CN111363367A - Low-temperature ceramic flame-retardant functional master batch and preparation method thereof - Google Patents
Low-temperature ceramic flame-retardant functional master batch and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a low-temperature ceramic flame-retardant functional master batch which comprises the following components in parts by mass: 10-25 parts of silicon rubber, 5-15 parts of silicone resin, 2-6 parts of aluminum hypophosphite, 2-10 parts of glass beads, 2-8 parts of montmorillonite, 10-25 parts of natural bone powder, 25-50 parts of synthetic ceramic bone powder, 1-2 parts of coupling agent, 1-3 parts of lubricant and 1-3 parts of dispersing agent. The invention also relates to a preparation method of the low-temperature ceramic flame-retardant functional master batch, which improves the dispersibility, increases the carbon forming rate and ensures that the carbon layer with the multi-dimensional stable structure has high precipitation rate and integrity rate. The flame-retardant master batch prepared by the invention can form a continuous compact ceramic oxygen-isolating layer under the low-temperature ceramic action when the material is attacked by flame, and has the characteristics of high efficiency and environmental protection.
Description
Technical Field
The invention belongs to the technical field of high polymer synthetic material composition functional master batches, and particularly relates to a low-temperature ceramic flame-retardant functional master batch and a preparation method thereof.
Background
The high polymer material is widely used in the industries of automobiles, electrical appliances, buildings and the like, so that the technical research on the flame-retardant master batch product is widely developed. The flame retardant solves the problem of dust pollution of the flame retardant through mother granulation, and solves the problems that the powdery flame retardant is low in flame retardant efficiency, needs various compounding, is difficult to disperse and has great influence on the mechanical property of a product when used in a form. The flame retardant improves the product stability and the production efficiency after the master batch granulation, so that the improvement of the material performance through the flame retardant master batch technology becomes necessary and trend for the development of the industry.
The material containing the flame-retardant master batch plays a flame-retardant protection role when encountering flame attack, and is realized by three principles:
1. the flame retardant forms a carbonization layer on the surface of the material to isolate oxygen transmission;
2. the heat is taken away by gasifying the fire retardant, and the surface temperature of the material is reduced;
3. the flame retardant interrupts the oxidation reaction of combustion.
The existing high-efficiency flame-retardant system represented by halogen and antimony has the problems of high smoke generation and environmental protection limitation of halogen; the phosphorus and nitrogen system has the problems of poor dispersion performance and high addition proportion, which affects the material performance; inorganic flame retardants such as magnesium and aluminum have low smoke generation but high addition rate and greatly reduce material properties. These drawbacks are also unavoidable even if the flame retardant improves the dispersion properties by masterbatch. Flame-retardant master batches developed by utilizing synthetic ceramic materials and technologies are also reported, but the problems of incompact structure, high breakage rate, poor coverage and the like of a ceramic formed carbon layer exist.
Disclosure of Invention
Compared with halogen, nitrogen, phosphorus or inorganic magnesium, aluminum and other series flame-retardant master batch products, the flame-retardant master batch obtained by the invention has the advantages of low smoke, no halogen, high flame-retardant grade and high smoke toxicity reaching the highest safety standard ZA1 grade of high polymer materials.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a low-temperature ceramic nonflammable functional master batch which comprises, by mass, 10-25 parts of silicone rubber, 5-15 parts of silicone resin, 2-6 parts of aluminum hypophosphite, 2-10 parts of glass beads, 2-8 parts of montmorillonite, 10-25 parts of natural bone meal, 25-50 parts of synthetic ceramic bone meal, 1-2 parts of a coupling agent, 1-3 parts of a lubricant and 1-3 parts of a dispersing agent.
Further, the silicone rubber is a mixture of dimethyl silicone rubber and methyl vinyl silicone rubber, and the mass ratio of the dimethyl silicone rubber to the methyl vinyl silicone rubber is 1: 1-3.
The silicone resin is powdery silicone resin, the silicon content is 70-99%, and the particle size is less than 5 um.
Further, the main chains of the dimethyl silicon rubber and the methyl vinyl silicon rubber are both composed of silicon and oxygen atoms alternately, and two or more than two organic groups are connected to the silicon atoms.
Further, the aluminum hypophosphite is diethyl aluminum hypophosphite or phenyl aluminum hypophosphite.
