CN109957242A - A kind of low-phosphorous fire-retardant biology base PA56 of thermoplastic halogen-free and PA66 composite material and preparation method - Google Patents
A kind of low-phosphorous fire-retardant biology base PA56 of thermoplastic halogen-free 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
- 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 low-phosphorous fire-retardant biology base PA56 of thermoplastic halogen-free and PA66 composite material and preparation methods, the composite material is at least prepared by the raw material of following mass percent: biology base PA56 10~70%, PA66 10~70%, fire retardant 5~20%, it is preferred that 5~7%, phosphorous flame-retardant synergist 1~10%, 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, is used directly for injection molding.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 fields, are related to a kind of low-phosphorous fire-retardant PA56 and PA66 composite wood of thermoplastic halogen-free
Material and preparation method thereof more particularly to a kind of low-phosphorous fire-retardant biology base PA56 of thermoplastic halogen-free and PA66 composite material and its preparation
Method.PA56 has bio-based source.PA56 the and PA66 composite material has good flame retardant effect, excellent mechanical property
And machinability, and there is environment-friendly advantage, can be used for injection molding has the electric of biological source requirement to various raw materials
Equipment and household appliances.
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 is a kind of new and effective fire retardant, is more and more paid attention in recent years, with halogenated flame retardant
It compares, nitrogenated flame retardant has small toxicity, flame retarding efficiency height, corrosivity small and the light stabilizer Lothrus apterus in material, heat point
Solve temperature height and advantages of environment protection.Nitrogenated flame retardant mainly includes the organic compounds containing nitrogens such as melamine, cdicynanmide, 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 nylon of even-odd structure, compared with PA66
Compared with for, in terms of chemical structure, PA56 and PA66 have certain structural similarity, the main distinction be PA56 monomer it
One 1,5- pentanediamine are a kind of five carbon diamines, and one of monomer of PA66 hexamethylene diamine is a kind of six carbon diamines.Chemical structure
On difference make PA56 and PA66 physicochemical properties have certain difference.Such as 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 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 polyamide-based product, if PA56 is that have centainly instead
Answer active crystalline polymer, with excellent mechanical property, wearability, self-lubrication, oil resistivity, corrosion resistance and preferably
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 and PA66 composite material.
Summary of the invention
The purpose of the present invention is to provide a kind of low-phosphorous fire-retardant biologies of thermoplastic halogen-free with excellent combination mechanical property
Base PA56 and PA66 composite material and preparation method, which, which belongs to, can satisfy electric and family
The novel environment friendly polymer material of electrical appliance equipment requirement, wherein the part material 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 low-phosphorous fire-retardant biology bases of environment-friendly thermoplastic Halogen
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%, preferably 5~7%；
Phosphorous flame-retardant synergist: 1~10%.
One of the polymerized monomer of biology base PA56 pentanediamine is obtained by biofermentation technique, polymerized monomer two oneself two
Acid can be to be obtained by biofermentation technique, is also possible to manufacture by petrochemical industry, but needs to guarantee to pass 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
Meet the organic carbon of the renewable source of ASTM D6866 standard.In the present invention, PA56 is biology base PA56 slice, and PA66 is
The 98wt% relative sulfuric acid viscosity of PA66 slice, PA56 and PA66 are 2.2~3.8, preferably 2.5~2.8, the viscosity specifically selected
Range, for the product for requiring mobility high, selects low-viscosity polyamides as raw material depending on downstream application difference.
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 nylon 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 the compatilizer 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
Glycidyl acrylate 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 anhydride are grafted hydrogen
Change one of butadiene-styrene block copolymer and maleic anhydride grafted ethene-butadiene-styrene copolymer or more
Kind.
It is many to can be used for the fire-retardant additive flame retardant of polyamide, mainly includes halogenated flame retardant, nitrogenated flame retardant, phosphorus system
Fire retardant, inorganic fire retardants and other kinds of fire retardant.For polyamide product, melamine cyanurate (MCA)
It is a kind of ideal fire retardant, MCA has the advantages that more than other fire retardants, and as MCA has, whiteness is high, excellent dispersion
Property, harmless, heat resistance of low toxicity itself it is high and with the characteristics such as other flame-retardant system compatibilities are strong.Add the modification of MCA fire retardant
Polyamide is 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 the composite material with the biology base PA56 and PA66 of fire-retardant characteristic, and this new material has it unique
Advantage, product can be applied to can be used for the electronic electric equipment and household electrical appliances that the various raw materials of injection molding have biological source requirement
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 present invention select diethyl hypophosphorous acid simultaneously
One of aluminium, hypo-aluminum orthophosphate, phenoxy cyclotriphosphazene and triphenyl phosphate are a variety of as fire retarding synergist, it is preferable that institute
Stating phosphorous flame-retardant synergist is liquid phosphorous fire retarding synergist.Preferably, diethyl hypo-aluminum orthophosphate and/or hypo-aluminum orthophosphate are averaged
Partial size is 1~10 micron, preferably 2~5 microns.
