7. a kind of modified PA56 composite material according to claim 1, it is characterised in that: the coupling agent is vinyl three
At least one of Ethoxysilane, gamma-aminopropyl-triethoxy-silane and phenylaminomethyl trimethoxy silane.
8. a kind of modified PA56 composite material according to claim 1, it is characterised in that: the nucleating agent is graphite oxide
Alkene, ethylene-acrylic acid copolymer, zinc oxide and sodium benzoate 1:(1-2 in mass ratio) (0.5-1.5): (0.5-1.5) compounding and
At.
9. a kind of preparation method of the modification PA56 composite material as described in claim 1-8 any one, it is characterised in that: packet
Include following steps:
(1) it is weighed according to parts by weight and is previously dried PA56 of the moisture content less than 0.2% and changes with organosilicon epoxy resin, toughening
Property agent, coupling agent, nucleating agent and filler mixing dispersion, temperature be 210-230 DEG C under the conditions of stir evenly, be made material
A；
(2) antioxidant, composite synergist and lubricant and material A are mixed into dispersion, is stirred under the conditions of temperature is 230-250 DEG C
It mixes uniformly, material B is made；
(3) material B is added in extrusion equipment from main spout, while glass fibre is added to extrusion equipment from side spout
In, it is kneaded, squeezed out and is granulated, obtain modified PA56 composite material.
10. a kind of preparation method of modified PA56 composite material according to claim 9, it is characterised in that: the extrusion
Each area's temperature of equipment is respectively as follows: one Qu Wendu: 210-220 DEG C, two area's temperature: 225-235 DEG C, three Qu Wendu: 240-255
DEG C, four Qu Wendu: 260-275 DEG C, five Qu Wendu: 285-295 DEG C, six Qu Wendu: 260-270 DEG C, seven area's temperature: 250-260
DEG C, eight area's temperature: 240-250 DEG C, nine Qu Wendu: 250-260 DEG C, revolving speed 100-150RPM, the side spout is located at five
Between area and 6th area.
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| CN115322566A (en) * | 2022-09-16 | 2022-11-11 | 无锡腾达精密模塑有限公司 | PA 66-based composite material for motor bearing retainer and preparation method thereof |
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| CN111454571A (en) * | 2020-04-07 | 2020-07-28 | 南京利华工程塑料有限公司 | Preparation method of glass fiber reinforced PA56/PP alloy material |
| CN115322566A (en) * | 2022-09-16 | 2022-11-11 | 无锡腾达精密模塑有限公司 | PA 66-based composite material for motor bearing retainer and preparation method thereof |
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Application publication date: 20191025 |