CN108239394A - A kind of lightweight halogen-free fire-retarding reinforced polyamide composition and preparation method thereof - Google Patents
A kind of lightweight halogen-free fire-retarding reinforced polyamide composition and preparation method thereof Download PDFInfo
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- CN108239394A CN108239394A CN201611221628.XA CN201611221628A CN108239394A CN 108239394 A CN108239394 A CN 108239394A CN 201611221628 A CN201611221628 A CN 201611221628A CN 108239394 A CN108239394 A CN 108239394A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
The invention discloses the preparation method of a kind of lightweight halogen-free fire-retarding reinforced polyamide composition and its composite material, which includes：Polyamide：25 65 parts by weight, fire retardant：5 15 parts by weight, retardant synergist：15 parts by weight, alkali-free glass fibre：20 40 parts by weight, modified Hollow Inorganic powder：5 27 parts by weight and, bulking agent：1 10 parts by weight, polyamide include polyamide 5X resins.The daiamid composition of the present invention, under the premise of polyamide compoiste material density is reduced, mechanical property, heat resistance, flame retardant property for making composite material etc. increases, the promotion of the density and mechanical performance of above-mentioned each ingredient and its content all to light flame-retardant reinforced polyamide plays the role of interwoveness, the lightweight halogen-free fire-retarding reinforced polyamide composition of the present invention, the new performance of polyamide compoiste material is imparted, available for the fields such as automobile instrument panel, building decoration, electric.
Description
Technical field
The present invention relates to a kind of lightweight halogen-free fire-retarding reinforced polyamide compositions and preparation method thereof.
Background technology
Polyamide refers to the polymer on macromolecular chain with amide groups repetitive unit, with good comprehensive performance,
Such as：High intensity and toughness, high-fire resistance, wearability, chemical resistance, also with self lubricity, self-extinguishment, easy processing etc.
Characteristic is to realize " mould Dai Gang " one of main polymeric material of theory.Since the 1950s, polymer modification is passed through
Method develops a series of Polyamide Engineering Plastic with more excellent properties, and application field is constantly expanded.
Polyamide modified is the hot topic studied now.A kind of new material with property is obtained by modified, is compared
It is a kind of relatively low cost, succinct and direct method for the research and development of new polymers.So-called polymer modification is exactly
Inorganic or organic substance is added in by physics and mechanical means in the polymer or different types of polymer is blended or used
Chemical method realizes the copolymerization of polymer, grafting, block, crosslinking or is combined the above method, makes being manufactured into for material to reach
This decline, moulding processability or end-use properties improved or make polymer material only surface and electricity, magnetic, light,
Heat, sound, burning etc. assign the effect of unique function.
Polymer modification key is " changing ", and it is exactly to bring out one's strengths to make up for one's weaknesses to change, and develops and retains the existing excellent properties of polymer,
The shortcomings that inhibiting and overcoming polymer, and assign polymer new performance according to actual needs.Polymer modification is exactly to polymerize
Seek a best equalization point between the performance of object, processing performance and production cost three.
During being modified to polyamide, it will usually select talcum powder, mica, calcium carbonate, wollastonite, glass fibers
The inorganic material such as dimension, fire retardant carry out blending and modifying, polyamide-based composite material are obtained, to further improve the firm of polyamide
Property, shows glossiness, flammability etc. at heat resistance, dimensional stability, chemical resistance.But the density of inorganic material usually compares
Polyamide it is big, the density for leading to composite material is excessive.
By taking glass fibre as an example, as a kind of inorganic non-metallic material haveing excellent performance, advantage is good insulating, heat-resisting
Property is strong, corrosion resistance is good, high mechanical strength.Glass fibre be typically used as reinforcing material in composite material, electrically insulating material and
Heat-insulating material, Related product are applied to national economy every field.But the density of glass fibre is in 2.4-2.6g/cm3
Between, it is one times of polyamide density or more, after the two is prepared into composite material, density is in 1.2-1.8g/cm3Between,
More than the density of base polyamide polyimide resin, so as to make it is application of the glass fiber-reinforced polyamide composite material in terms of lightweight
It is very limited.
Again by taking fire retardant as an example, Polyamide Engineering Plastic has flame retardant property very high in the application in electric field
It is required that.However, the self-extinguishment of polyamide can not meet the flame-retardancy requirements in electric field, therefore, needed in modifying process
Fire retardant is added, further improves the fire-retardant rank of Polyamide Engineering Plastic.
Also, in some application fields, it is desirable to which polyamide compoiste material not only has excellent performance, it is expected simultaneously
Composite material has lower density in itself, and such as automotive light weight technology it is expected the premise in the intensity and security performance for ensureing automobile
Under, the kerb weight (weight) of automobile is reduced as much as possible, so as to improve the dynamic property of automobile, reduces fuel consumption, the row of reduction
Gas pollutes.It has been proved that car mass reduces half, fuel consumption can also reduce nearly half for experiment.Due to environmentally friendly and energy saving
Needs, the lightweight of automobile has become the trend of world car development.
At present, the preparation of lightweight polyamide material is generally realized by foaming technique, such as expanded polystyrene (EPS) (XPS),
Expanded polypropylene (XPP) etc..But in foaming process, shape, size of microvesicle etc. are difficult to control, and usually make polyamide material product
Inside generates defect, loses part excellent performance, and expanded material, often due to stomata is bigger, defect is more, also often makes to gather
The mechanical property for closing object material significantly declines.
