CN109957238A - A kind of thermoplastic flame-proof biology base PA56 and PA66 composite material and preparation method - Google Patents
A kind of thermoplastic flame-proof biology base PA56 and PA66 composite material and preparation method Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/387—Borates
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- 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
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The present invention relates to a kind of thermoplastic flame-proof biology base PA56 and PA66 composite material and preparation methods, biology base PA56 and PA66 composite material are used directly for injection molding, it is mixed by the raw material of following mass percent and is prepared after double screw extruder is kneaded: biology base PA56 is 10~70%, PA66 is 10~70%, and fire retardant is 5~20%；It is 2~15% that the raw material, which can further include compatilizer, and other processing aids are 0.1~5%.Composite material of the invention has excellent comprehensive mechanical property, flame retardant property and processing performance.Meanwhile selected raw material has bio-based source just like PA56, has a clear superiority in low-carbon, environmental protection, can be improved product competitiveness.
Description
Technical field
The invention belongs to engineering plastics technical field, it is related to a kind of thermoplastic flame-proof PA56 and PA66 composite material and its system
Preparation Method more particularly to a kind of thermoplastic flame-proof biology base PA56 and PA66 composite material and preparation method.Wherein, PA56 has
There is bio-based source.Thermoplastic flame-proof biology base PA56 and PA66 composite material of the invention has good flame retardant effect, excellent
Different mechanical property and machinability, and there is environment-friendly advantage, it can be used for injection molding and various raw materials wanted with biological source
The electronic electric equipment and household appliances asked.
Background technique
Polyamide is commonly called as nylon, is a kind of to have good mechanical properties, electrical property, heat resistance, toughness, oil resistivity, wear-resisting
The polymer material of property, chemical resistance and self-lubrication, is widely used in the every field of national life and production.Together
When, nylon is a kind of self-extinguishing polymer material, that is, has certain anti-flammability, but its flame retardant property is poor, is hung down
Direct combustion burning can only achieve UL94V-2 grades, and generate drippage in combustion, so that it is deposited causes fire in use
Potential danger, especially in electronics field, therefore, to nylon flame-retardant modified, to become current academia and industry total
With the project of concern.
There are mainly three types of means for the flame-retardant modified approach of nylon: (1) adding fire retardant in modification process, that is, pass through
Fire retardant is added in nylon matrix by the method for physical mechanical mixing, it is made to obtain anti-flammability, its advantage is that it is easy to use, it fits
With wide, but there is larger impact to the service performance of nylon；(2) on polymer chain or product surface grafting or it is bonded fire-retardant base
Group, i.e. fire retardant are to participate in reacting as a kind of reaction monomers, and the main chain or side chain that are integrated to polyamide are up, make polyamide
Itself contains flame-retardant composition, its main feature is that stability is good, small toxicity, small on the influence of the service performance of material, anti-flammability is lasting, is
A kind of ideal solution, but operation and processing technology are complicated, use in practical applications not as good as additive flame retardant
Generally；(3) it is copolymerized with flame-retardant monomer, prepares intrinsic fire-retardant nylon.In comparison, the fire-retardant means of now widely used nylon
Fire retardant is mainly added in modification process.
Fire retardant is a kind of functional aid for assigning polymer flame retardancy, and fire-retardant primarily directed to high molecular material sets
Meter；There are many types for fire retardant, can be divided into additive flame retardant and reactive flame retardant by application method.Additive flame retardant
It is to be added in polymer to make polymer that there is flame retarding function by mechanical mix techniques, additive flame retardant is mainly organic at present
Fire retardant and inorganic fire retardants two major classes, wherein organic fire-retardant includes halogen system (organic chloride and organic bromide) and non-again
Halogen system (nitrogen system, phosphorus system, nitrogen phosphorus system, silicon systems, sulphur system, boron system etc.) two major classes.
Compared with other fire retardants, organic bromide has the advantage that (1) flame retarding efficiency height, and additive amount is few, to being hindered
Fire the processing performance and physicochemical property Small side effects of matrix；(2) there are excellent thermal stability and water-insoluble；(3) good dispersion,
There is preferable compatibility with material；(4) sufficient raw, it is mature preparation process, cheap；(5) pyrolysis temperature range
Narrow, the comparison of ingredients of fire retardation is concentrated, and concentration is big；(6) many kinds of, it is able to satisfy multiple polymers processing technology and fire-retardant
The requirement of product, has a wide range of application.
