CN118852508B - A kind of polypropylene composite material with weather resistance and flame retardancy and preparation method thereof - Google Patents
A kind of polypropylene composite material with weather resistance and flame retardancy and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种具有耐候性和阻燃性的聚丙烯复合材料及其制备方法，属于热塑性高分子聚合物材料领域。包括以下步骤：含苄基受阻酚抗氧剂、溴素和自由基引发剂反应得到溴化受阻酚抗氧剂；溴化受阻酚抗氧剂和氨基封端的有机硅氧烷反应得到受阻酚‑有机硅氧烷；受阻酚‑有机硅氧烷、碳碳双键封端的有机硅氧烷和有机弱酸反应得到碳碳双键封端的受阻酚‑有机硅氧烷；受阻酚‑有机硅氧烷和丙烯在复合催化剂的作用下聚合反应得到聚丙烯复合材料。本发明通过在聚丙烯制备过程中，通过共价交联将具有阻燃性能和抗氧化的功能基团直接引入到聚丙烯主链上，再通过聚合，从而得到具有耐候性和阻燃性能的聚丙烯复合材料。The invention discloses a polypropylene composite material with weather resistance and flame retardancy and a preparation method thereof, and belongs to the field of thermoplastic high molecular polymer materials. The invention comprises the following steps: a benzyl-containing hindered phenol antioxidant, bromine and a free radical initiator react to obtain a brominated hindered phenol antioxidant; a brominated hindered phenol antioxidant and an amino-terminated organosiloxane react to obtain a hindered phenol-organosiloxane; a hindered phenol-organosiloxane, a carbon-carbon double bond-terminated organosiloxane and an organic weak acid react to obtain a carbon-carbon double bond-terminated hindered phenol-organosiloxane; hindered phenol-organosiloxane and propylene are polymerized under the action of a composite catalyst to obtain a polypropylene composite material. The invention directly introduces a functional group with flame retardancy and antioxidant properties into the main chain of polypropylene by covalent crosslinking during the preparation process of polypropylene, and then obtains a polypropylene composite material with weather resistance and flame retardancy by polymerization.
Description
Technical Field
The invention belongs to the field of thermoplastic high polymer materials, and particularly relates to a polypropylene composite material with weather resistance and flame retardance and a preparation method thereof.
Background
The polymer materials are ubiquitous in modern life, and plastics, rubber, fibers, coatings, adhesives and the like are widely applied to the fields of building, electronics, automobiles, decoration, food packaging and the like, so that the development of the polymer materials has become one of important foundations for modern economic construction and technological development. Polypropylene (PP) is a thermoplastic polymer polymerized from propylene monomers, and is widely used in fields such as furniture daily necessities, pipe materials, automobile materials, food packaging, building materials, etc., because of its advantages of excellent processability (excellent mechanical properties and good toughness), excellent chemical stability (acid and alkali corrosion resistance), good shock absorbing properties, excellent wear resistance, and low price. The polypropylene material is widely applied, and provides great convenience for the production and life of people, but because the oxygen index of the polypropylene is only about 18%, the polypropylene material belongs to the category of inflammable materials, has the defects of inflammability, easy oxidation and the like, when fire occurs, the polypropylene material is extremely inflammable, a large amount of heat can be released in the combustion process, serious molten drop phenomenon exists, secondary fire is extremely easy to be caused by the molten drop with flame, and great life and property loss can be caused for people. Therefore, the improvement of the weather resistance and the flame retardance of the polypropylene material is of great significance for improving the application safety and the durability of the polypropylene material. In the prior art, for improving the weather resistance and flame retardant property of the polypropylene material, the weather resistance flame retardant polypropylene material is prepared by putting an antioxidant, a flame retardant and the polypropylene material into plastic processing equipment together and performing processing processes such as blending, granulating and forming.
The patent CN115477811A discloses a polypropylene composition for a high weather-resistant high-flame-retardant injection molding material and the polypropylene injection molding material, wherein polypropylene, fluorine-containing silane, a flame retardant, a copper-harm inhibitor, a processing aid and an antioxidant are used as raw materials, and the interaction of the polypropylene, the fluorine-containing silane, the flame retardant and the antioxidant improves the flame retardance and the weather resistance of the polypropylene injection molding material.
The patent CN102627805A discloses an environment-friendly high-flame-retardance high-weather-resistance polypropylene, which takes copolymerized polypropylene and/or homo-polymerized polypropylene as raw materials, and adds a flame retardant, an ultraviolet-resistant absorbent, a light stabilizer, an antioxidant, a copper-resistant agent and a processing aid for mixed processing, and improves the weather resistance and flame retardance of a polypropylene material through interaction of a halogen-free environment-friendly flame retardant, the ultraviolet-resistant absorbent and the light stabilizer.
