CN109942846B - Tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch and preparation method thereof - Google Patents
Tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 179
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- XUMFBUWGVLTWTH-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromo-2-methylpropoxy)-2-methylpropane Chemical compound BrCC(Br)(C)COCC(C)(Br)CBr XUMFBUWGVLTWTH-UHFFFAOYSA-N 0.000 title claims abstract description 95
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Abstract
The invention relates to tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch and a preparation method thereof, and solves the technical problems of low flame retardant content, yellow product color, poor product thermal stability and compatibility, large influence on the mechanical property of a material, toxicity, and large bioaccumulation and bioamplification effects in the preparation process of the flame retardant in the prior art. The invention provides tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch and a preparation method thereof, wherein the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch comprises the following raw material components in parts by weight: 40-45 parts of high-flow EBA resin, 30-35 parts of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, 15-20 parts of calcium stearate, 2-4 parts of hydrotalcite, 5-10 parts of flame retardant synergist, 4-5 parts of processing aid, 0.1-0.4 part of TGIC and 0.5-1 part of light stabilizer. The invention is widely applied to the technical field of flame retardant synthesis.
Description
Technical Field
The invention relates to the technical field of flame retardant synthesis, and particularly relates to tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch and a preparation method thereof.
Background
Hexabromocyclododecane (HBCD) is the most common flame retardant for EPS/XPS, and the annual usage amount is more than 35 ten thousand tons. In the field of EPS/XPS heat-insulating material flame retardant, the flame retardant always occupies more than 70 percent of market share. After years of use, hexabromocyclododecane is a Persistent Organic Pollutant (POPs), has strong bioaccumulation and biological amplification effects, has toxic hazard to human endocrine system and reproductive system, and is established as a control substance by EU ROHS instruction; the united nations 'stockholm convention on persistent organic pollutants' votes in 2013 agreed to pass a ban: the use of Hexabromocyclododecane (HBCD) is prohibited worldwide and this regulation has been implemented in the united states, the european union and japan. China also starts a market exit mechanism of hexabromocyclododecane, 20 months in 2017, the Ministry of environmental protection issues a notice of Ministry of toxic chemicals strictly restricted in China (2018), and the exemption period of hexabromocyclododecane is between EPS/XPS and 12 months and 25 days in 2021. Therefore, the key technology for synthesizing the hexabromocyclododecane substitute is broken through, and the research and development of the hexabromocyclododecane substitute and the industrialization are imminent. 24.9.2013, the united states Environmental Protection Agency (EPA) promulgates a report draft for a replacement for the flame retardant Hexabromocyclododecane (HBCD) according to the environmental design (DfE) project. It is clear that tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether is a good substitute for hexabromocyclododecane.
Tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch and products thereof are not reported in related patent documents at home and abroad, and samples trial-produced by domestic flame-retardant master batch processing enterprises have the defects of low flame retardant content, yellow product color, poor product thermal stability and compatibility, large consumption of flame-retardant master batch and the like, and cannot meet the use requirements of downstream customers.
At present, flame retardant modification of EPS/XPS heat insulation materials is mostly realized by directly adding flame retardants, but various flame retardants are mostly powder, so that the dispersibility is poor, the production process is not easy to control and operate, the flame retardant effect is difficult to ensure, and the like due to the direct addition, the problems can be well solved by using the flame retardant master batch, and the waste can be avoided and the environmental pollution can be reduced.
With the improvement of science and technology and the improvement of living standard, the status of polymer materials, especially synthetic polymers such as plastics and rubber, in the life of people is more and more important, and the application of the polymer materials is expanded year by year. However, most organic polymer materials have the characteristic of flammability in air to different degrees, and flame retardant modification of the organic polymer materials for application in various industries such as military, aerospace, transportation, electric power, civil and the like is a new problem. The thermoplastic ethylene-butyl acrylate copolymer (EBA) prepared by copolymerizing ethylene and butyl acrylate has good flexibility, impact resistance, bending fatigue resistance, thermal stability and processability, but the application of the EBA in some fields is hindered by the extremely combustible characteristic of the EBA, so that the preparation of the flame-retardant EBA material and the improvement of the use safety of the flame-retardant EBA material are very necessary. At present, the ideal method for modifying the flame retardance of plastics is to add products such as flame retardants or flame-retardant master batches to improve the fireproof performance of the plastics.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch which has high flame retardant content, milky product, high product thermal stability, good compatibility, small influence on the mechanical property of the material by using the flame-retardant master batch, no toxicity, no bioaccumulation and no biological amplification effect and the preparation method thereof.
