CN110577698A - special halogen-free flame-retardant synergistic functional master batch for PBT resin modification and preparation method thereof - Google Patents
special halogen-free flame-retardant synergistic functional master batch for PBT resin modification and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of plastic modification processing, in particular to a special halogen-free flame retardant synergistic functional master batch for modifying polyester engineering plastics and a preparation method thereof; the functional master batch takes multiple compound coated zinc diethylphosphinate as a phosphorus flame retardant, and the functional master batch comprises the following components in percentage by mass: 60.0-70.0 wt.% of multi-composite coated zinc diethylphosphinate, 16.0-22.0 wt.% of anhydrous zinc borate, 8.0-12.0 wt.% of ethylene-butyl acrylate copolymer, 3.0-5.0 wt.% of aliphatic copolyester, 0.5-1.0 wt.% of hyperbranched polyester and 0.3-0.5 wt.% of lubricant; compared with the traditional flame-retardant functional master batch, the functional master batch prepared by the invention obviously improves the heat resistance and the thermal stability of the zinc diethylphosphinate, so that the functional master batch is suitable for the high processing temperature required by the PBT resin, and the flame-retardant effect of the zinc diethylphosphinate on the PBT resin is effectively improved.
Description
Technical Field
The invention relates to the technical field of plastic modification processing, in particular to a special halogen-free flame-retardant synergistic functional master batch for modifying polyester engineering plastics and a preparation method thereof.
background
Polyester engineering plastics are important engineering materials which mainly comprise polybutylene terephthalate (PBT) and secondarily comprise polyethylene terephthalate (PET), and although the engineering plastics have excellent mechanical property, electrical property and good processing property, the polyester engineering plastics are the best macromolecules for manufacturing household and industrial electronic and electric products and parts. However, polyester engineering plastics are flammable high molecular materials, and the limit oxygen index of the polyester engineering plastics is only about 20 vol.%. Therefore, to realize the application in the field of electronic and electric appliances, flame retardant modification is often required to improve the use safety. The flame-retardant modification of the polyester engineering plastic can be realized by adding a flame retardant and carrying out melt blending through a double-screw extruder. The flame retardant can prevent the polyester engineering plastic from being ignited and inhibit flame propagation, and can effectively improve the anti-combustion performance of the polyester 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 bromine-containing flame retardant is generally accepted as the most effective flame retardant with wide applicability, convenient use, excellent flame retardant effect and high flame retardant efficiency for most general and engineering plastics, when a fire disaster occurs, the bromine-containing flame retardant materials can generate a large amount of smoke and toxic corrosive hydrogen halide gas to cause secondary harm, and the halogen-free flame retardant materials are gradually popularized and used in a plurality of flame retardant application fields at present. The halogen-free flame retardant mainly comprises phosphorus-nitrogen compounds and metal hydroxides, and the flame-retardant plastic has small smoke generation amount during combustion and does not generate toxic, harmful and corrosive gases, is called a pollution-free flame retardant and also becomes the development direction of the future plastic flame retardant technology.
The organic phosphonate is known as the most effective halogen-free flame retardant for polyester engineering plastics due to excellent flame retardance and good heat resistance and thermal stability, and has the advantages of small addition amount, excellent flame retardant effect, easy realization of high-grade flame retardant effect of UL 94V 0 and the like. Although aluminum diethylphosphinate and zinc diethylphosphinate in the organic phosphonate can be used for flame retardant modification of polyester engineering plastics, the polyester engineering plastics have the characteristic of easy moisture absorption, and the water resistance of the aluminum diethylphosphinate is obviously inferior to that of the zinc diethylphosphinate, so that the problems of poor flame retardant effect, material performance reduction and the like are caused when the flame retardant modified polyester engineering plastics are subjected to flame retardant modification. Therefore, zinc diethylphosphinate is the best organic phosphonate flame retardant for polyester engineering plastics recognized by the flame retardant science. However, although the heat resistance and thermal stability of zinc diethylphosphinate are higher than those of other phosphorus flame retardants, when the zinc diethylphosphinate is applied to a thermoplastic polymer material such as PBT resin with a processing temperature of more than 250 ℃, the zinc diethylphosphinate still has problems such as thermal decomposition during processing. In addition, the zinc diethylphosphinate has the problems of low fluidity, poor dispersibility, poor interfacial adhesion with a modified polymer and the like in the application process, so that the mechanical property and the flame retardant property of the material are reduced. In order to overcome the defects of flame retardance of the zinc diethylphosphinate in the flame retardant modification application process of a high-temperature thermoplastic polymer material, an organic polymer or inorganic material with a stable chemical structure and compact material quality is used as a wall material, and the zinc diethylphosphinate is coated by a chemical reaction method, so that the zinc diethylphosphinate can be effectively protected from the adverse effects of external environments such as external light, oxygen, water and the like, and the mutual friction between the zinc diethylphosphinate and other powder additives and the thermal decomposition of the zinc diethylphosphinate can be isolated in the blending thermal mechanical processing process of plastics, and the thermal decomposition of the zinc diethylphosphinate and other powder additives can be.
