CN109957243A - A kind of thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material and preparation method - Google Patents
A kind of thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material and preparation method Download PDFInfo
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/262—Alkali metal carbonates
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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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
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- 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
- C08L2205/02—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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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The present invention relates to a kind of thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material and preparation methods, PA56 the and PA66 composite material is at least prepared by the raw material of following mass percent: biology base PA56 10~70%, PA66 10~70%, MCA5~20%, the raw material of the composite material can also include 2~15wt% of compatilizer, 1~10wt% of fire retarding synergist, other processing aids are 0.1~5wt%.Composite material of the invention is used directly for injection molding, has the characteristics that excellent comprehensive mechanical property, flame retardant property, processing performance and amount of flame-retardant agent are low.Meanwhile one of selected raw material has bio-based source, 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, be related to a kind of thermoplastic halogen-free flame retarding PA56 and PA66 composite material and
Preparation method more particularly to a kind of thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material and preparation method.
PA56 has bio-based source.Composite products have good flame retardant effect, excellent mechanical property and machinability, and
With environment-friendly advantage, it can be used for electronic electric equipment and household appliances that the various raw materials of injection molding have biological source requirement.
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, polyamide is a kind of self-extinguishing polymer material, that is, has certain anti-flammability, but its flame retardant property is poor,
Vertical combustion can only achieve UL94V-2 grades, and generate drippage in combustion, cause fire in use so that depositing
Potential danger, especially in electronics field, therefore, to polyamide it is flame-retardant modified become current academia and industry
The project paid close attention to jointly.
There are mainly three types of means for the fire-retardant approach of polyamide: (1) adding fire retardant in modification process, that is, pass through object
Fire retardant is added in polyamide substrate by the method for reason mechanical mixture, 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 polyamide；(2) on polymer chain or product surface grafting or be bonded fire-retardant
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 polyamides
Amine 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,
It is a kind of ideal solution, but operation and processing technology are complicated, make in practical applications not as good as additive flame retardant
With universal；(3) it is copolymerized with flame-retardant monomer, prepares intrinsic Flameproof polyamide.In comparison, now widely used polyamide resistance
Combustion means mainly add fire retardant 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.
With the increasingly reinforcement of global safety environmental consciousness, requirement of the people to fire safety and fire block articles is increasingly
Height, low cigarette, less toxic environment friendly flame retardant are increasingly valued by people.Currently, halogenated flame retardant still makes extensively at home
With this based flame retardant can generate a large amount of flue dust and corrosive gas in thermal cracking and burning, and be possible to release
Toxic carcinogenic substance, such as more bromo benzos dislike English and more bromo benzofurans；And individual bromide fire retardants (such as more bromines are found in recent years
Diphenyl ether) to environment and human health, there are potentially hazardous property in itself, and this is obviously runed counter to current environmental requirement.European Union
From on January 1st, 2006, forbid containing polybrominated biphenyls and polybrominated diphenyl ethers in sold electronic electric equipment.
Nitrogenated flame retardant compared with halogenated flame retardant, have small toxicity, flame retarding efficiency are high, corrosivity is small, in material
Light stabilizer Lothrus apterus, thermal decomposition temperature is high and advantages of environment protection.Nitrogenated flame retardant mainly includes melamine, dicyan
The organic compounds containing nitrogens such as amine, guanidine and its derivative, wherein most widely used is melamine cyanurate salt (MCA).
Melamine cyanurate salt (MCA) is a kind of fire retardant of addition type, has nontoxic odorless, tasteless, decomposition temperature
It is high, not only good flame retardation effect, processing when the small compatibility polymeric matrix between of smog is good, nothing shows that transport phenomena etc. is excellent
Point is mainly used for the fire-retardant of the polymer materials such as polyamide, PBT, PP, epoxy resin, organosilicon, polyurethane, rubber.MCA resistance
Fuel efficiency fruit is good, can be used in combination with other auxiliary agents, with phosphorus system, bromine system, antimony system etc. it is combustion-supporting and be used in combination when have good association
Same effect.It is worth mentioning that effect becomes apparent from when MCA is fire-retardant applied to polyamide.
