CN109370210B - Efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 and preparation method thereof - Google Patents
Efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of plastic modification and processing, and particularly relates to a high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 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, 20.0-35.0 wt.% of high-flow nylon 6 resin, 3.0-10.0 wt.% of maleic anhydride grafted elastic ionomer, 3.0-6.0 wt.% of star nylon 6 resin and 0.1-0.3 wt.% of antioxidant; compared with the traditional plastic functional master batch, the functional master batch prepared by the invention avoids the mutual loss of modification efficiency caused by mutual shearing and abrasion of the glass fiber and the flame retardant in the processing process of the enhanced halogen-free flame-retardant nylon 6 modification system, simultaneously solves the problem of unmatched processing temperature of the two modification systems, and obviously enhances the modification efficiency of the two modification systems; the master batch has the characteristic of easy dispersion processing, can be directly mixed with nylon 6 resin simply according to the proportion and then is subjected to injection molding, and obtains excellent modification effect.
Description
Technical Field
The invention belongs to the technical field of plastic modification and processing, and particularly relates to an efficient enhanced halogen-free flame-retardant functional master batch capable of being directly applied to injection molding processing of nylon 6 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.
The nylon 6 is the engineering plastic with the largest global use amount at present, and the application field of the nylon 6 can be greatly expanded by carrying out high-performance and functional modification on the nylon 6. As an important nylon 6 modified material, the reinforced flame-retardant nylon 6 compound is widely applied to the fields of machinery, automobiles, track efficiency, electronic and electric appliances and the like. With the increasing awareness of environmental protection, the application of halogen-containing flame retardants in nylon 6 modification is limited, and the application of halogen-free flame retardant reinforced nylon 6 materials is promoted. However, in the process of preparing the special material for modifying the enhanced halogen-free flame retardant nylon 6, the inorganic enhanced fiber and the flame retardant are simultaneously added into the nylon 6 resin for melt blending and extrusion, and the typical phenomenon that the modification efficiency of the additive is damaged mutually occurs.
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 nylon 6 special material, the invention provides the high-efficiency reinforced flame-retardant functional master batch which can be directly applied to injection molding processing of nylon 6 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 nylon 6 and low-viscosity star nylon 6 resin, and is processed by a melt pultrusion method to prepare long fiber reinforced and toughened master batch; the B master batch mainly comprises a phosphorus-nitrogen compound flame retardant and a super-dispersible carrier resin, and is prepared into the halogen-free 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 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 processing temperature of the two modification systems of the glass fiber reinforced nylon 6 and the phosphorus-nitrogen compounded flame retardant nylon 6 is not matched is solved; and thirdly, 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. Maleic anhydride grafted elastic ionomer is respectively used as the carrier components of the A master batch and the B master batch, the reactive end group of the maleic anhydride grafted elastic ionomer can have the largest contact chance with the end group of the nylon 6 resin under the environment without interference of flame-retardant powder, the toughening effect of the maleic anhydride grafted elastic ionomer is exerted to the maximum extent, the interfacial cohesiveness among organic and inorganic components in the formula can be improved, the melt fluidity of the compound is improved, and the surface finish and the deformation resistance of the product are improved. 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 the nylon 6 resin according to a certain proportion and then injection molded according to the performance requirement, and other resins and/or master batches can be added for injection molding together: including but not limited to: nylon 66, co-polymerized nylon, color master batch, filling master batch, toughening master batch, nucleating master batch, chain extending master batch, lubricating master batch, antistatic master batch, anti-aging master batch, conductive master batch, heat conducting master batch, laser carving master batch, silicone master batch and antibacterial 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 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 nylon 6, 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:
the efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 is prepared by combining a master batch A and a master batch B, wherein the master batch A comprises the following components in percentage by mass: 50.0-70.0 wt.% of glass fiber, 20.0-35.0 wt.% of high-fluidity nylon 6 resin, 3.0-10.0 wt.% of maleic anhydride grafted elastic ionomer, 3.0-6.0 wt.% of star nylon 6 resin and 0.1-0.3 wt.% of antioxidant, wherein the B master batch comprises the following components in percentage by mass: 45.0 to 60.0wt.% of a phosphorus flame retardant, 20.0 to 40.0wt.% of a nitrogen flame retardant, 3.0 to 5.0wt.% of zinc borate, 5.0 to 8.0wt.% of a maleic anhydride-grafted elastomer ionomer, 3.0 to 6.0wt.% of a star nylon 6 resin, 1.0 to 2.0wt.% of a dispersant, and 0.5 to 1.0wt.% of a lubricant.
