CN113278203B - Preparation method and application of efficient halogen-free flame retardant for polypropylene - Google Patents
Preparation method and application of efficient halogen-free flame retardant for polypropylene Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a high-efficiency halogen-free flame retardant for polypropylene. According to the invention, the aluminum hypophosphite synthesized from sodium hypophosphite and aluminum sulfate is taken as a core material, and the magnesium hypophosphite and magnesium aluminum hypophosphite blend generated by the acid-base neutralization reaction of magnesium hydroxide is taken as a capsule material, so that the prepared coated product solves the problem that the aluminum hypophosphite flame retardant is flammable, and achieves the effect of self-extinguishing when encountering fire. The product is applied to a PP system and added with a synergistic compound, and the hexaphenoxycyclotriphosphazene in the synergistic agent is subjected to intercalation treatment, so that the temperature resistance of the synergistic compound can be improved, the synergistic compound cannot be decomposed at a processing temperature, the fluidity is good in the processing process, the compatibility with a base body is good, the efficient flame retardant effect is achieved under the condition of less addition amount, and the transparency and the mechanical property of the PP material are not obviously influenced. The product of the invention has the advantages of halogen-free environmental protection, flame retardance, high efficiency, migration resistance and the like.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to a preparation method and application of a high-efficiency halogen-free flame retardant for polypropylene.
Background
Polypropylene (PP) is non-toxic, light in weight, excellent in mechanical property, good in electrical insulation property and resistant to chemical corrosion, and is widely applied to the fields of packaging, textiles, building materials, automobiles, electronics/electrical and office supplies and the like. However, due to the structure of the PP, the oxygen index of the PP is only about 17.4 percent, and the PP is extremely easy to burn when meeting fire, thereby causing great damage to life and property. At present, flame retardance of PP materials mainly depends on halogen flame retardance of bromine and antimony, a flame retardant system of a phosphorus flame retardant and a charring agent and a flame retardant system of phosphorus and a low-halogen component, but the bromine and antimony flame retardant PP is not efficient, and the use of halogen is already forbidden; the addition amount of the flame retardant system of the phosphorus and the char forming agent is larger (more than 20 percent), although the flame retardant property of the PP product can be improved, the mechanical property of the PP material is greatly influenced.
Hypophosphite is a typical phosphorus-based environment-friendly flame retardant and has the advantages of no halogen, low toxicity, low smoke and the like. The flame retardant property of PP is well improved, but the flame retardant property of PP is flammable, safety accidents easily occur in the production process, the solubility of PP is high, the PP polymer has poor compatibility, the phenomena of migration and precipitation during the application process and poor fluidity, the PP material has great influence on the mechanical property, and the application range and the application effect of PP are limited to a certain extent.
CN201810930664.6 provides an inorganic coated aluminum hypophosphite and a preparation method thereof, the preparation method is to prepare aluminum hypophosphite coated by aluminum hydroxide precipitation, the product prepared by the method has improved weather resistance and ignition point, and no gel is caused and foaming is not influenced in the application of paint. CN202010877512.1 provides a preparation method of a modified aluminum hypophosphite flame retardant, which is characterized in that aluminum hydroxide, hypophosphorous acid, a silane coupling agent and polyethylene are used as raw materials in a kneading machine, aluminum hypophosphite is synthesized through a neutralization reaction, and then the modified aluminum hypophosphite flame retardant is obtained through thermal coating treatment of the silane coupling agent and the polyethylene. The method can directly obtain the modified aluminum hypophosphite flame retardant with good water resistance and good material compatibility under the environment-friendly synthesis process condition, and the cost is reduced. In both of the above patent documents, aluminum hypophosphite is coated and modified with aluminum hydroxide, but aluminum hydroxide has a low decomposition temperature and is decomposed at about 250 ℃, so that the flame retardancy and mechanical properties are affected when it is used in a high polymer, and the problem of aluminum hypophosphite itself cannot be really improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method and application of a high-efficiency halogen-free flame retardant for polypropylene. According to the invention, the aluminum hypophosphite synthesized from sodium hypophosphite and aluminum sulfate is taken as a core material, and the magnesium hypophosphite and magnesium aluminum hypophosphite blend generated by the acid-base neutralization reaction of magnesium hydroxide is taken as a capsule wall material, so that the prepared coated product solves the problem of flammability of the aluminum hypophosphite flame retardant, and achieves the effect of self-extinguishing when encountering fire. The product is applied to a PP system and added with a synergistic compound, and the hexaphenoxycyclotriphosphazene in the synergistic agent is subjected to intercalation treatment, so that the high temperature resistance of the synergistic compound can be improved, the synergistic compound cannot be decomposed at a processing temperature, the fluidity is good in the processing process, the compatibility with a matrix is good, the efficient flame retardant effect is achieved under a small addition amount, and the transparency and the mechanical property of the PP material are not obviously influenced. The product of the invention has the advantages of halogen-free environmental protection, flame retardance, high efficiency, migration resistance and the like.