It is blended in relatively simple in technique, the range of choice of component is larger, is made with property with can be convenient
New material is a key areas of material science, so have developed rapidly.So-called polymer blending refers to two or more
The physical mixture of the different homopolymer of molecular structure, copolymer or homopolymer and copolymer.The macromolecular of general two component it
Between not no covalent bond connection.The mixing of polymer is endothermic process, is dispersed in another polymer by a kind of polymer
Heterogeneous system.The purpose of blending is the polymeric material that prepare energy improve to some extent in certain performances or unique
Material.Polymer blend is a kind of multiphase polymer occurred earliest.
Polymer is blended closely related with the overall development of material science research.About the research that polymer is blended, have
Century-old history just has and shock proof polystyrene patent report is made by being blended early in early 20th century.Even to this day, gather
Basic research and applied basic research that object is blended are closed, is still the research hotspot of polymeric material field, in new mixture
It is all constantly making progress in terms of system and mechanism study；And the method for polymer blending modification is still in processing of high molecular material
One important industrial technology, application is among various plastics and rubber product.Many successes in Macromolecular materials industry
The exploitation of product is all closely to rely on polymer blending techniques.Blending theory is constantly brought forth new ideas with application technology, has been pushed poly-
Close the research and industrial applications of object 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.
PA56 is formed by 1,5- pentanediamine and adipic acid polycondensation.PA56 is a kind of polyamide of even-odd structure, with PA66 phase
Comparatively, PA56 and PA66 have certain structural similarity, and the main distinction is the monomer of PA56 in terms of chemical structure
One of pentanediamine be a kind of five carbon diamines, and one of monomer of PA66 hexamethylene diamine is a kind of six carbon diamines.In chemical structure
Difference make PA56 and PA66 physicochemical properties have certain difference.Such as the structural symmetry ratio of the repetitive unit of PA56
PA66 is lower, and 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 certain similitude 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,
With higher oxygen index (OI), there is 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 the Halogen with environmental protection feature hinders
Fire PA56/PA66 composite material.
Summary of the invention
The purpose of the present invention is to provide a kind of thermoplastic halogen-free flame retarding biology bases with excellent combination mechanical property
PA56 and PA66 composite material and preparation method, PA56 the and PA66 composite material are that can satisfy electric and household electric
The novel environment friendly polymer material of device equipment requirement, wherein at least partly raw material source of PA56 is obtained from biological fermentation process.
In order to achieve the above object, the technical solution of the present invention is to provide a kind of thermoplastic halogen-free flame retarding biology bases of environmental protection
PA56 and PA66 composite material, the composite material are at least prepared by the raw material of following mass percent.
Biology base PA56:10~75%；
PA66:10~75%；
Fire retardant: 5~20%, preferably 6~9%, the partial size of the fire retardant is 0.1~0.2 micron.
Wherein, one of polymerized monomer of biology base PA56 1,5- pentanediamine is obtained by biofermentation technique, polymerization
Two adipic acid sources of monomer can be to be obtained by biofermentation technique, is also possible to manufacture by petrochemical industry, but
Need guarantee the polymerized monomer as made from biological fermentation process quality account for biology base PA56 gross mass 47.17~
100wt%.Biology base PA56 includes the organic carbon for meeting the renewable source of ASTM D6866 standard.In the present invention, PA56
For biology base PA56 slice, PA66 is that PA66 is sliced, and the 98wt% relative sulfuric acid viscosity of PA56 and PA66 are 2.2~3.8, specifically
The range of viscosities of selection, for the product for requiring mobility high, selects low-viscosity polyamides to make depending on downstream application difference
For 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,
The raw material of the composite material can also include compatilizer, and the mass percent of Zhan Suoshu raw material is 2~15%.The compatilizer
Including either Methyl Methacrylate-Butadiene-Styrene Copolymer, methyl methacrylate-ethyl acrylate, random second
Alkene-butyl acrylate copolymer, random ethylene-methyl acrylate-copolymer-maleic anhydride, Ethylene-butyl acrylate-methyl-prop
Olefin(e) acid glycidyl ester copolymer, maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride stem grafting polyolefin
Elastomer, maleic anhydride grafting ethylene propylene diene rubber, maleic anhydride grafted ethene-vinyl acetate, maleic anhydride grafting hydrogenation
One of butadiene-styrene block copolymer and maleic anhydride grafted ethene-butadiene-styrene copolymer are a variety of.