Polyamide 5X is a kind of novel high molecular polymer, still the primary stage in research and development, therefore, using it as base
Material prepares lightweight polymeric material, is existing one great challenge of field of macromolecule polymerization.
Invention content
The present invention in order to overcome lightweight polymeric material in the prior art be difficult to meet existing requirement to lightweight, poor performance,
The problem of defect is more provide the preparation side of a kind of novel lightweight halogen-free fire-retarding reinforced polyamide composition and its composite material
Method.The present invention lightweight halogen-free fire-retarding reinforced polyamide composition can while global density is reduced, improve its mechanical property,
Heat resistance etc., while the processing fluidity of polyamide can be improved.
An object of the present invention：A kind of daiamid composition, the daiamid composition include each of following parts by weight
Ingredient：
Polyamide：25-65 parts by weight,
Fire retardant：5-15 parts by weight,
Retardant synergist：1-5 parts by weight,
Alkali-free glass fibre：20-40 parts by weight,
Modified Hollow Inorganic powder：5-27 parts by weight,
With bulking agent：1-10 parts by weight；
Wherein, the polyamide includes polyamide 5X resins.
The preferred technical solution of above-mentioned technical proposal is illustrated below：
A preferred technical solution of the invention, the polyamide 5X refer to 1,5- pentanediamines and dicarboxylic acids for monomer
It polymerize obtained polyamide.Wherein described dicarboxylic acids can be short chain diacid (carbon atom number is less than 10 in carbochain), also may be used
To be long carbochain biatomic acid；Wherein, the short chain diacid preferably includes succinic acid, glutaric acid, adipic acid, pimelic acid, and pungent two
Acid, azelaic acid, preferably decanedioic acid, adipic acid, decanedioic acid；The long carbochain biatomic acid preferably includes eleven carbon diacids, and 12
Carbon dicarboxylic acid, tridecanyldicarboxylic acid, tetradecane diacid, 15 carbon dicarboxylic acids, 16-dicarboxylic acid, seventeen carbon diacids, ten
Eight carbon dicarboxylic acids, maleic acid, Δ 9-1,18 octadecylene binary acid.
A preferred technical solution of the invention, the polyamide can also include its other than polyamide 5X resins
Its polyamide, other described polyamide include：Polyamide 6, polyamide 66, polyamide 69, polyamide 610, polyamide
612nd, it is one or more in polyamide 1010, polyamide 11, polyamide 12 and polyamide 1414.
A preferred technical solution of the invention, it is aggregated that the polyamide 5X includes the monomer of polyamide from biology base
Obtained polyamide；The biological poly amide monomer obtains preferably by biofermentation method or by sustainable day
Right compound is processed through chemical technology to be obtained.It is preferred that the 1,5- pentanediamines is obtain by biofermentation method.
A preferred technical solution of the invention, the polyamide 5X include the biomass source of 35-100%.
A preferred technical solution of the invention, the relative viscosity of 96% (mass percent) sulfuric acid of the polyamide 5X
For 2.4-3.2.
A preferred technical solution of the invention, the polyamide 5X preferred polyamides 56.The polyamide 56 be with 1,
5- pentanediamines and adipic acid are obtained for polymerizable raw material.The relative viscosity of 96% (mass percent) sulfuric acid of the polyamide 56 is excellent
Select 2.4-3.2.
A preferred technical solution of the invention, the modified Hollow Inorganic powder are included with coupling agent to Hollow Inorganic powder
Body is modified the modification Hollow Inorganic powder obtained after processing.The preferred 8-20 weights of parts by weight of the modified Hollow Inorganic powder
Measure part.
Wherein, the coupling agent includes：Silane coupling agent and/or titante coupling agent；
The silane coupling agent preferably includes：Gamma-aminopropyl-triethoxy-silane (NH2CH2CH2CH2Si(OC2H5)3,
Trade name：KH550), g- aminopropyl trimethoxysilanes (NH2(CH2)3Si(OCH3)3, trade name：KH551), γ-(2,3- rings
The third oxygen of oxygen) propyl trimethoxy silicane (CH2-CH(O)CH2-O(CH2)3Si(OCH3)3, trade name：KH560), γ-(methyl-prop
Alkene acyl-oxygen) propyl trimethoxy silicane (CH3CCH2COO(CH2)3Si(OCH3)3, trade name：KH570), N- β-(aminoethyl)-
γ-aminopropyltriethoxy dimethoxysilane (NH2CH2CH2NH2CH2CH2CH2SiCH3(OCH3)2, trade name：KH602)、N-β-
(aminoethyl)-γ-aminopropyltrimethoxysilane (NH2CH2CHNHCH2CH2CH2Si(OCH3)3, trade name：) and ethylene KH792
Ethyl triethoxy silicane alkane (CH2=CHSi (OCH2CH3)3, trade name：KH151 it is one or more in)；
The titante coupling agent preferably includes：Two oleic acid acyloxy of isopropyl (dioctyl phosphoric acid acyloxy) titanate esters
(C55H111O9Ti, trade name：NDZ101), three oleic acid acyloxy of isopropyl (trioctylphosphine phosphoric acid acyloxy) titanate esters
(C54H106O7Ti, trade name：NDZ105), isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters (C51H112O22P6Ti, commodity
Name：) and Di(dioctylpyrophosphato) ethylene titanate (C NDZ20134H74O16P4Ti, trade name：NDZ311 one in)
Kind is a variety of.
