CN109535559B - Efficient enhanced flame-retardant functional master batch for direct injection molding of polypropylene and preparation method thereof - Google Patents
Efficient enhanced flame-retardant 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 an efficient enhanced flame-retardant master batch capable of being 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: 50.0-70.0 wt.% of glass fiber, 15.0-35.0 wt.% of high-fluidity polypropylene, 5.0-10.0 wt.% of elastic ionomer, 3.0-6.0 wt.% of random polypropylene, 1.0-3.0 wt.% of maleic anhydride grafted polypropylene, 1.0-3.0 wt.% of polytetrafluoroethylene powder and 0.1-0.3 wt.% of antioxidant; the functional master batch has the characteristic of easy dispersion and processing, and can be simply mixed with polypropylene resin according to the proportion and then injection molded.
Description
Technical Field
The invention belongs to the technical field of plastic modification and processing, and particularly relates to an efficient enhanced flame-retardant 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, heat conduction, electric conduction and the like and excellent comprehensive performance, and modification additives and auxiliary agents of various materials and shapes need to be added for the preparation and processing of each modified 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 forms and the matrix resin are melted and blended on the same processing equipment (a double-screw extruder or an internal mixer), so that the modification efficiency is mutually damaged due to mutual shearing and abrasion; and the processing temperature difference of the melt blending of the modified additives and the additives made of different materials and the matrix resin is large, 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 reinforced flame-retardant plastic modification system, when glass fibers for reinforcement, an organic flame retardant and an inorganic flame-retardant synergist are simultaneously subjected to melt blending with matrix resin in a twin-screw extruder or an internal mixer, the length-diameter ratio of the fibers is greatly reduced due to mutual abrasion between the fibers and inorganic particles, so that the fiber reinforcement effect is deteriorated; the fiber and the organic flame retardant can also cause the decomposition of the flame retardant due to internal friction heat, and the flame retardant effect is seriously influenced. In addition, the processing temperature of the glass fiber reinforced plastic modified system is obviously different from that of the flame retardant modified plastic system, the processing temperature of the reinforced modified system is usually 40-70 ℃ higher than that of the flame retardant system, and if the two modified systems are subjected to melt blending under the same processing conditions of the same processing equipment, the modification effect of one system is 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 adopts the development idea of adopting the idea of combining double master batches with functions to implement the enhancement and the multi-function modification of the plastics. The method is characterized in that additives possibly with mutual loss of modification efficiency 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 problems of mutual loss of the performance of the modification additives and mismatching of processing temperature generated in the plastic enhancement and functional modification processing processes can be avoided, the maximum modification performance of the modification additives and the auxiliary agents made of 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 yield and saving the production energy consumption. The idea provides an important way for realizing efficient and energy-saving green plastic processing.
Disclosure of Invention
The reinforced flame-retardant polypropylene compound is a common plastic modified special particle and is widely applied to the field of manufacturing of industrial and civil electronic and electric appliances. However, in the process of processing and preparing the special material for reinforced flame-retardant polypropylene, the inorganic reinforced fiber and the flame retardant are simultaneously added into the polypropylene resin for melt blending and extrusion, and the typical phenomenon of mutual loss of the modification efficiency of the additive can occur. In order to solve the problem of mutual loss of modification efficiency in the preparation process of the existing glass fiber reinforced flame-retardant polypropylene special material, the invention provides the high-efficiency reinforced flame-retardant functional 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 glass fiber, high-flow polypropylene and low-viscosity elastomer toughening agent, and is processed by a melt pultrusion method to prepare long fiber reinforced toughening master batch; the B master batch mainly comprises a bromine-antimony compound flame retardant and super-dispersed carrier resin, 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 decomposition of the halogen flame retardant caused by internal friction heat generation generated by directly blending the glass fiber and the bromine flame retardant is avoided; the great reduction of the length-diameter ratio of the fiber caused by mutual shearing