CN101735681A - Polymer nanocomposite flame-retardant intumescent coating, preparation method and application thereof - Google Patents
Polymer nanocomposite flame-retardant intumescent coating, preparation method and application thereof Download PDFInfo
- Publication number
- CN101735681A CN101735681A CN200810176779A CN200810176779A CN101735681A CN 101735681 A CN101735681 A CN 101735681A CN 200810176779 A CN200810176779 A CN 200810176779A CN 200810176779 A CN200810176779 A CN 200810176779A CN 101735681 A CN101735681 A CN 101735681A
- Authority
- CN
- China
- Prior art keywords
- coating
- hydrotalcite
- polymer
- nano
- phosphorus compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a halogen-free flame-retardant nanocomposite polymer intumescent coating. The invention also relates to a method for preparing the nanocomposite polymer intumescent coating and application of the coating taken as a flame-retardant material.
Description
Technical field
The present invention relates to halogen free flame retardant nano-complex polymer foaming type coating that has good flame-retardance matter and its production and application.
Background technology
The widespread use of polymer materials has increased danger on fire greatly.In order to eliminate these problems, what use at present is the polymer materials that contains fire retardant.
Present known several based flame retardants that have.
First kind fire retardant comprises halogenated fire retardant, and they can stop free radical mechanism when combustion processes begins.But halogenated fire retardant produces opaque steam, toxicity and corrosive gases.
Second based flame retardant comprises inorganic hydroxide.Containing inorganic hydroxide as the shortcoming of the polymer materials of fire retardant is, owing in order to obtain to have the material of good flame-retardance, need working concentration to surpass the inorganic hydroxide of 50 weight % (gross weight in polymer materials is a benchmark).For example, in order to obtain to be included into the material of classification V0, in ethylene vinyl acetate, use the aluminium hydroxide of 70 weight % according to the UL94 standard.
But the inorganic hydroxide of high density is disadvantageous like this, because increased the weight of material like this, impels the mechanical properties of described material to descend rapidly.
The 3rd based flame retardant comprises organic and inorganic phosphorous compound.Phosphorus uses with element phosphor, form inorganic or organo phosphorous compounds usually.
But comprising phosphorus compound is that they produce potential toxicity to human and environment when polymer materials burns as the shortcoming of the polymer materials of fire retardant.
The toxicity of using phosphorus compound may cause as the fire retardant in the polymer materials relates generally to following several respects:
A) material will discharge the direct toxicity of organophosphorous fire retardant afterwards;
B) the direct toxicity of organo phosphorous compounds that in the polymeric material fuel combustion process, produces in the gas phase and inorganic phosphorous compound.
And another shortcoming that comprises the fire retardant of phosphorus compound is, normally neurotoxic agent of organo phosphorous compounds, and its effect has acute and chronic phase.The main acute effect of some organo phosphorous compoundss is anticholinesterase effects, and this effect has suppressed the effect of Pseudocholinesterase, thereby has increased the effect of vagusstoff.In some patents, this effect causes paralysis, in extreme case even cause death.
Therefore, need a kind of human and environment there be the protectiveness intumescent coating of toxic flame-retardant polymer material as plastics, timber and metal base.
Especially need a kind of like this polymer foaming type coating: the fire retardant that it contains the low weight percentage composition has flame retardant resistance and favorable mechanical character.
In polymer materials, known a specific class, it comprises the nano-complex polymer materials.
Patent application WO99/35186 has described a kind of preparation method of nano-complex polymer materials, and this nano-complex polymer materials comprises polymeric matrix and the clay that is incorporated in this matrix.
In document WO 99/35186, in polymer materials, mix layered double-hydroxide (doublehydroxide).Layered double-hydroxide is rare at nature, but can use several sinteticses, thereby they obtain the lipotropy surface through the organic anion modification.In polymeric matrix, use the clay of described modification that described clay is evenly dispersed in the polymeric matrix with nanometer level.The nano-complex polymer materials of describing in the document WO 99/35186 has thermotolerance.
But nano-complex polymer materials described in the prior does not have flame retardant resistance.
And nano-complex polymer materials described in the prior does not contain fire retardant.
Therefore, still need to have the low polymer foaming type coating of flame retardant resistance, mechanicalness and flame retardant agent content.
The purpose of this invention is to provide a kind of polymer nanocomposite intumescent coating with flame retardant resistance, this coating does not have toxicity to human and environment.
Another object of the present invention provides a kind of polymer nanocomposite intumescent coating with flame retardant resistance and good mechanical properties.
Another object of the present invention provides a kind of polymer nanocomposite intumescent coating with flame retardant resistance, and this coating contains the fire retardant of low weight percentage composition.