The patent CN108976591A discloses a preparation method of a high-weather-resistance flame-retardant polypropylene masterbatch, which is characterized in that a self-made weather-resistant agent, polypropylene, toner, a phosphorus flame retardant, fumed silica and an antioxidant are mixed and granulated, and the weather resistance and the flame resistance of the polypropylene masterbatch are improved by modifying and loading the weather-resistant agent and combining the interaction of the fumed silica, the phosphorus flame retardant and the antioxidant.
The invention discloses a high weather-resistant flame-retardant reinforced polypropylene composite material and a preparation method thereof, wherein polypropylene, a microencapsulated flame retardant, a flame-retardant synergist, a weather-resistant agent and a processing aid are mixed to prepare a polypropylene modified flame-retardant master batch, the polypropylene modified flame-retardant master batch is mixed with polypropylene, glass fibers, a compatilizer and the processing aid to prepare a long glass fiber reinforced polypropylene master batch, the long glass fiber reinforced polypropylene master batch is extruded and molded, a halogen flame retardant is subjected to microcapsule coating modification treatment, and a flame retardant system after the microcapsule treatment is coated in a local environment and is not contacted with a hindered amine light stabilizer even if decomposed to generate acidic substances in the use process, so that the excellent weather-resistant effect of the polypropylene is continuously exerted, a polypropylene matrix is effectively protected, and the weather resistance and flame retardance of the polypropylene material are further realized.
The aim of modifying the weather resistance and the flame retardance of the polypropylene is achieved by mixing the polypropylene with a corresponding flame retardant and antioxidant. The modification method is easy to cause adverse reaction with polypropylene at high temperature of mixed extrusion due to the use amount of the flame retardant and the antioxidant, so that molecular chains of the polypropylene are broken, and the mechanical property and the thermal stability of the polypropylene material are reduced.
Therefore, the monomer for synthesizing the polypropylene is modified, so that the polypropylene composite material with weather resistance and flame retardance is obtained through polymerization, and the defects of adverse reaction with the polypropylene caused by the addition of the flame retardant and the antioxidant can be avoided.
Disclosure of Invention
According to the defects of the prior art, the functional groups with flame retardant property and oxidation resistance are directly introduced into a polypropylene main chain through covalent crosslinking in the preparation process of polypropylene, and then the polypropylene composite material with weather resistance and flame retardant property is obtained through polymerization. Specifically, the technical scheme of the invention comprises the following contents:
a method for preparing a polypropylene composite material with weather resistance and flame retardance, the method comprising the steps of:
The method comprises the steps of drying a hindered phenol antioxidant containing benzyl, introducing the hindered phenol antioxidant containing benzyl into a reaction kettle containing a chlorine-containing solvent, introducing bromine and a free radical initiator into the reaction kettle, mixing and stirring, closing the reaction kettle, replacing air in the reaction kettle with inert gas, and heating to 60-80 ℃ for reacting for 5-10 hours to obtain a brominated hindered phenol antioxidant;
The brominated hindered phenol antioxidant, the amino-terminated organosiloxane and the anhydrous tetrahydrofuran are mixed according to the mass ratio of 1:1-2:3-4, and then heated to 40-50 ℃ for reflux reaction for 3-5 hours to obtain the hindered phenol-organosiloxane;
The hindered phenol-organosiloxane, the carbon-carbon double bond end-capped organosiloxane and the organic weak acid are mixed according to the mass ratio of 1:2-3:0.1-0.2, and then hydrolyzed for 30-50 min at 50-60 ℃ and condensed for 20-30 min at 90-110 ℃ to obtain the carbon-carbon double bond end-capped hindered phenol-organosiloxane;
And adding a composite catalyst into the hindered phenol-organosiloxane, then introducing propylene at an air-flow rate of 0.1-0.5 m 3/h, and heating to 50-70 ℃ for reaction for 10-15 h to obtain the polypropylene composite material.
Further, the benzyl-containing hindered phenol antioxidant comprises 2, 6-di-tert-butyl-p-ethylphenol or 2,2' -methylenebis (6-tert-butyl-4-cresol).
Further, the chlorine-containing solvent includes chlorobenzene or chloroform.
Further, the free radical initiator comprises benzoyl peroxide, dicumyl peroxide or methyl ethyl ketone peroxide, and the purpose of the free radical initiator is to generate free radicals under a heating environment to initiate homolytic cleavage of bromine, so that the free radicals react with hydrogen on benzyl carbon of the benzyl hindered phenol antioxidant.
Further, the mass ratio of the benzyl-containing hindered phenol antioxidant to the chlorine-containing solvent to the bromine to the free radical initiator is 1:2-3:1:0.1-0.3.
Further, the inert gas comprises helium or argon, and the purpose of introducing the inert gas is to exhaust oxygen in the air, so as to prevent the decomposition of bromine by the oxygen.