The zinc diethyl phosphinate flame-retardant plastic modification processing process also has another series of problems, for example, zinc diethyl phosphinate and related flame-retardant synergists (such as zinc borate and a char forming agent) are often powder and are added in large amounts, and when a twin-screw extruder is directly used for melt extrusion blending, due to the limited residence time of materials in the barrel of the extruder, the polymer is difficult to melt and fully mix with the flame retardant. In addition, because a large amount of flame retardant powder generates internal heat through mechanical friction in the blending and extrusion process, the flame retardant is decomposed to cause the damage of the flame retardant effect, and the reduction of the physical and mechanical properties of the modified plastic is also caused.
Disclosure of Invention
The purpose of the invention is: aiming at the application defects of poor high-temperature thermal stability, weak interface caking property, large flame retardant property loss, low fluidity, poor dispersibility and the like of zinc diethylphosphinate in the modification application process of halogen-free flame retardant polyester engineering plastics, the problems of flame retardant efficiency and reduced physical and mechanical properties caused by thermal degradation due to powder friction in the direct blending extrusion processing process of double screws and the like, and the defect that the traditional polymer or inorganic wall material single-layer coated zinc diethylphosphinate cannot provide enough protection is overcome, the invention provides a method for performing multiple composite coating on zinc diethylphosphinate by adopting a wall material with flame retardant synergy and compact material quality, and then banburying the zinc diethylphosphinate with corresponding flame retardant synergist and auxiliary agent at low temperature to prepare the halogen-free flame retardant synergistic functional master batch special for modifying the halogen-free flame retardant polyester engineering plastics.
Another object of the invention is: provides a preparation method of the halogen-free flame-retardant synergistic functional master batch special for modifying the polyester engineering plastics.
The effective method for solving the problem is to prepare the modified plastic by using the plastic functional master batch, namely, firstly, mixing and uniformly dispersing phosphorus flame retardants and nitrogen flame retardants which do not resist high temperature and other auxiliary agents, flame retardant synergist powder with low bulk density and difficult feeding, an easy-water-absorption auxiliary agent, liquid, a colloid auxiliary agent and the like by using the low-temperature and long-time kneading effect of an internal mixer, and then extruding and granulating the mixture 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 batches and the plastic raw materials are subjected to melt blending and extrusion granulation through a double-screw extruder, so that the dispersibility of phosphorus flame retardants represented by zinc diethylphosphinate and related flame-retardant synergists thereof in a resin matrix can be improved more effectively, the flame-retardant effect is enhanced, the thermal decomposition of materials caused by direct mutual frictional heat generation of the phosphorus flame retardants and the flame-retardant synergists such as anhydrous zinc borate 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 order to achieve the technical aim, the invention firstly adopts aluminum doped with zinc ionsThe sol is used as a raw material to coat the zinc diethyl phosphinate particles, and as the Zeta potential of the zinc diethyl phosphinate is a negative value and the Zeta potential of the aluminum sol is a positive value, the 'core-shell' structure microcapsule particles taking zinc ions doped aluminum hydroxide as a shell and zinc diethyl phosphinate 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·H2and O, a sheet-shaped inorganic nano material with a mesoporous structure ], wherein zirconium ions in molecules of the inorganic nano material can also perform passivation reaction with phytic acid, and hydroxyl functional groups on the surfaces of the inorganic nano material and carboxyl functional groups in the phytic acid can also be replaced to form a chemical bond combination, so that multiple composite coating of zinc diethylphosphinate is realized. And mixing the coated zinc diethyl phosphinate with auxiliary agents such as a flame-retardant synergist, a carrier, a dispersing agent and the like, and finally preparing the special flame-retardant functional master batch for halogen-free flame-retardant modification of the PBT resin by connecting an internal mixer in series with a single-screw extruder.
The specific technical scheme is as follows:
the special halogen-free flame-retardant synergistic functional master batch for modifying the polyester engineering plastics takes multiple compound coated zinc diethylphosphinate as a phosphorus flame retardant, and comprises the following components in percentage by mass: 60.0-70.0 wt.% of multi-composite coated zinc diethyl phosphinate, 16.0-22.0 wt.% of anhydrous zinc borate, 8.0-12.0 wt.% of ethylene-butyl acrylate copolymer, 3.0-5.0 wt.% of aliphatic copolyester, 0.5-1.0 wt.% of hyperbranched polyester and 0.3-0.5 wt.% of lubricant.