A preferred technical solution of the invention, the Hollow Inorganic powder include hollow glass micropearl, hollow ceramic powder,
One or more kinds of compositions in hollow titanium dioxide.Preferred 35-70 μm of the grain size of the Hollow Inorganic powder；The sky
The preferred 0.10-0.64g/m of real density of heart inorganic particle3。
A preferred technical solution of the invention, the modified Hollow Inorganic raw powder's production technology include the following steps：
(1) under agitation, it by the solution of the alcohol-water of misty coupling agent, sprays into Hollow Inorganic powder, mixes
It closes, obtains middle product；
(2) middle product is dried, you can.
Wherein, a concentration of 20-40% of the solution of the alcohol-water of the coupling agent, the percentage account for second for coupling agent
The mass percent of alcohol-water solution.
Wherein, the weight ratio of the Hollow Inorganic powder and the coupling agent is (5-25)：(0.01-2).
Wherein, the preferred 600-800rpm of rotating speed during the mixing.
Wherein, preferred 60-80 DEG C of the temperature during mixing.
Wherein, the time of the mixing preferred 3-5min.
Wherein, preferred 70-90 DEG C of the temperature of the drying, more preferable 75-85 DEG C.
Wherein, the time of the drying preferred 8-16h, most preferably more preferable 10-14h, 11-13h.
In the present invention, the fire retardant is this field conventional flame retardants.A preferred technical solution of the invention, the resistance
Combustion agent includes：Melamine cyanurate (MCA).
In the present invention, the retardant synergist is this field conventional flame retardant synergist.A preferred technical side of the invention
Case, the retardant synergist include：One kind in zinc borate, sodium-based montmorillonite, phenoxy cyclotriphosphazene and triphenyl phosphate or
It is a variety of.
In the present invention, the alkali-free glass fibre is also known as E glass fibres, refers to the low glass fibers of alkali metal oxide content
Dimension.In general, alkali-free glass fibre R2O content is less than 0.8%, and main component is aluminoborosilicate.
A preferred technical solution of the invention, a diameter of 6-15 μm of the alkali-free glass fibre.
A preferred technical solution of the invention, the bulking agent include：Methyl methacrylate-butadiene-styrene
Copolymer, methyl methacrylate-ethyl acrylate, random ethylene-butyl acrylate copolymer, random ethylene-acrylic acid first
Ester copolymer, random ethylene-methyl acrylate-copolymer-maleic anhydride, Ethylene-butyl acrylate-Glycidyl methacrylate are sweet
Grease copolymer, maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride stem grafting polyolefin elastomer, horse
Maleic anhydride grafted ethylene propylene diene rubber, maleic anhydride grafted ethene-vinyl acetate, maleic anhydride grafting hydrogenated butadiene-benzene
Ethylene block copolymer, maleic anhydride grafted ethene-butadiene-styrene copolymer, methyl methacrylate-butadiene-benzene
It is one or more in ethylene-dien terpolymer.
A preferred technical solution of the invention, the daiamid composition further include other auxiliary agents, wherein it is described other
Auxiliary agent includes：It is one or more in lubricant, nucleating agent and antioxidant.
A preferred technical solution of the invention, the content of other auxiliary agents is 1-5 parts by weight.
Wherein, the lubricant preferably includes：N, N'- ethylene bis stearamide, oxidized polyethylene wax, polyethylene-acetic acid
Ethylene waxes, partly-hydrolysed polyethylene wax, oleamide, erucyl amide, pentaerythritol stearate, montanate, calcium stearate,
It is one or more in zinc stearate, odium stearate, barium stearate and the macromolecule organic silicon.
Wherein, the nucleating agent preferably includes：P22, montanic acid calcium, montanic acid sodium, polyacrylic acid ionomer, organic illiteracy take off
It is one or more in soil, superfine talcum powder, ultra-fine mica, aluminium oxide and magnesia.
Wherein, antioxidant preferably includes：For N, N- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) oneself two
Amine, β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, three [2.4- di-tert-butyl-phenyls] phosphite esters,
Bis- (2,4- di-tert-butyl-phenyls) propionic acid] pentaerythritol diphosphites, 2,2- methylene-bis- (4- ethyl -6- tert-butyl phenols),
Inclined fourth support-bis--(the 6- tert-butyl-m-cresols) of 4,4-, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane and 1,3,
It is one or more in 5- trimethyls -2,4,6- three (- 4 hydroxybenzyl of 3,5- di-t-butyls) benzene.
It is a further object to provide a kind of preparation method of polyamide resin composite material, the preparation methods
Include the following steps：
By the polyamide, the modified Hollow Inorganic powder, the alkali-free glass fibre, the fire retardant, institute
Retardant synergist and the bulking agent are stated, as described above ratio, are uniformly mixed, extrusion molding, you can；
Or, by the polyamide, the modified Hollow Inorganic powder, the alkali-free glass fibre, the fire retardant,
The retardant synergist, the bulking agent and other described auxiliary agents, ratio, is uniformly mixed, extrusion molding, i.e., as described above
It can.