It is many to can be used for the fire-retardant additive flame retardant of nylon, mainly includes halogenated flame retardant, nitrogenated flame retardant, the resistance of phosphorus system
Fire agent, inorganic fire retardants and other kinds of fire retardant.For polyamide product, nitrogenated flame retardant such as melamine cyanogen
Lithate (MCA) is a kind of ideal fire retardant, MCA have the advantages that it is more than other fire retardants, as MCA have whiteness it is high,
It is excellent it is dispersed, low toxicity itself is harmless, heat resistance is high and with the characteristics such as other flame-retardant system compatibilities are strong.Add MCA resistance
The modified polyamide of agent is fired especially suitable for products such as production computer, facsimile machine, telephone set, duplicator, household electrical appliances.
MCA fire retardant is applied in biology base PA56 and PA66 composite material by the present invention.First passage of the present invention is blended
Modification technology, is prepared for biology base PA56 and the PA66 composite material with fire-retardant characteristic, and this new material has its unique
Advantage.Product can be applied to the electronic electric equipment that can be used for the various raw materials of injection molding with biological source requirement and household electrical appliances production
Product etc..
For MCA although having excellent flame retardant property, additive amount is bigger, at high cost, bears effect to the physical property of material
It should be obvious.In order to reduce additive amount, optimization physical property and raising flame retardant effect, the raw material of composite material of the invention further include
Fire retarding synergist, the mass percent of Zhan Suoshu raw material are 1~10%；Fire retarding synergist include either zinc borate, zinc oxide,
One of montmorillonite, antimony oxide, organic silicon fibre retardant SFR-100, potassium carbonate, calcium stearate are a variety of.
In the present invention, the raw material of the composite material further includes other processing aids, and mass percent is 0.1~5%, excellent
It is selected as 0.1~1%；
Preferably, other processing aids include either one of anti-dripping agent, antioxidant and lubricant or more
Kind；
The anti-dripping agent includes either ptfe micropowder (PTFE micro mist).Carrying out biology base PA56 and PA66
Before composite material, the fire retardant, the fire retarding synergist and the anti-dripping agent are premixed and surpassed in the ball mill
Refinement, makes 0.1~0.2 micron of average grain diameter of the fire retardant, the fire retarding synergist and the anti-dripping agent.
In the present invention, the antioxidant includes either N, and N- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) third
Acyl group) hexamethylene diamine, β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [2,4- di-tert-butyl-phenyls]
Phosphite 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-, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl)
One of butane and 1,3,5- trimethyl -2,4,6- three (- 4 hydroxybenzyl of 3,5- di-t-butyl) benzene are a variety of.
In the present invention, the lubricant includes either N, N'- ethylene bis stearamide, oxidized polyethylene wax, polyethylene-
Vinyl acetate wax, partly-hydrolysed polyethylene wax, oleamide, erucyl amide, pentaerythritol stearate, montanate, tristearin
One of sour calcium, zinc stearate, odium stearate, barium stearate, the macromolecule organic silicon (such as silicone powder) and amido silicon oil are more
Kind.The effect of the lubricant be it is various, as the main function of lubricant be reduce in extrusion process molecular resin chain
Frictional force, melt between section and the frictional force between process equipment, prevent resin caused by frictional heat generation from degrading, and guarantee compound
The performance of material will not be deteriorated because of thermal degradation.Lubricant can also reduce the apparent viscosity of resin, increase the mobility of resin,
Improve the processability of blend, improve processing efficiency.Furthermore lubricant can also prevent resin and mold from adhering, increases molding and add
The release property in working hour.