Polymer blending is a key areas of material science, closely related with the overall development of material science research.
About the research that polymer is blended, has century-old history.Even to this day, the basic research that polymer is blended is ground with application foundation
Study carefully, be still the research hotspot of polymeric material field, in terms of new co-mixing system and mechanism study all constantly obtain into
Exhibition；And the method for polymer blending modification is still an important industrial technology in processing of high molecular material, application is spread
Among various plastics and rubber product.The exploitation of many successful products in Macromolecular materials industry is all closely to rely on polymerization
Object blending technology.Blending theory is constantly brought forth new ideas with application technology, has pushed the research and industrial applications of polymer material.
Polymer material in national product using more and more extensive, the effect of performance becomes increasingly conspicuous, meanwhile, state's people's livelihood
Production is also higher and higher to the performance requirement of polymer material, and the performance of single polymers is difficult to meet the actual demand that produces, and
The mechanical performance of polymer material can be improved by blend modification technology, processing performance, reduce cost, expansion use scope.Altogether
Mixed modification technology is a kind of means that are most simple, the most frequently used, being also most effective polymer material processing and exploitation new product.
Polymer blending is the important means for improving another polymer performance using a kind of polymer or inorganic material, also
It is that two or more polymer or a kind of polymer and more than one inorganic material are passed through into blending technology by proper proportion
It is possible that eliminating and making up the disadvantage in single polymers performance, learn from other's strong points to offset one's weaknesses, it is possible to obtain single polymers are unable to reach
Performance, it is also possible to obtain high comprehensive performance and equilibrium ideal polymer material, be realize polymer material high-performance
Change, refine, the important channel of functionalization and differentiation.
PA56 is formed by 1,5- pentanediamine and adipic acid polycondensation.PA56 is a kind of nylon of even-odd structure, compared with PA66
Compared with for, in terms of chemical structure, PA56 and PA66 have structural similarity, and the main distinction is one of monomer of PA56 1,5-
Pentanediamine is a kind of five carbon diamines, and one of monomer of PA66 hexamethylene diamine is a kind of six carbon diamines.Difference in chemical structure
Not making the physicochemical properties of PA56 and PA66 has certain difference.On the one hand, the structural symmetry of the repetitive unit of PA56
Lower than PA66, the ability for forming hydrogen bond is weaker, so that hydrogen bond density in PA56 ontology be made not have the height of PA66；On the other hand,
The amide groups density ratio PA66 high of PA56, the electrostatic interaction between molecule segment are stronger；Factor of both comprehensive, make PA56 and
PA66 has high similarity in mechanical properties.
The difference of chemical structure also gives the characteristic that PA56 is different from PA66, such as: the nitrogen content ratio PA66 high of PA56, tool
There is higher oxygen index (OI), there may be certain advantage at flame-retardant modified aspect；For another example, hydrogen bond density ratio PA66 in PA56 ontology
Low, intermolecular hydrogen bonding is similarly low, and under shearing force, the freedom degree of segment is higher, so that it is higher to assign PA56 ratio PA66
Mobility etc..
The advantages of PA56 not only has itself, while also having the advantages that nylon-type product, if PA56 is that have certain reaction
Active crystalline polymer, with excellent mechanical property, wearability, self-lubrication, oil resistivity, corrosion resistance and preferable
Machine-shaping property etc..
The present invention is based on the above technical foundation, it is prepared for a kind of high comprehensive performance, and fire-retardant with environmental protection feature
PA56/PA66 composite material.
Summary of the invention
The purpose of the present invention is to provide a kind of thermoplastic flame-proof biology base PA56 with excellent combination mechanical property and
PA66 composite material belongs to and can satisfy electric and domestic electric appliance requirement novel environment friendly polymer material,
At least partly raw material source of middle PA56 is obtained from biological fermentation process.