The technical scheme adopted by the invention for solving the technical problem is as follows:
the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch comprises the following raw materials in parts by weight: 40-45 parts of high-flow EBA resin, 30-35 parts of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, 15-20 parts of calcium stearate, 2-4 parts of hydrotalcite, 5-10 parts of flame retardant synergist, 4-5 parts of processing aid, 0.1-0.4 part of TGIC and 0.5-1 part of light stabilizer.
Preferably, the raw materials comprise the following components in parts by weight: 42 parts of high-flow EBA resin, 32 parts of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, 18 parts of calcium stearate, 3 parts of hydrotalcite, 8 parts of flame retardant synergist, 5 parts of processing aid, 0.3 part of TGIC and 0.7 part of light stabilizer.
Preferably, the high flow EBA resin is 3717AC and the high flow EBA resin is dried at 80 ℃ to a moisture content of less than 100ppm before use.
Preferably, the flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether has a bromine content of not less than 65%, a melting point of 110-115 ℃, a 5% WLT of not less than 250 ℃ and a content of not less than 98.5%.
Preferably, the flame-retardant synergist is antimony trioxide or antimony trioxide treated by an aluminate coupling agent.
Preferably, the processing aid is polyethylene wax; the light stabilizer is an ultraviolet absorber.
The preparation method of the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch comprises the following steps:
1) weighing: weighing high-flow EBA resin, flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, calcium stearate, hydrotalcite, flame retardant synergist, processing aid, TGIC and light stabilizer according to the required weight parts;
2) mixing: adding half of the EBA resin and half of the processing aid weighed in the step 1) into a high-efficiency mixer for high-speed mixing and stirring, adding half of the flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether weighed in the step 1), and mixing and stirring; sequentially and respectively adding the rest parts by weight of EBA resin, the rest parts by weight of processing aid, the rest parts by weight of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, the calcium stearate, the hydrotalcite, the flame retardant synergist, the TGIC and the light stabilizer weighed in the step 1), mixing and stirring again until the mixture is uniformly mixed to obtain a mixture;
3) and (3) extruding and granulating: transferring the mixture prepared in the step 2) into a screw extruder, and performing melt extrusion granulation through the screw extruder to obtain the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch.
Preferably, in the step 3), when the screw extruder is subjected to melt extrusion granulation, a double vacuum system is started, the high-flow EBA resin carrier is firstly used for discharging, and after the discharged material stably flows out linearly, the mixture prepared in the step 2) is replaced for melt extrusion granulation.
Preferably, in the step 3), the rotating speed of the screw of the main machine of the screw extruder is 250r/min, and the melt pressure is 1.4 MPa.
Preferably, the melting temperature is set in a partition manner, and the set temperature in the partition manner is 20 ℃, 70 ℃, 90 ℃, 95 ℃, 95 ℃, 100 ℃, 110 ℃, 105 ℃, 100 ℃, 90 ℃, 80 ℃ and 80 ℃ in sequence.
The invention has the beneficial effects that:
(1) the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch prepared by the invention has good compatibility with a base material, small influence on the mechanical property of resin and small using amount of the flame-retardant master batch, and reduces the production cost while ensuring the excellent performance of a product.
The tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch and the preparation method thereof adopt tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether as a flame-retardant main body, special type EBA as a carrier, coat tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame retardant powder and assist auxiliary agents such as synergy and reinforcement to prepare the flame-retardant master batch with good compatibility.
(2) The tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch and the preparation method thereof have the advantages of simple process operation and easy implementation, and can be used for industrial production and implementation.
(3) The flame-retardant master batch is a granular product prepared by organic combination, modification treatment and synergistic effect of a plurality of flame-retardant components on the basis of a flame retardant. Different from a flame retardant, the flame-retardant master batch has the advantages of easiness in adding into resin, cleanness, sanitation, high flame-retardant efficiency, small addition amount, small influence on the mechanical property of the resin, difficulty in generating adverse phenomena such as layering, patterns and precipitation after adding, labor and material cost saving, time saving and the like. Therefore, the flame-retardant master batch becomes one of the best choices for realizing the fireproof requirements of the high polymer material products and becomes an effective substitute of flame retardant powder.
