CN109517259B - High-efficiency flame-retardant antibacterial functional master batch for direct injection molding of polypropylene and preparation method thereof - Google Patents
High-efficiency flame-retardant antibacterial functional master batch for direct injection molding of polypropylene and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of plastic modification and processing, and particularly relates to a high-efficiency flame-retardant antibacterial master batch which can be directly applied to injection molding processing of polypropylene products and a preparation method thereof; the functional master batch is formed by combining A master batch and B master batch, wherein the A master batch comprises the following components in percentage by mass: 6.0-10.0 wt.% of silver-zinc-loaded inorganic antibacterial agent, 50.0-70.0 wt.% of filler, 18.0-38.0 wt.% of elastic ionomer, 0.5-1.0 wt.% of dispersant and 0.5-0.1 wt.% of lubricant; compared with the traditional plastic functional master batch, the functional master batch prepared by the invention avoids the mutual loss of modification efficiency caused by the mutual reaction of silver, zinc ions and bromine ions under the direct strong shearing action of the double screws of the silver-loaded zinc inorganic antibacterial agent and the brominated flame retardant, and obviously improves the modification efficiency of the silver-loaded zinc inorganic antibacterial agent and the brominated flame retardant; the master batch has the characteristics of easy dispersion and easy processing, can be simply mixed with polypropylene resin according to the proportion and then is subjected to injection molding, and obtains excellent modification effect.
Description
Technical Field
The invention belongs to the technical field of plastic modification and processing, and particularly relates to a high-efficiency flame-retardant antibacterial master batch capable of being directly applied to injection molding processing of polypropylene products and a preparation method thereof.
Background
The method adopts a double-screw extruder to carry out melt blending, which is a traditional method for carrying out plastic modification, and utilizes the high-efficiency and excellent mixing efficiency of a co-rotating double-screw extruder to carry out continuous melt blending extrusion granulation on thermoplastic and various modification additives, and the prepared special modification material is used for injection or extrusion processing molding of various products again. The technical route not only effectively improves the physical and mechanical properties of the plastic product, such as strength, toughness, rigidity, creep resistance, bending resistance and the like, but also can endow the plastic product with special physical and chemical effects of flame retardance, electric conduction, heat conduction, magnetic conduction, static resistance, bacteria resistance and the like. Although the technical way occupies the mainstream position in the current plastic modification processing field, in the implementation process of the technology, all matrix resins and modification additives must be subjected to two melting processing thermal histories of twin-screw extrusion and injection molding, polymer molecular chains and related modification additives can be degraded to different degrees, and the final long-term service life of a plastic product is shortened. This route also increases the processing cycle and energy consumption of the modified plastics, contrary to the current basic concept of green sustainable industrial development. In addition, the modification additives of different shapes and different material qualities have great differences in processing equipment and processing technology, for example, a double-screw extruder can be used for processing to exert high-temperature and high-shear effects and exert modification effects such as strengthening and toughening to the maximum extent; by utilizing the low-temperature and long-time kneading effect of the internal mixer, various additives such as a temperature-resistant additive, a low-melting-point additive, low-bulk-density hard-feeding powder, an easy-water-absorption additive, a liquid and colloid additive, a whisker and the like can be fully mixed and uniformly dispersed, but the processing effect cannot be realized by adopting a double-screw extruder for melt extrusion and blending.
The mode of adopting plastic functional master batches to prepare modified plastics is an important measure in the development process of the current plastic modification technical field. The prepared functional master batch containing the high-concentration modified additive and the plastic raw material are subjected to melt blending and extrusion granulation through a double-screw extruder or an internal mixer, so that the dispersibility of the additive in a matrix can be effectively improved, a more excellent modification effect can be obtained, the dust pollution of a processing workshop can be reduced, and the method is one of important ways for realizing green processing of modified plastics. With the rapid development of the functional design and preparation technology of the plastic master batch, the plastic master batch has more and more powerful functions and more abundant varieties, the application field is also expanded continuously, and the masterbatching application of plastic modification is bound to become an indispensable common key technology in the field of clean production of modified plastics in the future.