The technical scheme of the invention is as follows: a preparation method of an efficient halogen-free flame retardant for polypropylene is characterized in that sodium hypophosphite and aluminum sulfate are synthesized into aluminum hypophosphite as a core material, magnesium hypophosphite and an aluminum magnesium hypophosphite mixture generated by adding magnesium hydroxide to perform acid-base neutralization reaction at 65-90 ℃ is added to serve as a capsule wall material, and an aluminum hypophosphite coated product (shown in figure 1) coated by the magnesium hypophosphite and the aluminum magnesium hypophosphite mixture is obtained, namely the efficient halogen-free flame retardant for polypropylene.
Preferably, the proportion of each raw material is as follows: 5-10 parts of magnesium hydroxide, 165 parts of aluminum sulfate and 150 parts of sodium hypophosphite. An appropriate amount of water (preferably 100-200 parts) is also added to the above reaction.
The preparation method comprises the following steps:
(1) adding water into sodium hypophosphite and aluminum sulfate at 90-120 ℃, stirring and dissolving the sodium hypophosphite and the aluminum sulfate respectively, then pouring the sodium hypophosphite solution into the aluminum sulfate solution, stirring and reacting at 90-120 ℃ for 4-8h to obtain aluminum hypophosphite slurry;
(2) and cooling the aluminum hypophosphite slurry to 65-90 ℃, adding magnesium hydroxide into water, stirring and dispersing, adding the obtained dispersion system into the aluminum hypophosphite slurry, carrying out heat preservation reaction for 2-5h, and then carrying out suction filtration and washing to obtain an aluminum hypophosphite coated product coated with a mixture of magnesium hypophosphite and aluminum magnesium hypophosphite, namely the efficient halogen-free flame retardant for polypropylene.
The sodium hypophosphite in the step (1) is preferably sodium hypophosphite monohydrate, and the aluminum sulfate is preferably aluminum sulfate octadecahydrate.
The magnesium hydroxide in the step (2) is one or two of magnesium hydroxide-3, magnesium hydroxide-8 and I-type magnesium hydroxide.
The halogen-free flame retardant (aluminum hypophosphite coated product) can be applied to preparation of polypropylene (various PP systems) with flame retardant effect.
The invention further discloses a preparation method of the polypropylene containing the halogen-free flame retardant (aluminum hypophosphite coated product), which is characterized in that 90-95 parts by weight of polypropylene, 5-10 parts by weight of halogen-free flame retardant (aluminum hypophosphite coated product) and 0.05-0.1 part by weight of synergistic compound are subjected to high-speed mixing, double-screw extrusion and injection molding to obtain the polypropylene with the flame retardant effect.
The synergistic compound comprises the following components in parts by weight: 5-25 parts of cumene, 45-65 parts of dicumyl peroxide (dicumyl peroxide) and 30-45 parts of hexaphenoxycyclotriphosphazene.
