CN108912445B - Halogen-free flame-retardant polyethylene material and preparation method thereof - Google Patents
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Abstract
The invention relates to a preparation method of a halogen-free flame-retardant polyethylene material, which comprises the following steps: preparing hybrid silicon spheres, preparing three-source integrated expanded flame-retardant molecules, carrying out graft copolymerization, treating expandable graphite and conductive carbon black by using a coupling agent, and extruding or pressing raw materials to form; the halogen-free flame-retardant polyethylene material comprises polyethylene, silicon dioxide/polyethyl methacrylate pentaerythritol phosphate melamine salt hybrid flame retardant, expandable graphite, conductive carbon black and coupling agent. The invention has the beneficial effects that: the silicon compound has good synergistic flame-retardant effect, the surface of the hybrid silicon ball containing vinyl is prepared, the hybrid silicon ball is rich in vinyl double bonds and is subjected to graft copolymerization with a vinyl monomer to form a crotch-shaped structure, and an organic-inorganic network is added into a high-molecular matrix, so that the dispersion effect of silicon in the matrix is improved, the formation of a continuous compact crosslinked carbon layer is facilitated, and the flame-retardant efficiency is improved; the addition of expandable graphite has great synergistic flame retarding effect.
Description
Technical Field
The invention relates to a halogen-free flame-retardant polyethylene material and a preparation method thereof.
Background
The traditional method for modifying PE flame retardance is to add a halogen-containing flame retardant, and the flame retardant has the characteristics of high flame retardant efficiency, small using amount, low price and the like, so the flame retardant occupies a dominant position in the field of PE flame retardance for a long time. However, with the progress of society and the enhancement of environmental awareness, the contradiction between the disadvantages of halogen-containing flame retardants and the demand for social development is becoming more and more acute. In the last 90 s, halogen-free flame retardant technology was developed rapidly. At present, the halogen-free flame retardant modification of PE still mainly comprises adding a flame retardant, and the common halogen-free flame retardants include: metal hydroxide flame retardants, phosphorus flame retardants, silicon flame retardants, intumescent flame retardants, and the like. The Intumescent Flame Retardant (IFR) is a most rapidly developed halogen-free flame retardant in recent years, and has the advantages of high flame retardant efficiency, low smoke, low toxicity, no corrosive gas release, molten drop resistance and the like. It also has significant disadvantages: (1) the existing intumescent flame retardant is mostly composed of polar micromolecular substances and has poor compatibility with a nonpolar PE matrix, so that the mechanical property and the processing property of the material are difficult to meet the use requirements; (2) most of the existing intumescent flame retardants have the problems of easy moisture absorption, easy migration and the like; (3) the existing intumescent flame retardant has insufficient thermal stability, is easy to generate esterification reaction in the processing process, releases water vapor and causes adverse effects on the appearance and mechanical properties of the product. (4) The flame retardant efficiency is not high, and the addition amount is larger.
In order to improve the compatibility of IFR and a polymer matrix, reduce the addition amount and hygroscopicity of IFR and improve the thermal stability of IFR, a single-component intumescent flame retardant which integrates an acid source, a gas source and a carbon source in a molecular structure becomes a hot point of research in recent years. The flame retardant can act in a shorter distance due to the acid source, the gas source and the carbon source, has higher flame retardant efficiency than the traditional IFR, but the char formation property is not ideal enough.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: based on the problems, the invention provides a halogen-free flame-retardant polyethylene material and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a halogen-free flame-retardant polyethylene material comprises the following steps:
(1) preparation of hybrid silicon spheres: adopting a mode of first acid hydrolysis and then base catalysis to prepare the vinyl triethoxysilane into a hybrid silicon ball containing vinyl, as shown in the following formula,
wherein the acid is inorganic acid or organic acid, specifically one of hydrochloric acid, nitric acid, acetic acid or formic acid; the alkali is ammonia water.
(2) Preparing three-source integrated expansion flame-retardant molecules: phosphorus oxychloride and pentaerythritol are subjected to esterification reaction to prepare intermediate product spiro phosphate diacid chloride, the spiro phosphate diacid chloride and beta hydroxyethyl methacrylate, melamine and triethylamine are subjected to substitution reaction to prepare 3- (ethyl methacrylate) -9- ((4, 6-diamino-1, 3, 5-triazine) amino) -3, 9-dioxo-2, 4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane phosphate (EADP) which is shown as the following formula,
wherein the molar ratio of phosphorus oxychloride to pentaerythritol is 3-10: 1, the mol ratio of spiro phosphate diacid chloride, beta hydroxyethyl methacrylate and melamine is 1: (1-2): (1-2).
