CN105038521B - A kind of metal Ludox expandable flame retardant coating and preparation method thereof - Google Patents
A kind of metal Ludox expandable flame retardant coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of metal Ludox expandable flame retardant coating and preparation method thereof, by silane coupler, metallic compound and H2O hybrid reactions obtain metal Ludox, are dissolved in acrylic acid, add epoxy acrylic resin and light trigger, coating is obtained, by coating even spread prepares coating, illumination curing film forming, metal Ludox expandable flame retardant coating is produced, with higher expandable flame retardant performance and good practicality.
Description
Technical field
The present invention relates to a kind of metal-silicon colloidal sol expandable flame retardant coating and preparation method thereof.
Background technology
Expansion type flame retardant has been a kind of new, efficient, environmental protection fire retardant since halogen containing flame-retardant, with low
The characteristics of poison, few cigarette, be most widely used fireproof coating kind in recent years.Wherein, silicon-series five-retardant is a kind of excellent resistance
Agent is fired, the good mechanical performance of anti-flaming dope, heat resistance and the protecting effect in terms of environment can be assigned, but silicon systems hinder
Combustion agent also have the shortcomings that at fire-retardant aspect it is a lot, at present, in order to make up this respect deficiency, it is necessary to be modified to it.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art part, there is provided a kind of metal-silicon colloidal sol expandable flame retardant
Coating and preparation method thereof, obtained metal-silicon colloidal sol expandable flame retardant coating has higher expandable flame retardant performance and good real
The property used.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of preparation method of metal-silicon colloidal sol expandable flame retardant coating, including：
1) by silane coupler, metallic compound and H2O be well mixed, regulation solution pH value be 1~2 after, 14~
45~55 DEG C are warming up in 16min, is further continued for after 1.5~2.5h of reaction, product at reduced pressure suction filtration produces metal-silicon colloidal sol；It is described
Silane coupling reagent KH-570, metallic compound, H20 mol ratio is 0.04~0.06：0.0015~0.24：0.02~0.03；
2) by step 1) in after obtained metal-silicon colloidal sol is well mixed with acrylamide, acrylic acid, add propylene oxide
Acid resin and light trigger, it is well mixed to obtain coating；The metal-silicon colloidal sol, acrylamide, acrylic acid, epoxy acrylic
Resin, the mass ratio of light trigger are 0.18~4.5：0.4~3.5:0.4~2.5:1.4~7:0.10~0.85；Applied described
Material is spread evenly across on the dry glass plate of cleaning, and illumination curing produces metal-silicon colloidal sol expandable flame retardant coating.
In one embodiment：The step 1) in, metallic compound is ZnCl2, the Silane coupling reagent KH-570, metallization
Compound, H20 mol ratio is 0.04~0.06：0.06~0.07：0.02~0.03, Zn-Si colloidal sols are made；The step 2)
In, Zn-Si colloidal sols, acrylamide, acrylic acid, epoxy acrylic resin, the mass ratio of light trigger are 0.28~3.5：1.5~
3:0.8~1.2:3.8~6.8：0.11~0.45.
In one embodiment：The step 1) in, metallic compound is ZnCl2, the Silane coupling reagent KH-570, metallization
Compound, H20 mol ratio is 0.04~0.06：0.06~0.07：0.02~0.03, Zn-Si colloidal sols are made；The step 2)
In, Zn-Si colloidal sols, acrylamide, acrylic acid, epoxy acrylic resin, the mass ratio of light trigger are 1.4~1.6：1.8~
2.2:0.9~1.1:5.4~5.6:0.38~0.42.
In one embodiment：The step 1) in, metallic compound is SnCl4·5H2O, the Silane coupling reagent KH-570,
Metallic compound, H20 mol ratio is 0.04~0.06：0.04~0.05：0.02~0.03, Sn-Si colloidal sols are made；The step
It is rapid 2) in, Sn-Si colloidal sols, acrylamide, acrylic acid, epoxy acrylic resin, light trigger mass ratio be 0.4~4.5：
1.8~2.2:0.8~1.2:2.5~7：0.1~0.45.
In one embodiment：The step 1) in, metallic compound is AlCl3·6H2O, the Silane coupling reagent KH-570,
Metallic compound, H20 mol ratio is 0.04~0.06：0.005~0.025：0.02~0.03, Al-Si colloidal sols are made；
Or：The step 1) in, metallic compound is MnCl2·4H2O, the Silane coupling reagent KH-570, metal compound
Thing, H20 mol ratio is 0.04~0.06：0.005~0.015：0.02~0.03, Mn-Si colloidal sols are made；
Or：The step 1) in, metallic compound is La (NO3)3·6H2O, the Silane coupling reagent KH-570, metallization
Compound, H20 mol ratio is 0.04~0.06：0.004~0.006：0.02~0.03, La-Si colloidal sols are made；
Or：The step 1) in, metallic compound is NaH2PO4·2H2O, the Silane coupling reagent KH-570, metallization
Compound, H20 mol ratio is 0.04~0.06：0.01~0.03：0.02~0.03, Na-Si colloidal sols are made.
