CN109535642B - Efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of polyformaldehyde and preparation method thereof - Google Patents
Efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of polyformaldehyde and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of plastic modification and processing, and particularly relates to an efficient enhanced halogen-free flame-retardant functional master batch which can be directly applied to injection molding processing of polyformaldehyde products and a preparation method thereof; the functional master batch is formed by combining A master batch and B master batch, wherein the A master batch comprises the following components in percentage by mass: 50.0-70.0 wt% of glass fiber, 22.0-40.0 wt% of high-flow polyformaldehyde, 5.0-7.0 wt% of polyoxyethylene, 1.0-3.0 wt% of polytetrafluoroethylene powder 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 decomposition of the flame retardant and the matrix resin caused by the mutual shearing, friction and heat generation between the glass fiber and the flame retardant in the processing process of the reinforced halogen-free flame retardant modification system of polyformaldehyde, simultaneously solves the problem of mutual loss of modification efficiency caused by the mismatching of the processing temperatures of the two modification systems, and obviously enhances the modification efficiency of the two modification systems.
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 polyformaldehyde 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.
Polyformaldehyde is an important engineering plastic, and although polyformaldehyde has good mechanical properties and electrical insulation properties, polyformaldehyde is extremely flammable and cannot be applied to the field of electronic and electrical appliances. By reinforcing and flame-retardant modifying polyformaldehyde, the application range of the polyformaldehyde in the field of manufacturing of industrial and civil electronic and electric appliances can be greatly expanded. However, the halogen flame retardant cannot retard polyoxymethylene because it easily causes zipper decomposition. The current research shows that only phosphorus/nitrogen halogen-free flame retardant has flame retardant effect on polyformaldehyde. However, in the processing and preparation process of the enhanced halogen-free flame-retardant modified special polyformaldehyde material, the inorganic enhanced glass fiber and the halogen-free flame retardant are added into the polyformaldehyde resin at the same time for melt blending extrusion, so that the problem of decomposition of the halogen-free flame retardant caused by mutual shearing, friction and heat generation of the fiber and the flame retardant can occur; and the polyformaldehyde has strong thermal sensitivity and can also cause associated thermal degradation reaction, so that the flame-retardant modification effect is severely restricted, and the mechanical property and long-term service performance of the material are reduced. In addition, the processing temperature of the glass fiber reinforced polyformaldehyde system is higher, the processing temperature of the halogen-free flame-retardant modified polyformaldehyde system is lower, and the two systems are processed simultaneously, so that the situation of mutual loss of modification energy efficiency can be caused.
Disclosure of Invention
In order to solve the problem of mutual loss of modification efficiency in the preparation process of the existing special material for modifying glass fiber reinforced halogen-free flame-retardant polyformaldehyde, the invention provides the efficient reinforced halogen-free flame-retardant functional master batch which can be directly applied to injection molding processing of polyformaldehyde 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 polyformaldehyde and low-viscosity polyoxyethylene, and is processed by a melt pultrusion method to prepare long fiber reinforced master batch; the B master batch mainly comprises a phosphorus-nitrogen compound flame retardant and high-compatibility ultra-dispersion carrier resin, and is prepared into the flame-retardant master batch through an internal mixer. The following technical advantages can be achieved by applying the method of respectively processing the two master batches: the method avoids the direct blending of the glass fiber and the phosphorus-nitrogen halogen-free flame retardant to generate internal friction heat, so that the decomposition of the halogen-free flame retardant is caused; the problem that the processing temperature of the two modification systems of the glass fiber reinforced polyformaldehyde and the phosphorus-nitrogen compounded flame-retardant polyformaldehyde 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. And fourthly, polylactic acid is used as a carrier component of the master batch, and the characteristic of good polyformaldehyde compatibility of the polylactic acid is utilized, so that the interfacial cohesiveness among organic and inorganic components in a formula can be improved, the melt fluidity of the compound is