At present, with the continuous expansion of the application field of plastics, the requirements on the performance of the plastics are higher and higher, many application fields need that the plastic products have multiple functions such as high strength, high toughness, high temperature resistance, flame retardance, antibiosis, heat conduction, electric conduction and the like and excellent comprehensive performance, and modification additives and auxiliary agents with various materials and shapes need to be added for the preparation and processing of each modification material, which provides great challenges for the traditional plastic modification technology. Although the development of the plastic functional master batch technology provides technical support for the challenge, a plurality of technical problems still exist in the actual operation process. The most important technical problems comprise the following three points: firstly, modifying additives and auxiliary agents with different materials and forms can exert respective modifying effects to the maximum extent by adopting different processing equipment and processes; secondly, the modification additives and the auxiliary agents with different materials and chemical compositions and the matrix resin are subjected to melt blending on the same processing equipment (a double-screw extruder or an internal mixer), so that the modification effects are mutually damaged due to mutual reaction or interference among effective components in the additives; the processing temperature of the melt blending of the modified additives and the additives of different materials and the matrix resin is greatly different, and if the blending is carried out in the same processing equipment at the same time, the problem of serious temperature mismatching is generated, so that the modification effect is poor. For example, for a flame-retardant antibacterial plastic modification system, when a silver-zinc-loaded inorganic antibacterial agent and a brominated flame retardant are simultaneously melt-blended with a matrix resin in a twin-screw extruder or an internal mixer, under the action of strong shearing of twin-screw, ion adsorption behaviors or even chemical reactions occur between silver and zinc ions and the brominated flame retardant, so that the modification effects of the silver and zinc ions are interfered, the antibacterial and flame-retardant effects of the silver and zinc ions are mutually damaged or even completely lost, and the modification effects of the silver and zinc ions and the brominated flame retardant are seriously influenced. Aiming at the modification system of the glass fiber reinforced flame retardant plastic, the problems of high fiber breakage rate and flame retardant decomposition of the glass fiber and the flame retardant under the strong shearing action of double screws exist, the processing temperature of the glass fiber reinforced flame retardant plastic is obviously different, wherein the processing temperature of the reinforced flame retardant plastic is 40-70 ℃ higher than that of the flame retardant plastic, and if the two modification systems are subjected to melt blending under the same processing condition of the same processing equipment, the modification effect of one system is necessarily damaged. The problem that modification efficiency of different additive systems is mutually damaged is particularly prominent in the implementation process of high-performance and multifunctional modification technology of plastics at present.
Aiming at the problems existing in the synchronous implementation process of high-performance and multifunctional modification of plastics, the invention discloses a development idea of implementing dual-function modification of plastics by adopting an idea of combining functions and double master batches. The method is characterized in that additives possibly with mutual loss of modification efficacy in blending processing are respectively prepared into A master batches and B master batches according to the characteristics of the materials of plastic modification additives, and respective highly uniform dispersion systems are respectively designed according to the characteristics of the structures, the materials and the physical properties of the modification additives contained in the two master batches. Then the two functional master batches are synchronously applied to injection molding processing of plastic products, so that the problem of mutual loss of modification functions caused by mutual interference between two modification additives with different chemical compositions in the plastic functional modification processing process can be avoided, the maximum modification efficiency of the modification additives and auxiliary agents with different materials can be exerted, and the re-extrusion granulation processing of the traditional functional master batches and matrix resin can be avoided, thereby effectively improving the plastic modification effect, reducing the production and processing cycle and saving the production energy consumption. The idea provides an important way for realizing efficient and energy-saving green plastic processing.
The flame-retardant antibacterial polypropylene compound is a common plastic modified special particle and is widely applied to the field of manufacturing household kitchen and bathroom appliances (such as toilet seat rings and covers, refrigerators and washing machine liners) and medical electronic and electric appliances. The traditional processing preparation method of the special modified material comprises the following steps: the silver-zinc-loaded inorganic antibacterial agent with excellent antibacterial function and the bromine-antimony compound flame retardant with high flame retardant efficiency are simultaneously added into the polypropylene resin, and the required special modified material is obtained by melt blending, extrusion and granulation through a double-screw extruder. However, in the processing process, the strong shearing action of the twin-screw leads to ion adsorption and even chemical reaction between silver and zinc ions and the brominated flame retardant, and interferes with the modification effects of the silver and zinc ions, so that the antibacterial and flame retardant effects of the twin-screw are mutually damaged and even completely fail. The typical additive modification efficiency mutual loss phenomenon seriously influences the modification effect of the brominated flame retardant and the silver-loaded zinc inorganic antibacterial agent.
