CN110669281B

CN110669281B - Special flame-retardant synergistic functional master batch for modifying polycarbonate and alloy thereof and preparation method thereof

Info

Publication number: CN110669281B
Application number: CN201910954661.0A
Authority: CN
Inventors: 李翰卿; 汪晓东
Original assignee: Jiangsu Wannapu New Material Technology Co ltd
Current assignee: Jiangsu Wannapu New Material Technology Co ltd
Priority date: 2019-10-09
Filing date: 2019-10-09
Publication date: 2022-08-19
Anticipated expiration: 2039-10-09
Also published as: CN110669281A

Abstract

The invention relates to the technical field of plastic modification processing, in particular to a polycarbonate and special flame-retardant synergistic functional master batch for modifying alloy thereof and a preparation method thereof; the functional master batch takes tetrabromobisphenol A carbonate oligomer which is coated by multiple compounds as a main flame retardant, and the functional master batch comprises the following components in percentage by mass: 55.0-70.0 wt% of multi-composite coated tetrabromobisphenol A carbonate oligomer, 15.0-30.0 wt% of sodium citrate, 10.0-14.0 wt% of ethylene-glycidyl acrylate copolymer, 0.0-4.0 wt% of aliphatic copolyester, 0.0-0.5 wt% of hyperbranched polyester, 0.5-1.0 wt% of dispersant and 0.3-0.5 wt% of lubricant; compared with the traditional plastic flame-retardant functional master batch, the flame-retardant synergistic functional master batch provided by the invention improves the thermal stability and the flow dispersibility of the three domestic brominated flame retardants, so that the flame-retardant efficiency is improved, the same flame-retardant effect as that of the traditional flame-retardant functional master batch can be obtained by using less master batch addition, and the mechanical property loss of the flame-retardant compound of the modified polycarbonate and the alloy thereof can be effectively reduced.

Description

Special flame-retardant synergistic functional master batch for modifying polycarbonate and alloy thereof and preparation method thereof

Technical Field

The invention relates to the technical field of plastic modification processing, in particular to a special flame-retardant synergistic functional master batch for modifying Polycarbonate (PC) and an alloy thereof and a preparation method thereof.

Background

Engineering plastics are widely applied to the fields of transportation tools such as household appliances, industrial electronic appliances, automobiles and the like due to excellent comprehensive physical and mechanical properties, heat resistance and good electrical properties, but when the engineering plastics are applied to product production, flame retardant modification is often required to improve the use safety of the engineering plastics. The flame retardant modification of the engineering plastics can be realized by adding a flame retardant and carrying out melt blending through a double-screw extruder. The flame retardant can prevent the plastic from being ignited and inhibit flame propagation, and can effectively improve the anti-combustion performance of the engineering plastic. Flame retardants are generally classified into halogen-based (halogen-based is also classified into chlorine-based and bromine-based), phosphorus-based, antimony-based, magnesium-based, boron-based, molybdenum-based, and the like, according to the classification of flame-retardant elements. Although the flame retardant is various at present, the high flame retardant efficiency can be really realized on most engineering plastics, and the selection of the brominated flame retardant is undoubtedly the best choice. The brominated flame retardant has the advantages of wide applicability, convenient use, excellent flame retardant effect, no toxicity and no public nuisance in the normal use and recovery process, is still widely applied to various fields of industry and national economy so far, plays a key role in safe fireproof materials and products, and is the organic flame retardant with the largest output in the world at present.

Polycarbonate (PC) is the second largest engineering plastic in the world, and is widely used in the field of electronics due to its excellent mechanical and electrical properties. The PC can also be blended with other engineering plastics such as styrene-butadiene-acrylonitrile copolymer (ABS), polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and the like to prepare plastic alloys, and the plastic alloys can generate complementary performance advantages so as to obtain wider application. The limiting oxygen index of PC and the alloy thereof is only about 24 vol.%, and the PC and the alloy thereof belong to easily combustible high polymer materials, and are subjected to flame retardant modification aiming at the PC and the alloy thereof applied to the field of electronic and electric appliances on the basis of safety consideration. The bromine flame retardant is a common flame retardant modification method for endowing PC and PC alloy with flame retardancy. However, the processing temperature of PC is high, which often leads to premature decomposition of the conventional brominated flame retardant during processing, and influences the appearance and performance of the product. Therefore, the high-grade flame retardant is required to be realized (reaching UL 94V-0 grade), good appearance and various performances are required to be kept, and the requirements on the quality, the thermal stability and the temperature resistance of the bromine flame retardant are high.

At present, tetrabromobisphenol A carbonate oligomer is the most commonly used brominated flame retardant for flame retardant modification of PC and PC alloy, the flame retardant effect of the brominated flame retardant is the best in all brominated flame retardants, and the flame retardant PC and PC alloy compound with flame retardance have better thermal stability and less mechanical property loss. At present, the production and manufacturing technology of high-efficiency high-quality brominated flame retardant which is coated with tetrabromobisphenol A carbonate oligomer and is commonly used for flame retardance of engineering plastics is still controlled by developed countries. The market of high-end brominated flame retardants at home and abroad is monopolized by international companies in developed countries such as Europe and America, and manufacturers of tetrabromobisphenol A carbonate oligomers at home have obvious difference with the developed countries due to the production technology, and the tetrabromobisphenol A carbonate oligomer flame retardant products have the defects of poor thermal stability, unstable bromine atoms in molecules, easy yellowing in the processing process and the like, and cannot compete with products at home and abroad. With the influence of foreign trade disputes and high duty, the economic performance of the common brominated flame retardants of engineering plastics such as tetrabromobisphenol A carbonate oligomers imported from developed countries is increasingly poor, and the production cost of using enterprises is increased, so that the competitiveness of manufactured products is reduced. Therefore, the development of high-quality tetrabromobisphenol A carbonate oligomer flame retardant in China is urgent. However, the synthesis process of such brominated flame retardants is complicated, and it is difficult to develop advanced production technology in a short time according to the current technical level of domestic enterprises, so that the product quality can catch up with the manufacturing level of brominated flame retardants in developed countries. Therefore, a simple and convenient way for effectively improving the defects of the domestic tetrabromobisphenol A carbonate oligomer in the application of PC and alloy engineering plastics thereof needs to be found.