The invention has the following beneficial effects:
(1) the coated product prepared by taking the aluminum hypophosphite as a core material and taking the mixture of magnesium hypophosphite and aluminum magnesium hypophosphite generated by acid-base neutralization reaction as a capsule material solves the problem that the aluminum hypophosphite flame retardant is flammable, and achieves the effect of self extinguishing when encountering fire. Meanwhile, after the aluminum hypophosphite is coated, the fluidity is good and the matrix compatibility is good in the processing process of preparing the flame-retardant PP. Meanwhile, the flame retardant for various PP systems can achieve high-efficiency flame retardant effect under the action of a synergistic compound and with less addition, and the transparency and mechanical properties of the PP material are not obviously affected;
(2) compared with the existing aluminum hypophosphite coating technology, the invention takes the mixture of magnesium hypophosphite and aluminum magnesium hypophosphite as the capsule wall material, the coated product has high temperature resistance (1 percent decomposition temperature reaches more than 325 ℃), the process is simple, the reaction condition is mild, and the industrial production is favorably realized.
(3) The coating product is applied to a PP system and added with a synergistic compound, cumene and dicumyl peroxide in the synergistic compound are used as a synergistic synergist for fireproof and flame retardant of polypropylene, so that the flame retardant effect is improved, the flame retardant amount is reduced, and the physical and mechanical properties of the polypropylene are improved (particularly the tensile strength is greatly improved); the hexaphenoxycyclotriphosphazene is subjected to intercalation treatment, so that the carbon forming amount is increased, the dropping speed of the polypropylene sample strip during combustion is slowed down, the heat is rapidly transferred to realize high-efficiency flame retardance, and the temperature resistance of the synergistic compound is improved, so that the synergistic compound cannot be decomposed at the processing temperature.
In a word, the method has the advantages of simple process and mild reaction conditions, and is favorable for realizing industrial production. The product of the invention has the advantages of halogen-free environmental protection, flame retardance, high efficiency, migration resistance, good mechanical property and the like.
Drawings
FIG. 1 is an electron microscope scanning picture of the high-efficiency halogen-free flame retardant (coated product) for polypropylene prepared by the invention.
Detailed Description
In order to better illustrate the technical solutions adopted by the present invention, the present invention is further described below with reference to specific examples, but the embodiments of the present invention are not limited by the following examples. The sodium hypophosphite used in the examples of the present invention was sodium hypophosphite monohydrate, the aluminum sulfate was aluminum sulfate octadecahydrate, and the following two substances were given in parts by weight of dry matter excluding crystal water. In the embodiment of the invention, the double-screw extruder adopts a 30-screw extruder, the feeding speed is 30rpm, and the temperature is controlled as follows: 175-195 ℃, and the processing temperature of the injection molding machine: the first stage temperature is 210 ℃, the second stage temperature is 210 ℃, and the blanking stage temperature is 205 ℃.
Example 1
(1) Respectively adding 135 parts of sodium hypophosphite and 146 parts of aluminum sulfate into a reaction container with water, heating and stirring to raise the temperature to 105 ℃, and keeping the constant temperature until the sodium hypophosphite and the aluminum sulfate are completely dissolved; then slowly adding the sodium hypophosphite solution into the aluminum sulfate solution, and stirring and reacting for 6 hours at 105 ℃ to obtain aluminum hypophosphite slurry;
(2) stopping heating, cooling, adding a magnesium hydroxide water dispersion system (8 parts of magnesium hydroxide is added into water and stirred and dispersed) when the aluminum hypophosphite slurry is cooled to 70 ℃, carrying out neutralization reaction on the magnesium hydroxide and the aluminum hypophosphite slurry at the constant temperature of 70 ℃, carrying out suction filtration and washing after 4h of reaction, and obtaining an aluminum hypophosphite product coated with magnesium hypophosphite and aluminum magnesium hypophosphite;
(3) 8 parts of the obtained coated product, 92 parts of polypropylene and 0.05 part of a synergist compound (the mass ratio of the isopropyl benzene to the dicumyl peroxide to the hexaphenoxycyclotriphosphazene is 10:50:35) are added into a high-speed mixer for high-speed mixing, a double-screw extruder is used for preparing a modified material, a standard sample sheet No. 1 is injection-molded by an injection molding machine, and various flame retardance and mechanical properties of the modified material are tested, and the results are shown in the following table 1.