Disclosure of Invention
In order to solve the problem of mutual loss of modification efficiency in the preparation process of the conventional special flame-retardant antibacterial polypropylene material, the invention provides the efficient flame-retardant antibacterial master batch which can be directly applied to injection molding processing of polypropylene plastic products and the preparation method thereof. The functional master batch is formed by combining A and B functional master batches. The A master batch mainly comprises a silver-zinc-loaded inorganic antibacterial agent, a low-viscosity elastomer and a random polypropylene carrier, and is prepared into antibacterial master batches through an internal mixer; the B master batch mainly comprises a bromine-antimony compound flame retardant and a high-dispersity carrier resin system, and is prepared into the flame-retardant master batch through an internal mixer. The following technical advantages can be achieved by applying the method of respectively processing the two master batches: the direct contact between the silver-zinc-loaded inorganic antibacterial agent and the brominated flame retardant is avoided, and the mutual loss of antibacterial and flame retardant efficiency caused by mutual interference between silver ions and zinc ions and the brominated flame retardant is avoided; secondly, a carrier resin with excellent compatibility with the basic resin, a super-lubrication and high-efficiency dispersion formula system are designed for the A master batch and the B master batch respectively, so that the modified polypropylene master batch is directly applied to injection molding of polypropylene products, and antioxidant consumption and flame retardant decomposition caused by repeated hot processing of modified materials are avoided; the inorganic filler is introduced into the A master batch, so that the silver-zinc-loaded inorganic antibacterial agent and the brominated flame retardant can be prevented from contacting with each other in the subsequent injection molding process of a product, and the ion adsorption and chemical reaction generated between silver and zinc ions and the brominated flame retardant are reduced, so that the mutual loss of the modification efficacy between the silver and zinc ions is avoided; because the silver-zinc-loaded inorganic antibacterial agent and the brominated flame retardant powder are respectively wrapped by different carrier resins, and because a single-screw melt propulsion mode is adopted in the injection molding machine, the shearing action of the screw is weak, the mutual contact between the silver-zinc-loaded inorganic antibacterial agent and the brominated flame retardant is basically eliminated in the molding process of plastics, and the flame retardant and antibacterial effects of plastic products are greatly ensured. The high-efficiency flame-retardant antibacterial functional master batch disclosed by the invention can be used for directly mixing the master batches A and B with polypropylene resin according to a certain proportion according to actual performance requirements and then carrying out injection molding, and can also be used for adding other functional master batches to carry out injection molding together: including but not limited to: the master batch has great design flexibility, can carry out multi-resin and multi-master batch combined injection molding according to different requirements of customers, and quickly, simply and conveniently meets the target requirement, thereby practicing the plastic modification formula with 1+1 being more than 2 and optimizing the design concept of the processing technology.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the high-efficiency flame-retardant antibacterial functional master batch for direct injection molding of polypropylene is prepared by combining A master batch and B master batch, wherein the A master batch comprises the following components in percentage by mass: 6.0-10.0 wt% of silver-zinc-loaded inorganic antibacterial agent, 50.0-70.0 wt% of filler, 18.0-38.0 wt% of elastic ionomer, 0.5-1.0 wt% of dispersing agent and 0.5-0.1 wt% of lubricant, wherein the B master batch comprises the following components in percentage by mass: 55.0-70.0 wt% of bromine-based flame retardant, 15.0-30.0 wt% of inorganic flame retardant synergist, 13.0-18.0 wt% of atactic polypropylene, 1.0-2.0 wt% of polytetrafluoroethylene powder, 0.5-1.0 wt% of dispersant and 0.5-1.0 wt% of lubricant.
Further, the silver-zinc-loaded inorganic antibacterial agent is zeolite, silica gel, glass, zirconium phosphate, calcium phosphate, zinc oxide or titanium dioxide powder loaded with silver and zinc ions.