Another object of the present invention provides a kind of polymer nanocomposite intumescent coating with flame retardant resistance, and this coating contains the phosphorus compound of low weight percentage composition as fire retardant.
The applicant has realized conspicuous purpose in these purposes and the following detailed description, and the applicant is surprised to find, and the polymer nanocomposite intumescent coating that comprises polymeric matrix and hydrotalcite has unexpected flame retardant resistance.
And the applicant has been found that and add the collaboration system that phosphorus compound can obtain hydrotalcite-phosphorus compound in the polymer nanocomposite intumescent coating that comprises hydrotalcite, can reduce the amount of the phosphorus compound that uses in the polymer materials.Therefore, in the nano-complex polymer foaming type coating that comprises polymeric matrix, add the polymer nanocomposite intumescent coating that phosphorus compound can obtain flame retardant resistance raising and low-phosphorous compounds content.
First purpose of the present invention is the application that comprises the nano-complex polymer foaming type coating of polymeric matrix and hydrotalcite, and this application characteristic is enumerated in appended independent claim.
Another object of the present invention is the nano-complex polymer foaming type coating that comprises polymeric matrix, hydrotalcite and phosphorus compound, and the feature of this coating is enumerated in appended independent claim.
Another object of the present invention is the method that preparation comprises the nano-complex polymer foaming type coating of polymeric matrix, hydrotalcite and phosphorus compound, and the feature of this method is enumerated in appended independent claim.
At last, another object of the present invention is the application that comprises the nano-complex polymer foaming type coating of polymeric matrix, hydrotalcite and phosphorus compound, and the feature of this application is enumerated in appended independent claim.
The use hydrotalcite can be in conjunction with the typical properties (low rate of heat release) of typical flame retardant resistance of inorganic hydroxide (thermal endothermic decomposition of splitting gas and dilution) and nano-complex.
The applicant has been found that, hydrotalcite is beneficial to the flame-retardant nature of polymer foaming type coating, this is because form carbon residue (coke) on material surface, and these carbon residues become the gentle barrier of heat, and discharges steam and carbonic acid gas in the process that they decompose.The heat absorption characteristics of described process and the diluting effect of flammable splitting gas in steam and carbonic acid gas have all increased temperature of combustion and/or the required time of combustion limits that reaches the mixture that contains splitting gas.
In framework of the present invention, the hydrotalcite of nano-dispersed is as fire retardant, and the nano-complex intumescent coating that contains it is a flame retardant resistance.
Flame resistivity or flame retardant resistance are by the character decision of each component of coating, and the factor that relates to thermotolerance is different.Flame resistivity is limited by several parameters, and for example: 1) ignition time, promptly material takes fire the required time in the presence of source of radiation; 2) flame spread rate of material; 3) rate of heat release; 4) Di Luo trend (tendency todripping).
Flame resistivity is measured with cone calorimetry, and this is a kind of device that is made of the cone of homogeneous radiation heat (simulated fire).In the presence of source of radiation, measure coating and take fire the required time.When coating is heated, begin to take place the thermolysis of described coating and the release of volatility and inflammable substance.When the concentration of described inflammable substance in the presence of ignition source (scintillator) reached combustion limits, described coating took fire.Then, infer the heat that time per unit produces, the i.e. amount of incendiary oxygen in the combustion processes by the observed value of ignition time and heat release.This is the state-of-the-art method that characterizes the parameter relevant with flame retardant resistance.
Method according to using can obtain different results, and this is not to be pure science applied because relate to the problem of flame retardant resistance.
The mechanism that relates to flame retardant resistance is different from and relates to stable on heating mechanism.Thermotolerance or thermostability are meant stability of factorization, and be relevant with mechanical properties, and test is determined according to thermogravimetric; This thermometrically is along with the changes in weight of temperature rising system or compound, and definite material temperature of beginning to degrade.
Relation between thermostability and the flame retardant resistance depends on chemical composition of paint.Thermotolerance is flame resistant signal sometimes, but does not have general rule.Between thermostability and flame retardant resistance, may have given relation, but flame resistivity coating always do not have high thermostability: by thermolysis, not only can discharge the inflammableness material, and can discharge incombustible.Thermostability relates to flame retardant resistance sometimes, because do not discharge combustible volatile matter, thereby also can not cause material on fire, but this is not general rule.But also there are some materials heat-resisting not fire-resistant.At this some examples are arranged.Aluminium hydroxide is a kind of at 300 ℃ of materials that begin to decompose, absorb heat and released vapour.Because the steam that discharges is reduced to the concentration of the gas that the matrix burning produces below the burning concentration of mixture, thereby has hindered and caught fire, the burning of the organic substrate that contains aluminium hydroxide of therefore having slowed down.Therefore, aluminium hydroxide is a kind of fire retardant that reduces thermostability.The thermostability of PVC is low, produces the material of blocking-up flame development in decomposition course.On the contrary, polycarbonate has quite high thermostability.
The applicant has carried out the test of hot analysis and burning aspect to some samples, the nano-complex polymer coating that comprises hydrotalcite with demonstration and the nano-complex polymer materials that comprises montmorillonite and comprise conventional flame retardant such as the micron composite materials of aluminium hydroxide is compared outstanding effect.Use the hydrotalcite of traditional filler such as aluminium hydroxide and micron dispersive hydrotalcite and Nano filling such as organic modification and montmorillonite prepared at concentrations sample with 5 weight %.Compatilizer modified hydrotalcite with tosic acid (pTSA) and m-sulfanilic acid (ABS) and so on.Specimen preparation comprises by mechanical stirring and supersound process filler and Nano filling is dispersed in the epoxy monomer of use.Reticulation agent Jeffammina D230 with stoichiometry is carried out to the net processing to resin at last, and cure cycle was carried out 5 hours at 90 ℃, and after fixing circulates in 110 ℃ to carry out 3 hours.
No matter be montmorillonite or hydrotalcite, the organically-modified of surface of clay all promoted them to mix in the Resins, epoxy.
For montmorillonite, organically-modified common be that the alkylammonium salt of 12-18 carries out with carbonatoms in the alkyl chain.Particularly, the primary alkyl ammonium salt that has 18-16 carbon atom in this use.Uncle's ammonium salt preferably, this is because it can react with Resins, epoxy, promotes to be incorporated in the resin.
Confirm all that in following two kinds of situations the process of mixing is effective: X-ray diffraction (XRD) test and transmission electron microscope (TEM) test show that for montmorillonite in the Resins, epoxy and hydrotalcite, the distance between the layer is respectively 5.6 nanometers and 7.6 nanometers.Although (basal distance) is bigger for the identity distance between the montmorillonite layer, confirmed that hydrotalcite is more effective: this shows that fire-retardant effect is not only relevant with the degree of scatter of Nano filling, and relevant with the character of described Nano filling.
Combustion testing shows that the nano-complex polymer coating that contains the hydrotalcite of modification has self-gravitation character, especially contains the coating of Resins, epoxy.Observe, compare, contain self-gravitation character more obvious (combustion testing is according to U194HB, and horizontal firing (Horizontal Burning) is carried out) described in the situation of compatible hydrotalcite of nano-dispersed with micron dispersive hydrotalcite.
The existence of phosphorus compound and nano-complex coating shows the synergistic effect of flame-retardant nature.Described synergistic effect can reduce the consumption of phosphorus compound astoundingly, thereby the phosphorous gas that produces in the reduction combustion processes is xicity related.Another advantage that low phosphorus content brings is to have improved mechanical properties greatly.And nano-complex has very high maximum processing temperature, and they still keep mechanical properties constant in this temperature.
Hydrotalcite is the layered hydroxide of the following hybrid metal of general formula: M
2+ (1-x)M
x 3+(OH)
2(A
N-)
X/nMH
2O.
This compounds has the brucite of being similar to Mg (OH)
2The octahedral crystal structure, two valency metal M wherein
2+By trivalent metal M
3+Partly similar shape replaces, and produces remaining surface charge on plane of crystal, and these electric charges are by the anion balance of solvation.Because this structure, hydrotalcite is an anionite, is similar to some laminated claies (silico-aluminate, for example montmorillonite), and wherein, the negative charge in the layer is by tradable positive charge balance.The compound that belongs to hydrotalcite is also referred to as anionic clay.Similarly the cationic clay hydrotalcite can carry out modification with the organic ion that mixes (promptly being incorporated between the layer), as nano-complex synthetic Nano filling.
In order to promote stratiform particulate nano-dispersed, can carry out ion-exchange to the negatively charged ion that is pre-existing in other organic ion, thereby make catalyst surface be lipotropy, therefore compatible with the polymeric matrix that wherein mixes laminate granular.
In a preferred embodiment of the present invention, use the hydrotalcite of its surface with the compatilizer modification.For example, described hydrotalcite can be synthetic hydrotalcite (Mg
4Al
2(CO
3) (OH)
123H
2O)
0.5, mean particle size is 2.26 microns, surface-area is 17 meters
2/ gram.
Preferably, use organic acid as compatilizer, for example be selected from down the organic acid of group: tosic acid (pTSA), p-hydroxybenzenyl sulfonate (IBS), m-sulfanilic acid (ABS), stearic acid (SA) or oleic acid, dodecylbenzene sulfonate, dodecyl sulfate.
Preferably, use tosic acid (pTSA) and/or m-sulfanilic acid (ABS) as compatilizer.
The hydrotalcite of surface with the compatilizer modification mixed in the polymer coating matrix.
In a preferred embodiment of the present invention, polymer coating matrix is selected from thermosetting polymer.
Preferably, thermosetting polymer is selected from down group: Resins, epoxy, polyester, vinyl ester, phenol resins.
Preferably, can use Resins, epoxy DER 331-DOW Chemical (Dow Chemical)-(DGEBA) as thermosetting polymer, the equivalent epoxy weight of this material is 182.0-192.0ASTMD1652-90, it is 11000-14000 (cPs) ASTMD445-94 that molecular-weight average is less than or equal to 700,25 ℃ viscosity.With molecular-weight average is that 230 reticulation agent Jeffammina D230 (amino-terminated polyoxypropylene diene) makes Resins, epoxy become net.
In another preferred embodiment of the present invention, polymer coating matrix is selected from thermoplastic polymer.
Preferably, thermoplastic polymer is selected from down group: polypropylene, polyethylene, polyethylene terephthalate.
In addition, use phosphorus compound as fire retardant.
Phosphorus compound is preferably from organizing down: organo phosphorous compounds, element phosphor, red phosphorus, ammonium polyphosphate, diammonium phosphate.
Preferably, use ammonium polyphosphate as phosphorus compound, for example ((APP), EXOLITAP422 are produced by CE company (Clariant EXOLIT AP 422) ammonium polyphosphate.
The composition that the weight percentage that it is benchmark that foundation nano-complex polymer coating of the present invention has following gross weight in the nano-complex polymer materials is represented.
For example, be benchmark in the gross weight of nano-complex polymer coating, polymer coating matrix is 50-99 weight %.
For example, be benchmark in the gross weight of nano-complex polymer coating, hydrotalcite is 1-30 weight %.
For example, be benchmark in the gross weight of nano-complex polymer coating, phosphorus compound is 0-35 weight %, preferably less than 30 weight %, is more preferably less than 20 weight %.
Purpose of the present invention also relates to the method that preparation comprises the nano-complex polymer coating of polymeric matrix, hydrotalcite and phosphorus compound.Described method is characterised in that it comprises the step that adds phosphorus compound.
For example, in first embodiment that uses thermosetting polymer, this method comprises the step that relates to following processing:
A) surface of usefulness compatilizer modified hydrotalcite;
B) hydrotalcite with modification is dispersed in the polymeric matrix;
C) heated polymerizable thing paint matrix dispersive hydrotalcite under mechanical stirring produces swelling effect;
D) add reticulation agent; And
E) disperse phosphorus compound.
In addition, this method comprises and pours into material in the mould and step of curing in thermal cycling.
For example, in second embodiment that uses thermoplastic polymer, this method comprises the step that relates to following processing:
A) surface of usefulness compatilizer modified hydrotalcite;
B) hydrotalcite and phosphorus compound directly are dispersed in the forcing machine.
C) described step is preferred step.
Phosphorus compound adds after step b) or after the step c).
Preferably, hydrotalcite is dispersed in the coating monomer with the concentration of 1-30 weight %; Heating was carried out 1-24 hour under the temperature of room temperature to 80 ℃, carried out under 80-180 ℃ temperature 5-8 hour.By at room temperature mechanical stirring 1-30 minute or by phosphorus compound being disperseed in the following heating of the temperature directly related (about 50 ℃ usually) with resin viscosity.The solidified thermal cycling was carried out under 20-120 ℃ temperature 2-24 hour, carried out under 80-160 ℃ temperature 1-5 hour.
More preferably, hydrotalcite is dispersed in the liquid coating monomer with the concentration of 1-10 weight %.
Heating was carried out under 60-120 ℃ temperature 2-12 hour, carried out under 100-160 ℃ temperature 1-3 hour.For example, can under 50 ℃, in 10 minutes, add phosphorus compound; The solidified thermal cycling was carried out under 50-80 ℃ temperature 3-7 hour, carried out under 100-130 ℃ temperature 2-3 hour.
More preferably, the concentration of hydrotalcite with 4-8 weight % is dispersed in the coating monomer; Heating was carried out 1-3 hour under about 70-90 ℃, preferred 80 ℃ temperature, carried out about 2 hours under 90-130 ℃, preferred 120 ℃ temperature; The solidified thermal cycling was carried out 4-6 hour, preferred 5 hours under about 40-60 ℃, preferred 50 ℃ temperature, under 90-120 ℃, preferred 110 ℃ temperature about 1-3 hour, preferred 2 hours.