enhanced, and the surface smoothness and the deformation resistance of the product are improved. In addition, aiming at the physical properties of the A master batch and the B master batch, the formula system design for promoting the lubrication and the efficient dispersion of the A master batch and the B master batch is implemented according to the physical properties of the loaded modified additives. Therefore, the master batches A and B can be directly and simply mixed with the polyformaldehyde resin according to a certain proportion and then injection molded according to the performance requirement, and other master batches can be added for injection molding together: including but not limited to: color masterbatch, filling masterbatch, toughening masterbatch, nucleating masterbatch, chain extension masterbatch, lubricating masterbatch, antistatic masterbatch, anti-aging masterbatch, conductive masterbatch, heat conductive masterbatch, laser etching masterbatch, silicone masterbatch and antibacterial masterbatch. Because the single-screw melt propelling mode is adopted in the injection molding machine, the shearing action on the glass fiber and the flame retardant is very weak, and the modification effects of the glass fiber and the flame retardant are basically not damaged. Therefore, the method not only effectively avoids the mutual loss of modification efficiency caused by secondary double-screw blending extrusion processing of the glass fiber and the flame retardant, greatly improves the enhanced flame-retardant modification effect of polyformaldehyde, 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 polyformaldehyde 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, 22.0-40.0 wt% of high-flow polyformaldehyde, 5.0-7.0 wt% of polyoxyethylene, 1.0-3.0 wt% of polytetrafluoroethylene powder and 0.1-0.3 wt% of antioxidant; the B master batch comprises the following components in percentage by mass: 50.0 to 60.0 wt.% of a phosphorus flame retardant, 30.0 to 40.0 wt.% of a nitrogen flame retardant, 5.0 to 8.0 wt.% of polylactic acid, and 2.0 to 5.0 wt.% of polyoxyethylene.
Further, the glass fiber is a continuous long glass fiber.
Further, the high flow polyoxymethylene has a melt flow index of greater than 45.0 g/10 min.
Further, the antioxidant is a compound composed of 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (trade name is antioxidant 3114), bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (trade name is antioxidant 626) and 5, 7-bis- (2, 2-dimethylethyl) -3- (3, 4-dimethylphenyl) -2-3 hydro-benzofuranone (trade name is antioxidant 168) in a mass ratio of 1:1: 1.
Further, the phosphorus flame retardant is one or two of ammonium polyphosphate and melamine polyphosphate.
Further, the nitrogen-based flame retardant is one or two of melamine cyanurate and melamine.
A method for preparing a high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of polyformaldehyde 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 polyformaldehyde, polyoxyethylene, polytetrafluoroethylene powder and an antioxidant according to a ratio, premixing the powder and the granules uniformly by using a high-speed mixer respectively, and adding the materials into a double-screw extruder through a main material hopper and an auxiliary material hopper to perform melt blending extrusion to prepare a composite melt;
(2) and (2) directly extruding the compound melt obtained in the step (1) into a die cavity of an impregnation die through a die connected with a head of a double-screw extruder, simultaneously, enabling continuous long glass fibers to enter the die cavity through the other die of the impregnation die, impregnating in the melt under the traction action of a godet roller in the die cavity, drawing out glass fiber tows impregnated in the melt from the die cavity, cooling, and cutting into strip-shaped granules with the length of 8-12 mm through a granulator to obtain the master batch A.
Furthermore, the temperature of each section from a charging barrel to a machine head of the double-screw extruder is controlled to be 185-195 ℃, and the rotating speed of the screw is 180-250 revolutions per minute; the temperature of a die cavity of the dipping die is controlled to be 190-198 ℃, and the speed of a tractor 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 polyformaldehyde 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, polylactic acid and polyoxyethylene according to a ratio, putting the phosphorus flame retardant, the nitrogen flame retardant, the polylactic acid and the polyoxyethylene 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 120-135 ℃, 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 polyformaldehyde, 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-fluidity polyformaldehyde and polyoxyethylene are used as the combined carrier of the long glass fiber reinforced master batch, so that the fluidity of the master batch A can be effectively improved, and the glass fiber obtains more excellent dispersion effect in a polyformaldehyde resin matrix when the high-fluidity polyformaldehyde and polyoxyethylene are used for injection molding of products.