Further, the amino-terminated organosiloxane comprises 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane or gamma-aminopropyl methyldiethoxysilane, the carbon-carbon double bond terminated organosiloxane comprises dimethoxymethyl vinyl silane, vinyl trimethoxysilane or vinyl triethoxysilane, the nitrogen atom of the amino-terminated organosiloxane acts as a nucleophile to attack the carbon atom of the brominated hindered phenol antioxidant attached to the bromine atom and replace the chlorine atom, and the carbon-carbon double bond terminated organosiloxane acts to provide a carbon-carbon double bond for polymerization with propylene.
Further, the weak organic acid includes acetic acid or propionic acid.
Further, the composite catalyst is formed by mixing a metallocene catalyst and triethylaluminum according to a mass ratio of 1:7-9, the metallocene catalyst reacts with triethylaluminum to remove a ligand of one metallocene so as to activate the metal, and an activated coordination complex is formed between the activated ligand and a carbon-carbon double bond after activation, so that polymerization reaction is initiated.
Further, the metallocene catalyst comprises titanocene dichloride or zirconocene dichloride.
Further, the mass ratio of the hindered phenol-organosiloxane to the composite catalyst is 1:0.008-0.01.
A polypropylene composite material prepared by a preparation method of a polypropylene composite material with weather resistance and flame retardance.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, a benzyl-containing hindered phenol antioxidant is modified, so that a functional group bromo is introduced to obtain a brominated hindered phenol antioxidant, then amino-terminated organosiloxane is introduced to the brominated hindered phenol antioxidant through nucleophilic reaction by utilizing the characteristic that carbon atoms connected by bromo are easy to attack by nucleophilic reagents, a bromine atom is replaced to obtain a hindered phenol-organosiloxane, then Si-OH bond is generated by utilizing organosiloxane hydrolysis, carbon-carbon double-bond-terminated organosiloxane is introduced to the hindered phenol-organosiloxane through condensation between Si-OH bonds to obtain carbon-carbon double-bond-terminated hindered phenol-organosiloxane, and then the carbon-carbon double-bond-terminated hindered phenol-organosiloxane is mixed with propylene under the action of a composite catalyst to react to obtain the polypropylene composite material with weather resistance and flame retardance. The invention utilizes the high bond energy of the siloxane bond to have thermal stability at high temperature, so that the prepared polypropylene composite material has a thermal stability structure, then the siloxane bond at high temperature can form a siloxane compound layer (such as a silicon dioxide layer), the protective layer can isolate oxygen and heat and prevent oxidation reaction in the combustion process, the polypropylene composite material containing the siloxane bond can not generate toxic and harmful gases such as chloride, and the like, has certain environmental protection, and the phenolic hydroxyl on the hindered phenol antioxidant has the function of releasing active hydrogen atoms to combine with other free radicals to realize antioxidation.
(2) According to the preparation method provided by the invention, as halogen atoms are replaced, the finally obtained polypropylene composite material does not contain halogen atoms, harmful gases such as hydrogen chloride and the like are not generated at high temperature, and the polypropylene composite material has good impact strength and tensile strength in mechanical properties, so that the weather resistance and flame retardance are realized, and meanwhile, the mechanical properties are optimized.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below by means of embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the present invention are commercially available or may be prepared by known methods.
Example 1:
The preparation method of the polypropylene composite material with weather resistance and flame retardance comprises the following preparation processes:
Pouring 2kg of chlorobenzene into a reaction kettle, then processing and drying 1kg of 2, 6-di-tert-butyl-p-ethylphenol by a 60 ℃ vacuum drying oven, then introducing into the reaction kettle for stirring and dissolving, then respectively introducing 1kg of bromine and 100g of benzoyl peroxide into the reaction kettle for uniformly mixing and stirring with the 2, 6-di-tert-butyl-p-ethylphenol, closing the reaction kettle, purging air in the reaction kettle by helium until the oxygen content inside the reaction kettle is detected to be lower than 0.5% by an oxygen content monitor, stopping purging, heating the reaction kettle to 60 ℃ at the moment, and performing timing reaction for 5 hours at the temperature. After the reaction, chlorobenzene was distilled off under reduced pressure to obtain brominated 2, 6-di-tert-butyl-p-ethylphenol.
1Kg of brominated 2, 6-di-tert-butyl-p-ethylphenol, 1kg of 3-aminopropyl trimethoxysilane and 3kg of anhydrous tetrahydrofuran are weighed, uniformly mixed and stirred, heated to 40 ℃ for reflux reaction for 3 hours, and then the anhydrous tetrahydrofuran is distilled off to obtain the 2, 6-di-tert-butyl-p-ethylphenol-organosiloxane.