One preferred embodiment in, the type of the hydrotalcite of use is MG61HT (Mg/Al=2, carbonate form), and is compatible with m-sulfanilic acid, is dispersed in the Resins, epoxy with the concentration of 4 weight %.
Under mechanical stirring, 80 ℃ of heating 2 hours and 120 ℃ of heating 2 hours, the reticulation agent of adding is Jeffammina D230, and its amount is 30phr (used weight resin 30%), and phosphorus compound is 20% ammonium polyphosphate.The solidified thermal cycling was carried out under 50 ℃ 5 hours, carried out under 110 ℃ 2 hours.
Be specially adapted to many application according to flame retardant resistance nano-complex coating of the present invention.Has favorable mechanical character according to material of the present invention.By obtaining various application according to nano-complex coating of the present invention.Their example comprises any application that needs flame resistant material.Particularly, can be used for fields such as civil engineering work, telecommunications, automobile, electric equipment products, furniture according to flame retardant resistance nano-complex coating of the present invention.
The flame retardant resistance nano-complex coating that comprises hydrotalcite and polymeric matrix can be used as the material of non structural component in the transportation means, has the environment of high risk on fire such as the insulation system in the power house, cable and fibre-optic coating.
The test of carrying out with cone calorimetry
In order to verify the flame retarding efficiency of nanocomposite samples, according to standard ASTM E 1354-97, use heat-curable matrix and thermoplastic matrix, utilize cone calorimetry to test.Will based on the nano-complex of hydrotalcite with make comparisons based on the nano-complex of montmorillonite and based on the non-halogenated flame retardent of ammonium polyphosphate.
The preparation sample
For three samples of various types of materials preparation, sample size is the 100x100x8 millimeter
3Select 5 class materials:
1. with 30phr reticulation agent Jeffammina D230 (amino-terminated polyoxypropylene diene) Resins, epoxy DER 331 into the net (DGEBA).
2. the Dellite AP (being produced by Laviosa) with Jeffammina D230 and 5 weight % (uses industry uncle ammonium salt C
16-C
18The montmorillonite of modification) Resins, epoxy DER 331 into the net.
3. use EXOLIT AP422 (ammonium polyphosphate (APP) is produced by Ke Lairuite (Clariant)) the Resins, epoxy DER 331 into the net of Jeffammina D230 and 5 weight %.
4. use hydrotalcite (MG61/pTS) the Resins, epoxy DER 331 into the net of the tosilate modification of Jeffammina D230 and 5 weight %.
5. use hydrotalcite (MG61/ABS) the Resins, epoxy DER 331 into the net of the amino phenyl sulfonyl hydrochlorate modification of Jeffammina D230 and 5 weight %.
The dispersion of ammonium polyphosphate (APP) was carried out by simple and mechanical stirring under 50 ℃ in 10 minutes.Nanocomposite samples is carried out the dissipation of heat processing, is also referred to as swelling treatment, and this processing is by stirring (about 400rpm) 12 hours fast and stirring under 120 ℃ temperature and carried out in 2 hours under 80 ℃ the temperature.Particularly, for the hydrotalcite of pTS modification, use acetone as solvent, this is because the consistency of filler and resin is low.The cure cycle that all samples experience is identical: handled 5 hours down at 50 ℃, handled 2 hours down at 110 ℃.Low initial temperature has been guaranteed slow one-tenth net, and resin viscosity declines to a great extent simultaneously; Described feature has promoted mixing of nano-complex.
The nanostructure of sample
The sample of series 2,4 and 5 is nanocomposite samples.
The XRD analysis of the sample of series 2 does not show diffraction peak, and the TEM test shows that interfloor distance is about 76 dusts.
The XRD test of the sample of series 4 shows that it has the structure of blending, and identity distance is 24 dusts.The interfloor distance of the sample of series 5 is 56 dusts (XRD and TEM tests).
Analysis to the cone calorimetry test result
The feature growth of rate of heat release (HRR) curve when having measured 5 class testings of materials by experiment.Table 1 comprises the related data of described 15 samples (3 samples of every kind of material of 5 kinds of materials), comprises the standard deviation (σ) between mean value (x) and two samples of every kind of material, and described mean value is with respect to the percent change (Δ) of the resin that does not contain filler.
