CN110607066A - Special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde and preparation method thereof - Google Patents
Special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde 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 polyformaldehyde modification and a preparation method thereof; the functional master batch takes multi-composite coated melamine polyphosphate as a phosphorus flame retardant, and the functional master batch comprises the following components in percentage by mass: 55.0-65.0 wt.% of multi-composite coated melamine polyphosphate, 20.0-30.0 wt.% of nitrogen flame retardant, 3.0-5.0 wt.% of dipentaerythritol, 10.0-12.0 wt.% of thermoplastic polyurethane, 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 thermal stability of the melamine polyphosphate and enhances the water resistance of the melamine polyphosphate, thereby more effectively improving the flame-retardant effect of the melamine polyphosphate on polyformaldehyde.
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 polyformaldehyde modification and a preparation method thereof.
Background
Polyformaldehyde is a kind of engineering plastic with a special molecular chain structure, and although the plastic has excellent comprehensive mechanical properties and electrical insulation properties, the carbon-oxygen main chain structure alternately appearing in the molecular chain makes the plastic become the most flammable material in all polymers, and the oxygen index is only 14.9 vol.%, which seriously hinders the application of polyformaldehyde in the fields of industry and household electronic and electric products. Effective flame-retardant modification can be carried out aiming at polyformaldehyde to improve the flame retardancy of the polyformaldehyde, so that the safety of the polyformaldehyde in use in electronic equipment is improved. The traditional general and engineering plastic flame retardant modification can be realized by adding halogen-containing or halogen-free flame retardant and carrying out melt blending through a double screw extruder, and the halogen-containing or halogen-free flame retardant can prevent the plastic from being ignited and inhibit flame propagation, and can effectively improve the flame resistance of the plastic. However, due to the special molecular chain structure of polyoxymethylene, the traditional halogen flame retardant not only can not effectively retard the flame of polyoxymethylene, but also has a combustion-supporting effect. Therefore, effective flame retardance of polyoxymethylene can be realized only by adding phosphorus flame retardants and nitrogen flame retardants to form an intumescent flame retardant system in polyoxymethylene at present. Among various phosphorus flame retardants suitable for polyoxymethylene, melamine polyphosphate is considered as the most effective group of halogen-free flame retardants, and the flame retardants simultaneously contain phosphorus and nitrogen atoms with more coordinated phosphorus/nitrogen element ratio, so that the flame retardants have more excellent flame retardant performance than other flame retardants such as ammonium polyphosphate flame retardants. As a safe and efficient synergistic phosphorus-nitrogen flame retardant, melamine polyphosphate is a main component of a polyformaldehyde intumescent halogen-free flame retardant system. However, the melamine polyphosphate has the problems of low thermal stability and hydrolysis resistance, low fluidity, poor dispersibility, poor interfacial adhesion with a modified polymer and the like, and particularly, the melamine polyphosphate is sensitive to water and strong in hygroscopicity, so that water absorbed by modified plastics is easy to migrate out of the interior of the materials, the flame retardance of the materials is damaged, and the mechanical property and the electrical property of the materials are also reduced.
In order to overcome the defects in the flame retardant application process of melamine polyphosphate, organic polymers or inorganic materials with stable chemical structures and compact materials are used as wall materials, and the melamine polyphosphate is coated by a chemical reaction method, so that the melamine polyphosphate can be effectively protected from the adverse effects of external environments such as external light, oxygen, water and the like, and can be isolated from mutual friction and other powder additives in the plastic blending thermomechanical processing process to delay the thermal decomposition of the melamine polyphosphate. Therefore, the inert material coating method is a simple and effective way for effectively improving the quality and application effect of the polyphosphate and the derivatives thereof. For example, chinese patents CN103980541A and CN105419391A disclose that melamine resin and melamine cyanurate are used as wall materials to coat ammonium polyphosphate and an implementation method thereof, respectively, thermal properties and water resistance of the polyphosphate coated with organic resin are significantly improved, and when the polyphosphate is applied to plastic flame retardation, the flame retardation of the material is significantly improved. In addition, Qin Megluu et al reported in the research on the application of modified ammonium polyphosphate coated with aluminum hydroxide and its flame retardant polyformaldehyde (journal of inorganic materials 2015, 30(12), 1267-1272) that the ammonium polyphosphate is coated by using aluminum hydroxide as a wall material through a sol-gel process, thereby not only effectively solving the problem of water resistance, but also promoting the formation of a more complete carbon layer structure in the combustion process of the flame retardant material, and further significantly improving the flame retardancy of the material. However, the above aspects are all interlayer coating, and the polymer coating layer also has the problems of loose structure, easy peeling of the protective layer in the process of material thermomechanical processing and the like, and is quite unfavorable for the application of melamine polyphosphate in flame retardant plastics.
