CN107523024B - Carbon nanotube base Chitosan Phosphate composite flame-retardant agent and its preparation method and application - Google Patents

Carbon nanotube base Chitosan Phosphate composite flame-retardant agent and its preparation method and application Download PDF

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CN107523024B
CN107523024B CN201710816983.XA CN201710816983A CN107523024B CN 107523024 B CN107523024 B CN 107523024B CN 201710816983 A CN201710816983 A CN 201710816983A CN 107523024 B CN107523024 B CN 107523024B
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牛梅
薛宝霞
杨永珍
彭云
宋英豪
白洁
杨雅茹
刘旭光
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Taiyuan University of Technology
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Abstract

The invention discloses a kind of carbon nanotube base Chitosan Phosphate composite flame-retardant agents and its preparation method and application, the composite flame-retardant agent is using CNTs as charcoal source, CS is gas source, phosphoric acid is acid source, CS is supported on CNTs surface modification and obtains CS-CNTs, then the one-component expansion type flame retardant that phosphorylation obtains is carried out to CS-CNTs with phosphoric acid.Composite flame-retardant agent mechanical strength of the present invention is good, the fire-retardant double effect with suppression cigarette can be played simultaneously, reduce the fire risk of polymer combustion, it is prepared into Flame-retardant PET composite material with melt-blending process blending in PET matrix, it can weaken deterioration of the fire retardant to PET mechanical property simultaneously improving Flame Retardancy.

Description

Carbon nanotube base Chitosan Phosphate composite flame-retardant agent and its preparation method and application
Technical field
The present invention relates to a kind of expansion type flame retardants, expand more particularly to a kind of integration based on carbon nanotube charcoal source Type fire retardant and preparation method thereof.
Background technique
Polyethylene terephthalate (PET) is a kind of thermal plasticity high polymer of function admirable, can be widely applied to fibre Dimension, packaging material, film, beverage bottle and engineering plastics etc..But PET is heated to be melted, decompose, burning, and limit oxygen index is only It is 21% or so, and has serious molten drop phenomenon, flame-retardant standard is far not achieved, its application is made to receive very big limitation.
With the continuous improvement that can be required material safety, the requirement in terms of and thermal stability fire-retardant to PET is also got over Come higher, exploitation has good stability, flame retardant effect is excellent, the fire retardant of high comprehensive performance is to improve the flame retardant property of PET, Through the research hotspot for becoming current PET technical field.
Expansion type flame retardant (IFR) mainly includes three kinds of acid source, charcoal source and gas source ingredients, by forming porous foamed char Fire retardation is played in condensed phase.The layer of charcoal of formation can obstruct extraneous heat and oxygen and enter material internal and resistance The flammable escaping gas generated inside barrier material enters combustion zone, reduces smoke amount when material combustion, layer of charcoal was formed The non-flammable gases such as the vapor generated in journey can be with the concentration of dilute combustion area imflammable gas, the nitrogen oxidation of gas source release The free radical generated in combustion process can be quenched to terminate chain reaction by closing object, while free radical is encountering the particle to form layer of charcoal When can also be quenched so that chain reaction terminate, play fire retardation.Thus, IFR has efficient, Halogen, low toxicity and low cigarette etc. special Property, become a kind of new flame retardant quickly grown in recent years.
IFR can be divided into multiple groups part and one-component two major classes.Multicomponent IFR is by acid source, charcoal source, gas source three classes compound The fire retardant being directly mixed to get by a certain percentage common are ammonium polyphosphate (APP), pentaerythrite (PER) and melamine (MA) system.And one pack system IFR is attributed to acid source, charcoal source and gas source in one molecule, i.e., " three-source integrated " class is fire-retardant Agent.
Compared with multicomponent IFR, the advantage of one-component IFR is embodied in the following aspects: 1) good thermal stability and Resistance to water soak；2) matrix compatibility and resistance to surface migration performance improve；3) higher flame retarding efficiency.