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 which takes pentaerythritol as a core and takes poly (dimethylolpropionic acid) as a branched chain.
Further, the lubricant is one of ethylene-vinyl acetate copolymer wax, ethylene-acrylic acid copolymer wax, E wax, OP wax and pentaerythritol stearate, wherein the ethylene-vinyl acetate copolymer wax is preferable.
Further, the multiple composite coated zinc diethyl phosphinate is zinc ion doped aluminum hydroxide, phytic acid and zirconium hydrogen phosphate coated zinc diethyl phosphinate.
Further, the preparation method of the multiple composite coated zinc diethylphosphinate comprises the following steps:
(1) Dispersing zinc diethyl phosphinate, aluminum sol and zinc oxide sol in absolute ethyl alcohol, heating and stirring uniformly, then dropwise adding ammonia water, adjusting the pH value of the reaction solution to be alkaline, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding is finished, continuously stirring for a period of time to finish the reaction; then washing, filtering and drying to obtain zinc ion doped aluminum hydroxide coated zinc diethylphosphinate;
(2) Dispersing the coated zinc diethylphosphinate in an alcohol organic solvent; and dissolving phytic acid in deionized water, uniformly dripping the phytic acid into alcohol organic solvent suspension containing the coated zinc diethylphosphinate, heating and uniformly stirring the solution to ensure that the phytic acid and the zinc ion coated with the zinc diethylphosphinate are subjected to passivation reaction by doping aluminum hydroxide shells, continuously stirring the solution for a period of time, adding zirconium hydrogen phosphate powder, stirring the solution for a period of time at the same temperature to stop the reaction, and then washing, filtering and drying the solution to obtain the multiple composite inorganic material coated zinc diethylphosphinate.
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 the reaction is finished after the dripping is finished and the stirring is continued for 3-4 hours; and then washing with clear water, filtering, and drying in an oven at 115-125 ℃ for 8-10 h to obtain zinc ion doped aluminum hydroxide coated zinc diethylphosphinate.
Further, the alcohol organic solvent in the step (2) is one of isopropanol, n-propanol, isobutanol or n-butanol, wherein isopropanol is preferred, the concentration of the phytic acid solution is 0.4-0.5 g/ml, the phytic acid is dropwise added at a constant speed, the heating and stirring temperature is 30-35 ℃, the phytic acid solution is continuously stirred for 1.5-2 hours, then zirconium hydrogen phosphate powder is added, the reaction is stopped after stirring for 2.5-3 hours at the same temperature, then the mixture is washed by clear water, filtered and dried in an oven at 115-125 ℃ for 10-12 hours, and the multi-composite inorganic material coated zinc diethylphosphinate is obtained.
Further, in the step (1), the mass ratio of the zinc diethyl phosphinate to the aluminum sol to the zinc oxide sol is 120:7: 1-120: 9:2, and in the step (2), the mass ratio of zinc ion doped aluminum hydroxide to the zinc diethyl phosphinate to the phytic acid to the zirconium hydrogen phosphate is 120:3: 5-120: 4.5: 5.
The method for preparing the halogen-free flame-retardant synergistic functional master batch special for modifying the polyester engineering plastics comprises the following steps:
(1) weighing multiple composite coated zinc diethylphosphinate, anhydrous zinc borate, ethylene-butyl acrylate copolymer, aliphatic copolyester, hyperbranched polyester and a lubricant according to a ratio, putting the materials into a high-speed mixer, uniformly mixing, and transferring the mixture into an internal mixer for hot mixing to obtain a bulk blend; the mixing temperature of the internal mixer is 100-125 ℃, and the mixing time is 15-20 minutes;
(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 halogen-free flame-retardant synergistic functional master batch; the screw rotating speed of the single-screw extruder is 150-200 r/min, and the barrel temperature is 150-160 ℃.
