CN117986633B - Preparation method and application of brominated flame retardant masterbatch - Google Patents
Preparation method and application of brominated flame retardant masterbatch Download PDFInfo
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Abstract
本发明公开了一种溴系阻燃剂母粒的制备方法及其应用，属于热塑性树脂阻燃技术领域，向反应器中加入OBDPE和DBDPE，形成DBDPE‑OBDPE溶液DOS，加入活性超细碳酸亚铁，搅拌混合均匀，冷却后破碎成初级粉末，并与协效阻燃剂和吸酸剂放入全方位行星式球磨机中球磨，球磨后的混合阻燃剂与相容剂、润滑剂、干燥的树脂混合，加入螺杆挤出机的料斗中，经挤出，造粒，得到溴系阻燃剂母粒，再与树脂混合，添加玻璃纤维，经螺杆挤出机挤出，制得样条，达到高阻燃性能和力学性能。本发明制备的阻燃剂母粒与树脂之间实现分子水平/纳米尺度的分散，并消除了HBr气体对环境的污染，减少了阻燃剂的用量，提高了树脂的耐热温度，增强了材料的力学性能，降低了生产成本。The invention discloses a preparation method and application of a bromine flame retardant masterbatch, belonging to the technical field of thermoplastic resin flame retardant, adding OBDPE and DBDPE into a reactor, forming a DBDPE-OBDPE solution DOS, adding active ultrafine ferrous carbonate, stirring and mixing evenly, breaking into primary powder after cooling, and putting into a full-scale planetary ball mill with a synergistic flame retardant and an acid absorber for ball milling, the mixed flame retardant after ball milling is mixed with a compatibilizer, a lubricant, and a dried resin, added to the hopper of a screw extruder, extruded, granulated, and a bromine flame retardant masterbatch is obtained, and then mixed with a resin, glass fiber is added, extruded by a screw extruder, and a strip is obtained, achieving high flame retardant performance and mechanical properties. The flame retardant masterbatch prepared by the present invention realizes molecular level/nanoscale dispersion between the resin, eliminates the pollution of HBr gas to the environment, reduces the amount of flame retardant, improves the heat-resistant temperature of the resin, enhances the mechanical properties of the material, and reduces production costs.
Description
Technical Field
The invention relates to the technical field of thermoplastic resin flame retardance, in particular to a preparation method and application of a brominated flame retardant master batch.
Background
Thermoplastic resins are widely used in the automotive industry, aerospace, infrastructure, and photovoltaic industries, among others. The glass fiber reinforced resin has the advantages of light weight, corrosion resistance and obvious improvement of mechanical properties. At present, when the glass fiber reinforced thermoplastic composite material is practically applied, higher requirements are put on flame retardant performance. Flame retardants that can be used in glass fiber reinforced thermoplastic resins are metal hydroxide flame retardants, nitrogen (N) flame retardants, phosphorus (P) flame retardants, P-N flame retardants (also known as intumescent flame retardants) and brominated flame retardants. The brominated flame retardant has the advantages of good stability, small addition amount, good compatibility with resin materials and small influence on the mechanical properties of the resin. However, HBr gas is generated under the high temperature condition of combustion, wherein the decabromodiphenyl ether flame retardant also generates harmful substances such as polybrominated dibenzofuran (PBDF)/polybrominated dibenzodioxin (PBDD) and the like in the flame retardant process, and is limited by RoHS (Restriction of Hazardous Substances).
However, a great deal of research shows that decabromodiphenylethane (DBDPE) does not contain ether bonds, PBDF/PBDD is not generated, and the flame retardant property is similar to that of decabromodiphenylether, so that DBDPE becomes a broad-spectrum additive flame retardant and is usually used in cooperation with antimony trioxide (AO). But the DBDPE has high melting point (357 ℃) and larger primary particle diameter (2-50 mu m) without melting in the screw extrusion process, so that the flame retardant DBDPE has poor dispersibility in resin melt, large addition amount and high cost ratio of raw materials, and the mechanical property of the composite material is also reduced. Octabromodiphenylethane (OBDPE) has similar molecular structure to DBDPE and similar flame retardant properties to DBDPE, but about 25% lower than DBDPE due to 2 Br atoms less per molecule.
How to fully exert the advantages of DBDPE, reduce the particle size of DBDPE, enhance the dispersion performance of DBDPE in resin, and eliminate the harm of HBr gas at the same time, thus becoming a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a preparation method and application of a brominated flame retardant master batch, which solve the comprehensive problems of high consumption of brominated flame retardant, poor dispersibility, generation of HBr gas and the like, the method ensures that a high-melting-point flame retardant DBDPE is dissolved in a low-melting-point OBDPE, and active superfine ferrous carbonate is used for preventing solidification and phase separation, and molecular level/nanoscale dispersion is realized with resin, so that pollution of HBr gas to the environment is eliminated, the consumption of flame retardant is reduced, the heat-resistant temperature of the resin is improved, and the production cost is reduced.
In order to achieve the above purpose, the invention provides a preparation method of a brominated flame retardant master batch, which specifically comprises the following steps:
s1, placing octabromodiphenyl ether OBDPE and decabromodiphenyl ethane DBDPE powder into a reactor, heating to OBDPE to melt, dissolving DBDPE in OBDPE liquid to form DBDPE-OBDPE solution DOS, adding active superfine ferrous carbonate powder into the DOS under strong stirring, stirring and mixing uniformly to form dispersion slurry, discharging the slurry while the slurry is hot, cooling to obtain a solid mixture of DBDPE, active superfine ferrous carbonate powder and OBDPE which are uniformly mixed to achieve uniform dispersed molecular level/nano scale, and crushing the solid mixture into primary powder;
S2, putting the mixture primary powder obtained in the step S1, the synergistic flame retardant and the acid absorber in proportion into an omnibearing planetary ball mill for ball milling to obtain a mixed flame retardant;
s3, placing the mixed flame retardant obtained in the step S2, the compatilizer, the lubricant and the dried resin into a high-speed stirrer for uniform mixing;
and S4, adding the mixture obtained in the step S3 into a hopper of a screw extruder, extruding, and granulating to obtain the brominated flame retardant master batch.