The particle size of the montmorillonite is less than 3 um;
the natural bone powder is bone charcoal powder prepared from ox bone and horse bone, and the particle size of the bone charcoal powder is D50 < 5 um;
the synthetic ceramic bone powder is tricalcium phosphate with the particle size of less than 5 um;
the coupling agent is a silane coupling agent and is of a structure type of RSiX3, an active R functional group of the coupling agent has affinity or reaction capability with the silicone rubber, and at least one group can form a chemical bond with an organic group of a silicone rubber main chain;
the dispersing agent is vinyl acetate copolymer wax;
the lubricant is Ethylene Bis Stearamide (EBS);
the particle size of the glass beads is less than 3 um.
The invention also provides a preparation method of the low-temperature ceramic flame-retardant functional master batch, which comprises the following steps:
(1) weighing the components according to a preset proportion;
(2) putting the aluminum hypophosphite, the glass beads, the montmorillonite, the natural bone meal and the synthetic ceramic bone meal weighed in the step (1) into a stirrer, stirring at a high speed for 15-30 minutes at the temperature of 100-120 ℃, then putting the coupling agent weighed in the step (1) into the stirrer, and continuously stirring at a high speed for 5-15 minutes; then, sequentially adding the silicon rubber, the silicone resin, the lubricant and the dispersant weighed in the step (1), stirring at a low speed for 10-15 minutes, and discharging for later use;
(3) and (3) putting the product obtained in the step (2) into an internal mixer for banburying, and then completing dispersion and fusion granulation in a double-screw extruder, wherein the feeding mode is forced two-way feeding, and one way is realized by forced side feeding.
Further, in the step (2), the rotation speed of the high-speed stirring is 1200-; the rotating speed of the low-speed stirring is 50-120 r/min.
Further, in the step (3), the product obtained in the step (2) is put into an internal mixer for banburying, and then is put into a parallel double-screw extruder for melting granulation, the length-diameter ratio of the screws is 40-46:1, and the two-way feeding is realized by forced side feeding, wherein the extrusion granulation temperature is 165-.
The invention has the following positive effects:
(1) the low-temperature ceramic flame-retardant functional master batch disclosed by the invention has the characteristics of no halogen, environmental protection, no dripping, low smoke rate and low smoke toxicity, and the smoke index effect can meet the highest flame-retardant safety standard ZA1 grade requirement of a high polymer material. The master batch can overcome the defects of brominated, nitrogen, phosphorus, inorganic flame retardants and flame-retardant master batches, and has the advantages of environmental protection, high efficiency and low smoke integration;
(2) the functional master batch can rapidly contract and crust at the low temperature of 300-400 ℃ when a material product is attacked by flame, has the characteristics of ablation resistance, smooth surface layer and low thermal conductivity, and flame retardant components wrapped between the silicon rubber and the silicon rubber form ceramic-like substances at the same time, so that oxygen can be isolated and combustion reaction can be blocked, the material can reach a higher flame retardant level, namely a flame retardant level, and the completeness of the product is ensured;
(3) the powder material in the technical components has the characteristics of extremely small particle size and difficult dispersion of particles, so that the coupling agent containing the RSiX3 structure is adopted for modification, activation and coating treatment, functional groups containing active R have affinity or reaction capacity with silicone rubber, and at least one group can form a chemical bond with a side chain organic group of the silicone rubber, so that tiny particles can be uniformly distributed in a multidimensional network structure, and the effect of good dispersion is improved and achieved. The crosslinking and dispersion are accomplished in the extrusion of internal mixing and melting;
(4) the technology of the invention utilizes natural bone powder and synthetic ceramic bone powder prepared from horses, cattle and the like as main carbon forming agents, and the combined application of synergistic components of glass beads, montmorillonite and aluminum hypophosphite increases the carbon forming amount and improves the stability of the carbon forming layer. The silicone rubber and the silicone resin are used as carrier dispersion materials and have high carbon forming property;
(5) the technology completes plasticization and melt extrusion through banburying and a double-screw extruder, and the high-concentration master batch material is prepared by spray hot-cutting grinding surface molding, so that the technology is simple and the production efficiency is high; the prepared flame retardant master batch has the characteristics of compact structure of a carbon forming layer, no breakage and good flowing coverage, has a high-efficiency flame retardant function, and overcomes and makes up the defects of other flame retardant systems.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
To better illustrate the invention, further examples are given below:
example 1
The embodiment provides a low-temperature ceramic flame-retardant functional master batch, which comprises the following components:
5kg of dimethyl silicone rubber, 10kg of methyl vinyl silicone rubber, 8kg of silicone resin, 5kg of diethyl aluminum hypophosphite, 2.5kg of glass microsphere, 2kg of montmorillonite, 20 kg of natural bone meal, 42 kg of synthetic ceramic bone meal, 1.5kg of coupling agent, 2kg of dispersing agent EVA wax and 2kg of lubricating agent EBS.