The technical scheme adopted by the invention has the beneficial effects that:
(1) Aiming at the defects that zinc diethylphosphinate has poor heat resistance and thermal stability, low fluidity and poor dispersibility under high-temperature conditions, and traditional wall materials cannot provide enough protection, and the like, zinc ion-doped aluminum hydroxide inorganic matter is selected to coat the zinc ion-doped aluminum hydroxide inorganic matter, then a compact and solid protective layer is formed by utilizing the passivation effect of phytic acid and zinc/aluminum ions, and then zirconium hydrogen phosphate nanosheets with mesoporous structures form the outermost layer structure of zinc diethylphosphinate microcapsules through the dual effects of phytic acid passivation and ion exchange adsorption, so that a multiple composite inorganic coating layer is formed. Compared with the traditional polymer or single-layer inorganic material coating layer, the multiple composite inorganic coating layer has a better thermal protection effect on the zinc diethylphosphinate, and particularly, the multiple inorganic shell passivated by the phytic acid provides a firmer and denser inorganic coating layer for the zinc diethylphosphinate than the traditional polymer and inorganic wall materials, so that the coated zinc diethylphosphinate can be more effectively protected, and the thermal decomposition temperature of the zinc diethylphosphinate is remarkably improved. Therefore, the coated zinc diethylphosphinate can obtain more excellent thermal stability.
(2) as a large amount of phosphorus-containing materials are introduced into the wall material coated with the zinc diethylphosphinate, the introduction of more phosphorus elements can effectively promote the formation of a thick carbon layer on the surface of a combustion product of the PBT resin compound in the combustion process of the halogen-free flame-retardant PBT resin compound, more remarkably enhance the compactness and structural stability of the carbon layer on the surface in the combustion process of the flame-retardant polymer, prevent the interior of the combustion product from contacting with oxygen, enable the flame retardant to play a synergistic flame-retardant role, and further effectively improve the flame-retardant property of the polyester engineering plastic.
(3) By introducing zirconium hydrogen phosphate with a mesoporous structure into the outermost coating layer of zinc diethylphosphinate, the zirconium hydrogen phosphate has a large specific surface area, a large surface charge density, a stable layered structure, and rich OH groups, can perform an ion exchange reaction, has a large ion exchange capacity, can perform a large adsorption effect on various small-molecule volatile matters in the thermal processing process of flame-retardant plastics, and can also perform a flame-retardant synergistic effect in a halogen-free flame-retardant system.
(4) The master batch formula with good compatibility with the polyester engineering plastic and good dispersion of the flame retardant powder is designed, and the master batch with the flame retardant function is obtained by mixing the master batch with an internal mixer at a low temperature for a long time, so that the flame retardant powder obtains an excellent pre-dispersion effect, and the decomposition of a phosphorus flame retardant caused by high-temperature thermal mechanical processing is avoided, thereby obtaining a better dispersion effect and excellent flame retardant property in the subsequent double-screw melt extrusion modification processing of the polyester engineering plastic; 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 halogen-free flame-retardant synergistic functional master batch improves the flame-retardant effect of the diethyl zinc phosphinate, can obtain the same flame-retardant effect as the traditional flame-retardant functional master batch by using less master batch addition amount, and can effectively reduce the mechanical property loss of the modified polyester engineering plastic compound.
(6) The special halogen-free flame retardant master batch for modifying the PBT resin, which is prepared by the invention, can be subjected to melt extrusion functional modification with double screws for various grades of PBT and PET resins, and can also be directly applied to injection molding of products after being simply mixed with the PBT or PET resin according to a certain proportion. The combination mode of the flame-retardant synergistic functional master batch 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 to adjust the performance and the cost, so that the target requirements of products can be quickly and simply met, and the plastic modification formula and the processing technology are optimized and designed.
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 halogen-free flame-retardant synergistic functional master batch special for modifying the polyester engineering plastics comprises the following raw materials in parts by mass:
| Multiple composite coated zinc diethyl phosphinate | 70.0 kg |
| anhydrous zinc borate | 16.0 kg |
| ethylene-butyl acrylate copolymer | 10.0 kg |
| Poly (ethylene succinate-butylene succinate) | 3.0 kg |
| hyperbranched polyester | 500.0 g |
| ethylene-vinyl acetate copolymer wax | 500.0 g |
The preparation method of the multiple composite coated zinc diethyl phosphinate used in the halogen-free flame retardant synergistic functional master batch special for modifying the polyester engineering plastic comprises the following steps:
Adding 230L of absolute ethyl alcohol, 120kg of diethyl zinc phosphinate, 7 kg of aluminum sol and 1 kg 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 10.0wt.% 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 perform sol-gel reaction, and after dropwise adding is completed, continuously stirring for 3.5 hours and then finishing the reaction; then washing with clean water, filtering, and drying in an oven at 125 ℃ for 8 hours to obtain zinc ion-doped aluminum hydroxide coated zinc diethylphosphinate. Dissolving 3 kg of phytic acid in 6L of deionized water in another glass container to prepare a solution with the concentration of 0.5 g/ml, putting 120kg of the obtained zinc ion-doped aluminum hydroxide-coated zinc diethylphosphinate and 230L of isopropanol into an enamel reaction kettle, uniformly stirring and adding to 30 ℃; uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 35 ℃, uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion coated with the zinc diethyl phosphinate are subjected to passivation reaction in an aluminum hydroxide shell, continuously stirring for 2 hours, adding 4.5 kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 3 hours to stop the reaction, washing with clear water, filtering, and drying in a 120 ℃ oven for 12 hours to obtain the multiple composite coated zinc diethyl phosphinate.
