CN110591341B - Special halogen-free flame-retardant synergistic functional master batch for nylon resin modification and preparation method thereof - Google Patents
Special halogen-free flame-retardant synergistic functional master batch for nylon 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 nylon resin modification and a preparation method thereof; the functional master batch takes multiple compound coated aluminum diethylphosphinate as a phosphorus flame retardant, and the functional master batch comprises the following components in percentage by mass: 55.0-65.0 wt.% of multiple composite coated diethyl aluminum phosphinate, 20.0-30.0 wt.% of anhydrous zinc borate, 8.0-10.0 wt.% of nylon 6 resin, 3.0-5.0 wt.% of star nylon, 0.5-1.0 wt.% of styrene-acrylonitrile copolymer coated polytetrafluoroethylene, 0.5-1.0 wt.% of dispersant 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 aluminum diethylphosphinate, so that the aluminum diethylphosphinate is suitable for the high processing temperature required by nylon resin, and the flame-retardant effect of the aluminum diethylphosphinate on the nylon 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 nylon resin modification and a preparation method thereof.
Background
As an important engineering plastic, nylon resin is widely applied to the fields of mechanical equipment, household appliances, industrial electronic appliances, automobiles and other vehicles. When the nylon resin is applied to the electronic and electrical fields, flame retardant modification is often required to improve the use safety of the nylon resin. 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 engineering plastics from being ignited and inhibit flame propagation, and can effectively improve the anti-combustion performance of the plastics. 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 existing brominated 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 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. The halogen-free flame retardant mainly comprises phosphorus-nitrogen compounds and metal hydroxides, and the flame-retardant engineering 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 flame-retardant technology of nylon engineering plastics in the future.
The diethyl aluminum phosphinate is a safe and efficient phosphorus flame retardant and also a main component of an intumescent halogen-free flame retardant system, and is widely used in the halogen-free flame retardant modification process of various high value-added engineering plastics. Although the heat resistance and the thermal stability of the aluminum diethylphosphinate are higher than those of other phosphorus flame retardants, when the aluminum diethylphosphinate is applied to nylon engineering plastics with the processing temperature higher than 250 ℃, particularly high-processing-temperature engineering plastics with the processing temperature higher than 300 ℃ such as high-temperature-resistant nylon resin, the aluminum diethylphosphinate still has the problems of thermal decomposition and the like in the processing process. In addition, aluminum 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 aluminum diethylphosphinate in the application process of flame retardance modification of engineering plastics at high processing temperature, the aluminum diethylphosphinate is coated by a chemical reaction method by adopting an organic polymer or inorganic material with a stable chemical structure and compact material as a wall material, so that the aluminum diethylphosphinate can be effectively protected from the adverse effects of external environments such as external light, oxygen, water and the like, and mutual friction between the aluminum diethylphosphinate and other powder additives and thermal decomposition of the aluminum diethylphosphinate can be isolated in the process of blending thermal mechanical processing with the engineering plastics.
The aluminum diethylphosphinate flame-retardant engineering plastic modification processing process also has another series of problems, for example, aluminum diethylphosphinate and related flame-retardant synergists (such as nitrogen flame retardants and char formers) are often powder and have large addition amount, and when a twin-screw extruder is directly used for melt extrusion blending, the polymer is difficult to melt and fully mix with the flame retardant due to the limited residence time of the materials in the barrel of the extruder. 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 engineering plastic is also caused.
