CN108239393A - A kind of lightweight daiamid composition and preparation method thereof - Google Patents
A kind of lightweight daiamid composition and preparation method thereof Download PDFInfo
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- CN108239393A CN108239393A CN201611221091.7A CN201611221091A CN108239393A CN 108239393 A CN108239393 A CN 108239393A CN 201611221091 A CN201611221091 A CN 201611221091A CN 108239393 A CN108239393 A CN 108239393A
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a kind of daiamid composition and preparation method thereof, which includes each ingredient of following parts by weight：Polyamide：55 95 parts by weight, modified Hollow Inorganic powder：5 37 parts by weight and, bulking agent：1 10 parts by weight；Wherein, the polyamide includes polyamide 5X resins.The present invention is using modified Hollow Inorganic powder, prepare lightweight polyamide, modified Hollow Inorganic powder and bulking agent have synergistic effect, under the premise of the density for reducing polyamide compoiste material, mechanical property, heat resistance for making composite material etc. increases, the promotion of the density and mechanical performance of the two and its content all to lightweight polyamide plays the role of interwoveness, the polyamide 5X resin combinations 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 daiamid 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.
In some application fields, it is desirable to which polyamide compoiste material not only has excellent performance, while it is expected compound
Material has lower density in itself, and such as automotive light weight technology it is expected under the premise of the intensity and security performance for ensureing automobile, to the greatest extent
The kerb weight (weight) of automobile is possibly reduced, so as to improve the dynamic property of automobile, fuel consumption is reduced, it is dirty to reduce exhaust
Dye.It has been proved that car mass reduces half, fuel consumption can also reduce nearly half for experiment.Due to environmental protection and energy-efficient need
Will, the lightweight of automobile has become the trend of world car development.Such as buoy again；The feature density 1.04- of polyamide
1.16 also become limit its key used.
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 method of a kind of novel lightweight daiamid composition and its composite material.The present invention's
Lightweight daiamid composition can improve its mechanical property, heat resistance etc., while can improve while global density is reduced
The processing fluidity of polyamide.
An object of the present invention：A kind of daiamid composition, the daiamid composition include each of following parts by weight
Ingredient：
Polyamide：55-95 parts by weight,
Modified Hollow Inorganic powder：5-37 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 daiamid composition can also include other other than polyamide 5X
Polyamide, other described polyamide include：Polyamide 6, polyamide 66, polyamide 69, polyamide 610, polyamide 612, polyamides
It is one or more in amine 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.
A preferred technical solution of the invention, the polyamide 5X monomers are obtained preferably by biofermentation method,
Or it is processed and obtained through chemical technology by sustainable native compound.It is preferred that the 1,5- pentanediamines is pass through biofermentation side
Method obtains.
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 (5-35)：(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.
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, daiamid composition further includes other auxiliary agents, wherein other described auxiliary agents
Including：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, the preparation method includes following
Step：
By the polyamide, the modified Hollow Inorganic powder and the bulking agent, ratio, is mixed as described above
Close uniform, extrusion molding, you can；
Or, by the polyamide, the modified Hollow Inorganic powder, the bulking agent and other described auxiliary agents, press
According to ratio as described above, it is uniformly mixed, extrusion molding, you can.
Wherein, it is preferred that first the polyamide and the bulking agent are uniformly mixed, then with the hollow nothing of the modification
Machine powder is uniformly mixed.
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 operation being uniformly mixed with the modified Hollow Inorganic powder, in double screw extruder into
Row, more preferably carries 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 when being uniformly mixed with the modified Hollow Inorganic powder, 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 mixer
Rotating speed be 600-800rpm, incorporation time 3-5min；
(2) main spout of the material through double screw extruder being uniformly mixed in step (1) is added in into double screw extruder
In, and will be added at the modified side spout of the Hollow Inorganic powder through double screw extruder, it is uniformly mixed, wherein, double spiral shells
The temperature of bar extruder temperature is 250-285 DEG C, and twin-screw rotating speed is 150-250pm.
Wherein, the side spout is the side at double screw extruder discharging die orifice 1/3-3/5 spiro rod lengths position
Spout.
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.
The present invention prepares lightweight polyamide using Hollow Inorganic powder is modified, wherein, modified Hollow Inorganic powder and increase-volume
Agent has synergistic effect, under the premise of polyamide compoiste material density is reduced, makes mechanical property, the heat resistance of composite material
Etc. increasing, the promotion of the two and its content, all density to lightweight polyamide and mechanical performance has inseparable
Effect, lightweight daiamid composition of the invention imparts the new performance of polyamide compoiste material, available for automobile instrument panel,
The fields such as 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 polyamide 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.
