Highly dispersed flame-retardant masterbatch and method for manufacturing the same

Abstract

The objective is to provide a highly dispersed flame-retardant masterbatch and a method for manufacturing the same. [Solution] The present invention belongs to the field of polymer materials and relates to a highly dispersed flame retardant masterbatch and a method for producing the same. The highly dispersed flame retardant masterbatch comprises, by weight, 8 to 30 parts by weight of a polymer, 30 to 95 parts by weight of a composite flame retardant containing antimony trioxide, borate, and an organophosphorus-nitrogen complex, 6 to 20 parts by weight of a plasticizer, and 0.1 to 15 parts by weight of an auxiliary agent, wherein the organophosphorus-nitrogen complex is one or more of a mixture of DOPO and MCA, polyphosphate melamine, and ammonium polyphosphate. The present invention significantly improves the flame retardant performance of the material by optimizing the recipe of the flame retardant.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials and relates to a highly dispersed flame retardant masterbatch and a manufacturing method thereof.

Background Art

[0002] With the progress of science and technology and the improvement of living standards, polymer materials such as plastics and rubbers have become increasingly important in people's lives, and their application ranges have been showing a tendency to expand year by year. However, most of the organic polymer materials show different flammabilities in the air, and the flammability of polymer materials brings adverse effects not only on safety and economy but also on environment, society and health. As a result, the applications of polymer materials in many industries such as military, aerospace, transportation, electric power and civilian needs are limited. Therefore, the flame retardant modification of these materials has become an important research topic. In the conventional combustion suppression methods, mainly by adding flame retardants, the fireproof performance of materials is improved. However, when most flame retardants are applied to plastic products, they affect the mechanical properties of the products, resulting in a decrease in mechanical properties (such as tensile strength, impact strength, etc.), and further having low dispersibility, difficult processing, and problems such as pollution caused by a large amount of dust.

[0003] To solve the above problems, flame-retardant masterbatches have emerged as needed. A flame-retardant masterbatch is a concentrate produced by dispersing a flame retardant at a high concentration in a carrier resin and manufacturing it through a special process. Such concentrates usually appear as particulate or paste-like substances. Flame-retardant masterbatches generally contain a flame retardant, carrier resin, and auxiliary agents, the auxiliary agents mainly including dispersants, stabilizers, and lubricants to improve the dispersibility and processing performance of the flame retardant. Compared to conventionally added flame retardants, flame-retardant masterbatches offer several advantages: by manufacturing a flame-retardant masterbatch, the dispersibility of the flame retardant in the resin is improved, the amount of flame retardant added is reduced, processing difficulty and costs are reduced, the influence of the flame retardant on the mechanical properties of the resin is reduced, and problems such as layering, patterning, and precipitation are less likely to occur after addition, the working environment is improved, and labor costs, material costs, and time are saved. For these reasons, the improvement of flame-retardant resin processing processes using masterbatch technology is already a trend in the industry.

[0004] Conventional flame-retardant masterbatches primarily use antimony trioxide (Sb2O3) as the single flame-retardant component. However, the price of antimony trioxide is affected by multiple factors and has been fluctuating significantly and steadily rising in recent years. Furthermore, the hue of antimony trioxide varies greatly depending on the mine, significantly impacting the color consistency of downstream products. Therefore, there is an urgent need to find flame-retardant masterbatches that partially replace antimony trioxide. Enhancing the flame-retardant performance of the base fabric with composite materials improves environmental protection, reduces material costs, and enhances market competitiveness. Flame-retardant masterbatches for manufacturing plastic composites need to possess not only good flame-retardant performance but also high thermal stability, processability and dispersibility, minimal impact on the mechanical performance of the product, and long-lasting flame-retardant properties. By optimizing recipes and production processes and developing multi-functional flame-retardant masterbatches, it is possible not only to solve many of the problems of conventional flame retardants but also to meet the requirements for high-performance flame-retardant materials in different industries and promote the widespread application of polymer materials in fields such as buildings, electrical appliances, transportation, and communications. [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] This invention provides a masterbatch that is highly dispersed and has excellent flame retardant properties, addressing the shortcomings of the prior art. [Means for solving the problem]

[0006] One objective of the present invention is achieved by the following technical solutions. A highly dispersed flame retardant masterbatch comprising, by weight, 8 to 30 parts of a high-molecular polymer, 30 to 95 parts of a composite flame retardant containing antimony trioxide, borate, and an organophosphorus-nitrogen complex, 6 to 20 parts of a plasticizer, and 0.1 to 15 parts of an auxiliary agent, wherein the organophosphorus-nitrogen complex is one or more of a mixture of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and melamine cyanurate, melamine polyphosphate, and ammonium polyphosphate.

[0007] Preferably, the composite flame retardant comprises a mixture of antimony trioxide, a borate, and an organophosphorus-nitrogen complex in a mass ratio of 1:(0.5~1.0):(0.5~1.0).

[0008] Preferably, the organophosphorus-nitrogen complex is a mixture of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and melamine cyanurate.

[0009] Preferably, the composite flame retardant comprises a mixture of antimony trioxide, a borate, 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, and melamine cyanurate in a mass ratio of 1:(0.5~1.0):(0.3~0.6):(0.2~0.4).

[0010] Preferably, the composite flame retardant comprises antimony trioxide, a borate, an organophosphorus-nitrogen complex, and a metal hydroxide.

[0011] Preferably, the composite flame retardant comprises antimony trioxide, a borate, 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, melamine cyanurate, and a metal hydroxide.

[0012] Preferably, the mass of the metal hydroxide is 0.1 to 10 wt% of the total mass of the composite flame retardant.

[0013] Preferably, the metal hydroxide is aluminum hydroxide and / or magnesium hydroxide.

[0014] Preferably, the borate is one or more metal salts of boric acid or metal salts of fluoroboric acid, and the metal is one or more of sodium, potassium, magnesium, barium, ammonium, calcium, manganese, nickel, copper, aluminum, zinc, cobalt, and zirconium.

[0015] Preferably, the borate is one or more of the following: calcium borate, cobalt borate, anhydrous zinc borate, zinc borate triahydrate, sodium orthoborate, sodium perborate, sodium metaborate, sodium tetraborate, ammonium metaborate, ammonium pentaborate, calcium metaborate, barium metaborate, barium tetraborate, potassium metaborate, potassium tetraborate, potassium pentaborate, magnesium orthoborate, magnesium metaborate, trimagnesium tetraborate, pentamagnesium tetraborate, potassium tetrafluoroborate, sodium tetrafluoroborate, ammonium tetrafluoroborate, zinc tetrafluoroborate, calcium tetrafluoroborate, magnesium tetrafluoroborate, and barium metaborate.

[0016] Preferably, the polymer is one or more of olefin-based polymers, ester-based polymers, ethylene-based polymers, styrene-based polymers, and polyurethanes.

[0017] Preferably, the polymer is one or more of polyvinyl chloride, PVC-vinyl acetate copolymer, or ethylene-vinyl acetate copolymer.

[0018] Preferably, the plasticizer is one or more of pyromellitic acid ester plasticizers, trimelite plasticizers, phthalate plasticizers, terephthalate plasticizers, phosphate plasticizers, and epoxidized vegetable oils.

[0019] Preferably, the plasticizer is one or more of dioctyl phthalate, dinonyl phthalate, diisodecyl phthalate, diundecyl phthalate, didodecyl phthalate, ditridecyl phthalate, dioctyl terephthalate, tris(isopropylphenyl) phosphate, tetrahalogenated dialkyl phthalate, tris(2-chloroethyl) phosphate, bisphenol A bis(diphenyl phosphate), or epoxidized soybean oil.