In the present invention, the preparation method of thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material includes following step
It is rapid:
1) by mass percentage, the fire retardant of raw material 5~20% is carried out to homogenization and fine in the ball mill to grain
Diameter is 0.1~0.2 micron, is then added in the side feed hopper of extruder；
2) by mass percentage, 10~75% biology base PA56,10~75% PA66 are mixed in high-speed mixer
It closes uniformly, is then added in the main feed hopper of extruder；Preferably, it is uniformly mixed in high-speed mixer, revolving speed 500~
700 revs/min, the time is 3~5 minutes；
(3) adjust extruder screw rod draw ratio be 1:40-52,300~600 revs/min of screw speed, extruder from
Each area's temperature setting of 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.
Preferably, in the step 1), the raw material further include account for the material quality percentage be 1~10% it is fire-retardant
0.1~2% modifying agent of synergist, the fire retardant of Zhan Suoshu and the fire retarding synergist gross mass；And/or
In the step 2), the raw material further includes accounting for the compatilizer that the mass percent of the raw material is 2~15%；It is excellent
Selection of land, the modifying agent include any one either in sodium caprolactam and silane resin acceptor kh-550.
The raw material of the composite material further includes other processing aids, and the mass percent of Zhan Suoshu raw material is 0.1~
5%, preferably 0.1~1%；Other processing aids include either one of anti-dripping agent, antioxidant and lubricant
Or it is a variety of；The mass percent that the anti-dripping agent accounts for the raw material is 0.1~1%；The anti-dripping agent is used for the step
1), the antioxidant and lubricant are used for the step 2).
In the present invention, infused after thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material is 6 hours dry at 80 DEG C
Test bars are moulded into, injection temperature is 260~275 DEG C.
In the present invention, the performance test of thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material is referring to subscript
It is quasi-:
1 testing standard table of table
It is each that thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material prepared by the present invention are applicable to injection molding
The components or structural material of the products such as kind electronics, electric appliance, furniture.It is even anti-that the present invention controls fire retardant, fire retarding synergist
The partial size of dripping agent, can not only reduce the dosage of fire retardant, but also can be further improved the impact resistance of composite material.
Specific embodiment
The present invention is described in further detail with reference to embodiments, but the present invention is not limited to these Examples.
Raw material information selected by the present invention is as follows:
Biology base PA56: Kai Sai (Jinxiang) biomaterial Co., Ltd, the polymerized monomer as made from biological fermentation process
Quality accounts for 100%, the 96wt% relative sulfuric acid viscosity 2.7 of the gross mass of the biology base PA56
PA66 (PA66): Pingdingshan Shenma Engineering Plastic Co., Ltd., 96wt% relative sulfuric acid viscosity 2.7
Melamine cyanurate (MCA, as fire retardant): Jinan Taixing Fine Chemicals Co., ltd
Zinc borate (ZnB4O7, as fire retarding synergist): Shandong Bo Ao Industrial Co., Ltd.
Zinc oxide (ZnO, as fire retarding synergist): Lian Da Fine Chemical Co., Ltd
Montmorillonite (MMT, as fire retarding synergist): Jiangsu Gukang New Material Co., Ltd.
Antimony oxide (Sb2O3, as fire retarding synergist): Zi Jiang Chemical Co., Ltd.
Organic silicon fibre retardant (RM4-7081, as fire retarding synergist): DOW CORNING (Shanghai) Co., Ltd.
Potassium carbonate (K2CO3, as fire retarding synergist): Zhengzhou Yu Teng chemical products Co., Ltd
Calcium stearate (CaSt2, as fire retarding synergist): Shanghai Hua Yi auxiliary chemicals Co., Ltd
Coupling agent KH-550: nine cherry new material Co., Ltd of Shanghai
Maleic anhydride stem grafting polyolefin elastomer (POE-g-MA, as compatilizer): Du Pont China Holding Co., Ltd.