(3) Graft copolymerization: dispersing the hybrid silicon spheres in an aqueous solution, adding EADP, styrene, an initiator and a chelating agent under the protection of inert gas, and carrying out graft copolymerization by a solution-in-situ polymerization method to obtain the silicon dioxide/polyethyl methacrylate pentaerythritol melamine phosphate hybrid flame retardant, which is shown as the following formula,
wherein the distilled water accounts for 80-89.995% of the total weight of the solution, the monomer accounts for 10-19.999% of the total weight of the solution, and the chelating agent accounts for 0.001-0.005% of the total weight of the solution; the hybrid silicon spheres account for 0.1-3% of the total weight of the monomer, the EADP accounts for 10-29.8% of the total weight of the monomer, the styrene accounts for 70-86% of the total weight of the monomer, and the initiator accounts for 0.1-1% of the total weight of the monomer.
The initiator is NaHSO3、K2S2O8And AIBA 2HCL, wherein the oxidation type initiator is K2S2O8And AIBA & 2HCL, accounting for 0.1-0.3% of the mass concentration of the solution, and a reduced initiator is NaHSO3Initiation of AIBA.2 HCL15-50% of the total mass of the agent, NaHSO3And K2S2O8In a molar ratio of 1: 2; the chelating agent is one of EDTA, DTPA, NTA or STPP; the inert gas is ammonia gas.
(4) Expandable graphite and conductive carbon black are treated by a coupling agent for later use.
Wherein the expandable graphite is sulfur-free expandable graphite with larger granularity, the expandable graphite takes natural crystalline flake graphite with the particle size of tens of microns as a raw material and H3PO4、HNO3Potassium permanganate is used as an oxidant for an intercalation agent, a chemical oxidation method is adopted for preparation, and the preparation conditions of the sulfur-free expandable graphite are as follows: the mass volume ratio of the graphite to the mixed acid liquid is 1 g: 5-10 ml of graphite and KMnO4The mass ratio of (1): 0.05-0.5, the reaction temperature is 30-50 ℃, and the reaction time is 30-90 min. The coupling agent is at least one of silane coupling agent, titanate coupling agent or aluminate coupling agent.
(5) And (4) uniformly mixing the expandable graphite treated by the coupling agent, the conductive carbon black, the silicon dioxide/polyethyl methacrylate pentaerythritol melamine phosphate hybrid flame retardant and the polyethylene.
The flame retardant is prepared from 100 parts of polyethylene, 5-40 parts of a silicon dioxide/polyethyl methacrylate pentaerythritol phosphate melamine salt hybrid flame retardant, 3-20 parts of expandable graphite, 0.1-5 parts of conductive carbon black and 0.1-5 parts of a coupling agent.
(6) And (5) extruding or pressing the raw materials obtained in the step (5) to obtain the halogen-free flame-retardant polyethylene material.
The halogen-free flame-retardant polyethylene material comprises 100 parts of polyethylene, 5-40 parts of silicon dioxide/polyethyl methacrylate pentaerythritol melamine phosphate hybrid flame retardant, 3-20 parts of expandable graphite, 0.1-5 parts of conductive carbon black and 0.1-5 parts of coupling agent.
Polyethylene is used as carrier resin; the coupling agent improves the adhesion between the organic resin and the inorganic surface and improves the mechanical property of the material; the conductive carbon black is an antistatic agent suitable for the composite material, the expandable graphite is used as one of the flame retardants of the composite material and is a good conductive material, and the surface resistance and the volume resistance of the material can be effectively reduced by the combined action of the conductive carbon black.