Weight loss
From the weight loss shown in the table 1, infer easily how surprising the effect of ammonium polyphosphate (APP) has; The weight in average loss is about 9.9%, promptly is lower than the weight loss of other sample.The weight loss of nanocomposite samples is about 90%, promptly increases by 5% for Dellite ammonium polyphosphate (DelAP) and MG61/pTS residual volume, and increases by 6% for MG61/ABS.Consider corresponding with compatilizer 40% Nano filling weight, then can observe the trend that the carbon residual volume of matrix rises.Especially, aspect the formation of promotion coke, hydrotalcite is more effective than montmorillonite, and this is because 40% weight loss takes place the brucite layer; And in two kinds of hydrotalcites of test, MG61/ABS provides higher carbonization.
Exothermic peak (PHHR)
And in this case, ammonium polyphosphate (APP) provides optimal results, promptly compares with the peak value 1181 of virgin resin, and peak value (449) has reduced 62%.But the peak value of MG61/ABS is 584, significantly reduces 51%.In addition, use an advantage of nano-complex hydrotalcite to be confirmed by reduce (being equivalent to 27%) of comparing montmorillonite peak value (861.5).Also absorbing is to use MG61/ABS can access rate of heat release (HRR) curved profile different with other nano-complex; In fact, in other sample, can observe in the back rate of heat release of catching fire and reach peak value immediately, and no longer increase.Different curved profiles seems and forms the infusible of anti-combustion swelling structurally associated.The flame resistivity of coke and MG61/ABS and MG61/pTS are similar, but in first kind of situation, and swelling effect is more obvious, this may be because in compatilizer, exist nitrogen and after discharge gaseous ammonia.
Rate of heat release
The effect value is identical in various samples, but the percentage ratio that rate of heat release reduces is lower.
Than extinguishing area (Specific extinction area)
The intensity of variation of cigarette opacity is lower in various samples, yet has only montmorillonite to show increase slightly (+3.2%) with respect to the virgin resin opaqueness.
Ignition time
Use ammonium polyphosphate (APP) to reduce thermostability, thereby will shorten 29% ignition time.(DelAP) do not change ignition time for the Dellite ammonium polyphosphate, shortens ignition time for MG61/pTS (10%), and prolongs slightly ignition time for MG61/ABS (2.7%).This difference is because the different in kind of employed compatilizer causes.In the situation of MG61/ABS (amino phenyl sulfonyl hydrochlorate) and Dellite ammonium polyphosphate (DelAP, uncle's ammonium salt), compatilizer and epoxide group reaction form a kind of and resin structure into the net; On the contrary, in the situation of MG61/pTS, compatilizer decomposes, and discharges inflammable gas subsequently, causes the burning of the material of expecting.
Combustion time
In this case, can observe distinct phenomenon in the situation of ammonium polyphosphate (APP) and nano-complex, this is because fire-retardant mechanism is different fully.The shortening of combustion time is given the credit to have formed and is protected base material to avoid the carbon-coating of radiations heat energy for ammonium polyphosphate (APP).In other situation, sample burnouts fully, but the shielding effect relevant with the intrinsic perviousness of used clay pervasion gas reduced rate of combustion, increased combustion time.Therefore, combustion time is long more, and the effect of Nano filling is big more.The splendid effect of ammonium polyphosphate (APP) is relevant with swelling effect: ratio of expansion (ratio of structural thickness and original depth after the swelling) is about 40.The carbon foam of Chan Shenging suffocates flame like this, prevents that lower-layer resin from burning.But, should point out that the coke that is produced has relatively poor mechanical properties, low to the tack of base material; Therefore, the result who obtains with cone calorimetry is also because sample levels placement and coke are positioned on the described sample causes.In fact, after end of test (EOT), if sample is put upside down, coke comes off fully, exposes unlapped lower-layer resin, and burning is proceeded.In order to understand the cognation of this phenomenon, should think that for vertical combustion test-types UL94VB the required concentration of ammonium polyphosphate (APP) is 30 weight % (for identical resin and reticulation agent DER331 Jeffammina).The 5 weight % concentration that picture is used for the cone calorimetry test are not enough, can observe the tendency that drippage or coke break away from.And, to compare with thermosetting polymer, the proneness of dripping described in the described thermoplastic polymer is more relevant certainly.One of character of nano-complex is to have reduced the proneness of drippage by the viscosity that increases melting product.This is the reason that collaboration system hydrotalcite-ammonium polyphosphate (APP) can be advantageously used in the UL94VB test, particularly for thermoplastic matrix.