In addition, a series of problems also exist in the modification processing process of melamine polyphosphate flame retardant plastics, for example, melamine polyphosphate and related flame retardant synergists (such as nitrogen flame retardants and char formers) are often powder and have large addition amount, and when a double-screw extruder is directly adopted for melt extrusion blending, the polymer is difficult to melt and fully mix with the flame retardant due to the limited residence time of materials in 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 plastic is also caused.
Disclosure of Invention
The purpose of the invention is: aiming at the application defects of strong hygroscopicity, poor thermal stability, weak interface caking property, large flame retardant property loss, low fluidity, poor dispersibility and the like of melamine polyphosphate in the application process of modifying halogen-free flame retardant polyformaldehyde, the problems of flame retardant efficiency and reduced physical and mechanical properties caused by thermal degradation due to powder friction in the process of direct double-screw blending extrusion processing and the like, and the defect that the traditional polymer or inorganic wall material single-layer coated melamine polyphosphate cannot provide enough protection is overcome, the invention provides a method for performing multiple composite coating on the melamine polyphosphate by adopting a wall material with flame retardant synergy and compact material, and then banburying the melamine polyphosphate with corresponding flame retardant synergist and auxiliary agent at low temperature to prepare the special halogen-free flame retardant synergistic master batch for modifying polyformaldehyde halogen-free flame retardant.
Another object of the invention is: provides a preparation method of the special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde.
The effective method for solving the problem is to prepare the modified plastic by using the plastic functional master batch, namely, firstly, the low-temperature and long-time kneading effect of an internal mixer is utilized to mix and uniformly disperse the phosphorus flame retardant and nitrogen flame retardant which are not temperature-resistant, the flame retardant synergist powder with low bulk density and difficult feeding, the auxiliary agent which is easy to absorb water, the liquid, the colloid auxiliary agent and the like, 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 phosphorus flame retardants represented by melamine polyphosphate and related flame-retardant synergists 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 retardants and the flame-retardant synergists 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, the invention firstly adopts zinc ion doped aluminum sol as a raw material to coat melamine polyphosphate particles, and as the Zeta potential of the melamine polyphosphate 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 melamine polyphosphate 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 flaky inorganic nano material with a mesoporous structure ], wherein zirconium ions in molecules can also perform a 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, so that the melamine polyphosphate is subjected to multiple composite coating. The coated melamine polyphosphate is mixed with auxiliary agents such as a flame-retardant synergist, a carrier, a dispersing agent and the like, and finally, the mixture is prepared into the special flame-retardant functional master batch for polyformaldehyde halogen-free flame-retardant modification through an internal mixer connected with a single-screw extruder in series.
The specific technical scheme is as follows:
the special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde takes multi-composite coated melamine polyphosphate as a phosphorus flame retardant, and comprises the following components in percentage by mass: 55.0-65.0 wt.% of multi-composite coated melamine polyphosphate, 20.0-30.0 wt.% of nitrogen flame retardant, 3.0-5.0 wt.% of dipentaerythritol, 10.0-12.0 wt.% of thermoplastic polyurethane, 0.5-1.0 wt.% of dispersant and 0.3-0.5 wt.% of lubricant.
Further, the nitrogen-based flame retardant is any one of melamine cyanurate and melamine polyphosphate.
Further, the thermoplastic polyurethane is any one of polyether type or polyester type thermoplastic polyurethane, wherein polyether type thermoplastic polyurethane is preferred.
Further, the dispersant is one of stearic acid, calcium stearate, zinc stearate, oleamide and mesoacid amide, wherein calcium stearate is preferred.
Further, the lubricant is one of polyethylene wax, ethylene bis stearamide and polydimethylsiloxane, wherein the polyethylene wax is preferred.