Further, the filler is any one or more of barium sulfate, talcum powder, calcium carbonate, mica powder, kaolin and glass fiber powder, and preferably the barium sulfate and the glass fiber powder are used in combination.
Further, the elastic ionomer is ethylene-acrylic acid copolymerized elastic ionomer crosslinked by sodium, calcium, magnesium, barium or zinc ions.
Further, the brominated flame retardant is any one or more of octabromoether, octabromoS ether, decabromodiphenylethane and ethyl-bis (tetrabromobenzodiimide), and the octabromoS ether is preferred.
Further, the inorganic flame-retardant synergist is one or two of antimony trioxide and zinc borate.
Further, the dispersant is one or more of stearic acid, calcium stearate, zinc stearate, oleamide and mesoacid amide.
Further, the lubricant is one or two of polyethylene wax, ethylene bis stearamide and polydimethylsiloxane.
A method for preparing high-efficiency flame-retardant antibacterial functional master batch for direct injection molding of polypropylene relates to a preparation method of A master batch and B master batch, and the preparation method of the A master batch comprises the following steps: weighing the silver-zinc-loaded inorganic antibacterial agent, the elastic ionomer, the filler, the dispersant and the lubricant according to the proportion, putting the materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing to obtain a bulk blend, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and carrying out melt extrusion and granulation to obtain the master batch A.
Further, the mixing temperature of the internal mixer is 100-125 ℃, and the mixing time is 15-20 minutes; the screw rotating speed of the single-screw extruder is 150-200 r/min, and the barrel temperature is 150-160 ℃.
A method for preparing high-efficiency flame-retardant antibacterial functional master batch for direct injection molding of polypropylene relates to a preparation method of A master batch and B master batch, and the preparation method of B master batch comprises the following steps: weighing the brominated flame retardant, the inorganic flame-retardant synergist, the atactic polypropylene, the polytetrafluoroethylene powder, the dispersant and the lubricant according to the proportion, putting the materials into a high-speed mixer for uniform mixing, transferring the mixture into an internal mixer for hot mixing to obtain a bulk blend, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and carrying out melt extrusion and granulation to obtain the B master batch.
Further, the mixing temperature of the internal mixer is 100-125 ℃, and the mixing time is 15-20 minutes; the screw rotating speed of the single-screw extruder is 150-200 r/min, and the barrel temperature is 150-160 ℃.
The technical scheme adopted by the invention has the beneficial effects that:
(1) aiming at the physical property characteristics of the modified additive, the silver-zinc antibacterial master batch (A master batch) and the bromine-antimony compound flame-retardant master batch (B master batch) are respectively prepared by adopting a method of separately processing the A master batch and the B master batch, so that the mutual loss of antibacterial and flame-retardant effects caused by ion adsorption or chemical reaction between silver and zinc ions and a bromine flame retardant when the silver-zinc-loaded inorganic antibacterial agent and the bromine flame retardant are directly melt, extruded and blended with polypropylene resin is effectively avoided.
(2) A carrier resin with excellent compatibility with the basic resin, a super-lubricating and high-efficiency dispersing formula system are designed aiming at the master batches A and B respectively, so that the modified master batches can be directly applied to injection molding of polypropylene products, and antioxidant consumption and flame retardant decomposition caused by repeated mechanical hot processing of modified materials are avoided.
(3) Different carrier resins are respectively applied to the A master batch and the B master batch, so that the silver-zinc-loaded inorganic antibacterial agent and the brominated flame retardant are respectively wrapped by the carrier resins in advance, and meanwhile, a large amount of inorganic filling blocking agent is introduced into the A master batch, so that the probability of mutual contact of the silver-zinc-loaded inorganic antibacterial agent and the brominated flame retardant in the injection molding process of the polypropylene product is greatly reduced, and the flame retardant and antibacterial modification effects of the polypropylene product are greatly ensured.