The flame retardant used in the invention is tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, and the flame retardant is a good substitute of Hexabromocyclododecane (HBCD).
Detailed Description
The present invention will be further described with reference to specific examples to assist understanding of the invention. The method used in the invention is a conventional production method if no special provisions are made; the starting materials used, unless otherwise specified, are conventional commercial products.
Example 1
The method for preparing the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch comprises the following steps:
1) weighing: weighing 40 parts of high-flow EBA resin, 30 parts of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, 15 parts of calcium stearate, 2 parts of hydrotalcite, 5 parts of flame retardant synergist antimony trioxide, 4 parts of processing aid polyethylene wax, 0.1 part of TGIC and 0.5 part of light stabilizer according to the required parts by weight; the type of the high-flow EBA resin is 3717AC, and the high-flow EBA resin needs to be dried at 80 ℃ until the moisture is less than 100ppm before use; the bromine content of the flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether is more than or equal to 65 percent, the melting point is 110-115 ℃, the 5 percent WLT is more than or equal to 250 ℃, and the content is more than or equal to 98.5 percent; the light stabilizer is ultraviolet absorbent phenyl salicylate.
2) Mixing: adding half of the EBA resin and half of the processing aid weighed in the step 1) into a high-efficiency mixer for high-speed mixing and stirring for 5min, adding half of the flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether weighed in the step 1), and mixing and stirring for 10 min; and sequentially adding the rest parts by weight of EBA resin, the rest parts by weight of processing aid, the rest parts by weight of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, the calcium stearate, the hydrotalcite, the flame retardant synergist, the TGIC and the light stabilizer weighed in the step 1), mixing and stirring for 10min again until the mixture is uniformly mixed to obtain a mixture.
3) And (3) extruding and granulating: transferring the mixture prepared in the step 2) into a screw extruder, starting a double vacuum system, performing melt extrusion granulation, water cooling, air drying, grain cutting, drying and packaging through the screw extruder to obtain the white tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch.
And (3) when the screw extruder is subjected to melt extrusion granulation, starting a double vacuum system, firstly, feeding the high-flow EBA resin carrier, and replacing the high-flow EBA resin carrier with the mixture prepared in the step 2) for feeding when the discharged material is stable and flows out linearly, wherein the feeding speed is set by the host machine to be 10KG/h, and performing melt extrusion granulation. The rotating speed of a screw of a main machine of the screw extruder is 250r/min, and the melt pressure is 1.4 MPa; the melting temperature is set in a subarea mode, and the subarea set temperature is 20 ℃, 70 ℃, 90 ℃, 95 ℃, 95 ℃, 100 ℃, 110 ℃, 105 ℃, 100 ℃, 90 ℃, 80 ℃ in sequence.
Example 2
The method for preparing the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch comprises the following steps:
1) weighing: weighing 45 parts of high-flow EBA resin, 35 parts of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, 20 parts of calcium stearate, 4 parts of hydrotalcite, 10 parts of flame retardant synergist antimony trioxide, 5 parts of processing aid polyethylene wax, 0.4 part of TGIC and 1 part of light stabilizer according to required parts by weight; the type of the high-flow EBA resin is 3717AC, and the high-flow EBA resin needs to be dried at 80 ℃ until the moisture is less than 100ppm before use; the bromine content of the flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether is more than or equal to 65 percent, the melting point is 110-115 ℃, the 5 percent WLT is more than or equal to 250 ℃, and the content is more than or equal to 98.5 percent; the light stabilizer is ultraviolet absorbent phenyl salicylate.
2) Mixing: adding half of the EBA resin and half of the processing aid weighed in the step 1) into a high-efficiency mixer for high-speed mixing and stirring for 10min, adding half of the flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether weighed in the step 1), and mixing and stirring for 10 min; and sequentially adding the rest parts by weight of EBA resin, the rest parts by weight of processing aid, the rest parts by weight of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, the calcium stearate, the hydrotalcite, the flame retardant synergist, the TGIC and the light stabilizer weighed in the step 1), mixing and stirring for 10min again until the mixture is uniformly mixed to obtain a mixture.