However, either multicomponent or one-component IFR, in use in the prevalence of two big defects.First is that IFR The mechanical strength that layer of charcoal is formed after burning is poor, easily collapses, and then influences flame retarding efficiency；Second is that compatibility between polymer compared with Difference has a huge impact the physical mechanical property of polymer.
From the angle of flame retarding efficiency, the Char Residues Structure that dilation is big and mechanical strength is high is conducive to fire-retardant.Therefore, it is The IFR for developing excellent combination property, selects suitable charcoal source to be even more important.Charcoal source in existing Intumscent Flame Retardant System is mostly low Molecular compound easily migrates, and has a negative impact to the mechanical performance of polymer, and exploitation enhances the novel of layer of charcoal intensity Charcoal source be very it is necessary to.
Research confirms that carbon nanotube (CNTs) is used as fire retardant, can carry out to polymer flame-retardant modified.Yin X.L. etc. (Flame-retardant polyamide 6/carbon nanotube nanofibers: processing and characterization. Journal of engineered fibers and fabrics, 2015, 10(3):1-11) CNTs is applied in daiamid-6 fiber, it was demonstrated that CNTs can improve the flame retardant property of daiamid-6 fiber and fabric.Ran S.Y. equal (Carbon nanotube bridged cerium phenylphosphonate hybrids, fabrication and their effects on the thermal stability and flame retardancy of the HDPE/ BFR composite. Journal of materials chemistry A, 2015,2 (9): 2999-3007) it has studied The influence of phenyl-phosphonic acid cerium and CNTs to high density polyethylene (HDPE) flame retardant property, discovery amination CNTs, which can be used as bridging agent, improves benzene The dispersibility of base phosphonic acids cerium, the two can cooperative flame retardant polyethylene.(the Effects of carbon nanotubes such as Du B.X. on the thermal stability and flame retardancy of intumescent flame-retarded polypropylene . Polymer degradation and stability, 2011, 96 (10):1725-1731.) It was found that CNTs can serve as synergist, the flame retardant property of expandable flame retardant PP composite material is influenced.Studies have shown that CNTs can be obvious Improve the Char Residues Structure formed after polymer combustion and intensity, mainly works in condensed phase.
Also there is similar report about CNTs is introduced Intumescent Retardant System as synergist.Poplar allusion quotation etc. (addition CNTs, The Research on synergistic effect investigation of materials journal that APP and ABS improves 6 flame retardant property of nylon, 2016,30 (3): 199- 208.) it is added to CNTs as synergist in nylon 6 (PA6)/ammonium polyphosphate (APP), foamed char structural research is found, CNTs facilitates layer of charcoal expansion and the raising of mechanical strength, to play excellent flame retardant property.(the Electrical such as Wu Z.F and flame-retardant properties of carbon nanotube/poly(ethylene terephthalate) composites containing bisphenol A bis(diphenyl phosphate). Polymer, 2013,54:3334-3340.) it is fire-retardant to the synergistic of PET that CNTs and diphenyl phosphoester are had studied, shows CNTs The consistency of foamed char not only can be improved in the reticular structure of formation, but also can more effectively support layer of charcoal, increases layer of charcoal Intensity, being exposed to its long-time under high temperature will not still collapse, crack, and gives full play to heat transmitting and " shielding " of Oxygen permeation is made With.
However, being mostly at present that CNTs is being introduced IFR with synergist " identity " by " stop " for the research of CNTs In system, and do not studied as the charcoal source in IFR system.