(4) By utilizing the super-lubrication effect of the polytetrafluoroethylene powder in the formula of the master batch A, the infiltration effect of the polyformaldehyde melt on the glass fiber tows can be effectively improved; when the master batch A and the master batch B are combined and applied to a polyformaldehyde product, the polytetrafluoroethylene powder can play the effect of an anti-dripping agent in the combustion process of the polyformaldehyde product, the halogen-free flame retardant property of the product is improved, and thus the modification effect of killing two birds with one stone is achieved.
(5) Aiming at the characteristics of strong heat sensitivity and narrow processing window of the polyformaldehyde resin, a high-efficiency high-thermal stability ternary antioxidant compounding system is designed, so that the polyformaldehyde resin can endure high temperature in an impregnation die for a long time without thermal decomposition in the long fiber fusion pultrusion processing process.
(6) The polylactic acid and the polyoxyethylene are used as combined carriers for preparing the B master batch, so that the phosphorus/nitrogen flame retardant and the polyformaldehyde can obtain good interface compatibility, and the good fiber dispersion effect can be obtained when the phosphorus/nitrogen flame retardant and the polyformaldehyde are directly used for injection molding processing of polyformaldehyde plastic products. Meanwhile, the polylactic acid is a natural char forming agent of the polyformaldehyde halogen-free flame retardant system due to the rich carbonyl and ester functional groups, so that the phenomenon of frosting on the surface of a polyformaldehyde product caused by small molecule migration after the char forming agent is added is avoided.
(7) Compared with the traditional plastic functional master batch, the high-efficiency enhanced halogen-free flame-retardant 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 which 1+1 is far more than 2, has the characteristics of easy dispersion and easy processing, and can be directly applied to the injection molding processing of plastic products after the A master batch and the B master batch are simply mixed with polyformaldehyde resin according to a certain proportion according to the performance requirements of the polyformaldehyde plastic products. Because the single-screw melt pushing mode is adopted in the injection molding machine, the shearing action on the glass fiber and the flame retardant is very weak, and the modification effects of the glass fiber and the flame retardant are basically not damaged, so that the problems of antioxidant loss, reinforcing fiber length-diameter ratio loss and matrix resin thermal cracking caused by the fact that matrix resin and modified master batches are subjected to melting and mixing twice or repeatedly through a processing machine in the conventional plastic modification process are solved, and the mechanical property and the long-term use of a polyformaldehyde product are obviously improved.
(8) The invention effectively improves the high-efficiency enhanced halogen-free flame-retardant modification efficiency of polyformaldehyde, simplifies the plastic modification processing steps, reduces the processing period, reduces the energy consumption, improves the production efficiency and truly 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 the resin raw material to adjust the performance and the cost of the master batch according to the requirements of customers in the injection molding process of polyformaldehyde plastic products. The method and the technology can be widely applied to injection molding and high-performance and functional modification integrated processing of various polyformaldehyde 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 polyformaldehyde 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:
| glass fiber | 70.0 kg |
| High flow polyoxymethylene | 22.0 kg |
| Polyethylene oxide | 6.0 kg |
| Polytetrafluoroethylene powder | 1.7 kg |
| Antioxidant agent | 300.0 g |
The antioxidant is a compound consisting of 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (the trade name is antioxidant 3114), bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (the trade name is antioxidant 626) and 5, 7-bis- (2, 2-dimethylethyl) -3- (3, 4-dimethylphenyl) -2-3 hydro-benzofuranone (the trade name is antioxidant 168) in a mass ratio of 1:1: 1.