The preparation method of the halogen-free flame-retardant synergistic functional master batch special for modifying the polyester engineering plastic 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 115 ℃, 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 halogen-free flame-retardant synergistic functional master batch; the screw rotating speed of the single-screw extruder is 180 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.
Example 2
The halogen-free flame-retardant synergistic functional master batch special for modifying the polyester engineering plastics comprises the following raw materials in parts by mass:
| Multiple composite coated zinc diethyl phosphinate | 60.0 kg |
| Anhydrous zinc borate | 22.0 kg |
| Ethylene-butyl acrylate copolymer | 12.0 kg |
| poly (ethylene succinate-butylene phenyl succinate) | 4.0 kg |
| Hyperbranched polyester | 1.5 kg |
| Ethylene-acrylic acid copolymer wax | 500.0 g |
The preparation method of the multiple composite coated zinc diethyl phosphinate used in the halogen-free flame retardant synergistic functional master batch special for modifying the polyester engineering plastic comprises the following steps:
Adding 230L of absolute ethyl alcohol, 120kg of diethyl zinc phosphinate, 8kg of aluminum sol and 1.5 kg 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 11.5wt.% 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 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 120 ℃ for 10 hours to obtain zinc ion-doped aluminum hydroxide coated zinc diethylphosphinate. Dissolving 3.6 kg of phytic acid in 9L of deionized water in another glass container to prepare a solution with the concentration of 0.4 g/ml, putting 120kg of the obtained zinc ion-doped aluminum hydroxide coated zinc diethylphosphinate and 230L of isopropanol into an enamel reaction kettle, uniformly stirring and adding to 30 ℃; uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 30 ℃, 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 zinc diethyl phosphinate have passivation reaction, continuously stirring for 2 hours, adding 5kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 3 hours to stop the reaction, washing with clear water, filtering, and drying in a 120 ℃ oven for 9 hours to obtain the multiple composite coated zinc diethyl phosphinate.
The preparation method of the halogen-free flame-retardant synergistic functional master batch special for modifying the polyester engineering plastic 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 115 ℃, 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 halogen-free flame-retardant synergistic functional master batch; the screw rotating speed of the single-screw extruder is 165 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.
Example 3
The halogen-free flame-retardant synergistic functional master batch special for modifying the polyester engineering plastics comprises the following raw materials in parts by mass:
| Multiple composite coated zinc diethyl phosphinate | 64.0 kg |
| Anhydrous zinc borate | 21.0 kg |
| Ethylene-butyl acrylate copolymer | 8.5 kg |
| Poly (ethylene succinate-butylene methylsuccinate) | 5.0 kg |
| Hyperbranched polyester | 1.2 kg |
| OP wax | 300.0 g |
The preparation method of the multiple composite coated zinc diethyl phosphinate used in the halogen-free flame retardant synergistic functional master batch special for modifying the polyester engineering plastic comprises the following steps:
Adding 230L of absolute ethyl alcohol, 120kg of diethyl zinc phosphinate, 7.5 kg of aluminum sol and 2 kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 37 ℃, then uniformly and dropwise adding 12.5 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 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 125 ℃ for 8 h to obtain zinc ion-doped aluminum hydroxide coated zinc diethylphosphinate. Dissolving 3 kg of phytic acid in 6L of deionized water in another glass container to prepare a solution with the concentration of 0.5 g/ml, putting 120kg of the obtained zinc ion-doped aluminum hydroxide-coated zinc diethylphosphinate and 230L of n-propanol into an enamel reaction kettle, uniformly stirring and adding to 33 ℃; uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 33 ℃, uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion coated with the zinc diethyl phosphinate are subjected to passivation reaction in the aluminum hydroxide shell, continuously stirring for 1.5 h, adding 4.8kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 3 h to stop the reaction, washing with clear water, filtering, and drying in a 115 ℃ oven for 12 h to obtain the multiple composite coated zinc diethyl phosphinate.
The preparation method of the halogen-free flame-retardant synergistic functional master batch special for modifying the polyester engineering plastic 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 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 halogen-free flame-retardant synergistic functional master batch; the screw rotating speed of the single-screw extruder is 200 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.