Preferably, in the step S1, the mass ratio of DBDPE to OBDPE is 1:1-5:1, and the liquid DOS is formed by putting the liquid DOS into a reactor to be melted OBDPE and dissolved into the DBDPE at a temperature of 170-200 ℃.
Preferably, the active superfine ferrous carbonate in the step S1 is superfine powder after being surface modified by cetyl trimethyl ammonium bromide salt, sodium dodecyl sulfonate, a silane coupling agent and a titanate coupling agent, the particle size range of the superfine ferrous carbonate is 100 nm-900 nm, and the addition amount of the ferrous carbonate is 0.25-0.25 wt.5 wt% of the total mass of the OBDPE and DBDPE.
Preferably, the synergistic flame retardant in the step S2 is AO, the acid absorber is HT or talcum powder, and the content of the primary powder of the mixture, the synergistic flame retardant and the acid absorber in the mixed flame retardant respectively account for 20% -50%, 10% -15% and 0% -20% of the content of the flame retardant master batch.
Preferably, the compatilizer in the step S3 is a polymer containing carboxyl, anhydride group, hydroxyl and ketone group which are chemically modified and account for 2% of the content of the flame retardant master batch, the lubricant is stearic acid and silicone master batch, and the stearic acid and the silicone master batch respectively account for 1.1% and 0.9% of the content of the flame retardant master batch.
Preferably, the resin in the step S3 is one of polyethylene, polypropylene, polystyrene, polyamide, polycarbonate, polyethylene terephthalate and polymethyl methacrylate.
Preferably, the highest temperature of the screw extruder extrusion in the step S4 is 10-20 ℃ higher than the melting point of the resin.
The invention provides an application of a brominated flame retardant master batch, which utilizes the prepared brominated flame retardant master batch to flame retardant thermoplastic resin.
The invention also provides application of the brominated flame retardant master batch, wherein the flame retardant master batch is mixed with resin, glass fibers are added, the flame retardant master batch accounts for 10% -30% of the total addition, the glass fibers account for 10% -50% of the total addition, and the brominated flame retardant sample bar is prepared by extrusion through a screw extruder.
Therefore, the preparation method and the application of the brominated flame retardant master batch have the following beneficial effects:
(1) By utilizing the characteristic that the OBDPE melting point is lower than the melting temperature of the resin, the DBDPE is dissolved by using the liquid OBDPE to achieve uniform molecular level/nano-scale mixing, and also by utilizing the characteristic that the OBDPE melting point is lower than the melting temperature of the resin, the DBDPE higher than the melting point of the resin can achieve near molecular level/nano-scale dispersion mixing in the resin;
(2) After the surface of the active superfine ferrous carbonate is modified, the active superfine ferrous carbonate has good compatibility with OBDPE and DBDPE, and the active superfine ferrous carbonate is added into OBDPE and DBDPE systems, and can prevent OBDPE and DBDPE from solidification and phase separation after cooling and solidification;
(3) Under the high temperature condition of combustion, the ferrous carbonate generates CO 2 and has flame retardant effect. The generated Fe 2O3 and HBr generated under the high temperature condition generate oxidation-reduction action to generate Fe, the Fe catalyzes resin to generate crystalline carbon with a graphene structure, and the crystalline carbon has higher oxygen resistance and plays a role in flame retardance;
(4) The hydrotalcite or talcum powder and the HBr can react to generate AlBr 3 and MgBr 2, so that the harm of HBr gas is eliminated, and simultaneously, the AlBr 3 also has better flame retardant property;
(5) The brominated flame retardant generally needs to be added with the antimonous oxide synergistic flame retardant, so that the flame retardants are uniformly mixed and better dispersed in the resin, and the ball milling method is adopted to mix the flame retardants, so that the particle size is greatly reduced, the supramolecular structure is formed between the flame retardants, the dispersion of the flame retardants in the resin is improved, the consumption of the flame retardants is reduced, the heat-resistant temperature of the resin is improved, the flame retardants are also different from the single flame retardant in thermal decomposition temperature, and the flame retardant performance is improved.
The technical scheme of the invention is further described in detail through examples.
Detailed Description
The technical scheme of the invention is further described below by examples.
In order to more clearly illustrate the present invention, the following description will clearly and completely describe the technical solutions in the embodiments of the present invention. It should be understood that the embodiments described are merely some of the embodiments of the present invention and are merely illustrative of the present invention and do not limit the scope of the present invention.
In the following examples, unless otherwise indicated, the starting materials or processing techniques are all conventional commercially available in the art.