In addition, in the implementation process of engineering plastic flame-retardant modification and processing technology, the flame retardant and the flame-retardant synergist are often powder and have large addition amount, and when a double-screw extruder is directly adopted for melt extrusion blending, the polymer is difficult to melt and fully mix with the flame retardant due to the limited residence time of materials in a machine barrel of the extruder. In addition, because the processing temperature of the engineering plastic is higher, a large amount of flame retardant powder generates more internal heat due to mutual mechanical friction in the blending and extrusion process, so that the brominated flame retardant is decomposed and bromine falls off, the flame retardant effect is damaged, the material is yellowed, and the physical and mechanical properties of the modified engineering plastic product are reduced.

Aiming at the quality and processing problems in the implementation process of the flame-retardant modification technology for PC and PC alloy by adopting the domestic tetrabromobisphenol A carbonate oligomer, the invention provides a brand-new solution thought: the domestic tetrabromobisphenol A carbonate oligomer is coated by adopting a multi-level high-density flame-retardant synergistic material, and then the coated brominated flame retardant, a flame-retardant synergistic agent, corresponding carrier resin and other auxiliary agents are compounded to prepare the flame-retardant functional master batch, so that the defects of poor thermal stability, easy decomposition, easy yellowing, poor fluidity, uneven dispersion, impaired flame-retardant effect and the like of the domestic brominated are overcome at the same time.

Disclosure of Invention

The purpose of the invention is: aiming at the quality and processing problems existing in the implementation process of flame retardant modification technology of PC and alloy engineering plastics by adopting domestic tetrabromobisphenol A carbonate oligomer, the flame retardant synergistic functional master batch special for modifying polycarbonate and alloy thereof is provided, compared with the traditional plastic flame retardant functional master batch, the flame retardant synergistic functional master batch improves the thermal stability and the flow dispersibility of the domestic tetrabromobisphenol A carbonate oligomer serving as a common brominated flame retardant for PC and alloy thereof, thereby improving the flame retardant efficiency, obtaining the same flame retardant effect as the traditional flame retardant functional master batch by using less master batch addition amount, and effectively reducing the mechanical property loss of modified PC and alloy composite materials thereof;

another object of the invention is: the method adopts multilayer high-density flame-retardant synergistic materials to coat commonly used brominated flame retardants of engineering plastics such as domestic tetrabromobisphenol A carbonate oligomers and the like, and then compounds the coated brominated flame retardants, flame-retardant synergistic agents, carrier resin and other additives to prepare the flame-retardant functional master batch, thereby solving the problems of poor thermal stability, easy decomposition, easy yellowing, poor fluidity, uneven dispersion, impaired flame-retardant effect and the like of the commonly used brominated flame retardants of the domestic tetrabromobisphenol A carbonate oligomers such as PC and alloys thereof in the processing process.

The method comprises the steps of coating tetrabromobisphenol A carbonate oligomer particles by using zinc ion doped aluminum sol as a raw material, wherein because the Zeta potential of the tetrabromobisphenol A carbonate oligomer is a negative value, and the Zeta potential of the aluminum sol is a positive value, the core-shell structure microcapsule particles taking zinc ion doped aluminum hydroxide as a shell and tetrabromobisphenol A carbonate oligomer as a core can be naturally formed through sol-gel reaction; then, utilizing the characteristic that phytic acid (also known as phytic acid, a cyclic compound containing six phosphate groups) is easy to react with divalent and trivalent metal ions to form an insoluble substance, adopting the phytic acid to perform passivation reaction with zinc/aluminum ions in the microcapsule shell layer to form a hard and compact coating layer; followed by addition of zirconium hydrogen phosphate [ Zr (HPO) ] ₄ ) ₂ ·H ₂ O, a sheet-like inorganic nanomaterial having a mesoporous structure]Zirconium ions in the molecules can also generate passivation reaction with phytic acid, and hydroxyl functional groups on the surfaces of the zirconium ions and carboxyl functional groups in the phytic acid can also be replaced to form a chemical bond combination body, so that multiple composite coating of tetrabromobisphenol A carbonate oligomer is realized. And mixing the coated tetrabromobisphenol A carbonate oligomer with auxiliary agents such as a flame-retardant synergist, a carrier, a dispersing agent and the like, and finally preparing the flame-retardant functional master batch special for PC flame-retardant modification by connecting a single-screw extruder in series through an internal mixer.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

the special flame-retardant synergistic functional master batch for modifying polycarbonate and alloy thereof takes a tetrabromobisphenol A carbonate oligomer which is subjected to multiple composite coating as a main flame retardant, and the functional master batch comprises the following components in percentage by mass: 55.0-70.0 wt% of multi-composite coated tetrabromobisphenol A carbonate oligomer, 15.0-30.0 wt% of sodium citrate, 10.0-14.0 wt% of carrier resin, 0.0-4.0 wt% of aliphatic copolyester, 0.0-0.5 wt% of hyperbranched polyester, 0.5-1.0 wt% of dispersant and 0.3-0.5 wt% of lubricant.

Further, the carrier resin is ethylene-glycidyl acrylate copolymer (EGMA), ethylene-methyl acrylate-glycidyl methacrylate copolymer (EMA-GMA) and ethylene-butyl acrylate-glycidyl methacrylate copolymer (EBA-GMA).

Further, the aliphatic copolymer is one of poly (ethylene succinate-butylene succinate), poly (ethylene succinate-butylene methylsuccinate) and poly (ethylene succinate-butylene phenylsuccinate), wherein poly (ethylene succinate-butylene succinate) is preferred.

Furthermore, the hyperbranched polyester is a four-arm polyester copolymer taking pentaerythritol as a core and poly (dimethylolpropionic acid) as a branched chain.

Further, the dispersant is one of aluminum stearate, calcium stearate, zinc stearate, stearic acid, pentaerythritol stearate, E wax, OP wax and ethylene bis stearamide.

Further, the lubricant is one of ethylene bis stearamide, pentaerythritol stearate, OP wax, E wax and ethylene-vinyl acetate copolymer wax.

Further, the multiple composite coated tetrabromobisphenol A carbonate oligomer is tetrabromobisphenol A carbonate oligomer coated with zirconium hydrogen phosphate powder, phytic acid and zinc ion doped aluminum hydroxide.

Further, the preparation method of the zirconium hydrogen phosphate powder, the phytic acid and the zinc ion doped aluminum hydroxide coated brominated flame retardant comprises the following steps:

(1) dispersing tetrabromobisphenol A carbonate oligomer, aluminum sol and zinc oxide sol in absolute ethyl alcohol, heating and stirring, dropwise adding ammonia water to adjust the pH of a reaction solution to be alkaline, continuously stirring for a period of time after dropwise adding is finished, ending the reaction, then washing and filtering, and drying a filtered substance to obtain zinc ion-doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer;

(2) dispersing the zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer obtained in the step (1) into an alcohol organic solvent to obtain a suspension, dissolving phytic acid in deionized water to form a phytic acid solution, dropwise adding the phytic acid solution into the suspension of the zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer, heating and stirring for a period of time, adding zirconium hydrogen phosphate powder, continuously stirring for a period of time at the same temperature, stopping reaction, washing with clear water, filtering, and drying to obtain the multiple composite inorganic material-coated tetrabromobisphenol A carbonate oligomer.