The flask is placed in a constant temperature water bath at 50 ℃, 1kg of 2, 6-di-tert-butyl p-ethylphenol-organosiloxane, 2kg of dimethoxy methyl vinyl silane and 100g of acetic acid are taken and mixed, then 1kg of deionized water is added for mixing and stirring reaction for 30min, and after the reaction is finished, the temperature is continuously increased to 90 ℃ for reaction for 20min, so that the carbon-carbon double bond-capped 2, 6-di-tert-butyl p-ethylphenol-organosiloxane is obtained. And (3) taking part of the 2, 6-di-tert-butyl p-ethylphenol-organosiloxane blocked by the carbon-carbon double bond, mixing and stirring with dichloromethane, and then dropwise adding reddish brown bromine water to the mixture, wherein reddish brown fading is observed, which indicates that the carbon-carbon double bond blocking construction is successful.
1Kg of carbon-carbon double bond end-capped 2, 6-di-tert-butyl-p-ethylphenol-organosiloxane was placed in a reaction kettle, a composite catalyst consisting of 1g of titanocene dichloride and 7g of triethylaluminum was added, propylene was introduced into the reaction kettle at a venting rate of 0.1m 3/h, and the polymerization reaction of the carbon-carbon double bond end-capped 2, 6-di-tert-butyl-p-ethylphenol-organosiloxane was carried out for 10h in an environment of 50 ℃. After the reaction is finished, pouring the solution in the reaction kettle into cold methanol solution to precipitate, and then filtering and drying to obtain the polypropylene composite material.
Example 2:
The preparation method of the polypropylene composite material with weather resistance and flame retardance comprises the following preparation processes:
Pouring 2kg of chlorobenzene into a reaction kettle, then processing and drying 1kg of 2, 6-di-tert-butyl-p-ethylphenol by a 60 ℃ vacuum drying oven, then introducing into the reaction kettle for stirring and dissolving, then respectively introducing 1kg of bromine and 200g of benzoyl peroxide into the reaction kettle for uniformly mixing and stirring with the 2, 6-di-tert-butyl-p-ethylphenol, closing the reaction kettle, purging air in the reaction kettle by helium until the oxygen content inside the reaction kettle is detected to be lower than 0.5 percent by an oxygen content monitor, stopping purging, heating the reaction kettle to 65 ℃ at the moment, and performing timing reaction for 6 hours at the temperature. After the reaction, chlorobenzene was distilled off under reduced pressure to obtain brominated 2, 6-di-tert-butyl-p-ethylphenol.
1Kg of brominated 2, 6-di-tert-butyl-p-ethylphenol, 1.5kg of 3-aminopropyl trimethoxysilane and 3kg of anhydrous tetrahydrofuran are weighed, uniformly mixed and stirred, heated to 40 ℃ for reflux reaction for 4 hours, and then the anhydrous tetrahydrofuran is distilled off to obtain the 2, 6-di-tert-butyl-p-ethylphenol-organosiloxane.
The flask was placed in a 50 ℃ constant temperature water bath, then 1kg of 2, 6-di-tert-butyl-p-ethylphenol-organosiloxane, 2kg of vinyltrimethoxysilane and 150g of acetic acid were mixed, then 1kg of deionized water was added, the mixture was stirred and reacted for 35min, and after the reaction was completed, the temperature was continuously raised to 95 ℃ and the reaction was continued for 20min to obtain carbon-carbon double bond-terminated 2, 6-di-tert-butyl-p-ethylphenol-organosiloxane. And (3) taking part of the 2, 6-di-tert-butyl p-ethylphenol-organosiloxane blocked by the carbon-carbon double bond, mixing and stirring with dichloromethane, and then dropwise adding reddish brown bromine water to the mixture, wherein reddish brown fading is observed, which indicates that the carbon-carbon double bond blocking construction is successful.
1Kg of carbon-carbon double bond end-capped 2, 6-di-tert-butyl-p-ethylphenol-organosiloxane was placed in a reaction kettle, a composite catalyst consisting of 1g of titanocene dichloride and 7g of triethylaluminum was added, propylene was introduced into the reaction kettle at a venting rate of 0.2m 3/h, and the polymerization reaction of the carbon-carbon double bond end-capped 2, 6-di-tert-butyl-p-ethylphenol-organosiloxane was carried out for 12h in an environment of 55 ℃. After the reaction is finished, pouring the solution in the reaction kettle into cold methanol solution to precipitate, and then filtering and drying to obtain the polypropylene composite material.
