CN110194872B - PVC smoke suppressant and preparation method thereof - Google Patents
PVC smoke suppressant and preparation method thereof Download PDFInfo
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- CN110194872B CN110194872B CN201910385884.XA CN201910385884A CN110194872B CN 110194872 B CN110194872 B CN 110194872B CN 201910385884 A CN201910385884 A CN 201910385884A CN 110194872 B CN110194872 B CN 110194872B
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Abstract
The invention discloses a PVC smoke suppressant and a preparation method thereofThe preparation method is as follows. The invention utilizes the interchangeability of hydrotalcite interlayer anions, and Fe (CN)6 3‑Or Fe (CN)6 4‑The interlayer is introduced to obtain an intercalated hydrotalcite material, the intercalated hydrotalcite material is calcined at high temperature to obtain a composite oxide LDO containing Fe, and the LDO is used as a smoke suppressant to be applied to PVC products. The preparation method is simple, the cost of raw materials is low, toxic and harmful substances are not contained, and the environment is not polluted; the smoke suppressant of the invention is added into 100g of PVC to effectively reduce the generation and release of aromatic compounds in the smoke precursor, so that the maximum smoke density value (Ds, max) is reduced from a blank 595.58 to 200.32, the smoke suppression rate is up to 66.37 percent, and the appearance and the service performance of the material are not influenced; the most important is that the smoke suppressant material not only can absorb chlorine effectively, but also can suppress the generation of harmful substances, and radically reduces the smoke release amount.
Description
Technical Field
The invention belongs to the technical field of preparation of smoke suppression materials, and particularly provides a PVC smoke suppression agent and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is one of five common plastics, is an ideal material due to low price and outstanding balance performance, and has the second place to the global yield of polyethylene. It can be made into soft, hard and semi-hard products according to the addition of different amounts of plasticizer, and can be widely applied to various fields. PVC contains a large amount of Cl element, has certain flame retardance, is easily changed into a combustible material along with the addition of a plasticizer, and can be degraded to generate HCl, CO and CO during combustion2And aromatic compounds and the like release a large amount of acidic and toxic gases, and simultaneously generate a large amount of smoke to cause secondary harm, seriously affect the life and property safety of people and pollute the living environment of people. According to the fact that the liquid is not completely mixed, more than 80% of people die in a fire because a large amount of smoke and CO generated during combustion are inhaled, and then the people are poisoned and suffocated after coma. Therefore, the research on effectively inhibiting the release of the smoke in the burning process of the PVC is importantTheoretical significance and practical value.
The layered composite oxide (LDO) is prepared by roasting a precursor LDHs. The oxide is alkaline, has strong adsorption capacity, and can be used as a PVC smoke suppressant, so that on one hand, physical adsorption can be utilized to reduce the escape of smoke particles and reduce the visible smoke amount; on the other hand, the alkaline property can be utilized to perform chemical reaction with acidic substance HCl generated by PVC cracking, so that the release of HCl gas is reduced, the content of chlorine element in gas phase is reduced, and the generation of polychlorinated aromatic compounds is reduced. And through regulating and controlling the laminated plates and the layers of the precursor LDHs, cations with the capability of electron acceptors can be designed, and complex anions of certain metal elements are introduced between the layers, so that the synergistic effect of the laminated plates and the layers is exerted, and chloride generated by HCl reaction absorbed by the laminated plates is Lewis acid, thereby promoting PVC to generate more trans-polyene structures in the cracking process, effectively inhibiting the generation of cis-olefin and improving the smoke suppression efficiency.
Currently, the smoke suppressant mainly used in the market is a molybdenum series, but the price is high; other organic smoke inhibitors have certain toxicity, so the development of novel environment-friendly smoke inhibitors has become a development trend. The layered composite oxide as a novel smoke suppressant has the advantages of good smoke suppression effect, low preparation cost, convenient storage and transportation and the like. The smoke suppressant provided by the invention is simple in preparation method, low in raw material cost, free of toxic and harmful substances, free of pollution to the environment, and obvious in smoke suppression effect by adding a small amount of smoke suppressant in a PVC material, and can effectively slow down smoke release, prolong rescue time, and reduce the number of people who are trapped in a fire disaster and die due to smoke poisoning, so that loss is reduced.