The raw material of the composite material further includes anti-dripping agent, and the mass percent ratio of Zhan Suoshu raw material is 0.1~2%；
Preferably, the anti-dripping agent is polytetrafluoroethylene (PTFE) (PTFE).
The raw material of the composite material can also include other processing aids, and mass percent is 0.1~5%；Preferably,
Other processing aids include one of antioxidant, lubricant and nucleating agent or a variety of.
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 and the macromolecule organic silicon (such as silicone powder) are a variety of.The effect of lubricant
Be it is various, if the main function of lubricant is the frictional force reduced in extrusion process between molecular resin segment, melt
Frictional force between process equipment prevents resin caused by frictional heat generation from degrading, and guarantees that the performance of composite material will not be because of
Thermal degradation and deteriorate.Lubricant can also reduce the apparent viscosity of resin, increase the mobility of resin, improve the processing of blend
Property, improve processing efficiency.Furthermore 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) 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.
Nucleating agent includes at least one organic nucleating agent and a kind of inorganic nucleator.Wherein, the organic nucleating agent includes
Either one of nucleating agent CAV102, montanic acid sodium, nylon 22, polyacrylic acid ionomer and sodium benzoate or a variety of.Institute
State inorganic nucleator include either talcum powder, organically-modified sodium-based montmorillonite (also known as organo montmorillonite), zeolite, oxidation
One of aluminium, mica, kaolin, magnesia, calcium carbonate and sodium carbonate are a variety of.
In the present invention, the preparation method of the low-phosphorous fire-retardant biology base PA56 of thermoplastic halogen-free and PA66 composite material includes as follows
Step:
(1) by mass percentage, the PA66 of the biology base PA56 of raw material 10~70%, 10~70% are uniformly mixed, it will
Uniformly mixed material is added by the main spout of double screw extruder；Preferably, it is uniformly mixed in high-speed mixer, institute
The revolving speed for stating high-speed mixer is 500~700 revs/min, and incorporation time is 3~5 minutes；Preferably, the raw material further includes 2
~15% compatilizer, 0.1~2% anti-dripping agent, 0.1~5% other processing aids；
(2) by mass percentage, the phosphorous flame-retardant synergist of the fire retardant of raw material 5~20% and 1~10% is mixed equal
It is even, uniformly mixed material is added by the side spout of double screw extruder；Preferably, it is mixed in high-speed mixer equal
Even, the revolving speed of the high-speed mixer is 400~600 revs/min, and incorporation time is 3~5 minutes；
The draw ratio of the screw rod of double screw extruder is 1:40-52, and 300~500 revs/min of screw speed, twin-screw squeezes
Out each area temperature of the machine 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 the low-phosphorous fire-retardant biology of thermoplastic halogen-free
Base PA56 and PA66 composite material.
In the present invention, the thermoplasticity prepared by double screw extruder enhances biology base PA56 and PA66 composite material 80
Drying is molded into test bars at DEG C after 6 hours, and injection temperature is 260~275 DEG C.
In the present invention, the performance test of biology base PA56 and PA66 composite material is referring to following standard:
1 performance test standard scale of table
Thermoplasticity prepared by the present invention enhances biology base PA56 and PA66 composite material, and comprehensive mechanical property is good, fire-retardant
Property is good, is applicable to the components or structural material of the 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.
As shown in table 2 and table 3, corresponding test result is listed in Table 4 below, selected for the embodiment of the present invention and the formula of comparative example
It is as follows with raw material information:
Biology base PA56: Kai Sai (Jinxiang) biomaterial Co., Ltd, the quality of polymerized monomer made from biological fermentation process
Account for 100%, the 96wt% relative sulfuric acid viscosity 2.7 of the gross mass of biology base PA56
PA66 (PA66): Pingdingshan Shenma Engineering Plastic Co., Ltd., 96wt% relative sulfuric acid viscosity 2.7
Melamine cyanurate (MCA, fire retardant): Jinan Taixing Fine Chemicals Co., ltd
Diethyl hypo-aluminum orthophosphate (ADP, fire retarding synergist): Tianjin development chemical industry Co., Ltd
Hypo-aluminum orthophosphate (PHA, fire retarding synergist): Foshan City Jinge Fire-fighting Materials Co., Ltd
Phenoxy cyclotriphosphazene (HPCTP, fire retarding synergist): Lijin perseverance reaches Chemical Co., Ltd.
Triphenyl phosphate (TPP, fire retarding synergist): Zhangjiagang Ya Rui Chemical 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 (CaSt2, lubricant): Shanghai Hua Yi auxiliary chemicals Co., Ltd
Nucleating agent P22: Brueggemann Asia Co., Ltd nucleating agent CAV102: Klein chemical industry (China) Co., Ltd
Organo montmorillonite (OMMT, inorganic nucleator): Jiangsu Gukang New Material Co., Ltd.
Talcum powder (Talc, 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 AO
1098): Ciba (China) Co., Ltd
PTFE micro mist (anti-dripping agent): Hubei Xin Mao new high-tech material Co., Ltd
Embodiment 1:
(1) it is uniformly mixed in a high speed mixer after weighing fire retardant, fire retarding synergist, mixing temperature is 25 DEG C, is turned
After 600 revs/min, incorporation time 3 minutes of speed, the storing that the material mixed is transferred to the side feed material of double screw extruder is held
In device；
(2) in height after biology base PA56, PA66, anti-dripping agent, compatilizer, lubricant, nucleating agent and antioxidant being weighed
Fast stirrer for mixing is uniform, after mixing temperature is 25 DEG C, 600 revs/min of revolving speed, incorporation time 3 minutes, the object that will mix
Material is transferred in the magazine for squeezing out owner's feeding；
(3) draw ratio for adjusting screw rod selected by twin-screw extrusion is 1:40, and 300 revs/min of screw speed, twin-screw squeezes
Each area temperature of the machine from 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 out,
Die temperature is 270 DEG C, obtains PA56 and PA66 composite material.
(4) composite material prepared by double screw extruder is sliced the drying at 80 DEG C and is molded into test specimens after 6 hours
Item, injection temperature are 260~275 DEG C.
Table 1 is the formula table of embodiment 1 to 5, and table 2 is the formula table of embodiment 6 to 8 and comparative example 1 to 2.Each embodiment,
In comparative example, HPCTP and TPP are liquid, extruder are added by liquid feeder, experimental procedure is corresponding to survey referring to embodiment 1
Test result is listed in Table 4 below:
Table 2: the formula table (unit: g) of embodiment 1 to 5
Table 3: the formula table (unit: g) of embodiment 6 to 8 and comparative example
The numerical value of table 2 and table 3 indicates grams.
Table 4: the performance comparison sheet of the composite material of each embodiment and comparative example
The embodiment of the present invention have with the consistent tensile property of comparative example and bending property, but have higher notch punching
Hit intensity can reach UL 94V0 (1.6mm) fire-retardant rank using less fire retardant, have environmental protection feature.
Result of the invention is also shown that liquid phosphorous fire retarding synergist is strong in the flame retardant property and notch shock for improving sample
Degree aspect is better than solid-state fire retarding synergist；For example, can be seen that addition than solid from the comparison of embodiment 3,4,5 and embodiment 1,2
The few liquid phosphorous fire retarding synergist of state fire retarding synergist amount, can be realized under the premise of with same flame retardant property, notch
Impact strength is improved.This is because liquid phosphorous fire retarding synergist not only has certain flame retardant synergism, while
It is a kind of ideal polyamide plasticizers of effect, can further promotes the dispersion of MCA and other synergists in nylon matrix,
Reduce internal friction when sub-chain motion, is conducive to energy dissipation of the sample when receiving impact, therefore using effect is more preferable.
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 (14)
1. a kind of composite material of the low-phosphorous fire-retardant biology base PA56 and PA66 of thermoplastic halogen-free, in which: 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 5~7%；
Phosphorous flame-retardant synergist: 1~10%.
2. the composite material of the low-phosphorous fire-retardant biology base PA56 and PA66 of thermoplastic halogen-free according to claim 1, in which: institute
The biology base PA56 stated 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. the composite material of the low-phosphorous fire-retardant biology base PA56 and PA66 of thermoplastic halogen-free according to claim 1 or 2,
In: the biology base PA56 is biology base PA56 slice, and the PA66 is PA66 slice, the biology base PA56 slice
It is 2.2~3.8 with the PA66 96wt% relative sulfuric acid viscosity being sliced, preferably 2.5~2.8.
4. the composite wood of the low-phosphorous fire-retardant biology base PA56 and PA66 of thermoplastic halogen-free according to claim 1-3
Material, 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. the composite wood of the low-phosphorous fire-retardant biology base PA56 and PA66 of thermoplastic halogen-free according to claim 1-4
Material, in which: the fire retardant includes either nitrogenated flame retardant, it is preferable that the fire retardant includes either melamine
Cyanurate.