The hybrid intumescent flame retardant is a main material for realizing flame retardance of the composite material, a complete and compact carbon layer is formed at high temperature, heat can be prevented from being transferred to a polymer of an inner layer, oxygen is prevented from entering the composite material, and a large amount of small molecular fuel generated by thermal degradation is prevented from being supplied to the combustion, so that the flame retardant effect can be effectively realized, phosphorus can promote the residual carbon content of the composite material, and silicon plays a role in reinforcing the carbon layer, and the purpose of high-efficiency flame retardance is achieved. Under the condition of high temperature, the phosphoric ester bond or P-O-C bond is firstly broken to release phosphoric acid, the phosphoric acid reacts with the carbon source to dehydrate and form carbon, and the gas source is heated to release non-combustible gas to promote the formation of the expansion type carbon layer. In the thermal oxidation degradation process, silicon dioxide can be gathered on the surface of the outer-layer carbon slag to play a role in reinforcing the carbon layer and crosslinking phosphorus into carbon. The existence of the organic-inorganic hybrid network in the composite material has higher thermal stability, and can play a role in improving the thermal stability and the antioxidant capacity in the material combustion process. The silicon network may also function as a hydroxyl radical trap.
When the expandable graphite is at high temperature, the expandable graphite expands rapidly to suffocate flame, and simultaneously, the generated graphite expanded material covers the surface of the base material, so that the contact of heat energy radiation and oxygen is isolated; acid radicals in the interlayer are released during expansion, so that the carbonization of the base material is promoted, and a good effect is achieved through various flame-retardant modes.
The two flame retardants have excellent synergistic flame retardant effect, form a continuous, compact and tough carbon layer on the surface of a polymer, and show a honeycomb structure inside. Acid radicals released by the expandable graphite during expansion convey an acid source for the expansion flame-retardant system.
The invention has the beneficial effects that: (1) the unimolecular reaction type IFR is synthesized and directly bonded on a PE chain, so that the compatibility of the flame retardant and PE is enhanced, and the problems of poor compatibility, easy precipitation, easy moisture absorption, poor thermal stability, poor migration resistance and the like of the traditional intumescent flame retardant system and a base material are solved. The three sources are integrated and can play a role according to an expansion flame-retardant mechanism, the number of components and the phase interface type in the flame-retardant PE are reduced, and the P, N, C in the synthesized flame retardant is proper in proportion, so that the synergistic effect of an acid source, a carbon source and a gas source can be played. The thermal stability meets the PE forming processing requirement;
(2) the silicon compound has good synergistic flame-retardant effect, the surface of the hybrid silicon ball containing vinyl is prepared, the hybrid silicon ball is rich in vinyl double bonds and is subjected to graft copolymerization with a vinyl monomer to form a crotch-shaped structure, and an organic-inorganic network is added into a polymer matrix, so that the dispersion effect of silicon in the matrix is improved, a continuous compact crosslinked carbon layer is favorably formed, and the flame-retardant efficiency is improved;
(3) the addition of the expandable graphite has a great synergistic flame-retardant effect, and the addition amount of the flame retardant can be effectively reduced. And expandable graphite with larger granularity is selected, so that the defect that the traditional powdery flame retardant cannot be uniformly dispersed is overcome. The conductive material is a good conductive material, can have excellent antistatic performance by being supplemented with a small amount of carbon black, and can effectively keep excellent mechanical properties of the material due to the lamellar structure of the conductive material;
(4) the PE material endows the material with excellent flame retardant property, has good antistatic property and can keep excellent mechanical property of the material. The prepared PE material is non-toxic and environment-friendly, has low smoke generation amount during combustion, does not generate toxic or harmful gas, and is a green and environment-friendly flame retardant material.
Detailed Description
The invention will now be further illustrated by reference to specific examples, which are intended to be illustrative of the invention and are not intended to be a further limitation of the invention.
(1) Preparation of vinyl-containing hybrid silicon spheres: putting 0.9g of Vinyltriethoxysilane (VTES) into a flask filled with 50mL of distilled water, adding hydrochloric acid to adjust the pH value of a solution in the flask to 3-5, and hydrolyzing the VTES for 1-3 h; and adding ammonia water with the mass concentration of 25% to adjust the pH value of liquid in the flask to 10-13, carrying out alkali catalytic condensation reaction for 2-5 h, centrifugally separating the product for 5-20 min (2000-3000 rpm), taking the lower layer precipitate, and drying to obtain the vinyl-containing hybrid silicon spheres.
(2) Preparation of EADP: firstly, Pentaerythritol (PER) (63.00g, 0.5mol) and phosphorus oxychloride (270m L, 3.0mol) are sequentially added into a 500ml four-mouth bottle provided with a condenser tube, a temperature control device, a stirring device and a tail gas absorption device, stirred and slowly heated. When the temperature is increased to 50 ℃, HCl begins to be generated, the system slowly becomes clear, when the temperature is increased to 78 ℃, the system is thoroughly clear, white precipitate is generated after continuous reaction, the temperature is increased to 103 ℃ after 4 hours of reaction, the reaction is carried out for 8 hours, then the reaction is cooled to room temperature, the filtration is carried out, the washing is carried out by dichloromethane, white sand-shaped solid is obtained, and then the drying is carried out in a vacuum oven, so as to obtain the intermediate spiro phosphate diacid chloride (SPDPC). Adding SPDPC (29.70g,0.1mol) and acetonitrile 400mL into a 1000mL reaction bottle provided with a magnetic stirring and refluxing device, stirring, controlling the temperature at 25 +/-1 ℃, dropwise adding beta-hydroxyethyl methacrylate (HEMA) (13.01g, 0.1mol) into the reaction bottle through a dropping funnel for 4h, adding triethylamine (10.12g, 0.1mol), and reacting for 12 h; adding melamine (12.60g, 0.1mol) and triethylamine (10.12g, 0.1mol), heating to 60 +/-1 ℃, and reacting for 12 h; and cooling to room temperature, performing suction filtration, and washing with cold water to obtain 40g of white solid, namely the intumescent flame retardant EADP.
(3) Placing 0.031g of hybrid silicon ball, 2.5g of EADP and 3.21g of one third of styrene in a container filled with 25ml of distilled water, ultrasonically dispersing for 10-30 min, introducing nitrogen for 20-40 min, adding 0.0025g of EDTA and 0.0053g of NaHSO3The temperature of the water bath is raised to 60 ℃, and the residual 6.42g of styrene monomer and 0.0256g of K are added2S2O4And 0.0312g of AIBA & 2HCl, the dripping time is about 15-30 min, the mixture reacts for 6-10 h at the temperature, and after the reaction is finished, the mixture is washed by absolute ethyl alcohol, filtered and dried in vacuum, and 10g of silicon dioxide/polyethylmethacrylate pentaerythritol phosphate melamine hybrid flame retardant is obtained.
(4) According to the parts by weight, 10 parts of expandable graphite treated by titanate coupling agent, 1 part of conductive carbon black, 30 parts of silicon dioxide/polyethyl methacrylate pentaerythritol melamine phosphate hybrid flame retardant and 100 parts of polyethylene are uniformly mixed; the antistatic halogen-free high-efficiency flame-retardant polyethylene material is prepared by the raw materials through a compression molding method.
The UL94 flame retardant test reaches V-0 grade, and the oxygen index is more than or equal to 32 percent.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (9)
1. A preparation method of a halogen-free flame-retardant polyethylene material is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of hybrid silicon spheres: preparing hybrid silicon spheres containing vinyl from vinyl triethoxysilane by means of acid hydrolysis and alkali catalysis;
(2) preparing three-source integrated expansion flame-retardant molecules: phosphorus oxychloride and pentaerythritol are subjected to esterification reaction to prepare an intermediate product of spiro phosphate diacid chloride, and the spiro phosphate diacid chloride is reacted with beta hydroxyethyl methacrylate, melamine and triethylamine to prepare 3- (ethyl methacrylate) -9- ((4, 6-diamino-1, 3, 5-triazine) amino) -3, 9-dioxo-2, 4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane phosphate EADP;
(3) graft copolymerization: dispersing the hybrid silicon spheres in a distilled water solution, adding EADP, styrene, an initiator and a chelating agent under the protection of inert gas, and carrying out graft copolymerization through a solution-in-situ polymerization method to obtain a silicon dioxide/polyethyl methacrylate pentaerythritol melamine phosphate hybrid flame retardant;
(4) processing expandable graphite and conductive carbon black by using a coupling agent for later use;
(5) uniformly mixing the expandable graphite treated by the coupling agent, the conductive carbon black, the silicon dioxide/polyethyl methacrylate pentaerythritol phosphate melamine salt hybrid flame retardant and the polyethylene in the step (4);
(6) and (5) extruding or pressing the raw materials obtained in the step (5) to obtain the halogen-free flame-retardant polyethylene material.