[0020] Preferably, the auxiliary agent includes one or more of a dispersant, a stabilizer, and a lubricant.

[0021] Preferably, the dispersant is polycaprolactone-modified nanocalcium carbonate, and the amount of the dispersant is 0.1 to 4 parts.

[0022] Preferably, the stabilizer is a liquid calcium-zinc stabilizer and a powdered calcium-zinc stabilizer, and the amount of stabilizer is 0.5 to 6.0 parts.

[0023] Preferably, the lubricant comprises one or more of a metal soap-based lubricant, a hydrocarbon-based lubricant, a fatty acid-based lubricant, and a fatty acid ester-based lubricant, and the lubricant is present in an amount of 0.1 to 3 parts.

[0024] Preferably, the method for producing the polycaprolactone-modified nanocalcium carbonate is: The process involves adding nanocalcium carbonate and polycaprolactone to a high-speed mixer and mixing them, raising the temperature to 70-100°C within 5-20 minutes, maintaining the temperature and continuing to stir for 5-60 minutes, discharging the mixture, and then cooling to obtain polycaprolactone-modified nanocalcium carbonate.

[0025] Preferably, the average particle diameter of nano calcium carbonate is 10 to 999 nm.

[0026] Preferably, the mass of polycaprolactone is 0.5 to 15 wt% of the mass of nano calcium carbonate.

[0027] Preferably, the rotation speed of the high-speed mixer is 500 to 10,000 revolutions per minute.

[0028] The second object of the present invention is achieved by the following technical solutions.

[0029] A method for producing a highly dispersed flame retardant masterbatch, comprising weighing each component of the highly dispersed flame retardant masterbatch, adding them to a mixing cylinder at 100 to 180 ° C and mixing for 5 to 50 minutes, transferring them to a three-roll mill for grinding and dispersion, and then pressing and forming the material subjected to the grinding and dispersion by a two-roll machine and shearing with a shearing machine to obtain a cake-shaped highly dispersed flame retardant masterbatch.

Effects of the Invention

[0030] Compared with the prior art, the present invention has the following beneficial effects. 1. Flame retardant performance: In this application, a composite flame retardant of antimony trioxide, borate, and organic phosphorus-nitrogen complex is adopted. After the organic phosphorus-nitrogen complex and borate burn and decompose, the active substances generated produce a synergistic effect with antimony trioxide, combine with the chlorine element in polyvinyl chloride to form an effective flame retardant barrier, and the composite flame retardant has a greater flame retardant effect than when antimony trioxide is used alone. Furthermore, when the organic phosphorus-nitrogen complex is a mixture of DOPO and MCA, the formed composite flame retardant of antimony trioxide, borate, DOPO, and MCA has higher flame retardant performance than the composite flame retardant composed of ammonium polyphosphate or melamine polyphosphate as the organic phosphorus-nitrogen complex. Furthermore, when the composite flame retardant further contains aluminum hydroxide and / or magnesium hydroxide, the synergistic effect of several materials results in a material exhibiting superior flame retardant properties.

[0031] 2. Dispersibility: In this invention, polycaprolactone is formed on the surface of nanocalcium carbonate by a high-temperature reaction at 70-100°C. The polycaprolactone melts into a liquid state at high temperatures and coats the surface of the nanocalcium carbonate. The resulting PCL-modified nanocalcium carbonate promotes uniform dispersion in the polymer and enhances the dispersion effect of other components in the polymer, such as flame retardants, thereby ensuring consistency and stability of product performance. Furthermore, when the amount of other components, such as flame retardants, added is the same, the addition of polycaprolactone-modified nanocalcium carbonate promotes the dispersion of the flame retardant, thus contributing to improved flame retardancy of plastic products.

[0032] 3. Thermal Stability: The present invention provides good light stability and thermal stability by mixing a liquid calcium zinc stabilizer and a powdered calcium zinc stabilizer in a specific mass ratio. This effectively prevents material aging caused by light irradiation and high temperatures, maintains the transparency and luster of the product, and improves the appearance and long-term usability of the product.

[0033] 4. Lubricity and processing performance: By combining a metal soap-based lubricant and polyethylene wax and using them as lubricants in the masterbatch of the present invention, a higher lubrication effect is achieved, reducing the difficulty of processing and avoiding malfunctions.

[0034] As described above, the present invention not only significantly improves the flame retardant performance of materials by optimizing the recipe of flame retardants and improving the selection of dispersants, stabilizers, and lubricants, but also improves stability and processing performance, reduces processing difficulty and cost, and has the potential for a wide range of applications. [Modes for carrying out the invention]

[0035] The following describes in detail embodiments of the highly dispersed flame-retardant masterbatch and the method for producing the highly dispersed flame-retardant masterbatch of the present invention. However, these embodiments are illustrative and the disclosure of the present invention is not limited thereto.

[0036] Highly dispersed flame-retardant masterbatch The highly dispersed flame-retardant masterbatch provided in the present invention comprises, by weight, 8 to 30 parts by high-molecular-weight polymer, 30 to 95 parts by composite flame retardant, 6 to 20 parts by plasticizer, and 0.1 to 15 parts by auxiliary agent.

[0037] Composite flame retardants in highly dispersed flame retardant masterbatches of the present invention: The composite flame retardant of the present invention comprises antimony trioxide, a borate, and an organophosphorus-nitrogen complex, wherein the organophosphorus-nitrogen complex is one or more of a mixture of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (DOPO) and melamine cyanurate (MCA), melamine polyphosphate, and ammonium polyphosphate.

[0038] Organophosphorus-nitrogen complexes and borates, after combustion and decomposition, produce active materials that synergistically interact with antimony trioxide, binding with chlorine elements in polyvinyl chloride to form an effective flame-retardant barrier. Therefore, using a composite flame retardant consisting of antimony trioxide, borate, and organophosphorus-nitrogen complexes results in a greater flame retardant effect than using antimony trioxide alone.

[0039] In some embodiments of the present invention, the composite flame retardant comprises a mixture of antimony trioxide, a borate, and an organophosphorus-nitrogen complex in a mass ratio of 1:(0.5~1.0):(0.5~1.0). More preferably, the composite flame retardant comprises a mixture of antimony trioxide, a borate, and an organophosphorus-nitrogen complex in a mass ratio of 1:(0.6~0.8):(0.6~0.8).

[0040] In some embodiments of the present invention, the organophosphorus-nitrogen complex is more preferably a mixture of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and melamine cyanurate.

[0041] The inventors inadvertently discovered that when the organophosphorus-nitrogen complex is a mixture of DOPO and MCA, the resulting composite flame retardant of antimony trioxide, borate, DOPO, and MCA has higher flame retardant performance than a composite flame retardant in which the organophosphorus-nitrogen complex consists of ammonium polyphosphate or polyphosphate melamine.

[0042] In some embodiments of the present invention, the organophosphorus-nitrogen complex is a mixture of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and melamine cyanurate in a mass ratio of (3-6):(2-4).

[0043] In some embodiments of the present invention, the composite flame retardant comprises a mixture of antimony trioxide, a borate, 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, and melamine cyanurate in a mass ratio of 1:(0.5~1.0):(0.3~0.6):(0.2~0.4).

[0044] In some embodiments of the present invention, the composite flame retardant preferably comprises antimony trioxide, a borate, an organophosphorus-nitrogen complex, and a metal hydroxide.