(4) Compared with the traditional plastic functional master batch, the high-efficiency flame-retardant antibacterial functional master batch provided by the invention skillfully utilizes the combination mode of two different functional master batches to be respectively processed, not only solves the problem that the modification efficiency of different additives is mutually damaged in the preparation and processing process of modified plastics, generates the modification effect of 1+1 to 2, has the characteristics of easy dispersion and easy processing, and can be directly applied to the injection molding processing of plastic products after the master batch A and the master batch B are simply mixed with polypropylene resin according to a certain proportion according to the performance requirements of the polypropylene products. Thereby simplifying the plastic modification processing steps, reducing the processing period, reducing the energy consumption, improving the production efficiency and really realizing the green chemical development concept.
(5) The combined functional master batch can flexibly adjust the combination mode of the master batch A and the master batch B and the proportion of the master batch A and the master batch B to resin raw materials to adjust the performance and the cost of the master batch according to the requirements of customers in the injection molding process of polypropylene plastic products. The method and the technology of the invention can be widely applied to the integrated processing of injection molding and functional modification of various polypropylene products with flame retardant and antibacterial performance requirements.
Detailed Description
The following examples are intended to provide those skilled in the art with a more complete understanding of the present invention, and are not intended to limit the scope of the present invention. Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
A high-efficiency flame-retardant antibacterial functional master batch for direct injection molding of polypropylene is prepared by combining a master batch A and a master batch B, wherein the master batch A comprises the following raw materials in parts by mass:
| silver-zinc-carried zeolite antibacterial agent | 10.0 kg |
| Barium sulfate | 40.0 kg |
| Glass fiber powder | 30.0 kg |
| Sodium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer | 18.0 kg |
| Stearic acid | 1.0 g |
| Ethylene bis stearamide | 1.0 g |
The B master batch comprises the following raw materials in parts by mass:
| octabromo S ether | 70.0 kg |
| Antimony trioxide | 15.0 kg |
| Atactic polypropylene | 13.0 kg |
| Polytetrafluoroethylene powder | 1.0 kg |
| Stearic acid | 500.0 g |
| Ethylene bis stearamide | 500.0 g |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer, and carrying out hot mixing to obtain a bulk blend, wherein the mixing temperature of the internal mixer is 115 ℃, and the mixing time is 18 minutes; and then feeding the obtained bulk blend into a single-screw extruder through a conical feeding machine, and carrying out melt extrusion and granulation to obtain the master batch A, wherein the screw rotating speed of the single-screw extruder is 160 revolutions per minute, and the temperature of a machine barrel is controlled to be 150-160 ℃ in a segmented manner.
The preparation method of the B master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 125 ℃, the mixing time is 15 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and carrying out melt extrusion and granulation to obtain the B master batch; the screw rotating speed of the single-screw extruder is 170 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.
Example 2
A high-efficiency flame-retardant antibacterial functional master batch for direct injection molding of polypropylene is prepared by combining a master batch A and a master batch B, wherein the master batch A comprises the following raw materials in parts by mass:
| silver-zinc-loaded porous glass antibacterial agent | 7.0 kg |
| Barium sulfate | 40.0 kg |
| Talcum powder | 23.0 kg |
| Zinc ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer | 28.0 kg |
| Oleic acid amides | 1.5 kg |
| Polyethylene wax | 500.0 g |
The B master batch comprises the following raw materials in parts by mass:
| decabromodiphenylethane | 50.0 kg |
| Octabromoether | 10.0 kg |
| Antimony trioxide | 16.5 kg |
| Zinc borate | 7.0 kg |
| Atactic polypropylene | 14.0 kg |
| Polytetrafluoroethylene powder | 1.5 kg |
| Oleic acid amides | 500.0 g |
| Polyethylene wax | 500.0 g |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer, and carrying out hot mixing to obtain a bulk blend, wherein the mixing temperature of the internal mixer is 120 ℃, and the mixing time is 20 minutes; and then feeding the obtained bulk blend into a single-screw extruder through a conical feeding machine, and carrying out melt extrusion and granulation to obtain the master batch A, wherein the screw rotating speed of the single-screw extruder is 165 revolutions per minute, and the temperature of a machine barrel is controlled to be 150-160 ℃ in a segmented manner.
The preparation method of the B master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 115 ℃, the mixing time is 20 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the B master batch; the screw rotating speed of the single-screw extruder is 180 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.