Further, the multi-composite coated melamine polyphosphate is zinc ion doped aluminum hydroxide, phytic acid and zirconium hydrogen phosphate coated melamine polyphosphate.
Further, the preparation method of the multi-composite coated melamine polyphosphate comprises the following steps:
(1) dispersing melamine polyphosphate, 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 liquid 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 and finishing the reaction; then washing, filtering and drying to obtain zinc ion doped aluminum hydroxide coated melamine polyphosphate;
(2) dispersing the coated melamine polyphosphate in an alcohol organic solvent; and dissolving phytic acid in deionized water, uniformly dripping the phytic acid into an alcohol organic solvent suspension containing the coated melamine polyphosphate, heating and uniformly stirring to ensure that the phytic acid and the zinc ion coated with the melamine polyphosphate are subjected to passivation reaction by doping an aluminum hydroxide shell, continuously stirring for a period of time, adding zirconium hydrogen phosphate powder, stirring at the same temperature for a period of time to stop the reaction, washing, filtering and drying to obtain the multi-composite inorganic material coated melamine polyphosphate.
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 the zinc ion doped aluminum hydroxide coated melamine polyphosphate.
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 melamine polyphosphate is obtained.
Further, in the step (1), the mass ratio of the melamine polyphosphate 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 the zinc ion-doped aluminum hydroxide-coated melamine polyphosphate to the phytic acid to the zirconium hydrogen phosphate is 120:3: 5-120: 4.5: 5.
The method for preparing the special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde comprises the following steps:
(1) weighing multiple composite coated melamine polyphosphate, a nitrogen flame retardant, dipentaerythritol, thermoplastic polyurethane, a dispersant 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 150-160 ℃, 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 temperature of the machine barrel is 160-170 ℃.
The technical scheme adopted by the invention has the beneficial effects that:
(1) aiming at the defects that melamine polyphosphate is easy to absorb water, easy to hydrolyze, poor in thermal stability, low in fluidity, poor in dispersibility, incapable of providing enough protection for traditional wall materials and the like, zinc ions are doped with an aluminum hydroxide inorganic substance to coat the melamine polyphosphate, 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 melamine polyphosphate microcapsules through the dual effects of phytic acid passivation and ion exchange adsorption, so that multiple composite inorganic coating layers are formed. Compared with the traditional polymer or single-layer inorganic material coating layer, the multiple composite inorganic coating layer has a better heat protection effect on melamine polyphosphate, and particularly, the multiple inorganic shell passivated by phytic acid provides a firmer and denser inorganic coating layer for the melamine polyphosphate than the traditional polymer and inorganic wall material, so that the coated melamine polyphosphate can be more effectively protected, and the thermal decomposition temperature of the melamine polyphosphate is obviously improved. Thus, the coated melamine polyphosphate can achieve more excellent thermal stability.
(2) As a large amount of phosphorus-containing materials are introduced into the wall material coated with the melamine polyphosphate, the introduction of more phosphorus elements can effectively promote the formation of a thick carbon layer on the surface of a polyformaldehyde compound combustion object in the combustion process of the halogen-free flame-retardant polyformaldehyde compound, more obviously enhance the compactness and structural stability of the surface carbon layer in the combustion process of the flame-retardant polymer, prevent the interior of the combustion object from contacting with oxygen, enable the flame retardant to play a synergistic flame-retardant role, and further effectively improve the flame-retardant property of polyformaldehyde.
(3) By introducing the zirconium hydrogen phosphate with a mesoporous structure into the outermost coating layer of the melamine polyphosphate, the zirconium hydrogen phosphate has a large specific surface area, is large in surface charge density, is in a stable layered structure, is rich in OH groups, can perform ion exchange reaction, has large ion exchange capacity, can generate a large adsorption effect on various small-molecule volatile matters in the thermal processing process of the flame-retardant plastic, and can also play a flame-retardant synergistic effect in a halogen-free flame-retardant system.
(4) The master batch formula with good compatibility with polyformaldehyde and good dispersibility of the flame retardant powder is designed, and the master batch with the flame retardant function is obtained by long-time mixing at a low temperature through an internal mixer, 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 polyformaldehyde twin-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 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 melamine polyphosphate, 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 polyformaldehyde compound.