2. The preparation method of the halogen-free flame-retardant polyethylene material according to claim 1, which is characterized by comprising the following steps: the acid in the step (1) is inorganic acid or organic acid, and is specifically one of hydrochloric acid, nitric acid, acetic acid or formic acid; the alkali is ammonia water.
3. The preparation method of the halogen-free flame-retardant polyethylene material according to claim 1, which is characterized by comprising the following steps: in the step (2), the molar ratio of phosphorus oxychloride to pentaerythritol is 3-10: 1, the mol ratio of spiro phosphate diacid chloride, beta hydroxyethyl methacrylate and melamine is 1: (1-2): (1-2).
4. The preparation method of the halogen-free flame-retardant polyethylene material according to claim 1, which is characterized by comprising the following steps: in the step (3), the distilled water accounts for 80-89.995% of the total weight of the solution, the monomer accounts for 10-19.999% of the total weight of the solution, and the chelating agent accounts for 0.001-0.005% of the total weight of the solution; the hybrid silicon spheres account for 0.1-3% of the total weight of the monomer, the EADP accounts for 10-29.8% of the total weight of the monomer, the styrene accounts for 70-86% of the total weight of the monomer, and the initiator accounts for 0.1-1% of the total weight of the monomer.
5. The preparation method of the halogen-free flame-retardant polyethylene material according to claim 1, which is characterized by comprising the following steps: the initiator in the step (3) is NaHSO3、K2S2O8And AIBA 2HCL, wherein the oxidation type initiator is K2S2O8And AIBA & 2HCL, accounting for 0.1-0.3% of the mass concentration of the solution, and a reduced initiator is NaHSO3AIBA & 2HCL accounts for 15-50% of the total mass of the initiator, and NaHSO3And K2S2O8In a molar ratio of 1: 2; the chelating agent is one of EDTA, DTPA, NTA or STPP; the inert gas is ammonia gas.
6. The preparation method of the halogen-free flame-retardant polyethylene material according to claim 1, which is characterized by comprising the following steps: the expandable graphite in the step (4) is sulfur-free expandable graphite with larger granularity, and the expandable graphite takes natural crystalline flake graphite with the particle size of tens of microns as a raw material and H3PO4、HNO3Potassium permanganate is used as an oxidant for an intercalation agent, a chemical oxidation method is adopted for preparation, and the preparation conditions of the sulfur-free expandable graphite are as follows: mass volume ratio of graphite to mixed acid liquid1 g: 5-10 ml of graphite and KMnO4The mass ratio of (1): 0.05-0.5, the reaction temperature is 30-50 ℃, and the reaction time is 30-90 min.
7. The preparation method of the halogen-free flame-retardant polyethylene material according to claim 1, which is characterized by comprising the following steps: the coupling agent in the step (4) is at least one of silane coupling agent, titanate coupling agent or aluminate coupling agent.
8. The preparation method of the halogen-free flame-retardant polyethylene material according to claim 1, which is characterized by comprising the following steps: in the step (5), 100 parts of polyethylene, 5-40 parts of silicon dioxide/polyethyl methacrylate pentaerythritol phosphate melamine hybrid flame retardant, 3-20 parts of expandable graphite, 0.1-5 parts of conductive carbon black and 0.1-5 parts of coupling agent.
9. The halogen-free flame-retardant polyethylene material prepared by the preparation method of the halogen-free flame-retardant polyethylene material of claim 1, which is characterized in that: the flame retardant comprises 100 parts of polyethylene, 5-40 parts of silicon dioxide/polyethyl methacrylate pentaerythritol melamine phosphate hybrid flame retardant, 3-20 parts of expandable graphite, 0.1-5 parts of conductive carbon black and 0.1-5 parts of coupling agent.
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| CN110644073B (en) * | 2019-09-09 | 2021-11-09 | 浙江恒澜科技有限公司 | Preparation method of polyester-nylon parallel composite elastic fiber |
| CN111057367B (en) * | 2019-11-26 | 2022-09-06 | 浙江恒逸石化研究院有限公司 | High-lasting flame-retardant nylon 6 and preparation method thereof |
| CN111040293B (en) * | 2019-12-17 | 2022-03-08 | 广东省石油与精细化工研究院 | Intumescent flame-retardant polypropylene and preparation method thereof |
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