[0045] When a composite flame retardant further contains aluminum hydroxide and / or magnesium hydroxide, the synergistic effect of several materials results in a material exhibiting superior flame retardant properties.

[0046] In some embodiments of the present invention, the composite flame retardant more preferably comprises antimony trioxide, a borate, 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, melamine cyanurate, and a metal hydroxide.

[0047] In some embodiments of the present invention, the mass of the metal hydroxide is preferably 0.1 to 10 wt% of the total mass of the composite flame retardant. More preferably, the mass of the metal hydroxide is 1 to 8 wt% of the total mass of the composite flame retardant, for example, 1, 2, 3, 4, 5, 6, 7, or 8 wt%. Preferably, the metal hydroxide is aluminum hydroxide and / or magnesium hydroxide.

[0048] The borate in the composite flame retardant of the present invention is one or more metal salts of boric acid or metal salts of fluoroboric acid. The metal here may be one or more of sodium, potassium, magnesium, barium, ammonium, calcium, manganese, nickel, copper, aluminum, zinc, cobalt, zirconium, etc.

[0049] The borates include, but are not limited to, one or more of the following: calcium borate, cobalt borate, anhydrous zinc borate, zinc borate triahydrate, sodium orthoborate, sodium perborate, sodium metaborate, sodium tetraborate, ammonium metaborate, ammonium pentaborate, calcium metaborate, barium metaborate, barium tetraborate, potassium metaborate, potassium tetraborate, potassium pentaborate, magnesium orthoborate, magnesium metaborate, trimagnesium tetraborate, pentamagnesium tetraborate, potassium tetrafluoroborate, sodium tetrafluoroborate, ammonium tetrafluoroborate, zinc tetrafluoroborate, calcium tetrafluoroborate, magnesium tetrafluoroborate, and barium metaborate.

[0050] Highly dispersed polymers in flame-retardant masterbatches of the present invention: The polymer in the highly dispersed flame-retardant masterbatch must have good compatibility with the polymer product to be applied. The specific type of polymer is selected according to the properties of the polymer product to be applied, and may be one or more of the following: olefin polymers, ester polymers, ethylene polymers, styrene polymers, polyurethanes, etc.

[0051] Examples of olefin polymers include polyethylene and polypropylene.

[0052] Examples of ester polymers include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), and polyethylene naphthalate (PEN).

[0053] Examples of ethylene-based polymers include polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and PVC-vinylate copolymer.

[0054] Examples of styrene-based polymers include polystyrene, styrene-acrylonitrile resin, and styrene-butadiene-acrylonitrile resin.

[0055] In some embodiments of the present invention, the polymer is one or more of polyvinyl chloride, polyethylene, polypropylene, polyurethane, polyester, polyvinyl alcohol, PVC-vinyl acetate copolymer, or ethylene-vinyl acetate copolymer.

[0056] In some embodiments of the present invention, the polymer is more preferably one or more of polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, or ethylene-vinyl acetate copolymer.

[0057] Plasticizer in a highly dispersed flame-retardant masterbatch of the present invention: In some embodiments of the present invention, the plasticizer is one or more pyromellitic acid ester plasticizers, trimelite plasticizers, phthalate plasticizers, terephthalate plasticizers, phosphate plasticizers, and epoxidized vegetable oils.

[0058] Examples of the pyromellitic acid ester plasticizers include one or more of the following: tetra-n-hexyl pyromellitic acid, tetra-n-heptyl pyromellitic acid, tetra-n-octyl pyromellitic acid, tetra(2-ethylhexyl) pyromellitic acid, tetra-n-nonyl pyromellitic acid, tetra-n-decyl pyromellitic acid, tetraisodecyl pyromellitic acid, tetra-n-undecyl pyromellitic acid, and tetra-n-dodecyl pyromellitic acid.

[0059] The trimellite-based plasticizer includes one or more of the following: trimellit acid trioctyl, trimellit acid triglyceride, etc.

[0060] The phthalate-based plasticizer includes one or more of the following: diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, diisodecyl phthalate, diundecyl phthalate, didodecyl phthalate, ditridecyl phthalate, bis-2-ethylhexyl phthalate, dicyclohexyl phthalate, dibenzyl phthalate, and dialkyl halogenated phthalate.

[0061] The terephthalate-based plasticizer includes one or more of the following: dioctyl terephthalate (DOTP), diisononyl terephthalate, diisodecyl terephthalate, and di(2-ethylhexyl) terephthalate.

[0062] The phosphate-based plasticizer includes one or more of the following: tris(isopropylphenyl) phosphate, tris(2-chloroethyl) phosphate, bisphenol A bis(diphenyl phosphate) (BDP), tris(2-chloroethyl) phosphate (TCEP), tris(butoxyethyl) phosphate, etc.

[0063] Examples of the epoxidized vegetable oils include epoxidized soybean oil and epoxidized linseed oil.

[0064] More preferably, the plasticizer is one or more of dioctyl phthalate, dinonyl phthalate, diisodecyl phthalate, diundecyl phthalate, didodecyl phthalate, ditridecyl phthalate, dioctyl terephthalate (DOTP), tris(isopropylphenyl) phosphate, tetrahalogenated dialkyl phthalate, tris(2-chloroethyl) phosphate (TCEP), bisphenol A bis(diphenyl phosphate) (BDP), or epoxidized soybean oil.

[0065] Auxiliary agent in the highly dispersed flame-retardant masterbatch of the present invention: In some embodiments of the present invention, the auxiliary agent includes one or more dispersants, stabilizers, and lubricants.

[0066] The dispersant of the present invention is preferably polycaprolactone (PCL)-modified nanocalcium carbonate.

[0067] In some embodiments of the present invention, the method for producing polycaprolactone-modified nanocalcium carbonate is as follows: The process involves adding nanocalcium carbonate and polycaprolactone to a high-speed mixer and mixing them, raising the temperature to 70-100°C within 5-20 minutes, maintaining the temperature and continuing to stir for 5-60 minutes, discharging the mixture, and then cooling to obtain polycaprolactone-modified nanocalcium carbonate.

[0068] In the method for producing polycaprolactone-modified nanocalcium carbonate, the average particle size of the nanocalcium carbonate is preferably 10 to 999 nm. Preferably, the mass of polycaprolactone is 0.5 to 15 wt% of the mass of nanocalcium carbonate, more preferably 1 to 10 wt%, and may be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt%. Preferably, the rotation speed of the high-speed mixer is 500 to 10,000 revolutions per minute.

[0069] Nanocalcium carbonate is applied to the masterbatch of the present invention as a functional ingredient, not only improving the mechanical properties and processability of polymer products, but also enhancing the dispersion effect of other components as a dispersant. Polycaprolactone is formed on the surface of the nanocalcium carbonate through a high-temperature reaction at 70-100°C. The polycaprolactone melts into a liquid state at high temperatures and coats the surface of the nanocalcium carbonate, reducing molecular forces between the nanocalcium carbonate powders, promoting its uniform dispersion in the polymer, enhancing the dispersion effect of other components in the polymer, such as flame retardants, and ensuring consistency and stability of product performance. Furthermore, when the amount of other components, such as flame retardants, added is the same, the addition of polycaprolactone-modified nanocalcium carbonate promotes the dispersion of the flame retardant, thus contributing to improved flame retardancy of plastic products.

[0070] The stabilizer of the present invention is preferably a liquid calcium-zinc stabilizer and a powdered calcium-zinc stabilizer. More preferably, the stabilizer is a mixture consisting of a liquid calcium-zinc stabilizer and a powdered calcium-zinc stabilizer in a mass ratio of 1:0.3 to 0.6.