Disclosure of Invention
The invention provides a PVC smoke suppressant and a preparation method thereof. The smoke suppressant is different from other smoke suppressants in that the smoke suppressant can radically suppress the generation of smoke and has high smoke suppression performance when added in a small amount. It is known that when PVC burns, a large amount of irritant toxic substances such as benzene, toluene and dioxin, which are released, contain a large amount of benzene rings in their composition structure, and when chlorine atoms are substituted with some groups on the benzene rings, polychlorinated aromatic hydrocarbon compounds are formed, and these compounds are aggregated together and become visible particles to the naked eye, i.e. smoke is released. When the layered composite oxide smoke suppressant is added into PVC, the content of benzene and chlorine in smoke products can be obviously reduced, and the smoke amount in the combustion process is further reduced radically.
The invention relates to a PVC smoke suppressant, which uses anions Fe (CN)6 3-Or Fe (CN)6 4-The intercalated functional material hydrotalcite is a precursor, and a composite oxide containing Fe is prepared by a high-temperature calcination method, namely the PVC smoke suppressant.
Said anion Fe (CN)6 3-Or Fe (CN)6 4-The structural general formula of the intercalated functional material hydrotalcite is [ M2+ 1-xM3 + x(OH)2]x+(An-)x/n·zH2O, wherein x is M3+/(M2++M3+) The value range of the quantity of the substances is more than or equal to 0.2 and less than or equal to 0.4; z is the amount of crystal water, and z is more than or equal to 0 and less than or equal to 6; m2+Represents Zn2+、Mg2+、Ni2+、Mn2+、Ca2+、Fe2+Either one or both of; m3+Represents Al3+、Fe3+、Co3+Any one of the above; a. then-Represents Fe (CN)6 3-Or Fe (CN)6 4-。
Said anion Fe (CN)6 3-Or Fe (CN)6 4-The intercalated functional material hydrotalcite is prepared through a coprecipitation method or a roasting reduction method.
The preparation method of the PVC smoke suppressant comprises the following steps:
(1) preparing hydrotalcite capable of intercalation;
(2) preparation of the anion Fe (CN)6 3-Or Fe (CN)6 4-Intercalated hydrotalcite;
(3) high temperature calcination was performed using a muffle furnace.
The specific operating conditions of the step (1) are as follows: dissolving soluble divalent metal salt and soluble trivalent metal salt in a molar ratio of 2-4 in a solvent for removing CO2The deionized water is prepared into mixed salt solution, wherein the concentration of divalent metal ions is 0.1-2 mol/L; dissolving NaOH in the solution to remove CO2Preparing an alkali solution with the same volume in the deionized water, wherein the ratio of the mole number of NaOH to the sum of the mole numbers of divalent metal ions and trivalent metal ions is 1-3; adding the prepared mixed salt solution and the alkali solution into a rotary liquid film reactor at the same flow rate to quickly nucleate, pouring the obtained slurry into a three-neck flask, and adding N2Crystallizing at 60-140 deg.C for 4-24 hr; then using CO removal2Washing the hydrotalcite with deionized water until the hydrotalcite is neutral to obtain slurry-like intercalated hydrotalcite; the soluble divalent metal salt is one or more of nitrates or chlorides of magnesium, zinc and cobalt; the soluble trivalent metal salt is one or more of nitrate or chloride of aluminum and iron.
The specific operating conditions of the step (2) are as follows: dispersing the intercalated hydrotalcite in CO removing agent2Is made into a suspension with the concentration of 0.05-1mol/L, and then K is added4[Fe(CN)6]Or K3[Fe(CN)6]Dissolved in CO for removing2In deionized water of (2) in N2Adding into the suspension of hydrotalcite under protection to make Fe (CN)6 3-Or Fe (CN)6 4-The content of (a) is 2-4 times of the mole number of hydrotalcite interlayer anions; rapidly stirring, reacting at 60-140 deg.C for 4-24 hr, filtering, and drying to obtain anion Fe (CN)6 3-Or Fe (CN)6 4-An intercalated hydrotalcite.
The specific operating conditions of the step (3) are as follows: reacting the anion Fe (CN)6 3-Or Fe (CN)6 4-And calcining the intercalated hydrotalcite in a muffle furnace at 350-800 ℃ for 0.5-8 hours to obtain a composite oxide containing Fe, namely the PVC smoke suppressant.
The PVC smoke suppressant is applied to the preparation of PVC products.
Compared with the existing smoke suppressant, the invention has the beneficial effects that: the preparation method of the smoke suppressant provided by the invention is simple, the cost of raw materials is low, toxic and harmful substances are not contained, and the smoke suppressant has no pollution to the environment; 4phr of PVC is added to 100g of PVC, so that the generation and release of aromatic compounds in the smoke precursor can be effectively reduced, and the smoke suppression effect is remarkable, the maximum smoke density value (Ds, max) is reduced to 200.32 from a blank 595.58, the smoke suppression rate is up to 66.37%, and the appearance and the service performance of the material are not influenced; the most important is that the smoke suppressant material not only can absorb chlorine effectively, but also can suppress the generation of harmful substances, and radically reduces the smoke release amount.