(6) The special halogen-free flame-retardant master batch for modifying polyformaldehyde prepared by the invention can be subjected to melt extrusion functional modification with a double screw for homopolymerization or copolymerization of formaldehyde, and can also be simply mixed with polyformaldehyde 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 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
A special halogen-free flame-retardant synergistic master batch for modifying polyformaldehyde comprises the following raw materials in parts by mass:
| multiple composite coated melamine polyphosphate | 65.0 kg |
| Melamine cyanurate | 20.0 kg |
| Bispentaerythritol | 4.2 kg |
| Polyether type thermoplastic polyurethane | 10.0 kg |
| Zinc stearate | 500.0 g |
| Polyethylene oxide wax | 300.0 g |
The preparation method of the multiple composite coated melamine polyphosphate used in the special polyformaldehyde modified halogen-free flame-retardant synergistic functional master batch comprises the following steps:
adding 230L of absolute ethyl alcohol, 120kg of melamine polyphosphate, 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 10.0 wt.% ammonia water at a uniform speed, controlling the pH value of the 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 clear water, filtering, and drying in an oven at 125 ℃ for 8 hours to obtain the zinc ion doped aluminum hydroxide coated melamine polyphosphate. 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 obtained zinc ion-doped aluminum hydroxide coated melamine polyphosphate 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 melamine polyphosphate are subjected to passivation reaction by doping 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 melamine polyphosphate.
The preparation method of the special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde 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 155 ℃, 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 160-170 ℃ in sections.
Example 2
A special halogen-free flame-retardant synergistic master batch for modifying polyformaldehyde comprises the following raw materials in parts by mass:
| multiple composite coated melamine polyphosphate | 55.0 kg |
| Melamine cyanurate | 30.0 kg |
| Bispentaerythritol | 3.0 kg |
| Polyether type thermoplastic polyurethane | 10.5 kg |
| Stearic acid calcium salt | 1.0 kg |
| Pentaerythritol stearate | 500.0 g |
The preparation method of the multiple composite coated melamine polyphosphate used in the special polyformaldehyde modified halogen-free flame-retardant synergistic functional master batch comprises the following steps:
adding 230L of absolute ethyl alcohol, 120kg of melamine polyphosphate, 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.% of 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 clear water, filtering, and drying in an oven at 120 ℃ for 10 hours to obtain the zinc ion doped aluminum hydroxide coated melamine polyphosphate. 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 obtained zinc ion-doped aluminum hydroxide coated melamine polyphosphate 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 constant speed to ensure that the phytic acid and the zinc ion coated with melamine polyphosphate are subjected to passivation reaction by doping an aluminum hydroxide shell, 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 melamine polyphosphate.
The preparation method of the special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde 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 157 ℃, 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 160-170 ℃ in sections.
Example 3
A preparation method of a multi-composite coated melamine polyphosphate used by a special halogen-free flame-retardant synergistic master batch modified by polyformaldehyde comprises the following steps:
adding 230L of absolute ethyl alcohol, 120kg of melamine polyphosphate, 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 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 generate sol-gel reaction, and after dropwise adding is completed, continuously stirring for 4 hours and then finishing the reaction; and 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 melamine polyphosphate. 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 obtained zinc ion-doped aluminum hydroxide coated melamine polyphosphate 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 zinc ion coated with melamine polyphosphate are subjected to passivation reaction by doping an aluminum hydroxide shell, continuously stirring for 1.5 h, adding 4.8 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 a 115 ℃ oven for 12 h to obtain the multiple composite coated melamine polyphosphate.
The special halogen-free flame-retardant synergistic master batch for polyformaldehyde comprises the following raw materials in parts by mass:
| multiple composite coated melamine polyphosphate | 60.0 kg |
| Melamine polyphosphate | 23.0 kg |
| Bispentaerythritol | 4.0 kg |
| Polyether type thermoplastic polyurethane | 12.0 kg |
| Stearic acid magnesium salt | 700.0 g |
| Ethylene-vinyl acetate copolymer wax | 300.0 g |
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 160 ℃, 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 160-170 ℃ in sections.