and abrasion between the inorganic flame-retardant synergist (such as antimony trioxide or zinc borate) and the glass fiber is avoided; solving the problem that the processing temperature of the melt blending of two modification systems of glass fiber reinforced polypropylene and bromine-antimony compound flame retardant polypropylene is not matched; and fourthly, preparing the reinforced master batch with larger fiber length-diameter ratio than the traditional chopped glass fiber reinforced master batch by utilizing a melt pultrusion technology. In addition, aiming at the physical properties of the A master batch and the B master batch, the formula system design for promoting the lubrication and the efficient dispersion of the A master batch and the B master batch is implemented according to the physical properties of the loaded modified additives. Therefore, the master batches A and B can be directly and simply mixed with the polypropylene resin according to a certain proportion and then subjected to injection molding according to performance requirements, and functional master batches can be added for injection molding together: including but not limited to: color masterbatch, filling masterbatch, toughening masterbatch, nucleating masterbatch, lubricating masterbatch, antistatic masterbatch, anti-aging masterbatch, conductive masterbatch, heat conductive masterbatch, laser etching masterbatch, silicone masterbatch and antibacterial masterbatch. Because the single-screw melt propelling mode is adopted in the injection molding machine, the shearing action on the glass fiber and the flame retardant is very weak, and the modification effects of the glass fiber and the flame retardant are basically not damaged. Therefore, the method not only effectively avoids the mutual loss of modification efficiency caused by secondary double-screw blending extrusion processing of the glass fiber and the flame retardant, greatly improves the enhanced flame-retardant modification effect of the polypropylene, but also enables the master batch of the invention to have great design flexibility, can carry out multi-resin and multi-master batch combined injection molding according to different requirements of customers, quickly and simply achieves the aim requirement, thereby practicing the optimal design concept of the plastic modification formula and the processing technology with 1+1 being more than 2.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a high-efficiency enhanced flame-retardant functional master batch for direct injection molding of polypropylene and a preparation method thereof are 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: 50.0-70.0 wt% of glass fiber, 15.0-35.0 wt% of high-fluidity polypropylene, 5.0-10.0 wt% of elastic ionomer, 3.0-6.0 wt% of random polypropylene, 1.0-3.0 wt% of maleic anhydride grafted polypropylene, 1.0-3.0 wt% of polytetrafluoroethylene powder and 0.1-0.3 wt% of antioxidant, 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, 5.0-10.0 wt% of elastic ionomer, 2.0-5.0 wt% of atactic polypropylene, 0.5-1.0 wt% of dispersant and 0.2-0.5 wt% of lubricant.
Further, the glass fiber is a continuous long glass fiber.
Further, the high flow polypropylene has a melt flow index of greater than 50.0 g/10 min.
Further, the elastic ionomer is ethylene-acrylic acid copolymerized elastic ionomer crosslinked by sodium, calcium, magnesium, barium or zinc ions.
Further, the antioxidant is a compound consisting of triethylene glycol bis beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (the trade name is antioxidant 245) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (the trade name is antioxidant 626) according to the mass ratio of 1: 1.
Furthermore, the bromine flame retardant is one or more of decabromodiphenylethane, ethyl-bis (tetrabromophthalimide) and brominated polystyrene, and is preferably used in combination with the decabromodiphenylethane and the ethyl-bis (tetrabromophthalimide).
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 a high-efficiency enhanced flame-retardant functional master batch for direct injection molding of polypropylene relates to a preparation method of an A master batch and a B master batch, and the preparation method of the A master batch comprises the following steps:
(1) weighing glass fiber, high-flow polypropylene, elastic ionomer, atactic polypropylene, maleic anhydride grafted polypropylene, polytetrafluoroethylene powder and an antioxidant according to a ratio, premixing the powder and the granules uniformly by using a high-speed mixer respectively, and adding the powder and the granules into a double-screw extruder through a main material hopper and an auxiliary material hopper to perform melt blending extrusion to prepare a composite melt;
(2) and (2) directly extruding the compound melt obtained in the step (1) into a die cavity of an impregnation die through a die connected with a head of a double-screw extruder, simultaneously, enabling continuous long glass fibers to enter the die cavity through the other die of the impregnation die, impregnating in the melt under the traction action of a godet roller in the die cavity, drawing out glass fiber tows impregnated in the melt from the die cavity, cooling, and cutting into strip-shaped granules with the length of 8-12 mm through a granulator to obtain the master batch A.