Embodiment 1
(PA56,2.72) 96% relative sulfuric acid viscosity is to polyamide 56：4195g
Hollow glass micropearl (56 μm of grain size, real density 0.32g/cm3, resistance to compression 13.78MPa)：500g
Bulking agent POE-g-MAH：250g
Coupling agent KH-550：5g
Other auxiliary combinations (including EBS, calcium stearate, montanic acid calcium, talcum powder, antioxidant 1098)：50g
The preparation method of 56 resin of lightweight polyamide：
(1) 5g KH-550 are scattered in 150g alcohol-waters (mass ratio 1：1) it in, then under high velocity agitation, will mix
Solution is uniformly sprayed at the surface of hollow glass micropearl, makes the uniform coated hollow glass bead of coupling agent；High-speed mixer turns
Speed is 600-800rpm, and mixing temperature is 60-80 DEG C, incorporation time 3-5min；
(2) uniformly mixed material under 80 DEG C of environment is dried into 12h, obtains modified hollow glass micropearl；
(3) polyamide 56 (PA56), POE-g-MAH, other auxiliary combinations are uniformly mixed in high-speed mixer, at a high speed
The rotating speed of mixing machine be 500-600rpm, mixed at room temperature, incorporation time 3-5min；
(4) the modification hollow glass micropearl that step (2) obtains is positioned in extruder side spout；Step (3) is mixed
Uniform material is closed to be positioned in the container of main feeding of extruder；
(5) 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 slice being prepared at 80 DEG C is dried into 6h, is then molded into standard testing batten, injection molding machine by iso standard
Each area's temperature setting of temperature 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 will
Test bars are sealed 48h at 23 DEG C, are tested according to iso standard.
Test result is referring to table 1.
Embodiment 2
(PA56,2.72) 96% relative sulfuric acid viscosity is to polyamide 56：3690g
Hollow glass micropearl (56 μm of grain size, real density 0.32g/cm3, resistance to compression 13.78MPa)：1000g
Bulking agent Lotryl 29MA03：250g
Coupling agent KH-550：10g
Other auxiliary combinations (including EBS, calcium stearate, montanic acid calcium, talcum powder, antioxidant 1098)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 3
(PA56,2.72) 96% relative sulfuric acid viscosity is to polyamide 56：3185g
Hollow glass micropearl (56 μm of grain size, real density 0.32g/cm3, resistance to compression 13.78MPa)：1500g
Bulking agent Lotader AX8900：250g
Coupling agent KH-550：15g
Other auxiliary combinations (including EBS, calcium stearate, montanic acid calcium, talcum powder, antioxidant 1098 etc.)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 4
(PA56,2.72) 96% relative sulfuric acid viscosity is to polyamide 56：3690g
Hollow glass micropearl (45 μm of grain size, real density 0.40g/cm3, resistance to compression 27.56MPa)：1000g
Bulking agent POE-g-MAH：250g
Coupling agent KH-550：10g
Other auxiliary combinations (including EBS, calcium stearate, montanic acid calcium, talcum powder, antioxidant 1098 etc.)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 5
(PA56,2.72) 96% relative sulfuric acid viscosity is to polyamide 56：3185g
Hollow glass micropearl (45 μm of grain size, real density 0.40g/cm3, resistance to compression 27.56MPa)：1500g
Bulking agent Lotryl 29MA03：250g
Coupling agent KH-550：15g
Other auxiliary combinations (including EBS, calcium stearate, montanic acid calcium, talcum powder, antioxidant 1098 etc.)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 6
(PA56,2.72) 96% relative sulfuric acid viscosity is to polyamide 56：4195g
Hollow glass micropearl (45 μm of grain size, real density 0.40g/cm3, resistance to compression 27.56MPa)：500g
Bulking agent Lotader AX8900：250g
Coupling agent KH-550：5g
Other auxiliary combinations (including EBS, calcium stearate, montanic acid calcium, talcum powder, antioxidant 1098 etc.)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 7
(PA56,2.72) 96% relative sulfuric acid viscosity is to polyamide 56：3185g
Hollow glass micropearl (45 μm of grain size, real density 0.46g/cm3, resistance to compression 41.34MPa)：1500g
Bulking agent POE-g-MA：250g
Coupling agent KH-550：15g
Other auxiliary combinations (including EBS, calcium stearate, montanic acid calcium, talcum powder, antioxidant 1098 etc.)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 8
(PA56,2.72) 96% relative sulfuric acid viscosity is to polyamide 56：4195g
Hollow glass micropearl (45 μm of grain size, real density 0.46g/cm3, resistance to compression 41.34MPa)：500g
Bulking agent Lotryl 29MA0：250g
Coupling agent KH-550：5g
Other auxiliary combinations (including EBS, calcium stearate, montanic acid calcium, talcum powder, antioxidant 1098 etc.)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 9
(PA56,2.72) 96% relative sulfuric acid viscosity is to polyamide 56：3690g
Hollow glass micropearl (45 μm of grain size, real density 0.46g/cm3, resistance to compression 41.34MPa)：1000g
Bulking agent Lotader AX8900：250g
Coupling agent KH-550：10g
Other auxiliary combinations (including EBS, calcium stearate, montanic acid calcium, talcum powder, antioxidant 1098 etc.)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Embodiment 10
(PA56,2.72) 96% relative sulfuric acid viscosity is to polyamide 56：1845g
(PA1010,2.66) 96% relative sulfuric acid viscosity is to polyamide 1010：1845g
Hollow glass micropearl (45 μm of grain size, real density 0.46g/cm3, resistance to compression 41.34MPa)：1000g
Bulking agent Lotader AX8900：250g
Coupling agent KH-550：10g
Other auxiliary combinations (including EBS, calcium stearate, montanic acid calcium, talcum powder, antioxidant 1098 etc.)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 1.