Disclosure of Invention
The purpose of the invention is: aiming at the application defects of poor heat resistance and thermal stability, weak interface caking property, large flame retardant property loss, low fluidity, poor dispersibility and the like of aluminum diethylphosphinate under high temperature conditions in the modification application process of the halogen-free flame retardant nylon resin, the problems of flame retardant efficiency and reduction of physical machinery and the like caused by thermal degradation due to powder friction in the direct blending extrusion processing process of double screws, and the defect that the traditional polymer or inorganic wall material single-layer coated aluminum diethylphosphinate cannot provide enough protection, the invention provides a method for performing multiple composite coating on the aluminum diethylphosphinate by adopting a wall material with flame retardant synergy and compact material, and then mixing the aluminum diethylphosphinate with corresponding flame retardant synergist and auxiliary agents through a continuous double-rotor internal mixer and extruding through a single-screw extruder to prepare the halogen-free flame retardant synergistic functional master batch special for modifying the halogen-free flame retardant nylon resin. Compared with the traditional plastic aluminum diethylphosphinate flame-retardant functional master batch, the flame-retardant synergistic functional master batch improves the high-temperature heat resistance, the thermal stability and the flow dispersibility of the aluminum diethylphosphinate, thereby improving the flame-retardant efficiency and the tolerance to higher processing temperature, obtaining the same flame-retardant effect as the traditional flame-retardant functional master batch with less master batch addition, and effectively reducing the mechanical property loss of the modified nylon resin compound;
another object of the invention is: provides a preparation method of the halogen-free flame-retardant synergistic functional master batch special for nylon resin modification.
The effective method for solving the problem is to prepare the modified plastic by using the plastic functional master batch, namely, firstly, the phosphorus flame retardant and the nitrogen flame retardant with poor thermal stability, other auxiliary agents, low-stacking-density and difficult-feeding flame-retardant synergist powder, the easy-water-absorption auxiliary agent, the liquid, the colloid auxiliary agent and the like are mixed and uniformly dispersed by using the lower processing temperature and the long-time kneading effect of a continuous double-rotor 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 batches and the plastic raw materials are subjected to melt blending and extrusion granulation through a double-screw extruder, so that the dispersibility of the phosphorus flame retardant represented by aluminum diethylphosphinate and the related flame-retardant synergist thereof in a resin matrix can be effectively improved, the flame-retardant effect is enhanced, the thermal decomposition of materials caused by direct mutual frictional heat generation of the phosphorus 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 order to realize the technical aim, firstly, aluminum diethyl phosphinate particles are coated by using zinc ion doped aluminum sol as a raw material, and as the Zeta potential of the aluminum 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 ion doped aluminum hydroxide as a shell and aluminum 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 ·H 2 O, a sheet having a mesoporous structureInorganic nanomaterial ] zirconium ions in the molecules can also perform 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 the aluminum diethylphosphinate can be subjected to multiple composite coating. And mixing the coated diethyl aluminum phosphinate 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 the halogen-free flame-retardant modification of the nylon resin by connecting a double-rotor continuous internal mixer in series with a single-screw extruder.
The specific technical scheme is as follows:
the halogen-free flame-retardant synergistic functional master batch special for nylon resin modification takes multiple compound coated aluminum diethylphosphinate as a phosphorus flame retardant, and comprises the following components in percentage by mass: 55.0 to 65.0 weight percent of multiple compound coated diethyl aluminium phosphinate, 15.0 to 30.0 weight percent of anhydrous zinc borate, 8.0 to 10.0 weight percent of nylon 6 resin, 3.0 to 5.0 weight percent of star nylon, 0.5 to 1.0 weight percent of styrene-acrylonitrile copolymer coated polytetrafluoroethylene, 0.5 to 1.0 weight percent of dispersant and 0.3 to 0.5 weight percent of lubricant.
Further, the star nylon is one of three-arm, four-arm, six-arm and eight-arm star nylon 6 resins, wherein the four-arm star nylon 6 resin is preferred.
Further, the dispersant is one of zinc stearate, aluminum stearate, magnesium stearate and lithium stearate, wherein zinc stearate is preferred.
Further, the lubricant is one of OP wax, E wax, ethylene-vinyl acetate copolymer wax and ethylene-acrylic acid copolymer wax, and the OP wax is preferable.
Further, the multiple composite coated aluminum diethylphosphinate is zinc ion doped aluminum hydroxide, phytic acid and zirconium hydrogen phosphate coated aluminum diethylphosphinate.