3) And (3) extruding and granulating: transferring the mixture prepared in the step 2) into a screw extruder, starting a double vacuum system, performing melt extrusion granulation, water cooling, air drying, grain cutting, drying and packaging through the screw extruder to obtain the white tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch.
And (3) when the screw extruder is subjected to melt extrusion granulation, starting a double vacuum system, firstly, feeding the high-flow EBA resin carrier, and replacing the high-flow EBA resin carrier with the mixture prepared in the step 2) for feeding when the discharged material is stable and flows out linearly, wherein the feeding speed is set by the host machine to be 10KG/h, and performing melt extrusion granulation. The screw rotating speed of the main machine of the screw extruder is 250r/min, and the melt pressure is 1.4 MPa. The melting temperature is set in a subarea mode, and the subarea set temperature is 20 ℃, 70 ℃, 90 ℃, 95 ℃, 95 ℃, 100 ℃, 110 ℃, 105 ℃, 100 ℃, 90 ℃, 80 ℃ in sequence.
Example 3
The method for preparing the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch comprises the following steps:
1) weighing: weighing 42 parts of high-flow EBA resin, 32 parts of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, 17 parts of calcium stearate, 3 parts of hydrotalcite, 6 parts of antimony trioxide treated by an aluminate coupling agent as a flame retardant synergist, 5 parts of processing aid polyethylene wax, 0.3 part of TGIC and 0.7 part of light stabilizer according to the required parts by weight; the type of the high-flow EBA resin is 3717AC, and the high-flow EBA resin needs to be dried at 80 ℃ until the moisture is less than 100ppm before use; the bromine content of the flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether is more than or equal to 65 percent, the melting point is 110-115 ℃, the 5 percent WLT is more than or equal to 250 ℃, and the content is more than or equal to 98.5 percent; the light stabilizer is ultraviolet absorbent phenyl salicylate.
2) Mixing: adding half of the EBA resin and half of the processing aid weighed in the step 1) into a high-efficiency mixer for high-speed mixing and stirring for 10min, adding half of the flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether weighed in the step 1), and mixing and stirring for 10 min; and sequentially adding the rest parts by weight of EBA resin, the rest parts by weight of processing aid, the rest parts by weight of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, the calcium stearate, the hydrotalcite, the flame retardant synergist, the TGIC and the light stabilizer weighed in the step 1), mixing and stirring for 10min again until the mixture is uniformly mixed to obtain a mixture.
3) And (3) extruding and granulating: transferring the mixture prepared in the step 2) into a screw extruder, starting a double vacuum system, performing melt extrusion granulation, water cooling, air drying, grain cutting, drying and packaging through the screw extruder to obtain the white tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch.
And (3) when the screw extruder is subjected to melt extrusion granulation, starting a double vacuum system, firstly, feeding the high-flow EBA resin carrier, and replacing the high-flow EBA resin carrier with the mixture prepared in the step 2) for feeding when the discharged material is stable and flows out linearly, wherein the feeding speed is set by the host machine to be 10KG/h, and performing melt extrusion granulation. The screw rotating speed of the main machine of the screw extruder is 250r/min, and the melt pressure is 1.4 MPa. The melting temperature is set in a subarea mode, and the subarea set temperature is 20 ℃, 70 ℃, 90 ℃, 95 ℃, 95 ℃, 100 ℃, 110 ℃, 105 ℃, 100 ℃, 90 ℃, 80 ℃ in sequence.
Example 4
The method for preparing the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch comprises the following steps:
1) weighing: weighing 44 parts of high-flow EBA resin, 34 parts of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, 18 parts of calcium stearate, 4 parts of hydrotalcite, 8 parts of antimony trioxide treated by aluminate coupling agent as flame retardant synergist, 5 parts of processing aid polyethylene wax, 0.3 part of TGIC and 0.9 part of light stabilizer according to required weight parts; the type of the high-flow EBA resin is 3717AC, and the high-flow EBA resin needs to be dried at 80 ℃ until the moisture is less than 100ppm before use; the bromine content of the flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether is more than or equal to 65 percent, the melting point is 110-115 ℃, the 5 percent WLT is more than or equal to 250 ℃, and the content is more than or equal to 98.5 percent; the light stabilizer is ultraviolet absorbent phenyl salicylate.