Natural macromolecular material chitosan (CS) is a kind of common CNTs modifying agent, at present CNTs/CS composite material master To be applied to the technical fields such as pharmaceutical carrier, molecular recognition and electrochemical sensor.Such as Payam M.A. (Wrapping carbon nanotubes by biopolymer chains: role of nanointerfaces in detection of vapors in conductive polymer composite transducers. Polymer composites, 2016, 37 (9): 2803-2810) by coating the biomass molecule chain that one layer of CS is formed on the surface CNTs, it is applied in polymer Sensing aspect；(the Comparison studies on covalently and non-covalently such as Gou Z.Q. modified MWNTs using chitosan and their starch nanocomposites. Food science & Technology, 2016,68 (3): 220-229) by covalently modifying preparation CNTs/CS compound with non-covalent bond；Zhao Ting Triumphant etc. (preparation of multi-walled carbon nanotube/Chitosan Composites and electrocatalysis characteristic China YouSe Acta Metallurgica Sinica, 2010, 20 (9): 1732-1735) CNTs/CS composite material is applied in terms of electro-catalysis.
Natural polymer carbohydrate is applied in expanding fire retardant system, has a large amount of research report.Such as Feng J.X. Deng (An intumescent flame retardant system using beta-cyclodextrin as a carbon source in poly lactic acid(PLA), Polymers for advanced technologies, 2011, 22:1115-1122) using cyclodextrin as charcoal source, applied in polylactic acid Intumescent Retardant System；(the chitosan phosphorus such as Wang Zhengzhou The synthesis of acid esters melamine salt fire retardant and application polymer material science and engineering in SBR, 2013,29 (4): 29-32) " three-source integrated " fire retardant is prepared for by base of chitosan；Guo Minghui etc. (lignin-base environment protecting fiber board it is fire-retardant Performance Journal of Building Materials, 2011,14 (5): 649-652) by base of lignin it is prepared for flame retardant fibre board.But Application of the CNTs/CS composite material in terms of flame retardant area is but rarely reported, although containing a large amount of amino in CS molecule, by it It should be theoretically feasible as the gas source of Intumescent Retardant System.
This is because being also rich in hydroxyl abundant in CS molecule other than containing a large amount of amino.If CNTs/CS answered Condensation material is applied in high molecular polymer, and under the conditions of the high temperature process of polymer, these hydroxyls are easy to occur intermolecular Dehydrating phenomena.This phenomenon particularly with polarity high molecular polymer such as PET be it is influential, high molecular polymer can be caused Degradation, and then the tensile strength of high molecular polymer is caused to reduce.Therefore, CNTs/CS composite material is not suitable for being directly applied to In polar high molecular polymer, to avoid the appearance of the intermolecular dehydrating phenomena of CS as far as possible.
Summary of the invention
The object of the present invention is to provide a kind of carbon nanotube base Chitosan Phosphate composite flame-retardant agent and the fire retardants Preparation method.
The application of the carbon nanotube base Chitosan Phosphate composite flame-retardant agent is provided, is another invention mesh of the invention 's.
Carbon nanotube base Chitosan Phosphate composite flame-retardant agent of the present invention is one kind using CNTs as charcoal source, natural high Molecular material CS is gas source, and phosphoric acid is acid source, and CS is first supported on CNTs surface modification and obtains CS-CNTs, then with phosphoric acid by CS- " three-source integrated " the one-component expansion type flame retardant obtained after CNTs phosphorylation.
In carbon nanotube base Chitosan Phosphate composite flame-retardant agent of the present invention, as charcoal source, gas source and acid source The mass ratio of raw material CNTs, CS and phosphoric acid is 1: 2~4: 5~10.
Further, it is carried out under the conditions of the phosphorylation to CS-CNTs is existing for the urea.
Further, the dosage of the urea is 0.5~1 times of CS-CNTs mass.
In carbon nanotube base Chitosan Phosphate composite flame-retardant agent of the invention, the raw material CNTs can be single wall carbon and receive Mitron (SWCNTs) or multi-walled carbon nanotube (MWCNTs).Preferably, the present invention uses the CNTs of carboxylated.