Example 1
The preparation and application of the brominated flame retardant master batch specifically comprises the following steps:
S1, putting DBDPE and OBDPE powder with the mass ratio of 5:1 into a reactor, heating to 180 ℃ to enable OBDPE to be melted, and dissolving DBDPE by using melted OBDPE liquid to form liquid DOS. Adding active superfine ferrous carbonate powder accounting for 0.25 wt% of the total mass of OBDPE and DBDPE into DOS under strong stirring, stirring and mixing uniformly to form stable dispersion slurry, discharging the slurry while hot, cooling to obtain a uniformly mixed and uniformly dispersed solid mixture of DBDPE, active superfine ferrous carbonate and OBDPE in molecular level/nanometer scale, and crushing the solid mixture into primary powder;
S2, weighing the mixture obtained in the step S1, wherein the content of the flame retardant master batch is 50%, the synergistic flame retardant AO, the content of which is 10%, and the acid absorber HT, the content of which is 5%, and putting the mixture into an omnibearing planetary ball mill for ball milling 4 h;
S3, uniformly mixing the flame retardant obtained in the step S2, 2% of compatilizer, 1.1% of stearic acid, 0.9% of silicone master batch and 30% of dry polypropylene in a high-speed stirrer;
s4, adding the mixture obtained in the step S3 into a hopper of a screw extruder, extruding, granulating to obtain brominated flame retardant master batches, and using the brominated flame retardant master batches as flame retardants for polypropylene resin;
S5, mixing 30% of the flame retardant master batch obtained in the step S4, 20% of glass fibers and dried 50% of polypropylene, and preparing a sample bar by a screw extruder to test the flame retardant property and the mechanical property.
The vertical burning level of the prepared sample strip is UL-94V-0 grade, and the mechanical property is improved by 34%.
Example 2
The preparation and application of the brominated flame retardant master batch specifically comprises the following steps:
S1, putting DBDPE and OBDPE powder with the mass ratio of 1:1 into a reactor, heating to 170 ℃ to enable OBDPE to be melted, and simultaneously dissolving DBDPE by using melted OBDPE liquid to form liquid DOS. Adding active superfine ferrous carbonate powder accounting for 2 wt% of the total mass of OBDPE and DBDPE into DOS under strong stirring, stirring and mixing uniformly to form stable dispersion slurry, discharging the slurry while hot, cooling to obtain a uniformly mixed and uniformly dispersed solid mixture of DBDPE, active superfine ferrous carbonate and OBDPE at a molecular level/nanometer scale, and crushing the solid mixture into primary powder;
S2, weighing the mixture obtained in the step S1 with the flame retardant master batch content of 35%, the synergistic flame retardant AO with the flame retardant master batch content of 15% and the acid absorber talcum powder with the flame retardant master batch content of 10%, and putting the mixture into an omnibearing planetary ball mill for ball milling for 4 h;
s3, uniformly mixing the flame retardant obtained in the step S2, 2% of compatilizer, 1.1% of stearic acid, 0.9% of silicone master batch and 35% of dry polyethylene in a high-speed stirrer;
S4, adding the mixture obtained in the step S3 into a hopper of a screw extruder, extruding, granulating to obtain brominated flame retardant master batches, and using the brominated flame retardant master batches as flame retardants for polyethylene resins;
S5, mixing 30% of the flame retardant master batch obtained in the step S4, 10% of glass fibers and 60% of dried polyethylene, and preparing a sample bar by a screw extruder to test the flame retardant property and the mechanical property.
The vertical burning level of the prepared sample strip is UL-94V-0 grade, and the mechanical property is improved by 21%.
Example 3
The preparation and application of the brominated flame retardant master batch specifically comprises the following steps:
S1, putting DBDPE and OBDPE powder with the mass ratio of 2:1 into a reactor, heating to 180 ℃ to enable OBDPE to be melted, and dissolving DBDPE by using melted OBDPE liquid to form liquid DOS. Adding active superfine ferrous carbonate powder accounting for 4 wt% of the total mass of OBDPE and DBDPE into DOS under strong stirring, stirring and mixing uniformly to form stable dispersion slurry, discharging the slurry while hot, cooling to obtain a uniformly mixed and uniformly dispersed solid mixture of DBDPE, active superfine ferrous carbonate and OBDPE at a molecular level/nanometer scale, and crushing the solid mixture into primary powder;
S2, weighing the mixture obtained in the step S1 with the flame retardant master batch content of 25%, the synergistic flame retardant AO with the flame retardant master batch content of 12% and the acid absorber HT with the flame retardant master batch content of 15%, and putting the mixture into an omnibearing planetary ball mill for ball milling 4 h;
S3, uniformly mixing the flame retardant obtained in the step S2, 2% of compatilizer, 1.1% of stearic acid, 0.9% of silicone master batch and 43% of dry polypropylene in a high-speed stirrer;
s4, adding the mixture obtained in the step S3 into a hopper of a screw extruder, extruding, granulating to obtain brominated flame retardant master batches, and using the brominated flame retardant master batches as flame retardants for polypropylene resin;
s5, mixing 25% of the flame retardant master batch obtained in the step S4, 50% of glass fiber and 30% of dried polypropylene, and preparing a sample bar by a screw extruder to test the flame retardant property and the mechanical property.
The vertical burning level of the prepared sample strip is UL-94V-0 grade, and the mechanical property is improved by 78%.
Example 4
The preparation and application of the brominated flame retardant master batch specifically comprises the following steps:
s1, putting DBDPE and OBDPE powder with the mass ratio of 5:1 into a reactor, heating to 170 ℃ to enable OBDPE to be melted, and dissolving DBDPE by using melted OBDPE liquid to form liquid DOS. Adding active superfine ferrous carbonate powder which is OBDPE to wt percent of the total mass of DBDPE into DOS under strong stirring, stirring and mixing uniformly to form stable dispersion slurry, discharging the slurry when the slurry is hot, cooling to obtain a uniformly mixed and uniformly dispersed solid mixture of DBDPE, active superfine ferrous carbonate and OBDPE in molecular level/nano scale, and crushing the solid mixture into primary powder;
s2, weighing the mixture obtained in the step S1 with the flame retardant master batch content of 40%, the synergistic flame retardant AO with the flame retardant master batch content of 10% and the acid absorber HT with the flame retardant master batch content of 15%, and putting the mixture into an omnibearing planetary ball mill for ball milling 4 h;
s3, uniformly mixing the flame retardant obtained in the step S2, 2% of compatilizer, 1.1% of stearic acid, 0.9% of silicone master batch and 30% of dried polycarbonate in a high-speed stirrer;
S4, adding the mixture obtained in the step S3 into a hopper of a screw extruder, extruding, granulating to obtain brominated flame retardant master batches, and using the brominated flame retardant master batches as flame retardants for polycarbonate resins;
s5, mixing 25% of the flame retardant master batch obtained in the step S4, 10% of glass fibers and 65% of dried polycarbonate, and preparing a sample bar by a screw extruder to test the flame retardant property and the mechanical property.