In one embodiment：The step 1) in, metallic compound is AlCl3·6H2O and ZnCl2, the silane coupler
KH-570, metallic compound, H20 mol ratio is 0.04~0.06：0.01~0.02：0.02~0.03, and AlCl3·6H2O
And ZnCl2Mol ratio be 0.003~0.005：0.01~0.012, Al-Zn-Si colloidal sols are made；The step 2) in, Al-
Zn-Si colloidal sols, acrylamide, acrylic acid, epoxy acrylic resin, the mass ratio of light trigger are 0.8~3.2：1.8~3.2:
0.8~1.7:3~6.5：0.1~0.45.
In one embodiment：The step 1) in, metallic compound is AlCl3·6H2O and NaH2PO4·2H2O, the silane
Coupling agent kh-570, metallic compound, H20 mol ratio is 0.04~0.06：0.005~0.015：0.02~0.03, and
AlCl3·6H2O and NaH2PO4·2H2O mol ratio is 0.002~0.003：0.007~0.008, Al-Na-Si colloidal sols are made；
Or：The step 1) in, metallic compound is AlCl3·6H2O and MnCl2·4H2O, the silane coupler KH-
570th, metallic compound, H20 mol ratio is 0.04~0.06：0.01~0.015：0.02~0.03, and AlCl3·6H2O and
MnCl2·4H2O mol ratio is 0.003~0.005：0.007~0.009, Al-Mn-Si colloidal sols are made；
Or：The step 1) in, metallic compound is ZnCl2And SnCl4·5H2O, the Silane coupling reagent KH-570, gold
Belong to compound, H20 mol ratio is 0.04~0.06：0.07~0.095：0.02~0.03, and ZnCl2And SnCl4·5H2O it
Mol ratio is 0.06~0.07：0.005~0.03, Zn-Sn-Si colloidal sols are made.
In one embodiment：The step 1) in, metallic compound is AlCl3·6H2O、ZnCl2And SnCl4·5H2O, it is described
Silane coupling reagent KH-570, metallic compound, H20 mol ratio is 0.04~0.06：0.01~0.02：0.02~0.03, and
AlCl3·6H2O、ZnCl2And SnCl4·5H2O mol ratio is 0.002~0.004：0.008~0.01：0.002~0.004,
Al-Zn-Sn-Si colloidal sols are made；The step 2) in, Al-Zn-Sn-Si colloidal sols, acrylamide, acrylic acid, epoxy acrylic tree
Fat, the mass ratio of light trigger are 1.4~3.2：0.8~2.2:0.4~1.2:2~5.5：0.1~0.35.
In one embodiment：The step 1) in, metallic compound is AlCl3·6H2O、SnCl4·5H2O and Na2SiO3, institute
State Silane coupling reagent KH-570, metallic compound, H20 mol ratio is 0.04~0.06：0.02~0.03：0.02~0.03,
And AlCl3·6H2O、NaH2PO4·2H2O and Na2SiO3Mol ratio be 0.002~0.004：0.005~0.007：0.01~
0.02, Si-Na-Al-Si colloidal sols are made；
Or：The step 1) in, metallic compound is AlCl3·6H2O、ZnCl2With Ni (NO3)2·6H2O, the silane
Coupling agent kh-570, metallic compound, H20 mol ratio is 0.04~0.06：0.01~0.02：0.02~0.03, and
AlCl3·6H2O、ZnCl2With Ni (NO3)2·6H2O mol ratio is 0.002~0.004：0.005~0.007：0.005~
0.007, Al-Zn-Ni-Si colloidal sols are made；
Or：The step 1) in, metallic compound is AlCl3·6H2O、SnCl4·5H2O and Ni (NO3)2·6H2O, institute
State Silane coupling reagent KH-570, metallic compound, H20 mol ratio is 0.04~0.06：0.01~0.015：0.02~0.03,
And AlCl3·6H2O、SnCl4·5H2O and Ni (NO3)2·6H2O mol ratio is 0.002~0.004：0.005~0.007：
0.002~0.004, Al-Sn-Ni-Si colloidal sols are made.
In one embodiment：The silane coupler is KH-570；The light trigger is light trigger 1173.
Reagent, instrument, method involved in the present invention etc., are this area routine techniques unless otherwise stated.
The technical program is compared with background technology, and it has the following advantages that：
1. the metal-silicon colloidal sol that the present invention is obtained, in combustion, silicon-containing material moves to material at slightly higher temperature
The surface of material, could be formed with effect protective layer, hinder the diffusion of heat transfer and imflammable gas, retarded combustion speed and heat are released
Speed is put, so as to improve anti-flammability；Meanwhile, metal ion can make material rapid-result soon as catalysis carbon-forming center in itself
Charcoal；Both can play excellent expandable flame retardant effect at combination, and oxygen index (OI) reaches as high as 46, and vertical combustion rank reaches V-0 grades.
2. the metal-silicon colloidal sol that the present invention is obtained also has solidification in itself, and metal-silicon colloidal sol also can be as fire-retardant
Monomer is used, using the metal-silicon colloidal sol expandable flame retardant coating of its preparation, and hardening time is shorter, and flame retardant effect is more preferable.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is KH-570 hydrolysate infrared spectrum spectrograms.
Fig. 2 is Zn-Si colloidal sol infrared spectrum spectrograms.
Fig. 3 is Zn-Si colloidal sol expandable flame retardant coating real-time infrared spectroscopy spectrograms.
Fig. 4 is Zn-Si colloidal sol expandable flame retardant coating thermogravimetric analysis figures.