Furthermore, the temperature of each section from a charging barrel to a machine head of the double-screw extruder is controlled to be 185-225 ℃, and the rotating speed of a screw is 150-200 revolutions per minute; the temperature of a die cavity of the dipping die is controlled to be 230-250 ℃, and the speed of a tractor is controlled to be 50-70 m/min.
A method for preparing a high-efficiency enhanced flame-retardant functional master batch for direct injection molding of polypropylene relates to a preparation method of an A master batch and a B master batch, and the preparation method of the B master batch comprises the following steps:
(1) weighing a brominated flame retardant, an inorganic flame-retardant synergist, an elastic ionomer, atactic polypropylene, a dispersant and a lubricant according to a ratio, putting the 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;
(2) and (2) feeding the bulk blend obtained in the step (1) into a single-screw extruder through a conical feeding machine, and performing melt extrusion and granulation to obtain the 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 method for separately processing the master batch A and the master batch B is adopted to respectively prepare the long glass fiber reinforced master batch (master batch A) and the bromine-antimony compound flame-retardant master batch (master batch B), thereby effectively avoiding the mutual loss of modification efficiency caused by mutual shearing and abrasion when polypropylene, glass fiber and bromine/antimony flame retardant are directly melted, blended and extruded, and simultaneously solving the technical problem of unmatched processing temperature of two modification systems, thereby obviously improving the respective modification efficiency of the two modified additives.
(2) The glass fiber reinforced long master batch (A master batch) is prepared by adopting a continuous long fiber pultrusion technology, so that the fiber length-diameter ratio which is larger than that of the traditional chopped glass fiber reinforced master batch can be obtained, and the reinforcing efficiency of the glass fiber is greatly improved.
(3) The high-flow polypropylene, the elastic ionomer, the atactic polypropylene and the maleic anhydride grafted polypropylene are used as the combined carrier of the glass fiber reinforced master batch, so that the interfacial cohesiveness of the glass fiber and the polypropylene can be effectively improved, and the high-flow characteristics of the carriers can be utilized, so that the glass fiber obtains a more excellent dispersion effect in a polypropylene resin matrix when the prepared A master batch is used for injection molding of products.
(4) By utilizing the super-lubrication effect of the polytetrafluoroethylene powder in the formula of the master batch A, the infiltration effect of the polypropylene melt on the glass fiber tows can be effectively improved; when the master batch A and the master batch B are combined and applied to polypropylene products, the polytetrafluoroethylene powder can play the effect of an anti-dripping agent in the combustion process of the products, and the flame retardant property of the products is improved, so that the modification effect of killing two birds with one stone is achieved.
(5) And the elastic ionomer with excellent flow property and the atactic polypropylene are also used as combined carriers for preparing the B master batch, so that different types of modified additives can obtain the effect of uniform dispersion in a resin matrix when the A master batch and the B master batch are jointly used for directly injection molding and processing polypropylene plastic products. The elastic ionomer is used as a carrier component of the A master batch and the B master batch at the same time, so that the high fluidity of the elastic ionomer can be utilized to provide excellent dispersibility for the modified additive, and the good toughening effect on the polypropylene can be exerted.
(6) Compared with the traditional plastic functional master batch, the high-efficiency enhanced flame-retardant 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 be much more than 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 plastic products. Because the single-screw melt pushing mode is adopted in the injection molding machine, the shearing action on the glass fiber and the flame retardant is very weak, and the modification effects of the glass fiber and the flame retardant are basically not damaged, so that the problems of antioxidant loss, reinforcing fiber length-diameter ratio loss and matrix resin thermal cracking caused by the fact that matrix resin and modified master batches are subjected to melting and mixing twice or repeatedly through a processing machine in the conventional plastic modification process are solved, and the mechanical property and the long-term use of a polypropylene product are obviously improved.