The vertical burning level of the prepared sample strip is UL-94V-0 grade, and the mechanical property is improved by 18 percent.
Example 5
The preparation and application of the brominated flame retardant master batch specifically comprises the following steps:
s1, putting DBDPE and OBDPE powder with the mass ratio of 3:1 into a reactor, heating to 200 ℃ to enable OBDPE to be melted, and dissolving DBDPE by using melted OBDPE liquid to form liquid DOS. Adding active superfine ferrous carbonate powder accounting for 5.5 wt% of the total mass of OBDPE and DBDPE into DOS under strong stirring, stirring and mixing uniformly to form stable dispersion slurry, discharging the slurry while hot, cooling to obtain a uniformly mixed and uniformly dispersed solid mixture of DBDPE, active superfine ferrous carbonate and OBDPE in molecular level/nanometer scale, and crushing the solid mixture into primary powder;
S2, weighing the mixture obtained in the step S1, the synergistic flame retardant AO and the acid absorber talcum powder, wherein the content of the synergistic flame retardant AO is 50% and the content of the flame retardant masterbatch is 10%, and the content of the acid absorber talcum powder is 5% of the flame retardant masterbatch, and putting the mixture and the synergistic flame retardant AO and the acid absorber talcum powder into an omnibearing planetary ball mill for ball milling 4 h;
S3, uniformly mixing the flame retardant obtained in the step S2, 2% of compatilizer, 1.1% of stearic acid, 0.9% of silicone master batch and 30% of dry polypropylene in a high-speed stirrer;
s4, adding the mixture obtained in the step S3 into a hopper of a screw extruder, extruding, granulating to obtain brominated flame retardant master batches, and using the brominated flame retardant master batches as flame retardants for polypropylene resin;
S5, mixing 15% of the flame retardant master batch obtained in the step S4, 30% of glass fibers and dry 55% of polypropylene, and preparing a sample bar by a screw extruder to test the flame retardant property and the mechanical property.
The vertical burning level of the prepared sample strip is UL-94V-0 grade, and the mechanical property is improved by 35%.
Example 6
The preparation and application of the brominated flame retardant master batch specifically comprises the following steps:
S1, putting DBDPE and OBDPE powder with the mass ratio of 4:1 into a reactor, heating to 200 ℃ to enable OBDPE to be melted, and dissolving DBDPE by using melted OBDPE liquid to form liquid DOS. Adding active superfine ferrous carbonate powder which is OBDPE and 3.5 wt percent of the total mass of DBDPE into DOS under strong stirring, stirring and mixing uniformly to form stable dispersoid slurry, discharging the slurry when the slurry is hot, cooling to obtain a uniformly mixed and uniformly dispersed solid mixture of DBDPE, active superfine ferrous carbonate and OBDPE in molecular level/nanometer scale, and crushing the solid mixture into primary powder;
S2, weighing the mixture obtained in the step S1 with the flame retardant master batch content of 45% and the synergistic flame retardant AO with the flame retardant master batch content of 15% and putting the mixture into an omnibearing planetary ball mill for ball milling 4 h;
S3, uniformly mixing the flame retardant obtained in the step S2, 2% of compatilizer, 1.1% of stearic acid, 0.9% of silicone master batch and 35% of dry polyamide in a high-speed stirrer;
S4, adding the mixture obtained in the step S3 into a hopper of a screw extruder, extruding, granulating to obtain brominated flame retardant master batches, and using the brominated flame retardant master batches as flame retardants for polyamide resins;
S5, mixing 30% of the flame retardant master batch obtained in the step S4, 20% of glass fibers and dried 50% of polyamide, and preparing a sample bar by a screw extruder to test the flame retardant property and the mechanical property.
The vertical burning level of the prepared sample strip is UL-94V-0 grade, and the mechanical property is improved by 32%.
Example 7
The preparation and application of the brominated flame retardant master batch specifically comprises the following steps:
S1, putting DBDPE and OBDPE powder with the mass ratio of 2:1 into a reactor, heating to 190 ℃ to enable OBDPE to be melted, and simultaneously dissolving DBDPE by using melted OBDPE liquid to form liquid DOS. Adding active superfine ferrous carbonate powder accounting for 1:1 wt% of the total mass of OBDPE and DBDPE into DOS under strong stirring, stirring and mixing uniformly to form stable dispersion slurry, discharging the slurry while hot, cooling to obtain a uniformly mixed and uniformly dispersed solid mixture of DBDPE, active superfine ferrous carbonate and OBDPE at a molecular level/nanometer scale, and crushing the solid mixture into primary powder;
s2, weighing the mixture obtained in the step S1 with the flame retardant master batch content of 35%, the synergistic flame retardant AO with the flame retardant master batch content of 12% and the acid absorber HT with the flame retardant master batch content of 15%, and putting the mixture into an omnibearing planetary ball mill for ball milling 4 h;
S3, uniformly mixing the flame retardant obtained in the step S2, 2% of compatilizer, 1.1% of stearic acid, 0.9% of silicone master batch and 33% of dry polypropylene in a high-speed stirrer;
s4, adding the mixture obtained in the step S3 into a hopper of a screw extruder, extruding, granulating to obtain brominated flame retardant master batches, and using the brominated flame retardant master batches as flame retardants for polypropylene resin;
S5, mixing 20% of the flame retardant master batch obtained in the step S4, 10% of glass fibers and 70% of dried polypropylene, and preparing a sample bar by a screw extruder to test the flame retardant property and the mechanical property.