The B master batch comprises the following raw materials in parts by mass:
| ammonium polyphosphate | 60.0 kg |
| Melamine cyanurate | 30.0 kg |
| Polylactic acid | 7.0 kg |
| Polyethylene oxide | 3.0 kg |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio, respectively putting two kinds of granules of high-flow polyformaldehyde and polyoxyethylene and two kinds of powder of polytetrafluoroethylene powder and antioxidant into different high-speed mixers for uniform mixing, respectively adding the mixed granule mixture and powder mixture into a double-screw extruder through a main material hopper and an auxiliary material hopper for melt blending and extrusion to prepare a compound melt, controlling the temperature of each section from a charging barrel to a machine head of the double-screw extruder to be 185-195 ℃, controlling the rotating speed of a screw to be 220 r/min, directly extruding the compound melt into a die cavity of an impregnation die through a die ring connected with the machine head of the double-screw extruder, simultaneously, introducing continuous long glass fibers (direct yarns) into the die cavity through the other die ring of the impregnation die, impregnating the continuous long glass fibers in the melt through the traction effect of a godet roller in the die cavity, controlling the die cavity temperature of the impregnation die to be 195 ℃, the speed of the tractor is controlled at 70 m/min, and the glass fiber tows impregnated by the melt are drawn out of the die cavity, cooled and cut into long-strip-shaped granules with the length of 11 mm 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 135 ℃, 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
The efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of polyformaldehyde 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:
| glass fiber | 50.0 kg |
| High flow polyoxymethylene | 40.0 kg |
| Polyethylene oxide | 6.7 kg |
| Polytetrafluoroethylene powder | 3.0 kg |
| Antioxidant agent | 300.0 g |
The antioxidant is a compound consisting of 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (the trade name is antioxidant 3114), bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (the trade name is antioxidant 626) and 5, 7-bis- (2, 2-dimethylethyl) -3- (3, 4-dimethylphenyl) -2-3 hydro-benzofuranone (the trade name is antioxidant 168) in a mass ratio of 1:1: 1.
The B master batch comprises the following raw materials in parts by mass:
| ammonium polyphosphate | 50.0 kg |
| Melamine cyanurate | 40.0 kg |
| Polylactic acid | 8.0 kg |
| Polyethylene oxide | 2.0 kg |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio, respectively putting two kinds of granules of high-flow polyformaldehyde and polyoxyethylene and two kinds of powder of polytetrafluoroethylene powder and antioxidant into different high-speed mixers for uniform mixing, respectively adding the mixed granule mixture and powder mixture into a double-screw extruder through a main material hopper and an auxiliary material hopper for melt blending and extrusion to prepare a compound melt, controlling the temperature of each section from a charging barrel to a machine head of the double-screw extruder to be 185-195 ℃, controlling the rotating speed of a screw to be 210 revolutions per minute, directly extruding the compound melt into a die cavity of an impregnation die through a die ring connected with the machine head of the double-screw extruder, simultaneously, introducing continuous long glass fibers (direct yarns) into the die cavity through the other die ring of the impregnation die, impregnating the continuous long glass fibers in the melt through the traction effect of a godet roller in the die cavity, controlling the die cavity temperature of the impregnation die to be 198 ℃, the speed of the tractor is controlled to be 65 m/min, the glass fiber tows impregnated by the melt are drawn out of the die cavity and cooled, and then are cut into strip-shaped granules with the length of 10 mm by a granulator, so that the master batch A is obtained.
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 132 ℃, 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 170 revolutions per minute, and the temperature of the machine barrel is controlled to be 160-165 ℃ in sections.
Example 3
The efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of polyformaldehyde 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:
| glass fiber | 61.0 kg |
| High flow polyoxymethylene | 30.0 kg |
| Polyethylene oxide | 6.7 kg |
| Polytetrafluoroethylene powder | 2.0 kg |
| Antioxidant agent | 300.0 g |
The antioxidant is a compound consisting of 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (the trade name is antioxidant 3114), bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (the trade name is antioxidant 626) and 5, 7-bis- (2, 2-dimethylethyl) -3- (3, 4-dimethylphenyl) -2-3 hydro-benzofuranone (the trade name is antioxidant 168) in a mass ratio of 1:1: 1.