Further, in the step (1), the heating and stirring temperature is 35-40 ℃, ammonia water is dripped at a constant speed, the mass fraction of the ammonia water is 10.0-12.5 wt.%, the pH value of the reaction solution is controlled to be 7.5-8.5, and after the dripping is finished, the reaction is finished after the stirring is continued for 3-4 hours; then washing with clear water, filtering, and drying in an oven at 110-120 ℃ for 8-10 h to obtain zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer;

the alcohol organic solvent in the step (2) is one of isopropanol, n-propanol, isobutanol or n-butanol, the heating and stirring temperature is 30-35 ℃, the concentration of phytic acid is 0.4-0.5 g/ml, the dropping of phytic acid is constant-speed dropping, the phytic acid solution is continuously stirred for 1.5-2 hours after being added, zirconium hydrogen phosphate powder is added, the reaction is stopped after the stirring is carried out for 2.5-3 hours at the same temperature, then the washing and the filtering are carried out by clear water, the drying is carried out in an oven at 110-120 ℃ for 10-12 hours, and the tetrabromobisphenol A carbonate oligomer is coated by the multiple composite inorganic material.

Further, in the step (1), the mass ratio of the tetrabromobisphenol A carbonate oligomer to the aluminum sol to the zinc oxide sol is 150:7: 1-150: 9:2, and in the step (2), the mass ratio of the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer to the phytic acid to the zirconium hydrogen phosphate is 150:3: 4-150: 4.5: 5.

A preparation method of a special flame-retardant synergistic functional master batch for modifying polycarbonate and alloy thereof comprises the following steps:

(1) weighing the raw materials according to the proportion, putting the raw materials into a high-speed mixer, uniformly mixing, and transferring the mixture into an internal mixer for hot mixing to obtain a bulk blend;

(2) feeding the bulk blend obtained in the step (1) into a single-screw extruder through a conical feeding machine, and performing melt extrusion and granulation to obtain the flame-retardant synergistic functional master batch; the mixing temperature of the internal mixer is 100-125 ℃, and the mixing time is 15-20 minutes; the screw rotating speed of the single-screw extruder is 150-200 r/min, and the barrel temperature is 120-160 ℃.

The flame retardant is prepared into the flame retardant master batch and then applied to the preparation and processing of flame retardant modified plastic products, and the flame retardant effect exerted by the flame retardant master batch is better than that of uncoated brominated flame retardants. And the tolerance of the prepared flame-retardant modified plastic in repeated thermal mechanical processing is greatly improved, and the flame-retardant modified plastic has good recycling and reprocessing and recycling characteristics. The invention provides an important way for realizing high-efficiency energy-saving flame-retardant modified plastic processing.

The technical scheme adopted by the invention has the beneficial effects that:

(1) aiming at the defects of high-temperature easy decomposition, low thermal stability, easy bromine falling, easy yellowing, low fluidity and poor dispersibility of domestic tetrabromobisphenol A carbonate oligomer serving as a brominated flame retardant commonly used for PC and PC alloy, zinc ion doped aluminum hydroxide inorganic matter is selected to coat the brominated tetrabromobisphenol A carbonate oligomer, then phytic acid and zinc/aluminum ion passivation are utilized to form a compact and solid protective layer, and then zirconium hydrogen phosphate nano-sheets with mesoporous structures form the outermost layer structure of tetrabromobisphenol A carbonate oligomer microcapsules through the dual actions of phytic acid passivation and ion exchange adsorption, so that a multiple composite inorganic coating layer is formed. Compared with the traditional polymer or a single-layer inorganic material coating layer, the multiple composite inorganic coating layer has a better thermal protection effect on the tetrabromobisphenol A carbonate oligomer, and particularly, the multiple inorganic shell passivated by phytic acid provides a firmer and denser inorganic coating layer for the tetrabromobisphenol A carbonate oligomer than the traditional polymer and inorganic wall materials, so that the coated tetrabromobisphenol A carbonate oligomer can be more effectively protected, and the thermal decomposition temperature of the coated tetrabromobisphenol A carbonate oligomer is obviously improved. Therefore, the coated tetrabromobisphenol A carbonate oligomer can obtain more excellent thermal stability.

(2) As a large amount of phosphorus-containing materials are introduced into the wall material coating the domestic tetrabromobisphenol A carbonate oligomer, the introduction of phosphorus elements can generate flame-retardant synergy with the tetrabromobisphenol A carbonate oligomer in the combustion process of the flame-retardant PC compound, promote the formation of a dense carbon layer on the surface of the PC compound combustion product, effectively improve the compactness and the structural stability of the surface carbon layer in the combustion process of the flame-retardant polymer, prevent the contact of the interior of the combustion product with oxygen, enable the flame retardant to play a role in flame retardance of synergy, and further effectively improve the flame retardance of PC.

(3) The zirconium hydrogen phosphate with a mesoporous structure is introduced into the outermost coating layer of the domestic tetrabromobisphenol A carbonate oligomer, and the zirconium hydrogen phosphate has a large specific surface area, large surface charge density, a stable layered structure and rich OH groups, can generate ion exchange reaction and large ion exchange capacity, can generate large adsorption of bromide ions and other small molecular products generated by the decomposition of the domestic tetrabromobisphenol A carbonate oligomer in the thermal processing process of the flame-retardant plastic, not only avoids the yellowing of materials caused by thermal decomposition products, but also can keep the original bromine content of the brominated flame retardant, thereby realizing the flame-retardant synergistic effect.

(4) The master batch formula which has good compatibility with PC and PC alloy and good dispersion of flame retardant powder is designed, and the master batch with the flame retardant function is obtained by long-time mixing at low temperature through an internal mixer, so that the flame retardant powder obtains excellent pre-dispersion effect, and brominated flame retardant decomposition caused by high-temperature thermal mechanical processing is avoided, and thus better dispersion effect and superior flame retardant property are obtained in subsequent double-screw melt extrusion modification processing of PC and PC alloy; meanwhile, the loss of physical and mechanical properties caused by direct blending with the flame retardant powder is reduced, so that the modification effect of killing two birds with one stone is achieved.