The vertical burning level of the prepared sample strip is UL-94V-0 grade, and the mechanical property is improved by 22%.
Example 8
The preparation and application of the brominated flame retardant master batch specifically comprises the following steps:
s1, putting DBDPE and OBDPE powder with the mass ratio of 1:1 into a reactor, heating to 180 ℃ to enable OBDPE to be melted, and dissolving DBDPE by using melted OBDPE liquid to form liquid DOS. Adding active superfine ferrous carbonate powder accounting for 1.5 wt% of the total mass of OBDPE and DBDPE into DOS under strong stirring, stirring and mixing uniformly to form stable dispersion slurry, discharging the slurry while hot, cooling to obtain a uniformly mixed and uniformly dispersed solid mixture of DBDPE, active superfine ferrous carbonate and OBDPE in molecular level/nanometer scale, and crushing the solid mixture into primary powder;
s2, weighing the mixture obtained in the step S1 with the flame retardant master batch content of 40%, the synergistic flame retardant AO with the flame retardant master batch content of 15% and the acid absorber HT with the flame retardant master batch content of 10%, and putting the mixture into an omnibearing planetary ball mill for ball milling 4 h;
S3, uniformly mixing the flame retardant obtained in the step S2 with 2% of compatilizer, 1.1% of stearic acid, 0.9% of silicone master batch and 30% of dry polyethylene terephthalate in a high-speed stirrer;
S4, adding the mixture obtained in the step S3 into a hopper of a screw extruder, extruding, granulating to obtain brominated flame retardant master batches, and using the brominated flame retardant master batches as flame retardants for polyethylene terephthalate resins;
S5, mixing 15% of the flame retardant master batch obtained in the step S4, 20% of glass fibers and 65% of dry polyethylene terephthalate, and preparing a sample bar by a screw extruder to test the flame retardant property and the mechanical property.
The vertical burning level of the sample bar prepared at this time is UL-94V-0 grade, and the mechanical property is improved by 37%.
Example 9
The preparation and application of the brominated flame retardant master batch specifically comprises the following steps:
S1, putting DBDPE and OBDPE powder with the mass ratio of 4:1 into a reactor, heating to 170 ℃ to enable OBDPE to be melted, and simultaneously dissolving DBDPE by using melted OBDPE liquid to form liquid DOS. Adding active superfine ferrous carbonate powder accounting for 0.25 wt% of the total mass of OBDPE and DBDPE into DOS under strong stirring, stirring and mixing uniformly to form stable dispersion slurry, discharging the slurry while hot, cooling to obtain a uniformly mixed and uniformly dispersed solid mixture of DBDPE, active superfine ferrous carbonate and OBDPE in molecular level/nanometer scale, and crushing the solid mixture into primary powder;
S2, weighing the mixture obtained in the step S1 with the flame retardant master batch content of 40%, the synergistic flame retardant AO with the flame retardant master batch content of 10% and the acid absorber HT with the flame retardant master batch content of 5%, and putting the mixture into an omnibearing planetary ball mill for ball milling 4 h;
S3, uniformly mixing the flame retardant obtained in the step S2, 2% of compatilizer, 1.1% of stearic acid, 0.9% of silicone master batch and 40% of dried polypropylene in a high-speed stirrer;
s4, adding the mixture obtained in the step S3 into a hopper of a screw extruder, extruding, granulating to obtain brominated flame retardant master batches, and using the brominated flame retardant master batches as flame retardants for polypropylene resin;
S5, mixing 10% of the flame retardant master batch obtained in the step S4, 50% of glass fiber and dried 40% of polypropylene, and preparing a sample bar by a screw extruder to test the flame retardant property and the mechanical property.
The vertical burning level of the prepared sample strip is UL-94V-0 grade, and the mechanical property is improved by 82%.
Example 10
The preparation and application of the brominated flame retardant master batch specifically comprises the following steps:
S1, putting DBDPE and OBDPE powder with the mass ratio of 3:1 into a reactor, heating to 190 ℃ to enable OBDPE to be melted, and simultaneously dissolving DBDPE by using melted OBDPE liquid to form liquid DOS. Adding active superfine ferrous carbonate powder accounting for 5.5 wt% of the total mass of OBDPE and DBDPE into DOS under strong stirring, stirring and mixing uniformly to form stable dispersion slurry, discharging the slurry while hot, cooling to obtain a uniformly mixed and uniformly dispersed solid mixture of DBDPE, active superfine ferrous carbonate and OBDPE in molecular level/nanometer scale, and crushing the solid mixture into primary powder;
S2, weighing the mixture obtained in the step S1 with the flame retardant master batch content of 35%, the synergistic flame retardant AO with the flame retardant master batch content of 12% and the acid absorber HT with the flame retardant master batch content of 20%, and putting the mixture into an omnibearing planetary ball mill for ball milling 4 h;
S3, uniformly mixing the flame retardant obtained in the step S2, 2% of compatilizer, 1.1% of stearic acid, 0.9% of silicone master batch and 28% of dry polystyrene in a high-speed stirrer;
S4, adding the mixture obtained in the step S3 into a hopper of a screw extruder, extruding, granulating to obtain brominated flame retardant master batches, and using the brominated flame retardant master batches as flame retardants for polystyrene resin;
s5, mixing 30% of the flame retardant master batch obtained in the step S4, 40% of glass fiber and 30% of dry polystyrene, and preparing a sample bar by a screw extruder to test the flame retardant property and the mechanical property.