2) Mixing: adding half of the EBA resin and half of the processing aid weighed in the step 1) into a high-efficiency mixer for high-speed mixing and stirring for 5-10min, adding half of the flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether weighed in the step 1), and mixing and stirring for 10 min; and sequentially adding the rest parts by weight of EBA resin, the rest parts by weight of processing aid, the rest parts by weight of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, the calcium stearate, the hydrotalcite, the flame retardant synergist, the TGIC and the light stabilizer weighed in the step 1), mixing and stirring for 10min again until the mixture is uniformly mixed to obtain a mixture.
3) And (3) extruding and granulating: transferring the mixture prepared in the step 2) into a screw extruder, starting a double vacuum system, performing melt extrusion granulation, water cooling, air drying, grain cutting, drying and packaging through the screw extruder to obtain the white tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch.
And (3) when the screw extruder is subjected to melt extrusion granulation, starting a double vacuum system, firstly, feeding the high-flow EBA resin carrier, and replacing the high-flow EBA resin carrier with the mixture prepared in the step 2) for feeding when the discharged material is stable and flows out linearly, wherein the feeding speed is set by the host machine to be 10KG/h, and performing melt extrusion granulation. The screw rotating speed of the main machine of the screw extruder is 250r/min, and the melt pressure is 1.4 MPa. The melting temperature is set in a subarea mode, and the subarea set temperature is 20 ℃, 70 ℃, 90 ℃, 95 ℃, 95 ℃, 100 ℃, 110 ℃, 105 ℃, 100 ℃, 90 ℃, 80 ℃ in sequence.
Example 5
The method for preparing the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch comprises the following steps:
1) weighing: weighing 42 parts of high-flow EBA resin, 32 parts of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, 18 parts of calcium stearate, 3 parts of hydrotalcite, 8 parts of antimony trioxide treated by aluminate coupling agent as flame retardant synergist, 5 parts of processing aid polyethylene wax, 0.3 part of TGIC and 0.7 part of light stabilizer according to the required weight parts; the type of the high-flow EBA resin is 3717AC, and the high-flow EBA resin needs to be dried at 80 ℃ until the moisture is less than 100ppm before use; the bromine content of the flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether is more than or equal to 65 percent, the melting point is 110-115 ℃, the 5 percent WLT is more than or equal to 250 ℃, and the content is more than or equal to 98.5 percent; the light stabilizer is ultraviolet absorbent phenyl salicylate.
2) Mixing: adding half of the EBA resin and half of the processing aid weighed in the step 1) into a high-efficiency mixer for high-speed mixing and stirring for 5-10min, adding half of the flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether weighed in the step 1), and mixing and stirring for 10 min; and sequentially adding the rest parts by weight of EBA resin, the rest parts by weight of processing aid, the rest parts by weight of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, the calcium stearate, the hydrotalcite, the flame retardant synergist, the TGIC and the light stabilizer weighed in the step 1), mixing and stirring for 10min again until the mixture is uniformly mixed to obtain a mixture.
3) And (3) extruding and granulating: transferring the mixture prepared in the step 2) into a screw extruder, starting a double vacuum system, performing melt extrusion granulation, water cooling, air drying, grain cutting, drying and packaging through the screw extruder to obtain the white tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch.
And (3) when the screw extruder is subjected to melt extrusion granulation, starting a double vacuum system, firstly, feeding the high-flow EBA resin carrier, and replacing the high-flow EBA resin carrier with the mixture prepared in the step 2) for feeding when the discharged material is stable and flows out linearly, wherein the feeding speed is set by the host machine to be 10KG/h, and performing melt extrusion granulation. The screw rotating speed of the main machine of the screw extruder is 250r/min, and the melt pressure is 1.4 MPa. The melting temperature is set in a subarea mode, and the subarea set temperature is 20 ℃, 70 ℃, 90 ℃, 95 ℃, 95 ℃, 100 ℃, 110 ℃, 105 ℃, 100 ℃, 90 ℃, 80 ℃ in sequence.