Example 3
A high-efficiency flame-retardant antibacterial functional master batch for direct injection molding of polypropylene is prepared by combining a master batch A and a master batch B, wherein the master batch A comprises the following raw materials in parts by mass:
| silver-zinc-loaded porous zirconium phosphate antibacterial agent | 6.0 kg |
| Barium sulfate | 40.0 kg |
| Calcium carbonate | 14.0 kg |
| Calcium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer | 38.0 kg |
| Zinc stearate | 1.5 kg |
| Polydimethylsiloxane | 500.0 g |
The B master batch comprises the following raw materials in parts by mass:
| octabromoether | 30.0 kg |
| Octabromo S ether | 30.0 kg |
| Antimony trioxide | 20.0 kg |
| Atactic polypropylene | 18.0 kg |
| Polytetrafluoroethylene powder | 1.0 kg |
| Zinc stearate | 500.0 g |
| Polydimethylsiloxane | 500.0 g |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer, and carrying out hot mixing to obtain a bulk blend, wherein the mixing temperature of the internal mixer is 100 ℃, and the mixing time is 20 minutes; and then feeding the obtained bulk blend into a single-screw extruder through a conical feeding machine, and carrying out melt extrusion and granulation to obtain the master batch A, wherein the screw rotating speed of the single-screw extruder is 150 revolutions per minute, and the temperature of a machine barrel is controlled to be 150-160 ℃ in a segmented manner.
The preparation method of the B master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 100 ℃, the mixing time is 20 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the B master batch; the screw rotating speed of the single-screw extruder is 150 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.
Example 4
A high-efficiency flame-retardant antibacterial functional master batch for direct injection molding of polypropylene is prepared by combining a master batch A and a master batch B, wherein the master batch A comprises the following raw materials in parts by mass:
| silver-zinc-loaded porous calcium phosphate antibacterial agent | 9.0 kg |
| Barium sulfate | 40.0 kg |
| Mica powder | 19.0 kg |
| Barium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer | 20.0 kg |
| Stearic acid calcium salt | 1.0 kg |
| Ethylene bis stearamide | 1.0 kg |
The B master batch comprises the following raw materials in parts by mass:
| octabromoether | 30.0 kg |
| Ethyl-bis (tetrabromophthalimide) | 30.0 kg |
| Antimony trioxide | 21.0 kg |
| Atactic polypropylene | 17.0 kg |
| Polytetrafluoroethylene powder | 1.0 kg |
| Stearic acid calcium salt | 500.0 g |
| Ethylene bis stearamide | 500.0 g |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer, and carrying out hot mixing to obtain a bulk blend, wherein the mixing temperature of the internal mixer is 120 ℃, and the mixing time is 20 minutes; and then feeding the obtained bulk blend into a single-screw extruder through a conical feeding machine, and carrying out melt extrusion and granulation to obtain the master batch A, wherein the screw rotating speed of the single-screw extruder is 175 r/min, and the barrel temperature is controlled to be 150-160 ℃ in a segmented manner.
The preparation method of the B master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 120 ℃, the mixing time is 17 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the B master batch; the screw rotating speed of the single-screw extruder is 185 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.
Example 5
A high-efficiency flame-retardant antibacterial functional master batch for direct injection molding of polypropylene is prepared by combining a master batch A and a master batch B, wherein the master batch A comprises the following raw materials in parts by mass:
| silver-zinc-loaded porous zinc oxide antibacterial agent | 9.0 kg |
| Barium sulfate | 40.0 kg |
| Kaolin clay | 30.0 kg |
| Magnesium ion crosslinked ethylene-acrylic acidCopolymerized elastomeric ionomers | 19.5 kg |
| Oleic acid amides | 1.0 kg |
| Polydimethylsiloxane | 500.0 g |
The B master batch comprises the following raw materials in parts by mass:
| decabromodiphenylethane | 45.0 kg |
| Octabromoether | 15.0 kg |
| Antimony trioxide | 24.0 kg |
| Atactic polypropylene | 13.5 kg |
| Polytetrafluoroethylene powder | 1.0 kg |
| Oleic acid amides | 1.0 kg |
| Polydimethylsiloxane | 500.0 g |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer, and carrying out hot mixing to obtain a bulk blend, wherein the mixing temperature of the internal mixer is 120 ℃, and the mixing time is 20 minutes; and then feeding the obtained bulk blend into a single-screw extruder through a conical feeding machine, and carrying out melt extrusion and granulation to obtain the master batch A, wherein the screw rotating speed of the single-screw extruder is 165 revolutions per minute, and the temperature of a machine barrel is controlled to be 150-160 ℃ in a segmented manner.