Wherein, it is preferred that the polyamide and the bulking agent are first uniformly mixed to obtain mixture A, alternatively, first will
The modified Hollow Inorganic powder, the fire retardant and the fire retarding synergist are uniformly mixed to obtain mixture B, then by the mixing
Object A and mixture B and the alkali-free glass fibre are uniformly mixed.
According to being commonly understood by for those skilled in the art, the preparation of mixture A and mixture B, there is no sequencings.
I.e.：It mixture A can first be prepared prepares mixture B again or first prepares mixture B and prepare mixture A again；Alternatively, the same time-division
Mixture A and mixture B are not prepared.
Wherein, it is preferred that the polyamide and the bulking agent are uniformly mixed, and are carried out in mixing machine.
Wherein, it is preferred that when the polyamide and the bulking agent are uniformly mixed, the rotating speed during mixing is
600-800rpm。
Wherein, it is preferred that when the polyamide and the bulking agent are uniformly mixed, the temperature of the mixing is 60-
80℃。
Wherein, it is preferred that the time that the polyamide and the bulking agent are uniformly mixed is 3-5min.
Wherein, it is preferred that the modified Hollow Inorganic powder, the fire retardant and the fire retarding synergist are uniformly mixed,
It is carried out in mixing machine.
Wherein, it is preferred that the modified Hollow Inorganic powder, the fire retardant and the fire retarding synergist are uniformly mixed
When, the rotating speed during mixing is 500-600rpm.
Wherein, it is preferred that the modified Hollow Inorganic powder, the fire retardant and the fire retarding synergist are uniformly mixed
When, the temperature of the mixing is room temperature.
Wherein, it is preferred that the modified Hollow Inorganic powder, the fire retardant and the fire retarding synergist were uniformly mixed
Time is 3-5min.
Wherein, it is preferred that the operation for being uniformly mixed the mixture A and mixture B and the alkali-free glass fibre,
It carries out in double screw extruder, is more preferably carried out in same phase double screw extruder.
Wherein, it is preferred that the temperature of the double screw extruder is 250-285 DEG C.
Wherein, it is preferred that the rotating speed of the double screw extruder is 150-250rpm, preferably 180-220rpm.
When further including other auxiliary agents in the polyamide, other described auxiliary agents and the polyamide and described
Bulking agent is uniformly mixed, then the operation after carrying out.
Wherein, it is preferred that a kind of preparation method of daiamid composition, the preparation method include the following steps：
(1) polyamide and the bulking agent are uniformly mixed in high-speed mixer, wherein, the high speed is mixed
The rotating speed of conjunction machine is 600-800rpm, incorporation time 3-5min；
(2) hollow glass micropearl, fire retardant, fire retarding synergist will be modified to be uniformly mixed in high-speed mixer, it is mixed at a high speed
The rotating speed of conjunction machine be 500-600rpm, mixed at room temperature, incorporation time 3-5min；
(3) main spout of the material through double screw extruder being uniformly mixed in step (1) is added in into double screw extruder
In, and be uniformly mixed at obtained side spout of the material through double screw extruder and add in step (2), by the alkali-free glass
Fiber is added in from another side spout, is uniformly mixed, wherein, the temperature of double screw extruder temperature is 250-285 DEG C, twin-screw
Rotating speed is 150-250pm.
Wherein, for add in the modified Hollow Inorganic powder, the fire retardant, the retardant synergist the side feed
Material mouth is the side spout at double screw extruder discharging die orifice 1/3-3/5 spiro rod lengths position.
Wherein, it is the side spout at nearly discharging die orifice for adding in another side spout of alkali-free glass fibre.
When further including other auxiliary agents in the polyamide, the auxiliary agent is in step (1), with the polyamide resin
Fat and the bulking agent are uniformly mixed.
According to this field routine, there is no limit can first carry out step (1) and carry out step again the sequence of step (1) and (2)
(2) or, first step (2) is carried out, then carries out step (1) or carries out step (1) and step (2) respectively simultaneously.
The present invention is using modified Hollow Inorganic powder, fire retardant, retardant synergist, alkali-free glass fibre and bulking agent, system
Standby lightweight halogen-free fire-retarding reinforced polyamide, wherein, modified Hollow Inorganic powder, fire retardant, retardant synergist, alkali-free glass fibre
And bulking agent, there is synergistic effect, under the premise of polyamide compoiste material density is reduced, make the mechanical property, resistance to of composite material
Hot property, flame retardant property etc. increase, and above-mentioned each ingredient and its content are all to the density of lightweight halogen-free fire-retarding reinforced polyamide
It improves and the promotion of mechanical performance plays the role of interwoveness, lightweight halogen-free fire-retarding reinforced polyamide composition of the invention is assigned
The performance that polyamide compoiste material is new is given, available for the fields such as automobile instrument panel, building decoration, electric.
On the other hand, the polyamide in the present invention preferably synthesizes to obtain by the monomer of polyamide from biology base.Currently,
For polyamide raw materials more than 99% from fossil fuel, biological poly amide just becomes Showed Very Brisk.The biology of large-scale production
Based polyamide mainly has full biological poly amide and part biological based polyamide, and full biological poly amide is with castor oil, glucose
For raw material, and one kind in the diamine of part biological based polyamide or binary acid starting material is from non-fossil fuel or primary former
Material is from fossil fuel.Compared with traditional polyamide, the industrial chain of biological poly amide is not only reduced to non-renewable resources
Consumption, and GHG emissions mitigation 50% or so.