In turn, the present invention also provides a kind of preparation method of carbon nanotube base Chitosan Phosphate composite flame-retardant agent, it is The aqueous solution of carboxylated CNTs is added in the aqueous solution of CS and carries out back flow reaction, adds glutaraldehyde, it is anti-in 60~90 DEG C Intermediate product CS-CNTs should be made；CS-CNTs is added in the dimethylformamide containing urea again, is dripped at 100~120 DEG C Add phosphoric acid, back flow reaction under inert gas shielding obtains reaction product PCS-CNTs.
In preparation method of the present invention, the carboxylated CNTs and CS are preferably configured to 0.1~0.2g/L's respectively Aqueous solution.
Wherein, further, it is preferable to use the acetic acid aqueous solutions of mass concentration 1~2% for the aqueous solution of the CS.
In turn, the back flow reaction of the carboxylated CNTs and CS is carried out at 60~95 DEG C, 6~9h of return time.
In above-mentioned preparation method, the mass ratio of the glutaraldehyde and CS that are added is 0.3~1: 1.
In turn, the reaction time after glutaraldehyde is added is 3~5h.
The preparation of intermediate product CS-CNTs stands 2~3h after the reaction was completed, by reaction solution, isolates reaction product, respectively It is washed using 1~2% acetic acid solution and deionized water, 100~110 DEG C of vacuum drying obtain intermediate product CS-CNTs.
In turn, the concentration of the CS-CNTs dimethyl formamide solution is preferably 0.1~0.15g/L.
The return time of the phosphorylation reaction is 3~6h.
It reacts obtained PCS-CNTs deionized water and ethyl alcohol sufficiently washs, 110~120 DEG C of vacuum drying obtain most Whole reaction product.
The present invention serves as " role " in charcoal source using CNTs as " member " in IFR system, has devised and is with CNTs Base, the expansion type flame retardant that carbon-collecting source, gas source and acid source are integrated.The Char Residues Structure dilation height and mechanics of fire retardant of the present invention Intensity is good, and flame retarding efficiency is more excellent.CS can not only be used for gas source, but also as the modifying agent of CNTs, contain in molecule a large amount of Hydroxyl and amino, backbone breaking can occur at 300 DEG C or so, generate a large amount of gas, can be used as the gas source of expanding fire retardant； Meanwhile CNTs specific surface area is larger, surface can be higher, be easy to happen reunion, phase weaker with the interface binding power of polymeric matrix Capacitive is poor, and after CS is modified, the surface CNTs can introduce a large amount of active group, provides greatly for next step functional modification The reaction active sites of amount, and improve the compatibility with polymeric matrix.Selection uses in phosphoric acid and CNTs surface C S molecule C6With C3On hydroxyl occur esterification, can not only reduce the hydroxyl quantity in CS molecule, and have also been introduced acid source and Ignition-proof element --- P, so as to complete using CNTs as the design of the Novel integrated intumescent flame retardant of base.
Composite fire retardant prepared by the present invention is had excellent performance, and not only has CNTs on reducing polymer heat release rate Advantage, and the acid source of CNTs surface modification and gas source can play effect in the gas phase, and then inhibit polymer combustion Production cigarette rate in the process, while the fire-retardant double effect with suppression cigarette is played, the fire danger of polymer combustion can be substantially reduced It is dangerous.
Composite flame-retardant agent prepared by the present invention can add in PET, be prepared into Flame-retardant PET composite material.System of the present invention Standby Flame-retardant PET composite material is while improving its flame retardant property, additionally it is possible to weaken the fire retardant of addition to PET mechanical property Deterioration.
Specifically, Flame-retardant PET composite material of the present invention is to lead to the PCS-CNTs composite flame-retardant agent of above-mentioned preparation Melt-blending process blending is crossed in PET matrix, prepares Flame-retardant PET composite material.
More specifically, the Flame-retardant PET composite material is to carry out PCS-CNTs and routine PET slice at 260~270 DEG C Melt blending prepares PCS-CNTs/PET slice, wherein the mass fraction that the PCS-CNTs accounts for PET matrix is 0.5~3%.