Example 4
A special halogen-free flame-retardant synergistic master batch for modifying polyformaldehyde comprises the following raw materials in parts by mass:
| multiple composite coated melamine polyphosphate | 58.0 kg |
| Melamine polyphosphate | 26.0 kg |
| Bispentaerythritol | 5.0 kg |
| Polyether type thermoplastic polyurethane | 10.0 kg |
| Stearic acid | 600.0 g |
| Polyethylene oxide wax | 400.0 g |
The preparation method of the multiple composite coated melamine polyphosphate used in the special polyformaldehyde modified halogen-free flame-retardant synergistic functional master batch comprises the following steps:
adding 230L of absolute ethyl alcohol, 120kg of melamine polyphosphate, 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 11.5 wt.% ammonia water at a uniform speed, controlling the pH value of the 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; and 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 melamine polyphosphate. 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 melamine polyphosphate 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 zinc ion coated with melamine polyphosphate are subjected to passivation reaction by doping 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 melamine polyphosphate.
The preparation method of the special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde 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 158 ℃, 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 160-170 ℃ in sections.
Example 5
A special halogen-free flame-retardant synergistic master batch for modifying polyformaldehyde comprises the following raw materials in parts by mass:
| multiple composite coated melaminePolyphosphate salt | 61.5 kg |
| Melamine cyanurate | 21.0 kg |
| Bispentaerythritol | 4.3 kg |
| Polyester-type thermoplastic polyurethane | 12.0 kg |
| Zinc stearate | 800.0 g |
| Pentaerythritol stearate | 400.0 g |
The preparation method of the multiple composite coated melamine polyphosphate used in the special polyformaldehyde modified halogen-free flame-retardant synergistic functional master batch comprises the following steps:
adding 230L of absolute ethyl alcohol, 120kg of melamine polyphosphate, 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 generate sol-gel reaction, and after dropwise adding is completed, continuously stirring for 4 hours and then finishing the reaction; and then washing with clear water, filtering, and drying in an oven at 120 ℃ for 10 h to obtain the zinc ion doped aluminum hydroxide coated melamine polyphosphate. 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 melamine polyphosphate and 230L of isobutanol into an enamel reaction kettle, stirring uniformly 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 melamine polyphosphate are subjected to passivation reaction by doping an aluminum hydroxide shell, 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 melamine polyphosphate.
The preparation method of the special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde 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 153 ℃, 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 160-170 ℃ in sections.
Example 6
A special halogen-free flame-retardant synergistic master batch for modifying polyformaldehyde comprises the following raw materials in parts by mass:
| multiple composite coated melamine polyphosphate | 59.0 kg |
| Melamine cyanurate | 25.0 kg |
| Bispentaerythritol | 4.0 kg |
| Polyether type thermoplastic polyurethane | 11.0 kg |
| Stearic acid calcium salt | 700.0 g |
| Polyethylene oxide wax | 300.0 g |
The preparation method of the multiple composite coated melamine polyphosphate used in the special polyformaldehyde modified halogen-free flame-retardant synergistic functional master batch comprises the following steps:
adding 230L of absolute ethyl alcohol, 120kg of melamine polyphosphate, 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 generate sol-gel reaction, and after dropwise adding 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 hours to obtain the zinc ion doped aluminum hydroxide coated melamine polyphosphate. 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 melamine polyphosphate 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 constant speed to ensure that the phytic acid and the zinc ion coated with melamine polyphosphate are subjected to passivation reaction by doping an 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 melamine polyphosphate.
The preparation method of the special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde 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 154 ℃, 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 160-170 ℃ in sections.
In order to verify the modification effect of the prepared flame-retardant synergistic functional master batch on polyformaldehyde, the flame-retardant synergistic functional master batches prepared in the embodiments 1 to 6 are mixed with polyformaldehyde resin according to the mass percentage of 28 wt.%, and are subjected to blending extrusion molding by a double-screw extruder, then are subjected to injection molding, and are subjected to combustion test sample strips, and then are subjected to flame-retardant performance detection. Meanwhile, the flame-retardant functional master batch is prepared by the same process as the comparative examples 1-6 according to the same components and proportions of the functional master batch obtained in the examples 1-6, but the melamine polyphosphate with the same brand but without coating is used as a main flame retardant, and then the flame-retardant functional master batch is mixed with the polyformaldehyde 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 in flame retardant property. The results of all performance tests are shown in table 1.