(7) The invention effectively improves the polypropylene enhanced flame-retardant modification efficiency, simplifies the plastic modification processing steps, reduces the processing period, reduces the energy consumption, improves the production efficiency and really realizes the green chemical development concept. 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 injection molding and high-performance and functional modification integrated processing of various polypropylene plastic products.
Detailed Description
The following examples are intended to provide those skilled in the art with a more complete understanding of the present invention, and are not intended to limit the scope of the present invention. Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
The high-efficiency enhanced flame-retardant functional master batch for direct injection molding of polypropylene comprises a master batch A and a master batch B, wherein the master batch A comprises the following raw materials in parts by mass:
| glass fiber | 70.0 kg |
| High flow polypropylene | 15.0 kg |
| Sodium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer | 8.0 kg |
| Atactic polypropylene | 4.0 kg |
| Maleic anhydride grafted polypropylene | 1.0 kg |
| Polytetrafluoroethylene powder | 1.7 kg |
| Antioxidant agent | 300.0 g |
The antioxidant is preferably a compound composed of triethylene glycol bis beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (trade name is antioxidant 245) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (trade name is antioxidant 626) in a mass ratio of 1: 1.
The B master batch comprises the following raw materials in parts by mass:
| decabromodiphenylethane | 40.0 kg |
| Ethyl-bis (tetrabromophthalimide) | 30.0 kg |
| Antimony trioxide | 15.0 kg |
| Sodium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer | 10.0 kg |
| Atactic polypropylene | 4.0 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, then respectively putting three material particles of high-flow polypropylene, sodium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer and maleic anhydride grafted polypropylene and three powder materials of random polypropylene, polytetrafluoroethylene powder and antioxidant into different high-speed mixers to be uniformly mixed, then respectively adding the mixed particle mixture and powder mixture into a double-screw extruder through main material hoppers and auxiliary material hoppers to carry out melt blending extrusion to prepare a compound melt, controlling the temperature of each section from a charging barrel to a machine head of the double-screw extruder to be 185-225 ℃, controlling the rotating speed of a screw to be 200 revolutions per minute, then directly extruding the compound melt into a die cavity of an impregnation die through a die connected with the machine head of the double-screw extruder, and simultaneously, feeding continuous long glass fibers (direct yarns) into the die cavity through another die of the impregnation die, dipping in the melt under the traction action of a godet roller in a die cavity, controlling the temperature of the die cavity of a dipping die at 245 ℃, controlling the speed of a tractor at 70 m/min, and cutting the glass fiber tows dipped in the melt into long-strip-shaped granules with the length of 10 mm by a granulator after the glass fiber tows are drawn out from the die cavity and cooled, thereby obtaining the master batch A.
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
The high-efficiency enhanced flame-retardant functional master batch for direct injection molding of polypropylene comprises a master batch A and a master batch B, wherein the master batch A comprises the following raw materials in parts by mass:
| glass fiber | 50.0 kg |
| High flow polypropylene | 35.0 kg |
| Zinc ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer | 7.0 kg |
| Atactic polypropylene | 5.0 kg |
| Maleic anhydride grafted polypropylene | 1.5 kg |
| Polytetrafluoroethylene powder | 1.2 kg |
| Antioxidant agent | 300.0 g |
The antioxidant is preferably a compound composed of triethylene glycol bis beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (trade name is antioxidant 245) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (trade name is antioxidant 626) in a mass ratio of 1: 1.