Example 3:
The preparation method of the polypropylene composite material with weather resistance and flame retardance comprises the following preparation processes:
Pouring 2.5kg of chlorobenzene into a reaction kettle, then processing and drying 1kg of 2, 6-di-tert-butyl-p-ethylphenol by a 60 ℃ vacuum drying oven, then introducing into the reaction kettle for stirring and dissolving, then introducing 1kg of bromine and 200g of dicumyl peroxide into the reaction kettle respectively, mixing and stirring uniformly with the 2, 6-di-tert-butyl-p-ethylphenol, closing the reaction kettle, purging air in the reaction kettle by helium until the oxygen content inside the reaction kettle is detected to be lower than 0.5%, stopping purging, heating the reaction kettle to 70 ℃ at the moment, and performing timing reaction for 8 hours at the temperature. After the reaction, chlorobenzene was distilled off under reduced pressure to obtain brominated 2, 6-di-tert-butyl-p-ethylphenol.
1Kg of brominated 2, 6-di-tert-butyl-p-ethylphenol, 1.5kg of 3-aminopropyl triethoxysilane and 3.5kg of anhydrous tetrahydrofuran are weighed, uniformly mixed and stirred, heated to 45 ℃ for reflux reaction for 4 hours, and then the anhydrous tetrahydrofuran is distilled off to obtain the 2, 6-di-tert-butyl-p-ethylphenol-organosiloxane.
The flask was placed in a thermostatic water bath at 55℃and then 1kg of 2, 6-di-tert-butyl-p-ethylphenol-organosiloxane, 2.5kg of vinyltrimethoxysilane and 150g of propionic acid were mixed, then 1kg of deionized water was added to mix and react for 40min, and after the reaction was completed, the temperature was continuously raised to 100℃and the reaction was continued for 25min to obtain carbon-carbon double bond-terminated 2, 6-di-tert-butyl-p-ethylphenol-organosiloxane. And (3) taking part of the 2, 6-di-tert-butyl p-ethylphenol-organosiloxane blocked by the carbon-carbon double bond, mixing and stirring with dichloromethane, and then dropwise adding reddish brown bromine water to the mixture, wherein reddish brown fading is observed, which indicates that the carbon-carbon double bond blocking construction is successful.
1Kg of carbon-carbon double bond end-capped 2, 6-di-tert-butyl-p-ethylphenol-organosiloxane was placed in a reaction kettle, a composite catalyst consisting of 1g of titanocene dichloride and 8g of triethylaluminum was added, propylene was introduced into the reaction kettle at a venting rate of 0.3m 3/h, and the polymerization reaction of the carbon-carbon double bond end-capped 2, 6-di-tert-butyl-p-ethylphenol-organosiloxane was carried out for 14h in an environment of 60 ℃. After the reaction is finished, pouring the solution in the reaction kettle into cold methanol solution to precipitate, and then filtering and drying to obtain the polypropylene composite material.
Example 4:
The preparation method of the polypropylene composite material with weather resistance and flame retardance comprises the following preparation processes:
Pouring 2.5kg of chloroform into a reaction kettle, then processing and drying 1kg of 2,2 '-methylenebis (6-tertiary butyl-4-cresol) by a 60 ℃ vacuum drying box, introducing into the reaction kettle, stirring and dissolving, introducing 1kg of bromine and 200g of methyl ethyl ketone peroxide into the reaction kettle respectively, mixing and stirring uniformly with the 2,2' -methylenebis (6-tertiary butyl-4-cresol), closing the reaction kettle, purging air in the reaction kettle by argon until the oxygen content in the reaction kettle is detected to be lower than 0.5%, stopping purging, and heating the reaction kettle to 75 ℃ at the moment and timing the reaction for 9 hours at the temperature. After the completion of the reaction, chlorobenzene was distilled off under reduced pressure to obtain brominated 2,2' -methylenebis (6-t-butyl-4-methylphenol).
1Kg of brominated 2,2 '-methylenebis (6-tert-butyl-4-cresol), 1.5kg of gamma-aminopropyl methyldiethoxysilane and 4kg of anhydrous tetrahydrofuran are weighed, uniformly mixed and stirred, heated to 50 ℃ for reflux reaction for 4 hours, and then the anhydrous tetrahydrofuran is distilled off to obtain the 2,2' -methylenebis (6-tert-butyl-4-cresol) -organosiloxane.
The flask was placed in a thermostatic water bath at 55℃and then 1kg of 2,2 '-methylenebis (6-t-butyl-4-cresol) -organosiloxane, 2.5kg of vinyltriethoxysilane and 200g of propionic acid were mixed, then 1kg of deionized water was added to mix and react for 45 minutes with stirring, and after the reaction was completed, the temperature was continuously raised to 105℃and the reaction was continued for 25 minutes to obtain carbon-carbon double bond-terminated 2,2' -methylenebis (6-t-butyl-4-cresol) -organosiloxane. Taking part of the 2,2' -methylene bis (6-tertiary butyl-4-cresol) -organosiloxane blocked by the carbon-carbon double bond, mixing and stirring the mixture with dichloromethane, then dripping reddish brown bromine water into the mixture, and observing the fading of reddish brown, thereby indicating that the carbon-carbon double bond blocking construction is successful.