The B master batch comprises the following raw materials in parts by mass:
| ammonium polyphosphate | 30.0 kg |
| Melamine polyphosphate | 25.0 kg |
| Melamine cyanurate | 35.0 kg |
| Polylactic acid | 7.0 kg |
| Polyethylene oxide | 3.0 kg |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio, respectively putting two kinds of granules of high-flow polyformaldehyde and polyoxyethylene and two kinds of powder of polytetrafluoroethylene powder and antioxidant into different high-speed mixers for uniform mixing, respectively adding the mixed granule mixture and powder mixture into a double-screw extruder through a main material hopper and an auxiliary material hopper for melt blending and extrusion to prepare a compound melt, controlling the temperature of each section from a charging barrel to a machine head of the double-screw extruder to be 185-195 ℃, controlling the rotating speed of a screw to be 240 revolutions per minute, directly extruding the compound melt into a die cavity of an impregnation die through a die ring connected with the machine head of the double-screw extruder, simultaneously, introducing continuous long glass fibers (direct yarns) into the die cavity through the other die ring of the impregnation die, impregnating the continuous long glass fibers in the melt through the traction effect of a godet roller in the die cavity, controlling the die cavity temperature of the impregnation die to be 197 ℃, the speed of the tractor is controlled to be 65 m/min, the glass fiber tows impregnated by the melt are drawn out of the die cavity and cooled, and then are cut into strip-shaped granules with the length of 8 mm by a granulator, so that the master batch A is obtained.
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 160-165 ℃ in sections.
Example 4
The efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of polyformaldehyde 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:
| glass fiber | 67.0 kg |
| High flow polyoxymethylene | 25.0 kg |
| Polyethylene oxide | 6.2 kg |
| Polytetrafluoroethylene powder | 1.5 kg |
| Antioxidant agent | 300.0 g |
The antioxidant is a compound consisting of 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (the trade name is antioxidant 3114), bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (the trade name is antioxidant 626) and 5, 7-bis- (2, 2-dimethylethyl) -3- (3, 4-dimethylphenyl) -2-3 hydro-benzofuranone (the trade name is antioxidant 168) in a mass ratio of 1:1: 1.
The B master batch comprises the following raw materials in parts by mass:
| ammonium polyphosphate | 25.0 kg |
| Melamine polyphosphate | 25.0 kg |
| Melamine cyanurate | 20.0 kg |
| Melamine | 20.0 kg |
| Polylactic acid | 5.0 kg |
| Polyethylene oxide | 5.0 kg |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio, respectively putting two kinds of granules of high-flow polyformaldehyde and polyoxyethylene and two kinds of powder of polytetrafluoroethylene powder and antioxidant into different high-speed mixers for uniform mixing, respectively adding the mixed granule mixture and powder mixture into a double-screw extruder through a main material hopper and an auxiliary material hopper for melt blending and extrusion to prepare a compound melt, controlling the temperature of each section from a charging barrel to a machine head of the double-screw extruder to be 185-195 ℃, controlling the rotating speed of a screw to be 230 r/min, directly extruding the compound melt into a die cavity of an impregnation die through a die ring connected with the machine head of the double-screw extruder, simultaneously, introducing continuous long glass fibers (direct yarns) into the die cavity through the other die ring of the impregnation die, impregnating the continuous long glass fibers in the melt through the traction effect of a godet roller in the die cavity, controlling the die cavity temperature of the impregnation die to be 195 ℃, the speed of the tractor is controlled at 70 m/min, and the glass fiber tows impregnated by the melt are drawn out of the die cavity, cooled and cut into strip-shaped granules with the length of 10 mm by a granulator, so that the master batch A is obtained.