[0071] Calcium zinc stabilizers possess excellent light-stabilizing properties, preventing material aging caused by light irradiation, maintaining product transparency and luster, and enhancing product appearance. Furthermore, their excellent thermal-stabilizing properties effectively prevent material decomposition at high temperatures, ensuring long-term product performance. Calcium zinc stabilizers are primarily available in two forms: liquid and powder. Liquid calcium zinc stabilizers have high compatibility with polymers, are easily mixed, and are readily processed. Powdered calcium zinc stabilizers offer high stability, are suitable for high-temperature processing conditions, and provide superior stabilization. During production, typically, a single liquid or powdered calcium zinc stabilizer is selected and applied according to actual needs. In this invention, a mixture of liquid and powdered calcium zinc stabilizers in a specific mass ratio is used. As a result, it has been found that this mixture exhibits a higher stabilization effect than a single liquid or powdered calcium zinc stabilizer.

[0072] The lubricant of the present invention comprises one or more of the following: a metal soap-based lubricant, a hydrocarbon-based lubricant, a fatty acid-based lubricant, and a fatty acid ester-based lubricant.

[0073] Examples of metal soap-based lubricants include one or more of the following: zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, and lead stearate.

[0074] Examples of the hydrocarbon-based lubricant include one or more waxes, natural waxes, microcrystalline waxes, polyethylene waxes, halogenated hydrocarbons, and the like.

[0075] Examples of fatty acid-based lubricants include one or more of stearic acid, palmitic acid, oleic acid, linoleic acid, and myristic acid.

[0076] Examples of fatty acid ester-based lubricants include one or more of the following: stealth, palmate, oleate, linolenic acid ester, myristate, etc.

[0077] Preferably, the lubricant is a metal soap-based lubricant and polyethylene wax.

[0078] More preferably, the lubricant is a mixture of a metal soap-based lubricant and polyethylene wax in a mass ratio of 1:0.1 to 0.5.

[0079] The combination of a metal soap-based lubricant, such as zinc stearate or calcium stearate, and polyethylene wax (i.e., low molecular weight polyethylene with a molecular weight of 1000 to 5000) as a lubricant in the masterbatch of the present invention has a higher lubricating effect, which helps to reduce the cohesive force between polymer molecules and reduce internal friction. Thus, it reduces melt viscosity and improves melt fluidity. This improved fluidity ensures the smoothness of the product surface, reduces air bubbles, and reduces defects such as weld lines.

[0080] In some embodiments of the present invention, the auxiliary agent comprises a dispersant, a stabilizer, and a lubricant, wherein in the highly dispersed flame-retardant masterbatch, the amount of dispersant is 0.1 to 4 parts, the amount of stabilizer is 0.5 to 6.0 parts, and the amount of lubricant is 0.1 to 3 parts.

[0081] In some embodiments of the present invention, the auxiliary agent further comprises a series of substances, such as colorants and antistatic agents, that enable the improvement or imparting of specific properties of the polymer.

[0082] Manufacturing method for highly dispersed flame-retardant masterbatches The method for producing a highly dispersed flame-retardant masterbatch provided in the present invention is: The process includes weighing each component of a highly dispersed flame-retardant masterbatch, adding them to a mixing cylinder at 100-180°C and mixing for 5-50 minutes, transferring the mixture to a three-roll press for abrasive dispersion, and then press-forming the abrasive-dispersed material using a two-roll press and shearing it with a shearing machine to obtain a mochi-like, highly dispersed flame-retardant masterbatch.

[0083] Preferably, the polishing dispersion process is carried out 2 to 4 times, with each polishing session lasting 10 to 30 minutes.

[0084] Preferably, the drum temperature of a two-roll machine is 80-120°C.

[0085] The technical solutions of the present invention will be further explained below with reference to specific examples. The specific examples described herein are intended only to aid in understanding the present invention and should not be understood as specifically limiting the invention. Unless otherwise specified, the raw materials used in the examples of the present invention are all common in the art, and the methods used in the examples are all conventional methods in the art.

[0086] The raw material sources in the examples and comparative examples are as follows: The polyvinyl chloride is DG-700, purchased from Tianjin Bohua Chemical Development Co., Ltd. The PVC-vinyl acetate copolymer is CP-430 from Hanhua Company. Zinc borate triahydrate is purchased from Shandong Boao Industrial Co., Ltd. The melamine polyphosphate is Budit 3141, purchased from Budenheim. The ammonium polyphosphate is HT-208, purchased from Shandong Taixing New Materials Co., Ltd. The melamine cyanurate (MCA) is Melapur MC25, produced by BASF. The nanocalcium carbonate has an average particle size of 30 nm and is purchased from Shandong Haize Nanomaterials Co., Ltd. The polycaprolactone (PCL) is Esun 500C, purchased from Shenzhen Guanghua Weiye Co., Ltd. The liquid calcium zinc stabilizer is JCZ-100, purchased from Zhejiang Jiaao Environmental Protection Technology Co., Ltd. The powdered calcium zinc stabilizer is JCZ-6503B, also purchased from Zhejiang Jiaao Environmental Protection Technology Co., Ltd.

[0087] Example 1 The highly dispersed flame-retardant masterbatch provided by this embodiment contains, by parts by weight, the following components: The composition is as follows: polyvinyl chloride: 6 parts, composite flame retardant: 80 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.0 part, powdered calcium zinc stabilizer: 0.5 parts, zinc stearate: 1 part, polyethylene wax: 0.4 parts, polycaprolactone-modified nanocalcium carbonate: 2 parts. Here, the composite flame retardant is a mixture of antimony trioxide, zinc borate 3.5 hydrate, and melamine polyphosphate, with the parts of antimony trioxide, zinc borate 3.5 hydrate, and melamine polyphosphate being 34 parts, 23 parts, and 23 parts, respectively.

[0088] The method for producing polycaprolactone-modified nanocalcium carbonate is as follows: The process involves adding 93 parts nanocalcium carbonate and 7 parts polycaprolactone to a high-speed mixer at 3000 rpm and mixing, raising the temperature to 80°C within 10 minutes, maintaining the temperature and continuing to stir for 30 minutes, discharging the mixture, and cooling to obtain polycaprolactone-modified nanocalcium carbonate.

[0089] This embodiment is, The present invention further provides a method for producing a highly dispersed flame-retardant masterbatch, which includes weighing each component of a highly dispersed flame-retardant masterbatch in the above-mentioned weights, adding them to a mixing cylinder at 150°C and mixing for 30 minutes, transferring them to a three-roll machine for polishing dispersion, polishing three times for 20 minutes each time, and then press-molding the polished and dispersed material using a two-roll machine (drum temperature 100°C) and shearing it with a shearing machine to obtain a mochi-like highly dispersed flame-retardant masterbatch.

[0090] Example 2 The highly dispersed flame-retardant masterbatch provided by this embodiment contains the following components by weight: The composition is as follows: polyvinyl chloride: 6 parts, composite flame retardant: 80 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.0 part, powdered calcium zinc stabilizer: 0.5 parts, zinc stearate: 1 part, polyethylene wax: 0.4 parts, polycaprolactone-modified nanocalcium carbonate: 2 parts. Here, the composite flame retardant is a mixture of antimony trioxide, zinc borate triaquinolahydrate, and ammonium polyphosphate, with the amounts of antimony trioxide, zinc borate triaquinolahydrate, and ammonium polyphosphate being 34 parts, 23 parts, and 23 parts, respectively.