The B master batch comprises the following raw materials in parts by mass:
| decabromodiphenylethane | 35.0 kg |
| Brominated polystyrene | 20.0 kg |
| Antimony trioxide | 20.0 kg |
| Zinc borate | 10.0 kg |
| Zinc ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer | 8.5 kg |
| Atactic polypropylene | 5.0 kg |
| Oleic acid amides | 1.0 kg |
| 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, then respectively putting three material particles of high-flow polypropylene, zinc ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer and maleic anhydride grafted polypropylene and three powder materials of random polypropylene, polytetrafluoroethylene powder and antioxidant into different high-speed mixers to be uniformly mixed, then respectively adding the mixed particle mixture and powder mixture into a double-screw extruder through main material hoppers and auxiliary material hoppers to carry out melt blending extrusion to prepare a compound melt, controlling the temperature of each section from a charging barrel to a machine head of the double-screw extruder to be 185-225 ℃, controlling the rotating speed of a screw to be 180 r/min, directly extruding the compound melt into a die cavity of an impregnation die through a die connected with the machine head of the double-screw extruder, and simultaneously, feeding continuous long glass fibers (direct yarns) into the die cavity through the other die cavity of the impregnation die, dipping in the melt under the traction action of a godet roller in a die cavity, controlling the temperature of the die cavity of a dipping die at 230 ℃, controlling the speed of a tractor at 65 m/min, and cutting the glass fiber tows dipped in the melt into long-strip-shaped granules with the length of 12 mm by a granulator after being drawn out of the die cavity and cooled, thereby obtaining the master batch A.
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 110 ℃, 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 160 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.
Example 3
The high-efficiency enhanced flame-retardant functional master batch for direct injection molding of polypropylene comprises a master batch A and a master batch B, wherein the master batch A comprises the following raw materials in parts by mass:
| glass fiber | 60.0 kg |
| High flow polypropylene | 28.0 kg |
| Calcium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer | 5.7 kg |
| Atactic polypropylene | 3.0 kg |
| Maleic anhydride grafted polypropylene | 2.0 kg |
| Polytetrafluoroethylene powder | 1.0 kg |
| Antioxidant agent | 300.0 g |
The antioxidant is preferably a compound composed of triethylene glycol bis beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (trade name is antioxidant 245) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (trade name is antioxidant 626) in a mass ratio of 1: 1.
The B master batch comprises the following raw materials in parts by mass:
| decabromodiphenylethane | 40.0 kg |
| Ethyl-bis (tetrabromophthalimide) | 30.0 kg |
| Antimony trioxide | 15.0 kg |
| Calcium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer | 10.0 kg |
| Atactic polypropylene | 4.0 kg |
| Zinc stearate | 800.0 g |
| Polydimethylsiloxane | 200.0 g |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, then respectively putting three material particles of high-flow polypropylene, calcium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer and maleic anhydride grafted polypropylene and three powder materials of random polypropylene, polytetrafluoroethylene powder and antioxidant into different high-speed mixers to be uniformly mixed, then respectively adding the mixed particle mixture and powder mixture into a double-screw extruder through main material and auxiliary material hoppers to carry out melt blending extrusion to prepare a compound melt, controlling the temperature of each section from a charging barrel to a machine head of the double-screw extruder to be 185-225 ℃, controlling the rotating speed of a screw to be 160 revolutions per minute, then directly extruding the compound melt into a die cavity of an impregnation die through a die connected with the machine head of the double-screw extruder, and simultaneously, feeding continuous long glass fibers (direct yarns) into the die cavity through another die cavity of the impregnation die, dipping in the melt under the traction action of a godet roller in a die cavity, controlling the temperature of the die cavity of a dipping die at 240 ℃, controlling the speed of a tractor at 70 m/min, and cutting the glass fiber tows dipped in the melt into long-strip-shaped granules with the length of 10 mm by a granulator after the glass fiber tows are drawn out from the die cavity and cooled, thereby obtaining the master batch A.
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
The high-efficiency enhanced flame-retardant functional master batch for direct injection molding of polypropylene comprises a master batch A and a master batch B, wherein the master batch A comprises the following raw materials in parts by mass:
| glass fiber | 65.0 kg |
| High flow polypropylene | 20.0 kg |
| Barium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer | 10.0 kg |
| Atactic polypropylene | 2.0 kg |
| Maleic anhydride grafted polypropylene | 1.0 kg |
| Polytetrafluoroethylene powder | 1.7 kg |
| Antioxidant agent | 300.0 g |
The antioxidant is preferably a compound composed of triethylene glycol bis beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (trade name is antioxidant 245) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (trade name is antioxidant 626) in a mass ratio of 1: 1.