(5) Compared with the traditional plastic flame-retardant functional master batch, the flame-retardant synergistic functional master batch provided by the invention improves the thermal stability and the flow dispersibility of the domestic brominated flame retardant, thereby improving the flame-retardant efficiency, obtaining the same flame-retardant effect as the traditional flame-retardant functional master batch by using less master batch addition amount, and effectively reducing the mechanical property loss of the modified PC composite material.

(6) The PC modified special flame-retardant functional master batch prepared by the invention can be used for the double-screw melt extrusion functional modification of various grades of PC and alloys formed by PC and resins such as ABS, PBT, PET and the like, and can also be directly applied to the injection molding of products after being simply mixed with PC and corresponding alloy resins according to a certain proportion. The combination mode of the flame-retardant synergistic functional master batches and other functional master batches and the proportion of the master batches to resin raw materials can be flexibly prepared according to different performance requirements of customers, so that the performance and the cost of the master batches can be adjusted, the target requirements of products can be quickly and simply met, and the plastic modification formula and processing process optimization design concept can be practiced.

Detailed Description

The following examples are intended to provide those skilled in the art with a more complete understanding of the present invention, and are not intended to limit the scope of the present invention. Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.

Example 1

The special flame-retardant synergistic functional master batch for modifying the polycarbonate and the alloy thereof comprises the following raw materials in parts by mass:

the preparation method of the functional master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 125 ℃, the mixing time is 16 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame-retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 170 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.

The preparation method of the multiple composite coated tetrabromobisphenol A carbonate oligomer used in the functional master batch comprises the following steps:

adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A carbonate oligomer, 7kg of aluminum sol and 1kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 40 ℃, then uniformly dropwise adding 10.0 wt.% ammonia water at a uniform speed, controlling the pH value of a reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding is completed, continuously stirring for 4 hours and then finishing the reaction; then washing with clean water, filtering, and drying in a drying oven at 110 ℃ for 8 hours to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer. Dissolving 4kg of phytic acid in 8L of deionized water in another glass container to prepare a solution with the concentration of 0.5g/ml, putting 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer and 250L of isopropanol into an enamel reaction kettle, uniformly stirring and adding to 30 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 30 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the tetrabromobisphenol A carbonate oligomer have passivation reaction, continuously stirring for 2 hours, then adding 5kg of zirconium hydrogen phosphate powder, stirring for 3 hours at the same temperature to stop the reaction, then washing with clear water, filtering, and drying in a 110 ℃ oven for 12 hours to obtain the multiple composite coated tetrabromobisphenol A carbonate oligomer.

Example 2

the preparation method of the functional master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 110 ℃, the mixing time is 20 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame-retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 160 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.

adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A carbonate oligomer, 8kg of aluminum sol and 1.5kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 35 ℃, then uniformly dropwise adding 11.0 wt.% ammonia water at a uniform speed, controlling the pH value of a reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after the dropwise addition is finished, continuously stirring for 3.5 hours and finishing the reaction; then washing with clear water, filtering, and drying in a baking oven at 120 ℃ for 9 hours to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer. In another glass container, 3.6kg of phytic acid is dissolved in 9L of deionized water to prepare a solution with the concentration of 0.4g/ml, 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer and 250L of isopropanol are put into an enamel reaction kettle, stirred uniformly and added to 30 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 30 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the tetrabromobisphenol A carbonate oligomer have passivation reaction, continuously stirring for 2 hours, adding 4.5kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 2.5 hours, stopping the reaction, washing with clear water, filtering, and drying in a 115 ℃ oven for 12 hours to obtain the multiple composite coated tetrabromobisphenol A carbonate oligomer.

Example 3

The special flame-retardant synergistic functional master batch for modifying polycarbonate and alloy thereof comprises the following raw materials in parts by mass:

the preparation method of the functional master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 100 ℃, and the mixing time is 20 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 150 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.

adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A carbonate oligomer, 9kg of aluminum sol and 2kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 38 ℃, then uniformly dropwise adding 12.5wt.% ammonia water at a uniform speed, controlling the pH value of a reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding is completed, continuously stirring for 4 hours and then finishing the reaction; then washing with clear water, filtering, and drying in an oven at 115 ℃ for 10h to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer. Dissolving 3kg of phytic acid in 6L of deionized water in another glass container to prepare a solution with the concentration of 0.5g/ml, putting 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer and 250L of n-propanol into an enamel reaction kettle, uniformly stirring and adding to 35 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 35 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the tetrabromobisphenol A carbonate oligomer have passivation reaction, continuously stirring for 1.5h, then adding 5kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 3h, stopping the reaction, then washing with clear water, filtering, and drying in a 110 ℃ oven for 12h to obtain the multiple composite coated tetrabromobisphenol A carbonate oligomer.

Example 4

the preparation method of the functional master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 120 ℃, the mixing time is 17 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame-retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 185 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections. The preparation method of the multiple composite coated tetrabromobisphenol A carbonate oligomer used in the functional master batch comprises the following steps:

the preparation method of the multiple composite coated tetrabromobisphenol A carbonate oligomer used in the functional master batch comprises the following steps: adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A carbonate oligomer, 7.5kg of aluminum sol and 2kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 35 ℃, then uniformly dropwise adding 12.0 wt.% ammonia water at a uniform speed, controlling the pH value of a reaction solution to 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding, continuously stirring for 4 hours and then finishing the reaction; then washing with clean water, filtering, and drying in a baking oven at 120 ℃ for 9 hours to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer. Dissolving 4.5kg of phytic acid in 9L of deionized water in another glass container to prepare a solution with the concentration of 0.5g/ml, putting 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer and 250L of isobutanol into an enamel reaction kettle, stirring uniformly and adding to 30 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 30 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the tetrabromobisphenol A carbonate oligomer have passivation reaction, continuously stirring for 1.5h, then adding 4.5kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 2.5h, stopping the reaction, then washing with clear water, filtering, and drying in a 120 ℃ oven for 11h to obtain the multiple composite coated tetrabromobisphenol A carbonate oligomer.