Fig. 5 is Zn-Si colloidal sol expandable flame retardant coating HRR analysis charts.
Fig. 6 is Al-Si colloidal sols (I) expandable flame retardant coating transmittance figure.
Fig. 7 is Al-Si colloidal sols (II) expandable flame retardant coating transmittance figure.
Fig. 8 is Mn-Si colloidal sol expandable flame retardant coating transmittance figures.
Fig. 9 is La-Si colloidal sol expandable flame retardant coating transmittance figures.
Figure 10 is Sn-Si colloidal sol expandable flame retardant coating transmittance figures.
Figure 11 is Zn-Si colloidal sol expandable flame retardant coating transmittance figures.
Figure 12 is Al-Na-Si colloidal sol expandable flame retardant coating transmittance figures.
Figure 13 is Al-Mn-Si colloidal sol expandable flame retardant coating transmittance figures.
Figure 14 is Al-Zn-Si colloidal sol expandable flame retardant coating transmittance figures.
Figure 15 is Al-Zn-Sn-Si colloidal sol expandable flame retardant coating transmittance figures.
Figure 16 is Al-Zn-Ni-Si colloidal sol expandable flame retardant coating transmittance figures.
Figure 17 is Al-Sn-Ni-Si colloidal sol expandable flame retardant coating transmittance figures.
Figure 18 is Zn-Sn-Si colloidal sols (I) expandable flame retardant coating transmittance figure.
Figure 19 is Zn-Sn-Si colloidal sols (II) expandable flame retardant coating transmittance figure.
Figure 20 be Zn-Si colloidal sol expandable flame retardant coating burns breeze patterns, be followed successively by from left to right embodiment 34,35,36,
37th, 38,39,40,41 Zn-Si colloidal sol expandable flame retardant coating burns breeze patterns.
Embodiment
Present disclosure is illustrated below by embodiment：
Embodiment 1~93
1) according to the ratio in table 1, by 0.05mol Silane coupling reagent KH-570s, 0.002~0.23mol metallic compounds
And 0.025mol H2O is poured into single-necked flask, and flask is placed in oil bath pan, and it is well mixed using electric stirring, is used
HCl regulation solution pH value be 1~2 after, 50 DEG C are warming up in 15min, be further continued for reaction 2h after, product at reduced pressure suction filtration produces phase
The metal-silicon colloidal sol answered；
2) according to the ratio of table 2~17, by step 1) in obtained metal-silicon colloidal sol mixed with acrylamide, acrylic acid,
First hand operated mixing adds epoxy acrylic resin (EA) and light trigger 1173, continued after ultrasonic vibration makes it well mixed again
Ultrasonic vibration is well mixed to obtain coating；Glass plate is cleaned up, and drying is cleaned with absolute ethyl alcohol, with 100 μm of wet film systems
The coating is spread evenly across on the glass plate of cleaning drying by standby device, is prepared the coating that thickness is 100 μm, is used
1000W/cm2High voltage mercury lamp radiation coating make its film-forming, produce corresponding metal-silicon colloidal sol expandable flame retardant coating.
The metal-silicon sol formulation of table 1
Table 2 Al-Si colloidal sols (I) expandable flame retardant coating formula
The Mn-Si colloidal sol expandable flame retardant coating formulas of table 3
The La-Si colloidal sol expandable flame retardant coating formulas of table 4
The Na-Si colloidal sol expandable flame retardant coating formulas of table 5
Table 6 Al-Si colloidal sols (II) expandable flame retardant coating formula
The Sn-Si colloidal sol expandable flame retardant coating formulas of table 7
The Zn-Si colloidal sol expandable flame retardant coating formulas of table 8
The Al-Na-Si colloidal sol expandable flame retardant coating formulas of table 9
The Al-Mn-Si colloidal sol expandable flame retardant coating formulas of table 10
The Al-Zn-Si colloidal sol expandable flame retardant coating formulas of table 11
Table 12 Zn-Sn-Si colloidal sols (I) expandable flame retardant coating formula
Table 13 Zn-Sn-Si colloidal sols (II) expandable flame retardant coating formula
The Si-Na-Al-Si colloidal sol expandable flame retardant coating formulas of table 14
The Al-Zn-Ni-Si colloidal sol expandable flame retardant coating formulas of table 15
The Al-Zn-Sn-Si colloidal sol expandable flame retardant coating formulas of table 16
The Al-Sn-Ni-Si colloidal sol expandable flame retardant coating formulas of table 17
The effect of following experimental examples can be achieved in above-described embodiment：
Experimental example 1：Zn-Si colloidal sol infrared analysis
IR Characterization is carried out to sample using German BRUKER company's Ts ENSOR27 types Fourier infrared spectrograph, model is scanned
Enclose for 500~4000cm-1.By solid sample and KBr according to mass ratio 1：30 proportioning is mixed, after grinding is uniform, tabletting
Detection, then Direct Uniform is applied on the chip of KBr product liquid, is detected.
The Zn-Si colloidal sols obtained in embodiment 34~41 are subjected to infrared spectrum analysis as stated above, as shown in Figure 2,
KH-570 infrared spectrum spectrogram (Fig. 1) is contrasted, in 1107cm-1Place occurs in that a new peak, and this is Si-O-Zn absorption
Peak, illustrates ZnCl2Reacted with KH-570 so that Zn in the form of chemical bond to be connected in KH-570, so as to prove shape
Into Zn-Si colloidal sols.