[0091] The method for producing polycaprolactone-modified nanocalcium carbonate and the method for producing a highly dispersed flame-retardant masterbatch are the same as in Example 1.

[0092] Example 3 The highly dispersed flame-retardant masterbatch provided by this embodiment contains the following components by weight: The composition is as follows: polyvinyl chloride: 6 parts, composite flame retardant: 80 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.0 part, powdered calcium zinc stabilizer: 0.5 parts, zinc stearate: 1 part, polyethylene wax: 0.4 parts, polycaprolactone-modified nanocalcium carbonate: 2 parts. Here, the composite flame retardant is a mixture of antimony trioxide, zinc borate 3.5 hydrate, DOPO, and MCA, with the parts of antimony trioxide, zinc borate 3.5 hydrate, DOPO, and MCA being 34 parts, 23 parts, 13 parts, and 10 parts, respectively.

[0093] The method for producing polycaprolactone-modified nanocalcium carbonate and the method for producing a highly dispersed flame-retardant masterbatch are the same as in Example 1.

[0094] Example 4 The highly dispersed flame-retardant masterbatch provided by this embodiment contains the following components by weight: The composition is as follows: polyvinyl chloride: 6 parts, composite flame retardant: 80 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.0 part, powdered calcium zinc stabilizer: 0.5 parts, zinc stearate: 1 part, polyethylene wax: 0.4 parts, polycaprolactone-modified nanocalcium carbonate: 2 parts. Here, the composite flame retardant is a mixture of antimony trioxide, zinc borate 3.5 hydrate, DOPO, and MCA, with the parts of antimony trioxide, zinc borate 3.5 hydrate, DOPO, and MCA being 30 parts, 22 parts, 18 parts, and 10 parts, respectively.

[0095] The method for producing polycaprolactone-modified nanocalcium carbonate and the method for producing a highly dispersed flame-retardant masterbatch are the same as in Example 1.

[0096] Example 5 The highly dispersed flame-retardant masterbatch provided by this embodiment contains the following components by weight: The composition is as follows: polyvinyl chloride: 6 parts, composite flame retardant: 80 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.0 part, powdered calcium zinc stabilizer: 0.5 parts, zinc stearate: 1 part, polyethylene wax: 0.4 parts, polycaprolactone-modified nanocalcium carbonate: 2 parts. Here, the composite flame retardant is a mixture of antimony trioxide, zinc borate 3.5 hydrate, DOPO, MCA, and aluminum hydroxide, with the parts of antimony trioxide, zinc borate 3.5 hydrate, DOPO, MCA, and aluminum hydroxide being 33 parts, 22 parts, 12 parts, 9 parts, and 4 parts, respectively.

[0097] The method for producing polycaprolactone-modified nanocalcium carbonate and the method for producing a highly dispersed flame-retardant masterbatch are the same as in Example 1.

[0098] Example 6 The highly dispersed flame-retardant masterbatch provided by this embodiment contains the following components by weight: The composition is as follows: polyvinyl chloride: 6 parts, composite flame retardant: 80 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.0 part, powdered calcium zinc stabilizer: 0.5 parts, zinc stearate: 1 part, polyethylene wax: 0.4 parts, polycaprolactone-modified nanocalcium carbonate: 2 parts. Here, the composite flame retardant is a mixture of antimony trioxide, zinc borate 3.5 hydrate, DOPO, MCA, and magnesium hydroxide, with the parts of antimony trioxide, zinc borate 3.5 hydrate, DOPO, MCA, and magnesium hydroxide being 29, 21, 17, 9, and 4 parts, respectively.

[0099] The method for producing polycaprolactone-modified nanocalcium carbonate and the method for producing a highly dispersed flame-retardant masterbatch are the same as in Example 1.

[0100] Example 7 The highly dispersed flame-retardant masterbatch provided by this embodiment contains the following components by weight: The composition is as follows: polyvinyl chloride: 6 parts, composite flame retardant: 80 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.0 part, powdered calcium zinc stabilizer: 0.5 parts, zinc stearate: 1 part, polyethylene wax: 0.4 parts, nanocalcium carbonate: 2 parts. Here, the composite flame retardant is a mixture of antimony trioxide, zinc borate 3.5 hydrate, DOPO, and MCA, with the parts of antimony trioxide, zinc borate 3.5 hydrate, DOPO, and MCA being 34 parts, 23 parts, 13 parts, and 10 parts, respectively.

[0101] The method for producing a highly dispersed flame-retardant masterbatch is the same as in Example 1.

[0102] Example 8 The highly dispersed flame-retardant masterbatch provided by this embodiment contains the following components by weight: The composition is as follows: polyvinyl chloride: 6 parts, composite flame retardant: 80 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.0 part, powdered calcium zinc stabilizer: 0.5 parts, zinc stearate: 1 part, polyethylene wax: 0.4 parts, polycaprolactone: 0.14 parts, nanocalcium carbonate: 1.86 parts. Here, the composite flame retardant is a mixture of antimony trioxide, zinc borate triathylene hydrate, DOPO, and MCA, with the parts of antimony trioxide, zinc borate triathylene hydrate, DOPO, and MCA being 34 parts, 23 parts, 13 parts, and 10 parts, respectively.

[0103] The method for producing a highly dispersed flame-retardant masterbatch provided by this embodiment is: The process involves weighing the above-mentioned quantities of polyvinyl chloride, composite flame retardant, epoxidized soybean oil, BDP, liquid calcium-zinc stabilizer, powdered calcium-zinc stabilizer, zinc stearate, polyethylene wax, polycaprolactone, and nanocalcium carbonate, adding them to a mixing cylinder at 150°C and mixing for 30 minutes, transferring the mixture to a three-roll press for polishing and dispersion, polishing three times for 20 minutes each time, and then press-molding the polished and dispersed material using a two-roll press (drum temperature 100°C) and shearing it with a shearing machine to obtain a mochi-like, highly dispersed flame-retardant masterbatch.

[0104] Example 9 The highly dispersed flame-retardant masterbatch provided by this embodiment contains the following components by weight: The composition is as follows: polyvinyl chloride: 6 parts, composite flame retardant: 80 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.5 parts, zinc stearate: 1 part, polyethylene wax: 0.4 parts, polycaprolactone-modified nanocalcium carbonate: 2 parts. Here, the composite flame retardant is a mixture of antimony trioxide, zinc borate 3.5 hydrate, DOPO, and MCA, with the parts of antimony trioxide, zinc borate 3.5 hydrate, DOPO, and MCA being 34 parts, 23 parts, 13 parts, and 10 parts, respectively.

[0105] The method for producing polycaprolactone-modified nanocalcium carbonate and the method for producing a highly dispersed flame-retardant masterbatch are the same as in Example 1.

[0106] Example 10 The highly dispersed flame-retardant masterbatch provided by this embodiment contains the following components by weight: The composition is as follows: polyvinyl chloride: 6 parts, composite flame retardant: 80 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, powdered calcium zinc stabilizer: 1.5 parts, zinc stearate: 1 part, polyethylene wax: 0.4 parts, polycaprolactone-modified nanocalcium carbonate: 2 parts. Here, the composite flame retardant is a mixture of antimony trioxide, zinc borate 3.5 hydrate, DOPO, and MCA, with the parts of antimony trioxide, zinc borate 3.5 hydrate, DOPO, and MCA being 34 parts, 23 parts, 13 parts, and 10 parts, respectively.