1Kg of carbon-carbon double bond end-capped 2,2 '-methylenebis (6-tert-butyl-4-cresol) -organosiloxane was placed in a reaction kettle and a composite catalyst consisting of 1g of zirconium and 8g of triethylaluminum was added, propylene was introduced into the reaction kettle at a vent rate of 0.4m 3/h, and the 2,2' -methylenebis (6-tert-butyl-4-cresol) -organosiloxane end-capped with a carbon-carbon double bond was polymerized in an environment at 65℃for 14h. After the reaction is finished, pouring the solution in the reaction kettle into cold methanol solution to precipitate, and then filtering and drying to obtain the polypropylene composite material.
Example 5:
The preparation method of the polypropylene composite material with weather resistance and flame retardance comprises the following preparation processes:
Pouring 3kg of chloroform into a reaction kettle, then processing and drying 1kg of 2,2 '-methylenebis (6-tertiary butyl-4-cresol) by a 60 ℃ vacuum drying oven, introducing into the reaction kettle, stirring and dissolving, introducing 1kg of bromine and 300g of methyl ethyl ketone peroxide into the reaction kettle respectively, mixing and stirring uniformly with the 2,2' -methylenebis (6-tertiary butyl-4-cresol), closing the reaction kettle, purging air in the reaction kettle by argon until the oxygen content in the reaction kettle is detected to be lower than 0.5%, stopping purging, heating the reaction kettle to 80 ℃ at the moment, and performing timing reaction for 10 hours at the temperature. After the completion of the reaction, chlorobenzene was distilled off under reduced pressure to obtain brominated 2,2' -methylenebis (6-t-butyl-4-methylphenol).
1Kg of brominated 2,2 '-methylenebis (6-tert-butyl-4-cresol), 2kg of gamma-aminopropyl methyldiethoxysilane and 4kg of anhydrous tetrahydrofuran are weighed, uniformly mixed and stirred, heated to 50 ℃ for reflux reaction for 5 hours, and then the anhydrous tetrahydrofuran is distilled off to obtain the 2,2' -methylenebis (6-tert-butyl-4-cresol) -organosiloxane.
The flask was placed in a 60 ℃ thermostatic water bath, then 1kg of 2,2 '-methylenebis (6-tert-butyl-4-cresol) -organosiloxane, 3kg of vinyltriethoxysilane and 200g of propionic acid were mixed, then 1kg of deionized water was added to mix and react for 50min, and after the reaction was completed, the temperature was continuously raised to 110 ℃ to react for 30min to obtain carbon-carbon double bond-terminated 2,2' -methylenebis (6-tert-butyl-4-cresol) -organosiloxane. Taking part of the 2,2' -methylene bis (6-tertiary butyl-4-cresol) -organosiloxane blocked by the carbon-carbon double bond, mixing and stirring the mixture with dichloromethane, then dripping reddish brown bromine water into the mixture, and observing the fading of reddish brown, thereby indicating that the carbon-carbon double bond blocking construction is successful.
1Kg of carbon-carbon double bond end-capped 2,2 '-methylenebis (6-tert-butyl-4-cresol) -organosiloxane was placed in a reaction kettle and a composite catalyst consisting of 1g of zirconium and 9g of triethylaluminum was added, propylene was introduced into the reaction kettle at a vent rate of 0.5m 3/h, and the 2,2' -methylenebis (6-tert-butyl-4-cresol) -organosiloxane end-capped with a carbon-carbon double bond was polymerized in an environment at 70℃for 15 hours. After the reaction is finished, pouring the solution in the reaction kettle into cold methanol solution to precipitate, and then filtering and drying to obtain the polypropylene composite material.
Comparative example 1:
The preparation method of the polypropylene composite material with weather resistance and flame retardance comprises the following preparation processes:
The benzyl-containing hindered phenol antioxidant 2,2' -methylenebis (6-tert-butyl-4-methylphenol) of example 5 was replaced with 2, 6-di-tert-butyl-p-methylphenol, with the remaining conditions being identical to those of example 5.
Comparative example 2:
The preparation method of the polypropylene composite material with weather resistance and flame retardance comprises the following preparation processes:
the benzyl-containing hindered phenol antioxidant 2,2' -methylenebis (6-tert-butyl-4-methylphenol) of example 5 was substituted for n-stearyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, the remaining conditions being the same as in example 5.
Comparative example 3:
The preparation method of the polypropylene composite material with weather resistance and flame retardance comprises the following preparation processes:
1kg of vinyltriethoxysilane was placed in a reaction vessel containing 3kg of anhydrous tetrahydrofuran and a composite catalyst consisting of 1g of zirconium and 9g of triethylaluminum was added, and propylene was introduced into the reaction vessel at a aeration rate of 0.5m 3/h to polymerize with vinyltriethoxysilane in an environment at 70℃for 15 hours. After the reaction is finished, pouring the solution in the reaction kettle into cold methanol solution to precipitate, and then filtering and drying to obtain the polypropylene composite material.