In order to achieve the above object, technical program of the present invention lies in provide a kind of thermoplastic flame-proof biology base PA56 and PA66
Composite material, the composite material are at least prepared by the raw material of following mass percent.
Biology base PA56:10~70%；
PA66:10~70%；
Fire retardant: 5~20%.
Wherein, one of polymerized monomer of biology base PA56 pentanediamine is obtained by biofermentation technique, polymerized monomer it
Two adipic acid sources can be to be obtained by biofermentation technique, is also possible to manufacture by petrochemical industry, is passed through biology
The quality of polymerized monomer made from fermentation method accounts for 47.17~100wt% of the gross mass of biology base PA56.Biology base PA56 includes symbol
Close the organic carbon of the renewable source of ASTM D6866 standard.In the present invention, biology base PA56 is biology base PA56 slice, PA66
For PA66 slice, the 98wt% relative sulfuric acid viscosity of PA56 slice and PA66 slice is 2.2~3.8, preferably 2.5~2.8, specific to select
Range of viscosities according to downstream application it is different depending on, for the product for requiring mobility high, select low-viscosity polyamides as raw material.
PA56 and PA66 has certain similitude in terms of chemical structure, but the difference on molecular structure causes two kinds to gather
There are some differences for amide.On the one hand, the presence of hydrogen bond makes the two have certain compatibility；On the other hand, the difference in structure
It is different it is different with molecular symmetry cause hydrogen bond density to reduce, thus reduce by two kinds of polyamide between compatibility.Therefore, PA56 and
PA66 has limited compatibility, and addition compatilizer can be further improved the compatibility between two kinds of polymer.In the present invention,
Compatilizer include either Methyl Methacrylate-Butadiene-Styrene Copolymer, methyl methacrylate-ethyl acrylate,
Random ethylene-butyl 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 are grafted ethylene propylene diene rubber, maleic anhydride grafted ethene-vinyl acetate, maleic acid
Acid anhydride is grafted one in hydrogenated butadiene-styrene block copolymer and maleic anhydride grafted ethene-butadiene-styrene copolymer
Kind is a variety of.In the present invention, the mass percent that the dosage of compatilizer accounts for raw material is 2~15%.
The additive flame retardant of thermoplastic flame-proof biology base PA56 and PA66 composite material for use in the present invention mainly wraps
Include halogenated flame retardant, nitrogenated flame retardant, phosphorus flame retardant, inorganic fire retardants and other kinds of fire retardant.From using effect
From the point of view of dosage, in polyamide flame-retardant system, the preferred bromide fire retardant of halogen containing flame-retardant, the bromide fire retardant include or
It is poly- ethylene bromide, decabromodiphenyl oxide (deca-BDE), ten bromine ethylbenzenes, decabromodiphenylethane, tetrabromobisphenol A, brominated
One of oxygen resin, hexabromocyclododecane, eight bromo ether are a variety of.The advantages of bromide fire retardant, is: to modified composite material
The negative effect of mechanical performance is small, good with the compatibility of matrix resin, even if than under relatively severe condition without precipitation phenomenon；Its
Decomposition temperature at 200~300 DEG C, matches mostly with the decomposition temperature of various polymer, can the best time in gas phase and
Condensed phase plays fire retardation simultaneously；Also have the characteristics that additive amount is small, sufficient raw, manufacturing process maturation etc. is resistance
Fire one kind that effect is best in agent.
Wherein, decabromodiphenylethane has the characteristics that heat resistance, light resistance and is not easy leaching, these features are superior to ten
Dibromodiphenyl ether.Decabromodiphenylethane have with the consistent anti-flammability of deca-BDE, and burning when do not generate carcinogen
More bromine dioxin, toxicity is also lower than deca-BDE, especially suitable for producing computer, facsimile machine, telephone set, duplicator, household electrical appliances
Equal products.
The present invention by decabromodiphenylethane fire retardant be applied to thermoplastic flame-proof biology base biology base PA56 of the invention and
In PA66 composite material.First passage blend modification technology of the present invention, be prepared for having fire-retardant characteristic biology base PA56 and
The composite material of PA66, this new material have its unique advantages, and product can be applied to can be used for the various raw materials of injection molding
Electronic electric equipment and household appliances for being required with biological source etc..