The vertical burning level of the prepared sample strip is UL-94V-0 grade, and the mechanical property is improved by 63%.
Example 11
The preparation and application of the brominated flame retardant master batch specifically comprises the following steps:
S1, putting DBDPE and OBDPE powder with the mass ratio of 2:1 into a reactor, heating to 190 ℃ to enable OBDPE to be melted, and simultaneously dissolving DBDPE by using melted OBDPE liquid to form liquid DOS. Adding active superfine ferrous carbonate powder accounting for 2.25 wt% of the total mass of OBDPE and DBDPE into DOS under strong stirring, stirring and mixing uniformly to form stable dispersion slurry, discharging the slurry while hot, cooling to obtain a uniformly mixed and uniformly dispersed solid mixture of DBDPE, active superfine ferrous carbonate and OBDPE in molecular level/nanometer scale, and crushing the solid mixture into primary powder;
s2, weighing the mixture obtained in the step S1 with the flame retardant master batch content of 45%, the synergistic flame retardant AO with the flame retardant master batch content of 15% and the acid absorber talcum powder with the flame retardant master batch content of 5%, and putting the mixture into an omnibearing planetary ball mill for ball milling 4 h;
S3, uniformly mixing the flame retardant obtained in the step S2 with 2% of compatilizer, 1.1% of stearic acid, 0.9% of silicone master batch and 30% of dried polymethyl methacrylate in a high-speed stirrer;
s4, adding the mixture obtained in the step S3 into a hopper of a screw extruder, extruding, granulating to obtain brominated flame retardant master batches, and using the brominated flame retardant master batches as flame retardants for polymethyl methacrylate resin;
S5, mixing 30% of the flame retardant master batch obtained in the step S4, 10% of glass fibers and 60% of dried polymethyl methacrylate, and preparing a sample bar by a screw extruder to test the flame retardant property and the mechanical property.
The vertical burning level of the prepared sample strip is UL-94V-0 grade, and the mechanical property is improved by 18 percent.
Example 12
The preparation and application of the brominated flame retardant master batch specifically comprises the following steps:
S1, putting DBDPE and OBDPE powder with the mass ratio of 3:1 into a reactor, heating to 200 ℃ to enable OBDPE to be melted, and dissolving DBDPE by using melted OBDPE liquid to form liquid DOS. Adding active superfine ferrous carbonate powder accounting for 4.5 wt% of the total mass of OBDPE and DBDPE into DOS under strong stirring, stirring and mixing uniformly to form stable dispersion slurry, discharging the slurry while hot, cooling to obtain a uniformly mixed and uniformly dispersed solid mixture of DBDPE, active superfine ferrous carbonate and OBDPE in molecular level/nanometer scale, and crushing the solid mixture into primary powder;
s2, weighing the mixture obtained in the step S1 with the flame retardant master batch content of 40%, the synergistic flame retardant AO with the flame retardant master batch content of 12% and the acid absorber HT with the flame retardant master batch content of 15%, and putting the mixture into an omnibearing planetary ball mill for ball milling 4 h;
S3, uniformly mixing the flame retardant obtained in the step S2, 2% of compatilizer, 1.1% of stearic acid, 0.9% of silicone master batch and 28% of dry polystyrene in a high-speed stirrer;
S4, adding the mixture obtained in the step S3 into a hopper of a screw extruder, extruding, granulating to obtain brominated flame retardant master batches, and using the brominated flame retardant master batches as flame retardants for polystyrene resin;
s5, mixing 25% of the flame retardant master batch obtained in the step S4, 20% of glass fibers and dry 55% of polystyrene, and preparing a sample bar by a screw extruder to test the flame retardant property and the mechanical property.
The vertical burning level of the prepared sample strip is UL-94V-0 grade, and the mechanical property is improved by 42%.
Comparative example 1
S1, weighing flame retardants DBDPE and OBDPE, active superfine ferrous carbonate, synergistic flame retardant AO and acid absorber HT, and putting the materials into an omnibearing planetary ball mill for ball milling 4: 4 h. Wherein the mass ratio of DBDPE to OBDPE is 5:1, which accounts for 50: 50 wt% of the mass of the flame retardant master batch, the active superfine ferrous carbonate accounts for 0.25: 0.25 wt% of the total mass of OBDPE and DBDPE, and the AO and HT account for 10% and 5% of the mass of the flame retardant master batch respectively.
S2, uniformly mixing the flame retardant obtained in the step S1, the compatilizer, stearic acid, the silicone master batch and the dried polypropylene in a high-speed stirrer. Wherein, the compatilizer, stearic acid, silicone master batch and polypropylene respectively account for 2 percent, 1.1 percent, 0.9 percent and 30 percent of the mass of the flame retardant master batch.
S3, adding the mixture obtained in the step S2 into a hopper of a screw extruder, extruding, granulating to obtain flame retardant master batches, and using the flame retardant master batches as flame retardants for polypropylene resin;
And S4, mixing the glass fiber, the dried polypropylene and the flame retardant master batch obtained in the step S3, and preparing a spline by a screw extruder to test the flame retardant property and the mechanical property. Wherein, the glass fiber, the polypropylene and the flame retardant master batch respectively account for 20 percent, 50 percent and 30 percent of the mass of the sample strip.
The vertical burning level of the prepared sample strip is UL-94V-1 grade, and the mechanical property is improved by 27%. As is clear from comparative example 1, flame retardant OBDPE and DBDPE were directly mixed with other substances and added to the matrix, the flame retardant was unevenly dispersed during extrusion, the particle size was large, the mechanical properties were reduced by 7% as compared with example 1, and the flame retardant properties of the bars were reduced to UL-94V-1 grade.