Specific embodiment
The present invention is described in further detail with reference to embodiments, but the present invention is not limited to these Examples.
The method for testing performance of lightweight halogen-free fire-retarding reinforced polyamide resin is with reference to testing standard once in the present invention：
Density：ISO 1183-1:The non-foam plastic density assay method first part of 2004 plastics：Infusion process, liquid ratio
Weight method and titration；
Tensile property：ISO 527-2:The measure of 1993 plastic tensile performances, second part：Molding and extruding plastics testing
Condition；
Bending property：ISO 178:2001 plastics bending properties are tested；
Izod notched impact strength：ISO 180:The measure of 2001 plastics Chalpy impact performances；
Flame retardant property (vertical combustion performance)：UL-94 plastic material combustion testings.
Embodiment 1
Polyamide 56 (PA56, relative sulfuric acid viscosity 2.72)：3085g
Flame-retardants melamine cyanurate：350g
Retardant synergist zinc borate：150g
Alkali-free glass fibre：1000g
Hollow glass micropearl (56 μm of grain size, real density 0.32g/cm3, resistance to compression 13.78MPa)：250g
Bulking agent Methyl Methacrylate-Butadiene-Styrene Copolymer MBS：100g
Coupling agent KH-550：2.5g
Other auxiliary combinations (including EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098)：
62.5g
The preparation method of 56 resin of lightweight halogen-free fire-retarding reinforced polyamide：
(1) 50g coupling agents KH-550 is scattered in 150g alcohol-waters (mass ratio 1：1) in, then under high velocity agitation will
Mixed solution is uniformly sprayed at the surface of hollow glass micropearl, makes the uniform coated hollow glass bead of coupling agent；High-speed mixer
Rotating speed for 600-800rpm, mixing temperature is 60-80 DEG C, incorporation time 3-5min；
(2) and then by uniformly mixed material 12h is dried under 80 DEG C of environment, obtains modified hollow glass micropearl；
(3) polyamide 56 (PA56), bulking agent, other auxiliary combinations are uniformly mixed in high-speed mixer, it is mixed at a high speed
The rotating speed of conjunction machine be 500-600rpm, mixed at room temperature, incorporation time 3-5min；
(4) modification hollow glass micropearl, fire retardant, the retardant synergist obtained step (2) mixes in high-speed mixer
Close uniform, the rotating speed of high-speed mixer is 500-600rpm, mixed at room temperature, incorporation time 3-5min；
(5) the uniformly mixed material that step (3) obtains is positioned in the main spout of extruder；Step (4) is obtained
To uniformly mixed material be positioned over close to main feeding side side feeding container in；Alkali-free glass fibre is positioned over simultaneously
In the side feeding container of die orifice side；
(6) double screw extruder squeezes out, and each area's (from main feeding section to die head) temperature setting is followed successively by：180℃、220℃、
240 DEG C, 260 DEG C, 270 DEG C, 270 DEG C and 265 DEG C, twin-screw rotating speed is 200rpm；
Wherein, according to this field routine, step (1) and (2), and step (3) can be carried out at the same time, and can also first be carried out
Step (1) and (2) carry out step (2) or, first carry out step (3), then carry out step (1) and (2) again.
The dry 6h at 80 DEG C is sliced by obtained, then prepares test bars, each area's temperature of extruder temperature by iso standard
Degree setting is followed successively by (from spout to nozzle)：240 DEG C, 250 DEG C, 260 DEG C, 265 DEG C and 265 DEG C.
Then test bars are sealed 48h at 23 DEG C, mechanical property is tested according to iso standard, anti-flammability
It can be according to UL-94 plastic material combustion testings.
Test result is referring to table 1.
Embodiment 2
Polyamide 56 (PA56, relative sulfuric acid viscosity 2.72)：2332.5g
Flame-retardants melamine cyanurate：350g
Retardant synergist phenoxy cyclotriphosphazene：150g
Alkali-free glass fibre：1500g
Hollow glass micropearl (56 μm of grain size, real density 0.32g/cm3, resistance to compression 13.78MPa)：500g
Bulking agent MBS：100g
Coupling agent KH-550：5g
Other auxiliary combinations (including EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098)：
62.5g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 3
Polyamide 56 (PA56, relative sulfuric acid viscosity 2.72)：1580g
Flame-retardants melamine cyanurate：350g
Retardant synergist triphenyl phosphate：150g
Alkali-free glass fibre：2000g
Hollow glass micropearl (56 μm of grain size, real density 0.32g/cm3, resistance to compression 13.78MPa)：750g
Bulking agent MBS：100g
Coupling agent KH-550：7.5g
Other auxiliary combinations (including EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098)：
62.5g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 4
Polyamide 56 (PA56, relative sulfuric acid viscosity 2.72)：2585g
Flame-retardants melamine cyanurate：350g
Retardant synergist triphenyl phosphate：150g
Alkali-free glass fibre：1500g
Hollow glass micropearl (45 μm of grain size, real density 0.40g/cm3, resistance to compression 27.56MPa)：250g
Bulking agent MBS：100g
Coupling agent KH-550：2.5g
Other auxiliary combinations (including EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098)：
62.5g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 5
Polyamide 56 (PA56, relative sulfuric acid viscosity 2.72)：1832.5g
Flame-retardants melamine cyanurate：350g
Retardant synergist zinc borate：150g
Alkali-free glass fibre：2000g
Hollow glass micropearl (45 μm of grain size, real density 0.40g/cm3, resistance to compression 27.56MPa)：500g