Example 5

the preparation method of the functional master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 100 ℃, the mixing time is 20 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame-retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 150 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.

adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A carbonate oligomer, 8.5kg of aluminum sol and 1.5kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 35 ℃, then uniformly dropwise adding 11.5 wt.% ammonia water at a uniform speed, controlling the pH value of the reaction liquid to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after the dropwise addition is finished, continuously stirring for 3 hours and finishing the reaction; then washing with clean water, filtering, and drying in a baking oven at 120 ℃ for 10 hours to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer. Dissolving 3.2kg of phytic acid in 8L of deionized water in another glass container to prepare a solution with the concentration of 0.4g/ml, putting 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer and 250 n-butyl alcohol into an enamel reaction kettle, uniformly stirring and adding to 35 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 35 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the tetrabromobisphenol A carbonate oligomer have passivation reaction, continuously stirring for 2 hours, then adding 5kg of zirconium hydrogen phosphate powder, stirring for 3 hours at the same temperature to stop the reaction, then washing with clear water, filtering, and drying in a 120 ℃ oven for 12 hours to obtain the multiple composite coated tetrabromobisphenol A carbonate oligomer.

Example 6

the preparation method of the functional master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 125 ℃, the mixing time is 18 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 160 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.

adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A carbonate oligomer, 7kg of aluminum sol and 1.5kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 40 ℃, then uniformly dropwise adding 10.5 wt.% ammonia water at a uniform speed, controlling the pH value of a reaction solution to 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding, continuously stirring for 3.5 hours and then finishing the reaction; then washing with clear water, filtering, and drying in an oven at 115 ℃ for 8 hours to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer. In another glass container, 3.5kg of phytic acid is dissolved in 7L of deionized water to prepare a solution with the concentration of 0.5g/ml, 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer and 250L of isopropanol are put into an enamel reaction kettle, stirred uniformly and added to 32 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 32 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the tetrabromobisphenol A carbonate oligomer have passivation reaction, continuously stirring for 1.5h, then adding 4kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 3h to stop the reaction, then washing with clear water, filtering, and drying in a 110 ℃ oven for 12h to obtain the multiple composite coated tetrabromobisphenol A carbonate oligomer.

In order to verify the modification effect of the flame-retardant synergistic functional master batch prepared by the invention on PC, the flame-retardant synergistic functional master batch prepared in the embodiment 1-6 is mixed with PC resin according to the mass percentage of 15 wt.%, and the mixture is subjected to blending extrusion molding by a double-screw extruder, then is subjected to injection molding, and is subjected to combustion test sample strip, and then is subjected to flame-retardant performance detection. Meanwhile, according to the same components and proportions of the functional master batches obtained in the examples 1-6, but tetrabromobisphenol A carbonate oligomer with the same brand but without coating is used as a main flame retardant, the flame-retardant functional master batches are prepared by the same process and used as comparative examples 1-6, and then are mixed with PC resin according to the same mass percentage, and are subjected to blending processing by a double-screw extruder, injection molding is carried out on test sample strips, and the flame-retardant performance of the test sample strips is detected. The results of all performance tests are shown in table 1.

The data in table 1 show that the flame retardance and yellowing resistance of the PC compound modified by the flame-retardant synergistic functional master batch prepared by the embodiment of the invention are obviously superior to those of the PC compound modified by the flame-retardant functional master batch prepared by the uncoated tetrabromobisphenol A carbonate oligomer under the condition of completely identical components and mixture ratio. In addition, from the results of the fluidity spiral length test, it was also found that the fluidity of the PC compound modified by the examples of the present invention was significantly higher than that of the comparative examples. Therefore, by using the flame-retardant synergistic functional master batch, the flame-retardant modification effect of the domestic brominated flame retardant on the PC resin is greatly improved, the defect of poor yellowing resistance of the domestic brominated flame retardant is effectively overcome, the melt fluidity of the modified PC compound is improved, the processing performance of the modified PC compound is enhanced, and the appearance quality of the product is improved, so that the master batch makes a contribution to the improvement of the use reliability of the domestic brominated flame retardant and the sustainable development concept of green processing of plastic modification.

Table 1 shows the comparison of the performance of the functional masterbatches prepared in examples 1 to 6 with PC composites modified with the same formulation but using the uncoated tetrabromobisphenol A carbonate oligomer

TABLE 1

Example 7

The preparation method of the functional master batch comprises the following steps:

weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 125 ℃, the mixing time is 16 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame-retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 170 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.

Example 8

weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 110 ℃, the mixing time is 20 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame-retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 160 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.

Example 9

adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A carbonate oligomer, 9kg of aluminum sol and 2kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 38 ℃, then uniformly dropwise adding 12.5wt.% ammonia water at a uniform speed, controlling the pH value of a reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding is completed, continuously stirring for 4 hours and then finishing the reaction; then washing with clear water, filtering, and drying in an oven at 115 ℃ for 10h to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer. Dissolving 3kg of phytic acid in 6L of deionized water in another glass container to prepare a solution with the concentration of 0.5g/ml, putting 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer and 250L of n-propanol into an enamel reaction kettle, uniformly stirring and adding to 35 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 35 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the tetrabromobisphenol A carbonate oligomer have passivation reaction, continuously stirring for 1.5h, then adding 5kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 3h to stop the reaction, then washing with clear water, filtering, and drying in a 110 ℃ oven for 12h to obtain the multiple composite coated tetrabromobisphenol A carbonate oligomer.

weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 100 ℃, and the mixing time is 20 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 150 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.

Example 10

adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A carbonate oligomer, 7.5kg of aluminum sol and 2kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 35 ℃, then uniformly dropwise adding 12.0 wt.% ammonia water at a uniform speed, controlling the pH value of a reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding is finished, continuously stirring for 4 hours and finishing the reaction; then washing with clear water, filtering, and drying in a baking oven at 120 ℃ for 9 hours to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer. Dissolving 4.5kg of phytic acid in 9L of deionized water in another glass container to prepare a solution with the concentration of 0.5g/ml, putting 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer and 250L of isobutanol into an enamel reaction kettle, stirring uniformly and adding to 30 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 30 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the tetrabromobisphenol A carbonate oligomer have passivation reaction, continuously stirring for 1.5h, then adding 4.5kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 2.5h, stopping the reaction, then washing with clear water, filtering, and drying in a 120 ℃ oven for 11h to obtain the multiple composite coated tetrabromobisphenol A carbonate oligomer.

weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame retardant and synergistic functions, wherein the mixing temperature of the internal mixer is 120 ℃ and the mixing time is 17 minutes; the screw rotating speed of the single-screw extruder is 185 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.