Experimental example 2：Zn-Si colloidal sol expandable flame retardant coatings REAL TIME INFRARED THERMAL IMAGE is analyzed
REAL TIME INFRARED THERMAL IMAGE can be used for condensed phase in the metal-silicon colloidal sol expandable flame retardant coating thermal degradation process prepared by research
Learn the change of structure.
It refer in the Zn-Si colloidal sol expandable flame retardant coating REAL TIME INFRARED THERMAL IMAGE analysis results obtained in Fig. 3, embodiment 38, figure
As can be seen that 3458cm-1The absworption peak at place is-OH absworption peak, and the peak disappears at 300 DEG C, illustrates that degraded is complete；
2946cm-1The absworption peak at place is-CH3With-CH2Absworption peak, the peak gradually dies down with the rise of temperature, disappeared at 390 DEG C
Lose complete；1718cm-1Place is the C=O of carboxyl absworption peak, and the peak gradually dies down with the rise of temperature, is disappeared at 270 DEG C
Completely；1672cm-1It is the absworption peak of the carbonyl of amide groups, the peak gradually dies down with the rise of temperature, has been disappeared at 300 DEG C
Entirely, 1617cm-1Place and 1530cm-1Locate as the stretching vibration absworption peak of-N-C=O (acid amides), absworption peak base at 300 DEG C
This degraded is complete, 1125cm-1Place is Si-O-Zn absworption peak, is degraded at 270 DEG C complete, shows that now zinc ion turns into not
Restricted free ion, can be with catalytic polymer into charcoal.This Si-O-Zn degrades what is decomposed in advance completely at 270 DEG C
Phenomenon, is conducive to improving coating into charcoal effect and fire resistance.Final polymer is degraded completely near 390 DEG C, and higher than
During this temperature, only in 1611cm-1There is the characteristic absorption peak of fused ring compound in place.In summary, the coating is in 390 DEG C of degraded bases
This completely, and forms good fire-retardant layer of charcoal.
Experimental example 3：Zn-Si colloidal sol expandable flame retardant coating thermogravimetric analysis
The heat endurance of obtained solidify coating is studied by thermogravimetric analysis.By sample SDT2960 type thermogravimetric analysis
Instrument is analyzed.Temperature control is in room temperature between 800 DEG C, and programming rate is 10 DEG C/min, is measured in atmosphere.
Fig. 4 is refer to, is the Zn-Si colloidal sol expandable flame retardant coating thermal gravimetric analysis results obtained in embodiment 37~41, heat
Weight analysis refer to that under the temperature control function of program the weight of coating changes with the situation of change of temperature.It can be seen by Fig. 4
Go out, the thermal degradation process of coating is divided into three phases, and 0~200 DEG C, degradation curve is very gentle, and this is due to coating own absorption
Fraction water evaporation caused by, 200 DEG C~400 DEG C coatings degraded than very fast, slope of a curve is than larger, and in drop
CO is generated during solution2, at 400~800 DEG C, the degradation speed of coating is slack-off, finally tends towards stability.Illustrate that Zn-Si is molten
Glue expandable flame retardant coating has very high stability in high temperature.
Experimental example 4：Zn-Si colloidal sol expandable flame retardant coatings HRR is analyzed
According to GB/T 16172-2007 standards, the measure of HRR is carried out with JCZ-1 cone amount instrument.
Fig. 5 is refer to, is the Zn-Si colloidal sol expandable flame retardant coatings HRR point obtained in embodiment 34,37~41
Analyse result, it can be seen from the figure that, it is different, the heat release of blank group embodiment 34 to be formulated different its HRR of coating
Speed highest, is 368kWm-2And its to start time of heat release also fast with respect to other groups.The best group of fire retardation is to implement
Example 38, that is, when Zn-Si sol contents are 15%, its HRR is minimum, is 198kWm-2, the fire-retardant effect of coating
Preferably, combustion intensity is minimum for fruit.
Experimental example 5：Metal-silicon colloidal sol expandable flame retardant coating transmittance is analyzed
The measure of coating transmittance uses ultraviolet/visible spectrophotometer, first that the metal-silicon made is molten during measure
Glue expandable flame retardant coating, is cut into the strip for accounting for the size of cuvette 2/3, uses blank cuvette for control group, is in wavelength
It is measured between 190-800nm.Coating transmittance be primarily used to characterize coating UV-vis light area to the absorption of light with
Through situation.The more high then coating transparency of transmitance is higher, and when as transparent flame-retardant coating, its effect is better.
Fig. 6~19 are obtained metal-silicon colloidal sol expandable flame retardant coating transmittance analysis result in section Example.It please look into
Read Fig. 6 and Fig. 7, it can be seen that the transmissivity of Al-Si colloidal sol expandable flame retardant coatings reduces with the increase of Al-Si sol contents：
With AlCl3·6H2The increase of O content, the transmissivity increase of Al-Si colloidal sol expandable flame retardant coatings.It is that Al-Si is molten in embodiment 21
When glue content is 3%, transmissivity highest is close to 80%.