The B master batch comprises the following raw materials in parts by mass:
| decabromodiphenylethane | 30.0 kg |
| Brominated polystyrene | 30.0 kg |
| Antimony trioxide | 17.0 kg |
| Zinc borate | 8.0 kg |
| Barium ion crosslinked ethylene-propyleneOlefine acid copolymerized elastic ionomer | 7.0 kg |
| Atactic polypropylene | 7.0 kg |
| Stearic acid calcium salt | 600.0 g |
| Ethylene bis stearamide | 400.0 g |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, then respectively putting three material particles of high-flow polypropylene, barium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer and maleic anhydride grafted polypropylene and three powder materials of random polypropylene, polytetrafluoroethylene powder and antioxidant into different high-speed mixers to be uniformly mixed, then respectively adding the mixed particle mixture and powder mixture into a double-screw extruder through main material hoppers and auxiliary material hoppers to carry out melt blending extrusion to prepare a compound melt, controlling the temperature of each section from a charging barrel to a machine head of the double-screw extruder to be 185-225 ℃, controlling the rotating speed of a screw to be 190 revolutions per minute, directly extruding the compound melt into a die cavity of an impregnation die through a die connected with the machine head of the double-screw extruder, and simultaneously, feeding continuous long glass fibers (direct yarns) into the die cavity through another die cavity of the impregnation die, dipping in the melt under the traction action of a godet roller in a die cavity, controlling the temperature of the die cavity of a dipping die to 235 ℃, and controlling the speed of a tractor to be 70 m/min, and cutting the glass fiber tows dipped in the melt into long-strip-shaped granules with the length of 9 mm by a granulator after being drawn out of the die cavity and cooled, thereby obtaining the master batch A.
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
The high-efficiency enhanced flame-retardant functional master batch for direct injection molding of polypropylene comprises a master batch A and a master batch B, wherein the master batch A comprises the following raw materials in parts by mass:
| glass fiber | 55.0 kg |
| High flow polypropylene | 32.0 kg |
| Magnesium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer | 6.0 kg |
| Atactic polypropylene | 4.0 kg |
| Maleic anhydride grafted polypropylene | 1.7 kg |
| Polytetrafluoroethylene powder | 1.0 kg |
| Antioxidant agent | 300.0 g |
The antioxidant is preferably a compound composed of triethylene glycol bis beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (trade name is antioxidant 245) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (trade name is antioxidant 626) in a mass ratio of 1: 1.
The B master batch comprises the following raw materials in parts by mass:
| decabromodiphenylethane | 35.0 kg |
| Ethyl-bis (tetrabromophthalimide) | 25.0 kg |
| Antimony trioxide | 25.0 kg |
| Magnesium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer | 8.5 kg |
| Atactic polypropylene | 5.0 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, then respectively putting three material particles of high-flow polypropylene, magnesium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer and maleic anhydride grafted polypropylene and three powder materials of random polypropylene, polytetrafluoroethylene powder and antioxidant into different high-speed mixers to be uniformly mixed, then respectively adding the mixed particle mixture and powder mixture into a double-screw extruder through main material hoppers and auxiliary material hoppers to carry out melt blending extrusion to prepare a compound melt, controlling the temperature of each section from a charging barrel to a machine head of the double-screw extruder to be 185-225 ℃, controlling the rotating speed of a screw to be 175 r/min, directly extruding the compound melt into a die cavity of an impregnation die through a die connected with the machine head of the double-screw extruder, and simultaneously, feeding continuous long glass fibers (direct yarns) into the die cavity through the other die cavity of the impregnation die, dipping in the melt under the traction action of a godet roller in a die cavity, controlling the temperature of the die cavity of a dipping die to be 247 ℃, controlling the speed of a tractor to be 60 m/min, and cutting the glass fiber tows dipped in the melt into long-strip-shaped granules with the length of 9 mm by a granulator after being drawn out from the die cavity and cooled, thereby obtaining the master batch A.
