CN109486154B - Efficient halogen-free enhanced flame-retardant functional master batch for direct injection molding of PC-ABS (polycarbonate-acrylonitrile butadiene styrene) alloy and preparation method thereof - Google Patents
Efficient halogen-free enhanced flame-retardant functional master batch for direct injection molding of PC-ABS (polycarbonate-acrylonitrile butadiene styrene) alloy and preparation method thereof Download PDFInfo
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- C08K7/14—Glass
Abstract
The invention belongs to the technical field of plastic modification and processing, and particularly relates to an efficient enhanced halogen-free flame-retardant functional master batch which can be directly applied to injection molding processing of PC/ABS alloy 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: 50.0-60.0 wt.% of glass fiber, 20.0-25.0 wt.% of high-flow PC resin, 10.0-15.0 wt.% of ABS resin, 5.0-10.0 wt.% of thermoplastic styrene elastomer, 2.0-3.0 wt.% of styrene-maleic anhydride random copolymer, 1.0-2.0 wt.% of hyperbranched polyester and 0.1-0.3 wt.% of antioxidant; compared with the traditional plastic functional master batch, the functional master batch avoids the mutual loss of modification efficiency caused by mutual shearing and abrasion of the glass fiber and the flame retardant in the processing process, and obviously improves the modification efficiency of the glass fiber and the flame retardant compared with the traditional reinforced halogen-free flame retardant system; the master batch has the characteristics of easy dispersion and easy processing, and can be directly and simply mixed with PC/ABS alloy 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 halogen-free flame-retardant functional master batch capable of being directly applied to injection molding processing of PC/ABS alloy 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.
Polycarbonate (PC)/styrene-polybutadiene-styrene copolymer (ABS) alloy is the engineering plastic with the largest global use amount at present, and the application field of the PC/ABS alloy can be greatly expanded by performing high-performance and functional modification on the PC/ABS alloy. As an important PC/ABS alloy modified material, the reinforced flame-retardant PC/ABS alloy composite is widely applied to the fields of machinery, automobiles, rail efficiency, electronic and electric appliances and the like. With the increasing awareness of environmental protection, the application of halogen-containing flame retardants in the modification of PC/ABS alloys is limited, and the application of enhanced halogen-free flame-retardant PC/ABS alloy materials is popularized. However, in the process of preparing the enhanced halogen-free flame-retardant PC/ABS alloy modified special material, the inorganic reinforced fiber and the flame retardant are simultaneously added into the PC/ABS alloy resin for melt blending extrusion, and the typical phenomenon of mutual loss of the modification efficiency of the additive can occur.
Disclosure of Invention
In order to solve the problem of mutual loss of modification efficiency in the preparation process of the existing glass fiber reinforced flame-retardant PC/ABS alloy special material, the invention provides the high-efficiency reinforced flame-retardant functional master batch which can be directly applied to injection molding processing of PC/ABS alloy plastic products and the preparation method thereof. The functional master batch is formed by combining A and B functional master batches. The master batch A mainly comprises chopped glass fiber, high-flow PC resin, ABS resin, thermoplastic styrene elastomer, styrene-maleic anhydride random copolymer and hyperbranched polyester with ultrahigh dispersion capacity, and is prepared into reinforced master batch through high-temperature melt extrusion of a double-screw extruder; the B master batch mainly comprises a bromine-antimony compound flame retardant, a thermoplastic styrene elastomer, a low molecular weight polyphenylene ether, a styrene-maleic anhydride random copolymer and a hyperbranched polyester super-dispersible carrier resin, and is prepared into the halogen-free flame retardant master batch through low-temperature mixing of 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 phosphorus/nitrogen flame retardant caused by internal friction heat generation generated by directly blending the glass fiber and the phosphorus/nitrogen flame retardant is avoided; the problem