It can be seen from Fig. 8~11 in 400~800nm visible region, remaining metal-silicon is molten in addition to metallic sodium
The highest transmissivity of glue expandable flame retardant coating is all higher than 70%, and transmissivity is preferable.The ultraviolet light transmission of the flame retardant coating containing Zn with
ZnCl2The increase change of content is smaller, illustrates ZnCl2Content on the influence of the transmissivity of metal-silicon colloidal sol expandable flame retardant coating compared with
It is small, transmissivity preferably Zn-Si colloidal sols expandable flame retardant coating and Sn-Si colloidal sol expandable flame retardant coatings.
As seen from Figure 12, the transmissivity of Al-Na-Si colloidal sols expandable flame retardant coating with Al-Na-Si sol contents increasing
Plus change greatly, blank group transmissivity is very low, and transmissivity is substantially reduced with the increase of Al-Na-Si sol contents；By Figure 13
It can be seen that the transmissivity of Al-Mn-Si colloidal sols is more steady with the changes of contents of Al-Mn-Si colloidal sols, substantially transmissivity is with gold
The increase of category-Si sol contents and raise.Comparatively the transmissivity of Al-Mn-Si colloidal sols expandable flame retardant coating is more stable, may
Be Al, Mn compatibility it is more preferable.
Comparison diagram 14,15 is it can be seen that the transmissivity of Al-Zn-Si colloidal sol expandable flame retardant coatings is with Al-Zn-Si sol contents
Increase and raise, the transmissivity change for adding metal-silicon colloidal sol expandable flame retardant coating after Sn is little.Transmissivity is relatively preferable,
Basically reach 70%.Illustrate that transmissivity influences of the Sn on Al-Zn-Si colloidal sol expandable flame retardant coatings is smaller.
Comparison diagram 16,17 is it can be seen that the transmissivity of Al-Zn-Ni-Si colloidal sol expandable flame retardant coatings preferably, is all higher than
70%, the Al-Zn-Ni-Si colloidal sol expandable flame retardant coatings up to prepared in embodiment 49, transmissivity close to 80%,
And the transmissivity of Al-Sn-Ni-Si colloidal sol expandable flame retardant coatings is changed greatly, and transmissivity between 190~600nm it is relatively low
40% or so.Understand, influences of the Zn to coating transmittance is less than Sn.
Comparison diagram 18,19 is it can be seen that the change of two kinds of metallic compound contents of Zn, Sn is to the metal-silicon colloidal sol that is made
Transmissivity influence is smaller, and as Zn-Sn-Si sol contents change in 400~800nm visible region, Zn-Sn-Si is molten
The transmissivity of glue expandable flame retardant coating is basically unchanged, and Zn-Sn-Si sol contents in Zn-Sn-Si colloidal sol expandable flame retardant coatings
Change it is smaller on the influence of the transmissivity of coating.
In summary：The transmissivity of metal-silicon colloidal sol expandable flame retardant coating subtracts with the increase of metal-silicon sol content
Small, the transmissivity of remaining metal-silicon colloidal sol expandable flame retardant coating is higher in addition to Al-Sn-Ni-Si colloidal sol expandable flame retardant coatings,
Up to more than 70%.
Experimental example 6：Metal-silicon colloidal sol expandable flame retardant coating is fire-retardant and Analysis of Physical
Coating hardness is determined：Standard with GB/T 6739 to determine.Specifically method of testing is：Coating to be measured is fixed
On the horizontal level, then the pencil cut it is stuck on request on propeller, it is in 45° angle with film to make it, and shaking screw rod makes
Pencil is with about 1mms-1Speed promote, since most hard pencil, the pencil of each hardness level draws five roads, until five roads
Untill cut does not scratch film, the hardness of this pencil is the hardness for representing surveyed coating.Chinese board pencil is selected in this test, firmly
Degree scope is 3B~6H, and wherein 6H is most hard, and 3B is most soft.
The carbon yield that burns is determined：When carbon yield is determined, first the sample of required measure is weighed up, sample carried out in air
Burning, and weigh the sample quality after burning.Carbon yield is measured as follows.
Wherein, m1、m2The quality of sample before and after respectively burning.
Coating limited oxygen index is determined：By GB2406-96 standards, it is measured with oxygen index measurer.Limited oxygen index
For the critical solubility of oxygen, when measurement, the length of flame is about 10mm, and the duration of ignition is：30s.I.e.：Light a fire 30s, batten
It can't burn, must also be toward eminence although the burning length that can burn in other words is less than 40mm, then it represents that oxygen concentration is relatively low
Adjust；If batten can be lighted in 30s, and batten burning length more than 40mm, then it represents that oxygen concentration is high, it is necessary to turn down.
So tested, until finding a critical oxygen concentration, i.e., as the limited oxygen index of the sample.
Vertical combustion rank UL-94 is tested：By GB 2408-80 standard testing UL-94, in WC-5400 type horizontal verticals
Tested on burning analyzer.Time of extinguishing is escape to as criterion from burning things which may cause a fire disaster using the sample of measure, by test result point
For Three Estate：V-0, V-1 and V-2 grades.Wherein V-0 is best, and required standard is pressed in continuous mode, is chosen after sample, will
It is fixed on the place away from 30cm above flame, then starts from below, with burning things which may cause a fire disaster continuous action 10s, if after flame leaves
Sample self-extinguishment immediately, will also act on 10s with flame continuation again.
Table 18 is refer to, is that the metal-silicon colloidal sol expandable flame retardant coating obtained in the embodiment of the present invention 1~93 is fire-retardant and thing
Manage performance analysis data.