Wherein the silicone resin is powdery silicone resin, the silicon content is 70-99%, and the particle size is less than 5 um.
The main chains of the dimethyl silicon rubber and the methyl vinyl silicon rubber are both composed of silicon and oxygen atoms alternately, and the silicon atoms are connected with two or more than two organic groups.
The particle size of the montmorillonite is less than 3 um;
the natural bone powder is bone charcoal powder prepared from ox bone and horse bone, and the particle size of the bone charcoal powder is D50 < 5 um;
the synthetic ceramic bone powder is tricalcium phosphate with particle size less than 5 um.
The coupling agent is a silane coupling agent and is of a structure type of RSiX3, an active R functional group of the coupling agent has affinity or reaction capability with the silicone rubber, and at least one group can form a chemical bond with an organic group of a silicone rubber main chain;
the particle size of the glass beads is less than 3 um.
In the formula, dimethyl silicone rubber, methyl vinyl silicone rubber and silicone resin are used as carrier materials, wherein the flame retardant is diethyl aluminum hypophosphite, glass beads, montmorillonite, natural bone powder and synthetic ceramic bone powder, and the auxiliary agents are coupling agents, dispersing agents and lubricating agents. In the embodiment, the concentration proportion of the flame retardant component is 71.5%.
The embodiment of the invention comprises the following process steps:
(1) weighing the components according to a preset proportion;
(2) putting the weighed diethyl aluminum hypophosphite, the glass beads, the montmorillonite, the natural bone meal and the synthetic ceramic bone meal into a stirrer. Stirring at 120 ℃ for 30 minutes at a high speed, then adding the coupling agent components weighed in the step (1), continuously stirring at the high speed for 15 minutes, then sequentially adding the dimethyl silicone rubber, the methyl vinyl silicone rubber, the silicone resin, the lubricant and the dispersant components weighed in the step (1), and stirring at a low speed for 15 minutes;
in the step, the rotating speed of high-speed stirring is 1200 revolutions per minute; the rotating speed of the low-speed stirring is 100 revolutions per minute
(3) And (3) putting the product obtained in the step (2) into an internal mixer for internal mixing, and putting the product into a double-screw extruder to complete dispersion and melting granulation. The feeding mode is forced two-way feeding, wherein one way is realized by forced side feeding, the model of the double-screw extruder is 72 type parallel double screws, the length-diameter ratio is 46:1, the extrusion granulation temperature is 160-.
The flame-retardant master batch prepared finally in the step 1 and the engineering plastic PBT are mixed and injected, the adding proportion is 80:20, the testing limit oxygen index is 31 percent, and the flame retardant test of UL-94V0 grade (1.6 mm) can be passed; the flame-retardant master batch prepared in the step 1 and polypropylene are mixed and injected, the addition mass ratio is 75:25, and the test limit oxygen index is 32.5 percent, so that the flame retardant test of UL-94V0 grade (1.6 mm) is passed.
Example 2
The embodiment provides a low-temperature ceramic flame-retardant functional master batch, which comprises the following components:
10kg of dimethyl silicone rubber, 15kg of methyl vinyl silicone rubber, 12kg of silicone resin, 2kg of diethyl aluminum hypophosphite, 2kg of glass microsphere, 5kg of montmorillonite, 16kg of natural bone meal, 32 kg of synthetic ceramic bone meal, 2kg of coupling agent, 2.5kg of dispersing agent EVA wax and 1.5kg of lubricating agent EBS.
Wherein the silicone resin is powdery silicone resin, the silicon content is 70-99%, and the particle size is less than 5 um.
The main chains of the dimethyl silicon rubber and the methyl vinyl silicon rubber are both composed of silicon and oxygen atoms alternately, and the silicon atoms are connected with two or more than two organic groups.
The particle size of the montmorillonite is less than 3 um;
the natural bone powder is bone charcoal powder prepared from ox bone and horse bone, and the particle size of the bone charcoal powder is D50 < 5 um;
the synthetic ceramic bone powder is tricalcium phosphate with particle size less than 5 um.