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
The high-efficiency enhanced flame-retardant functional master batch for direct injection molding of polypropylene comprises a master batch A and a master batch B, wherein the master batch A comprises the following raw materials in parts by mass:
| glass fiber | 65.0 kg |
| High flow polypropylene | 20.0 kg |
| Sodium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer | 6.0 kg |
| Atactic polypropylene | 3.0 kg |
| Maleic anhydride grafted polypropylene | 3.0 kg |
| Polytetrafluoroethylene powder | 2.7 kg |
| Antioxidant agent | 300.0 g |
The antioxidant is preferably a compound composed of triethylene glycol bis beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (trade name is antioxidant 245) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (trade name is antioxidant 626) in a mass ratio of 1: 1.
The B master batch comprises the following raw materials in parts by mass:
| ethyl-bis (tetrabromobenzo-o)Dimethyl imide) | 40.0 kg |
| Brominated polystyrene | 25.0 kg |
| Antimony trioxide | 20.0 kg |
| Zinc borate | 9.0 kg |
| Sodium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer | 5.0 kg |
| Atactic polypropylene | 5.0 kg |
| Zinc stearate | 800.0 g |
| Ethylene bis stearamide | 200.0 g |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, then respectively putting three material particles of high-flow polypropylene, sodium ion crosslinked ethylene-acrylic acid copolymerized elastic ionomer and maleic anhydride grafted polypropylene and three powder materials of random polypropylene, polytetrafluoroethylene powder and antioxidant into different high-speed mixers to be uniformly mixed, then respectively adding the mixed particle mixture and powder mixture into a double-screw extruder through main material hoppers and auxiliary material hoppers to carry out melt blending extrusion to prepare a compound melt, controlling the temperature of each section from a charging barrel to a machine head of the double-screw extruder to be 185-225 ℃, controlling the rotating speed of a screw to be 195 revolutions per minute, then directly extruding the compound melt into a die cavity of an impregnation die through a die connected with the machine head of the double-screw extruder, and simultaneously, feeding continuous long glass fibers (direct yarns) into the die cavity through the other die cavity of the impregnation die, dipping in the melt by the traction action of a godet roller in a die cavity, controlling the die cavity temperature of a dipping die at 246 ℃, controlling the speed of a tractor at 50 m/min, and cutting the glass fiber tows dipped in the melt into long-strip-shaped granules with the length of 11 mm by a granulator after being drawn out of the die cavity and cooled, thereby obtaining the master batch A.
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 glass fibers in examples 1-6 were continuous long glass fibers and the high flow polypropylene had a melt flow index greater than 50.0 g/10 min.
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 enhanced flame-retardant 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 mixed with polypropylene resin according to the respective mass percentage of 25 wt.%, test sample strips are directly injected and molded, 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 data in table 1 show that the tensile strength, notch impact strength and flame retardant property of the plastic product prepared by the embodiment of the invention are obviously superior to those of the plastic product processed by a double-screw extruder and then injection molded after being applied to direct injection molding of polypropylene under the condition that the components and the proportion are completely the same. 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 from the functional master batches prepared in examples 1 to 6 with the polypropylene test specimens injection molded from the same raw material formulation after processing in a twin screw extruder.
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 (8)
1. The high-efficiency enhanced flame-retardant 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: 50.0-70.0 wt.% of glass fiber, 15.0-35.0 wt.% of high-fluidity polypropylene, 5.0-10.0 wt.% of elastic ionomer, 3.0-6.0 wt.% of random polypropylene, 1.0-3.0 wt.% of maleic anhydride grafted polypropylene, 1.0-3.0 wt.% of polytetrafluoroethylene powder, 0.1-0.3 wt.% of antioxidant,
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, 5.0-10.0 wt% of elastic ionomer, 2.0-5.0 wt% of random polypropylene, 0.5-1.0 wt% of dispersant and 0.2-0.5 wt% of lubricant;
the elastic ionomer is an ethylene-acrylic acid copolymerized elastic ionomer crosslinked by sodium, calcium, magnesium, barium or zinc ions; the glass fiber is continuous long glass fiber, and the melt flow index of the high-flow polypropylene is more than 50.0 g/10 min.