Control group 1
The method for preparing the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch comprises the following steps:
1) weighing: weighing 42 parts of high-flow EBA resin, 32 parts of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, 18 parts of calcium stearate, 3 parts of hydrotalcite, 8 parts of antimony trioxide treated by aluminate coupling agent as flame retardant synergist, 5 parts of processing aid polyethylene wax and 0.7 part of light stabilizer according to the required weight parts; the type of the high-flow EBA resin is 3717AC, and the high-flow EBA resin needs to be dried at 80 ℃ until the moisture is less than 100ppm before use; the bromine content of the flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether is more than or equal to 65 percent, the melting point is 110-115 ℃, the 5 percent WLT is more than or equal to 250 ℃, and the content is more than or equal to 98.5 percent; the light stabilizer is ultraviolet absorbent phenyl salicylate.
2) Mixing: adding half of the EBA resin and half of the processing aid weighed in the step 1) into a high-efficiency mixer for high-speed mixing and stirring for 5-10min, adding half of the flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether weighed in the step 1), and mixing and stirring for 10 min; and sequentially adding the rest parts by weight of EBA resin, the rest parts by weight of processing aid, the rest parts by weight of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, the calcium stearate, the hydrotalcite, the flame retardant synergist and the light stabilizer weighed in the step 1), mixing and stirring for 10min again until the mixture is uniformly mixed to obtain a mixture.
3) And (3) extruding and granulating: transferring the mixture prepared in the step 2) into a screw extruder, starting a double vacuum system, performing melt extrusion granulation, water cooling, air drying, grain cutting, drying and packaging through the screw extruder to obtain the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch.
And (3) when the screw extruder is subjected to melt extrusion granulation, starting a double vacuum system, firstly, feeding the high-flow EBA resin carrier, and replacing the high-flow EBA resin carrier with the mixture prepared in the step 2) for feeding when the discharged material is stable and flows out linearly, wherein the feeding speed is set by the host machine to be 10KG/h, and performing melt extrusion granulation. The screw rotating speed of the main machine of the screw extruder is 250r/min, and the melt pressure is 1.4 MPa. The melting temperature is set in a subarea mode, and the subarea set temperature is 20 ℃, 70 ℃, 90 ℃, 95 ℃, 95 ℃, 100 ℃, 110 ℃, 105 ℃, 100 ℃, 90 ℃, 80 ℃ in sequence.
The properties of the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame retardant masterbatch of the present invention are further illustrated by the test report below.
1. Object and method
(1) The test substance: tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch produced by the preparation methods given in examples 1 to 5 of the present invention is used as a sample to be tested, tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch produced by the preparation method given in a control group 1 is used as a sample to be compared, wherein the process parameters of the preparation method of the control group 1 are the same as those of the preparation method of example 5, only are different from those of the raw material components of example 5, and no TGIC is added in the raw material components of the control group 1; control 2 was a commercial hexabromocyclododecane flame retardant masterbatch.
Respectively adding 7 weight percent of flame-retardant master batch into the flame-retardant master batch of tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether test sample and the flame-retardant master batch of a control group 1 and a control group 2, which are produced in the embodiments 1 to 5, into an EBA resin base material, uniformly mixing in a mixer, and performing injection molding to obtain flame-retardant EBA product test samples 1 to 5, the EBA product control group 1 and the EBA product control group 2; control 3 is an EBA resin substrate without the addition of flame retardant masterbatch.
(2) Test method
And (5) detecting the mechanical property and the combustion property of the EBA product.
2. Test results and conclusions
The results of the comparison of the mechanical properties of the materials are shown in Table 1.
TABLE 1 results of mechanical Properties and Combustion Properties of EBA articles
Ignition time in table 1: the flame vertically ignites the sample, leaves the flame after 10s, and if the flame is self-extinguished, the flame is re-ignited, the time from the ignition of the sample to the leaving of the flame is gradually shortened until the sample is not extinguished after leaving the flame, the used time is recorded, and the longer the ignition time of the sample is, the better the flame-retardant effect is. Therefore, the flame retardant performance of the EBA resin base material is improved by adding the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame retardant master batch of the invention into the EBA resin base material, and the flame retardant effect of the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame retardant master batch of the invention is better than that of the common hexabromocyclododecane flame retardant master batch of the control group 2.