Example 4
The halogen-free flame-retardant synergistic functional master batch special for modifying the polyester engineering plastics comprises the following raw materials in parts by mass:
| Multiple composite coated zinc diethyl phosphinate | 63.0 kg |
| Anhydrous zinc borate | 18.0 kg |
| Ethylene-butyl acrylate copolymer | 12.0 kg |
| Poly (ethylene succinate-butylene succinate) | 5.0 kg |
| hyperbranched polyester | 1.5 kg |
| E wax | 500.0 g |
The preparation method of the multiple composite coated zinc diethyl phosphinate used in the halogen-free flame retardant synergistic functional master batch special for modifying the polyester engineering plastic comprises the following steps:
Adding 230L of absolute ethyl alcohol, 120kg of diethyl zinc phosphinate, 9 kg of aluminum sol and 1 kg 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 11.5wt.% 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 perform sol-gel reaction, and after dropwise adding is completed, continuously stirring for 3.5 hours and then finishing the reaction; then washing with clean water, filtering, and drying in an oven at 125 ℃ for 8 h to obtain zinc ion-doped aluminum hydroxide coated zinc diethylphosphinate. Dissolving 4.5 kg of phytic acid in 9L of deionized water in another glass container to prepare a solution with the concentration of 0.5 g/ml, putting 120kg of obtained zinc ion-doped aluminum hydroxide-coated zinc diethylphosphinate and 230L of n-butanol into an enamel reaction kettle, uniformly stirring and adding to 35 ℃; uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 35 ℃, uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion coated with the zinc diethyl phosphinate are subjected to passivation reaction in an aluminum hydroxide shell, continuously stirring for 2 hours, adding 4.6 kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 3 hours to stop the reaction, washing with clear water, filtering, and drying in a 125 ℃ oven for 11 hours to obtain the multiple composite coated zinc diethyl phosphinate.
The preparation method of the halogen-free flame-retardant synergistic functional master batch special for modifying the polyester engineering plastic 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 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 halogen-free flame-retardant synergistic functional master batch; 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 5
The halogen-free flame-retardant synergistic functional master batch special for modifying the polyester engineering plastics comprises the following raw materials in parts by mass:
| Multiple composite coated zinc diethyl phosphinate | 64.0 kg |
| anhydrous zinc borate | 19.4 kg |
| Ethylene-propyleneCopolymer of butyl enoate | 11.0 kg |
| Poly (ethylene succinate-butylene methylsuccinate) | 4.0 kg |
| Hyperbranched polyester | 1.2 kg |
| Pentaerythritol stearate | 400.0 g |
The preparation method of the multiple composite coated zinc diethyl phosphinate used in the halogen-free flame retardant synergistic functional master batch special for modifying the polyester engineering plastic comprises the following steps:
adding 230L of absolute ethyl alcohol, 120kg of diethyl zinc phosphinate, 8.5 kg of aluminum sol and 2 kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 40 ℃, then uniformly and dropwise adding 12.0wt.% ammonia water at a constant 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 is completed, continuously stirring for 4 hours and then finishing the reaction; then washing with clean water, filtering, and drying in an oven at 120 ℃ for 10h to obtain zinc ion-doped aluminum hydroxide coated zinc diethylphosphinate. Dissolving 3.2 kg of phytic acid in 8L of deionized water in another glass container to prepare a solution with the concentration of 0.4 g/ml, putting 120kg of the obtained zinc ion-doped aluminum hydroxide-coated zinc diethylphosphinate and 230L of isobutanol into an enamel reaction kettle, uniformly stirring and adding to 35 ℃; uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 35 ℃, uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion coated with the zinc diethyl phosphinate are subjected to passivation reaction in an aluminum hydroxide shell, continuously stirring for 2 hours, adding 4.8kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 3 hours to stop the reaction, washing with clear water, filtering, and drying in a 125 ℃ oven for 11 hours to obtain the multiple composite coated zinc diethyl phosphinate.
the preparation method of the halogen-free flame-retardant synergistic functional master batch special for modifying the polyester engineering plastic 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 halogen-free flame-retardant synergistic functional master batch; the screw rotating speed of the single-screw extruder is 155 r/min, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.