Further, the glass fiber is a continuous long glass fiber.
Further, the intrinsic viscosity of the high-fluidity nylon 6 is 1.8-2.0.
Further, the star-shaped nylon 6 resin is star-shaped nylon 6 with three arms, four arms, six arms or eight arms.
Further, the maleic anhydride grafted elastomer ionomer is maleic anhydride grafted ethylene-octene-acrylic acid copolymerized elastomer ionomer crosslinked by sodium, calcium, magnesium, barium or zinc ions.
Further, the antioxidant is a compound consisting of 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (the trade name is antioxidant 1330) and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite (the trade name is antioxidant S9228) according to the mass ratio of 1: 1.
Further, the phosphorus flame retardant is any one or two of diethyl aluminum hypophosphite, methyl ethyl aluminum hypophosphite, ammonium polyphosphate and melamine polyphosphate.
Further, the nitrogen-based flame retardant is one or two of melamine cyanurate and melamine.
Further, the dispersant is one or more of zinc stearate, aluminum stearate, magnesium stearate and lithium stearate.
Further, the lubricant is one or more of ethylene-vinyl acetate copolymer wax, ethylene-acrylic acid copolymer wax, E wax, OP wax and polydimethylsiloxane.
A method for preparing a high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 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 nylon 6 resin, star-shaped nylon 6 resin, maleic anhydride grafted elastomer ionomer and antioxidant according to a ratio, premixing powder and granules uniformly by using a high-speed mixer respectively, and adding the powder and 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 8-10 mm through a granulator to obtain the master batch A.
Further, the temperature of each section from a charging barrel to a machine head of the double-screw extruder is controlled to be 230-280 ℃, 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 275-285 ℃, and the speed of a traction machine is controlled to be 50-70 m/min.
A method for preparing a high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 relates to a preparation method of a master batch A and a master batch B, and the preparation method of the master batch B comprises the following steps:
(1) weighing a phosphorus flame retardant, a nitrogen flame retardant, zinc borate, star-shaped nylon 6 resin, a maleic anhydride grafted elastomer ionomer, a dispersant 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 temperature of the machine barrel is 160-165 ℃.
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 nylon 6, 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 modified systems are not matched is solved, thereby obviously improving the respective modified 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 nylon 6, the low-viscosity star nylon 6 and the maleic anhydride grafted elastic ionomer are used as the combined carrier of the glass fiber reinforced master batch, so that the interfacial adhesion between the glass fiber and the nylon 6 is effectively improved, and the high-flow characteristics of the carriers are utilized, so that the glass fiber obtains a more excellent dispersion effect in a nylon 6 resin matrix when the prepared A master batch is used for injection molding of products.
(4) The maleic anhydride grafted elastic ionomer with excellent flow property and the low-viscosity star nylon 6 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 nylon 6 plastic products. The maleic anhydride grafted elastic ionomer is simultaneously used as a carrier component of the A master batch and the B master batch, so that the high fluidity of the maleic anhydride grafted elastic ionomer can be utilized to provide excellent dispersibility for the modified additive, and the good toughening effect on nylon 6 can be exerted.
(5) 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 much greater 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 the A master batch and the B master batch are simply mixed with nylon 6 resin according to a certain proportion according to the performance requirements of the nylon 6 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 melted and mixed 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 nylon 6 product are obviously improved.
(6) The invention effectively improves the enhanced flame-retardant modification efficiency of nylon 6, 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 nylon 6 plastic products. The method and the technology can be widely applied to injection molding and high-performance and functional modification integrated processing of various nylon 6 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
A high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 is formed by combining A master batch and B master batch, wherein the A master batch comprises the following raw materials in percentage by mass:
the antioxidant is a compound consisting of 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (the trade name is antioxidant 1330) 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, respectively putting two kinds of granules of high-flow nylon 6 and maleic anhydride grafted sodium ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer and two kinds of powder of four-armed star nylon 6 and antioxidant into different high-speed mixers to be uniformly mixed, respectively adding the mixed granule 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 230-280 ℃, 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 neck ring 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 neck ring 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 to be 285 ℃, controlling the speed of a tractor to be 70 m/min, drawing out the glass fiber tows dipped in the melt from the die cavity, cooling, and cutting into strip-shaped granules with the length of 10mm by a granulator to obtain 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 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 180 revolutions per minute, and the temperature of the machine barrel is controlled to be 160-165 ℃ in sections.