In the present invention, the raw material of the composite material can also include fire retarding synergist, and the mass percent of Zhan Suoshu raw material is
2-10%；Preferably, the fire retarding synergist includes either one of antimony oxide, zinc borate and zinc oxide or a variety of.
The raw material of the composite material can also include other processing aids, and the mass percent of Zhan Suoshu raw material is 0.1
~5%, other processing aids include one of antioxidant, lubricant, nucleating agent or a variety of.Wherein it is preferred to described
It include organic nucleating agent and inorganic nucleator in nucleating agent.Organic nucleating agent include either nucleating agent CAV102, montanic acid sodium,
One of montanic acid calcium, P22, polyacrylic acid ionomer and sodium benzoate are a variety of.Inorganic nucleator includes either talcum
One of powder, organically-modified sodium-based montmorillonite, zeolite, aluminium oxide, mica, kaolin, magnesia, calcium carbonate and sodium carbonate
Or it is a variety of.The average grain diameter of inorganic nucleator is 1~10 micron, preferably 2~5 microns.
In the present invention, lubricant includes either 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,
One of zinc stearate, odium stearate, barium stearate, the macromolecule organic silicon (such as silicone powder) and amido silicon oil are a variety of.Profit
The main function of lubrication prescription is between the frictional force reduced in extrusion process between molecular resin segment, melt and process equipment
Frictional force prevents resin caused by frictional heat generation from degrading, guarantees that the performance of composite material will not be deteriorated because of thermal degradation.Lubrication
Agent can also reduce the apparent viscosity of resin, increase the mobility of resin, improve the processability of blend, improve processing efficiency.Again
Person, lubricant, which also has, prevents resin and mold from adhering, and increases release property when processing and forming.
In the present invention, antioxidant includes either N, and N- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono)
Hexamethylene diamine, β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [2,4- di-tert-butyl-phenyl] phosphorous acid
Ester, bis- (2,4- di-tert-butyl-phenyl) propionic acid] pentaerythritol diphosphites, 2,2- methylene-bis- (4- ethyl -6- tert-butyl
Phenol), inclined fourth support-bis--(the 6- tert-butyl-m-cresol) of 4,4-, (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane of 1,1,3- tri- and
One of 1,3,5- trimethyl -2,4,6- three (- 4 hydroxybenzyl of 3,5- di-t-butyl) benzene is a variety of.
The raw material of the composite material further includes PA56/PA66 copolymer, and the mass percent of Zhan Suoshu raw material is 3~
7%, the molar ratio of PA56 and PA66 is 1:1, the 96wt% of the PA56/PA66 copolymer in the PA56/PA66 copolymer
Relative sulfuric acid viscosity is 2.2~3.8, and preferably 2.5~2.8.In the present invention, it is compound that thermoplasticity enhances biology base PA56 and PA66
The preparation method of material includes the following steps:
(1) by mass percentage, by the biology base PA56 of raw material 10~70%, 10~70wt% PA66 after mixing
It is added from the main spout of double screw extruder；Preferably, it is uniformly mixed in high-speed mixer, the revolving speed of high-speed mixer is
500~700 revs/min, incorporation time is 3~5 minutes；
(2) by mass percentage, by the fire retardant and 2 of 5~20wt% of the fire retardant of 5~20wt% of raw material or raw material
The fire retarding synergist of~10wt% after mixing, is added from the side spout of double screw extruder；Preferably, in high-speed stirred
It is uniformly mixed in machine, the revolving speed of high-speed mixer is 400~600 revs/min, and incorporation time is 3~5 minutes；
(3) draw ratio of the screw rod of double screw extruder is 1:40~52,300~600 revs/min of screw speed, described
Each area temperature of the double screw extruder from main spout to die orifice is followed successively by 80 ± 10 DEG C, 220 ± 10 DEG C, 250 ± 10 DEG C, 270
± 10 DEG C, 280 ± 10 DEG C, 280 ± 10 DEG C, 275 ± 10 DEG C, die temperature are 270 ± 10 DEG C, and thermoplastic flame-proof biology base is made
The composite material of PA56 and PA66.
Further, in the step (1), the raw material further includes the compatilizer and/or 0.1~5wt% of 2~15wt%
Other processing aids.
In the present invention, it is molded after the composite material of thermoplasticity enhancing biology base PA56 and PA66 are 6 hours dry at 80 DEG C
At test bars, injection temperature is 260~275 DEG C.
In the present invention, the performance test of the composite material of thermoplasticity enhancing biology base PA56 and PA66 is referring to following standard:
1 testing standard table of table
The present invention is based on inventors to find that PA56 and PA66 has synergistic effect in terms of impact resistance.The present invention
The composite material comprehensive mechanical property especially impact resistance of prepared thermoplasticity enhancing biology base PA56 and PA66 are good, can
Components or structural material suitable for products such as the various electronics of injection molding, electric appliance, furniture.
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 embodiment of the present invention be formulated as shown in table 2 and table 3, corresponding test result is listed in Table 4 below, selected raw material and its
Source information is as follows:
The matter of polymerized monomer made from biological fermentation process is crossed by biology base PA56: Kai Sai (Jinxiang) biomaterial Co., Ltd
Amount accounts for 100%, the 96wt% relative sulfuric acid viscosity 2.7 of the gross mass of the biology base PA56
Copolymer nylon (PA56/PA66): the molar ratio of Kai Sai biological industry Co., Ltd, PA56 and PA66 are 1:1,
96wt% relative sulfuric acid viscosity 2.7
PA66: Pingdingshan Shenma Engineering Plastic Co., Ltd., 96wt% relative sulfuric acid viscosity 2.7
Decabromodiphenylethane (fire retardant): Shandong Tianyi Chemical Co., Ltd.
Antimony oxide (fire retarding synergist): Xinghua work Co., Ltd, Shandong section
Zinc oxide (fire retarding synergist): traditional Chinese medicines chemical reagent Co., Ltd
Zinc borate (fire retarding synergist): Shandong Bo Ao Industrial Co., Ltd.
Maleic anhydride stem grafting polyolefin elastomer (POE-g-MA, compatilizer): Du Pont China Holding Co., Ltd.
N, N'- ethylene bis stearamide (EBS, lubricant): Suzhou Lian Sheng chemical company
Calcium stearate (lubricant): Shanghai Hua Yi auxiliary chemicals Co., Ltd
Zinc stearate (lubricant): Shanghai Hua Yi auxiliary chemicals Co., Ltd
Montanic acid calcium (lubricant): Shanghai Hua Yi auxiliary chemicals Co., Ltd
Amido silicon oil (lubricant): Shanghai Hua Yi auxiliary chemicals Co., Ltd
Silicone (lubricant): Kai Jie plastic toughening Materials Co., Ltd, Jiande City
Nucleating agent P22 (organic nucleating agent): Brueggemann Asia Co., Ltd
CAV102 (organic nucleating agent): Klein chemical industry (China) Co., Ltd
Polyethylene acrylic acid ionomer: Co., Ltd in Honeywell
Organically-modified sodium-based montmorillonite (also known as organo montmorillonite) (inorganic nucleator): the limited public affairs of Jiangxi Gu Kang new material
Department
Talcum powder (inorganic nucleator): Heilungkiang is prosperous to reach mining industry
Antioxidant is N, N- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (antioxidant 1098):
Ciba (China) Co., Ltd.
The preparation method of the embodiment of the present invention and the composite material of comparative example includes the following steps:
(1) by mass percentage, by biology base PA56, PA66, compatilizer, other processing aids (including antioxidant, lubrication
Agent, nucleating agent) it is uniformly mixed in a high speed mixer, the revolving speed of high-speed mixer is 700 revs/min, and incorporation time is 4 points
Clock, uniformly mixed material are added by the main spout of double screw extruder.
(2) by mass percentage, fire retardant and fire retarding synergist are uniformly mixed in a high speed mixer, high-speed mixer
Revolving speed be 450 revs/min, incorporation time is 4 minutes, and uniformly mixed material passes through the first side feed material of double screw extruder
Mouth is added.