Comparative example 2
S1, weighing DBDPE and OBDPE powder according to a mass ratio of 5:1, adding the powder into a reactor, heating to 180 ℃ to enable OBDPE to be molten, simultaneously dissolving the DBDPE by using OBDPE liquid which is molten to form liquid DOS, adding 0.25% of active superfine ferrous carbonate under the stirring condition to form stable dispersoid, discharging the stable dispersoid from the reactor while the stable dispersoid is hot, cooling to obtain a solid mixture, and crushing the solid mixture into powder.
S2, weighing the synergistic flame retardant AO, the acid absorber HT, the compatilizer, the stearic acid, the silicone master batch, the polypropylene and the powder obtained in the step S1, and uniformly mixing in a high-speed stirrer. Wherein the powder obtained by AO, HT, compatilizer, stearic acid, silicone master batch, polypropylene and S1 respectively accounts for 10%, 5%, 2%, 1.1%, 0.9%, 30% and 50% of the mass of the flame retardant master batch.
S3, adding the mixture obtained in the step S2 into a hopper of a screw extruder, extruding, granulating to obtain flame retardant master batches, and using the flame retardant master batches as flame retardants for polypropylene resin;
And S4, mixing the glass fiber, the dried polypropylene and the flame retardant master batch obtained in the step S3, and preparing a spline by a screw extruder to test the flame retardant property and the mechanical property. Wherein, the glass fiber, the polypropylene and the flame retardant master batch respectively account for 20 percent, 50 percent and 30 percent of the mass of the sample strip.
The vertical burning level of the prepared sample strip is UL-94V-1 level, the mechanical property is improved by 21%, and compared with the example 1, the flame retardant and other powder materials are not ball-milled, the granularity of the flame retardant in the sample strip is large, the dispersion is poor, the flame retardance still does not reach V-0 level although superfine active ferrous carbonate is added, and the mechanical property is reduced by 13% compared with the example 1.
Comparative example 3
S1, weighing flame retardants DBDPE and OBDPE, adding the flame retardants DBDPE and OBDPE into a reactor, heating to 180C under stirring, melting the OBDPE, dissolving the DBDPE to obtain a solution of the two, discharging the solution from the reactor while the solution is hot, cooling to obtain a solid mixture, and crushing the solid mixture into powder.
S2, weighing the powder obtained by the synergistic flame retardant AO, the acid absorber HT and the S1, and putting the powder into an omnibearing planetary ball mill for ball milling 4 h. Wherein the mass ratio of DBDPE to OBDPE is 5:1, accounting for 50: 50 wt% of the mass of the flame retardant master batch, and AO and HT respectively account for 10% and 5% of the mass of the flame retardant master batch.
And S3, uniformly mixing the flame retardant obtained in the step S1, the compatilizer, stearic acid, the silicone master batch and the dried polypropylene in a high-speed stirrer. Wherein, the compatilizer, stearic acid, silicone master batch and polypropylene respectively account for 2 percent, 1.1 percent, 0.9 percent and 30 percent of the mass of the flame retardant master batch.
S4, adding the mixture obtained in the step S3 into a hopper of a screw extruder, extruding, granulating to obtain flame retardant master batches, and using the flame retardant master batches as flame retardants for polypropylene resin;
S5, mixing the glass fiber, the dried polypropylene and the flame retardant master batch obtained in the step S3, and preparing a spline by a screw extruder to test the flame retardant property and the mechanical property. Wherein, the glass fiber, the polypropylene and the flame retardant master batch respectively account for 20 percent, 50 percent and 30 percent of the mass of the sample strip.
The vertical burning level of the prepared sample strip is UL-94V-1 grade, and the mechanical property is improved by 30%. As is clear from comparative example 1, the mechanical properties were reduced by 4% without adding ultrafine activated iron carbonate to the flame retardant, but the flame retardant properties of the sample bars were reduced to UL-94V-1 grade.
Comparative example 4
S1, weighing a flame retardant DBDPE, a synergistic flame retardant AO and an acid absorber HT, and putting the materials into an omnibearing planetary ball mill for ball milling 4 h. Wherein DBDPE, AO and HT respectively account for 50%, 10% and 5% of the mass of the flame retardant master batch.
S2, uniformly mixing the flame retardant obtained in the step S1, the compatilizer, stearic acid, the silicone master batch and the dried polypropylene in a high-speed stirrer. Wherein, the compatilizer, stearic acid, silicone master batch and polypropylene respectively account for 2 percent, 1.1 percent, 0.9 percent and 30 percent of the mass of the flame retardant master batch.
S3, adding the mixture obtained in the step S2 into a hopper of a screw extruder, extruding, granulating to obtain flame retardant master batches, and using the flame retardant master batches as flame retardants for polypropylene resin;
And S4, mixing the glass fiber, the dried polypropylene and the flame retardant master batch obtained in the step S3, and preparing a spline by a screw extruder to test the flame retardant property and the mechanical property. Wherein, the glass fiber, the polypropylene and the flame retardant master batch respectively account for 20 percent, 50 percent and 30 percent of the mass of the sample strip.
The vertical burning level of the prepared sample strip is UL-94V-1 grade, and the mechanical property is improved by 25%. As is clear from comparative example 1, no ultrafine activated iron carbonate is added to the flame retardant, and OBDPE is not added to melt and dissolve DBDPE, so that the flame retardant is unevenly dispersed, has large granularity in the extrusion process, the mechanical property is reduced by 9% compared with example 1, and the flame retardant property of the sample bar is reduced to UL-94V-1 level.
Comparative example 5
S1, uniformly mixing the flame retardant DBDPE, the compatilizer, stearic acid, the silicone master batch and the dried polypropylene in a high-speed stirrer. Wherein DBDPE, compatilizer, stearic acid, silicone master batch and polypropylene respectively account for 50%, 2%, 1.1%, 0.9% and 30% of the mass of the flame retardant master batch.