The coupling agent is a silane coupling agent and is of a structure type of RSiX3, an active R functional group of the coupling agent has affinity or reaction capability with the silicone rubber, and at least one group can form a chemical bond with an organic group of a silicone rubber main chain;
the particle size of the glass beads is less than 3 um.
In the formula, the dimethyl silicone rubber, the methyl vinyl silicone rubber and the silicone resin are used as carrier materials, and the rest components form a flame retardant and an auxiliary agent component, wherein the concentration ratio of the flame retardant component in the embodiment is 57%.
The embodiment of the invention comprises the following process steps:
(1) weighing the components according to a preset proportion;
(2) putting the weighed diethyl aluminum hypophosphite, the glass beads, the montmorillonite, the natural bone meal and the synthetic ceramic bone meal into a stirrer. Stirring at 120 ℃ for 30 minutes at a high speed, then adding the coupling agent component weighed in the step (1), continuously stirring at the high speed for 15 minutes, then sequentially adding dimethyl silicone rubber, methyl vinyl silicone rubber, silicone resin, a lubricant and a dispersant component, stirring at a low speed for 10 minutes, and discharging for later use.
In the step, the rotating speed of high-speed stirring is 1300 revolutions per minute; the rotation speed of the low speed stirring is 80 rpm.
(3) And (3) putting the product obtained in the step (2) into an internal mixer for internal mixing, then putting the obtained product into a double-screw extruder to complete dispersion and fusion granulation, wherein the feeding mode is forced double-way feeding, one way of feeding is realized through forced side feeding, the model of the double-screw extruder is 72 type parallel double screws, the length-diameter ratio is 40:1, the extrusion granulation temperature is 160-.
The flame-retardant master batch prepared finally in the step 2 is mixed with engineering plastic PBT for injection molding, the adding ratio is 80:20, the measured limit oxygen index is 28.6%, and the flame retardant test of UL-94V0 grade (1.6 mm) is passed.
The flame-retardant master batch prepared finally in the step 2 is mixed with polypropylene for injection molding, the addition mass ratio is 75:25, the measured limit oxygen index is 29.7%, and the flame retardant test of UL-94V0 grade (1.6 mm) is passed.
Example 3
The embodiment provides a low-temperature ceramic flame-retardant functional master batch, which comprises the following components:
10kg of dimethyl silicone rubber, 12kg of methyl vinyl rubber, 15kg of silicone resin, 4kg of diethyl aluminum hypophosphite, 2kg of glass microsphere, 2kg of montmorillonite, 17kg of natural bone meal, 34 kg of synthetic ceramic bone meal, 1.5kg of coupling agent, 1.5kg of dispersing agent EVA wax and lubricant EBS1 kg.
Wherein the silicone resin is powdery silicone resin, the silicon content is 70-99%, and the particle size is less than 5 um.
The main chains of the dimethyl silicon rubber and the methyl vinyl silicon rubber are both composed of silicon and oxygen atoms alternately, and the silicon atoms are connected with two or more than two organic groups.
The particle size of the montmorillonite is less than 3 um;
the natural bone powder is bone charcoal powder prepared from ox bone and horse bone, and the particle size of the bone charcoal powder is D50 < 5 um;
the synthetic ceramic bone powder is tricalcium phosphate with particle size less than 5 um.
The coupling agent is a silane coupling agent and is of a structure type of RSiX3, an active R functional group of the coupling agent has affinity or reaction capability with the silicone rubber, and at least one group can form a chemical bond with an organic group of a silicone rubber main chain;
the particle size of the glass beads is less than 3 um.
In the formula, the dimethyl silicone rubber, the methyl vinyl silicone rubber and the silicone resin are used as carrier materials, and the rest components form a flame retardant and an auxiliary agent component, wherein the concentration ratio of the flame retardant component is 59 percent in the embodiment.
The embodiment of the invention also provides a preparation method of the low-temperature ceramic flame-retardant functional master batch, which comprises the following process steps:
(1) weighing the components according to a preset proportion;
(2) putting the weighed diethyl aluminum hypophosphite, the glass beads, the montmorillonite, the natural bone meal and the synthetic ceramic bone meal into a stirrer. Stirring at 110 ℃ for 20 minutes at a high speed, then adding the coupling agent components weighed in the step (1), continuously stirring at the high speed for 12 minutes, then sequentially adding the dimethyl silicone rubber, the methyl vinyl silicon, the silicone resin, the lubricant and the dispersant components weighed in the step (1), stirring at a low speed for 10 minutes, and discharging for later use.