(3) draw ratio of the screw rod of double screw extruder be 1:40,400 revs/min of screw speed, double screw extruder from
Each area's temperature of main spout to die orifice is followed successively by 80 DEG C, 220 DEG C, 250 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 275 DEG C, die orifice temperature
Degree is 270 DEG C, obtains thermoplastic flame-proof enhancing biology base PA56 and PA66 composite material.
The preparation method of the embodiment of the present invention and the composite material of comparative example is as described above.
Table 2: the formula table (unit: g) of embodiment 1 to embodiment 7
Table 3: the formula table (unit: g) of embodiment 8 to embodiment 12 and comparative example
Table 4: the performance comparison sheet of the composite material of various examples and comparative examples
The data from table 4 are as it can be seen that in terms of the mechanical properties such as tensile strength, bending die, thermoplastic flame-proof of the invention
The performance of PA56 and PA66 composite material is consistent substantially with the mechanical property of comparative example 1 and comparative example 2, but of the invention is answered
Condensation material has higher impact resistance；Especially after adding PA56/66 copolymer, the impact resistance of composite material into
One step improves.
With comparative example 2 merely using PA66 as the composite material of matrix compared with, under the conditions of amount of flame-retardant agent is consistent, this hair
Bright composite material has a higher flame retardant rating, this and PA56, PA66 there is some difference in chemical structure related, PA56
There is higher nitrogen content than PA66, increase the nitrogen content in molecule, be conducive to the flame retardant rating for improving high molecular material.
This hair can be understood and used the above description of the embodiments is intended to facilitate those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments,
Those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be in this hairs
Within bright protection scope.
Claims (16)
1. a kind of thermoplastic flame-proof biology base PA56 and PA66 composite material, it is characterised in that: the composite material at least by with
The raw material of lower mass percent is prepared:
Biology base PA56:10~70%；
PA66:10~70%；
Fire retardant: 5~20%.
2. thermoplastic flame-proof biology base PA56 and PA66 composite material according to claim 1, in which: the biology base
PA56 includes the organic carbon for meeting the renewable source of ASTM D6866 standard；And/or
At least one polymerized monomer of the biology base PA56 is made by biological fermentation process, as made from biological fermentation process
The quality of polymerized monomer accounts for 47.17~100wt% of the gross mass of the biology base PA56.
3. thermoplastic flame-proof biology base PA56 and PA66 composite material according to claim 1 or 2, in which: the life
Object base PA56 is biology base PA56 slice, and the PA66 is PA66 slice, and the biology base PA56 slice and the PA66 are cut
The 96wt% relative sulfuric acid viscosity of piece is 2.2~3.8, and preferably 2.5~2.8.
4. thermoplastic flame-proof biology base PA56 and PA66 composite material according to claim 1-3, in which: this is multiple
The raw material of condensation material further includes compatilizer, and the mass percent of Zhan Suoshu raw material is 2~15%；
Preferably, the compatilizer includes either Methyl Methacrylate-Butadiene-Styrene Copolymer, methacrylic acid
Methyl esters-ethyl acrylate, random ethylene-butyl acrylate copolymer, random ethylene-methyl acrylate-copolymer-maleic anhydride,
Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer, maleic anhydride grafted polyethylene, maleic anhydride grafting are poly-
Propylene, maleic anhydride stem grafting polyolefin elastomer, maleic anhydride are grafted ethylene propylene diene rubber, maleic anhydride grafted ethene-acetic acid
Vinyl acetate, maleic anhydride grafting hydrogenated butadiene-styrene block copolymer and maleic anhydride grafted ethene-butadiene-benzene second
One of alkene copolymer is a variety of.
5. thermoplastic flame-proof biology base PA56 and PA66 composite material according to claim 1-4, in which: described
Fire retardant include either bromide fire retardant, it is highly preferred that the fire retardant include either decabromodiphenylethane.
6. thermoplastic flame-proof biology base PA56 and PA66 composite material according to claim 1-5, in which: described
The raw material of composite material further includes fire retarding synergist, and the mass percent of Zhan Suoshu raw material is 2-10%；
Preferably, the fire retarding synergist includes either one of antimony oxide, zinc borate and zinc oxide or a variety of.
7. thermoplastic flame-proof biology base PA56 and PA66 composite material according to claim 1-6, in which: described
The raw material of composite material further includes other processing aids, and the mass percent of Zhan Suoshu raw material is 0.1~5%；
Preferably, other processing aids include one of antioxidant, lubricant and nucleating agent or a variety of.
8. thermoplastic flame-proof biology base PA56 and PA66 composite material according to claim 7, in which: the nucleating agent packet
Include organic nucleating agent and inorganic nucleator.
9. thermoplastic flame-proof biology base PA56 and PA66 composite material according to claim 8, in which: it is described it is organic at
Core agent includes either nucleating agent CAV102, montanic acid sodium, montanic acid calcium, P22 and polyethylene acrylic acid ionomer and benzoic acid
One of sodium is a variety of.
10. thermoplastic flame-proof biology base PA56 and PA66 composite material according to claim 8, in which: described is inorganic
Nucleating agent include either talcum powder, organically-modified sodium-based montmorillonite, zeolite, aluminium oxide, mica, kaolin, magnesia, carbon
One of sour calcium and sodium carbonate are a variety of.
11. thermoplastic flame-proof biology base PA56 and PA66 composite material according to claim 10, in which: it is described it is inorganic at
The average grain diameter of core agent is 1~10 micron, preferably 2~5 microns.
12. thermoplastic flame-proof biology base PA56 and PA66 composite material according to claim 7, in which: the lubricant
Including either N, N'- ethylene bis stearamide, oxidized polyethylene wax, ethylene vinyl acetate wax, partly-hydrolysed polyethylene
It is wax, oleamide, erucyl amide, pentaerythritol stearate, montanate, calcium stearate, zinc stearate, odium stearate, hard
One of resin acid barium, the macromolecule organic silicon and amido silicon oil are a variety of；Preferably, the macromolecule organic silicon is silicone powder.
13. thermoplastic flame-proof biology base PA56 and PA66 composite material according to claim 7, in which: the antioxidant
Including either N, N- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, β-(3,5- di-t-butyl -4-
Hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [2,4- di-tert-butyl-phenyl] phosphite esters, bis- (2,4- di-tert-butyl-phenyl) seasons
Penta tetrol diphosphites, 2,2- methylene-bis- (4- ethyl -6- tert-butyl phenol), 4,4- inclined fourth support-bis--(first between 6- tert-butyl
Phenol), (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane of 1,1,3- tri- and (bis- uncle of 3,5- of 1,3,5- trimethyl -2,4,6- three
- 4 hydroxybenzyl of butyl) one of benzene or a variety of.
14. thermoplastic flame-proof biology base PA56 and PA66 composite material according to claim 1, in which: the composite wood
The raw material of material further includes PA56/PA66 copolymer, and the mass percent of Zhan Suoshu raw material is 3~7%, and the PA56/PA66 is total
The molar ratio of PA56 and PA66 is 1:1 in polymers, and the 96wt% relative sulfuric acid viscosity of the PA56/PA66 copolymer is 2.2
~3.8, preferably 2.5~2.8.
15. a kind of preparation method of thermoplastic flame-proof biology base PA56 and PA66 composite material, it is characterised in that: including walking as follows
It is rapid:
(1) by mass percentage, by the biology base PA56 of 10~70wt% of raw material, 10~70wt% PA66 after mixing from
The main spout of double screw extruder is added；Preferably, it is uniformly mixed in high-speed mixer, the revolving speed of high-speed mixer is
500~700 revs/min, incorporation time is 3~5 minutes；
(2) by mass percentage, by the fire retardant of 5~20wt% of the fire retardant of 5~20wt% of raw material or raw material and 2~
The fire retarding synergist of 10wt% after mixing, is added from the side spout of double screw extruder；Preferably, in high-speed mixer
In be uniformly mixed, the revolving speed of high-speed mixer is 400~600 revs/min, and incorporation time is 3~5 minutes；
(3) draw ratio of the screw rod of double screw extruder be 1:40~52,300~600 revs/min of screw speed, double spiral shells
Each area temperature of the bar extruder from main spout to die orifice is followed successively by 80 ± 10 DEG C, 220 ± 10 DEG C, 250 ± 10 DEG C, 270 ± 10
DEG C, 280 ± 10 DEG C, 280 ± 10 DEG C, 275 ± 10 DEG C, die temperature be 270 ± 10 DEG C, be made thermoplasticity enhancing biology base PA56
With PA66 composite material.
16. the preparation method of thermoplastic flame-proof biology base PA56 and PA66 composite material as claimed in claim 15, wherein institute
It states in step (1), the raw material further includes the compatilizer of 2~15wt% and/or other processing aids of 0.1~5wt%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591350A (en) * | 2019-09-03 | 2019-12-20 | 会通新材料(上海)有限公司 | Smoke-inhibiting polyamide composition and preparation method thereof |
| CN114316584A (en) * | 2021-12-24 | 2022-04-12 | 浙江普利特新材料有限公司 | Brominated flame-retardant high-heat-resistance bio-based polyamide composition and preparation method thereof |
| CN114672104A (en) * | 2022-04-13 | 2022-06-28 | 潍坊秀隆新材料有限公司 | Environment-friendly methyl octabromoether flame-retardant master batch and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105331092A (en) * | 2014-08-07 | 2016-02-17 | 上海凯赛生物技术研发中心有限公司 | Highly wear-resistant bio-based polyamide composite material and preparation method thereof |
| CN106280431A (en) * | 2016-08-30 | 2017-01-04 | 厦门建霖工业有限公司 | A kind of bio-based nylon composite materials and its preparation method and application |
| WO2017026749A1 (en) * | 2015-08-13 | 2017-02-16 | 에스케이케미칼주식회사 | Polymer resin composition and molded product thereof |
| CN106867249A (en) * | 2017-02-24 | 2017-06-20 | 上海凯赛生物技术研发中心有限公司 | One kind enhancing static resistant polyamide composite and preparation method thereof |
| CN106867250A (en) * | 2017-02-24 | 2017-06-20 | 上海凯赛生物技术研发中心有限公司 | A kind of daiamid composition for quick injection molding and preparation method thereof |
-
2017
- 2017-12-14 CN CN201711338561.2A patent/CN109957238B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105331092A (en) * | 2014-08-07 | 2016-02-17 | 上海凯赛生物技术研发中心有限公司 | Highly wear-resistant bio-based polyamide composite material and preparation method thereof |
| WO2017026749A1 (en) * | 2015-08-13 | 2017-02-16 | 에스케이케미칼주식회사 | Polymer resin composition and molded product thereof |
| CN106280431A (en) * | 2016-08-30 | 2017-01-04 | 厦门建霖工业有限公司 | A kind of bio-based nylon composite materials and its preparation method and application |
| CN106867249A (en) * | 2017-02-24 | 2017-06-20 | 上海凯赛生物技术研发中心有限公司 | One kind enhancing static resistant polyamide composite and preparation method thereof |
| CN106867250A (en) * | 2017-02-24 | 2017-06-20 | 上海凯赛生物技术研发中心有限公司 | A kind of daiamid composition for quick injection molding and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杨明山等: "《现代工程塑料改性——理论与实践》", 31 July 2009, 中国轻工业出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591350A (en) * | 2019-09-03 | 2019-12-20 | 会通新材料(上海)有限公司 | Smoke-inhibiting polyamide composition and preparation method thereof |
| CN114316584A (en) * | 2021-12-24 | 2022-04-12 | 浙江普利特新材料有限公司 | Brominated flame-retardant high-heat-resistance bio-based polyamide composition and preparation method thereof |
| CN114316584B (en) * | 2021-12-24 | 2024-05-07 | 浙江普利特新材料有限公司 | Brominated flame-retardant high-heat-resistance bio-based polyamide composition and preparation method thereof |
| CN114672104A (en) * | 2022-04-13 | 2022-06-28 | 潍坊秀隆新材料有限公司 | Environment-friendly methyl octabromoether flame-retardant master batch and preparation method and application thereof |
| CN114672104B (en) * | 2022-04-13 | 2023-07-21 | 潍坊秀隆新材料有限公司 | Environment-friendly methyl octabromoether flame-retardant master batch and preparation method and application thereof |
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