Comparative example 4:
The preparation method of the polypropylene composite material with weather resistance and flame retardance comprises the following preparation processes:
1kg of dimethoxymethylvinylsilane, 1kg of vinyltrimethoxysilane and 1kg of vinyltriethoxysilane were placed in a reaction vessel containing 6kg of anhydrous tetrahydrofuran and a composite catalyst consisting of 3g of zirconium and 25g of triethylaluminum was added thereto, and propylene was introduced into the reaction vessel at a vent rate of 0.5m 3/h to polymerize with vinyltriethoxysilane in an environment of 70℃for 15 hours. After the reaction is finished, pouring the solution in the reaction kettle into cold methanol solution to precipitate, and then filtering and drying to obtain the polypropylene composite material.
Although the flame retardant property of the polypropylene material can be improved by independently introducing the carbon-carbon double bond terminated organosiloxane, the improvement effect is not obvious, the use amount of the carbon-carbon double bond terminated organosiloxane and the use amount of the composite catalyst are further increased, the improvement is not great, and the weather resistance and the mechanical property of the polypropylene composite material are also poor.
The polypropylene composite materials obtained in examples 1 to 5 and comparative examples 1 to 4 were respectively measured for oxygen index OI according to the standard of "GB/T2406.2-2009 plastics was measured for combustion behavior by oxygen index method", and the polypropylene composite materials obtained in examples 1 to 5 and comparative examples 1 to 4 were respectively measured for impact strength and tensile strength according to the standard of "GB/T1843-2008 plastics cantilever beam impact strength" and "GB/T1040.1-2018 plastics tensile property", and the results are shown in Table 1:
TABLE 1 results of impact Strength and tensile Strength test
| Material source | Oxygen index OI (%) | Impact strength (J/m 2) | Tensile Strength (MPa) |
| Example 1 | 23.3 | 6317.6 | 36 |
| Example 2 | 29.8. | 6651.3 | 43 |
| Example 3 | 33.5 | 7208.2 | 51 |
| Example 4 | 35.4 | 7441.4 | 56 |
| Example 5 | 36.2 | 7501.8 | 58 |
| Comparative example 1 | 16.2 | 3421.5 | 23 |
| Comparative example 2 | 20.1 | 3564.3 | 27 |
| Comparative example 3 | 22.8 | 3528.1 | 28 |
| Comparative example 4 | 24.5 | 3784.5 | 31 |
The polypropylene composite materials obtained in examples 1 to 5 and comparative examples 1 to 4 were subjected to irradiation treatment with a UV-313 ultraviolet lamp for 100 hours, and then the impact strength and the tensile strength were measured in accordance with "measurement of impact Strength of Plastic cantilever of GB/T1843-2008" and "measurement of tensile Property of Plastic of GB/T1040.1-2018", respectively, and the results are shown in Table 2:
TABLE 2 test results of impact Strength and tensile Strength of irradiation treatment with UV-313 ultraviolet light tube
From the above experimental results, it can be seen that:
(1) As can be seen from examples 1-5, the polypropylene composite material prepared by the preparation method provided by the invention has good weather resistance and flame retardance, good mechanical properties of impact strength and tensile strength, and good retention rate of impact strength and retention rate of tensile strength after ultraviolet ageing treatment.
(2) As can be seen from comparative example 1, the antioxidant 2, 6-di-tert-butyl-p-methylphenol has no benzyl group, cannot introduce bromine atoms, and cannot generate subsequent nucleophilic substitution reaction, so that hindered phenol antioxidant cannot be introduced onto polypropylene through polymerization reaction, and finally the synthesized polypropylene composite material has poor weather resistance and flame retardant effect, and as can be seen from comparative example 2, the steric hindrance of molecules participating in reaction is increased due to the long carbon chain of octadecane on one side containing the benzyl group, the reactivity is reduced, the antioxidant active ingredient and flame retardant structure carried by the synthesized polypropylene composite material are less, and the weather resistance and flame retardant effect are poor. As can be seen from a comparison of example 5 and comparative examples 1 and 2, the benzyl group-containing hindered phenol antioxidant used in the present invention has a specific selectivity in chemical structure.
(3) It can be seen from comparative examples 3 and 4 that the addition of the carbon-carbon double bond-terminated organosiloxane alone can improve the flame retardant property of the polypropylene material, but the improvement effect is not obvious, the addition of the carbon-carbon double bond-terminated organosiloxane and the addition of the composite catalyst is not great, and the weather resistance and mechanical properties of the polypropylene composite material are also poor.