In the step, the rotating speed of high-speed stirring is 1500 revolutions per minute; the rotation speed of the low-speed stirring is 110 rpm.
(3) And (3) putting the product obtained in the step (2) into an internal mixer for internal mixing, then putting the obtained product into a double-screw extruder to complete dispersion and fusion granulation, wherein the feeding mode is forced double-way feeding, one way of feeding is realized through forced side feeding, the type of the double-screw extruder is 72 type parallel double screws, the length-diameter ratio is 44:1, the extrusion granulation temperature is 165-185 ℃, and the product is formed by a ground spray forced cooling granulation process. Form the functional masterbatch of example 2.
The flame-retardant master batch prepared finally in the step 3 is mixed with engineering plastic PBT for injection molding, the adding proportion is 80:20, the limiting oxygen index is 28.9 percent, and the flame retardant test of UL-94V0 (1.6 mm) is passed.
The flame-retardant master batch prepared finally in the step 3 is mixed with polypropylene for injection molding, the addition mass ratio is 75:25, the measured limit oxygen index is 29.8 percent, and the flame-retardant test of UL-94V0 grade (1.6 mm) is passed.
Example 4
The embodiment provides a low-temperature ceramic flame-retardant functional master batch, which comprises the following components:
5kg of dimethyl silicone rubber, 5kg of methyl vinyl silicone rubber, 5kg of silicone resin, 4kg of phenyl aluminum hypophosphite, 10g of glass microsphere, 5kg of montmorillonite, 10kg of natural bone meal, 50kg of synthetic ceramic bone meal, 1kg of coupling agent, 3kg of dispersing agent EVA wax and lubricant EBS2 kg.
Wherein the silicone resin is powdery silicone resin, the silicon content is 70-99%, and the particle size is less than 5 um.
The main chains of the dimethyl silicon rubber and the methyl vinyl silicon rubber are both composed of silicon and oxygen atoms alternately, and the silicon atoms are connected with two or more than two organic groups.
The particle size of the montmorillonite is less than 3 um;
the natural bone powder is bone charcoal powder prepared from ox bone and horse bone, and the particle size of the bone charcoal powder is D50 < 5 um;
the synthetic ceramic bone powder is tricalcium phosphate with particle size less than 5 um.
The coupling agent is a silane coupling agent and is of a structure type of RSiX3, an active R functional group of the coupling agent has affinity or reaction capability with the silicone rubber, and at least one group can form a chemical bond with an organic group of a silicone rubber main chain;
the particle size of the glass beads is less than 3 um.
In the formula, dimethyl silicone rubber, methyl vinyl silicone rubber and silicone resin are used as carrier materials, the flame retardant is phenyl aluminum hypophosphite, glass beads, montmorillonite, natural bone powder and synthetic ceramic bone powder, and the auxiliary agent is a coupling agent, a dispersing agent and a lubricating agent. In the embodiment, the concentration proportion of the flame retardant component is 79%.
The present example follows the following process steps:
(1) weighing the components according to a preset proportion;
(2) and putting the weighed phenyl aluminium hypophosphite, the glass beads, the montmorillonite, the natural bone meal and the synthetic ceramic bone meal into a stirrer. Stirring at 100 ℃ for 15 minutes at a high speed, then adding the coupling agent components weighed in the step (1), continuously stirring at the high speed for 15 minutes, then sequentially adding dimethyl silicone rubber, methyl vinyl silicone, silicone resin, a lubricant and a dispersant component, stirring at a low speed for 12 minutes, and discharging for later use; in the step, the rotating speed of high-speed stirring is 1500 revolutions per minute; the rotating speed of the low-speed stirring is 50 revolutions per minute;
(3) and (3) putting the product obtained in the step (2) into an internal mixer for internal mixing, putting the obtained product into a double-screw extruder to complete dispersion and fusion granulation, wherein the feeding mode is forced double-path feeding, one path of feeding is realized by forced side feeding, the model of the double-screw extruder is 72 type parallel double screws, the length-diameter ratio is 41:1, the extrusion granulation temperature is 170-.
The flame-retardant master batch prepared finally in the step 4 is mixed with engineering plastic PBT for injection molding, the addition mass ratio is 80:20, the measured limit oxygen index is 32.2%, and the flame-retardant test of UL-94V0 (1.6 mm) grade is passed.