Example 6
The halogen-free flame-retardant synergistic functional master batch special for modifying the polyester engineering plastics comprises the following raw materials in parts by mass:
| Multiple composite coated zinc diethyl phosphinate | 66.0 kg |
| Anhydrous zinc borate | 18.0 kg |
| Ethylene-butyl acrylate copolymer | 11.0 kg |
| Poly (ethylene succinate-butylene succinate) | 3.3 kg |
| hyperbranched polyester | 1.2 kg |
| Ethylene-acrylic acid copolymer wax | 500.0 g |
the preparation method of the multiple composite coated zinc diethyl phosphinate used in the halogen-free flame retardant synergistic functional master batch special for modifying the polyester engineering plastic comprises the following steps:
Adding 230L of absolute ethyl alcohol, 120kg of diethyl zinc phosphinate, 7.5 kg of aluminum sol and 1.5 kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 38 ℃, then uniformly and dropwise adding 10.5 wt.% ammonia water at a constant speed, controlling the pH value of a reaction solution to 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to perform sol-gel reaction, and after dropwise adding is completed, continuously stirring for 3.5 hours and then finishing the reaction; then washing with clean water, filtering, and drying in an oven at 125 ℃ for 8 hours to obtain zinc ion-doped aluminum hydroxide coated zinc diethylphosphinate. Dissolving 3.5 kg of phytic acid in 7L of deionized water in another glass container to prepare a solution with the concentration of 0.5 g/ml, putting 120kg of obtained zinc ion-doped aluminum hydroxide coated zinc diethylphosphinate and 230L of isopropanol into an enamel reaction kettle, uniformly stirring and adding to 30 ℃; uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 30 ℃, uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the zinc ion coated with the zinc diethyl phosphinate are subjected to passivation reaction in the aluminum hydroxide shell, continuously stirring for 1.5 h, adding 4 kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 3 h to stop the reaction, washing with clear water, filtering, and drying in an oven at 115 ℃ for 12 h to obtain the multiple composite coated zinc diethyl phosphinate.
the preparation method of the halogen-free flame-retardant synergistic functional master batch special for modifying the polyester engineering plastic 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 halogen-free flame-retardant synergistic functional master batch; 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.
In order to verify the modification effect of the flame-retardant synergistic functional master batch prepared by the invention on polyester engineering plastics, the flame-retardant synergistic functional master batch prepared in the embodiment 1-6 is mixed with PBT 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 to obtain a 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 batch obtained in the examples 1-6, but the same-grade uncoated zinc diethylphosphinate is used as a main flame retardant, the flame-retardant functional master batch is prepared by the same process and used as a comparative example 1-6, and then the flame-retardant functional master batch is mixed with PBT resin according to the same mass percentage, is subjected to blending processing by a double-screw extruder, is subjected to injection molding to form a test sample strip, and is detected for the flame-retardant performance. The results of all performance tests are shown in table 1.
Table 1 comparison of the performance of the functional masterbatches prepared in examples 1-6 with PBT polyester engineering plastics modified with the functional masterbatches of the same formulation but prepared without the zinc diethylphosphinate coating.
TABLE 1
The data in table 1 show that, under the condition that the components and the proportion are completely the same, the flame retardant property of the PBT polyester engineering plastic compound modified by the special halogen-free flame retardant synergistic functional master batch for the PBT resin prepared by the embodiment of the invention is obviously superior to that of the PBT polyester engineering plastic compound modified by the halogen-free flame retardant functional master batch prepared by uncoated zinc diethylphosphinate. In addition, from the results of the length test of the fluidity spiral line, the PBT polyester engineering plastic compound modified by the embodiment of the invention has obviously higher fluidity than that of the comparative example. Therefore, by utilizing the halogen-free flame-retardant synergistic functional master batch, the flame-retardant modification effect of the zinc-phosphorus diethylphosphinate flame retardant on the PBT polyester engineering plastic is greatly improved, the defects of poor mechanical property and poor electrical property caused by poor water resistance of the flame-retardant synergistic functional master batch are effectively overcome, the melt flowability of the modified PBT polyester engineering plastic compound is improved, and the processing property of the modified PBT polyester engineering plastic compound is enhanced, so that the halogen-free flame-retardant synergistic functional master batch makes a contribution to the development progress of a halogen-free flame-retardant modification technology and the sustainable development concept of realizing green processing of plastic modification.
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 (10)
1. The special halogen-free flame-retardant synergistic master batch for modifying the polyester engineering plastics is characterized in that: the functional master batch takes multiple compound coated zinc diethylphosphinate as a phosphorus flame retardant, and the functional master batch comprises the following components in percentage by mass: 60.0-70.0 wt.% of multi-composite coated zinc diethyl phosphinate, 16.0-22.0 wt.% of anhydrous zinc borate, 8.0-12.0 wt.% of ethylene-butyl acrylate copolymer, 3.0-5.0 wt.% of aliphatic copolyester, 0.5-1.0 wt.% of hyperbranched polyester and 0.3-0.5 wt.% of lubricant.
2. The special halogen-free flame retardant synergistic functional master batch for modifying polyester engineering plastics 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), wherein the poly (ethylene succinate-butylene succinate) is preferable.