The flame retardant property of PET not only can be improved in PCS-CNTs/PET composite material prepared by the present invention, but also can be bright The aobvious production cigarette rate reduced in PET combustion process.Simultaneously as three kinds of functional components of PCS-CNTs composite flame-retardant agent collection are one Body, relative to directly three kinds of ingredients of independent addition, hence it is evident that reduce each component to the evil in terms of PET composite material mechanical property Change.
PCS-CNTs/PET composite material prepared by the present invention has excellent spinning property, can be applicable in fiber, makees For yarn, textile.
Detailed description of the invention
Fig. 1 is the scanning electron microscope and energy spectrum analysis figure of raw material CNTs.
Fig. 2 is the scanning electron microscope and energy spectrum analysis figure that embodiment prepares PCS-CNTs.
Fig. 3 is the infrared spectrum comparison diagram of CNTs and PCS-CNTs.
Fig. 4 is the thermogravimetric curve comparison diagram of CNTs and PCS-CNTs.
Fig. 5 is the heat release rate curve graph of PCS-CNTs/PET flame retardant composite material.
Fig. 6 is the production cigarette rate profile of PCS-CNTs/PET flame retardant composite material.
Specific embodiment
Following embodiments are only the preferred technical solution of the present invention, are not used to carry out any restrictions to the present invention.For For those skilled in the art, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made Any modification, equivalent substitution, improvement and etc., should all be included in the protection scope of the present invention.
Embodiment.
2g CS is dissolved in 2% acetic acid of 200ml, 12h is stirred under room temperature, makes it completely dissolved.
CNTs, the ultrasonic disperse 30min of 1g carboxylated are added in 50ml deionized water, above-mentioned CS solution is added, heats up To 95 DEG C of back flow reaction 6h, 0.5g glutaraldehyde is added, 3h is reacted at 60 DEG C, stands 2h later.It is isolated from reaction solution anti- Product is answered, is largely washed with 2% acetic acid solution and deionized water respectively, is dried in vacuo, obtains product CS-CNTs.
1.2g CS-CNTs, 0.7g urea are taken, is added in 100ml dimethylformamide (DMF), is heated to 110 DEG C, stirring Lower 85% phosphoric acid of dropwise addition 2ml, back flow reaction 3h under nitrogen protection.After reaction, it is sufficiently washed with deionized water and ethyl alcohol anti- Product is answered, is dried in vacuo, obtains product PCS-CNTs powder.
PET is sliced the dry 12h in 120 DEG C of vacuum drum drying equipments, PCS-CNTs powder is 110 in vacuum drying oven DEG C be dried 5h.
Double screw extruder is heated to 255 DEG C, the dry PET slice of 330g is weighed, is added to double screw extruder Main spout, PCS-CNTs powder 3.3g are added from the side spout of double screw extruder, and melt blending cuts extruded stock wire drawing The PCS-CNTs/PET slice of mass fraction 1% is made in grain.
Comparative example.
Respectively by the dry PCS-CNTs powder of 330g dry PET slice and 3.3g from the twin-screw for being heated to 260 DEG C The main feeding and side spout of extruder are added, melt blending, wire drawing pelletizing, and the CNTs/PET slice of mass fraction 1% is made.
With scanning electron microscope (SEM) and energy spectrum analysis (EDS) respectively the appearance structure to CNTs and PCS-CNTs and element at Divide and carries out preliminary characterization.Fig. 1 (a) is the appearance structure figure of CNTs, shows that CNTs is distributed in a tubular form in figure, and exist between CNTs Tangling phenomenon, in conjunction with CNTs surface-element in Fig. 1 (b) EDS as a result, pure CNTs phosphorus content is higher, oxygen content is lower, shows carbon There are a small amount of oxygen-containing functional groups for nanotube surface.It is compared with Fig. 1 (a) it is found that tangling between the pipe of PCS-CNTs in Fig. 2 (a) existing As weakening, in conjunction with the EDS result in Fig. 2 (b) it is found that other than C, O element, a small amount of N and a large amount of P elements are introduced into, and illustrate shell Glycan and phosphoric acid have successfully been modified on the surface of CNTs.