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 5
The efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of polyformaldehyde 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:
| glass fiber | 65.0 kg |
| High flow polyoxymethylene | 27.0 kg |
| Polyethylene oxide | 6.2 kg |
| Polytetrafluoroethylene powder | 1.5 kg |
| Antioxidant agent | 300.0 g |
The antioxidant is a compound consisting of 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (the trade name is antioxidant 3114), bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (the trade name is antioxidant 626) and 5, 7-bis- (2, 2-dimethylethyl) -3- (3, 4-dimethylphenyl) -2-3 hydro-benzofuranone (the trade name is antioxidant 168) in a mass ratio of 1:1: 1.
The B master batch comprises the following raw materials in parts by mass:
| ammonium polyphosphate | 50.0 kg |
| Melamine cyanurate | 30.0 kg |
| Melamine | 10.0 kg |
| Polylactic acid | 7.0 kg |
| Polyethylene oxide | 3.0 kg |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio, respectively putting two kinds of granules of high-flow polyformaldehyde and polyoxyethylene and two kinds of powder of polytetrafluoroethylene powder and antioxidant into different high-speed mixers for uniform mixing, respectively adding the mixed granule mixture and powder mixture into a double-screw extruder through a main material hopper and an auxiliary material hopper for melt blending and extrusion to prepare a compound melt, controlling the temperature of each section from a charging barrel to a machine head of the double-screw extruder to be 185-195 ℃, controlling the rotating speed of a screw to be 210 revolutions per minute, directly extruding the compound melt into a die cavity of an impregnation die through a die ring connected with the machine head of the double-screw extruder, simultaneously, introducing continuous long glass fibers (direct yarns) into the die cavity through the other die ring of the impregnation die, impregnating the continuous long glass fibers in the melt through the traction effect of a godet roller in the die cavity, controlling the die cavity temperature of the impregnation die to be 195 ℃, the speed of the tractor is controlled at 70 m/min, and the glass fiber tows impregnated by the melt are drawn out of the die cavity, cooled and cut into strip-shaped granules with the length of 12 mm 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 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 195 revolutions per minute, and the temperature of the machine barrel is controlled in a segmented mode at 160-165 ℃.
Example 6
The efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of polyformaldehyde 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:
| glass fiber | 67.0 kg |
| High flow polyoxymethylene | 25.0 kg |
| Polyethylene oxide | 6.5 kg |
| Polytetrafluoroethylene powder | 1.2 kg |
| Antioxidant agent | 300.0 g |
The antioxidant is a compound consisting of 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (the trade name is antioxidant 3114), bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (the trade name is antioxidant 626) and 5, 7-bis- (2, 2-dimethylethyl) -3- (3, 4-dimethylphenyl) -2-3 hydro-benzofuranone (the trade name is antioxidant 168) in a mass ratio of 1:1: 1.
The B master batch comprises the following raw materials in parts by mass:
| ammonium polyphosphate | 45.0 kg |
| Melamine cyanurate | 30.0 kg |
| Melamine | 15.0 kg |
| Polylactic acid | 6.0 kg |
| Polyethylene oxide | 4.0 kg |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio, respectively putting two kinds of granules of high-flow polyformaldehyde and polyoxyethylene and two kinds of powder of polytetrafluoroethylene powder and antioxidant into different high-speed mixers for uniform mixing, respectively adding the mixed granule mixture and powder mixture into a double-screw extruder through a main material hopper and an auxiliary material hopper for melt blending and extrusion to prepare a compound melt, controlling the temperature of each section from a charging barrel to a machine head of the double-screw extruder to be 185-195 ℃, controlling the rotating speed of a screw to be 245 r/min, directly extruding the compound melt into a die cavity of an impregnation die through a die ring connected with the machine head of the double-screw extruder, simultaneously, feeding continuous long glass fibers (direct yarns) into the die cavity through the other die ring of the impregnation die, impregnating the continuous long glass fibers in the melt through the traction effect of a godet roller in the die cavity, controlling the die cavity temperature of the impregnation die to be 192 ℃, the speed of the tractor is controlled at 70 m/min, and the glass fiber tows impregnated by the melt are drawn out of the die cavity, cooled and cut into long-strip-shaped granules with the length of 11 mm 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 132 ℃, 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 185 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 polyoxymethylene had a melt flow index of greater than 45.0 g/10 min.