Further, the preparation method of the multiple composite coated aluminum diethylphosphinate comprises the following steps:
(1) Dispersing aluminum diethylphosphinate, aluminum sol and zinc oxide sol in absolute ethyl alcohol, heating and stirring uniformly, then dropwise adding ammonia water, adjusting the pH value of a 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 diethyl aluminum phosphinate;
(2) Dispersing the coated aluminum diethylphosphinate in an alcohol organic solvent; and dissolving phytic acid in deionized water, uniformly dropwise adding the phytic acid into an alcohol organic solvent suspension containing the aluminum diethylphosphinate, heating and uniformly stirring to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the aluminum diethylphosphinate are subjected to passivation reaction, continuously stirring for a period of time, adding zirconium hydrogen phosphate powder, stirring at the same temperature for a period of time to stop reaction, washing, filtering and drying to obtain the multiple composite inorganic material coated aluminum 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; then washing with clean water, filtering, and drying in an oven at the temperature of 115-125 ℃ for 8-10 h to obtain the zinc ion doped aluminum hydroxide coated aluminum diethylphosphinate.
Further, the alcohol organic solvent in the step (2) is one of isopropanol, n-propanol, isobutanol or n-butanol, wherein isopropanol and a phytic acid solution with the concentration of 0.4-0.5 g/ml are preferably selected, phytic acid is dropwise added at a constant speed, the heating and stirring temperature is 30-35 ℃, after the phytic acid solution is added and continuously stirred for 1.5-2 h, zirconium hydrogen phosphate powder is added, the reaction is stopped after stirring for 2.5-3 h at the same temperature, then washing and filtering are carried out by clear water, and drying is carried out in an oven at 115-125 ℃ for 10-12 h, so that the multi-composite inorganic material coated aluminum diethylphosphinate is obtained.
Further, in the step (1), the mass ratio of the aluminum diethylphosphinate to the aluminum sol to the zinc oxide sol is 120 to 7.
The method for preparing the halogen-free flame-retardant synergistic functional master batch special for nylon resin modification comprises the following steps:
(1) Weighing multiple composite coated aluminum diethylphosphinate, anhydrous zinc borate, nylon 6 resin, star nylon, styrene-acrylonitrile copolymer coated polytetrafluoroethylene, a dispersing agent and a lubricating agent according to the proportion, putting the materials into a high-speed mixer, uniformly mixing, and then feeding the materials into a double-rotor continuous internal mixer by a feeder to carry out plasticizing and mixing; the rotor speed of the double-rotor continuous internal mixer is 75-100 r/min, and the mixing temperature is 220-250 ℃;
(2) Directly feeding the mixed material obtained in the step (1) into a single-screw extruder, 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 220-250 ℃.
The technical scheme adopted by the invention has the beneficial effects that:
(1) Aiming at the defects that the heat resistance and the heat stability of the diethyl aluminum phosphinate are poor, the fluidity is low, the dispersibility is poor, the traditional wall material cannot provide enough protection and the like, the zinc ion doped aluminum hydroxide inorganic matter is selected to coat the diethyl aluminum phosphinate, then a compact and solid protective layer is formed by utilizing the passivation effect of phytic acid and zinc/aluminum ions, and then the zirconium hydrogen phosphate nanosheet with the mesoporous structure forms the outermost layer structure of the diethyl aluminum phosphinate microcapsule 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 diethyl aluminum phosphinate, and particularly, the multiple inorganic shell passivated by the phytic acid provides a firmer and denser inorganic coating layer for the diethyl aluminum phosphinate than the traditional polymer and inorganic wall materials, so that the coated diethyl aluminum phosphinate can be more effectively protected, and the thermal decomposition temperature of the coated diethyl aluminum phosphinate is remarkably improved. Therefore, the coated aluminum diethylphosphinate can obtain more excellent heat resistance and thermal stability.
(2) Because a large amount of phosphorus-containing materials are introduced into the wall material coated with the aluminum diethylphosphinate, the introduction of more phosphorus elements can effectively promote the formation of a thick carbon layer on the surface of a nylon resin composite comburent in the combustion process of the halogen-free flame-retardant nylon resin composite, more obviously enhance the compactness and structural stability of the carbon layer on the surface in the combustion process of the flame-retardant polymer, prevent the contact of the interior of the comburent with oxygen, and enable the flame retardant to play a synergistic flame-retardant role, thereby more effectively improving the flame-retardant property of the nylon resin.