According to the detection results of the mechanical properties and the combustion properties of the EBA product in the table 1, 7 weight percent of the flame-retardant master batch is added with the EBA resin base material and uniformly mixed in a mixer, and the flame-retardant EBA product test samples 1-5, the EBA product control group 1 and the EBA product control group 2 are obtained through injection molding; the comparison group 3 is an EBA resin base material without adding the flame-retardant master batch, the mechanical properties of EBA product test samples 1-5 are hardly reduced compared with the mechanical properties of the EBA resin base material without adding the flame-retardant master batch, however, the mechanical properties of the comparison group 2 are reduced to a certain extent when adding the commercially available hexabromocyclododecane flame-retardant master batch, so that the mechanical properties of the EBA resin base material are hardly influenced by the addition of the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch, the flame-retardant property of the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch is remarkably improved, and the ignition time is remarkably improved from 24.8s to 39.2s to 45.2s, further explaining that the compatibility of the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch is good.
Tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batches prepared in the embodiments 1 to 5 of the invention have the following appearance: the granules have uniform size, no granule adhesion phenomenon, white color and wide application range.
The flame-retardant master batch is a granular product prepared by organic combination, modification treatment and synergistic effect of a plurality of flame-retardant components on the basis of a flame retardant. Different from a flame retardant, the flame-retardant master batch has the advantages of easiness in adding into resin, cleanness, sanitation, high flame-retardant efficiency, small addition amount, small influence on the mechanical property of the resin, difficulty in generating adverse phenomena such as layering, patterns and precipitation after adding, labor and material cost saving, time saving and the like. Therefore, the flame-retardant master batch becomes one of the best choices for realizing the fireproof requirements of the high polymer material products and becomes an effective substitute of flame retardant powder.
Compared with the prior art, the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch prepared by the invention has the advantages of good flame-retardant effect, good dispersibility, wide adaptability, convenience in use and the like, and can realize halogen-free flame retardance, environmental protection and high efficiency and meet the UL94V-0 level flame-retardant performance requirement when used in an EPS/XPS heat-insulating material, so that the flame-retardant master batch has remarkable social and economic benefits. In particular, tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether is used for replacing the traditional hexabromocyclododecane, the hexabromocyclododecane has strong bioaccumulation and biological amplification effects and has toxic hazard to human endocrine systems and reproductive systems, and the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether used in the invention is nontoxic, has no bioaccumulation and biological amplification effects as a flame retardant, accords with the green, energy-saving and environment-friendly concept pursued by the current society, and is beneficial to sustainable development. The flame retardant used in the invention is tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, and the flame retardant is a good substitute of Hexabromocyclododecane (HBCD).
In the raw material components for preparing the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch, TGIC (1,3, 5-triglycidyl-S-triazine trione; tris (epoxypropyl isocyanurate)) is white particles or powder, is a heterocyclic epoxy compound, has good heat resistance and weather resistance, adhesion and excellent high-temperature performance, and has a melting point of 88-98 ℃. The main applications in the prior art are: used as a crosslinking curing agent of pure polyester powder coating and used as a crosslinking curing agent of carboxyl-containing Polyacrylate (PA). In the formula of the invention, TGIC is used as an antioxidant, and compared with the performance of tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batches of examples 1 to 5 in the table 1 and the performance of tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batches of a comparison group 1, the preparation method process parameters of the comparison group 1 are the same as those of the preparation method of the example 5, only different from the raw material components of the example 5, no TGIC is added in the raw material components of the comparison group 1, and when only a small amount of TGIC exists in the raw material components of the examples 1 to 5, the oxidation process of the polymer can be delayed or inhibited, so that the aging of the polymer is prevented, the service life of the polymer is prolonged, the influence on the mechanical property of an EBA product is obviously improved, and the combustion performance of the EBA product is also obviously improved.
According to the preparation method of the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch, the temperature of each area of a screw extruder is accurately controlled according to the characteristic requirement of a master batch melting process, so that the sufficient melting and molecular polymerization effects of the raw materials prepared from the master batch are ensured; then, a high-frequency pulse current is used for generating an alternating magnetic field changing at a high speed, so that a metal melting cylinder generates vortex to enable a metal material to rapidly heat, the diffusion activation performance of a molecular chain of a high-molecular mixed polymer melt is improved, tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether is used as a flame retardant main body, special type EBA is used as a carrier, tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame retardant powder is coated, and auxiliary agents such as synergistic agents, reinforcing agents and the like are used for preparing flame retardant master batches with good compatibility.