that the melt blending processing temperature of two modification systems of the glass fiber reinforced PC/ABS alloy and the phosphorus-nitrogen compounded flame-retardant PC/ABS alloy is not matched is solved; the use of the ultra-dispersion resin and the auxiliary agent system with lower processing temperature as carriers is beneficial to improving the dispersion of the flame retardant in the plastic matrix, obviously reduces the processing and preparation temperature of the phosphorus/nitrogen-containing flame retardant master batch, and avoids the thermal decomposition of the flame retardant; the random copolymer of styrene and maleic anhydride is used as the carrier component of the A and B master batches, so that the interfacial cohesiveness between the fiber and the matrix can be improved, and the compatibilization effect between the PC/ABS alloy resin and the carrier resin can be realized; introducing low molecular weight polyphenylene ether as a carrier into the B master batch is favorable for improving the dispersibility and the compatibility with a matrix of the phosphorus/nitrogen flame retardant, can also play a role of a charring agent and promotes the flame retardant effect of the phosphorus/nitrogen flame retardant. In addition, aiming at the physical properties of the modified additive loaded by 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. Therefore, the master batches A and B can be directly and simply mixed with PC/ABS alloy resin according to a certain proportion and then injection molded according to performance requirements, and other resins and/or master batches can be added for injection molding together: including but not limited to: PC resin, ABS resin, color master batch, antibacterial master batch, weather-resistant master batch and antistatic master batch. 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 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 PC/ABS alloy, and practices the optimal design concept of the plastic modification formula with the ratio of 1+1 to 2 and the processing technology.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of the PC/ABS alloy is formed by combining A master batch and B master batch, wherein the A master batch comprises the following components in percentage by mass: 50.0-60.0 wt% of glass fiber, 20.0-25.0 wt% of high-fluidity PC resin, 10.0-15.0 wt% of ABS resin, 5.0-10.0 wt% of thermoplastic styrene elastomer, 2.0-3.0 wt% of styrene-maleic anhydride random copolymer, 1.0-2.0 wt% of hyperbranched polyester and 0.1-0.3 wt% of antioxidant, wherein the B master batch comprises the following components in percentage by mass: 40.0-60.0 wt.% of phosphorus flame retardant, 25.0-45.0 wt.% of nitrogen flame retardant, 5.0-10.0 wt.% of thermoplastic styrene elastomer, 3.0-5.0 wt.% of low molecular weight polyphenylene ether, 2.0-3.0 wt.% of styrene-maleic anhydride random copolymer, 1.0-2.0 wt.% of hyperbranched polyester and 0.5-1.0 wt.% of lubricant.
Furthermore, the glass fiber is a fixed-length chopped fiber with the length distribution of 3.0-5.0 mm.
Further, the high flow PC resin has a melt index greater than 15g/10 min.
Further, the molecular weight of the low molecular weight polyphenyl ether is 3000-10000 g/mol.
Further, the thermoplastic styrene elastomer is one or more of styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-hydrogenated butadiene-styrene block copolymer (SEBS), and styrene-hydrogenated isoprene-styrene block copolymer (sesis), and preferably SEBS.
Furthermore, the hyperbranched polyester is a four-arm polyester copolymer which takes pentaerythritol as a core and takes poly (dimethylolpropionic acid) as a branched chain.
Further, the antioxidant is a compound consisting of 4- [ (4, 6-dioctylthio-1, 3, 5-triazin-2-yl) ] -2, 6-di-tert-butylphenol (trade name is antioxidant 565) and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite (trade name is antioxidant S9228) in a mass ratio of 1: 1.
Further, the phosphorus flame retardant is one or more of triphenyl phosphate, resorcinol bis (diphenyl phosphate), bisphenol a bis (diphenyl phosphate), resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ], diethyl aluminum hypophosphite, methyl ethyl aluminum hypophosphite, calcium hypophosphite, ammonium polyphosphate and melamine polyphosphate.
Further, the nitrogen-based flame retardant is one or two of melamine cyanurate and melamine.
Further, the lubricant is one or more of E wax, OP wax, pentaerythritol stearate and ethylene bis stearamide.