Example 11

adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A carbonate oligomer, 7kg of aluminum sol and 1.5kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 40 ℃, then uniformly dropwise adding 10.5 wt.% ammonia water at a uniform speed, controlling the pH value of a reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after the dropwise addition is finished, continuously stirring for 3.5 hours and finishing the reaction; then washing with clean water, filtering, and drying in an oven at 115 ℃ for 8 hours to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer. Dissolving 3.5kg of phytic acid in 7L of deionized water in another glass container to prepare a solution with the concentration of 0.5g/ml, putting 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer and 250L of isopropanol into an enamel reaction kettle, uniformly stirring and adding to 32 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 32 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the tetrabromobisphenol A carbonate oligomer have passivation reaction, continuously stirring for 1.5h, then adding 4kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 3h, stopping the reaction, then washing with clear water, filtering, and drying in a 110 ℃ oven for 12h to obtain the multiple composite coated tetrabromobisphenol A carbonate oligomer.

weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 125 ℃, the mixing time is 18 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 160 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.

Example 12

adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A carbonate oligomer, 7kg of aluminum sol and 1.5kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring, heating to 40 ℃, then uniformly dripping 10.5 wt.% ammonia water at constant speed, controlling the pH value of a reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to perform sol-gel reaction, and after finishing dripping, continuing stirring for 3.5 hours and finishing the reaction; then washing with clean water, filtering, and drying in an oven at 115 ℃ for 8 hours to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer. In another glass container, 3.5kg of phytic acid is dissolved in 7L of deionized water to prepare a solution with the concentration of 0.5g/ml, 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer and 250L of isopropanol are put into an enamel reaction kettle, stirred uniformly and added to 32 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 32 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the tetrabromobisphenol A carbonate oligomer have passivation reaction, continuously stirring for 1.5h, then adding 4kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 3h to stop the reaction, then washing with clear water, filtering, and drying in a 110 ℃ oven for 12h to obtain the multiple composite coated tetrabromobisphenol A carbonate oligomer.

weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 125 ℃, the mixing time is 18 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame-retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 160 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.

The polycarbonate alloy in examples 7 to 12 is a PC/ABS alloy, and in order to verify the modification effect of the flame-retardant synergistic functional master batch prepared in the present invention on the PC/ABS alloy, the flame-retardant synergistic functional master batch prepared in examples 7 to 12 was mixed with a PC/ABS alloy resin in an amount of 20 wt.%, and the mixture was extruded by a twin-screw extruder to form a material, and then a combustion test specimen was injection-molded, and then the flame-retardant performance test was performed. Meanwhile, according to the same components and proportions of the functional master batches obtained in the examples 7-12, but tetrabromobisphenol A carbonate oligomer with the same brand but without coating is used as a main flame retardant, the flame-retardant functional master batches are prepared by the same process and used as the comparative examples 7-12, and then are mixed with PC/ABS alloy resin according to the same mass percentage, and are subjected to blending processing by a double-screw extruder, injection molding is carried out to obtain test sample strips, and the flame-retardant performance of the test sample strips is detected. The results of all performance tests are shown in table 2.

The data in table 2 show that the flame retardance and yellowing resistance of the PC/ABS alloy composite modified by the flame-retardant synergistic functional master batch special for the PC/ABS alloy prepared by the embodiment of the invention are obviously superior to those of the PC/ABS alloy composite modified by the flame-retardant functional master batch prepared by the uncoated tetrabromobisphenol A carbonate oligomer under the condition that the components and the mixture ratio are completely the same. In addition, from the results of the length test of the fluidity spiral line, the PC/ABS alloy compound modified by the embodiment of the invention has obviously higher fluidity than that of the comparative example. Therefore, by using the flame-retardant synergistic functional master batch, the flame-retardant modification effect of the domestic brominated flame retardant on the PC/ABS alloy resin is greatly improved, the defect of poor yellowing resistance of the PC/ABS alloy resin is effectively overcome, the melt flowability of the modified PC/ABS alloy compound is improved, the processing performance of the modified PC/ABS alloy compound is enhanced, and the appearance quality of the product is improved, so that the master batch makes a contribution to the sustainable development concept of improving the use reliability of the domestic brominated flame retardant and realizing the green processing of plastic modification.

Table 2 shows the comparison of the performance of the PC/ABS alloy composites modified with the functional master batches prepared in examples 7-12 and the functional master batches prepared in the same formula but using uncoated tetrabromobisphenol A carbonate oligomer

TABLE 2

Example 13

adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A carbonate oligomer, 7kg of aluminum sol and 1kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and heating to 40 ℃, then uniformly dropwise adding 10.0 wt.% ammonia water at a constant speed, controlling the pH value of a reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to perform sol-gel reaction, and after dropwise addition is completed, continuously stirring for 4 hours and then finishing the reaction; then washing with clean water, filtering, drying in a drying oven at 110 ℃ for 8 hours to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer. Dissolving 4kg of phytic acid in 8L of deionized water in another glass container to prepare a solution with the concentration of 0.5g/ml, putting 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer and 250L of isopropanol into an enamel reaction kettle, uniformly stirring and adding to 30 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 30 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the tetrabromobisphenol A carbonate oligomer have passivation reaction, continuously stirring for 2 hours, then adding 5kg of zirconium hydrogen phosphate powder, stirring for 3 hours at the same temperature to stop the reaction, then washing with clear water, filtering, and drying in a 110 ℃ oven for 12 hours to obtain the multiple composite coated tetrabromobisphenol A carbonate oligomer.

weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame retardant and synergistic functions, wherein the mixing temperature of the internal mixer is 125 ℃ and the mixing time is 16 minutes; the screw rotating speed of the single-screw extruder is 170 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.

Example 14

adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A carbonate oligomer, 8kg of aluminum sol and 1.5kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 35 ℃, then uniformly dripping 11.0 wt.% ammonia water at constant speed, controlling the pH value of a reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to perform sol-gel reaction, and after finishing dripping, continuing stirring for 3.5 hours and finishing the reaction; then washing with clean water, filtering, and drying in a baking oven at 120 ℃ for 9h to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer. In another glass container, 3.6kg of phytic acid is dissolved in 9L of deionized water to prepare a solution with the concentration of 0.4g/ml, 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer and 250L of isopropanol are put into an enamel reaction kettle, stirred uniformly and added to 30 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 30 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the tetrabromobisphenol A carbonate oligomer have passivation reaction, continuously stirring for 2 hours, adding 4.5kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 2.5 hours, stopping the reaction, washing with clear water, filtering, and drying in a 115 ℃ oven for 12 hours to obtain the multiple composite coated tetrabromobisphenol A carbonate oligomer.

weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame retardant and synergistic functions, wherein the mixing temperature of the internal mixer is 110 ℃ and the mixing time is 20 minutes; the screw rotating speed of the single-screw extruder is 160 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.