The flame-retardant master batch prepared finally in the step 4 is mixed with polypropylene for injection molding, the addition mass ratio is 75:25, the measured limit oxygen index is 32.7%, and the flame-retardant test of UL-94V0 (1.6 mm) grade is passed.
Example 5
The embodiment provides a low-temperature ceramic flame-retardant functional master batch, which comprises the following components:
5kg of dimethyl silicone rubber, 15kg of methyl vinyl silicon, 5kg of silicone resin, 6kg of phenyl aluminum hypophosphite, 6kg of glass microsphere, 3kg of montmorillonite, 25kg of natural bone meal, 30kg of synthetic ceramic bone meal, 1.5kg of coupling agent, 1kg of dispersing agent EVA wax and 2.5kg of lubricating agent EBS.
Wherein the silicone resin is powdery silicone resin, the silicon content is 70-99%, and the particle size is less than 5 um.
The main chains of the dimethyl silicon rubber and the methyl vinyl silicon rubber are both composed of silicon and oxygen atoms alternately, and the silicon atoms are connected with two or more than two organic groups.
The particle size of the montmorillonite is less than 3 um;
the natural bone powder is bone charcoal powder prepared from ox bone and horse bone, and the particle size of the bone charcoal powder is D50 < 5 um;
the synthetic ceramic bone powder is tricalcium phosphate with particle size less than 5 um.
The coupling agent is a silane coupling agent and is of a structure type of RSiX3, an active R functional group of the coupling agent has affinity or reaction capability with the silicone rubber, and at least one group can form a chemical bond with an organic group of a silicone rubber main chain;
the particle size of the glass beads is less than 3 um.
In the formula of the functional master batch, dimethyl silicone rubber, methyl vinyl silicone rubber and silicone resin are used as carrier materials, and the other components form a flame retardant and an auxiliary agent component, wherein the flame retardant is phenyl aluminium hypophosphite, glass beads, montmorillonite, natural bone powder and synthetic ceramic bone powder, and the auxiliary agent is a coupling agent, a dispersing agent and a lubricating agent. In this example, the concentration ratio of the flame retardant component is 70%.
The embodiment of the invention also provides a preparation method of the low-temperature ceramic flame-retardant functional master batch, which comprises the following process steps:
(1) weighing the components according to a preset proportion;
(2) and putting the weighed phenyl aluminium hypophosphite, the glass beads, the montmorillonite, the natural bone meal and the synthetic ceramic bone meal into a stirrer. Stirring at 110 ℃ for 20 minutes at a high speed, then adding the coupling agent components weighed in the step (1), continuously stirring at the high speed for 5 minutes, then sequentially adding the dimethyl silicone rubber, methyl vinyl silicon, silicone resin, lubricant and dispersant components weighed in the step (1), stirring at a low speed for 10 minutes, and discharging for later use;
in the step, the rotating speed of high-speed stirring is 1300 revolutions per minute; the rotating speed of the low-speed stirring is 120 revolutions per minute
(3) And (3) putting the product obtained in the step (2) into an internal mixer for internal mixing, putting the obtained product into a double-screw extruder to complete dispersion and melting granulation, wherein the feeding mode is forced double-path feeding, one path of feeding is realized by forced side feeding, the model of the double-screw extruder is 72 type parallel double screws, the length-diameter ratio is 42:1, the extrusion granulation temperature is 175-.
The flame-retardant master batch prepared finally in the step 4 is mixed with engineering plastic PBT for injection molding, the addition mass ratio is 80:20, the measured limit oxygen index is 29.9%, and the flame retardant test of UL-94V0 grade (1.6 mm) is passed.
The flame-retardant master batch prepared finally in the step 4 is mixed with polypropylene for injection molding, the addition mass ratio is 75:25, the measured limit oxygen index is 31.2%, and the flame-retardant test of UL-94V0 (1.6 mm) grade is passed.
Example 6
The embodiment provides a low-temperature ceramic flame-retardant functional master batch, which comprises the following components:
5kg of dimethyl silicone rubber, 12kg of methyl vinyl silicon, 5kg of silicone resin, 6kg of phenyl aluminum hypophosphite, 6kg of glass microsphere, 8kg of montmorillonite, 25kg of natural bone meal, 25kg of synthetic ceramic bone meal, 1.5kg of coupling agent, 1kg of dispersing agent EVA wax and lubricant EBS3 kg.