(3) By introducing the zirconium hydrogen phosphate with a mesoporous structure into the outermost coating layer of the aluminum diethylphosphinate, the zirconium hydrogen phosphate has a large specific surface area, a large surface charge density, a stable layered structure, rich OH groups, capability of generating ion exchange reaction, large ion exchange capacity, capability of generating a large adsorption effect on various small-molecule volatile matters in the thermal processing process of the flame-retardant engineering plastic, and capability of playing a flame-retardant synergistic effect in a halogen-free flame-retardant system.
(4) The master batch formula which is good in compatibility with nylon resin and good in dispersion of flame retardant powder is designed, and the efficient plasticizing function of a double-rotor continuous internal mixer on low bulk density powder and a high-melting-point resin carrier is utilized, so that the flame retardant powder obtains an excellent pre-dispersion effect, and decomposition of a phosphorus flame retardant caused by high-temperature thermal mechanical processing is avoided, and thus a better dispersion effect and excellent flame retardant property are obtained in subsequent nylon resin double-screw melt extrusion modification processing; meanwhile, the loss of physical and mechanical properties caused by direct blending with the flame retardant powder is reduced, so that a double-effect modification effect 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 aluminum phosphinate, can obtain the same flame-retardant effect as the traditional flame-retardant functional master batch by using less master batch addition, and can effectively reduce the mechanical property loss of the modified nylon resin compound.
(6) The halogen-free flame-retardant functional master batch special for nylon resin modification prepared by the invention can be subjected to double-screw melt extrusion functional modification with nylon resins such as nylon 6, nylon 66 and high-temperature resistant nylon of various brands, and can also be simply mixed with the nylon resin according to a certain proportion and then directly applied to injection molding of products. 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 halogen-free flame-retardant synergistic functional master batch special for nylon resin modification comprises the following raw materials in parts by mass:
| multiple composite coated diethyl aluminium phosphinate | 65.0 kg |
| Anhydrous zinc borate | 20.0 kg |
| Nylon 6 resin | 10.0 kg |
| Four-arm star nylon 6 resin | 3.0 kg |
| Styrene-acrylonitrile copolymer coated polytetrafluoroethylene | 1.0 kg |
| Zinc stearate | 500.0 g |
| OP wax | 500.0 g |
The preparation method of the multiple composite coated aluminum diethylphosphinate used in the halogen-free flame retardant synergistic functional master batch special for nylon resin modification comprises the following steps:
adding 230L of absolute ethyl alcohol, 120kg of aluminum diethylphosphinate, 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 the zinc ion doped aluminum hydroxide coated aluminum diethylphosphinate. Dissolving 3 kg of phytic acid in 6L of deionized water in another glass container to prepare a solution with the concentration of 0.5g/ml, putting 120kg of the obtained zinc ion-doped aluminum hydroxide-coated diethyl aluminum phosphinate and 230L 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 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 diethyl aluminum phosphinate have passivation reaction, continuously stirring for 2 hours, then adding 4.5 kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 3 hours, stopping the reaction, then washing with clear water, filtering, and drying in a 120 ℃ oven for 12 hours to obtain the multiple composite coated aluminum diethyl phosphinate.
The preparation method of the halogen-free flame-retardant synergistic functional master batch special for nylon resin modification 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, feeding the raw materials into a double-rotor continuous internal mixer by using a feeder to perform plasticizing and mixing, wherein the rotor speed is 100 revolutions per minute, the mixing temperature is 250 ℃, directly feeding the obtained mixed material into a single-screw extruder, 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 r/min, and the temperature of the machine barrel is controlled in 220-250 ℃ in sections.