Table 1：The performance of lightweight polyamide 5X (PA56) composition compares
Wherein, comparative example it is corresponding be PA56 resins each performance parameter.
As seen from the above table：Modified Hollow Inorganic powder and bulking agent, can be compound in reduction under the conditions of specific ratio
While density of material, tensile strength, bending strength, bending modulus and the notch impact strength of composite material are improved.
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 (11)
1. a kind of daiamid composition, it is characterised in that：The daiamid composition includes each ingredient of following parts by weight：
Polyamide：55-95 parts by weight,
Modified Hollow Inorganic powder：5-37 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, the dicarboxylic acids includes：Succinic acid, glutaric acid, adipic acid, heptan two
Acid, suberic acid, azelaic acid, decanedioic acid, eleven carbon diacids, dodecanedicarboxylic acid, tridecanyldicarboxylic acid, tetradecane diacid,
15 carbon dicarboxylic acids, 16-dicarboxylic acid, seventeen carbon diacids, octadecane diacid, maleic acid and Δ 9-1,18 octadecylenes two
It is one or more in first acid.
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 obtained preferably by biofermentation method；The polyamide 5X preferably includes 35-
100% biomass source；
The polyamide 5X includes polyamide 56；The preferred 2.4-3.2 of relative viscosity of 96% sulfuric acid of the polyamide 56；
And/or the daiamid composition further includes other polyamide other than polyamide 5X, other described polyamide include：
Polyamide 6, polyamide 66, polyamide 69, polyamide 610, polyamide 612, polyamide 1010, polyamide 11,12 and of polyamide
It is one or more in polyamide 1414.
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 trimethoxies silicon, γ-(2,
The third oxygen of 3- epoxies) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, N- β-(aminoethyl)-
γ-aminopropyltriethoxy dimethoxysilane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane and vinyl triethoxyl
It is one or more in silane；
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 the solution of alcohol-water for coupling agent；
And/or the weight ratio of the Hollow Inorganic powder and the coupling agent is (5-35)：(0.01-2)；
And/or the rotating speed during mixing is 600-800rpm；
And/or the temperature during mixing is 60-80 DEG C；
And/or the time of the mixing is 3-5min；
And/or the temperature of the drying is 70-90 DEG C, preferably 75-85 DEG C；
And/or the time of the drying is 8-16h, preferably 10-14h, more preferable 11-13h.
8. 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.
9. the daiamid composition as described in claim any one of 1-8, it is characterised in that：The daiamid composition further includes it
His auxiliary agent, wherein other described auxiliary agents include：It is one or more in lubricant, nucleating agent and antioxidant；Other described auxiliary agents
The preferred 1-5 parts by weight of content.
10. a kind of method that polyamide resin composite material is prepared with any one of the claim 1-9 daiamid compositions,
It is characterized in that：The preparation method includes the following steps：By the polyamide, the modified Hollow Inorganic powder and institute
It states bulking agent to be uniformly mixed, extrusion molding, you can；
Or, by the polyamide, the modified Hollow Inorganic powder, the bulking agent and other described auxiliary agents, according to such as
Ratio described in claim 1-9 is uniformly mixed, extrusion molding, you can.
11. preparation method as claimed in claim 10, it is characterised in that：
First the polyamide and the bulking agent are uniformly mixed, then are uniformly mixed with the modified Hollow Inorganic powder；
And/or the polyamide and the bulking agent be when being uniformly mixed, the rotating speed during mixing is 600-800rpm；
And/or when the polyamide and the uniformly mixed bulking agent, the temperature of the mixing is 60-80 DEG C；
And/or the time that the polyamide and the bulking agent are uniformly mixed is 3-5min；
And/or the operation being uniformly mixed with the modified Hollow Inorganic powder, it is carried out in double screw extruder；
And/or preferred 250-285 DEG C of the temperature of the double screw extruder；
And/or the rotating speed preferred 150-250rpm, more preferably 180-220rpm of the double screw extruder；
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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| CN111269564A (en) * | 2018-12-04 | 2020-06-12 | 上海凯赛生物技术股份有限公司 | Polyamide 5X abrasive wire and preparation method and application thereof |
| CN111592755A (en) * | 2019-02-21 | 2020-08-28 | 上海凯赛生物技术股份有限公司 | Enhanced bio-based polyamide 56 composition and preparation method thereof |
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