A method for preparing a high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of PC/ABS alloy 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 chopped glass fiber, high-flow PC resin, ABS resin, thermoplastic styrene elastomer, styrene-maleic anhydride random copolymer, hyperbranched polyester and antioxidant according to the proportion, and putting granules and powder in a high-speed mixer for uniform mixing;
(2) and (2) feeding the mixture obtained in the step (1) and the weighed chopped glass fibers into a double-screw extruder through a conical feeder and a side feeder respectively for blending extrusion and granulation to obtain the master batch A.
Furthermore, the screw rotating speed of the double-screw extruder is 200-300 revolutions per minute, and the temperature of the machine barrel is 220-260 ℃.
A method for preparing a high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of PC/ABS alloy relates to a preparation method of a master batch A and a preparation method of a master batch B, wherein the preparation method of the master batch B comprises the following steps:
(1) weighing a phosphorus flame retardant, a nitrogen flame retardant, a thermoplastic styrene elastomer, a low molecular weight polyphenylene ether, a styrene-maleic anhydride random copolymer, a hyperbranched polyester and a lubricant according to a ratio, putting the materials into a high-speed mixer, uniformly mixing, and transferring the mixture into an internal mixer for hot mixing to obtain a bulk blend;
(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 110-130 ℃, 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 phosphorus-nitrogen compound flame retardant master batch (master batch B), so that the damage of flame retardant efficiency caused by the decomposition of the halogen-free flame retardant due to mutual shearing and frictional heat when the PC/ABS alloy, the glass fiber and the halogen-free flame retardant are directly melted, blended and extruded is effectively avoided, and the technical problem that the processing temperatures of two modification systems are not matched is solved, thereby obviously improving the respective modification efficiency of the two modified additives.
(2) The master batch B skillfully adopts the low molecular weight polyphenylene ether as a carrier, which is beneficial to improving the dispersibility and the compatibility with a matrix of the phosphorus/nitrogen flame retardant, can also play a role of a charring agent, promotes the flame retardant effect of the phosphorus/nitrogen flame retardant, and simultaneously avoids the surface frosting phenomenon of a PC/ABS alloy product caused by the migration of small molecules after the charring agent is added.
(3) The resin combined carrier with high dispersibility and high compatibility is adopted in the A master batch and the B master batch, so that the interface cohesiveness of the glass fiber and the PC/ABS alloy matrix can be effectively improved, and the glass fiber and the flame retardant can obtain better dispersion effect in the PC/ABS alloy resin matrix when the glass fiber and the flame retardant are directly used for injection molding processing of PC/ABS alloy plastic products, so that more excellent reinforcing and flame-retardant effects are obtained.
(4) Compared with the traditional plastic functional master batch, the functional master batch prepared 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 which is far more than 2, but also has the characteristics of easy dispersion and easy processing, and can be directly applied to the injection molding processing of plastic products after simply mixing the master batch A and the master batch B with PC/ABS alloy resin according to a certain proportion according to the performance requirements of the PC/ABS alloy 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 batch 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 PC/ABS alloy product are obviously improved.
(5) The invention effectively improves the enhanced flame-retardant modification efficiency of the PC/ABS alloy, simplifies the plastic modification processing steps, reduces the processing period, reduces the energy consumption, improves the production efficiency and really realizes the development concept of green chemical industry. 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 PC/ABS alloy plastic products. The method and the technology of the invention can be widely applied to the injection molding and high-performance and functional modification integrated processing of various PC/ABS alloy 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 efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of the PC/ABS alloy is formed by combining A master batch and B master batch, wherein the A master batch comprises the following raw materials in parts by mass:
the antioxidant is a compound consisting of 4- [ (4, 6-dioctylthio-1, 3, 5-triazine-2-yl) ] -2, 6-di-tert-butylphenol (the trade name is antioxidant 565) and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite (the trade name is antioxidant S9228) according to the mass ratio of 1: 1.