Example 2
The halogen-free flame-retardant synergistic functional master batch special for nylon resin modification comprises the following raw materials in parts by mass:
| multiple composite coated diethyl aluminium phosphinate | 55.0 kg |
| Anhydrous zinc borate | 30.0 kg |
| Nylon 6 resin | 8.5 kg |
| Three-arm star nylon 6 resin | 5.0 kg |
| Styrene-acrylonitrile copolymer coated polytetrafluoroethylene | 500.0 g |
| Aluminum stearate | 700.0 g |
| E wax | 300.0 g |
The preparation method of the multiple composite coated aluminum diethylphosphinate used in the halogen-free flame retardant synergistic functional master batch special for nylon resin modification comprises the following steps:
adding 230L of absolute ethyl alcohol, 120kg of aluminum diethylphosphinate, 8 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 35 ℃, then uniformly dropwise adding 11.5 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 perform 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 baking oven at 120 ℃ for 10 hours to obtain the zinc ion doped aluminum hydroxide coated aluminum diethylphosphinate. In another glass container, 3.6 kg of phytic acid is dissolved in 9L of deionized water to prepare a solution with the concentration of 0.4 g/ml, 120kg of the obtained zinc ion-doped aluminum hydroxide-coated diethyl phosphinic acid and 230L of isopropanol are put into an enamel reaction kettle, stirred uniformly and added 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 aluminum hydroxide shell doped with zinc ions coated with the aluminum diethylphosphinate have passivation reaction, continuously stirring for 2 hours, adding 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 9 hours to obtain the multiple composite coated aluminum diethylphosphinate.
The preparation method of the halogen-free flame-retardant synergistic functional master batch special for nylon resin modification 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, feeding the raw materials into a double-rotor continuous internal mixer by using a feeder to perform plasticizing and mixing, wherein the rotor speed is 75 revolutions per minute, the mixing temperature is 220 ℃, directly feeding the obtained mixed material into a single-screw extruder, 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 220-250 ℃ in sections.
Example 3
The halogen-free flame-retardant synergistic functional master batch special for nylon resin modification comprises the following raw materials in parts by mass:
| multiple composite coated diethyl aluminium phosphinate | 60.0 kg |
| Anhydrous zinc borate | 28.0 kg |
| Nylon 6 resin | 8.0 kg |
| Six-arm star nylon 6 resin | 2.0 kg |
| Styrene-acrylonitrile copolymer coated polytetrafluoroethylene | 700.0 g |
| Stearic acid magnesium salt | 1.0 kg |
| Ethylene-vinyl acetate copolymer wax | 300.0 g |
The preparation method of the multiple composite coated aluminum diethylphosphinate used in the halogen-free flame retardant synergistic functional master batch special for nylon resin modification comprises the following steps:
adding 230L of absolute ethyl alcohol, 120kg of aluminum diethylphosphinate, 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 12.5wt.% 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 perform 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 125 ℃ for 8 h to obtain the zinc ion-doped aluminum hydroxide coated aluminum diethylphosphinate. Dissolving 3 kg of phytic acid in 6L of deionized water in another glass container to prepare a solution with the concentration of 0.5g/ml, putting 120kg of the obtained zinc ion-doped aluminum hydroxide-coated diethyl aluminum phosphinate and 230L of n-propanol into an enamel reaction kettle, uniformly stirring and adding to 33 ℃; and 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 aluminum hydroxide shell doped with zinc ions coated with the aluminum diethylphosphinate have passivation reaction, continuously stirring for 1.5 h, adding 4.8 kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 3h to stop the reaction, washing with clear water, filtering, and drying in a 115 ℃ oven for 12h to obtain the multiple composite coated aluminum diethylphosphinate.
The preparation method of the halogen-free flame-retardant synergistic functional master batch special for nylon resin modification 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, feeding the raw materials into a double-rotor continuous internal mixer by using a feeder to perform plasticizing and mixing, wherein the rotor speed is 85 revolutions per minute, the mixing temperature is 230 ℃, directly feeding the obtained mixed materials into a single-screw extruder, 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 r/min, and the temperature of the machine barrel is controlled to be 220-250 ℃ in sections.