The UL94 combustion testing
In order to find to obtain the Cmin of APP in the required Resins, epoxy (der331) of material V0 (UL94 standard), carried out one group of test: find that described concentration is 30%.Condition of cure is to handle 5 hours down at 50 ℃, handles 2 hours down at 110 ℃.For relatively, prepared one group of sample that contains the MG61/ABS of 4 weight %, to find to obtain the Cmin of the required APP of material V0: this concentration is 20%.Therefore, use nano-complex hydrotalcite (4%) will realize that required ammonium polyphosphate (APP) concentration of rank V0 is reduced to 20 weight % from 30 weight %.
Table 1
Claims (13)
1. nano-complex polymer coating, it comprises polymeric matrix, hydrotalcite and phosphorus compound.
2. coating as claimed in claim 1 is characterized in that, the compatilizer modification of the surface of described hydrotalcite; Preferred described compatilizer is an organic acid.
3. coating as claimed in claim 2 is characterized in that, described organic acid is selected from down group: tosic acid (pTSA), p-hydroxybenzenyl sulfonate (IBS), m-sulfanilic acid (ABS), stearic acid or oleic acid.
4. as each described coating in the claim 1 to 3, it is characterized in that described polymeric matrix is a thermosetting polymer.
5. coating as claimed in claim 4 is characterized in that, described thermosetting polymer is selected from down group: Resins, epoxy, polyester, vinyl ester or phenol resins.
6. as each described coating in the claim 1 to 3, it is characterized in that described polymeric matrix is a thermoplastic polymer.
7. coating as claimed in claim 6 is characterized in that, described thermoplastic polymer is selected from down group: polypropylene, polyethylene, polyethylene terephthalate.
8. as each described coating in the claim 1 to 7, it is characterized in that described phosphorus compound is selected from down group: organo phosphorous compounds, element phosphor, red phosphorus, ammonium polyphosphate or diammonium phosphate.
9. coating as claimed in claim 8 is characterized in that described phosphorus compound is an ammonium polyphosphate.
10. coating as claimed in claim 8 is characterized in that, is benchmark in the gross weight of described material, and the content of described phosphorus compound is less than 35 weight %.
11. prepare the method for flame retardant resistance nano-complex coating, this method may further comprise the steps:
A) with compatilizer hydrotalcite is carried out surface modification;
B) hydrotalcite with modification is dispersed in the polymer coating matrix;
C) in polymer coating matrix, add reticulation agent;
D) in polymer coating matrix, add phosphorus compound;
E) pour in the mould; With
F) solidify the coating that obtains by thermal cycling.
12. the nano-complex polymer coating that comprises polymeric matrix and hydrotalcite has application in the article of flame retardant resistance in preparation.
13. have application in the article of flame retardant resistance in preparation as each described coating in the claim 1 to 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810176779A CN101735681A (en) | 2008-11-18 | 2008-11-18 | Polymer nanocomposite flame-retardant intumescent coating, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810176779A CN101735681A (en) | 2008-11-18 | 2008-11-18 | Polymer nanocomposite flame-retardant intumescent coating, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101735681A true CN101735681A (en) | 2010-06-16 |
Family
ID=42459725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810176779A Pending CN101735681A (en) | 2008-11-18 | 2008-11-18 | Polymer nanocomposite flame-retardant intumescent coating, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101735681A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329567A (en) * | 2011-07-13 | 2012-01-25 | 大连美宸特科技有限公司 | Liquid rubber spray paint containing hydrotalcite |
| CN104293113A (en) * | 2014-10-20 | 2015-01-21 | 苏州常熟荣大威尔科技有限公司 | Gas pressure reducer |
| CN104761970A (en) * | 2015-03-18 | 2015-07-08 | 蚌埠市高华电子有限公司 | Radiative heat-insulation aqueous coating being good in waterproof effect and preparation method thereof |
| CN105440564A (en) * | 2015-12-30 | 2016-03-30 | 衢州学院 | Halogen-free and flame-retardant ABS (acrylonitrile butadiene styrene) composite and preparation method thereof |
| CN108084472A (en) * | 2017-12-11 | 2018-05-29 | 北京理工大学 | Hydrotalcite/phosphorus-nitrogen containing flame retardant compositional flame-retardant PET material and preparation method thereof |
| CN110183684A (en) * | 2019-06-13 | 2019-08-30 | 西北师范大学 | A kind of modified oil shale semicoke and preparation method thereof and the application in high molecular material |