Above-mentioned conclusion can also further be verified by infrared spectroscopy qualitative analysis.Curve (a) gives in Fig. 3 The infrared spectrogram of CNTs, in contrast, in the infrared spectrogram of curve (b) CS-CNTs, 3373cm-1、2976cm-1Respectively For-OH and-NH2Stretching vibration peak, 2889cm-1For the stretching vibration peak of carbocyclic ring on CS, 1092cm-1And 1045cm-1For- CH2The stretching vibration of OH, the two peaks are the crystallization sensitivity peak of CS, 883cm-1For the peak C-O, these are all the characteristic peaks of CS, are said It is bright after CS is modified, CS is successfully supported on CNTs.Compared with curve (a), (b), after phosphoric acid is modified, former CS-CNTs - NH2、-CH2OH absorption peak disappears, 1280cm-1、965cm-1There is P=O, the peak P-O-C and 720cm in place-1Place is stretching for P-O Contracting vibration peak illustrates that phosphate radical is successfully modified on CS-CNTs.
Fig. 4 is the heat stability testing result of CNTs, CS-CNTs, PCS-CNTs and determining for CNTs area load amount respectively Amount analysis.By curve (a) it is found that the temperature of initial decomposition of CNTs is 588 DEG C, the carbon left at 700 DEG C is 87.05%；It is bent In line (b), the temperature of initial decomposition of CS-CNTs advances to 331 DEG C, is the decomposition of CNTs area load CS, at 700 DEG C Carbon left is 82.75%, and primary Calculation CNTs surface C S load capacity is about 5%；PCS- compared with curve (b), in curve (c) CNTs occur again at about 550 DEG C or so one it is obvious weightless, this is mainly due to the phosphorylation modification of CNTs surface C S, Carbon left at 700 DEG C is 39.64%, calculates that the load capacity of the surface CNTs PCS is about 40%.
In order to verify the fire retarding effect of PCS-CNTs, PCS-CNTs/PET and CNTs/PET flame retardant composite material is used respectively Cone calorimetry (CONE) test is carried out, wherein the content of CNTs and PCS-CNTs is 1% in PET.Fig. 5 gives PET resistance The heat release rate curve (HRR) of retardant composite material.
Heat release rate peak value (pk-HRR) is important one of the fire behavior parameter of material, is worth smaller, the danger of fire Property is with regard to smaller.As shown in Figure 5, the pk-HRR of pure PET is up to 511kW/m2.And after adding 1% CNTs in PET matrix, The pk-HRR value of CNTs/PET composite material falls to 463kW/m2, up to 9.4%, this is primarily due to burned fall CNTs can form a network-like heat-insulated layer of charcoal in journey, this conclusion is verified by most scholars.
After the PCS-CNTs of same addition 1%, the pk-HRR value of PET is by 511kW/m2Drop to 341kW/m2, fall Up to 33.3%, flame retardant effect is obvious.This is primarily due in the preparation process of PCS-CNTs, urea elder generation and phosphoric acid It reacts, esterification then occurs with the part of hydroxyl of CNTs surface C S and forms Chitosan Phosphate, introduces simultaneously Ignition-proof element N and P, in combustion process, the intermolecular hydroxyl of CS can occur dehydration condensation and generate a part of water, and shell is poly- Sugar phosphate, which decomposes, generates metaphosphoric acid, and polymerization reaction occurs between phosphoric acid and generates polyphosphoric acid etc., metaphosphoric acid and polyphosphoric acid etc. can be catalyzed PET resolves into carbon and water, reduces the heat of combustion process generation, plays " chemical barrier " effect；In addition CNTs is mutually wound For the network structure of formation to " physical barrier " effect of heat and oxygen, two-way interaction enhances final carbon residue structure, rises To condensed phase fire retarding effect, to reduce the generation of heat release rate.
Fig. 6 is the production cigarette rate profile of PET flame retardant composite material.With the production cigarette of pure PET and CNTs/PET composite material Rate curve is compared, and the production cigarette rate curve and peak value of PCS-CNTs/PET composite material are all located under the two, illustrates PCS- CNTs has certain suppression cigarette effect.This is mainly due to amino of chitosan decomposition, produce a large amount of non-flammable gases ammonias (NH3), the concentration of fuel gas in combustion process is diluted, to reduce the generation of smoke in combustion process, plays gas Mutually fire-retardant effect.
Therefore, individually 1% CNTs of addition is flame-retardant modified to PET progress, since physical barrier of the CNTs to heat and oxygen is imitated It answers, the heat release rate generated in combustion process can be reduced, but to production cigarette rate without obvious effect；And functionalization is carried out to CNTs After modification, making its fire retarding effect no longer is single " physical barrier ", but is provided with the dual fire retarding effect of solid phase and gas phase, So as to reduce heat release rate simultaneously and produce cigarette rate.
Table 1 gives the limit oxygen index (LOI) and tensile strength of pure PET and PET flame retardant composite material.
Under same amount, the LOI value highest of PCS-CNTs/PET composite material.LOI value is higher, illustrates the self-extinguishment of material Property is stronger, and flame retardant property is stronger.
In conjunction with Analysis of tensile strength it is found that compared with pure PET (51.1MPa), the tensile strength of CNTs/PET composite material Be remarkably reinforced, though and the PCS-CNTs/PET tensile strength of functionalization is declined, its fall is only 6.6%, is not influenced Its using effect further illustrates that CNTs can be used as Novel carbon source, carries out functional modification and to become efficient expansion type fire-retardant Agent.

Claims (8)

1. a kind of carbon nanotube base Chitosan Phosphate composite flame-retardant agent is using carboxylated CNTs as charcoal source, CS is gas source, phosphoric acid For acid source, the aqueous solution of carboxylated CNTs is added in the aqueous solution of CS and carries out back flow reaction, adds glutaraldehyde, in 60~ CS is supported on the surface carboxylated CNTs by 90 DEG C of reactions, and modification obtains intermediate product CS-CNTs, then CS-CNTs addition is contained In the dimethylformamide of urea, be added dropwise phosphoric acid at 100~120 DEG C, back flow reaction under inert gas shielding, to CS-CNTs into The one-component expansion type flame retardant PCS-CNTs that row phosphorylation obtains.
2. composite flame-retardant agent according to claim 1, it is characterized in that the mass ratio of carboxylated CNTs, CS and phosphoric acid is 1: 2~4: 5~10.
3. composite flame-retardant agent according to claim 1 or 2, it is characterized in that the dosage of the urea is CS-CNTs mass 0.5~1 times.
4. composite flame-retardant agent according to claim 1 or 2, it is characterized in that the carboxylated CNTs and CS is configured to respectively The aqueous solution of 0.1~0.2g/L.
5. composite flame-retardant agent according to claim 1 or 2, it is characterized in that the CS aqueous solution is with mass concentration 1~2% Acetic acid aqueous solution be solvent.
6. composite flame-retardant agent according to claim 1 or 2, it is characterized in that the mass ratio of the glutaraldehyde and CS are 0.3~1 ∶1。
7. composite flame-retardant agent described in any one of claims 1 to 6 is preparing the application in Flame-retardant PET composite material.
8. a kind of Flame-retardant PET composite material, is that composite flame-retardant agent described in any one of claims 1 to 6 is passed through melt blending Method blending is prepared in PET matrix, and the mass fraction that the composite flame-retardant agent accounts for PET matrix is 0.5~3%.
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