Example 15

adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A carbonate oligomer, 9kg of aluminum sol and 2kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 38 ℃, then uniformly dropwise adding 12.5wt.% ammonia water at a uniform speed, controlling the pH value of a reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding is completed, continuously stirring for 4 hours and then finishing the reaction; then washing with clean water, filtering, and drying in an oven at 115 ℃ for 10h to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer. Dissolving 3kg of phytic acid in 6L of deionized water in another glass container to prepare a solution with the concentration of 0.5g/ml, putting 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer and 250L of n-propanol into an enamel reaction kettle, uniformly stirring and adding to 35 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 35 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the tetrabromobisphenol A carbonate oligomer have passivation reaction, continuously stirring for 1.5h, then adding 5kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 3h to stop the reaction, then washing with clear water, filtering, and drying in a 110 ℃ oven for 12h to obtain the multiple composite coated tetrabromobisphenol A carbonate oligomer.

weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 100 ℃, the mixing time is 20 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame-retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 150 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.

Example 16

adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A carbonate oligomer, 7.5kg of aluminum sol and 2kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 35 ℃, then uniformly dropwise adding 12.0 wt.% ammonia water at a uniform speed, controlling the pH value of a reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding is finished, continuously stirring for 4 hours and finishing the reaction; then washing with clean water, filtering, and drying in a baking oven at 120 ℃ for 9 hours to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer. Dissolving 4.5kg of phytic acid in 9L of deionized water in another glass container to prepare a solution with the concentration of 0.5g/ml, putting 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer and 250L of isobutanol into an enamel reaction kettle, stirring uniformly and adding to 30 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 30 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the tetrabromobisphenol A carbonate oligomer have passivation reaction, continuously stirring for 1.5h, then adding 4.5kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 2.5h, stopping the reaction, then washing with clear water, filtering, and drying in a 120 ℃ oven for 11h to obtain the multiple composite coated tetrabromobisphenol A carbonate oligomer.

weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 120 ℃, the mixing time is 17 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame-retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 185 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.

Example 17

adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A carbonate oligomer, 8.5kg of aluminum sol and 1.5kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 35 ℃, then uniformly dropwise adding 11.5 wt.% ammonia water at a uniform speed, controlling the pH value of a reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding is completed, continuously stirring for 3 hours and then finishing the reaction; then washing with clean water, filtering, and drying in a drying oven at 120 ℃ for 10 hours to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer. Dissolving 3.2kg of phytic acid in 8L of deionized water in another glass container to prepare a solution with the concentration of 0.4g/ml, putting 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer and 250 n-butyl alcohol into an enamel reaction kettle, uniformly stirring and adding to 35 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 35 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the tetrabromobisphenol A carbonate oligomer have passivation reaction, continuously stirring for 2 hours, then adding 5kg of zirconium hydrogen phosphate powder, stirring for 3 hours at the same temperature to stop the reaction, then washing with clear water, filtering, and drying in a 120 ℃ oven for 12 hours to obtain the multiple composite coated tetrabromobisphenol A carbonate oligomer.

Example 18

adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A carbonate oligomer, 7kg of aluminum sol and 1.5kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 40 ℃, then uniformly dropwise adding 10.5 wt.% ammonia water at a uniform speed, controlling the pH value of a reaction solution to 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding, continuously stirring for 3.5 hours and then finishing the reaction; then washing with clean water, filtering, drying in an oven at 115 ℃ for 8 hours to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer. In another glass container, 3.5kg of phytic acid is dissolved in 7L of deionized water to prepare a solution with the concentration of 0.5g/ml, 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A carbonate oligomer and 250L of isopropanol are put into an enamel reaction kettle, stirred uniformly and added to 32 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 32 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the tetrabromobisphenol A carbonate oligomer have passivation reaction, continuously stirring for 1.5h, then adding 4kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 3h, stopping the reaction, then washing with clear water, filtering, and drying in a 110 ℃ oven for 12h to obtain the multiple composite coated tetrabromobisphenol A carbonate oligomer.

In examples 13 to 18, the polycarbonate and the alloy thereof are PC/PBT alloy, and in order to verify the modification effect of the flame-retardant and synergistic functional master batch prepared in examples 13 to 18 on the PC/PBT alloy, the flame-retardant and synergistic functional master batch prepared in examples 13 to 18 was mixed with the PC/PBT alloy resin in a mass percentage of 20 wt.%, and was subjected to blending extrusion molding by a twin-screw extruder, injection molding to obtain a combustion test specimen, and then, the flame-retardant performance test was performed. Meanwhile, according to the same components and proportions of the functional master batches obtained in the examples 13-18, tetrabromobisphenol A carbonate oligomer which has the same brand but is not coated is used as a main flame retardant, the flame-retardant functional master batches are prepared by the same process to be used as the comparative examples 13-18, and are mixed with PC/PBT alloy resin according to the same mass percentage, and are subjected to blending processing by a double-screw extruder, and then injection molding is carried out to obtain test sample strips, and the flame retardant property of the test sample strips is detected. The results of all performance tests are shown in table 3.

The data in Table 3 show that the flame retardance and yellowing resistance of the PC/PBT alloy composite modified by the PC/PBT alloy modified special flame-retardant synergistic functional master batch prepared by the embodiment of the invention are obviously superior to those of the PC/PBT alloy composite modified by the flame-retardant functional master batch prepared by the uncoated tetrabromobisphenol A carbonate oligomer under the condition that the components and the mixture ratio are completely the same. In addition, from the results of the fluidity spiral length test, it is also found that the fluidity of the PC/PBT alloy compound modified by the embodiment of the invention is obviously higher than that of the comparative example. Therefore, by using the master batch with the flame-retardant synergistic function, the flame-retardant modification effect of domestic brominated flame retardants on PC/PBT alloy resin is greatly improved, the defect of poor yellowing resistance of the PC/PBT alloy resin is effectively overcome, the melt fluidity of the modified PC/PBT alloy compound is improved, the processing performance of the modified PC/PBT alloy compound is enhanced, and the appearance quality of the modified PC/PBT alloy compound is improved, so that the master batch makes a contribution to the improvement of the use reliability of the domestic brominated flame retardants and the realization of the sustainable development concept of green plastic modification processing.