3. The special halogen-free flame retardant synergistic functional master batch for modifying polyester engineering plastics 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.
4. the special halogen-free flame retardant synergistic functional master batch for modifying polyester engineering plastics according to claim 1, which is characterized in that: the lubricant is one of ethylene-vinyl acetate copolymer wax, ethylene-acrylic acid copolymer wax, E wax, OP wax and pentaerythritol stearate, wherein the ethylene-vinyl acetate copolymer wax is preferred.
5. The special halogen-free flame retardant synergistic functional master batch for modifying polyester engineering plastics according to claim 1, which is characterized in that: the multiple compound coated zinc diethyl phosphinate is zinc ion doped aluminum hydroxide, phytic acid and zirconium hydrogen phosphate coated zinc diethyl phosphinate.
6. The special halogen-free flame retardant synergistic functional master batch for modifying polyester engineering plastics according to claim 1, which is characterized in that: the preparation method of the multiple composite coated zinc diethyl phosphinate comprises the following steps:
(1) Dispersing zinc diethyl phosphinate, aluminum sol and zinc oxide sol in absolute ethyl alcohol, heating and stirring uniformly, then dropwise adding ammonia water, adjusting the pH value of the reaction solution to be alkaline, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding is finished, continuously stirring for a period of time to finish the reaction; then washing, filtering and drying to obtain zinc ion doped aluminum hydroxide coated zinc diethylphosphinate;
(2) Dispersing the coated zinc diethylphosphinate in an alcohol organic solvent; and dissolving phytic acid in deionized water, uniformly dropwise adding the phytic acid into an isopropanol suspension containing the coated zinc diethylphosphinate, heating and uniformly stirring the solution to ensure that the phytic acid and the zinc ion coated zinc diethylphosphinate doped aluminum hydroxide shell generate passivation reaction, continuously stirring the solution for a period of time, adding zirconium hydrogen phosphate powder, stirring the solution for a period of time at the same temperature to stop the reaction, and then washing, filtering and drying the solution to obtain the multiple composite inorganic material coated zinc diethylphosphinate.
7. The special halogen-free flame retardant synergistic functional master batch for modifying polyester engineering plastics according to claim 6, which is characterized in that: 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 the reaction is finished after the dripping is finished and the stirring is continued for 3-4 hours; and then washing with clear water, filtering, and drying in an oven at 115-125 ℃ for 8-10 h to obtain zinc ion doped aluminum hydroxide coated zinc diethylphosphinate.
8. The special halogen-free flame retardant synergistic functional master batch for modifying polyester engineering plastics according to claim 6, which is characterized in that: the alcohol organic solvent in the step (2) is one of isopropanol, n-propanol, isobutanol or n-butanol, the concentration of a phytic acid solution is 0.4-0.5 g/ml, the phytic acid is dropwise added at a constant speed, the heating and stirring temperature is 30-35 ℃, the phytic acid solution is continuously stirred for 1.5-2 hours, then zirconium hydrogen phosphate powder is added, the reaction is stopped after the phytic acid solution is stirred for 2.5-3 hours at the same temperature, then the washing and filtering are carried out by clear water, and the drying is carried out in an oven at the temperature of 115-125 ℃ for 10-12 hours, so that the zinc diethylphosphinate coated by the multi-composite inorganic material is obtained.
9. The special halogen-free flame retardant synergistic functional master batch for modifying polyester engineering plastics according to claim 6, which is characterized in that: in the step (1), the mass ratio of the zinc diethyl phosphinate to the aluminum sol to the zinc oxide sol is 120:7: 1-120: 9:2, and in the step (2), the mass ratio of zinc ion doped aluminum hydroxide to the zinc diethyl phosphinate to the phytic acid to the zirconium hydrogen phosphate is 120:3: 4-120: 4.5: 5.
10. The method for preparing the halogen-free flame retardant synergistic functional master batch special for modifying the polyester engineering plastic, which is disclosed by any one of claims 1 to 9, is characterized by comprising the following steps: the method comprises the following steps:
(1) Weighing multiple composite coated zinc diethylphosphinate, anhydrous zinc borate, ethylene-butyl acrylate copolymer, aliphatic copolyester, hyperbranched polyester and a lubricant according to a ratio, putting the materials into a high-speed mixer, uniformly mixing, and transferring the mixture into an internal mixer for hot mixing to obtain a bulk blend; the mixing temperature of the internal mixer is 100-125 ℃, and the mixing time is 15-20 minutes;
(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 halogen-free flame-retardant synergistic functional master batch; the screw rotating speed of the single-screw extruder is 150-200 r/min, and the barrel temperature is 150-160 ℃.
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