Example 4
The halogen-free flame-retardant synergistic functional master batch special for nylon resin modification comprises the following raw materials in parts by mass:
| multiple composite coated diethyl aluminium phosphinate | 61.0 kg |
| Anhydrous zinc borate | 25.0 kg |
| Nylon 6 resin | 8.0 kg |
| Four-arm star nylon 6 resin | 4.0 kg |
| Styrene-acrylonitrile copolymer coated polytetrafluoroethylene | 1.0 kg |
| Lithium stearate | 600.0 g |
| Ethylene-acrylic acid copolymer wax | 400.0 g |
The preparation method of the multiple composite coated aluminum diethylphosphinate used in the halogen-free flame retardant synergistic functional master batch special for nylon resin modification comprises the following steps:
adding 230L of absolute ethyl alcohol, 120kg of aluminum diethylphosphinate, 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 heating to 40 ℃, then uniformly dropwise adding 11.5 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 perform sol-gel reaction, and after the dropwise addition is completed, continuously stirring for 3.5 hours and then finishing the reaction; then washing with clear water, filtering, and drying in an oven at 125 ℃ for 8 h to obtain the zinc ion-doped aluminum hydroxide coated aluminum 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 0.5g/ml, putting 120kg of the obtained zinc ion-doped aluminum hydroxide-coated diethyl aluminum phosphinate and 230L of 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 ℃, uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the aluminum hydroxide shell doped with zinc ions coated with the aluminum diethylphosphinate have passivation reaction, 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 aluminum diethylphosphinate.
The preparation method of the halogen-free flame-retardant synergistic functional master batch special for nylon resin modification 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, feeding the raw materials into a double-rotor continuous internal mixer by using a feeder to perform plasticizing and mixing, wherein the rotor speed is 90 revolutions per minute, the mixing temperature is 240 ℃, directly feeding the obtained mixed materials 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 r/min, and the temperature of the machine barrel is controlled in 220-250 ℃ in sections.
Example 5
The halogen-free flame-retardant synergistic functional master batch special for nylon resin modification comprises the following raw materials in parts by mass:
| multiple composite coated aluminum diethylphosphinate | 55.0 kg |
| Anhydrous zinc borate | 31.0 kg |
| Nylon 6 resin | 9.0 kg |
| Six-arm star nylon 6 resin | 3.0 kg |
| Styrene-acrylonitrile copolymer coated polytetrafluoroethylene | 800.0 g |
| Zinc stearate | 700.0 g |
| OP wax | 500.0 g |
The preparation method of the multiple composite coated aluminum diethylphosphinate used in the halogen-free flame retardant synergistic functional master batch special for nylon resin modification comprises the following steps:
adding 230L of absolute ethyl alcohol, 120kg of aluminum diethylphosphinate, 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 dropwise adding 12.0 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 adding is completed, continuously stirring for 4 hours and then finishing the reaction; then washing with clear water, filtering, and drying in a baking oven at 120 ℃ for 10h to obtain the zinc ion-doped aluminum hydroxide coated aluminum diethylphosphinate. In another glass container, 3.2 kg of phytic acid is dissolved in 8L of deionized water to prepare a solution with the concentration of 0.4 g/ml, 120kg of the obtained zinc ion-doped aluminum hydroxide-coated diethyl aluminum phosphinate and 230L of isobutanol are put into an enamel reaction kettle and are stirred uniformly and added to 35 ℃; and 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 aluminum hydroxide shell doped with zinc ions coated with the aluminum diethylphosphinate have passivation reaction, continuously stirring for 2 hours, adding 4.8 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 aluminum diethylphosphinate.
The preparation method of the halogen-free flame-retardant synergistic functional master batch special for nylon resin modification 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, feeding the raw materials into a double-rotor continuous internal mixer by using a feeder to perform plasticizing and mixing, wherein the rotor speed is 95 revolutions per minute, the mixing temperature is 235 ℃, directly feeding the obtained mixed material into a single-screw extruder, 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 220-250 ℃ in sections.
Example 6
The halogen-free flame-retardant synergistic functional master batch special for nylon resin modification comprises the following raw materials in parts by mass:
| multiple composite coated diethyl aluminium phosphinate | 58.0 kg |
| Anhydrous zinc borate | 30.0 kg |
| Nylon 6 resin | 6.0 kg |
| Eight-arm star nylon 6 resin | 4.0 kg |
| Styrene-acrylonitrile copolymer coated polytetrafluoroethylene | 600.0 g |
| Zinc stearate | 900.0 g |
| E wax | 500.0 g |
The preparation method of the multiple composite coated aluminum diethylphosphinate used in the halogen-free flame retardant synergistic functional master batch special for nylon resin modification comprises the following steps:
adding 230L of absolute ethyl alcohol, 120kg of aluminum diethylphosphinate, 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 be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to perform sol-gel reaction, and after the dropwise addition 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 the zinc ion doped aluminum hydroxide coated aluminum 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 0.5g/ml, putting 120kg of the obtained zinc ion-doped aluminum hydroxide-coated diethyl aluminum phosphinate and 230L 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 ℃, uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and the aluminum hydroxide shell doped with zinc ions coated with the aluminum diethylphosphinate have passivation reaction, continuously stirring for 1.5 h, adding 4 kg of zirconium hydrogen phosphate powder, stirring at the same temperature for 3h to stop the reaction, washing with clear water, filtering, and drying in an oven at 115 ℃ for 12h to obtain the multiple composite coated aluminum diethylphosphinate.
The preparation method of the halogen-free flame-retardant synergistic functional master batch special for nylon resin modification 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, feeding the raw materials into a double-rotor continuous internal mixer by using a feeder to perform plasticizing and mixing, wherein the rotor speed is 80 revolutions per minute, the mixing temperature is 230 ℃, directly feeding the obtained mixed material into a single-screw extruder, and performing melting, 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 r/min, and the barrel temperature is controlled in 220-250 deg.c.
In order to verify the modification effect of the flame-retardant synergistic functional master batch prepared by the invention on nylon resin, the flame-retardant synergistic functional master batches prepared in the embodiments 1 to 6 are respectively mixed with high-temperature-resistant nylon resin, nylon 6 resin and nylon 66 according to the mass percent of 8 wt.%, and are subjected to blending extrusion molding by a double-screw extruder, then injection molding combustion test sample strips are formed, and then the flame-retardant performance is detected. Meanwhile, the functional master batches obtained in the examples 1-6 have the same components and proportions, but the aluminum diethylphosphinate with the same grade 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 1-6, and then are respectively mixed with three nylon resins 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 tables 1-3.
Table 1 comparison of the performance of the functional masterbatches prepared in examples 1-6 with a high temperature resistant nylon resin composite of the same formulation but modified with the functional masterbatch prepared without the aluminum diethylphosphinate coating.
TABLE 1
Table 2 comparison of the performance of the functional masterbatches prepared in examples 1-6 with nylon 6 composites modified with the same formulation but with the functional masterbatch prepared without the aluminum diethylphosphinate coating.
TABLE 2
Table 3 comparison of the performance of the functional masterbatches prepared in examples 1-6 with nylon 66 composites modified with the same formulation but using the functional masterbatch prepared without the coating of aluminum diethylphosphinate.
TABLE 3
The data in tables 1-3 show that the flame retardant performance of the modified three nylon resin compounds prepared by the halogen-free flame retardant synergistic functional master batch special for the nylon resin prepared by the embodiment of the invention is obviously superior to that of the modified nylon resin compound prepared by the halogen-free flame retardant functional master batch which is not coated with the diethyl aluminum phosphinate 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 was also found that the fluidity of the nylon resin composite modified by the examples of the present invention was significantly higher 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 diethyl phosphinic acid aluminum phosphorus flame retardant on the nylon resin is greatly improved, the defects of poor mechanical property and electrical property caused by poor water resistance of the diethyl phosphinic acid aluminum phosphorus flame retardant are effectively overcome, the melt fluidity of the halogen-free flame-retardant modified nylon resin compound is improved, and the processing property of the halogen-free flame-retardant modified nylon resin compound is enhanced, so that the halogen-free flame-retardant synergistic functional master batch makes a contribution to the development progress of the 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 (5)