The metal-silicon colloidal sol expandable flame retardant coating of table 18 is fire-retardant and Analysis of Physical
Embodiment 1~5 is the fire-retardant and physical property of Al-Si colloidal sol expandable flame retardant coatings, by table it can be seen that Al-Si is molten
The carbon yield highest 24.75% of glue expandable flame retardant coating, oxygen index (OI) is 31, and fire-retardant rank is V-0 grades.
Embodiment 6~10 is the fire-retardant and physical property of Mn-Si colloidal sol expandable flame retardant coatings, by table it can be seen that Mn-Si
The hardness of colloidal sol expandable flame retardant coating, carbon yield are of a relatively high, and carbon yield is up to 35.47%, and oxygen index (OI) is up to 43, fire-retardant
Rank is V-0.
Embodiment 11~15 is the fire-retardant and physical property of La-Si colloidal sol expandable flame retardant coatings, by table it can be seen that La-Si
The carbon yield of colloidal sol expandable flame retardant coating is relatively low, and when the content of La-Si colloidal sols is 30%, carbon yield is up to 20.93%, oxygen
Index is 27.
Embodiment 16~19 is the fire-retardant and physical property of Na-Si colloidal sol expandable flame retardant coatings, when Na-Si sol contents are
Preferably, carbon yield is up to 19.62% to the fire resistance of coating, and oxygen index (OI) is 26 when 15%, and fire-retardant rank is V-0 grades.
Embodiment 20~26 is the fire-retardant and physical property of Al-Si colloidal sol expandable flame retardant coatings, is implemented it can be seen from table
In example 24 when Al-Si sol contents are 40%, the carbon yield of coating is up to 21.24%, and oxygen index (OI) is 27, and fire-retardant rank is
V-0 grades.
Embodiment 27~33 is the fire-retardant and physical property of Sn-Si colloidal sol expandable flame retardant coatings, it can be seen that Sn-Si colloidal sols are swollen
In the embodiment 32 of swollen flame retardant coating, i.e., when the amount of Sn-Si colloidal sols is 30%, the fire-retardant and physical property of coating is best, carbon residue
Rate is 34.74%, and oxygen index (OI) is 41, and fire-retardant rank is V-0 grades, and the fire-retardant rank of this coating reaches V-0 grades, and oxygen index (OI) is equal
It is a kind of relatively good fire-retardant product of fire resistance up to more than 25.
Embodiment 34~41 is the fire-retardant and physical property of Zn-Si colloidal sol expandable flame retardant coatings, when the content of Zn-Si colloidal sols
For 15%, the carbon yield of coating is up to 38.37%, and oxygen index (OI) is 46, and fire-retardant rank is V-0 grades, and all metal-silicon colloidal sols
Only Zn-Si colloidal sol expandable flame retardant coatings have expansion in expandable flame retardant coating and highest expansion multiple reaches 100 times, illustrate Zn-
The flame retardant coating fire resistance of Si colloidal sols is best.
Embodiment 42~46 is the fire-retardant and physical property of Al-Na-Si colloidal sol expandable flame retardant coatings, when Al-Na-Si colloidal sols
Content be 13%, the carbon yield of coating is up to 23.25%, and oxygen index (OI) is 26, fire-retardant rank be V-0 grades.
Embodiment 47~52 be Mn-Al-Si colloidal sol expandable flame retardant coatings fire-retardant and physical property, by table it can be seen that
The fire-retardant and physical property of Mn-Al-Si colloidal sol expandable flame retardant coatings embodiment 52 is best, and the carbon yield of coating is
18.80%, hardness is 6H, and oxygen index (OI) is 23, and fire-retardant rank is V-1 grades.
Embodiment 53~58 be Al-Zn-Si colloidal sol expandable flame retardant coatings fire-retardant and physical property, by table it can be seen that
Al-Zn-Si colloidal sol expandable flame retardant coating highests carbon yield is 23.42%, and oxygen index (OI) is 28, and fire-retardant rank is V-0 grades, now
The content of Al-Zn-Si colloidal sols is 25%.Compare 42-46 group Al-Na-Si colloidal sol expandable flame retardants coating, 47-52 groups Mn- simultaneously
The fire-retardant and physical property of Al-Si colloidal sol expandable flame retardant coatings is understood：The fire-retardant and thing of Al-Zn-Si colloidal sol expandable flame retardant coatings
Manage better performances.
Embodiment 59~66 be Zn-Sn-Si colloidal sol expandable flame retardant coatings fire-retardant and physical property, by table it can be seen that
The fire-retardant and physical property of Zn-Sn-Si colloidal sol expandable flame retardant coatings compares with 53-58 groups, and carbon yield, hardness of coating etc. have increasing
Plus, highest carbon yield reaches 30.98%, and oxygen index (OI) reaches that 38, UL-94 burning ranks are all V-0 grades in addition to blank group, and coating
There is slight expansion.
Embodiment 67~73 is the fire-retardant and physical property of Zn-Sn-Si colloidal sol expandable flame retardant coatings, and highest carbon yield is
31.10%, oxygen index (OI) is 37, and fire-retardant rank is V-0 grades, and the expansion effect of coating improves, and illustrates that Zn has increase
The effect of flame retardant coating expansion effect, still further it can be seen that Zn have improve coating carbon yield effect, further illustrate metal-
It is Zn that preferable metal is acted in Ludox.