N, N'- ethylene bis stearamide (EBS, as lubricant): Suzhou Lian Sheng chemical company
N, N- be bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (antioxidant 1098): Ciba
(China) Co., Ltd
PTFE (anti-dripping agent): Hubei Xin Mao new high-tech material Co., Ltd
Embodiment 1:
(1) fire retardant, fire retarding synergist, anti-dripping agent, modifying agent are put into ball mill and carry out mixing and fine, ball
Grind temperature be 25 DEG C, ball grinder revolving speed be 200 revs/min, Ball-milling Time 24 hours, until partial size be 0.1~0.2 micron, then
It is added in the side feed hopper of extruder；
(2) biology base PA56, PA66, compatilizer, lubricant and antioxidant are uniformly mixed in high-speed mixer, mixing
After 25 DEG C of temperature, 600 revs/min of revolving speed, incorporation time 3 minutes, it is added in the main feed hopper of extruder；
(3) draw ratio of screw rod selected by melting extrusion be 1:40,300 revs/min of screw speed, each area's temperature of extruder
It is arranged from feeding to die orifice and 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 temperature 270
DEG C, obtain thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material.
The formula of the composite material of Examples 1 to 7 is as shown in table 2, embodiment 8~12 and comparative example 1~2 formula such as table 3
It is shown, wherein fire retardant selected by comparative example, fire retarding synergist, anti-droplet dew agent do not undergo ball-milling treatment, embodiment and right
The experimental procedure of ratio is listed in Table 4 below referring to embodiment 1, corresponding test result:
Table 2: the formula table (unit: g) of the composite material of Examples 1 to 7
Table 3: the formula table (unit: g) of the composite material of embodiment 8 and 9 and comparative example
Table 4: the performance comparison sheet of the composite material of embodiment and comparative example
The experimental results showed that can not only be reduced by ball milling process control fire retardant, fire retarding synergist and anti-dripping agent
The dosage of fire retardant, but also can be further improved the impact resistance of composite 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 (12)
1. a kind of thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material, it is characterised in that: the composite material is at least
It is prepared by the raw material of following mass percent:
Biology base PA56:10~70%；
PA66:10~70%；
Fire retardant: 5~20%, preferably 6~9%, the partial size of the fire retardant is 0.1~0.2 micron.
2. thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material according to claim 1, wherein 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 the 47.17~100% of the gross mass of the biology base PA56.
3. thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material according to claim 1 or 2, wherein described
Biology base PA56 be biology base PA56 slice, the PA66 is that PA66 is sliced, the described biology base PA56 slice with it is described
PA66 slice 96wt% relative sulfuric acid viscosity be 2.2~3.8.
4. thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material according to claim 1-3, in which:
The raw material of the composite 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, metering system
Sour methyl esters-ethyl acrylate, random ethylene-butyl acrylate copolymer, random ethylene-methyl acrylate-maleic anhydride
Object, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer, maleic anhydride grafted polyethylene, maleic anhydride grafting
Polypropylene, maleic anhydride stem grafting polyolefin elastomer, maleic anhydride are grafted ethylene propylene diene rubber, maleic anhydride grafted ethene-second
Vinyl acetate, maleic anhydride grafting hydrogenated butadiene-styrene block copolymer and maleic anhydride grafted ethene-butadiene-benzene
One of ethylene copolymer is a variety of.
5. thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material according to claim 1-4, in which:
The fire retardant includes either nitrogenated flame retardant, it is preferable that the fire retardant includes either melamine cyanurate.
6. thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material according to claim 1-5, in which:
The raw material of the composite material further includes fire retarding synergist, and the mass percent of Zhan Suoshu raw material is 1~10%；
Preferably, the fire retarding synergist includes either zinc borate, zinc oxide, montmorillonite, antimony oxide, organosilicon resistance
Fire one of agent SFR-100, potassium carbonate and calcium stearate or a variety of；And/or
Preferably, the partial size of the fire retarding synergist is 0.1~0.2 micron.
7. according to described in any item thermoplastic halogen-free flame retarding biology base PA56 and the PA66 composite materials of claim 5 or 6,
In, modifier modification is passed through on the surface of the fire retardant and the fire retarding synergist, and the modifying agent includes either
Any one in sodium caprolactam and silane resin acceptor kh-550；Preferably, the quality of the modifying agent is the resistance
Fire the 0.1~2% of agent and the fire retarding synergist gross mass.
8. thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material according to claim 7, in which: described compound
The raw material of material further includes other processing aids, and the mass percent of Zhan Suoshu raw material is 0.1~5%, preferably 0.1~1%；
Preferably, other processing aids include either one of anti-dripping agent, antioxidant and lubricant or a variety of；
It is highly preferred that the antioxidant includes either N, N- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) oneself
Diamines, 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) pentaerythritol diphosphites, 2,2- methylene-bis- (4- ethyl -6- tert-butyl phenol), 4,
Inclined fourth support-bis--(the 6- tert-butyl-m-cresol) of 4-, (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane of 1,1,3- tri- and 1,3,5-
One of trimethyl -2,4,6- three (- 4 hydroxybenzyl of 3,5- di-t-butyl) benzene is a variety of；And/or
It is highly preferred that the 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 and amido silicon oil are a variety of；It is highly preferred that described
The macromolecule organic silicon is silicone powder.
9. thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material according to claim 8, in which: the anti-drop
Falling agent and accounting for the mass percent of the raw material is 0.1~1%；And/or
Preferably, the anti-dripping agent is ptfe micropowder；And/or
Preferably, the partial size of the anti-dripping agent is 0.1~0.2 micron.
10. a kind of preparation method of thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material, which is characterized in that including such as
Lower step:
1) by mass percentage, the fire retardant of raw material 5~20% is subjected to homogenization in the ball mill and fine to partial size is
0.1~0.2 micron, then obtained fire retardant systems are added in the side feed hopper of extruder；
2) by mass percentage, the PA66 of the biology base PA56 of raw material 10~75%, 10~75% are uniformly mixed, are then added
In the main feed hopper of the extruder；Preferably, it is uniformly mixed in high-speed mixer, 500~700 revs/min of revolving speed, when
Between be 3~5 minutes；
3) draw ratio for adjusting the screw rod of the extruder is 1:40~52, and 300~600 revs/min of screw speed, extruder is each
Each area temperature of area's temperature setting from main spout to die orifice be 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, obtain thermoplastic halogen-free flame retarding biology
Base PA56 and PA66 composite material.
11. the preparation method of thermoplastic halogen-free flame retarding biology base PA56 and the PA66 composite material as described in right wants 10, wherein
In the step 1), the raw material further includes accounting for fire retarding synergist, the Zhan Suoshu that the material quality percentage is 1~10%
The modifying agent of fire retardant and 0.1~2wt% of the fire retarding synergist gross mass；And/or
In the step 2), the raw material further includes accounting for the compatilizer that the mass percent of the raw material is 2~15%；
Preferably, the modifying agent includes any one either in sodium caprolactam and silane resin acceptor kh-550.
12. the preparation method of thermoplastic halogen-free flame retarding biology base PA56 and the PA66 composite material as described in right wants 11, wherein
The raw material of the composite material further includes other processing aids, and the mass percent of Zhan Suoshu raw material is 0.1~5%, preferably
0.1~1%；Other processing aids include either one of anti-dripping agent, antioxidant and lubricant or a variety of；It is described
The mass percent that anti-dripping agent accounts for the raw material is 0.1~1%；The anti-dripping agent is used for the step 1), the antioxygen
Agent and lubricant are used for the step 2).
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