Table 3 shows the comparison of the performance of the PC/PBT alloy composites modified with the functional master batches prepared in examples 13 to 18 and the functional master batches prepared in the same formulation but using uncoated tetrabromobisphenol A carbonate oligomer

TABLE 3

In summary, the following steps:

the organic polymer or inorganic material with stable chemical structure and compact material is used as a wall material, and the domestic brominated flame retardant is coated by a chemical reaction method, so that the coated brominated flame retardant can be effectively protected from the adverse effects of external environments such as external light, oxygen, water and the like, and can be isolated from mutual friction with resin and other additives and delayed from thermal decomposition in the process of blending thermal mechanical processing with engineering plastics such as PC, alloy and the like. Therefore, the method for coating the flame retardant by adopting the inert material is a simple and effective way for effectively improving the quality and the application effect of the domestic brominated flame retardant special for PC and PC alloy.

The modified plastic is prepared by a plastic functional master batch mode, namely, firstly, the bromine flame retardant which does not resist temperature, other auxiliary agents, the flame retardant synergist powder with low bulk density and difficult feeding, the auxiliary agent which is easy to absorb water, liquid, colloid auxiliary agent and the like are mixed and uniformly dispersed by utilizing the low-temperature and long-time kneading effect of an internal mixer, and then, the mixture is extruded and granulated by a single-screw extruder to prepare the flame retardant functional master batch containing the high-concentration flame retardant. In the implementation process of plastic flame-retardant modification, the flame-retardant functional master batch and the engineering plastic raw materials are subjected to melt blending and extrusion granulation through a double-screw extruder, so that the dispersity of the domestic brominated flame retardant and the flame-retardant synergist in a resin matrix can be effectively improved, the flame-retardant effect is enhanced, the material yellowing caused by direct mutual friction heat generation of the domestic brominated flame retardant and the flame-retardant synergist is eliminated, and the dust pollution of a processing workshop can be reduced. Due to the comprehensive technical advantages, the method for preparing the flame-retardant modified plastic by adopting the flame-retardant functional master batch becomes an important measure in the field of the current flame-retardant modification technology of the plastic, and is also one of important ways for realizing green processing of the modified plastic.

In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims

1. A special flame-retardant synergistic functional master batch for modifying polycarbonate and alloy thereof is characterized in that: the functional master batch takes a tetrabromobisphenol A carbonate oligomer which is coated by multiple compounds as a main flame retardant, and the functional master batch comprises the following components in percentage by mass: 55.0-70.0 wt% of multi-composite coated tetrabromobisphenol A carbonate oligomer, 15.0-30.0 wt% of sodium citrate, 10.0-14.0 wt% of carrier resin, 0.0-4.0 wt% of aliphatic copolyester, 0.0-0.5 wt% of hyperbranched polyester, 0.5-1.0 wt% of dispersant and 0.3-0.5 wt% of lubricant;

the multiple composite coated tetrabromobisphenol A carbonate oligomer is tetrabromobisphenol A carbonate oligomer coated with zirconium hydrogen phosphate powder, phytic acid and zinc ion doped aluminum hydroxide;

the preparation method of the zirconium hydrogen phosphate powder, the phytic acid and the zinc ion doped aluminum hydroxide coated brominated flame retardant comprises the following steps:

(2) dispersing the zinc ion-doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer obtained in the step (1) into an alcohol organic solvent to obtain a suspension, dissolving phytic acid in deionized water to form a phytic acid solution, dropwise adding the phytic acid solution into the suspension of the zinc ion-doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer, heating and stirring for a period of time, adding zirconium hydrogen phosphate powder, continuously stirring for a period of time at the same temperature, stopping reaction, washing with clear water, filtering, and drying to obtain a multiple composite inorganic material coated tetrabromobisphenol A carbonate oligomer;

in the step (1), the heating and stirring temperature is 35-40 ℃, ammonia water is dropwise added at a constant speed, the mass fraction of the ammonia water is 10.0-12.5 wt.%, the pH value of the reaction solution is controlled to be 7.5-8.5, and after the dropwise addition is finished, the reaction is finished after continuously stirring for 3-4 hours; then washing with clear water, filtering, and drying in an oven at 110-120 ℃ for 8-10 h to obtain zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer;

the alcohol organic solvent in the step (2) is one of isopropanol, n-propanol, isobutanol or n-butanol, the heating and stirring temperature is 30-35 ℃, the concentration of phytic acid is 0.4-0.5 g/ml, the dropping of phytic acid is constant-speed dropping, the phytic acid solution is continuously stirred for 1.5-2 hours after being added, zirconium hydrogen phosphate powder is added, the reaction is stopped after the stirring is carried out for 2.5-3 hours at the same temperature, then the washing and the filtering are carried out by clear water, and the drying is carried out in a drying oven at 110-120 ℃ for 10-12 hours, so that the tetrabromobisphenol A carbonate oligomer coated with the multiple composite inorganic material is obtained;

in the step (1), the mass ratio of the tetrabromobisphenol A carbonate oligomer to the aluminum sol to the zinc oxide sol is 150:7: 1-150: 9:2, and in the step (2), the mass ratio of the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A carbonate oligomer to the phytic acid to the zirconium hydrogen phosphate is 150:3: 4-150: 4.5: 5.

2. The special flame-retardant synergistic functional master batch for modifying polycarbonate and the alloy thereof according to claim 1, which is characterized in that: the carrier resin is ethylene-glycidyl acrylate copolymer EGMA, ethylene-methyl acrylate-glycidyl methacrylate copolymer EMA-GMA and ethylene-butyl acrylate-glycidyl methacrylate copolymer EBA-GMA.

3. The special flame-retardant synergistic functional master batch for modifying polycarbonate and alloy thereof according to claim 1, which is characterized in that: the aliphatic copolymer is one of poly (ethylene succinate-butylene succinate), poly (ethylene succinate-butylene methylsuccinate) and poly (ethylene succinate-butylene phenylsuccinate).

4. The special flame-retardant synergistic functional master batch for modifying polycarbonate and the alloy thereof according to claim 1, which is characterized in that: the hyperbranched polyester is a four-arm polyester copolymer which takes pentaerythritol as a core and takes poly (dimethylolpropionic acid) as a branched chain.

5. The special flame-retardant synergistic functional master batch for modifying polycarbonate and alloy thereof according to claim 1, which is characterized in that: the dispersant is one of aluminum stearate, calcium stearate, zinc stearate, stearic acid, pentaerythritol stearate, E wax, OP wax and ethylene bis stearamide.

6. The special flame-retardant synergistic functional master batch for modifying polycarbonate and the alloy thereof according to claim 1, which is characterized in that: the lubricant is one of ethylene bis stearamide, pentaerythritol stearate, OP wax, E wax and ethylene-vinyl acetate copolymer wax.

7. The method for preparing the special flame-retardant synergistic functional master batch for modifying polycarbonate and the alloy thereof according to claim 1, which is characterized by comprising the following steps: the method comprises the following steps: