CN106497042A - Environment-friendly type bromine system fire-retardant nylon composite and preparation method thereof - Google Patents
Environment-friendly type bromine system fire-retardant nylon composite and preparation method thereof Download PDFInfo
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- CN106497042A CN106497042A CN201610964379.7A CN201610964379A CN106497042A CN 106497042 A CN106497042 A CN 106497042A CN 201610964379 A CN201610964379 A CN 201610964379A CN 106497042 A CN106497042 A CN 106497042A
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
Abstract
The present invention relates to polymeric material field, specifically disclose a kind of environment-friendly type bromine system fire-retardant nylon composite, in parts by weight, including following raw material, 40～100 parts of polyamide, 1～10 part of polybenzimidazoles, 3～10 parts of ethylene vinyl acetate copolymer, 5～15 parts of SEBS, 5～12 parts of maleic anhydride modified polypropylene, 3～10 parts of cyclodextrin polyethylene glycol complex, 5～20 parts of liquid paraffin, 3～20 parts of filler, 1～3 part of bromide fire retardant, 1～5 part of synergistic flame retardant.
Description
Technical field
The present invention relates to polymeric material field, more particularly to environment-friendly type bromine system fire-retardant nylon composite and its preparation side
Method.
Background technology
Polyamide (PA) is the kind that yield is maximum in five large-engineering plastics, kind is most, purposes is most wide.Polyamide has
Good combination property, such as mechanical property, thermostability, wear-resisting, cold-resistant, corrosion-resistant, chemical proofing, nontoxic, self-lubricating
Property and easy-formation processing.Thus can be widely applied to mechanical building, auto parts and components, electronic device, chemical industry equipment, aviation,
The fields such as metallurgy.
Polyamide is commonly called as nylon (PA), is the analog thermoplastic tree containing recurring amide radical group (- NHCO-) on molecular backbone
Fat general name.Non-modified polyamide fire resistance is poor, in use easily initiation fire.Therefore in electronic apparatus etc.
Field is required for carrying out polyamide flame-retardant modified when applying.Can be used for the flame-retardant modified fire retardant species of polyamide mainly has halogen
System, phosphorus system, nitrogen system etc..Halogen system Flameproof polyamide is most widely used at present.And halogenated flame retardant generally needs fire-retardant association of arranging in pairs or groups
The fire resistance that effect agent can be only achieved, fire retarding synergist the most frequently used at present have antimony oxide, Firebrake ZB etc..State in 2011
Issue control antimony ore exploitation total amount and require that antimony is resource continuous in short supply, causes antimony oxide price constantly to be ascended to heaven, seeks in soil resource portion
Antimony oxide succedaneum is looked for bring into schedule.And the phase ratio creepage tracking using antimony oxide as fire retarding synergist refers to
Number (CTI) is relatively low, will be typically less than 300V.
This project technical problem to be solved is to overcome fire retarding synergist three in existing halogen system fire-retardant nylon system
Aoxidize two antimony inadequate resources, a kind of not high defect of CTI values, there is provided Flame-retardant nylon composite.
Content of the invention
In order to solve above-mentioned technical problem, the first aspect of the invention is multiple there is provided a kind of environment-friendly type bromine system fire-retardant nylon
Condensation material, in parts by weight, including following raw material, 40～100 parts of polyamide, 1～10 part of polybenzimidazoles, ethylene-vinegar
3～10 parts of vinyl acetate copolymer, 5～15 parts of SEBS, 5～12 parts of maleic anhydride modified polypropylene, cyclodextrin-Polyethylene Glycol
3～10 parts of complex, 5～20 parts of liquid paraffin, 3～20 parts of filler, 1～3 part of bromide fire retardant, 1～5 part of synergistic flame retardant.
In a preferred embodiment, the environment-friendly type bromine system fire-retardant nylon composite, in parts by weight, including
Following raw material, 60～80 parts of polyamide, 5～10 parts of polybenzimidazoles, 6～9 parts of ethylene-vinyl acetate copolymer,
10～12 parts of SEBS, 8～10 parts of maleic anhydride modified polypropylene, 5～8 parts of cyclodextrin-polyethylene glycol complex, liquid paraffin
13～18 parts, 10～15 parts of filler, 1～3 part of bromide fire retardant, 3～5 parts of synergistic flame retardant.
In a preferred embodiment, the environment-friendly type bromine system fire-retardant nylon composite, in parts by weight, including
Following raw material, 80 parts of polyamide, 8 parts of polybenzimidazoles, 7 parts of ethylene-vinyl acetate copolymer, 11 parts of SEBS, Malaysia
9 parts of anhydride-modified polypropylene, 8 parts of cyclodextrin-polyethylene glycol complex, 16 parts of liquid paraffin, 12 parts of filler, bromide fire retardant 2
Part, 4 parts of synergistic flame retardant.
In a preferred embodiment, the synergistic flame retardant is nano aluminium oxide.
In a preferred embodiment, the particle diameter of the nano aluminium oxide is 10～50 nanometers.
In a preferred embodiment, the synergistic flame retardant is nanometer alumina modified acrylic resin.
In a preferred embodiment, the weight ratio between the nano aluminium oxide and acrylic resin is 1：(1～
10).
In a preferred embodiment, Polyethylene Glycol and cyclodextrin in the cyclodextrin-polyethylene glycol complex
Weight ratio is 1：(1～3).
In a preferred embodiment, described filler is meso-porous nano silicon dioxide.
The second aspect of the invention provides the preparation method of environment-friendly type bromine system fire-retardant nylon composite, at least includes
Following steps：
S1：Each component raw material is weighed according to parts by weight, by polyamide, polybenzimidazoles, ethylene-vinyl acetate
After copolymer, SEBS, maleic anhydride modified polypropylene, cyclodextrin-polyethylene glycol complex, bromide fire retardant mix, add high
In fast blender, at 30～100 DEG C, 60～200min is stirred；
S2：To in step S1, synergistic flame retardant, filler is added, continue 40～100min of stirring, obtain mixed material；
S3：Mixed material in step S2 is added double screw extruder, screw speed is controlled for 50～250r/min, temperature
Spend for 100～300 DEG C, melting extrusion pelletize obtains environment-friendly type bromine system fire-retardant nylon composite.
The above-mentioned of the application and other features, aspect and advantage are more readily understood with reference to described further below.
Specific embodiment
The participation in the election detailed description for being preferable to carry out method of the invention below and including embodiment this can be more easily understood
Bright content.Unless otherwise defined, all technology used herein and scientific terminology have common with art of the present invention
The identical implication that technical staff is generally understood that.When there is contradiction, the definition in this specification is defined.
As used herein term " by ... prepare " synonymous with "comprising".Term "comprising" used herein, " including ",
" with ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily solely those key elements, but can include other not expressly listed key element or
The intrinsic key element of this kind of compositionss, step, method, product or device.
Conjunction " Consists of " excludes any key element that does not point out, step or component.If be used in claim, this
It is closed that phrase will make claim so as to not comprising the material in addition to the material that those describe, but relative normal
Except rule impurity.When phrase " Consists of " is occurred in be rather than immediately following after theme in the clause of claim main body,
Which is only limited to the key element described in the clause；Other key elements are not excluded outside as the overall claim.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value is limited, this is appreciated that and specifically discloses by any range limit or preferred value and any scope
All scopes that arbitrary pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numerical range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers within the range and fraction.
Singulative includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or " arbitrarily
A kind of " refer to that the item for describing thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this concrete
Quantity, also includes the acceptable part without causing the correction of the change of related basic function being close to the quantity.Phase
Answer, with " about ", a numerical value of the modification such as " about ", mean and the invention is not restricted to the exact numerical.In some examples, approximately
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope is limited can be with
Combination and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
Additionally, key element of the present invention or the indefinite article " one kind " before component and " one " are to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also includes plural form, unless the obvious purport of the quantity refers to singulative.
" polymer " means the polymerizable compound prepared by the monomer by the identical or different type that is polymerized.Generic term
" polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".
" copolymer " means the polymer prepared by least two different monomers that are polymerized.Generic term " copolymer " includes
(which is general with term " terpolymer " for term " copolymer " (its typically in order to refer to the polymer prepared by two kinds of different monomers)
In order to refer to the polymer prepared by three kinds of different monomers).Which is also comprising the polymerization manufactured by four or more kinds of monomers of polymerization
Thing." blend " means the polymerization that two or more polymer is mixed by physics or chemistry method jointly and formed
Thing.
In order to solve above-mentioned technical problem, the first aspect of the invention is multiple there is provided a kind of environment-friendly type bromine system fire-retardant nylon
Condensation material, in parts by weight, including following raw material, 40～100 parts of polyamide, 1～10 part of polybenzimidazoles, ethylene-vinegar
3～10 parts of vinyl acetate copolymer, 5～15 parts of SEBS, 5～12 parts of maleic anhydride modified polypropylene, cyclodextrin-Polyethylene Glycol
3～10 parts of complex, 5～20 parts of liquid paraffin, 3～20 parts of filler, 1～3 part of bromide fire retardant, 1～5 part of synergistic flame retardant.
In a preferred embodiment, the environment-friendly type bromine system fire-retardant nylon composite, in parts by weight, including
Following raw material, 60～80 parts of polyamide, 5～10 parts of polybenzimidazoles, 6～9 parts of ethylene-vinyl acetate copolymer,
10～12 parts of SEBS, 8～10 parts of maleic anhydride modified polypropylene, 5～8 parts of cyclodextrin-polyethylene glycol complex, liquid paraffin
13～18 parts, 10～15 parts of filler, 1～3 part of bromide fire retardant, 3～5 parts of synergistic flame retardant.
In a preferred embodiment, the environment-friendly type bromine system fire-retardant nylon composite, in parts by weight, including
Following raw material, 80 parts of polyamide, 8 parts of polybenzimidazoles, 7 parts of ethylene-vinyl acetate copolymer, 11 parts of SEBS, Malaysia
9 parts of anhydride-modified polypropylene, 8 parts of cyclodextrin-polyethylene glycol complex, 16 parts of liquid paraffin, 12 parts of filler, bromide fire retardant 2
Part, 4 parts of synergistic flame retardant.
Polyamide
Term " polyamide " refers to the compound of birdsing of the same feather flock together in main chain with amido link (- NHCO-).
" polyamide " in the present invention is not particularly limited, and can enumerate for example：By diamine and binary carboxylic
Polyamide obtained from the polycondensation of acid, by polyamide obtained from the ring-opening polymerisation of lactams, pass through aminocarboxylic
Acid self condense obtained from polyamide and the copolymerization by constituting the two or more monomer of these polyamides
Obtained from copolymer.
In a preferred embodiment, the polyamide is selected from：Aliphatic polyamide resin, aromatic series polyamides
At least one or several mixing in polyimide resin.
The aliphatic polyamide resin is the polyamide resin that aliphatic diamine and aliphatic dicarboxylic acid are prepared
Fat, the polyamide that the polyamide or amino carboxylic acid that lactams are prepared is prepared.
The aliphatic diamine can include tetra-methylenedimine, hexamethylene diamine, eight methylene diamines, nine Asias
Methanediamine, 11 methylene diamines, ten dimethylene diamidogen etc..
The aliphatic dicarboxylic acid can include adipic acid, dicarboxylic acids in heptan, pungent dicarboxylic acids, nonyl dicarboxylic acids, hendecane
Dicarboxylic acids, dodecanedicarboxylic acid etc..
In a preferred embodiment, the preferred compositions of the aliphatic diamine and aliphatic dicarboxylic acid are six
Methylene diamine and adipic acid.
The lactams can include alpha-pyrrolidone, epsilon-caprolactams, omega-lauric lactam, ε-oenantholcatam etc..
The amino carboxylic acid can include 6-aminocaprolc acid, 7- aminoheptylic acids, 11- aminoundecanoic acids, 12- amino 12
Acid etc..
Above-mentioned aliphatic diamine, aliphatic dicarboxylic acid, lactams and amino carboxylic acid can be used alone one kind,
Can be used with two kinds of combination of the above.
As the specific example of the aliphatic polyamide resin formed by above-mentioned monomer component, can include：Gather oneself
Amide, nylon 11, poly-lauramide, nylon 46, poly hexamethylene adipamide pentanediamine, polyhexamethylene adipamide, the poly- last of the ten Heavenly stems
Two acyl hexamethylene diamines, nylon 612, poly hexamethylene adipamide hendecane diamidogen etc..
The manufacture method of aliphatic polyamide resin is not particularly limited.Can include for example, the presence of (1) in amine
Under, fatty polyamide raw material is polymerized or copolymerization using method known to melt polymerization, polymerisation in solution, solid phase etc.
Manufacture method；(2), after manufacture aliphatic polyamide resin, method of melting mixing etc. is carried out in the presence of amine.
The aliphatic polyamide resin commercially available can also be obtained, and that can enumerated has：Polycaprolactam, nylon 11,
Poly-lauramide, nylon 46, poly hexamethylene adipamide pentanediamine, polyhexamethylene adipamide, polyhexamethylene sebacamide, poly- 12
Two acyl hexamethylene diamine of alkane, poly hexamethylene adipamide hendecane diamidogen etc..
The aromatic polyamide resin refers to a kind of fragrant adoption of at least fragrant family monomer component containing composition
Amide resin.
Can there are, with aromatic diamine and aliphatic dicarboxylic acid or aliphatic diamine and aromatic dicarboxylic
Carboxylic acid is raw material, by aromatic polyamide resin obtained from their polycondensation.
Poly-paraphenylene terephthalamide's nonamethylene diamine (polyamide 9T), poly- terephthaldehyde can be included as aromatic polyamide resin
Acyl hexamethylene diamine (polyamide 6 T), poly-6I hexamethylene isoterephalamide (polyamide 6 I), poly- terephthalate p-phenylenediamine, poly hexamethylene adipamide oneself
Diamidogen/poly- hexamethylene terephthalamide copolymer (polyamide 66/6T), poly- hexamethylene terephthalamide/polycaprolactam amine copolymer
Thing (polyamide 6 T/6), polyhexamethylene adipamide/poly-6I hexamethylene isoterephalamide copolymer (polyamide 66/6I), poly- isophthalic two
Formyl hexamethylene diamine/polycaprolactam co-polymer (polyamide 6 I/6), poly-lauramide/poly- hexamethylene terephthalamide copolymer
(polyamide 12/6T), polyhexamethylene adipamide/poly- hexamethylene terephthalamide/poly-6I hexamethylene isoterephalamide copolymer (polyamides
Amine 66/6T/6I), polyhexamethylene adipamide/polycaprolactam/poly-6I hexamethylene isoterephalamide copolymer (polyamide 66/6/
6I), poly- hexamethylene terephthalamide/poly-6I hexamethylene isoterephalamide copolymer (polyamide 6 T/6I), poly- paraphenylene terephthalamide oneself two
Amine/poly- (paraphenylene terephthalamide's 2 methyl pentamethylenediamine) copolymer (polyamide 6 T/M5T), poly hexamethylene adipamide benzene dimethylamine (polyamide
) and their mixture or copolymer resinses etc. MXD6.Additionally, in above-mentioned formula, T represents that p-phthalic acid, I represent isophthalic two
Formic acid.
From the present invention, from the point of view of flame retardant effect, the polyamide is preferably aromatic polyamide resin.
In a preferred embodiment, the aromatic polyamide resin is selected from poly- hexamethylene terephthalamide, gathers
The mixing of one or more in terephthalate p-phenylenediamine, poly-paraphenylene terephthalamide's nonamethylene diamine, poly hexamethylene adipamide benzene dimethylamine.
Polybenzimidazoles
Term " polybenzimidazoles " refers to the compound of birdsing of the same feather flock together of the benzo five-membered heterocycle containing nitrogen-atoms in strand, by aromatics
Tetramine and aliphatic series or aromatic dicarboxylic acid polycondensation reaction and be obtained.
Polybenzimidazoles in the present invention can be the polybenzimidazoles of commercially available any trade mark.
In a preferred embodiment, the polybenzimidazoles is sulfonate polybenzimidazole, and the sulfonated polyphenyl is simultaneously
Imidazoles is obtained for aromatics tetramine and the dicarboxylic acids polycondensation reaction containing sulfonic acid group.
Sulfonate polybenzimidazole in the present invention is commercially available, it is also possible to by side known to those skilled in the art
Method synthesis is obtained.
In a preferred embodiment, the preparation method of the sulfonate polybenzimidazole is：
The polyphosphoric acids of certain mass are weighed in three-neck flask, connects gas access, drying tube, gas outlet and machinery
Agitator, is passed through noble gases, and the ratio for adding 1 mole of tetramine, the polyphosphoric acids and tetramine after 3～5min is 180g/
10mmol, after tetramine is uniformly dispersed being dissolved in polyphosphoric acids, adds 0.05～0.1 mole of sulfonation diacid and 0.9
～0.95 mole of non-sulfonated diacid, adds phosphorus pentoxide to strengthen the absorption to reaction product water afterwards, starts simultaneously at and stir
Intensification is mixed, 200 DEG C are warming up to, 20h is reacted at such a temperature；After question response system temperature is cooled to 150 DEG C, deionized water is poured into
In, cyclic washing removes polyphosphoric acids；Afterwards product is poured into and is stirred in the sodium hydrate aqueous solution that mass fraction is 7%-10%
24h is mixed, deionized water cyclic washing removes sodium hydroxide afterwards, and dry for standby at 60 DEG C, obtains sulfonation in vacuum drying oven
Polybenzimidazoles.
Wherein, what the tetramine can be enumerated has：DAB, 3,3', 4,4'- tetramino diphenyl ether, 3,
3', 4,4'- tetramino diphenyl sulphone (DPS), 3,3', 4,4'- tetramino benzophenone, 1,2,4,5- tetramino benzene, 1,2,5,6- tetraminos
Any one or more in naphthalene.
What the non-sulfonated diacid can be enumerated has：Isophthalic acid, terephthalic acids, 4,4 '-biphenyl dicarboxylic acid, Isosorbide-5-Nitrae-naphthalene two
Formic acid, diphenic acid (2,2 '-diphenyl dicarboxylic acid), phenyl indane dicarboxylic acid, 1,6- naphthalenedicarboxylic acids, NDA, 4,4 '-two
Phenyl ether dioctyl phthalate, 4, any one or more in 4 '-diphenylsulfide dioctyl phthalate, adipic acid and dodecanedioic acid.
What the sulfonation diacid can be enumerated has：2,5- dicarboxyl benzenesulfonic acids, 3,5- dicarboxyl benzenesulfonic acids, 2,5- dicarboxyls
Base-Isosorbide-5-Nitrae-benzenedisulfonic acid, 4,6- dicarboxyl -1,3- benzenedisulfonic acids, 2,2 '-disulfo -4,4 '-diphenyl dicarboxylic acid, 3,3 '-two sulphurs
Base -4, any one or more in 4 '-biphenyl dicarboxylic acid.
Ethylene-vinyl acetate copolymer
Term " EVA " refers to ethylene-vinyl acetate copolymer.
Wherein, vinyl acetate (VA) content is 1%～20%.
The EVA used in embodiment in the present invention is not particularly limited, and is commercially available acquisition.
The EVA for being used is commercially available acquisition.
SEBS
Term " SEBS " is referred to polystyrene as end segment, with the ethylene-butene copolymer that polybutadiene hydrogenation is obtained
Linear three block copolymer for intermediate elastic block.
In a preferred embodiment, the SEBS is modified by maleic acid anhydride graft SEBS.
In one embodiment, the preparation method of the modified by maleic acid anhydride graft SEBS is：
SEBS is pressed 20 with maleic anhydride monomer：, than mix homogeneously, the DCP for adding SEBS mass 10% is (adjacent for 1 weight
Dioctyl phthalate) it is grafted through double screw extruder frit reaction as initiator and MAH-g-SEBS is obtained.
MAH percent graftings are determined using following methods：
Weigh 0.5g MAH-g-SEBS to be dissolved in the hot dimethylbenzene of 50mL, add 10mL until completely dissolved in system
The NaOH- ethanol solution of 0.1mol/L, flow back 10 minutes, the anhydride group in maleic anhydride is fully reacted with alkali, after while hot
Micro deionized water (50 μ l) or pyridine/DMF are added in system, promotes anhydride to be hydrolyzed into carboxylic acid.It is simultaneously introduced 3 drop phenolphthalein
Indicator, is titrated to terminal with hydrochloric acid/isopropanol afterwards.If HCl/ aqueous isopropanols concentration is C (mol/L), M (g) sample is titrated,
Volume V1 (mL) solution is consumed, blank titration consumes V2 (mL), and percent grafting G is calculated as follows：
G=C (V2-V1) × 98/ (2 × M × 1000) × 100%
In formula, 98 is MAH molecular weight.
In a preferred embodiment, in the MAH-g-SEBS, the percent grafting of MAH is 2%～7%；Preferably,
In the MAH-g-SEBS, the percent grafting of MAH is 5%.
Maleic anhydride modified polypropylene
Term " maleic anhydride modified polypropylene " refers to maleic anhydride grafted PP.
In the present invention, the preparation method of maleic anhydride grafted PP is not particularly limited, and can obtain for commercially available
, it is also possible to by solwution method, supercritical CO2The those skilled in the art such as solwution method, fusion method, radiation method and solid phase method institute is ripe
The method synthesis that knows is obtained.
For example, maleic anhydride grafted PP is prepared with fusion method：By styrene and initiator peroxidating two
Isopropylbenzene mixes, dissolving, is made into the styrene solution of initiator.By polypropylene and maleic anhydride mixing resulting mixture, by poly- third
Alkene is input into double screw extruder with the mixture of maleic anhydride, after which melts, by the styrene solution of initiator in twin screw
The different barrel section continuous metering inputs of extruder, carry out melting graft reaction, obtain maleic anhydride grafted PP.
In the maleic anhydride grafted PP, the percent grafting of maleic anhydride is 3%～10%；More preferably
5%～8%；Much further preferably from 5%.
In the present invention, in embodiment and comparative example, the percent grafting of maleic anhydride is tested using acid-base titrations.
The main process of acid-base titrations：Weigh 0.5g maleic anhydride grafted PPs and be dissolved in the hot dimethylbenzene of 50mL
In, add the NaOH- ethanol solution of 10mL 0.1mol/L until completely dissolved in system, flow back 10 minutes, make maleic anhydride
In anhydride group fully react with alkali, after add micro deionized water (50 μ l) or pyridine/DMF while hot in system, promote
Enter anhydride and be hydrolyzed into carboxylic acid.3 drop phenolphthalein indicators are simultaneously introduced, are titrated to terminal with hydrochloric acid/isopropanol afterwards.If HCl/ isopropanols
Solution concentration is C (mol/L), titrates M (g) sample, consumes volume V1 (mL) solution, and blank titration consumes V2 (mL), percent grafting G
It is calculated as follows：
G=C (V2-V1) × 98/ (2 × M × 1000) × 100%
In formula, 98 is MAH molecular weight.
Cyclodextrin-polyethylene glycol complex
Term " cyclodextrin-polyethylene glycol complex " refers to that cyclodextrin penetrates peg molecule chain formation comprising compound
Thing.
In a preferred embodiment, the preparation method of cyclodextrin-polyethylene glycol complex is：At 30～80 DEG C
Under, cyclodextrin is soluble in water, the saturated aqueous solution of cyclodextrin is obtained.Again in the saturated aqueous solution of cyclodextrin, poly- second is added
Glycol, wherein, Polyethylene Glycol is 1 with the weight ratio of cyclodextrin：(1～3), mechanical agitation 2h, under room temperature, stand 30h, are sunk
Starch.By precipitate vacuumizing filtration, wash, 30 DEG C are dried under vacuum to constant weight, obtain cyclodextrin-polyethylene glycol complex.
In a preferred embodiment, the weight average molecular weight of the Polyethylene Glycol is：10000～1000000.
The measure of the Weight-average molecular of Polyethylene Glycol adopts GPC method.
Heretofore described cyclodextrin is not particularly limited, and can be cyclodextrin, or and cyclodextrin derives
Thing.
Heretofore described cyclodextrin and cyclodextrin derivative are such as, but not limited to, cyclodextrin such as alpha-cyclodextrin, β-ring
Dextrin and gamma-cyclodextrin；Cyclodextrin derivative for example Dimethyl cyclodextrin, glucose cyclodextrin, 2- Hydroxyproply-α-cyclodextrins, 2,
Bis--O- methyl-alphacyclodextrins of 6-, 6-O- α-malt-base-alpha-cyclodextrin, 6-O- α-D- glucityls-alpha-cyclodextrin, six (2,3,
Tri--O- acetyl group of 6-)-alpha-cyclodextrin, six (2,3,6- tri--O- methyl)-alpha-cyclodextrin, six (6-O- tosyls)-α-ring
Dextrin, six (6- amino -6- deoxidations)-alpha-cyclodextrin, six (the bromo- 6- deoxidations of 2,3- acetyl group -6-)-alpha-cyclodextrin, six (2,3,6-
Three-O- octyl groups)-alpha-cyclodextrin, list (2-O- phosphoryls)-alpha-cyclodextrin, list [2, (3)-O- (carboxymethyl)]-alpha-cyclodextrin, eight
(6-O- t-butyldimethylsilyls)-alpha-cyclodextrin, succinyl-alpha-cyclodextrin, glucuronyl- glucityl-β-ring paste
Essence, seven (2,6- bis--O- methyl)-beta-schardinger dextrin-, seven (2,6- bis--O- ethyls)-beta-schardinger dextrin-, seven (6-O- sulfo groups)-β-ring paste
Essence, seven (2,3- bis--O- acetyl group -6-O- sulfo groups)-beta-schardinger dextrin -, seven (2,3- bis--O- methyl -6-O- sulfo groups)-beta-schardinger dextrin -,
Seven (2,3,6- tri--O- acetyl group)-beta-schardinger dextrin-, seven (2,3,6- tri--O- benzoyls)-beta-schardinger dextrin-, seven (2,3,6- tri--
O- methyl)-beta-schardinger dextrin -, seven (3-O- acetyl group -2, bis--O- methyl of 6-)-beta-schardinger dextrin -, seven (2,3-O- acetyl group -6- are bromo-
6- deoxidations)-beta-schardinger dextrin-, 2- hydroxyethyl-β-cyclodextrins, HP-β-CD, 2-HP-BETA-CD, (2- hydroxyls-
3-N, N, N- dimethylamino) propyl-beta-cyclodextrin, 6-O- α-malt sugar group-beta-cyclodextrin, methyl-B-cyclodextrin, six (6- ammonia
Base -6- deoxidations)-beta-schardinger dextrin -, double (6- nitrine -6- deoxidations)-beta-schardinger dextrin -s, list (2-O- phosphoryls)-beta-schardinger dextrin -, six [6-
Deoxidation -6- (1- imidazole radicals)]-beta-schardinger dextrin -, single acetyl group-beta-cyclodextrin, triacetyl group-beta-cyclodextrin, monochloro triazine radical-β -
Cyclodextrin, 6-O- α-D- glucose group-beta-cyclodextrins, 6-O- α-D-Maltose group-beta-cyclodextrin, succinyl-beta-cyclodextrin, succinum
Acyl-(2- hydroxypropyls)-beta-schardinger dextrin-, 2- carboxymethyl-beta-cyclodextrins, 2- carboxyethyls-beta-schardinger dextrin-, fourth group-beta-cyclodextrin, sulphur third
Group-beta-cyclodextrin, 6- monodeoxy -6- monoamine group-beta-cyclodextrins, silicyl [bis--O- second of (6-O- fert-butyidimethylsilyls) 2,3-
Acyl group]-beta-schardinger dextrin-, 2- ethoxys-gamma-cyclodextrin, 2- hydropropyl-y-cyclodextrins, butyl-gamma-cyclodextrin, 3A- amino-
3A- deoxidations-(2AS, 3AS)-gamma-cyclodextrin, list -2-O- (p-toluenesulfonyl)-gamma-cyclodextrin, list -6-O- are (to toluene sulphur
Acyl group)-gamma-cyclodextrin, list -6-O- sym-trimethylbenzene. sulfonyls-gamma-cyclodextrin, eight (2,3,6- tri--O- methyl)-γ-ring paste
Essence, eight (2,6- bis--O- phenyl)-gamma-cyclodextrin, eight (6-O- t-butyldimethylsilyls)-gamma-cyclodextrins and eight (2,
3,6- tri--O- acetyl group)-gamma-cyclodextrin.These cyclodextrin can be used alone or are used in combination with which.Wherein, α-
Cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin and its derivant are preferred.Further, preferably beta-schardinger dextrin-.
The present inventor is found through experiments, and the nylon used in this application by cyclodextrin-polyethylene glycol complex is combined
Uniform network structure can be formed in material, be to contain substantial amounts of hydroxyl in cyclodextrin-polyethylene glycol complex the reason for possible
Base, these hydroxyls can form the hydrogen bond of complexity with substantial amounts of hydroxyl, carboxyl, amide groups in nylon composite materials.
Liquid paraffin
Term " liquid paraffin " is also known as white oil, mineral oil.
The present invention is not particularly limited to white oil, commercially available acquisition.Preferably, the liquid of conformance with standard Q/MSH32-2009
State paraffin.
Filler
Filler in the present invention can both be inorganic filler and organic filler.
Can include in described filler：Silicon dioxide, aluminium oxide, kaolinite, wollastonite, Muscovitum, Talcum, clay, thin,tough silk
Muscovitum, magnesium carbonate, magnesium sulfate, calcium oxide, carborundum, antimony trisulphide, Tin disulfide, copper sulfide, iron sulfide, bismuth sulfide, zinc sulfide,
Metal dust, glass powder, glass flake, montmorillonite, glass microballoon etc..
As fiberfill, can enumerate：Glass fibre, carbon fiber, metallic fiber, graphite fibre, silicon dioxide fibre,
Silica alumina fiber, alumina fibre, Zirconium oxide fibre, boron nitride fiber, silicon nitride fiber, boron fibre, metatitanic acid
Potassium whisker, aluminium borate whisker, magnesium system whisker, silicon systems whisker etc..
In a preferred embodiment, described filler is meso-porous nano silicon dioxide.
In the present invention, the meso-porous nano silicon dioxide is commercially available acquisition.
Bromide fire retardant
In the present invention, the bromide fire retardant may refer to brominated Polystyrene, brominated polystyrene, brominated polyphenylene support ether
In any one.
The brominated Polystyrene, can enumerated have：Polydibromstyrol, poly- phenylstilbene bromide, poly- pentabromo- styrene,
Poly- tribromo α-methyl styrene etc..
Above-mentioned brominated Polystyrene can be by carrying out bromination acquisition, the opposing party by polystyrene or poly alpha methylstyrene
Face, brominated polystyrene can be obtained by brominated styrene or bromination α-methyl styrene are carried out polymerization.
In the present invention, as bromide fire retardant, it is preferred to use in advance by monomer bromination after, repolymerization contains poly- bromination benzene second
The brominated flame retardant material of alkene.
In the present invention, as bromide fire retardant, in addition to above-mentioned brominated polystyrene, it is also possible to following bromine compoundss.
That can enumerated has：HBB, pentabromoethyl benzene, hexabromobiphenyl, decabrominated dipheny, hexabromo diphenylate, eight bromines
Diphenylate, decabrominated dipheny oxide, tetrabromobisphenol A and tetrabromobisphenol A-bis- (hydroxyethyl ethers), tetrabromobisphenol A-bis- (2,3-
Dibromopropyl ether), tetrabromobisphenol A-bis- (bromoethyl ether), tetrabromobisphenol A derivant, the tetrabromo such as tetrabromobisphenol A-bis- (allyl ether)
The tetrabromo-bisphenol s derivant such as bisphenol S and tetrabromo-bisphenol s-bis- (hydroxyethyl ethers), tetrabromo-bisphenol s-bis- (2,3- dibromopropyl ether),
Tetrabromo anhydrous phthalic acid derivant, the ethylene such as the double tetrabromo phthalandione acid imides of tetrabromo anhydrous phthalic acid, tetrabromo phthalandione acid imide, ethylene are double
(5,6- dibromo norbornane -2,3- dicarboxyl imines), three-(2,3- dibromopropyl -1)-isocyanates, hexabromo cyclopentadiene hydrocarbon
Diels-Alder adduct, triazolyl benzylamine, tribromo phenyl acrylate, the double tribromo phenyl ether of ethylene, second
The double phenyl-pentabromides of alkene, the double penta-bromophenyl ethers of ethylene, ten tetrabromo diphenol oxygen benzene, brominated polyphenylene support oxide, brominated epoxy resin, bromination
Merlon, poly- pentabromobenzyl acrylate, eight bromonaphthalenes, pentabromo- hexamethylene, HBCD, double (tribromo phenyl) fumaric acid
Amide, N- methyl hexabromo diphenylamines etc..
Synergistic flame retardant
Term " synergistic flame retardant " can be commercially available any synergistic flame retardant.
In a preferred embodiment, the synergistic flame retardant is nano aluminium oxide.
The commercially available acquisition of nano aluminium oxide in the present invention, it is also possible to by known to those skilled in the art any one
The method synthesis of kind is obtained.
In the present invention, nano aluminium oxide is commercially available acquisition, is purchased from Dongguan Dong Chao new materials Science and Technology Ltd..
In a preferred embodiment, the particle diameter of the nano aluminium oxide is 10～100 nanometers.
In a preferred embodiment, the environment-friendly type bromine system fire-retardant nylon composite, the synergistic flame retardant
For nanometer alumina modified acrylic resin.
In a preferred embodiment, the weight ratio between the nano aluminium oxide and acrylic resin is 1：(1～
10).
In a preferred embodiment, the preparation method of described " nanometer alumina modified acrylic resin " is：
Acrylic resin is dissolved in ethanol, nano aluminium oxide is added, acrylic resin and nano aluminium oxide are mixed
After closing uniformly, first supersound process 30min under supersonic frequency 22kHz, power 150W, then in microwave frequency 3000MHz, power
Microwave treatment 20min under 400W, obtains nanometer alumina modified acrylic resin.
The inventors discovered that, introducing cyclodextrin-polyethylene glycol complex in nylon composite materials on the one hand can be with Buddhist nun
Imperial composite has the preferable compatibility, and on the other hand, it can form inierpeneirating network structure in system, work as composite
During burning, barrier layer can be formed after cyclodextrin-polyethylene glycol complex and synergistic flame retardant compounding, so as to ensure that fire-retardant effect
Really.
The inventors discovered that adding the nanometer alumina modified acrylic resin of synergistic flame retardant, nanometer alumina modified propylene
There can be the preferable compatibility with nylon composite materials containing acrylic resin in acid resin；Meanwhile, nanometer alumina modified
Acrylic resin can be interacting with cyclodextrin-polyethylene glycol complex so that synergistic flame retardant can be very good to disperse
In system.When burnt, fire retardant is cooperated with synergistic flame retardant, can be formed with fine and close aluminium oxide barrier layer,
And then play fire retardation.Using the filler meso-porous nano silicon dioxide of ad hoc structure, can be formed in nylon system very thin
Porous layer, porous layer can play fire retardation, further improve flame retardant effect.
Additionally, in environment-friendly type bromine system fire-retardant nylon composite in the present invention, can also include polyethylene, polypropylene,
Polystyrene, acrylonitrile/styrene resin, metha crylic resin, vinyl chloride, polyamide, polyacetals, super high molecular weight are gathered
Ethylene, polybutylene terephthalate (PBT), polymethylpentene, Merlon, polyphenylene sulfide, polyethers ether ether ketone, liquid crystal polymer,
Politef, Polyetherimide, polyarylate, polysulfones, polyether sulfone, polyamidoimide, phenol, carbamide, melamine, unsaturation are poly-
The resins such as ester, alkyd resin, epoxy resin, diallyl phthalate.
Other
Various additives can be contained within the scope without prejudice to the object of the present invention.As the specific example of additive, also
Antioxidant, UV absorbent can be included, dispersant, antibacterial, pigment, enter delustering agent, heat stabilizer, weather resisting agent, ultraviolet
The additive of light absorbers, nucleator, plasticizer, fire retardant, antistatic agent, anti-coloring agent, anti-condensation gelatinizing agent etc..
As antioxidant, it is not particularly limited, that can enumerated has：Copper compound, organic or inorganic halogen-based compounds,
Hinered phenols, hindered amines, hydrazine, sulfur class compound, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite etc. Phosphorus
The antioxidant of compound etc..
As UV absorbent, it is not particularly limited, that can enumerated has：2- (2- hydroxy-5-methyl base phenyl) benzo
Triazole, 2- (2- hydroxyl -5- butyl phenyls) benzotriazole, 2- (2- hydroxyl -5- octyl phenyls) benzotriazole, 2- (the 3- tert-butyl groups -
2- hydroxy-5-methyl base phenyl) benzotriazole such as -5- chlorobenzotriazoles, 2- (bis- tertiary pentyl -2- hydroxy phenyls of 3,5-) benzotriazole
It is UV absorbent；The benzophenone such as ESCALOL 567,2- hydroxyl -4- n-octyl epoxide benzophenone
It is UV absorbent；2- [double (2,4- the 3,5-dimethylphenyls) -1,3,5- triazine -2- bases of 4,6-] -5- (octyl group epoxide) phenol, 2-
The triazine system UV absorbent such as (4,6- diphenyl -1,3,5- triazine -2- bases) -5- (hexyl epoxide) phenol；Salicylic acid is to uncle
The salicylate such as butyl phenyl ester, phenyl salicylate system UV absorbent etc..
As dispersant, it is not particularly limited, that can enumerated has：Bisamide class dispersant, paraffin class dispersant, organic
The various dispersants such as metallic salt dispersant.
As antibacterial, it is not particularly limited, that can enumerated has：Silver ion class antibacterial, zinc oxide, copper oxide, phosphorus
Acid dihydride ammonium, lithium carbonate, anilid class, imidazoles, thiazoless, isothiazolone derivative, quaternary ammonium salt, double croak classes, phenols
Formic acid, sorbic acid, organic iodine, nitrile, sulfur cyanogen, copper agent, three halogenation allyl compounds, organic nitrogen sulfur compound, chitin, mustard
End, Oleum Ricini, Wasabia japonic (Euterma Wasabi).
As pigment, it is not particularly limited, that can enumerated has：C.I. pigment yellow 1, C.I. pigment yellows 3, C.I. pigment yellows
12nd, the yellow such as C.I. pigment yellow 13s, C.I. pigment yellow 13s 8, C.I. pigment yellows 150, C.I. pigment yellows 180, C.I. pigment yellows 185
Series pigments；C.I. the redness such as paratonere 1, C.I. paratoneres 2, C.I. pigment red 3s, C.I. paratoneres 254, C.I. paratoneres 177
Series pigments；C.I. pigment blue 15, C.I. pigment blue 15s:3rd, C.I. pigment blue 15s:4th, C.I. pigment blue 15s:6 grades blueness series pigments；
C.I. pigment Violet 23:19th, C.I. pigment green 36s etc..
As inorganic pigment, it is not particularly limited, can enumerates：White carbon black, lampblack, acetylene black, bone black, thermal black, channel process
The black inorganic pigment such as white carbon black, furnace black, titanium be black；Titanium Dioxide, barium sulfate, brium carbonate, calcium sulfate, Calcium Carbonate, white mica, stone
Stamen, aluminium oxide are white, strontium molybdate, white lead (zinc carbonate), zinc sulfide, zinc sulfate, silicon dioxide antimony trioxide, titanium phosphate, ceruse, hydrogen
Lead oxide, alkali formula zinc molybdate, alkali formula calcium molybdate, Zinc oxide/titanium dioxide composite oxides, aluminium oxide/magnesium oxide combined oxidation
White inorganic pigments such as thing, calcium oxide/zirconia composite oxide etc..In black inorganic pigment, from black colorant, spreadability
Etc. aspect set out, preferably graphite, white carbon black.As the commercially available product of graphite, can enumerate：BF-1AT、BF-3KT、G-6S、G-3、
CMW-350, SMF, EMF, WF-15C (in above, getting over the manufacture of Co., Ltd. of graphite industry institute) etc..As the shape of graphite, do not limit
Due to squamous, earthy, spherical etc., or the expanded graphite of expansion by heating.In addition, graphite can be natural stone
Ink can also be Delanium.
As the commercially available product of white carbon black, can enumerate：MA series (Mitsubishi chemical Co., Ltd's manufacture)；Printex series,
SpecialBlack series, ColorBlack series (above EvonikJapanCo., Ltd. system)；Monarch series, REGAL
Series, BLACKPEARLS480, PEARLS130, VULCANXC72R, ELFTEX-8 (above CabotJapanCorporation
Manufacture)；RAVEN series (manufacture of CarbonColumbia companies) etc..
In white inorganic pigment, from aspects such as color white, spreadabilities, be preferably selected from Titanium Dioxide, calcium sulfate,
At least one in Calcium Carbonate, more preferably Titanium Dioxide.Titanium Dioxide can be any one of rutile-type, Detitanium-ore-type etc..
As the commercially available product of Titanium Dioxide, can enumerate：TA series, TR series (above Fuji Titanium Industry Co., Ltd.
System)；R series, PF series, CR series, PC series (above Ishihara Sangyo Kaisha, Ltd.'s manufacture) etc..
The second aspect of the invention provides the preparation method of environment-friendly type bromine system fire-retardant nylon composite, at least includes
Following steps：
S1：Each component raw material is weighed according to parts by weight, by polyamide, polybenzimidazoles, ethylene-vinyl acetate
After copolymer, SEBS, maleic anhydride modified polypropylene, cyclodextrin-polyethylene glycol complex, bromide fire retardant mix, add high
In fast blender, at 30～100 DEG C, 60～200min is stirred；
S2：To in step S1, synergistic flame retardant, filler is added, continue 40～100min of stirring, obtain mixed material；
S3：Mixed material in step S2 is added double screw extruder, screw speed is controlled for 50～250r/min, temperature
Spend for 100～300 DEG C, melting extrusion pelletize obtains environment-friendly type bromine system fire-retardant nylon composite.
The present invention is specifically described below by embodiment.Be necessary it is pointed out here that, following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some nonessential modifications and adaptations that content according to the invention described above is made, still fall within protection scope of the present invention.
In addition, if do not have other explanation, raw materials used be all commercially available, be purchased from traditional Chinese medicines chemical reagent.
Embodiment 1：
Embodiments of the invention 1 provide a kind of environment-friendly type bromine system fire-retardant nylon composite, in parts by weight, including with
Lower raw material, 40 parts of polyamide, 10 parts of polybenzimidazoles, 3 parts of ethylene-vinyl acetate copolymer, 15 parts of SEBS, Malaysia
12 parts of anhydride-modified polypropylene, 3 parts of cyclodextrin-polyethylene glycol complex, 5 parts of liquid paraffin, 3 parts of filler, bromide fire retardant 1
Part, 1 part of synergistic flame retardant.
The polyamide is poly- hexamethylene terephthalamide, is purchased from Mitsui chemistry；
The polybenzimidazoles is purchased from German Gai Er；
The ethylene-vinyl acetate copolymer is purchased from Dupont；
The SEBS is purchased from Taiwan rubber；
The maleic anhydride modified polypropylene is purchased from modest three Chemical Industry Science Co., Ltd in Guangzhou, and the percent grafting of maleic anhydride is
5%；
The liquid paraffin is purchased from Guangzhou Chen Xin Chemical Co., Ltd.s；
Described filler is nano silicon, is purchased from Nanjing Tian Hang new materials company limited；
The bromide fire retardant is polydibromstyrol, is purchased from U.S.'s Chemtura；
The preparation method of the cyclodextrin-polyethylene glycol complex is：
At 50 DEG C, will be soluble in water for the beta-schardinger dextrin-of 10g, the saturated aqueous solution of beta-schardinger dextrin-is obtained.Again to β-ring paste
In the saturated aqueous solution of essence, the Polyethylene Glycol (weight average molecular weight of Polyethylene Glycol is 10000) of 10g, mechanical agitation 2h, room are added
Under temperature, 30h is stood, thing is precipitated.By precipitate vacuumizing filtration, wash, 30 DEG C are dried under vacuum to constant weight, obtain ring paste
Essence-polyethylene glycol complex.
The synergistic flame retardant is nano aluminium oxide, and nano aluminium oxide, the particle diameter of nano aluminium oxide are purchased from east for 10 nanometers
The super new material Science and Technology Ltd.s of Guan Dong.
The preparation method of environment-friendly type bromine system fire-retardant nylon composite, comprises the following steps：
S1：Each component raw material is weighed according to parts by weight, by polyamide, polybenzimidazoles, ethylene-vinyl acetate
Copolymer, SEBS, maleic anhydride modified polypropylene, cyclodextrin-polyethylene glycol complex, liquid paraffin, bromide fire retardant mixing
Afterwards, add in homogenizer, at 100 DEG C, stir 60min；
S2：To in step S1, synergistic flame retardant, filler is added, continue stirring 100min, obtain mixed material；
S3：Mixed material in step S2 being added double screw extruder, screw speed being controlled for 250r/min, temperature is
300 DEG C, melting extrusion pelletize obtains environment-friendly type bromine system fire-retardant nylon composite.
Embodiment 2：
Embodiments of the invention 2 provide a kind of environment-friendly type bromine system fire-retardant nylon composite, in parts by weight, including with
Lower raw material, 100 parts of polyamide, 1 part of polybenzimidazoles, 10 parts of ethylene-vinyl acetate copolymer, 5 parts of SEBS, Malaysia
5 parts of anhydride-modified polypropylene, 10 parts of cyclodextrin-polyethylene glycol complex, 20 parts of liquid paraffin, 20 parts of filler, bromide fire retardant 3
Part, 5 parts of synergistic flame retardant.
In embodiment 2, polyamide, polybenzimidazoles, ethylene-vinyl acetate copolymer, SEBS, maleic anhydride change
Property polypropylene, cyclodextrin-polyethylene glycol complex, liquid paraffin, filler, bromide fire retardant are with embodiment 1.
Difference is, the synergistic flame retardant is nano aluminium oxide, nano aluminium oxide, and the particle diameter of nano aluminium oxide is 50
Nanometer.
The preparation method of environment-friendly type bromine system fire-retardant nylon composite is with embodiment 1.
Embodiment 3：
Embodiments of the invention 3 provide a kind of environment-friendly type bromine system fire-retardant nylon composite, in parts by weight, including with
Lower raw material, 60 parts of polyamide, 10 parts of polybenzimidazoles, 6 parts of ethylene-vinyl acetate copolymer, 10 parts of SEBS, Malaysia
8 parts of anhydride-modified polypropylene, 5 parts of cyclodextrin-polyethylene glycol complex, 13 parts of liquid paraffin, 10 parts of filler, bromide fire retardant 1
Part, 3 parts of synergistic flame retardant.
In embodiment 3, polyamide, polybenzimidazoles, ethylene-vinyl acetate copolymer, SEBS, maleic anhydride change
Property polypropylene, cyclodextrin-polyethylene glycol complex, liquid paraffin, filler, bromide fire retardant are with embodiment 1.
Difference is, the synergistic flame retardant is nano aluminium oxide, nano aluminium oxide, and the particle diameter of nano aluminium oxide is 90
Nanometer.
The preparation method of environment-friendly type bromine system fire-retardant nylon composite is with embodiment 1.
Embodiment 4：
Embodiments of the invention 4 provide a kind of environment-friendly type bromine system fire-retardant nylon composite, in parts by weight, including with
Lower raw material, 80 parts of polyamide, 5 parts of polybenzimidazoles, 9 parts of ethylene-vinyl acetate copolymer, 12 parts of SEBS, maleic acid
10 parts of anhydride modification polypropylene, 8 parts of cyclodextrin-polyethylene glycol complex, 18 parts of liquid paraffin, 15 parts of filler, bromide fire retardant 3
Part, 5 parts of synergistic flame retardant.
In embodiment 4, polyamide, polybenzimidazoles, ethylene-vinyl acetate copolymer, SEBS, maleic anhydride change
Property polypropylene, cyclodextrin-polyethylene glycol complex, liquid paraffin, filler, bromide fire retardant are with embodiment 1.
The preparation method of environment-friendly type bromine system fire-retardant nylon composite is with embodiment 1.
Difference is, the synergistic flame retardant is nano aluminium oxide, nano aluminium oxide, and the particle diameter of nano aluminium oxide is
100.
Embodiment 5：
Embodiments of the invention 5 provide a kind of environment-friendly type bromine system fire-retardant nylon composite, in parts by weight, including with
Lower raw material, 80 parts of polyamide, 8 parts of polybenzimidazoles, 7 parts of ethylene-vinyl acetate copolymer, 11 parts of SEBS, maleic acid
9 parts of anhydride modification polypropylene, 8 parts of cyclodextrin-polyethylene glycol complex, 16 parts of liquid paraffin, 12 parts of filler, 2 parts of bromide fire retardant,
4 parts of synergistic flame retardant.
In embodiment 5, polyamide, polybenzimidazoles, ethylene-vinyl acetate copolymer, SEBS, maleic anhydride change
Property polypropylene, cyclodextrin-polyethylene glycol complex, liquid paraffin, filler, bromide fire retardant, the same embodiment of synergistic flame retardant
1.
Difference is, the synergistic flame retardant is nano aluminium oxide, nano aluminium oxide, and the particle diameter of nano aluminium oxide is 90
Nanometer.
The preparation method of environment-friendly type bromine system fire-retardant nylon composite is with embodiment 1.
Embodiment 6：
Embodiments of the invention 6 provide a kind of environment-friendly type bromine system fire-retardant nylon composite, in parts by weight, including with
Lower raw material, 80 parts of polyamide, 8 parts of polybenzimidazoles, 7 parts of ethylene-vinyl acetate copolymer, 11 parts of SEBS, maleic acid
9 parts of anhydride modification polypropylene, 8 parts of cyclodextrin-polyethylene glycol complex, 16 parts of liquid paraffin, 12 parts of filler, 2 parts of bromide fire retardant,
4 parts of synergistic flame retardant.
In embodiment 6, polyamide, polybenzimidazoles, ethylene-vinyl acetate copolymer, SEBS, maleic anhydride change
Property polypropylene, cyclodextrin-polyethylene glycol complex, liquid paraffin, filler, bromide fire retardant are with embodiment 5.
The synergistic flame retardant be nanometer alumina modified acrylic resin, the system of nanometer alumina modified acrylic resin
Preparation Method is：
Acrylic resin is dissolved in ethanol, nano aluminium oxide is added, acrylic resin and nano aluminium oxide are mixed
After closing uniformly, (wherein, the weight ratio between nano aluminium oxide and acrylic resin is 1：1) frequency be 22kHz, power 150W
Lower supersound process 30min, then microwave treatment 20min under microwave frequency 3000MHz, power 400W, obtains nano aluminium oxide
Acrylic resin modified.
The preparation method of environment-friendly type bromine system fire-retardant nylon composite is with embodiment 1.
Embodiment 7：
Embodiments of the invention 7 provide a kind of environment-friendly type bromine system fire-retardant nylon composite, in parts by weight, including with
Lower raw material, 80 parts of polyamide, 8 parts of polybenzimidazoles, 7 parts of ethylene-vinyl acetate copolymer, 11 parts of SEBS, maleic acid
9 parts of anhydride modification polypropylene, 8 parts of cyclodextrin-polyethylene glycol complex, 16 parts of liquid paraffin, 12 parts of filler, 2 parts of bromide fire retardant,
4 parts of synergistic flame retardant.
In embodiment 7, polyamide, polybenzimidazoles, ethylene-vinyl acetate copolymer, SEBS, maleic anhydride change
Property polypropylene, cyclodextrin-polyethylene glycol complex, liquid paraffin, filler, bromide fire retardant are with embodiment 6.
Difference is, in nanometer alumina modified acrylic resin, the weight ratio of nano aluminium oxide and acrylic resin
For：1：10.
The preparation method of environment-friendly type bromine system fire-retardant nylon composite is with embodiment 1.
Embodiment 8：
Embodiments of the invention 8 provide a kind of environment-friendly type bromine system fire-retardant nylon composite, in parts by weight, including with
Lower raw material, 80 parts of polyamide, 8 parts of sulfonate polybenzimidazole, 7 parts of ethylene-vinyl acetate copolymer, 11 parts of SEBS, horse
Come 9 parts of anhydride-modified polypropylene, 8 parts of cyclodextrin-polyethylene glycol complex, 16 parts of liquid paraffin, 12 parts of filler, bromide fire retardant
2 parts, 4 parts of synergistic flame retardant.
In embodiment 8, polyamide, polybenzimidazoles, ethylene-vinyl acetate copolymer, SEBS, maleic anhydride change
Property polypropylene, cyclodextrin-polyethylene glycol complex, liquid paraffin, filler, bromide fire retardant are with embodiment 6.
The preparation method of sulfonate polybenzimidazole is：
The polyphosphoric acids of certain mass are weighed in three-neck flask, connects gas access, drying tube, gas outlet and machinery
Agitator, is passed through noble gases, adds the ratio of 1 mole of 3,3'- diaminobenzidines, the polyphosphoric acids and tetramine after 5min
Example is 180g/10mmol, after 3,3'- diaminobenzidines are uniformly dispersed being dissolved in polyphosphoric acids, adds 0.05 mole
2,5- dicarboxyls benzenesulfonic acid and 0.95 mole of 1,6- naphthalenedicarboxylic acids, add phosphorus pentoxide to produce reaction to strengthen afterwards
The absorption of thing water, starts simultaneously at stirring and heats up, be warming up to 200 DEG C, reacts 20h at such a temperature；Question response system temperature is cooled down
To after 150 DEG C, pour in deionized water, cyclic washing removes polyphosphoric acids；Product is poured into hydrogen that mass fraction is 7% afterwards
24h is stirred in aqueous solution of sodium oxide, and deionized water cyclic washing removes sodium hydroxide afterwards, is dried in vacuum drying oven at 60 DEG C
Dry standby, obtain sulfonate polybenzimidazole.
The preparation method of environment-friendly type bromine system fire-retardant nylon composite is with embodiment 1.
Embodiment 9：
Embodiments of the invention 9 provide a kind of environment-friendly type bromine system fire-retardant nylon composite, in parts by weight, including with
Lower raw material, 80 parts of polyamide, 8 parts of sulfonate polybenzimidazole, 7 parts of ethylene-vinyl acetate copolymer, 11 parts of SEBS, horse
Come 9 parts of anhydride-modified polypropylene, 8 parts of cyclodextrin-polyethylene glycol complex, 16 parts of liquid paraffin, 12 parts of filler, bromide fire retardant
2 parts, 4 parts of synergistic flame retardant.
Polyamide in embodiment 9, polybenzimidazoles, ethylene-vinyl acetate copolymer, maleic anhydride modified poly- third
Alkene, cyclodextrin-polyethylene glycol complex, liquid paraffin, filler, bromide fire retardant are with embodiment 8.
The SEBS is modified by maleic acid anhydride graft SEBS, and its preparation method is：
SEBS is pressed 20 with maleic anhydride monomer：, than mix homogeneously, the DCP for adding SEBS mass 10% is (adjacent for 1 weight
Dioctyl phthalate) it is grafted through double screw extruder frit reaction as initiator and MAH-g-SEBS is obtained.
The preparation method of environment-friendly type bromine system fire-retardant nylon composite is with embodiment 1.
Embodiment 10：
Embodiments of the invention 10 provide a kind of environment-friendly type bromine system fire-retardant nylon composite, in parts by weight, including
Following raw material, 80 parts of polyamide, 8 parts of sulfonate polybenzimidazole, 7 parts of ethylene-vinyl acetate copolymer, maleic anhydride connect
Branch 11 parts of modified SEBS, 9 parts of maleic anhydride modified polypropylene, 8 parts of cyclodextrin-polyethylene glycol complex, 16 parts of liquid paraffin,
12 parts of filler, 2 parts of bromide fire retardant, 4 parts of synergistic flame retardant.
In embodiment 10, polyamide, polybenzimidazoles, ethylene-vinyl acetate copolymer, maleic anhydride grafting change
Property SEBS, maleic anhydride modified polypropylene, cyclodextrin-polyethylene glycol complex, liquid paraffin, filler, bromide fire retardant with
Embodiment 9.
Described filler is meso-porous nano silicon dioxide, and meso-porous nano silicon dioxide is SBA-15, if being purchased from Liuzhou thinks nanometer
Material Science and Technology Ltd..
Comparative example 1：
With embodiment 5, difference is the comparative example 1 of the present invention, does not include cyclodextrin-polyethylene glycol complex.
Comparative example 2：
With embodiment 5, difference is the comparative example 2 of the present invention, and the synergistic flame retardant is antimony oxide.
Performance evaluation
Carry out testing fire resistance and oxygen index (OI) test by the sample that embodiment 1～10 and comparative example 1～2 are obtained.
Method of testing is as follows：
1st, anti-flammability：It is measured according to UL94 standards；
2nd, burning-point：Tested using the automatic open-cup flash point in Cleveland and burning-point tester CLA 4；
3rd, creepage trace index：Tested according to GB/T 4207-84.
Concrete data are shown in Table 1.
1 the performance test results of table
From table 1 it follows that environment-friendly type bromine system fire-retardant nylon composite has extraordinary fire resistance and very
High burning-point, for example, the product that embodiment 10 is obtained, its burning-point are 830 DEG C, i.e., when temperature reaches more than 830 DEG C, just flammable
Burn, be compared with the of 500 DEG C with the burning-point of nylon, achieve unexpected technique effect.Meanwhile, embodiment 1～10 in the present invention
In the product burning that obtains be any abnormal flavour of appearance, further widened the application of nylon composite materials.
Aforesaid example is merely illustrative, for explaining some features of the method for the invention.Appended right will
The scope as wide as possible for being intended to require to be contemplated that is sought, and embodiments as presented herein is only according to all possible enforcement
The explanation of the embodiment of the selection of the combination of example.Therefore, the purpose of applicant is that appended claim is not illustrated this
The selectional restriction of the example of bright feature.Some numerical rangies used also include sub- model within the claims
Enclose, the change in these scopes also should be construed to be covered by appended claim in the conceived case.
Claims (10)
1. a kind of environment-friendly type bromine system fire-retardant nylon composite, in parts by weight, it is characterised in that including following raw material, polyamides
40～100 parts of polyimide resin, 1～10 part of polybenzimidazoles, 3～10 parts of ethylene-vinyl acetate copolymer, 5～15 parts of SEBS,
5～12 parts of maleic anhydride modified polypropylene, 3～10 parts of cyclodextrin-polyethylene glycol complex, 5～20 parts of liquid paraffin, filler 3
～20 parts, 1～3 part of bromide fire retardant, 1～5 part of synergistic flame retardant.
2. environment-friendly type bromine system fire-retardant nylon composite as claimed in claim 1, in parts by weight, it is characterised in that include
Following raw material, 60～80 parts of polyamide, 5～10 parts of polybenzimidazoles, 6～9 parts of ethylene-vinyl acetate copolymer,
10～12 parts of SEBS, 8～10 parts of maleic anhydride modified polypropylene, 5～8 parts of cyclodextrin-polyethylene glycol complex, liquid paraffin
13～18 parts, 10～15 parts of filler, 1～3 part of bromide fire retardant, 3～5 parts of synergistic flame retardant.
3. environment-friendly type bromine system fire-retardant nylon composite as claimed in claim 1, in parts by weight, it is characterised in that include
Following raw material, 80 parts of polyamide, 8 parts of polybenzimidazoles, 7 parts of ethylene-vinyl acetate copolymer, 11 parts of SEBS, Malaysia
9 parts of anhydride-modified polypropylene, 8 parts of cyclodextrin-polyethylene glycol complex, 16 parts of liquid paraffin, 12 parts of filler, bromide fire retardant 2
Part, 4 parts of synergistic flame retardant.
4. the environment-friendly type bromine system fire-retardant nylon composite as described in any one of claims 1 to 3, it is characterised in that the association
Effect fire retardant is nano aluminium oxide.
5. environment-friendly type bromine system fire-retardant nylon composite as claimed in claim 4, it is characterised in that the nano aluminium oxide
Particle diameter is 10～100 nanometers.
6. the environment-friendly type bromine system fire-retardant nylon composite as described in any one of claims 1 to 3, it is characterised in that the association
Effect fire retardant is nanometer alumina modified acrylic resin.
7. environment-friendly type bromine system fire-retardant nylon composite as claimed in claim 6, it is characterised in that the nano aluminium oxide with
Weight ratio between acrylic resin is 1：(1～10).
8. environment-friendly type bromine system fire-retardant nylon composite as claimed in claim 1, it is characterised in that the cyclodextrin-poly- second
In glycol complex, Polyethylene Glycol is 1 with the weight ratio of cyclodextrin：(1～3).
9. environment-friendly type bromine system fire-retardant nylon composite as claimed in claim 1, it is characterised in that described filler is received for mesoporous
Rice silicon dioxide.
10. the preparation method of the environment-friendly type bromine system fire-retardant nylon composite as described in claim 1～9, it is characterised in that extremely
Comprise the following steps less：
S1：Each component raw material is weighed according to parts by weight, by polyamide, polybenzimidazoles, ethylene-vinyl acetate copolymerization
After thing, SEBS, maleic anhydride modified polypropylene, cyclodextrin-polyethylene glycol complex, bromide fire retardant mix, high-speed stirring is added
Mix in machine, at 30～100 DEG C, stir 60～200min；
S2：To in step S1, synergistic flame retardant, filler is added, continue 40～100min of stirring, obtain mixed material；
S3：Mixed material in step S2 being added double screw extruder, screw speed being controlled for 50～250r/min, temperature is
100～300 DEG C, melting extrusion pelletize obtains environment-friendly type bromine system fire-retardant nylon composite.
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| US10899884B2 (en) | 2018-11-29 | 2021-01-26 | International Business Machines Corporation | Flame-retardant polyetheretherketone-based compounds |
| CN115746549A (en) * | 2022-11-30 | 2023-03-07 | 江苏金发科技新材料有限公司 | Polyamide composition and preparation method and application thereof |
| CN115894944A (en) * | 2023-01-06 | 2023-04-04 | 四川科宏达集团有限责任公司 | Modified functional surfactant derivative, preparation method and application |
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