6. the composite wood of the low-phosphorous fire-retardant biology base PA56 and PA66 of thermoplastic halogen-free according to claim 1-5
Material, in which: the phosphorous flame-retardant synergist includes either diethyl hypo-aluminum orthophosphate, hypo-aluminum orthophosphate, phenoxy cyclotriphosphazene
With one of triphenyl phosphate or a variety of；Preferably, the phosphorous flame-retardant synergist includes either liquid phosphorous fire-retardant association
Imitate agent.
7. the composite material of the low-phosphorous fire-retardant biology base PA56 and PA66 of thermoplastic halogen-free according to claim 6, in which: two
The average grain diameter of ethyl hypo-aluminum orthophosphate and/or hypo-aluminum orthophosphate is 1~10 micron, preferably 2~5 microns.
8. the composite wood of the low-phosphorous fire-retardant biology base PA56 and PA66 of thermoplastic halogen-free according to claim 1-7
Material, wherein the raw material of the composite material further includes anti-dripping agent, and the mass percent ratio of Zhan Suoshu raw material is 0.1~2%；
Preferably, the anti-dripping agent is polytetrafluoroethylene (PTFE).
9. the composite wood of the low-phosphorous fire-retardant biology base PA56 and PA66 of thermoplastic halogen-free according to claim 1-8
Material, the raw material of the composite material further include 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.
10. the composite material of the low-phosphorous fire-retardant biology base PA56 and PA66 of thermoplastic halogen-free according to claim 9, wherein
The lubricant includes either N, N'- ethylene bis stearamide, oxidized polyethylene wax, ethylene vinyl acetate wax, part soap
Change polyethylene wax, oleamide, erucyl amide, pentaerythritol stearate, montanate, calcium stearate, zinc stearate, tristearin
One of sour sodium, barium stearate, the macromolecule organic silicon and amido silicon oil are a variety of；It is highly preferred that the macromolecule organic silicon
It is silicone powder.
11. according to the composite material of the low-phosphorous fire-retardant biology base PA56 and PA66 of the described in any item thermoplastic halogen-frees of claim 9,
Wherein, the antioxidant includes that live is N, and N- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine,
It is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [2.4- di-tert-butyl-phenyl] phosphite esters, double
(2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, 2,2- methylene-bis- (4- ethyl -6- tert-butyl phenol), 4,4- are inclined
Fourth support-bis--(6- tert-butyl-m-cresol), (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane of 1,1,3- tri- and 1,3,5- front three
One of base -2,4,6- three (- 4 hydroxybenzyl of 3,5- di-t-butyl) benzene is a variety of.
12. according to the composite wood of the low-phosphorous fire-retardant biology base PA56 and PA66 of the described in any item thermoplastic halogen-frees of claim 2-10
Material, wherein the nucleating agent includes at least one organic nucleating agent and a kind of inorganic nucleator；
Preferably, the organic nucleating agent includes either nucleating agent CAV102, montanic acid sodium, montanic acid calcium, P22, polypropylene
One of sour ionomer and sodium benzoate are a variety of；
Preferably, the inorganic nucleator include either talcum powder, organically-modified sodium-based montmorillonite, zeolite, aluminium oxide, cloud
One of mother, kaolin, magnesia, calcium carbonate and sodium carbonate are a variety of.
13. a kind of preparation method of the composite material of the low-phosphorous fire-retardant biology base PA56 and PA66 of thermoplastic halogen-free, in which: including such as
Lower step:
(1) by mass percentage, through double spiral shells after the PA66 of the biology base PA56 of raw material 10~70%, 10~70% being uniformly mixed
The main spout of bar extruder is added in the double screw extruder；Preferably, it is uniformly mixed in high-speed mixer, it is described
The revolving speed of high-speed mixer is 500~700 revs/min, and incorporation time is 3~5 minutes；
(2) by mass percentage, by the fire retardant of raw material 5~20% and 1~10% phosphorous flame-retardant synergist after mixing
It is added in the double screw extruder by the side spout of double screw extruder；
(3) draw ratio of the screw rod of the double screw extruder is set as 1:40-52, screw speed is 300~500 revs/min,
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, obtain the low-phosphorous resistance of thermoplastic halogen-free
Fire biology base PA56 and PA66 composite material.
14. the preparation side of the composite material of the low-phosphorous fire-retardant biology base PA56 and PA66 of thermoplastic halogen-free as claimed in claim 13
Method, wherein the raw material further include:
2~15% compatilizer, and/or
0.1~2% anti-dripping agent, and/or
0.1~5% other processing aids.
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| CN201711343372.4A CN109957242A (en) | 2017-12-14 | 2017-12-14 | A kind of low-phosphorous fire-retardant biology base PA56 of thermoplastic halogen-free and PA66 composite material and preparation method |
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