Example 2
(1) Respectively adding 142 parts of sodium hypophosphite and 154 parts of aluminum sulfate into a reaction container with water, starting heating and stirring, heating to 115 ℃, and keeping constant temperature until the sodium hypophosphite and the aluminum sulfate are completely dissolved; then slowly adding the sodium hypophosphite solution into the aluminum sulfate clear solution, and stirring and reacting at 110 ℃ for 4 hours to obtain aluminum hypophosphite slurry;
(2) stopping heating, cooling, adding a magnesium hydroxide water dispersion system (9.5 parts of magnesium hydroxide is added into water and stirred for dispersion) when the aluminum hypophosphite slurry is cooled to 80 ℃, carrying out neutralization reaction on the magnesium hydroxide and the aluminum hypophosphite slurry at the constant temperature of 75 ℃, carrying out suction filtration and washing after the reaction is carried out for 3 hours, and obtaining an aluminum hypophosphite product coated with magnesium hypophosphite and aluminum magnesium hypophosphite;
(3) 6.5 parts of the obtained coated product, 93.5 parts of polypropylene and 0.02 part of a synergist compound (the mass ratio of the isopropyl benzene to the dicumyl peroxide to the hexaphenoxycyclotriphosphazene is 15:60:40) are added into a high-speed mixer to be mixed at a high speed, a double-screw extruder is used for preparing a modified material, a standard sample sheet No. 2 is injection-molded by an injection molding machine, and various flame retardant and mechanical properties of the modified material are tested, and the results are shown in the following table 1.
Example 3
(1) Respectively adding 126 parts of sodium hypophosphite and 138 parts of aluminum sulfate into a reaction container added with water, starting heating and stirring, heating to 95 ℃, and keeping constant temperature until the sodium hypophosphite and the aluminum sulfate are completely dissolved; then slowly adding the sodium hypophosphite solution into the aluminum sulfate solution, and stirring and reacting for 5 hours at 95 ℃ to obtain aluminum hypophosphite slurry;
(2) stopping heating, cooling, adding a magnesium hydroxide water dispersion system (6 parts of magnesium hydroxide is added into water and stirred and dispersed) when the aluminum hypophosphite slurry is cooled to 70 ℃, carrying out neutralization reaction on the magnesium hydroxide and the aluminum hypophosphite slurry at the constant temperature of 80 ℃, carrying out suction filtration and washing after the reaction is carried out for 2.5 hours, and obtaining an aluminum hypophosphite product coated with magnesium hypophosphite and aluminum magnesium hypophosphite;
(3) the obtained 7 parts of coated product, 93 parts of polypropylene and 0.04 part of synergist compound (the mass ratio of isopropyl benzene, dicumyl peroxide and hexaphenoxycyclotriphosphazene is 20:55:35) are added into a high-speed mixer for high-speed mixing, a double-screw extruder is used for preparing a modified material, a standard sample 3# is injection-molded by an injection molding machine, and various flame retardance and mechanical properties of the modified material are tested, and the results are shown in the following table 1.
Test examples
The standard sample sheets 1#, 2#, 3# injected by the injection molding machine used in the embodiments 1, 2, 3 are tested for flame retardance and mechanical property. And the flame retardant performance and the mechanical performance of a standard PP (T30S) sample (PP (T30S) is respectively mixed with the halogen-free flame retardant system and the bromine antimony system in a high-speed mixer after being added with the halogen-free flame retardant system (ammonium polyphosphate: pentaerythritol: 4:1) and the bromine antimony system (decabromodiphenylethane: antimony trioxide: 3:1) at high speed, a double-screw extruder is used for preparing a modified material, and a standard sample sheet is injection-molded by an injection molding machine) are compared, and the results are shown in the following table 1.
TABLE 1 comparison of the flame retardant and mechanical properties of the No. 1, No. 2 and No. 3 flame retardants prepared by the present invention with those of halogen-free and bromine antimony flame retardants
The results shown by table 1 show: the flame retardant is applied to polypropylene, the transparency of the material is not influenced, the added synergistic synergist of the cumene and the dicumyl peroxide in the synergistic compound is used as a synergistic synergist for fireproof and flame retardant, the polypropylene can reach V-0 level under an extremely low addition amount, and the mechanical property (especially tensile strength) of the polypropylene is improved; and the hexaphenoxycyclotriphosphazene is subjected to intercalation treatment, so that the carbon forming amount is increased, and the dropping speed of the polypropylene sample strip during combustion is slowed down, so that heat is rapidly transferred to realize high-efficiency flame retardance.