The preparation method of the B master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 100 ℃, the mixing time is 20 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the B master batch; the screw rotating speed of the single-screw extruder is 150 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.
Example 6
A high-efficiency flame-retardant antibacterial functional master batch for direct injection molding of polypropylene is prepared by combining a master batch A and a master batch B, wherein the master batch A comprises the following raw materials in parts by mass:
| silver-zinc-loaded porous zirconium phosphate antibacterial agent | 8.0 kg |
| Talcum powder | 40.0 kg |
| Glass fiber powder | 20.0 kg |
| Sodium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer | 31.0 kg |
| Zinc stearate | 500.0 g |
| Ethylene bis stearamide | 500.0 g |
The B master batch comprises the following raw materials in parts by mass:
| decabromodiphenylethane | 30.0 kg |
| Octabromo S ether | 28.0 kg |
| Antimony trioxide | 16.0 kg |
| Zinc borate | 8.0 kg |
| Atactic polypropylene | 15.0 kg |
| Polytetrafluoroethylene powder | 1.5 kg |
| Zinc stearate | 1.0 kg |
| Ethylene bis stearamide | 500.0 g |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer, and carrying out hot mixing to obtain a bulk blend, wherein the mixing temperature of the internal mixer is 120 ℃, and the mixing time is 20 minutes; and then feeding the obtained bulk blend into a single-screw extruder through a conical feeding machine, and carrying out melt extrusion and granulation to obtain the master batch A, wherein the screw rotating speed of the single-screw extruder is 195 revolutions per minute, and the temperature of a machine barrel is controlled to be 150-160 ℃ in a segmented manner.
The preparation method of the B master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 125 ℃, the mixing time is 18 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and carrying out melt extrusion and granulation to obtain the B master batch; the screw rotating speed of the single-screw extruder is 160 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.
The master batch A and the master batch B are mixed according to any mass ratio, and the components in the rest part of the invention can be expressed according to any ratio without explicitly written proportional relationship.
In order to verify the modification effect of the high-efficiency flame-retardant antibacterial master batch for direct injection molding of polypropylene, the master batch A and the master batch B prepared in the embodiments 1 to 6 are respectively mixed with polypropylene resin according to the mass percentages of 10 wt.% and 40 wt.%, and are directly injected to mold a test sample strip, and then various performance tests are carried out; meanwhile, the test specimens obtained in examples 1 to 6 were injection-molded with the same components and compounding ratios by blending with a twin-screw extruder as a control, and the properties were measured. All the results of the property tests are shown in Table 1 (wherein comparative examples 1 to 6 are the same compositions and compounding ratios as those in examples 1 to 6, respectively, and the properties of the specimens were measured by injection molding after processing with a twin-screw extruder).
The reference of the data in table 1 shows that the antibacterial property and the flame retardant property of the plastic product of the high-efficiency flame-retardant antibacterial master batch for direct injection molding of polypropylene prepared by the embodiment of the invention are obviously superior to those of the injection molded product processed by a double-screw extruder under the condition that the components and the proportion are completely the same after the master batch is applied to direct injection molding of polypropylene. By utilizing the functional master batch, the processing steps of polypropylene resin modification are greatly simplified, the processing efficiency is improved, the energy consumption is reduced, the modification effect is obviously enhanced, and the sustainable development concept of green processing of plastic preparation is realized.