Example 2
A high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 is formed by combining A master batch and B master batch, wherein the A master batch comprises the following raw materials in percentage by mass:
the antioxidant is a compound consisting of 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (the trade name is antioxidant 1330) 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, respectively putting two kinds of granules of high-flow nylon 6 and maleic anhydride grafted zinc ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer and two kinds of powder of three-armed star nylon 6 and antioxidant into different high-speed mixers to be uniformly mixed, respectively adding the mixed granule 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 230-280 ℃, controlling the rotating speed of a screw to be 200 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 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 280 ℃, controlling the speed of a tractor at 70 m/min, drawing out the glass fiber tows dipped in the melt from the die cavity, cooling, and cutting into strip-shaped granules with the length of 12mm by a granulator to obtain 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 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 190 revolutions per minute, and the temperature of the machine barrel is controlled to be 160-165 ℃ in sections.
Example 3
A high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 is formed by combining A master batch and B master batch, wherein the A master batch comprises the following raw materials in percentage by mass:
the antioxidant is a compound consisting of 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (the trade name is antioxidant 1330) 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, respectively putting two kinds of granules of high-flow nylon 6 and maleic anhydride grafted barium ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer and two kinds of powder of three-armed star nylon 6 and antioxidant into different high-speed mixers to be uniformly mixed, then respectively adding the mixed granule 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 230-280 ℃, controlling the rotating speed of a screw to be 200 revolutions per minute, directly extruding the compound melt into a die cavity of an impregnation die through a neck ring 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 neck ring 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 280 ℃, controlling the speed of a tractor at 70 m/min, drawing out the glass fiber tows dipped in the melt from the die cavity, cooling, and cutting into strip-shaped granules with the length of 8mm by a granulator to obtain 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 160-165 ℃ in sections.
Example 4
A high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 is formed by combining A master batch and B master batch, wherein the A master batch comprises the following raw materials in percentage by mass:
the antioxidant is a compound consisting of 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (the trade name is antioxidant 1330) 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, respectively putting two kinds of granules of high-flow nylon 6 and maleic anhydride grafted calcium ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer and two kinds of powder of six-armed star nylon 6 and antioxidant into different high-speed mixers to be uniformly mixed, respectively adding the mixed granule 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 230-280 ℃, controlling the rotating speed of a screw to be 150 revolutions per minute, directly extruding the compound melt into a die cavity of an impregnation die through a neck ring 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 neck ring 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 275 ℃, controlling the speed of a tractor at 70 m/min, drawing out the glass fiber tows dipped in the melt from the die cavity, cooling, and cutting into long strip-shaped granules with the length of 8mm by a granulator to obtain 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 160-165 ℃ in sections.
Example 5
A high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 is formed by combining A master batch and B master batch, wherein the A master batch comprises the following raw materials in percentage by mass:
the antioxidant is a compound consisting of 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (the trade name is antioxidant 1330) 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, respectively putting two kinds of granules of high-flow nylon 6 and maleic anhydride grafted magnesium ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer and two kinds of powder of four-arm star nylon 6 and antioxidant into different high-speed mixers to be uniformly mixed, respectively adding the mixed granule 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 material cylinder to a machine head of the double-screw extruder to be 230-280 ℃, controlling the rotating speed of a screw to be 150 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 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 285 ℃, controlling the speed of a tractor to be 70 m/min, drawing out the glass fiber tows dipped in the melt from the die cavity, cooling, and cutting into long strip-shaped granules with the length of 11mm by a granulator to obtain 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 160-165 ℃ in sections.
Example 6
A high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 is formed by combining A master batch and B master batch, wherein the A master batch comprises the following raw materials in percentage by mass:
the antioxidant is a compound consisting of 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (the trade name is antioxidant 1330) 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, respectively putting two kinds of granules of high-flow nylon 6 and maleic anhydride grafted sodium ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer and two kinds of powder of four-arm star nylon 6 and antioxidant into different high-speed mixers to be uniformly mixed, respectively adding the mixed granule 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 230-280 ℃, controlling the rotating speed of a screw to be 195 revolutions per minute, directly extruding the compound melt into a die cavity of an impregnation die through a neck ring 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 neck ring 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 282 ℃ and the speed of a tractor at 70 m/min, drawing out the glass fiber tows dipped in the melt from the die cavity, cooling and cutting into strip-shaped granules with the length of 9mm by a granulator so as to obtain 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 130 ℃, 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 165 revolutions per minute, and the temperature of the machine barrel is controlled to be 160-165 ℃ in sections.