The B master batch comprises the following raw materials in parts by mass:
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 high-flow PC resin, the ABS resin, the SEBS, the SMA, the hyperbranched polyester and the antioxidant into a high-speed mixer for uniform mixing, then feeding the obtained mixture and the weighed chopped glass fibers into a double-screw extruder through a conical feeder and a side feeder respectively for blending extrusion and granulation to obtain the A master batch, wherein the temperature of each section from a charging barrel to a machine head of the double-screw extruder is controlled to be 220-260 ℃, and the rotating speed of a screw is 250 revolutions per minute.
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 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 185 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.
Example 2
The efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of the PC/ABS alloy is formed by combining A master batch and B master batch, wherein the A master batch comprises the following raw materials in parts by mass:
the antioxidant is a compound consisting of 4- [ (4, 6-dioctylthio-1, 3, 5-triazine-2-yl) ] -2, 6-di-tert-butylphenol (the trade name is antioxidant 565) and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite (the trade name is antioxidant S9228) according to the mass ratio of 1: 1.
The B master batch comprises the following raw materials in parts by mass:
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 high-flow PC resin, the ABS resin, the SEIS, the SMA, the hyperbranched polyester and the antioxidant into a high-speed mixer for uniform mixing, then feeding the obtained mixture and the weighed chopped glass fibers into a double-screw extruder through a conical feeder and a side feeder respectively for blending extrusion and granulation to obtain the A master batch, wherein the temperature of each section from a charging barrel to a machine head of the double-screw extruder is controlled to be 220-260 ℃, and the rotating speed of a screw is 230 r/min.
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 130 ℃, 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 175 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.
Example 3
The efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of the PC/ABS alloy is formed by combining A master batch and B master batch, wherein the A master batch comprises the following raw materials in parts by mass:
the antioxidant is a compound consisting of 4- [ (4, 6-dioctylthio-1, 3, 5-triazine-2-yl) ] -2, 6-di-tert-butylphenol (the trade name is antioxidant 565) and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite (the trade name is antioxidant S9228) according to the mass ratio of 1: 1.
The B master batch comprises the following raw materials in parts by mass:
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 high-flow PC resin, the ABS resin, the SBS, the SMA, the hyperbranched polyester and the antioxidant into a high-speed mixer for uniform mixing, then feeding the obtained mixture and the weighed chopped glass fibers into a double-screw extruder through a conical feeder and a side feeder respectively for blending extrusion and granulation to obtain the master batch A, wherein the temperature of each section from a charging barrel to a machine head of the double-screw extruder is controlled to be 220-260 ℃, and the rotating speed of a screw is 200 revolutions per minute.
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 130 ℃, 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 200 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.
Example 4
The efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of the PC/ABS alloy is formed by combining A master batch and B master batch, wherein the A master batch comprises the following raw materials in parts by mass:
the antioxidant is a compound consisting of 4- [ (4, 6-dioctylthio-1, 3, 5-triazine-2-yl) ] -2, 6-di-tert-butylphenol (the trade name is antioxidant 565) and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite (the trade name is antioxidant S9228) according to the mass ratio of 1: 1.
The B master batch comprises the following raw materials in parts by mass:
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 high-flow PC resin, the ABS resin, the SIS, the SMA, the hyperbranched polyester and the antioxidant into a high-speed mixer for uniform mixing, then feeding the obtained mixture and the weighed chopped glass fibers into a double-screw extruder through a conical feeder and a side feeder respectively for blending extrusion and granulation to obtain the A master batch, wherein the temperature of each section from a charging barrel to a machine head of the double-screw extruder is controlled to be 220-260 ℃, and the rotating speed of a screw is 220 r/min.
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 128 ℃, 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 185 revolutions per minute, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.