[0107] The method for producing polycaprolactone-modified nanocalcium carbonate and the method for producing a highly dispersed flame-retardant masterbatch are the same as in Example 1.

[0108] Example 11 The highly dispersed flame-retardant masterbatch provided by this embodiment contains the following components by weight: The composition is as follows: polyvinyl chloride: 6 parts, composite flame retardant: 80 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 0.5 parts, powdered calcium zinc stabilizer: 1 part, zinc stearate: 1 part, polyethylene wax: 0.4 parts, and polycaprolactone-modified nanocalcium carbonate: 2 parts. Here, the composite flame retardant is a mixture of antimony trioxide, zinc borate 3.5 hydrate, DOPO, and MCA, with the parts of antimony trioxide, zinc borate 3.5 hydrate, DOPO, and MCA being 34 parts, 23 parts, 13 parts, and 10 parts, respectively.

[0109] The method for producing polycaprolactone-modified nanocalcium carbonate and the method for producing a highly dispersed flame-retardant masterbatch are the same as in Example 1.

[0110] Example 12 The highly dispersed flame-retardant masterbatch provided by this embodiment contains the following components by weight: The composition is as follows: polyvinyl chloride: 6 parts, composite flame retardant: 80 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.0 part, powdered calcium zinc stabilizer: 0.5 parts, zinc stearate: 1.4 parts, polycaprolactone-modified nanocalcium carbonate: 2 parts. Here, the composite flame retardant is a mixture of antimony trioxide, zinc borate triaquinola hydrate, DOPO, and MCA, with the parts of antimony trioxide, zinc borate triaquinola hydrate, DOPO, and MCA being 34 parts, 23 parts, 13 parts, and 10 parts, respectively.

[0111] The method for producing polycaprolactone-modified nanocalcium carbonate and the method for producing a highly dispersed flame-retardant masterbatch are the same as in Example 1.

[0112] Example 13 The highly dispersed flame-retardant masterbatch provided by this embodiment contains the following components by weight: The composition is as follows: polyvinyl chloride: 6 parts, composite flame retardant: 80 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.0 part, powdered calcium zinc stabilizer: 0.5 parts, polyethylene wax: 1.4 parts, and polycaprolactone-modified nanocalcium carbonate: 2 parts. Here, the composite flame retardant is a mixture of antimony trioxide, zinc borate triaquinola hydrate, DOPO, and MCA, with the parts of antimony trioxide, zinc borate triaquinola hydrate, DOPO, and MCA being 34 parts, 23 parts, 13 parts, and 10 parts, respectively.

[0113] The method for producing polycaprolactone-modified nanocalcium carbonate and the method for producing a highly dispersed flame-retardant masterbatch are the same as in Example 1.

[0114] Example 14 The highly dispersed flame-retardant masterbatch provided by this embodiment contains the following components by weight: The composition is as follows: polyvinyl chloride: 6 parts, composite flame retardant: 80 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.0 part, powdered calcium zinc stabilizer: 0.5 parts, zinc stearate: 0.7 parts, polyethylene wax: 0.7 parts, and polycaprolactone-modified nanocalcium carbonate: 2 parts. Here, the composite flame retardant is a mixture of antimony trioxide, zinc borate 3.5 hydrate, DOPO, and MCA, with the parts of antimony trioxide, zinc borate 3.5 hydrate, DOPO, and MCA being 34 parts, 23 parts, 13 parts, and 10 parts, respectively.

[0115] The method for producing polycaprolactone-modified nanocalcium carbonate and the method for producing a highly dispersed flame-retardant masterbatch are the same as in Example 1.

[0116] Example 15 The highly dispersed flame-retardant masterbatch provided by this embodiment contains the following components by weight: The composition is: polyvinyl chloride: 4 parts, PVC-vinyl acetate copolymer: 1 part, composite flame retardant: 85 parts, epoxidized soybean oil: 5 parts, TCEP: 7 parts, liquid calcium zinc stabilizer: 0.5 parts, powdered calcium zinc stabilizer: 0.3 parts, zinc stearate: 0.5 parts, polyethylene wax: 0.2 parts, and polycaprolactone-modified nanocalcium carbonate: 1.5 parts.

[0117] Here, the composite flame retardant is a mixture of antimony trioxide, zinc borate 3.5 hydrate, DOPO, and MCA, with the parts amounts of antimony trioxide, zinc borate 3.5 hydrate, DOPO, and MCA being 36 parts, 28 parts, 11 parts, and 10 parts, respectively.

[0118] The method for producing polycaprolactone-modified nanocalcium carbonate is as follows: The process involves adding 90 parts nanocalcium carbonate and 10 parts polycaprolactone to a high-speed mixer at 5000 rpm and mixing, raising the temperature to 85°C within 15 minutes, maintaining the temperature and continuing to stir for 20 minutes, discharging the mixture, and cooling to obtain polycaprolactone-modified nanocalcium carbonate.

[0119] This embodiment is, The present invention further provides a method for producing a highly dispersed flame-retardant masterbatch, which includes weighing each component of a highly dispersed flame-retardant masterbatch in the above-mentioned weights, adding them to a mixing cylinder at 160°C and mixing for 25 minutes, transferring them to a three-roll machine for polishing dispersion, polishing four times for 15 minutes each time, and then press-molding the polished and dispersed material using a two-roll machine (drum temperature 110°C) and shearing it with a shearing machine to obtain a mochi-like highly dispersed flame-retardant masterbatch.

[0120] Comparative Example 1 Comparative Example 1 differs from Example 3 in that the flame retardant in Comparative Example 1 is antimony trioxide. In other words, the highly dispersed flame-retardant masterbatch provided in the comparative example contains the following components by weight: The composition is: polyvinyl chloride: 6 parts, antimony trioxide: 80 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.0 part, powdered calcium zinc stabilizer: 0.5 parts, zinc stearate: 1 part, polyethylene wax: 0.4 parts, polycaprolactone-modified nanocalcium carbonate: 2 parts.

[0121] The method for producing polycaprolactone-modified nanocalcium carbonate and the method for producing a highly dispersed flame-retardant masterbatch are the same as in Example 3.

[0122] Comparative Example 2 Comparative Example 2 differs from Example 3 in that the flame retardant in Comparative Example 2 is zinc borate tri-molecule. In other words, the highly dispersed flame-retardant masterbatch provided in the comparative example contains the following components by weight: Polyvinyl chloride: 6 parts, zinc borate triahydrate: 80 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.0 part, powdered calcium zinc stabilizer: 0.5 parts, zinc stearate: 1 part, polyethylene wax: 0.4 parts, polycaprolactone-modified nanocalcium carbonate: 2 parts.

[0123] The method for producing polycaprolactone-modified nanocalcium carbonate and the method for producing a highly dispersed flame-retardant masterbatch are the same as in Example 3.

[0124] Comparative Example 3 Comparative Example 3 differs from Example 3 in that the flame retardants in Comparative Example 3 are antimony trioxide and zinc borate 3.5 hydrate. In other words, the highly dispersed flame-retardant masterbatch provided in the comparative example contains the following components by weight: Polyvinyl chloride: 6 parts, antimony trioxide: 57 parts, zinc borate triahydrate: 23 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.0 part, powdered calcium zinc stabilizer: 0.5 parts, zinc stearate: 1 part, polyethylene wax: 0.4 parts, polycaprolactone-modified nanocalcium carbonate: 2 parts.

[0125] The method for producing polycaprolactone-modified nanocalcium carbonate and the method for producing a highly dispersed flame-retardant masterbatch are the same as in Example 3.