Claims (6)
1. A preparation method of polypropylene containing halogen-free flame retardant is characterized in that 90-95 parts by weight of polypropylene, 5-10 parts by weight of halogen-free flame retardant and 0.05-0.1 part by weight of synergistic compound are subjected to high-speed mixing, twin-screw extrusion and injection molding to obtain polypropylene with flame retardant effect; the synergistic compound comprises the following components in parts by weight: 5-25 parts of isopropyl benzene, 45-65 parts of dicumyl peroxide and 30-45 parts of hexaphenoxycyclotriphosphazene;
the preparation method of the halogen-free flame retardant comprises the following steps: the aluminum hypophosphite synthesized by sodium hypophosphite and aluminum sulfate is taken as a core material, then magnesium hydroxide is added to carry out acid-base neutralization reaction at 65-90 ℃ to generate a magnesium hypophosphite and aluminum magnesium hypophosphite mixture which is taken as a capsule material, and an aluminum hypophosphite coated product coated by the magnesium hypophosphite and aluminum magnesium hypophosphite mixture is obtained, so that the halogen-free flame retardant is obtained.
2. The preparation method of polypropylene containing halogen-free flame retardant according to claim 1, wherein the halogen-free flame retardant comprises the following raw materials in parts by weight: 5-10 parts of magnesium hydroxide, 165 parts of aluminum sulfate and 150 parts of sodium hypophosphite.
3. The method as claimed in claim 2, wherein the halogen-free flame retardant is added in an amount of 100 parts to 200 parts.
4. The process for preparing polypropylene containing halogen-free flame retardant according to any of claims 1 to 3, wherein the process for preparing the halogen-free flame retardant comprises the steps of:
(1) adding water into sodium hypophosphite and aluminum sulfate at 90-120 ℃, stirring and dissolving the sodium hypophosphite and the aluminum sulfate respectively, then pouring the sodium hypophosphite solution into the aluminum sulfate solution, stirring and reacting at 90-120 ℃ for 4-8h to obtain aluminum hypophosphite slurry;
(2) and cooling the aluminum hypophosphite slurry to 65-90 ℃, adding magnesium hydroxide into water, stirring and dispersing, adding the obtained dispersion system into the aluminum hypophosphite slurry, carrying out heat preservation reaction for 2-5h, carrying out suction filtration and washing to obtain an aluminum hypophosphite coated product coated with a mixture of magnesium hypophosphite and aluminum magnesium hypophosphite, and thus obtaining the halogen-free flame retardant.
5. The method according to claim 4, wherein the sodium hypophosphite in step (1) is sodium hypophosphite monohydrate, and the aluminum sulfate is aluminum sulfate octadecahydrate; the magnesium hydroxide in the step (2) is one or two of magnesium hydroxide-3, magnesium hydroxide-8 and I-type magnesium hydroxide.
6. The polypropylene produced by the production process according to claim 4.
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| WO2013045965A1 (en) * | 2011-09-28 | 2013-04-04 | Italmatch Chemicals S.P.A. | Halogen-free flame retardant polyesters composition |
| CN104448555B (en) * | 2014-11-21 | 2017-01-11 | 济南泰星精细化工有限公司 | Preparation method of halogen-free fire retardant for polypropylene |
| CN106554612B (en) * | 2015-09-29 | 2019-08-06 | 万华化学集团股份有限公司 | Halogen-free fire retardation thermoplastic polyurethane elastic composition and its product, fire retardant packet |
| CN105694221B (en) * | 2016-03-21 | 2018-07-03 | 中山康诺德新材料有限公司 | A kind of highly effective flame-retardant polyolefin composition |
| CN106674605B (en) * | 2016-12-29 | 2018-08-21 | 济南泰星精细化工有限公司 | A kind of PP environment-friendlyflame flame retardants and preparation method thereof |
| CN107254106A (en) * | 2017-05-26 | 2017-10-17 | 合肥会通新材料有限公司 | A kind of stratiform hypophosphites flame-proof reinforced polypropylene composite material and preparation method thereof |
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