Example 5
The efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of the PC/ABS alloy is formed by combining A master batch and B master batch, wherein the A master batch comprises the following raw materials in parts by mass:
the antioxidant is a compound consisting of 4- [ (4, 6-dioctylthio-1, 3, 5-triazine-2-yl) ] -2, 6-di-tert-butylphenol (the trade name is antioxidant 565) and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite (the trade name is antioxidant S9228) according to the mass ratio of 1: 1.
The B master batch comprises the following raw materials in parts by mass:
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 high-flow PC resin, the ABS resin, the SEBS, the SMA, the hyperbranched polyester and the antioxidant into a high-speed mixer for uniform mixing, then feeding the obtained mixture and the weighed chopped glass fibers into a double-screw extruder through a conical feeder and a side feeder respectively for blending extrusion and granulation to obtain the A master batch, wherein the temperature of each section from a charging barrel to a machine head of the double-screw extruder is controlled to be 220-260 ℃, and the rotating speed of a screw is 220 r/min.
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 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 efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of the PC/ABS alloy is formed by combining A master batch and B master batch, wherein the A master batch comprises the following raw materials in parts by mass:
the antioxidant is a compound consisting of 4- [ (4, 6-dioctylthio-1, 3, 5-triazine-2-yl) ] -2, 6-di-tert-butylphenol (the trade name is antioxidant 565) and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite (the trade name is antioxidant S9228) according to the mass ratio of 1: 1.
The B master batch comprises the following raw materials in parts by mass:
the preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio, putting the high-flow PC resin, the ABS resin, the SEIS, the SMA, the hyperbranched polyester and the antioxidant into a high-speed mixer for uniform mixing, then feeding the obtained mixture and the weighed chopped glass fibers into a double-screw extruder through a conical feeder and a side feeder respectively for blending extrusion and granulation to obtain the A master batch, wherein the temperature of each section from a charging barrel to a machine head of the double-screw extruder is controlled to be 220-260 ℃, and the rotating speed of a screw is 200 revolutions per minute.
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 155 r/min, and the temperature of the machine barrel is controlled to be 150-160 ℃ in sections.
The hyperbranched polyesters in examples 1 to 6 are four-arm polyester copolymers having pentaerythritol as the core and poly (dimethylolpropionic acid) as the branched chain.
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 halogen-free flame-retardant functional master batch for direct injection molding of the PC/ABS alloy, the master batch A and the master batch B prepared in the embodiments 1 to 6 are mixed with the PC/ABS alloy according to the respective mass percentage of 25wt.%, 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 high-efficiency enhanced halogen-free flame-retardant master batch for direct injection molding of the PC/ABS alloy prepared by the embodiment of the invention is applied to direct injection molding of the PC/ABS alloy, and the tensile strength, the notch impact strength and the flame retardant property of a plastic product are obviously superior to the performance of an injection molded product after being processed by a double-screw extruder under the condition that the components and the proportion are completely the same. By utilizing the functional master batch, the modification processing steps of the PC/ABS alloy 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 PC/ABS alloy test specimens directly injection molded from the functional master batches prepared in examples 1-6 and PC/ABS alloy test specimens injection molded from the same raw material formulation by processing with 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 (10)
1. The high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of the PC/ABS alloy 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: 50.0-60.0 wt.% of glass fiber, 20.0-25.0 wt.% of high-flow PC resin, 10.0-15.0 wt.% of ABS resin, 5.0-10.0 wt.% of thermoplastic styrene elastomer, 2.0-3.0 wt.% of styrene-maleic anhydride random copolymer, 1.0-2.0 wt.% of hyperbranched polyester and 0.1-0.3 wt.% of antioxidant, wherein the glass fiber is chopped fiber with the length distribution of 3.0-5.0 mm, and the melt index of the high-flow PC resin is more than 15g/10min,
the B master batch comprises the following components in percentage by mass: 40.0-60.0 wt.% of phosphorus flame retardant, 25.0-45.0 wt.% of nitrogen flame retardant, 5.0-10.0 wt.% of thermoplastic styrene elastomer, 3.0-5.0 wt.% of low molecular weight polyphenylene ether, 2.0-3.0 wt.% of styrene-maleic anhydride random copolymer, 1.0-2.0 wt.% of hyperbranched polyester and 0.5-1.0 wt.% of lubricant, wherein the molecular weight of the low molecular weight polyphenylene ether is 3000-10000 g/mol.