The glass fibers in examples 1-6 were continuous long glass fibers, and the high flow nylon 6 had an intrinsic viscosity of 1.8 to 2.0.
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 nylon 6, the master batch A and the master batch B prepared in the embodiments 1-6 are mixed with nylon 6 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 are obviously superior to those of the plastic product which is processed by a double screw extruder and then injection molded after the high-efficiency enhanced halogen-free flame retardant functional master batch for direct injection molding of nylon 6 prepared by the embodiment of the invention is applied to direct injection molding of nylon 6 under the condition that the components and the proportion are completely the same. By utilizing the functional master batch, the processing steps of nylon 6 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 in plastic preparation is realized. TABLE 1 comparison of the performance of the nylon 6 test specimens directly injection molded from the functional master batches prepared in examples 1 to 6 with nylon 6 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 (10)
1. The high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 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, 20.0-35.0 wt.% of high-flow nylon 6 resin, 3.0-10.0 wt.% of maleic anhydride grafted elastomer ionomer, 3.0-6.0 wt.% of star nylon 6 resin and 0.1-0.3 wt.% of antioxidant,
the B master batch comprises the following components in percentage by mass: 45.0-60.0 wt.% of phosphorus flame retardant, 20.0-40.0 wt.% of nitrogen flame retardant, 3.0-5.0 wt.% of zinc borate, 5.0-8.0 wt.% of maleic anhydride grafted elastomer ionomer, 3.0-6.0 wt.% of star nylon 6 resin, 1.0-2.0 wt.% of dispersant, and 0.5-1.0 wt.% of lubricant;
the high-flow nylon 6 has an intrinsic viscosity of 1.8 to 2.0,
the glass fiber is continuous long glass fiber.
2. The efficient reinforced halogen-free flame retardant master batch for direct injection molding of nylon 6 according to claim 1, which is characterized in that: the star-shaped nylon 6 is one or more of three-arm, four-arm, six-arm and eight-arm star-shaped nylon 6 resin.
3. The efficient reinforced halogen-free flame retardant master batch for direct injection molding of nylon 6 according to claim 1, which is characterized in that: the maleic anhydride grafted elastomer ionomer is a maleic anhydride grafted ethylene-octene-acrylic acid copolymerized elastomer ionomer crosslinked by sodium, calcium, magnesium, barium or zinc ions.
4. The efficient reinforced halogen-free flame retardant master batch for direct injection molding of nylon 6 according to claim 1, which is characterized in that: the antioxidant is a compound consisting of 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene 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 nylon 6 according to claim 1, which is characterized in that: the phosphorus flame retardant is any one or two of diethyl hypophosphite aluminum, methyl ethyl hypophosphite aluminum, 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 nylon 6 according to claim 1, which is characterized in that: the dispersant is one or more of zinc stearate, aluminum stearate, magnesium stearate and lithium stearate; the lubricant is one or more of ethylene-vinyl acetate copolymer wax, ethylene-acrylic acid copolymer wax, E wax, OP wax and polydimethylsiloxane.
7. The method for preparing the high-efficiency enhanced halogen-free flame retardant functional master batch for direct injection molding of nylon 6 as claimed in 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 glass fiber, high-flow nylon 6 resin, star-shaped nylon 6 resin, maleic anhydride grafted elastomer ionomer and antioxidant according to a ratio, premixing powder and granules uniformly by using a high-speed mixer respectively, and adding the powder and 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 8-10 mm through a granulator to obtain the master batch A.
8. The preparation method of the efficient reinforced halogen-free flame retardant functional master batch for direct injection molding of nylon 6 according to claim 7, characterized in that: 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 230-280 ℃, 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 275-285 ℃, and the speed of a traction machine is controlled to be 50-70 m/min.
9. The method for preparing the high-efficiency enhanced halogen-free flame retardant functional master batch for direct injection molding of nylon 6 as claimed in 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, zinc borate, star-shaped nylon 6 resin, a maleic anhydride grafted elastomer ionomer, a dispersant 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-efficient reinforced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 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 ℃, and the mixing time is 15-20 minutes; the screw rotating speed of the single-screw extruder is 150-200 r/min, and the temperature of the machine barrel is 160-165 ℃.
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