TABLE 1 comparison of the Performance of the polypropylene test specimens directly injection molded with the master batches prepared in examples 1 to 6 with the polypropylene test specimens injection molded after processing with a twin screw extruder according to the same raw material formulation
TABLE 1
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (9)
1. The high-efficiency flame-retardant antibacterial master batch for direct injection molding of polypropylene is characterized in that: the functional master batch is formed by combining A master batch and B master batch, wherein the A master batch comprises the following components in percentage by mass: 6.0-10.0 wt% of silver-zinc-loaded inorganic antibacterial agent, 50.0-70.0 wt% of filler, 18.0-38.0 wt% of elastic ionomer, 0.5-1.0 wt% of dispersing agent and 0.5-0.1 wt% of lubricant, wherein the B master batch comprises the following components in percentage by mass: 55.0-70.0 wt% of a brominated flame retardant, 15.0-30.0 wt% of an inorganic flame retardant synergist, 13.0-18.0 wt% of atactic polypropylene, 1.0-2.0 wt% of polytetrafluoroethylene powder, 0.5-1.0 wt% of a dispersant and 0.5-1.0 wt% of a lubricant;
the filler is any one or more of barium sulfate, talcum powder, calcium carbonate, mica powder, kaolin and glass fiber powder;
the elastic ionomer is ethylene-acrylic acid copolymerized elastic ionomer crosslinked by sodium, calcium, magnesium, barium or zinc ions.
2. The high-efficiency flame-retardant antibacterial master batch for direct injection molding of polypropylene according to claim 1, which is characterized in that: the silver-zinc-loaded inorganic antibacterial agent is zeolite loaded with silver and zinc ions, porous silica gel, porous glass, porous zirconium phosphate, porous calcium phosphate, porous zinc oxide or porous titanium dioxide powder.
3. The high-efficiency flame-retardant antibacterial master batch for direct injection molding of polypropylene according to claim 1, which is characterized in that: the brominated flame retardant is any one or more of octabromoether, octabromoS ether, decabromodiphenylethane and ethyl-bis (tetrabromophthalimide).
4. The high-efficiency flame-retardant antibacterial master batch for direct injection molding of polypropylene according to claim 1, which is characterized in that: the inorganic flame-retardant synergist is one or two of antimony trioxide and zinc borate.
5. The high-efficiency flame-retardant antibacterial master batch for direct injection molding of polypropylene according to claim 1, which is characterized in that: the dispersant is one or more of stearic acid, calcium stearate, zinc stearate, oleamide and mesoacid amide; the lubricant is one or two of polyethylene wax, ethylene bis stearamide and polydimethylsiloxane.
6. The method for preparing the high-efficiency flame-retardant antibacterial functional master batch for direct injection molding of polypropylene according to any one of claims 1 to 5, is characterized by comprising the following steps: the preparation method of the A master batch comprises the following steps: weighing the silver-zinc-loaded inorganic antibacterial agent, the filler, the elastic ionomer, the dispersant and the lubricant according to the proportion, putting the mixture into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing to obtain a bulk blend, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and carrying out melt extrusion and granulation to obtain the master batch A.
7. The preparation method of the high-efficiency flame-retardant antibacterial functional master batch for direct injection molding of polypropylene according to claim 6, wherein the preparation method comprises the following steps: the processing technology of the A master batch comprises the following steps: the mixing temperature of the internal mixer is 100-125 ℃, and the mixing time is 15-20 minutes; the screw rotating speed of the single-screw extruder is 150-200 r/min, and the barrel temperature is 150-160 ℃.
8. The method for preparing the high-efficiency flame-retardant antibacterial functional master batch for direct injection molding of polypropylene according to any one of claims 1 to 5, is characterized by comprising the following steps: the preparation method of the B master batch comprises the following steps: weighing the brominated flame retardant, the inorganic flame-retardant synergist, the atactic polypropylene, the polytetrafluoroethylene powder, the dispersant and the lubricant according to the proportion, putting the materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer, carrying out hot mixing to obtain a bulk blend, feeding the obtained bulk blend into a single-screw extruder through a conical feeding machine, carrying out melt extrusion and granulation to obtain the B master batch.
9. The preparation method of the high-efficiency flame-retardant antibacterial functional master batch for direct injection molding of polypropylene according to claim 8, wherein the preparation method comprises the following steps: the processing technology of the B master batch comprises the following steps: the mixing temperature of the internal mixer is 100-125 ℃, and the mixing time is 15-20 minutes; the screw rotating speed of the single-screw extruder is 150-200 r/min, and the barrel temperature is 150-160 ℃.
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