1. A special halogen-free flame-retardant synergistic functional master batch for nylon resin modification is characterized in that: the functional master batch takes multiple compound coated aluminum diethylphosphinate as a phosphorus flame retardant, and the functional master batch comprises the following components in percentage by mass: 55.0-65.0 wt.% of multiple composite coated diethyl aluminum phosphinate, 20.0-30.0 wt.% of anhydrous zinc borate, 8.0-10.0 wt.% of nylon 6 resin, 3.0-5.0 wt.% of star nylon, 0.5-1.0 wt.% of styrene-acrylonitrile copolymer coated polytetrafluoroethylene, 0.5-1.0 wt.% of dispersant and 0.3-0.5 wt.% of lubricant;
the multiple composite coated aluminum diethylphosphinate is zinc ion doped aluminum hydroxide, phytic acid and zirconium hydrogen phosphate coated aluminum diethylphosphinate;
the preparation method of the multiple composite coated aluminum diethylphosphinate comprises the following steps:
(1) Dispersing aluminum diethylphosphinate, 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 the dropwise adding is finished, continuously stirring for a period of time and finishing the reaction; then washing, filtering and drying to obtain zinc ion doped aluminum hydroxide coated diethyl aluminum phosphinate;
(2) Dispersing the coated aluminum diethylphosphinate in an alcohol organic solvent; dissolving phytic acid in deionized water, uniformly dropwise adding the phytic acid into an isopropanol suspension containing aluminum diethylphosphinate, heating and uniformly stirring to ensure that the phytic acid and an aluminum hydroxide shell doped with zinc ions of aluminum diethylphosphinate are subjected to passivation reaction, continuously stirring for a period of time, adding zirconium hydrogen phosphate powder, stirring for a period of time at the same temperature to stop reaction, washing, filtering and drying to obtain multiple composite inorganic material coated aluminum diethylphosphinate;
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 the reaction is finished after the dropwise addition is finished and stirring is continued for 3-4 hours; 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 diethyl aluminum phosphinate;
the alcohol organic solvent in the step (2) is isopropanol, the concentration of the phytic acid solution is 0.4-0.5 g/ml, the phytic acid is uniformly dripped, the heating and stirring temperature is 30-35 ℃, the phytic acid solution is continuously stirred for 1.5-2 h after being added, zirconium hydrogen phosphate powder is added, the reaction is stopped after the stirring is carried out for 2.5-3 h 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 h, so as to obtain the multiple composite inorganic material coated aluminum diethylphosphinate;
in the step (1), the mass ratio of the aluminum diethylphosphinate to the aluminum sol to the zinc oxide sol is 120.
2. The special halogen-free flame-retardant synergistic functional master batch for nylon resin modification according to claim 1, characterized in that: the star-shaped nylon is one of three-arm, four-arm, six-arm and eight-arm star-shaped nylon 6 resin.
3. The special halogen-free flame retardant synergistic functional master batch for nylon resin modification according to claim 1, which is characterized in that: the dispersing agent is one of zinc stearate, aluminum stearate, magnesium stearate and lithium stearate, and the lubricating agent is one of OP wax, E wax, ethylene-vinyl acetate copolymer wax and ethylene-acrylic acid copolymer wax.
4. The special halogen-free flame retardant synergistic functional master batch for nylon resin modification according to claim 1, which is characterized in that: the dispersing agent is zinc stearate.
5. The preparation method of the halogen-free flame retardant synergistic functional master batch special for nylon resin modification according to any one of claims 1 to 4, characterized by comprising the following steps: the method comprises the following steps:
(1) Weighing multiple composite coated aluminum diethylphosphinate, anhydrous zinc borate, nylon 6 resin, star nylon, styrene-acrylonitrile copolymer coated polytetrafluoroethylene, a dispersing agent and a lubricating agent according to the proportion, putting the materials into a high-speed mixer, uniformly mixing, and then feeding the materials into a double-rotor continuous internal mixer by a feeder to carry out plasticizing and mixing; the rotor speed of the double-rotor continuous internal mixer is 75-100 r/min, and the mixing temperature is 220-250 ℃;
(2) Directly feeding the mixed material obtained in the step (1) into a single-screw extruder, 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 cylinder temperature is 220-250 ℃.
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| CN114478625B (en) * | 2022-03-10 | 2022-11-25 | 江苏利思德新材料股份有限公司 | Aluminum diethylphosphinate crystal with low fine powder content as well as preparation method and application thereof |
| CN115160762B (en) * | 2022-06-27 | 2024-03-15 | 广东中德电缆有限公司 | Silane crosslinked SEBS-based halogen-free flame-retardant elastomer and preparation method thereof |
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