Embodiment 74~76 is the fire-retardant and physical property of Si-Al-Na-Si colloidal sol expandable flame retardant coatings, it can be seen that：Apply
The carbon yield of layer is below 20%, oxygen index (OI) and is less than V-1 less than 25, burning rank.
Embodiment 77~82 is the fire-retardant and physical property of Al-Zn-Ni-Si colloidal sol expandable flame retardant coatings, the highest of coating
Carbon yield is 24.61%, hardness be 5H and more than, burning rank reach V-0 grades, oxygen index (OI) is more than 27, of a relatively high.
Embodiment 83~88 is the fire-retardant and physical property of Al-Zn-Sn-Si colloidal sol expandable flame retardant coatings, can be seen by table
Go out, the carbon yield of coating is of a relatively high, up to 29.17%, hardness is 6H, oxygen index (OI) is 36, burning rank is V-0
Level, the fire-retardant and physical property of coating is relatively preferable.
Embodiment 89~93 is the fire-retardant and physical property of Al-Sn-Ni-Si colloidal sol expandable flame retardant coatings, the highest of coating
Carbon yield is 26.66%, and highest oxygen index (OI) is 29, and burning rank is essentially V-0.
In summary：Preferably, wherein Zn contents are 15%, 20% to Zn-Si colloidal sol expandable flame retardant coating expansions flame retardant effect
Two groups of sample expansion effects it is best.The effect of the catalysis carbon-forming of metal ion is Zn>Sn>Mn>La>Na>Al.
It is described above, only present pre-ferred embodiments, therefore the scope that the present invention is implemented can not be limited according to this, i.e., according to
The equivalent changes and modifications that the scope of the claims of the present invention and description are made, all should still belong in the range of the present invention covers.
Claims (10)
1. a kind of preparation method of metal-silicon colloidal sol expandable flame retardant coating, it is characterised in that：Including：
1) by Silane coupling reagent KH-570, metallic compound and H2O be well mixed, regulation solution pH value be 1~2 after, 14~
45~55 DEG C are warming up in 16min, is further continued for after 1.5~2.5h of reaction, product at reduced pressure suction filtration produces metal-silicon colloidal sol；It is described
Silane coupling reagent KH-570, metallic compound, H2O mol ratio is 0.04~0.06：0.0015~0.24：0.02~0.03；
2) by step 1) in after obtained metal-silicon colloidal sol is well mixed with acrylamide, acrylic acid, add epoxy acrylic tree
Fat and light trigger, it is well mixed to obtain coating；The metal-silicon colloidal sol, acrylamide, acrylic acid, epoxy acrylic resin,
The mass ratio of light trigger is 0.18~4.5：0.4~3.5:0.4~2.5:1.4~7:0.10~0.85；The coating is equal
Even to be coated on the dry glass plate of cleaning, illumination curing produces metal-silicon colloidal sol expandable flame retardant coating.
2. a kind of preparation method of metal-silicon colloidal sol expandable flame retardant coating according to claim 1, it is characterised in that：Institute
State step 1) in, metallic compound is ZnCl2, the Silane coupling reagent KH-570, metallic compound, H2O mol ratio is 0.04
~0.06：0.06~0.07：0.02~0.03, Zn-Si colloidal sols are made；The step 2) in, Zn-Si colloidal sols, acrylamide, third
Olefin(e) acid, epoxy acrylic resin, the mass ratio of light trigger are 0.28~3.5：1.5~3:0.8~1.2:3.8~6.8：0.11
~0.45.
3. a kind of preparation method of metal-silicon colloidal sol expandable flame retardant coating according to claim 1, it is characterised in that：Institute
State step 1) in, metallic compound is ZnCl2, the Silane coupling reagent KH-570, metallic compound, H2O mol ratio is 0.04
~0.06：0.06~0.07：0.02~0.03, Zn-Si colloidal sols are made；The step 2) in, Zn-Si colloidal sols, acrylamide, third
Olefin(e) acid, epoxy acrylic resin, the mass ratio of light trigger are 1.4~1.6：1.8~2.2:0.9~1.1:5.4~5.6:
0.38~0.42.
4. a kind of preparation method of metal-silicon colloidal sol expandable flame retardant coating according to claim 1, it is characterised in that：Institute
State step 1) in, metallic compound is SnCl4·5H2O, the Silane coupling reagent KH-570, metallic compound, H2O mol ratio
For 0.04~0.06：0.04~0.05：0.02~0.03, Sn-Si colloidal sols are made；The step 2) in, Sn-Si colloidal sols, propylene
Acid amides, acrylic acid, epoxy acrylic resin, the mass ratio of light trigger are 0.4~4.5：1.8~2.2:0.8~1.2:2.5~
7：0.1~0.45.