S2, adding the mixture obtained in the step S1 into a hopper of a screw extruder, extruding, granulating to obtain flame retardant master batches, and using the flame retardant master batches as flame retardants for polypropylene resin;
and S3, mixing the glass fiber, the dried polypropylene and the flame retardant master batch obtained in the step S2, and preparing a spline by a screw extruder to test the flame retardant property and the mechanical property. Wherein, the glass fiber, the polypropylene and the flame retardant master batch respectively account for 20 percent, 50 percent and 30 percent of the mass of the sample strip.
The vertical burning level of the prepared sample strip is UL-94V-1 grade, and the mechanical property is improved by 18 percent. As is clear from comparative example 1, no ultrafine activated iron carbonate was added to the flame retardant, no OBDPE was added to melt and dissolve DBDPE, and the flame retardant DBDPE was not ball-milled, the flame retardant was extremely unevenly dispersed during extrusion, and had a large particle size, and the mechanical properties were reduced by 16% as compared with example 1, and the flame retardant properties of the sample bars were reduced to UL-94V-1 grade.
Therefore, the preparation and application method of the brominated flame retardant master batch provided by the invention can dissolve the high-melting-point flame retardant DBDPE in the low-melting-point OBDPE and realize molecular level/nanoscale dispersion with the resin, so that the pollution of HBr gas to the environment is eliminated, the consumption of the flame retardant is reduced, the heat-resistant temperature of the resin is improved, and the production cost is reduced.
It should be noted that the above-mentioned embodiments are merely for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted by the same, and the modified or substituted technical solution may not deviate from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. The preparation method of the brominated flame retardant master batch is characterized by comprising the following steps of:
s1, placing octabromodiphenyl ether OBDPE and decabromodiphenyl ethane DBDPE powder into a reactor, heating to OBDPE to melt, dissolving DBDPE in OBDPE liquid to form DBDPE-OBDPE solution DOS, adding active superfine ferrous carbonate powder into the DOS under strong stirring, stirring and mixing uniformly to form dispersion slurry, discharging the slurry while the slurry is hot, cooling to obtain a solid mixture of DBDPE, active superfine ferrous carbonate powder and OBDPE which are uniformly mixed to achieve uniform dispersed molecular level/nano scale, and crushing the solid mixture into primary powder;
S2, putting the mixture primary powder obtained in the step S1, the synergistic flame retardant and the acid absorber in proportion into an omnibearing planetary ball mill for ball milling to obtain a mixed flame retardant;
s3, placing the mixed flame retardant obtained in the step S2, the compatilizer, the lubricant and the dried resin into a high-speed stirrer for uniform mixing;
s4, adding the mixture obtained in the step S3 into a hopper of a screw extruder, extruding, and granulating to obtain brominated flame retardant master batches;
In the step S1, the mass ratio of DBDPE to OBDPE is 1:1-5:1, and the DBDPE is melted OBDPE and dissolved in a reactor, so that the temperature for forming liquid DOS is 170-200 ℃;
The active superfine ferrous carbonate in the step S1 is superfine powder subjected to surface modification by cetyl trimethyl ammonium bromide salt, sodium dodecyl sulfonate, a silane coupling agent and a titanate coupling agent, the particle size range of the superfine ferrous carbonate powder is 100 nm-900 nm, and the addition amount of the active superfine ferrous carbonate is 0.25 wt% -5.5 wt% of the total mass of the DBDPE and OBDPE.
2. The method for preparing a brominated flame retardant masterbatch according to claim 1, wherein the synergistic flame retardant in the step S2 is AO, the acid absorber is HT or talcum powder, and the contents of the primary powder, the synergistic flame retardant and the acid absorber in the mixed flame retardant respectively account for 20% -50%, 10% -15% and 0% -20% of the content of the flame retardant masterbatch.
3. The method for preparing a brominated flame retardant masterbatch according to claim 1, wherein the compatibilizer in the step S3 is a compatibilizer containing maleic anhydride or acrylic acid grafted polymer and accounts for 3% of the content of the masterbatch, the lubricant is stearic acid and silicone masterbatch, and the stearic acid and silicone masterbatch respectively account for 0.5% and 1.5% of the content of the masterbatch.
4. The method of claim 1, wherein the resin in the step S3 is one of polyethylene, polypropylene, polystyrene, polyamide, polycarbonate, polyethylene terephthalate and polymethyl methacrylate.
5. The method of claim 1, wherein the highest temperature of extrusion by the screw extruder in the step S4 is 10-20 ℃ higher than the melting point of the resin.
6. The use of a brominated flame retardant masterbatch prepared by the method for preparing a brominated flame retardant masterbatch according to any one of claims 1-5, characterized in that the prepared brominated flame retardant masterbatch is used for flame retarding a thermoplastic resin.
7. The application of the brominated flame retardant master batch prepared by the preparation method of the brominated flame retardant master batch of claim 6 is characterized in that the brominated flame retardant master batch is mixed with resin, glass fibers are added, the flame retardant master batch accounts for 10% -30% of the total addition, the glass fibers account for 10% -50% of the total addition, and the brominated flame retardant sample is prepared by extrusion through a screw extruder.
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| IL80021A (en) * | 1985-11-13 | 1993-04-04 | Bromine Compounds Ltd | Granular flame retardant agents, process for their preparation and articles obtained thereby |
| IL109251A (en) * | 1993-04-07 | 1999-05-09 | Great Lakes Chemical Corp | Brominated diphenylalkane products processes for their preparation and flame-retardant formulations containing them |
| CN100358973C (en) * | 2006-11-24 | 2008-01-02 | 北京理工大学 | A kind of brominated composite flame retardant and its preparation method and application |
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