Bulking agent MBS：100g
Coupling agent KH-550：5g
Other auxiliary combinations (including EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098)：
62.5g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 6
Polyamide 56 (PA56, relative sulfuric acid viscosity 2.72)：2580g
Flame-retardants melamine cyanurate：350g
Retardant synergist phenoxy cyclotriphosphazene：150g
Alkali-free glass fibre：1000g
Hollow glass micropearl (45 μm of grain size, real density 0.40g/cm3, resistance to compression 27.56MPa)：750g
Bulking agent MBS：100g
Coupling agent KH-550：7.5g
Other auxiliary combinations (including EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098)：
62.5g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 7
Polyamide 56 (PA56, relative sulfuric acid viscosity 2.72)：2085g
Flame-retardants melamine cyanurate：350g
Retardant synergist phenoxy cyclotriphosphazene：150g
Alkali-free glass fibre：2000g
Hollow glass micropearl (45 μm of grain size, real density 0.46g/cm3, resistance to compression 41.34MPa)：250g
Bulking agent MBS：100g
Coupling agent KH-550：2.5g
Other auxiliary combinations (including EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098)：
62.5g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 8
Polyamide 56 (PA56, relative sulfuric acid viscosity 2.72)：2832.5g
Flame-retardants melamine cyanurate：350g
Retardant synergist triphenyl phosphate：150g
Alkali-free glass fibre：1000g
Hollow glass micropearl (45 μm of grain size, real density 0.46g/cm3, resistance to compression 41.34MPa)：500g
Bulking agent MBS：100g
Coupling agent KH-550：5g
Other auxiliary combinations (including EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098)：
62.5g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 9
Polyamide 56 (PA56, relative sulfuric acid viscosity 2.72)：2080g
Flame-retardants melamine cyanurate：350g
Retardant synergist zinc borate：150g
Alkali-free glass fibre：1500g
Hollow glass micropearl (45 μm of grain size, real density 0.46g/cm3, resistance to compression 41.34MPa)：750g
Bulking agent MBS：100g
Coupling agent KH-550：7.5g
Other auxiliary combinations (including EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098)：
62.5g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 10
Polyamide 56 (PA56, relative sulfuric acid viscosity 2.72)：1709.5g
Polyamide 1010 (PA1010, relative sulfuric acid viscosity 2.66)：1123g
Flame-retardants melamine cyanurate：350g
Retardant synergist zinc borate：150g
Alkali-free glass fibre：1000g
Hollow glass micropearl (56 μm of grain size, real density 0.32g/cm3, resistance to compression 13.78MPa)：500g
Bulking agent MBS：100g
Coupling agent KH-550：5g
Other auxiliary combinations (including EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098)：
62.5g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 11
Polyamide 56 (PA56, relative sulfuric acid viscosity 2.72)：1309.5g
Polyamide 1010 (PA1010, relative sulfuric acid viscosity 2.66)：923g
Flame-retardants melamine cyanurate：350g
Retardant synergist phenoxy cyclotriphosphazene：150g
Alkali-free glass fibre：1500g
Hollow glass micropearl (45 μm of grain size, real density 0.40g/cm3, resistance to compression 27.56MPa)：500g
Bulking agent MBS：100g
Coupling agent KH-550：5g
Other auxiliary combinations (including EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098)：
62.5g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 12
Polyamide 56 (PA56, relative sulfuric acid viscosity 2.72)：1009.5g
Polyamide 1010 (PA1010, relative sulfuric acid viscosity 2.66)：723g
Flame-retardants melamine cyanurate：350g
Retardant synergist triphenyl phosphate：150g
Alkali-free glass fibre：2000g
Hollow glass micropearl (45 μm of grain size, real density 0.46g/cm3, resistance to compression 41.34MPa)：500g
Bulking agent MBS：100g
Coupling agent KH-550：5g
Other auxiliary combinations (including EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098)：
62.5g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Comparative example 1
Polyamide 56 (PA56, relative sulfuric acid viscosity 2.72)：3332.5g
Flame-retardants melamine cyanurate：350g
Retardant synergist zinc borate：150g
Alkali-free glass fibre：1000g
Bulking agent MBS：100g
Other auxiliary combinations (including EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098)：
62.5g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Comparative example 2
Polyamide 56 (PA56, relative sulfuric acid viscosity 2.72)：2837.5g
Flame-retardants melamine cyanurate：350g
Retardant synergist phenoxy cyclotriphosphazene：150g
Alkali-free glass fibre：1500g
Bulking agent MBS：100g
Other auxiliary combinations (including EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098)：
62.5g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Comparative example 3
Polyamide 56 (PA56, relative sulfuric acid viscosity 2.72)：2337.5g
Flame-retardants melamine cyanurate：350g
Retardant synergist triphenyl phosphate：150g
Alkali-free glass fibre：2000g
Bulking agent MBS：100g
Other auxiliary combinations (including EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098)：
62.5g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Table 1：The performance of lightweight halogen-free fire-retarding reinforced polyamide composition compares
As seen from the above table：Modified Hollow Inorganic powder, alkali-free glass fibre, fire retardant, retardant synergist and bulking agent,
Under the conditions of specific ratio, the same of composite density (density of composite material can reduce by more than 10%) can reduced
When, improve tensile strength, bending strength, bending modulus notch impact strength and the flame retardant property of composite material.