The foregoing embodiments have described the technical solutions and advantageous effects of the present invention in detail, and it should be understood that the foregoing embodiments are merely specific examples of the present invention, and are not intended to limit the present invention. The present invention is subject to various changes and modifications without departing from the spirit and scope thereof, and such changes and modifications fall within the scope of the invention as hereinafter claimed.
Claims (9)
1. A method for preparing a polypropylene composite material with weather resistance and flame retardance, which is characterized by comprising the following steps:
The method comprises the steps of drying a hindered phenol antioxidant containing benzyl, introducing the hindered phenol antioxidant containing benzyl into a reaction kettle containing a chlorine-containing solvent, introducing bromine and a free radical initiator into the reaction kettle, mixing and stirring, closing the reaction kettle, replacing air in the reaction kettle with inert gas, and heating to 60-80 ℃ for reacting for 5-10 hours to obtain a brominated hindered phenol antioxidant;
The brominated hindered phenol antioxidant, the amino-terminated organosiloxane and the anhydrous tetrahydrofuran are mixed according to the mass ratio of 1:1-2:3-4, and then heated to 40-50 ℃ for reflux reaction for 3-5 hours to obtain the hindered phenol-organosiloxane;
The hindered phenol-organosiloxane, the carbon-carbon double bond end-capped organosiloxane and the organic weak acid are mixed according to the mass ratio of 1:2-3:0.1-0.2, and then hydrolyzed for 30-50 min at 50-60 ℃ and condensed for 20-30 min at 90-110 ℃ to obtain the carbon-carbon double bond end-capped hindered phenol-organosiloxane;
Adding a composite catalyst into the hindered phenol-organosiloxane, then introducing propylene at an air flow rate of 0.1-0.5 m3/h, and heating to 50-70 ℃ for reaction for 10-15 h to obtain the polypropylene composite material;
the composite catalyst is formed by mixing a metallocene catalyst and triethylaluminum according to a mass ratio of 1:7-9.
2. The method for preparing a polypropylene composite material having weather resistance and flame retardancy as claimed in claim 1, wherein the hindered phenol antioxidant containing benzyl group comprises 2, 6-di-tert-butyl-p-ethylphenol or 2,2' -methylenebis (6-tert-butyl-4-cresol).
3. The method for preparing a polypropylene composite material having weather resistance and flame retardancy as claimed in claim 1, wherein the chlorine-containing solvent comprises chlorobenzene or chloroform.
4. The method for preparing a polypropylene composite material having weather resistance and flame retardancy as claimed in claim 1, wherein the radical initiator comprises benzoyl peroxide, dicumyl peroxide or methylethyl ketone peroxide.
5. The preparation method of the polypropylene composite material with weather resistance and flame retardance is characterized by comprising the steps of, by mass, 1:2-3:1:0.1-0.3 of a benzyl-containing hindered phenol antioxidant, a chlorine-containing solvent and a bromine-free radical initiator.
6. The method of preparing a polypropylene composite having weatherability and flame retardancy as defined in claim 1, wherein the amino-terminated organosiloxane comprises 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane or γ -aminopropyl methyldiethoxysilane, and the carbon-carbon double bond-terminated organosiloxane comprises dimethoxymethyl vinyl silane, vinyl trimethoxysilane or vinyl triethoxysilane.
7. The method for preparing a polypropylene composite material having weather resistance and flame retardancy as claimed in claim 1, wherein said organic weak acid comprises acetic acid or propionic acid.
8. The preparation method of the polypropylene composite material with weather resistance and flame retardance according to claim 1, wherein the mass ratio of the hindered phenol-organosiloxane to the composite catalyst is 1:0.008-0.01.
9. A polypropylene composite material prepared by the method for preparing a polypropylene composite material having weather resistance and flame retardance according to any one of claims 1 to 8.
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| CA2055662A1 (en) * | 1991-01-11 | 1992-07-12 | Edwin Boudreaux Jr. | Process to graft steroregular polymers of branched, higher alpha-olefins and compositions thereof |
| CN103980401A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Nanoparticle/polypropylene random copolymer compound resin for 3D printing, preparation method and application thereof |
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| WO2014113046A1 (en) * | 2013-01-18 | 2014-07-24 | Dow Global Technologies Llc | Polymerization processes for high molecular weight polyolefins |
| CN110343329B (en) * | 2018-04-03 | 2022-03-11 | 万华化学（宁波）有限公司 | Halogen-free flame-retardant polypropylene material and preparation method thereof |
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| CA2055662A1 (en) * | 1991-01-11 | 1992-07-12 | Edwin Boudreaux Jr. | Process to graft steroregular polymers of branched, higher alpha-olefins and compositions thereof |
| CN103980401A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Nanoparticle/polypropylene random copolymer compound resin for 3D printing, preparation method and application thereof |
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