[0126] Comparative Example 4 Comparative Example 4 differs from Example 3 in that the flame retardants in Comparative Example 4 are antimony trioxide, zinc borate 3.5 hydrate, and DOPO. In other words, the highly dispersed flame-retardant masterbatch provided in the comparative example contains the following components by weight: Polyvinyl chloride: 6 parts, antimony trioxide: 34 parts, zinc borate triahydrate: 23 parts, DOPO: 23 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.0 part, powdered calcium zinc stabilizer: 0.5 parts, zinc stearate: 1 part, polyethylene wax: 0.4 parts, polycaprolactone-modified nanocalcium carbonate: 2 parts.

[0127] The method for producing polycaprolactone-modified nanocalcium carbonate and the method for producing a highly dispersed flame-retardant masterbatch are the same as in Example 3.

[0128] Comparative Example 5 Comparative Example 5 differs from Example 3 in that the flame retardants in Comparative Example 5 are antimony trioxide, zinc borate 3.5 hydrate, and MCA. In other words, the highly dispersed flame-retardant masterbatch provided in the comparative example contains the following components by weight: Polyvinyl chloride: 6 parts, antimony trioxide: 34 parts, zinc borate triahydrate: 23 parts, MCA: 23 parts, epoxidized soybean oil: 5 parts, BDP: 5 parts, liquid calcium zinc stabilizer: 1.0 part, powdered calcium zinc stabilizer: 0.5 parts, zinc stearate: 1 part, polyethylene wax: 0.4 parts, polycaprolactone-modified nanocalcium carbonate: 2 parts.

[0129] The method for producing polycaprolactone-modified nanocalcium carbonate and the method for producing a highly dispersed flame-retardant masterbatch are the same as in Example 3. JPEG0007869843000001.jpg107170JPEG0007869843000002.jpg183170

[0130] Performance testing 1. Flame retardant: (1) UL94 Vertical Combustion Test: Experiment A: 8g of each example and comparative example flame-retardant masterbatch was injection molded with 180g of polyvinyl chloride masterbatch to obtain samples with dimensions of 125mm x 13mm x 4mm. A vertical combustion test was performed in accordance with the UL94 standard, and the combustion grades were classified as V0, V1, V2, and none.

[0131] Experiment B: 5g of each example and comparative example flame-retardant masterbatch was injection molded with 180g of polyvinyl chloride masterbatch to obtain samples with dimensions of 125mm x 13mm x 4mm. A vertical combustion test was performed in accordance with the UL94 standard, and the combustion grades were classified as V0, V1, V2, and none.

[0132] (2) Limiting Oxygen Index (LOI): 8 g of each example and comparative example flame retardant masterbatch was injection molded with 180 g of polyvinyl chloride masterbatch to obtain a sample with dimensions of 120 mm × 10 mm × 4 mm. The minimum oxygen concentration, expressed as a volume percentage, that is just enough to maintain the combustion of the material in an oxygen-nitrogen mixed gas stream was obtained by measurement in accordance with the ASTMD2863 standard. See Table 4 for the results.

[0133] 2. Heat resistance: 8g of the flame-retardant masterbatch of Examples 3, 9-11 was injection molded with 100g of polyvinyl chloride masterbatch to obtain a specimen measuring 150mm x 150mm x 2mm. The specimen was sheared into two pieces, one of which was used as a reference sample and stored at room temperature. The other piece was subjected to a heat resistance test at 200±2℃ (20min), and the color difference between the test specimen and the light-shielded reference sample was expressed as ΔE. In the formula JPEG0007869843000003.jpg10170, ΔL represents the difference in brightness, Δa represents the difference in red-green intensity, and Δb represents the difference in yellow-blue intensity. A smaller ΔE value indicates that the two colors are closer together, meaning higher heat resistance. See Table 2 for the results.

[0134] 3. Migration Resistance: 8g of each example and comparative example flame-retardant masterbatch was injection-molded with 180g of polyvinyl chloride masterbatch. A 5cm x 5cm film was sheared from each and placed between two 7cm x 7cm black polyvinyl chloride flexible films. Using a smooth-surfaced press roll, the air between the black polyvinyl chloride flexible film and the experimental specimen was pushed out, ensuring that they bonded tightly. A pressure of 5kg was applied and the assembly was placed in an 80°C dryer for 24 hours. The test combination was removed, the black polyvinyl chloride flexible film was separated from the experimental specimen, and the assembly was cooled to room temperature. The migration grade of the masterbatch was determined by visually comparing the black area (edge ​​portion) of the black polyvinyl chloride flexible film that was not bonded to the experimental specimen with the colored area of ​​the black polyvinyl chloride flexible film that was bonded to the specimen. Grade 5 indicates no migration, and Grade 1 indicates significant migration. See Table 4 for the results.

[0135] 4. Lubricity: 8g of each of the flame-retardant masterbatches from Examples 3, 12-14 was injection molded with 100g of polyvinyl chloride masterbatch. Subsequently, the melt flow rate (MFR value) of the sample was measured using a melt flow rate tester at 190°C with a 5KG weight. This indicates that a higher MFR value indicates a higher lubrication effect. See Table 3 for the results. JPEG0007869843000004.jpg33170

[0136] As can be seen from Table 2, Example 9, which used a liquid calcium-zinc stabilizer, had a ΔE of 0.72 after high-temperature treatment, while Example 10, which used a powdered calcium-zinc stabilizer, had a high ΔE of 0.68 after high-temperature treatment. Mixing liquid and powdered calcium-zinc stabilizers helps improve the heat resistance of the material, so the ΔE of Examples 3 and 11 was lower than that of Examples 9 and 10. In particular, Example 3 had the lowest ΔE, indicating that the calcium-zinc stabilizer mixture used in Example 3 has higher thermal stability performance. JPEG0007869843000005.jpg38170

[0137] As can be seen from Table 3, in Example 12, a single zinc stearate was used as the lubricant, and in Example 13, a single polyethylene wax was used as the lubricant, resulting in relatively low MFR values ​​for the polymers. When zinc stearate and polyethylene wax are mixed and used as a lubricant, the lubrication effect is improved, as expressed by the increased MFR values ​​of the polymers, as shown in Examples 3 and 14. In particular, Example 3 shows a higher lubrication effect by using a more appropriate mass ratio of zinc stearate and polyethylene wax. JPEG0007869843000006.jpg124170

[0138] In the UL94 tests of Group A, because the flame retardant content in the samples is relatively high, the flame retardancy grades of the samples in Examples 1 to 15 can all reach V0, while the samples in Comparative Examples 1 to 5 can only reach V1. Even if the flame retardant content in the samples of Group B is reduced, the flame retardancy grades of the samples in Examples 3 to 6 and 9 to 15 can still reach V0, while the flame retardancy grades of the samples in Examples 1 to 2, 7 to 8 and Comparative Examples 3 to 5 are V1, and the flame retardancy grade of the sample in Comparative Examples 1 to 2 can only reach V2. From these experimental results, it is clear that when the flame retardant is antimony trioxide, zinc borate 3.5hydrate, and an organophosphorus-nitrogen complex, its flame retardancy performance is superior to that of antimony trioxide, zinc borate 3.5hydrate, or a mixture of both, and is superior to a mixed flame retardant consisting of antimony trioxide, zinc borate 3.5hydrate, and DOPO or MCA. Furthermore, when the organophosphorus-nitrogen complex is a mixture of DOPO and MCA, the resulting composite flame retardant of antimony trioxide, zinc borate triahydrate, DOPO, and MCA exhibits higher flame retardancy than composite flame retardants where the organophosphorus-nitrogen complex consists of ammonium polyphosphate or polyphosphate melamine. Additionally, if the composite flame retardant further contains aluminum hydroxide and / or magnesium hydroxide, the material exhibits even better flame retardancy.