2. The high-efficiency enhanced flame-retardant master batch for direct injection molding of polypropylene according to claim 1, wherein the high-efficiency enhanced flame-retardant master batch comprises: the antioxidant is a compound consisting of triethylene glycol bis beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite in a mass ratio of 1: 1.
3. The high-efficiency enhanced flame-retardant master batch for direct injection molding of polypropylene according to claim 1, wherein the high-efficiency enhanced flame-retardant master batch comprises: the brominated flame retardant is any one or more of decabromodiphenylethane, ethyl-bis (tetrabromophthalimide) and brominated polystyrene, and the inorganic flame retardant synergist is any one or two of antimony trioxide and zinc borate.
4. The high-efficiency enhanced flame-retardant master batch for direct injection molding of polypropylene according to claim 1, wherein the high-efficiency enhanced flame-retardant master batch comprises: 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.
5. The method for preparing the high-efficiency enhanced flame-retardant master batch for direct injection molding of polypropylene according to any one of claims 1 to 4, which is characterized by comprising the following steps: the preparation method of the A master batch comprises the following steps:
(1) weighing glass fiber, high-flow polypropylene, elastic ionomer, atactic polypropylene, maleic anhydride grafted polypropylene, polytetrafluoroethylene powder and an antioxidant according to a ratio, premixing the powder and the granules uniformly by using a high-speed mixer respectively, and adding the powder and the granules into a double-screw extruder through a main material hopper and an auxiliary material hopper to perform melt blending extrusion to prepare a composite melt;
(2) and (2) directly extruding the compound melt obtained in the step (1) into a die cavity of an impregnation die through a die connected with a head of a double-screw extruder, simultaneously, enabling continuous long glass fibers to enter the die cavity through the other die of the impregnation die, impregnating in the melt under the traction action of a godet roller in the die cavity, drawing out glass fiber tows impregnated in the melt from the die cavity, cooling, and cutting into strip-shaped granules with the length of 8-12 mm through a granulator to obtain the master batch A.
6. The preparation method of the high-efficiency enhanced flame-retardant functional master batch for direct injection molding of polypropylene according to claim 5, wherein the preparation method comprises the following steps: the processing technology of the A master batch comprises the following steps: the temperature of each section from a charging barrel to a machine head of the double-screw extruder is controlled to be 185-225 ℃, and the rotating speed of a screw is 150-200 revolutions per minute; the temperature of a die cavity of the dipping die is controlled to be 230-250 ℃, and the speed of a tractor is controlled to be 50-70 m/min.
7. The method for preparing the high-efficiency enhanced flame-retardant master batch for direct injection molding of polypropylene according to any one of claims 1 to 4, which is characterized by comprising the following steps: the preparation method of the B master batch comprises the following steps:
(1) weighing a brominated flame retardant, an inorganic flame-retardant synergist, an elastic ionomer, atactic polypropylene, a dispersant and a lubricant according to a ratio, putting the 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;
(2) and (2) feeding the bulk blend obtained in the step (1) into a single-screw extruder through a conical feeding machine, and performing melt extrusion and granulation to obtain the B master batch.
8. The preparation method of the high-efficiency enhanced flame-retardant functional master batch for direct injection molding of polypropylene according to claim 7, 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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| CN103113661A (en) * | 2011-11-17 | 2013-05-22 | 合肥杰事杰新材料股份有限公司 | High-strength high-toughness flame-retardant polypropylene composite and preparation method thereof |
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| CN102964674A (en) * | 2011-09-01 | 2013-03-13 | 合肥杰事杰新材料股份有限公司 | Ultrahigh-toughness flame-retardant polypropylene composite material and preparation method thereof |
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