| CN110423051A (en) * | 2019-07-26 | 2019-11-08 | 山东康氧之家新材料科技有限责任公司 | A kind of biomass oxygen cotton mud |
-
2008
- 2008-11-18 CN CN200810176779A patent/CN101735681A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329567A (en) * | 2011-07-13 | 2012-01-25 | 大连美宸特科技有限公司 | Liquid rubber spray paint containing hydrotalcite |
| CN104293113A (en) * | 2014-10-20 | 2015-01-21 | 苏州常熟荣大威尔科技有限公司 | Gas pressure reducer |
| CN104761970A (en) * | 2015-03-18 | 2015-07-08 | 蚌埠市高华电子有限公司 | Radiative heat-insulation aqueous coating being good in waterproof effect and preparation method thereof |
| CN105440564A (en) * | 2015-12-30 | 2016-03-30 | 衢州学院 | Halogen-free and flame-retardant ABS (acrylonitrile butadiene styrene) composite and preparation method thereof |
| CN108084472A (en) * | 2017-12-11 | 2018-05-29 | 北京理工大学 | Hydrotalcite/phosphorus-nitrogen containing flame retardant compositional flame-retardant PET material and preparation method thereof |
| CN110183684A (en) * | 2019-06-13 | 2019-08-30 | 西北师范大学 | A kind of modified oil shale semicoke and preparation method thereof and the application in high molecular material |
| CN110183684B (en) * | 2019-06-13 | 2021-10-15 | 烟台佳合高分子材料有限公司 | Modified oil shale semicoke, preparation method thereof and application thereof in high polymer material |
| CN110423051A (en) * | 2019-07-26 | 2019-11-08 | 山东康氧之家新材料科技有限责任公司 | A kind of biomass oxygen cotton mud |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhan et al. | Synergistic effects of sepiolite on the flame retardant properties and thermal degradation behaviors of polyamide 66/aluminum diethylphosphinate composites | |
| Laoutid et al. | New prospects in flame retardant polymer materials: From fundamentals to nanocomposites | |
| Lim et al. | A review of application of ammonium polyphosphate as intumescent flame retardant in thermoplastic composites | |
| Su et al. | Synergistic effect of zinc hydroxystannate with intumescent flame-retardants on fire retardancy and thermal behavior of polypropylene | |
| Lu et al. | A review on flame retardant technology in China. Part II: flame retardant polymeric nanocomposites and coatings | |
| CN101735681A (en) | Polymer nanocomposite flame-retardant intumescent coating, preparation method and application thereof | |
| Feng et al. | Synergistic effect of La2O3 on the flame retardant properties and the degradation mechanism of a novel PP/IFR system | |
| Prabhakar et al. | A review on the flammability and flame retardant properties of natural fibers and polymer matrix based composites | |
| Davies et al. | The sensitisation of thermal decomposition of ammonium polyphosphate by selected metal ions and their potential for improved cotton fabric flame retardancy | |
| Vannier et al. | The use of POSS as synergist in intumescent recycled poly (ethylene terephthalate) | |
| Qin et al. | Study on inorganic modified ammonium polyphosphate with precipitation method and its effect in flame retardant polypropylene | |
| Qu et al. | A novel intumescent flame retardant and smoke suppression system for flexible PVC | |
| De Fenzo et al. | Effects of zinc-based flame retardants on the degradation behaviour of an aerospace epoxy matrix | |
| Gibertini et al. | Silica-encapsulated red phosphorus for flame retardant treatment on textile | |
| Qin et al. | Synergistic effect of modified expanded graphite and zinc borate on the flammability, thermal stability and crystallization behavior of LLDPE/EVA composites with Mg (OH) 2/Al (OH) 3 | |
| Wu et al. | Synergist flame retarding effect of ultrafine zinc borate on LDPE/IFR system | |
| Kang et al. | Effect of hollow glass microsphere on the flame retardancy and combustion behavior of intumescent flame retardant polypropylene composites | |
| Zhuo et al. | The synergistic effect of hollow glass microsphere in intumescent flame-retardant epoxy resin | |
| Mahajan et al. | Hydrated and anhydrous zinc borate fillers for tuning the flame retardancy of epoxy nanocomposites | |
| Zhou et al. | In situ synthesis of layered double hydroxides-silicon dioxide hybrids and its flame retardancy in EVA composites | |
| Polat et al. | Use of boron oxide and boric acid to improve flame retardancy of an organophosphorus compound in neat and fiber reinforced polyamide‐6 | |
| Catarina et al. | Development of acrylic‐based powder coatings with incorporation of montmorillonite clays | |
| CN106397963B (en) | A kind of halogen-free intumescent flame-retardant EVA based composites and preparation method thereof | |
| Mahajan et al. | Stannate and surface functionalized molybdate of zinc for enhanced flame retardancy of epoxy nanocomposites | |
| Chen et al. | Synergistic effects of iron powder on intumescent flame retardant polypropylene system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100616 |