Table 1 performance comparison of the functional masterbatches prepared in examples 1-6 with polyoxymethylene compounds modified with the same formulation but with the functional masterbatch prepared without the melamine polyphosphate 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 modified polyformaldehyde compound prepared by adopting the special polyformaldehyde halogen-free flame retardant synergistic functional master batch prepared by the embodiment of the invention is obviously superior to that of the polyformaldehyde compound modified by adopting the non-coated melamine polyphosphate halogen-free flame retardant functional master batch. In addition, from the results of the fluidity spiral length test, it was also found that the modified polyoxymethylene compounds of the examples of the present invention had a significantly higher fluidity than the comparative examples. Therefore, by using the halogen-free flame-retardant synergistic functional master batch, the flame-retardant modification effect of the melamine polyphosphate flame retardant on the polyformaldehyde resin is greatly improved, the defects of poor mechanical property and poor electrical property caused by poor water resistance of the melamine polyphosphate flame retardant are effectively overcome, the melt flowability of the modified polyformaldehyde compound is improved, and the processing property of the modified polyformaldehyde 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 (9)
1. A special halogen-free flame-retardant synergistic master batch for modifying polyformaldehyde is characterized in that: the functional master batch takes multi-composite coated melamine polyphosphate as a phosphorus flame retardant, and the functional master batch comprises the following components in percentage by mass: 55.0-65.0 wt.% of multi-composite coated melamine polyphosphate, 20.0-30.0 wt.% of nitrogen flame retardant, 3.0-5.0 wt.% of dipentaerythritol, 10.0-12.0 wt.% of thermoplastic polyurethane, 0.5-1.0 wt.% of dispersant and 0.3-0.5 wt.% of lubricant.
2. The special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde according to claim 1, which is characterized in that: the nitrogen-containing flame retardant is any one of melamine cyanurate and melamine polyphosphate, and the thermoplastic polyurethane is any one of polyether type or polyester type thermoplastic polyurethane, wherein the polyether type thermoplastic polyurethane is preferred.
3. The special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde according to claim 1, which is characterized in that: the dispersing agent is one of stearic acid, calcium stearate, zinc stearate and magnesium stearate, and the lubricating agent is one of polyoxyethylene wax, pentaerythritol stearate and ethylene-vinyl acetate copolymer wax.
4. The special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde according to claim 1, which is characterized in that: the multi-composite coated melamine polyphosphate is zinc ion doped aluminum hydroxide, phytic acid and zirconium hydrogen phosphate coated melamine polyphosphate.
5. The special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde according to claim 1, which is characterized in that: the preparation method of the multi-composite coated melamine polyphosphate comprises the following steps:
(1) dispersing melamine polyphosphate, 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 liquid 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 and finishing the reaction; then washing, filtering and drying to obtain zinc ion doped aluminum hydroxide coated melamine polyphosphate;
(2) dispersing the coated melamine polyphosphate in an alcohol organic solvent; and dissolving phytic acid in deionized water, uniformly dripping the phytic acid into isopropanol suspension containing the coated melamine polyphosphate, heating and uniformly stirring to ensure that the phytic acid and the zinc ion-doped aluminum hydroxide shell coated with the melamine polyphosphate generate 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 the reaction, washing, filtering and drying to obtain the multi-composite inorganic material coated melamine polyphosphate.
6. The special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde according to claim 5, 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 the zinc ion doped aluminum hydroxide coated melamine polyphosphate.
7. The special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde according to claim 5, 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 solution is washed by clear water and filtered, and the solution is dried in an oven at the temperature of 115-125 ℃ for 10-12 hours, so that the multi-composite inorganic material coated melamine polyphosphate is obtained.
8. The special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde according to claim 5, which is characterized in that: in the step (1), the mass ratio of the melamine polyphosphate 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 the zinc ion-doped aluminum hydroxide-coated melamine polyphosphate to the phytic acid to the zirconium hydrogen phosphate is 120:3: 4-120: 4.5: 5.
9. The method for preparing the special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde according to any one of claims 1-8, which is characterized by comprising the following steps: the method comprises the following steps:
(1) weighing multiple composite coated melamine polyphosphate, a nitrogen flame retardant, dipentaerythritol, thermoplastic polyurethane, a dispersant 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 150-160 ℃, 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 temperature of the machine barrel is 160-170 ℃.
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