For being modified Hollow Inorganic powder, to the items of lightweight halogen-free fire-retarding reinforced polyamide resin composite materials
It can have a certain impact.Also, further, in order to realize better effect, inventor is investigated modified Hollow Inorganic
Influence of the various parameters performance of powder to entire lightweight halogen-free fire-retarding reinforced polyamide resin composite materials is found：It is modified empty
The improvement of the real density of heart inorganic particle, compression strength etc., can realize better effect.Also, modified Hollow Inorganic powder
Dosage also have an impact to the mechanical property of composite material.Modified Hollow Inorganic powder can serve as lubricant in itself, not only have
Conducive to the dispersion of promotion alkali-free glass fibre and fire retardant/retardant synergist, and lightweight halogen-free flame-proof reinforced poly acyl can be made
The reservation length of glass fibre is more than the sample without addition modification Hollow Inorganic powder in polyimide resin composite material, be conducive into
One step improves the mechanical property of lightweight halogen-free fire-retarding reinforced polyamide resin composite materials.Simultaneously as modified Hollow Inorganic powder
The lubricating action of body reduces flame retardant grade Partial digestion caused by shearing heating in process, is also beneficial to fire retardant in base
Dispersion in body, the efficiency for being conducive to improve fire retardant play.
Also, in terms of the selection of retardant synergist, phenoxy cyclotriphosphazene and triphenyl phosphate ratio zinc borate are selected more
Be conducive to improve the mechanical property of composite material.
The above-mentioned description to embodiment be in order to further illustrate with the application of the invention, therefore, the present invention is not limited to implement
Invention content cited by example, those skilled in the art do not depart from the improvement that scope is made according to the announcement of invention
With modification all within protection scope of the present invention.
Claims (13)
1. a kind of daiamid composition, it is characterised in that：The daiamid composition includes each ingredient of following parts by weight：
Polyamide：25-65 parts by weight,
Fire retardant：5-15 parts by weight,
Retardant synergist：1-5 parts by weight,
Alkali-free glass fibre：20-40 parts by weight,
Modified Hollow Inorganic powder：5-27 parts by weight,
With bulking agent：1-10 parts by weight；
Wherein, the polyamide includes polyamide 5X resins.
2. daiamid composition as described in claim 1, it is characterised in that：The polyamide 5X refers to 1,5- pentanediamines and two
First carboxylic acid is the polyamide that monomer polymerization obtains；Wherein described dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid,
Suberic acid, azelaic acid, decanedioic acid, eleven carbon diacids, dodecanedicarboxylic acid, tridecanyldicarboxylic acid, tetradecane diacid, 15
Carbon dicarboxylic acid, 16-dicarboxylic acid, seventeen carbon diacids, octadecane diacid, maleic acid and Δ 9-1,18 octadecylene binary acid
In it is one or more.
3. daiamid composition as claimed in claim 2, it is characterised in that：
The polyamide 5X includes the aggregated obtained polyamide of the monomer of polyamide from biology base；
The biological poly amide monomer is preferably obtained by biofermentation method；The polyamide 5X preferably includes 35-100%
Biomass source；
The polyamide 5X preferred polyamides 56；The relative viscosity of 96% sulfuric acid of the polyamide 5X is 2.4-3.2；
And/or the polyamide further includes other polyamides other than polyamide 5X resins, other described polyamide
Including：Polyamide 6, polyamide 66, polyamide 69, polyamide 610, polyamide 612, polyamide 1010, polyamide 11, polyamide
12 and polyamide 1414 in it is one or more.
4. the daiamid composition as described in claim any one of 1-3, it is characterised in that：The modified Hollow Inorganic powder includes
The modification Hollow Inorganic powder obtained after processing is modified Hollow Inorganic powder with coupling agent；
The preferred 8-20 parts by weight of parts by weight of the modified Hollow Inorganic powder.
5. daiamid composition as claimed in claim 4, it is characterised in that：The coupling agent includes：Silane coupling agent and/or
Titante coupling agent；
The silane coupling agent preferably includes：Gamma-aminopropyl-triethoxy-silane, g- aminopropyl trimethoxysilanes, γ-
(the third oxygen of 2,3- epoxies) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, N- β-(ammonia second
Base) three second of-γ-aminopropyltriethoxy dimethoxysilane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane and vinyl
It is one or more in oxysilane；
The titante coupling agent preferably includes：It is two oleic acid acyloxy of isopropyl (dioctyl phosphoric acid acyloxy) titanate esters, different
Three oleic acid acyloxy of propyl (trioctylphosphine phosphoric acid acyloxy) titanate esters, (dioctylphyrophosphoric acid acyloxy) titanate esters of isopropyl three and
It is one or more in Di(dioctylpyrophosphato) ethylene titanate；
The Hollow Inorganic powder includes one or more in hollow glass micropearl, hollow ceramic powder, hollow titanium dioxide；Institute
State preferred 35-70 μm of the grain size of Hollow Inorganic powder；The preferred 0.10-0.64g/m of real density of the Hollow Inorganic powder3。
6. daiamid composition as claimed in claim 4, it is characterised in that：The modified Hollow Inorganic raw powder's production technology packet
Include following steps：
(1) under agitation, it by the solution of the alcohol-water of misty coupling agent, sprays into Hollow Inorganic powder, mixing obtains
Middle product；
(2) middle product is dried, you can.