Wherein the silicone resin is powdery silicone resin, the silicon content is 70-99%, and the particle size is less than 5 um.
The main chains of the dimethyl silicon rubber and the methyl vinyl silicon rubber are both composed of silicon and oxygen atoms alternately, and the silicon atoms are connected with two or more than two organic groups.
The particle size of the montmorillonite is less than 3 um;
the natural bone powder is bone charcoal powder prepared from ox bone and horse bone, and the particle size of the bone charcoal powder is D50 < 5 um;
the synthetic ceramic bone powder is tricalcium phosphate with particle size less than 5 um.
The coupling agent is a silane coupling agent and is of a structure type of RSiX3, an active R functional group of the coupling agent has affinity or reaction capability with the silicone rubber, and at least one group can form a chemical bond with an organic group of a silicone rubber main chain;
the particle size of the glass beads is less than 3 um.
In the formula of the functional master batch, dimethyl silicone rubber, methyl vinyl silicone rubber and silicone resin are used as carrier materials, and the other components form a flame retardant and an auxiliary agent component, wherein the flame retardant is phenyl aluminium hypophosphite, glass beads, montmorillonite, natural bone powder and synthetic ceramic bone powder, and the auxiliary agent is a coupling agent, a dispersing agent and a lubricating agent. In this embodiment, the concentration ratio of the flame retardant component is 72%.
The embodiment of the invention also provides a preparation method of the low-temperature ceramic flame-retardant functional master batch, which comprises the following process steps:
(1) weighing the components according to a preset proportion;
(2) and putting the weighed phenyl aluminium hypophosphite, the glass beads, the montmorillonite, the natural bone meal and the synthetic ceramic bone meal into a stirrer. Stirring at 110 ℃ for 20 minutes at a high speed, then adding the coupling agent components weighed in the step (1), continuously stirring at the high speed for 5 minutes, then sequentially adding the dimethyl silicone rubber, methyl vinyl silicon, silicone resin, lubricant and dispersant components weighed in the step (1), stirring at a low speed for 10 minutes, and discharging for later use;
in the step, the rotating speed of high-speed stirring is 1300 revolutions per minute; the rotating speed of the low-speed stirring is 120 revolutions per minute
(4) And (3) putting the product obtained in the step (2) into an internal mixer for internal mixing, putting the obtained product into a double-screw extruder to complete dispersion and fusion granulation, wherein the feeding mode is forced double-path feeding, one path of feeding is realized by forced side feeding, the model of the double-screw extruder is 72 type parallel double screws, the length-diameter ratio is 41:1, the extrusion granulation temperature is 165-195 ℃, and the product is prepared and formed by adopting a ground spray forced cooling granulation process.
The flame-retardant master batch prepared finally in the step 4 is mixed with engineering plastic PBT for injection molding, the addition mass ratio is 80:20, the measured limit oxygen index is 29.9%, and the flame retardant test of UL-94V0 grade (1.6 mm) is passed.
The flame-retardant master batch prepared finally in the step 4 is mixed with polypropylene for injection molding, the addition mass ratio is 75:25, the measured limit oxygen index is 31.2%, and the flame-retardant test of UL-94V0 (1.6 mm) grade is passed.
In conclusion, the invention utilizes the characteristic that natural animal bone charcoal powder contains about 30 percent of calcium and 15 percent of phosphorus, compounds synthetic ceramic powder as a main carbon forming agent, and synergistically increases the carbon forming quantity and the carbon forming efficiency through aluminum hypophosphite, glass beads and montmorillonite to prepare the high-efficiency and environment-friendly flame retardant functional master batch.
Comparative flame retardancy test example
1. Mixing the flame-retardant master batch prepared in the example 1 and Beijing Yanshan petrochemical polypropylene with the model number of K8303, performing injection molding according to the proportion of 75:25 to obtain a sample strip with the thickness of 1.6mm, and performing a comparative flame-retardant test to form a comparative example 1;
2. mixing flame retardant master batches containing piperazine pyrophosphate and melamine (produced by Shijiazhuang Jindi chemical Co., Ltd., content concentration of 82%) and Beijing Yanshan petrochemical polypropylene with the model number of K8303, and performing a comparative flame retardance test by mixing and injection molding according to a ratio of 75:25 to obtain a sample strip with the thickness of 1.6mm to form a comparative example 2;
3. mixing and injection molding flame-retardant master batches containing magnesium hydroxide and zinc borate (85% concentration, produced by Shijiazhuang Jindi chemical Co., Ltd.) and Beijing Yanshan petrochemical polypropylene with the model number of K8303 according to a ratio of 45:55 to obtain a sample strip with the thickness of 1.6mm, and performing a comparative flame-retardant test to form a comparative example 3;
4. a flame-retardant master batch (85% concentration, produced by Shijiazhuang Jindi chemical Co., Ltd.) containing decabromodiphenylethane and antimony trioxide and Beijing Yanshan petrochemical polypropylene type K8303 were mixed in a ratio of 75:25 and injection-molded into a 1.6mm sample strip, and a comparative flame-retardant test was performed to form comparative example 4.