[0139] Regarding the effect of the dispersant, the dispersant in Example 7 was unmodified nanocalcium carbonate, and the dispersant in Example 8 was also unmodified nanocalcium carbonate, with polycaprolactone added and directly mixed with all the raw materials. As a result, it was found that the dispersibility of Examples 7 and 8 was low, and small amounts of white dot-like material precipitated during the migration resistance test, indicating that the dispersibility of the flame retardant in polyvinyl chloride was low and the flame retardant performance was reduced. This shows that the selection of an appropriate dispersant is very important for the effective dispersion of the flame retardant and for ensuring effective flame retardancy.

[0140] Each aspect, example, and feature of the present invention is illustrative in all aspects and should be considered not to limit the invention, and the scope of the invention is limited solely by the claims. Those skilled in the art will be able to conceive of other embodiments, modifications, and uses without departing from the spirit and scope of the invention as required.

[0141] In the manufacturing method of the present invention, the order of each step is not limited to those listed, and variations in the order of each step, which can be made without creative effort by those skilled in the art, are also covered within the scope of the present invention. Furthermore, two or more steps or operations can be performed simultaneously.

[0142] Finally, it should be noted that the specific examples described herein are merely illustrative and do not limit the embodiments of the invention. Those skilled in the art can make various modifications, additions, or substitutions to the described examples, and it is not necessary, nor is it possible, to illustrate all embodiments. These obvious changes or variations, derived from the substantial spirit of the invention, still fall within the scope of protection of the invention, and any interpretation of them as additional limitations would be a breach of the spirit of the invention.

Claims

1. A highly dispersed flame retardant masterbatch comprising, by weight, 8 to 30 parts of a polymer that is one or two of polyvinyl chloride, PVC-vinyl acetate copolymer, 30 to 95 parts of a composite flame retardant comprising a mixture of antimony trioxide, borate, and an organophosphorus-nitrogen complex in a mass ratio of 1:(0.5 to 1.0):(0.5 to 1.0), 6 to 20 parts of a plasticizer, and 0.1 to 15 parts of an auxiliary agent, characterized in that the organophosphorus-nitrogen complex is one or more of a mixture of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and melamine cyanurate, melamine polyphosphate, and ammonium polyphosphate.

2. The highly dispersed flame retardant masterbatch according to claim 1, characterized in that the composite flame retardant comprises a mixture of antimony trioxide, a borate, 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, and melamine cyanurate in a mass ratio of 1:(0.5-1.0):(0.3-0.6):(0.2-0.4).

3. The highly dispersed flame retardant masterbatch according to claim 1, characterized in that the composite flame retardant comprises antimony trioxide, a borate, an organophosphorus-nitrogen complex, and a metal hydroxide.

4. The highly dispersed flame retardant masterbatch according to claim 1, characterized in that the composite flame retardant comprises antimony trioxide, a borate, 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, melamine cyanurate, and a metal hydroxide.

5. The mass of the metal hydroxide is 0.1 to 10 wt% of the total mass of the composite flame retardant. The highly dispersed flame-retardant masterbatch according to claim 3 or 4, characterized in that the metal hydroxide is aluminum hydroxide and / or magnesium hydroxide.

6. The borate is one or more metal salts of boric acid or metal salts of fluoroboric acid, and the metal is one or more of sodium, potassium, magnesium, barium, ammonium, calcium, manganese, nickel, copper, aluminum, zinc, cobalt, and zirconium. and / or, the highly dispersed flame-retardant masterbatch according to claim 1, characterized in that the plasticizer is one or more of pyromellitic acid ester plasticizers, trimelite plasticizers, phthalate plasticizers, terephthalate plasticizers, phosphate plasticizers, and epoxidized vegetable oils.

7. The borate is one or more of the following: calcium borate, cobalt borate, anhydrous zinc borate, zinc borate tri.5 hydrate, sodium orthoborate, sodium perborate, sodium metaborate, sodium tetraborate, ammonium metaborate, ammonium pentaborate, calcium metaborate, barium metaborate, barium tetraborate, potassium metaborate, potassium tetraborate, potassium pentaborate, magnesium orthoborate, magnesium metaborate, trimagnesium tetraborate, pentamagnesium tetraborate, potassium tetrafluoroborate, sodium tetrafluoroborate, ammonium tetrafluoroborate, zinc tetrafluoroborate, calcium tetrafluoroborate, magnesium tetrafluoroborate, and barium metaborate. and / or, the plasticizer is one or more of dioctyl phthalate, dinonyl phthalate, diisodecyl phthalate, diundecyl phthalate, didodecyl phthalate, ditridecyl phthalate, dioctyl terephthalate, tris(isopropylphenyl) phosphate, tetrahalogenated dialkyl phthalate, tris(2-chloroethyl) phosphate, bisphenol A bis(diphenyl phosphate), and epoxidized soybean oil, characterized in that the highly dispersed flame-retardant masterbatch according to claim 1.

8. The aforementioned auxiliary agent includes one or more dispersants, stabilizers, and lubricants. The aforementioned dispersant is polycaprolactone-modified nanocalcium carbonate. The aforementioned stabilizer is a liquid calcium-zinc stabilizer and a powdered calcium-zinc stabilizer. The highly dispersed flame-retardant masterbatch according to claim 1, characterized in that the lubricant comprises one or more of the following: a metal soap-based lubricant, a hydrocarbon-based lubricant, a fatty acid-based lubricant, and a fatty acid ester-based lubricant.

9. The auxiliary agent comprises a dispersant, a stabilizer, and a lubricant, and in the highly dispersed flame-retardant masterbatch, the amount of dispersant is 0.1 to 4 parts, the amount of stabilizer is 0.5 to 6.0 parts, and the amount of lubricant is 0.1 to 3 parts, characterized in that the highly dispersed flame-retardant masterbatch is as described in claim 1.

10. A method for producing a highly dispersed flame-retardant masterbatch according to claim 1, characterized by comprising weighing each component of a highly dispersed flame-retardant masterbatch, adding them to a mixing cylinder at 100 to 180°C and mixing for 5 to 50 minutes, transferring the mixture to a three-roll machine for polishing and dispersion, and then press-molding the polished and dispersed material using a two-roll machine and shearing it with a shearing machine to obtain a mochi-like highly dispersed flame-retardant masterbatch.

11. A method for producing a highly dispersed flame-retardant masterbatch according to claim 8, wherein the method for producing polycaprolactone-modified nanocalcium carbonate is: A method for producing a highly dispersed flame-retardant masterbatch, characterized by including the following steps: adding nanocalcium carbonate and polycaprolactone to a high-speed mixer and mixing them; raising the temperature to 70 to 100°C within 5 to 20 minutes; maintaining the temperature and continuing to stir for 5 to 60 minutes; discharging the mixture; and cooling to obtain polycaprolactone-modified nanocalcium carbonate.

12. The average particle size of nanocalcium carbonate is 10 to 999 nm. And / or, the mass of polycaprolactone is 0.5 to 15 wt% of the mass of nanocalcium carbonate. The method for producing a highly dispersed flame-retardant masterbatch according to claim 11, characterized in that the rotation speed of the high-speed mixer is 500 to 10,000 revolutions per minute.

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