7. daiamid composition as claimed in claim 6, it is characterised in that：The concentration of the solution of the alcohol-water of the coupling agent
For 20-40%, the percentage accounts for the mass percent of ethanol-water solution for coupling agent；
And/or the weight ratio of the Hollow Inorganic powder and the coupling agent is (5-25)：(0.01-2)；
And/or the preferred 600-800rpm of rotating speed during the mixing；
And/or preferred 60-80 DEG C of temperature during the mixing；
And/or the time preferred 3-5min of the mixing；
And/or preferred 70-90 DEG C, more preferable 75-85 DEG C of the temperature of the drying；
And/or the time preferred 8-16h, most preferably more preferable 10-14h, 11-13h of the drying.
8. the daiamid composition as described in claim any one of 1-3, it is characterised in that：The fire retardant includes：Melamine
Cyanurate；
And/or the retardant synergist includes：In zinc borate, sodium-based montmorillonite, phenoxy cyclotriphosphazene and triphenyl phosphate
It is one or more.
9. the daiamid composition as described in claim any one of 1-3, it is characterised in that：The alkali-free glass fibre it is a diameter of
6-15μm。
10. the daiamid composition as described in claim any one of 1-3, it is characterised in that：The bulking agent includes：Metering system
Sour methyl esters-butadiene-styrene copolymer, methyl methacrylate-ethyl acrylate, random ethylene-butyl acrylate copolymerization
Object, random ethylene-methyl acrylate copolymer, random ethylene-methyl acrylate-copolymer-maleic anhydride, ethylene-acrylic acid fourth
Ester-glycidyl methacrylate copolymer, maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride
Grafted polyolefin olefin elastomer, maleic anhydride grafting ethylene propylene diene rubber, maleic anhydride grafted ethene-vinyl acetate, maleic acid
Acid anhydride grafting hydrogenated butadiene-styrene block copolymer, maleic anhydride grafted ethene-butadiene-styrene copolymer, methyl-prop
It is one or more in e pioic acid methyl ester-butadiene-styrene terpolymer.
11. the daiamid composition as described in claim any one of 1-3, it is characterised in that：The daiamid composition further includes
Other auxiliary agents；Other wherein described auxiliary agents include：It is one or more in lubricant, nucleating agent and antioxidant；Described other help
The preferred 1-5 parts by weight of content of agent.
12. a kind of side that polyamide resin composite material is prepared with any one of the claim 1-11 daiamid compositions
Method, it is characterised in that：The preparation method includes the following steps：
By the polyamide, the modified Hollow Inorganic powder, the alkali-free glass fibre, the fire retardant, the resistance
Synergist and the bulking agent are fired, according to the ratio as described in claim 1-11, is uniformly mixed, extrusion molding, you can；
Or, by the polyamide, the modified Hollow Inorganic powder, the alkali-free glass fibre, the fire retardant, described
Retardant synergist, the bulking agent and other described auxiliary agents according to the ratio as described in claim 1-11, are uniformly mixed, squeeze out
Molding, you can.
13. method as claimed in claim 12, it is characterised in that：
The polyamide and the bulking agent are first uniformly mixed to obtain mixture A, alternatively, first by the modified Hollow Inorganic
Powder, the fire retardant and the fire retarding synergist are uniformly mixed to obtain mixture B, then by the mixture A and mixture B and institute
Alkali-free glass fibre is stated to be uniformly mixed；
The preparation of mixture A and mixture B first prepare mixture A and prepare mixture B again without sequencing；Or, first prepare mixing
Object B prepares mixture A again；Or, prepare mixture A and mixture B respectively simultaneously；
And/or, it is preferred that when the polyamide and the bulking agent are uniformly mixed, the rotating speed during mixing is 600-
800rpm；
And/or, it is preferred that when the polyamide and the bulking agent are uniformly mixed, the temperature of the mixing is 60-80
℃；
And/or, it is preferred that the time that the polyamide and the bulking agent are uniformly mixed is 3-5min；
And/or, it is preferred that when the modified Hollow Inorganic powder, the fire retardant and the fire retarding synergist are uniformly mixed, institute
Rotating speed when stating mixing is 500-600rpm；
And/or, it is preferred that when the modified Hollow Inorganic powder, the fire retardant and the fire retarding synergist are uniformly mixed, institute
The temperature for stating mixing is room temperature；
And/or, it is preferred that the modified Hollow Inorganic powder, the fire retardant and the fire retarding synergist be uniformly mixed when
Between be 3-5min；
And/or, it is preferred that the operation for being uniformly mixed the mixture A and mixture B and the alkali-free glass fibre, double
It carries out in screw extruder, is more preferably carried out in same phase double screw extruder；
And/or, it is preferred that the temperature of the double screw extruder is 250-285 DEG C；
And/or, it is preferred that the rotating speed of the double screw extruder is 150-250rpm, more preferably 180-220rpm；
When further including other auxiliary agents in the polyamide, other described auxiliary agents and the polyamide and the increase-volume
Agent is uniformly mixed, then the operation after carrying out.
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