2. The efficient reinforced halogen-free flame retardant master batch for direct injection molding of PC/ABS alloy according to claim 1, characterized in that: the thermoplastic styrene elastomer is one or more of styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-hydrogenated butadiene-styrene block copolymer (SEBS) and styrene-hydrogenated isoprene-styrene block copolymer (SEIS).
3. The efficient reinforced halogen-free flame retardant master batch for direct injection molding of PC/ABS alloy according to claim 1, characterized in that: the hyperbranched polyester is a four-arm polyester copolymer which takes pentaerythritol as a core and takes poly (dimethylolpropionic acid) as a branched chain.
4. The efficient reinforced halogen-free flame retardant master batch for direct injection molding of PC/ABS alloy according to claim 1, characterized in that: the antioxidant is a compound consisting of 4- [ (4, 6-dioctylthio-1, 3, 5-triazine-2-yl) ] -2, 6-di-tert-butylphenol and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite in a mass ratio of 1: 1.
5. The efficient reinforced halogen-free flame retardant master batch for direct injection molding of PC/ABS alloy according to claim 1, characterized in that: the phosphorus flame retardant is one or more of triphenyl phosphate, resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ], diethyl aluminum hypophosphite, methyl ethyl aluminum hypophosphite, calcium hypophosphite, ammonium polyphosphate and melamine polyphosphate; the nitrogen flame retardant is one or two of melamine cyanurate and melamine.
6. The efficient reinforced halogen-free flame retardant master batch for direct injection molding of PC/ABS alloy according to claim 1, characterized in that: the lubricant is one or more of E wax, OP wax, pentaerythritol stearate and ethylene bis stearamide.
7. The method for preparing the high-efficiency enhanced halogen-free flame retardant functional master batch for the direct injection molding of the PC/ABS alloy according to any one of claims 1 to 6, is characterized in that: the preparation method of the A master batch comprises the following steps:
(1) weighing chopped glass fiber, high-flow PC resin, ABS resin, thermoplastic styrene elastomer, styrene-maleic anhydride random copolymer, hyperbranched polyester and antioxidant according to the proportion, and putting granules and powder in a high-speed mixer for uniform mixing;
(2) and (2) feeding the mixture obtained in the step (1) and the weighed chopped glass fibers into a double-screw extruder through a conical feeder and a side feeder respectively for blending extrusion and granulation to obtain the master batch A.
8. The preparation method of the highly effective enhanced halogen-free flame retardant functional master batch for PC/ABS alloy direct injection molding according to claim 7, characterized in that: the processing technology of the A master batch comprises the following steps: the screw rotating speed of the double-screw extruder is 200-300 revolutions per minute, and the temperature of the machine barrel is 220-260 ℃.
9. The method for preparing the high-efficiency enhanced halogen-free flame retardant functional master batch for the direct injection molding of the PC/ABS alloy according to any one of claims 1 to 6, is characterized in that: the preparation method of the B master batch comprises the following steps:
(1) weighing a phosphorus flame retardant, a nitrogen flame retardant, a thermoplastic styrene elastomer, a low molecular weight polyphenylene ether, a styrene-maleic anhydride random copolymer, a hyperbranched polyester and a lubricant according to a ratio, putting the materials into a high-speed mixer, uniformly mixing, and transferring the mixture into an internal mixer for hot mixing to obtain a bulk blend;
(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.
10. The preparation method of the highly effective enhanced halogen-free flame retardant functional master batch for PC/ABS alloy direct injection molding according to claim 9, characterized in that: the processing technology of the B master batch comprises the following steps: the mixing temperature of the internal mixer is 110-130 ℃, 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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