Drawings
FIG. 1 shows LDHs-Cl and LDHs-Fe (CN) in example 1 of the present invention6An infrared spectrum of (1). The anions Fe (CN) are clearly observed6 4-Infrared characteristic absorption Peak, indicating LDHs-Fe (CN)6The preparation is successful.
FIG. 2 is a graph showing the effect of smoke density test on a PVC blank sample in a comparative example and a PVC/LDO composite sample obtained in example 1.
FIG. 3 is a graph showing the mass spectra of chlorine-containing substances and benzene measured in thermogravimetric mass spectrometry of a PVC blank sample in a comparative example and a PVC/LDO composite sample obtained in example 1, and it can be seen that the release amount of the PVC/LDO composite sample is obviously reduced.
Detailed Description
In order that the invention may be better understood, the invention will now be further illustrated by reference to the following examples, but the invention is not limited thereto.
Example 1:
step A: according to the molar ratio Zn: al ═ 2: 1 proportion of 16.356gZnCl2And 8g AlCl3Dissolved in 150mL to remove CO2Is prepared into the solution containing [ Zn ] in deionized water2+]＝0.8mol/L、[Al3+]0.4mol/L mixed salt solution; weighing 14.4g NaOH dissolved in 150mL to remove CO2Preparing an alkali solution in the deionized water.
And B: preparing intercalation hydrotalcite by nucleation/crystallization isolation method, mixing the salt solution and alkali in step AThe solution was added dropwise at the same flow rate to a colloid mill rotating at 3000rmp, and the resulting slurry was quickly transferred to a 500mL three-necked flask, heated with an electric heating mantle, and heated in N2Crystallizing at 100 deg.C for 6 hr, cooling to room temperature, and removing CO2Washing the slurry to neutrality by using deionized water to obtain the Zn capable of being intercalated2Al-LDHs。
And C: the slurry hydrotalcite Zn is2Al-LDHs are dispersed in the catalyst for removing CO2The deionized water is prepared into suspension with the concentration of 0.02 mol/L; weighing 28.98g of K4[Fe(CN)6]Dissolved in a small amount to remove CO2In deionized water of (2) in N2Adding the solution into hydrotalcite suspension under atmosphere, stirring, crystallizing at 100 deg.C for 8 hr to obtain Fe (CN)6 4-And (3) intercalating hydrotalcite, and finally placing the filter cake in a 60 ℃ oven for drying and grinding to obtain intercalated hydrotalcite powder.
Step D: and (3) putting the powdery hydrotalcite into a muffle furnace, and calcining for 4 hours at 500 ℃ to obtain the layered composite oxide smoke suppressant LDO containing Fe.
Step E: weighing the Fe (CN) prepared above6 4-5g of intercalated hydrotalcite and 5g of calcined LDO4g which are layered composite oxides are respectively added into 100g of PVC powder, 2g of tribasic lead sulfate, 2g of dibasic lead stearate and 40g of DOP are added, after full stirring, a double-roll open mill is used for mixing, the uniformly mixed PVC material is placed into a flat-plate vulcanizing instrument to be pressed into sheets, and the sheets with the thickness of 75 multiplied by 1mm are processed to test the smoke density. Wherein the mixing temperature is 170 ℃, the mould pressing temperature is 170 ℃ and the mould pressing pressure is 10 MPa.
Example 2:
step A: according to molar ratio Mg: zn: al — 3: 1: 2 23.077gMg (NO) was weighed out accurately3)2·6H2O、8.924gZn(NO3)2·6H2O and 22.508gAl (NO)3)3·9H2Dissolving O in 150mL to remove CO2Is prepared into the product containing [ Mg ] in deionized water2+]＝0.6mol/L、[Zn2+]＝0.2mol/L、[Al3+]0.4mol/L mixed salt solution; weighing 14.4g NaOH dissolved in 150mL to remove CO2Deionization ofPreparing aqueous alkali.