5. a kind of preparation method of metal-silicon colloidal sol expandable flame retardant coating according to claim 1, it is characterised in that：Institute
State step 1) in, metallic compound is AlCl3·6H2O, the Silane coupling reagent KH-570, metallic compound, H2O mol ratio
For 0.04~0.06：0.005~0.025：0.02~0.03, Al-Si colloidal sols are made；
Or：The step 1) in, metallic compound is MnCl2·4H2O, the Silane coupling reagent KH-570, metallic compound,
H2O mol ratio is 0.04~0.06：0.005~0.015：0.02~0.03, Mn-Si colloidal sols are made；
Or：The step 1) in, metallic compound is La (NO3)3·6H2O, the Silane coupling reagent KH-570, metal compound
Thing, H2O mol ratio is 0.04~0.06：0.004~0.006：0.02~0.03, La-Si colloidal sols are made；
Or：The step 1) in, metallic compound is NaH2PO4·2H2O, the Silane coupling reagent KH-570, metallic compound,
H2O mol ratio is 0.04~0.06：0.01~0.03：0.02~0.03, Na-Si colloidal sols are made.
6. a kind of preparation method of metal-silicon colloidal sol expandable flame retardant coating according to claim 1, it is characterised in that：Institute
State step 1) in, metallic compound is AlCl3·6H2O and ZnCl2, the Silane coupling reagent KH-570, metallic compound, H2O
Mol ratio be 0.04~0.06：0.01~0.02：0.02~0.03, and AlCl3·6H2O and ZnCl2Mol ratio be 0.003
~0.005：0.01~0.012, Al-Zn-Si colloidal sols are made；The step 2) in, Al-Zn-Si colloidal sols, acrylamide, propylene
Acid, epoxy acrylic resin, the mass ratio of light trigger are 0.8~3.2：1.8~3.2:0.8~1.7:3~6.5：0.1~
0.45。
7. a kind of preparation method of metal-silicon colloidal sol expandable flame retardant coating according to claim 1, it is characterised in that：Institute
State step 1) in, metallic compound is AlCl3·6H2O and NaH2PO4·2H2O, the Silane coupling reagent KH-570, metal compound
Thing, H2O mol ratio is 0.04~0.06：0.005~0.015：0.02~0.03, and AlCl3·6H2O and NaH2PO4·2H2O
Mol ratio be 0.002~0.003：0.007~0.008, Al-Na-Si colloidal sols are made；
Or：The step 1) in, metallic compound is AlCl3·6H2O and MnCl2·4H2O, the Silane coupling reagent KH-570,
Metallic compound, H2O mol ratio is 0.04~0.06：0.01~0.015：0.02~0.03, and AlCl3·6H2O and
MnCl2·4H2O mol ratio is 0.003~0.005：0.007~0.009, Al-Mn-Si colloidal sols are made；
Or：The step 1) in, metallic compound is ZnCl2And SnCl4·5H2O, the Silane coupling reagent KH-570, metallization
Compound, H2O mol ratio is 0.04~0.06：0.07~0.095：0.02~0.03, and ZnCl2And SnCl4·5H2O mole
Than for 0.06~0.07：0.005~0.03, Zn-Sn-Si colloidal sols are made.
8. a kind of preparation method of metal-silicon colloidal sol expandable flame retardant coating according to claim 1, it is characterised in that：Institute
State step 1) in, metallic compound is AlCl3·6H2O、ZnCl2And SnCl4·5H2O, the Silane coupling reagent KH-570, metal
Compound, H2O mol ratio is 0.04~0.06：0.01~0.02：0.02~0.03, and AlCl3·6H2O、ZnCl2With
SnCl4·5H2O mol ratio is 0.002~0.004：0.008~0.01：0.002~0.004, Al-Zn-Sn-Si is made molten
Glue；The step 2) in, Al-Zn-Sn-Si colloidal sols, acrylamide, acrylic acid, epoxy acrylic resin, the quality of light trigger
Than for 1.4~3.2：0.8~2.2:0.4~1.2:2~5.5：0.1~0.35.
9. a kind of preparation method of metal-silicon colloidal sol expandable flame retardant coating according to claim 1, it is characterised in that：Institute
State step 1) in, metallic compound is AlCl3·6H2O、SnCl4·5H2O and Na2SiO3, the Silane coupling reagent KH-570, gold
Belong to compound, H2O mol ratio is 0.04~0.06：0.02~0.03：0.02~0.03, and AlCl3·6H2O、NaH2PO4·
2H2O and Na2SiO3Mol ratio be 0.002~0.004：0.005~0.007：0.01~0.02, Si-Na-Al-Si is made molten
Glue；
Or：The step 1) in, metallic compound is AlCl3·6H2O、ZnCl2With Ni (NO3)2·6H2O, it is described silane coupled
Agent KH-570, metallic compound, H2O mol ratio is 0.04~0.06：0.01~0.02：0.02~0.03, and AlCl3·
6H2O、ZnCl2With Ni (NO3)2·6H2O mol ratio is 0.002~0.004：0.005~0.007：0.005~0.007, it is made
Al-Zn-Ni-Si colloidal sols；
Or：The step 1) in, metallic compound is AlCl3·6H2O、SnCl4·5H2O and Ni (NO3)2·6H2O, the silane
Coupling agent kh-570, metallic compound, H2O mol ratio is 0.04~0.06：0.01~0.015：0.02~0.03, and
AlCl3·6H2O、SnCl4·5H2O and Ni (NO3)2·6H2O mol ratio is 0.002~0.004：0.005~0.007：
0.002~0.004, Al-Sn-Ni-Si colloidal sols are made.
10. a kind of preparation method of metal-silicon colloidal sol expandable flame retardant coating according to any one of claim 1 to 9, its
It is characterised by：The silane coupler is KH-570；The light trigger is light trigger 1173.
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