The comparison results are shown in Table 1
TABLE 1
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A low-temperature ceramic flame-retardant functional master batch and a preparation method thereof are characterized in that: the silicon rubber comprises, by mass, 10-25 parts of silicon rubber, 5-15 parts of silicone resin, 2-6 parts of aluminum hypophosphite, 2-10 parts of glass microspheres, 2-8 parts of montmorillonite, 10-25 parts of natural bone powder, 25-50 parts of synthetic ceramic bone powder, 1-2 parts of a coupling agent, 1-3 parts of a lubricant and 1-3 parts of a dispersing agent.
2. The low-temperature ceramic fire-retardant functional master batch according to claim 1, characterized in that: the silicone rubber is a mixture of dimethyl silicone rubber and methyl vinyl silicone rubber, and the mass ratio of the dimethyl silicone rubber to the methyl vinyl silicone rubber is 1: 1-3;
the silicone resin is powdery silicone resin, the silicon content is 70-99%, and the particle size is less than 5 um.
3. The low-temperature ceramic fire-retardant functional master batch according to claim 2, characterized in that: the main chains of the dimethyl silicon rubber and the methyl vinyl silicon rubber are both composed of silicon and oxygen atoms alternately, and the silicon atoms are connected with two or more than two organic groups.
4. The low-temperature ceramic fire-retardant functional master batch according to claim 1, characterized in that: the aluminum hypophosphite is diethyl aluminum hypophosphite or phenyl aluminum hypophosphite;
the particle size of the montmorillonite is less than 3 um;
the natural bone powder is bone charcoal powder prepared from ox bone and horse bone, and the particle size of the bone charcoal powder is D50 < 5 um;
the synthetic ceramic bone powder is tricalcium phosphate with the particle size of less than 5 um;
the coupling agent is a silane coupling agent and is of a structure type of RSiX3, an active R functional group of the coupling agent has affinity or reaction capability with the silicone rubber, and at least one group can form a chemical bond with an organic group of a silicone rubber main chain;
the dispersing agent is vinyl acetate copolymer wax;
the lubricant is Ethylene Bis Stearamide (EBS);
the particle size of the glass beads is less than 3 um.
5. The preparation method of the low-temperature ceramic flame-retardant functional master batch is characterized by comprising the following steps of:
(1) weighing the components according to a preset proportion;
(2) putting the aluminum hypophosphite, the glass beads, the montmorillonite, the natural bone meal and the synthetic ceramic bone meal weighed in the step (1) into a stirrer, stirring at a high speed for 15-30 minutes at the temperature of 100-120 ℃, then putting the coupling agent weighed in the step (1) into the stirrer, and continuously stirring at a high speed for 5-15 minutes; then, sequentially adding the silicon rubber, the silicone resin, the lubricant and the dispersant weighed in the step (1), stirring at a low speed for 10-15 minutes, and discharging for later use;
(3) and (3) putting the product obtained in the step (2) into an internal mixer for banburying, and then completing dispersion and fusion granulation in a double-screw extruder, wherein the feeding mode is forced two-way feeding, and one way is realized by forced side feeding.
6. The method of claim 5, wherein: in the step (2), the rotation speed of the high-speed stirring is 1200 and 1500 revolutions per minute; the rotating speed of the low-speed stirring is 50-120 r/min.
7. The method of claim 5, wherein: and (3) putting the product obtained in the step (2) into an internal mixer for banburying, then putting the banbury mixer into a parallel double-screw extruder for melting granulation, wherein the length-diameter ratio of screws is 40-46:1, and the double-way feeding is realized by forced side feeding, the extrusion granulation temperature is 165-195 ℃, and the ground spray forced cooling granulation process is adopted for preparation and molding.
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