In conclusion, the tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch and the preparation method thereof have the advantages of simple process operation and easy implementation, and can be used for industrial production and implementation; the flame-retardant master batch has good compatibility with a base material, has small influence on the mechanical property of resin, has small using amount, ensures that the product has excellent performance, and reduces the production cost.
However, the above description is only an embodiment of the present invention, and the scope of the present invention should not be limited by this, and all equivalent changes and modifications made in the claims of the present invention should be covered by the present invention.
Claims (7)
1. The tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch is characterized by comprising the following raw material components in parts by weight: 40-45 parts of EBA resin 3717AC, 30-35 parts of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, 15-20 parts of calcium stearate, 2-4 parts of hydrotalcite, 5-10 parts of flame retardant synergist, 4-5 parts of processing aid polyethylene wax, 0.1-0.4 part of antioxidant TGIC and 0.5-1 part of light stabilizer ultraviolet absorbent; the flame-retardant synergist is antimony trioxide or antimony trioxide treated by an aluminate coupling agent.
2. The flame-retardant masterbatch of tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether according to claim 1, wherein the raw materials comprise, in parts by weight: 42 parts of EBA resin 3717AC, 32 parts of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, 18 parts of calcium stearate, 3 parts of hydrotalcite, 8 parts of flame retardant synergist, 5 parts of processing aid polyethylene wax, 0.3 part of TGIC and 0.7 part of light stabilizer ultraviolet absorber.
3. The flame-retardant masterbatch of tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether according to claim 1, wherein the EBA resin 3717AC is dried at 80 ℃ until the moisture content is less than 100ppm before use.
4. The flame-retardant masterbatch of tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether as claimed in claim 1, wherein the flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether has a bromine content of 65% or more, a melting point of 110-.
5. The method for preparing tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant masterbatch according to any one of claims 1 to 4, comprising the steps of:
1) weighing: weighing EBA resin 3717AC, flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, calcium stearate, hydrotalcite, flame retardant synergist, processing aid, TGIC and light stabilizer according to required weight parts;
2) mixing: adding half of the EBA resin and half of the processing aid weighed in the step 1) into a high-efficiency mixer for high-speed mixing and stirring, adding half of the flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether weighed in the step 1), and mixing and stirring; sequentially and respectively adding the rest parts by weight of EBA resin, the rest parts by weight of processing aid, the rest parts by weight of flame retardant tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether, the calcium stearate, the hydrotalcite, the flame retardant synergist, the TGIC and the light stabilizer weighed in the step 1), mixing and stirring again until the mixture is uniformly mixed to obtain a mixture;
3) and (3) extruding and granulating: transferring the mixture prepared in the step 2) into a screw extruder, and performing melt extrusion granulation through the screw extruder to obtain tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant master batch; and (3) when the screw extruder is subjected to melt extrusion granulation, starting a double-vacuum system, feeding by using an EBA resin 3717AC carrier, and replacing the mixture prepared in the step 2) for melt extrusion granulation after the discharged material is stable and flows out linearly.
6. The method for preparing tetrabromobisphenol A bis (2, 3-dibromo-2-methylpropyl) ether flame-retardant masterbatch according to claim 5, wherein in step 3), the screw rotation speed of the main machine of the screw extruder is 250r/min, and the melt pressure is 1.4 MPa.
7. The method of claim 5, wherein the melting temperature is set in a zone-by-zone manner, and the set temperature in the zone-by-zone manner is 20 ℃, 70 ℃, 90 ℃, 95 ℃, 100 ℃, 110 ℃, 105 ℃, 100 ℃, 90 ℃, 80 ℃ and 80 ℃ in sequence.
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Effective date of registration: 20240612 Address after: 261108 East of Lingang Road and north of Liaohe West Street, Binhai Economic and Technological Development Zone, Weifang City, Shandong Province Patentee after: Weifang Runpu Chemical Co.,Ltd. Country or region after: China Address before: 262737 South expansion of Lingang Industrial Park, Binhai Economic and Technological Development Zone, Weifang City, Shandong Province Patentee before: SHANDONG RUNKE CHEMICAL Co.,Ltd. Country or region before: China |