And B: preparing intercalation hydrotalcite by nucleation/crystallization isolation method, dripping the mixed salt solution and alkali solution in step A into a colloid mill with 3000rmp of rotation speed at the same flow rate, rapidly transferring the obtained slurry into a 500mL three-neck flask, heating with an electric heating jacket, and adding N2Crystallizing at 100 deg.C for 6 hr, cooling to room temperature, and removing CO2The slurry is washed to be neutral by the deionized water to obtain the intercalation Mg1.5Zn0.5Al-LDHs。
And C: mixing the above slurry hydrotalcite Mg1.5Zn0.5Al-LDHs are dispersed in the catalyst for removing CO2The deionized water is prepared into suspension with the concentration of 0.02 mol/L; weighing 28.98g of K4[Fe(CN)6]Dissolved in a small amount to remove CO2In deionized water of (2) in N2Adding the solution into hydrotalcite suspension under atmosphere, stirring, crystallizing at 100 deg.C for 8 hr to obtain Fe (CN)6 4-And (3) intercalating hydrotalcite, and finally placing the filter cake in a 60 ℃ oven for drying and grinding to obtain intercalated hydrotalcite powder.
Step D: and (3) putting the powdery hydrotalcite into a muffle furnace, and calcining for 4 hours at 500 ℃ to obtain the layered composite oxide smoke suppressant LDO containing Fe.
Comparative example:
100g of PVC powder is taken, 2g of tribasic lead sulfate, 2g of dibasic lead stearate and 40g of DOP are added, after full stirring, a double-roll mill is used for mixing, the uniformly mixed PVC material is placed in a flat-plate vulcanizing machine to be pressed into tablets, and the tablets are processed into sheets of 75X 1mm for testing smoke density. Wherein the mixing temperature is 170 ℃, the mould pressing temperature is 170 ℃ and the mould pressing pressure is 10 MPa.
Respectively carrying out smoke density test on each prepared PVC sample, wherein the test standard is GB/T8323.2-2008, a flameless combustion mode is adopted, and the test radiation intensity is 25kW/m2The test time is 20 min. Table 1 shows the maximum smoke density test data for PVC composites with different smoke suppressants added.
TABLE 1
The comparison experiment can obtain that:
the precursor hydrotalcite is calcined at high temperature, and the obtained layered composite oxide is used as a smoke suppressant for PVC products, so that the smoke suppression effect is remarkably improved. The LDO has stronger basicity than common hydrotalcite, can absorb more HCl gas and reduce the release of chloride, and reacts to generate more Lewis acid substances, so that the inhibition effect is enhanced, the generation amount of benzene is greatly reduced, and the smoke inhibition performance is improved. Thereby inventing a novel smoke suppressant material with high efficiency.
It is to be understood that the above are merely illustrative of the principles and implementations of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.
Claims (2)
1. A preparation method of a PVC smoke suppressant is characterized by comprising the following steps:
(1) dissolving soluble divalent metal salt and soluble trivalent metal salt in a molar ratio of 2-4 in a solvent for removing CO2The deionized water is prepared into mixed salt solution, wherein the concentration of divalent metal ions is 0.1-2 mol/L; dissolving NaOH in the solution to remove CO2Preparing an alkali solution with the same volume in the deionized water, wherein the ratio of the mole number of NaOH to the sum of the mole numbers of divalent metal ions and trivalent metal ions is 1-3; adding the prepared mixed salt solution and the alkali solution into a rotary liquid film reactor at the same flow rate to quickly nucleate, pouring the obtained slurry into a three-neck flask, and adding N2Crystallizing at 60-140 deg.C for 4-24 hr; then using CO removal2Washing the hydrotalcite with deionized water until the hydrotalcite is neutral to obtain slurry-like intercalated hydrotalcite; the soluble divalent metal salt is one or more of nitrates or chlorides of magnesium, zinc and cobalt; the soluble trivalent metal salt is aluminum nitrate or iron nitrateOne or more of acid salt or chloride salt;
(2) dispersing the intercalated hydrotalcite in CO removing agent2Is made into a suspension with the concentration of 0.05-1mol/L, and then K is added4[Fe(CN)6]Or K3[Fe(CN)6]Dissolved in CO for removing2In deionized water of (2) in N2Adding into the suspension of hydrotalcite under protection to make Fe (CN)6 3-Or Fe (CN)6 4-The content of (a) is 2-4 times of the mole number of hydrotalcite interlayer anions; rapidly stirring, reacting at 60-140 deg.C for 4-24 hr, filtering, and drying to obtain anion Fe (CN)6 3-Or Fe (CN)6 4-Intercalated hydrotalcite;
(3) reacting the anion Fe (CN)6 3-Or Fe (CN)6 4-And calcining the intercalated hydrotalcite in a muffle furnace at 350-800 ℃ for 0.5-8 hours to obtain a composite oxide containing Fe, namely the PVC smoke suppressant.
2. Use of a PVC smoke suppressant prepared according to the process of claim 1 in the preparation of a PVC product.
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