The master batch A and the master batch B are mixed according to any mass ratio, and the components in the rest part of the invention can be expressed according to any ratio without explicitly written proportional relationship.
In order to verify the modification effect of the high-efficiency enhanced flame-retardant master batch for direct injection molding of polyformaldehyde prepared by the invention, the master batch A and the master batch B prepared in the embodiments 1-6 are simultaneously mixed with polypropylene resin according to the respective mass percentage of 25 wt.%, test sample strips are directly injected and molded, and then various performance tests are carried out; meanwhile, the test specimens obtained in examples 1 to 6 were injection-molded with the same components and compounding ratios by blending with a twin-screw extruder as a control, and the properties were measured. All the results of the property tests are shown in Table 1 (wherein comparative examples 1 to 6 are the same compositions and compounding ratios as those in examples 1 to 6, respectively, and the properties of the specimens were measured by injection molding after processing with a twin-screw extruder).
The reference of the data in table 1 shows that the high-efficiency enhanced flame-retardant master batch for direct injection molding of polyformaldehyde prepared by the embodiment of the invention is applied to direct injection molding of polyformaldehyde, and the tensile strength, notch impact strength and flame retardant property of a plastic product are obviously superior to those of a plastic product which is processed by a double-screw extruder and then subjected to injection molding under the condition that the composition and the proportion are completely the same. By utilizing the functional master batch, the modification processing steps of the polyformaldehyde resin 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 properties of the functional master batches prepared in examples 1 to 6, which were directly injection molded into polyoxymethylene test specimens, and the test specimens which were injection molded into polyoxymethylene test specimens after processing with the same raw material formulation by a twin screw extruder.
TABLE 1
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (8)
1. The high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of polyformaldehyde 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, 22.0-40.0 wt.% of high-flow polyformaldehyde, 5.0-7.0 wt.% of polyoxyethylene, 1.0-3.0 wt.% of polytetrafluoroethylene powder and 0.1-0.3 wt.% of antioxidant,
the B master batch comprises the following components in percentage by mass: 50.0-60.0 wt.% of phosphorus flame retardant, 30.0-40.0 wt.% of nitrogen flame retardant, 5.0-8.0 wt.% of polylactic acid and 2.0-5.0 wt.% of polyoxyethylene;
the melt flow index of the high-flow polyformaldehyde is more than 45.0 g/10 min; the glass fiber is continuous long glass fiber.
2. The efficient enhanced halogen-free flame-retardant master batch for direct injection molding of polyoxymethylene according to claim 1, wherein: the antioxidant is a compound consisting of 1,3, 5-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite and 5, 7-di- (2, 2-dimethylethyl) -3- (3, 4-dimethylphenyl) -2-3 hydro-benzofuranone in a mass ratio of 1:1: 1.
3. The efficient enhanced halogen-free flame-retardant master batch for direct injection molding of polyoxymethylene according to claim 1, wherein: the phosphorus flame retardant is one or two of ammonium polyphosphate and melamine polyphosphate.
4. The efficient enhanced halogen-free flame-retardant master batch for direct injection molding of polyoxymethylene according to claim 1, wherein: the nitrogen flame retardant is one or two of melamine cyanurate and melamine.
5. The method for preparing the high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of polyoxymethylene according to any one of claims 1 to 4, wherein the method comprises the following steps: the preparation method of the A master batch comprises the following steps:
(1) weighing continuous long glass fiber, high-flow polyformaldehyde, polyoxyethylene, polytetrafluoroethylene powder and an antioxidant according to a ratio, premixing the powder and the granules uniformly by using a high-speed mixer respectively, and adding the powder and the granules into a double-screw extruder through a main material hopper and an auxiliary material hopper to perform melt blending extrusion to prepare a composite melt;
(2) and (2) directly extruding the compound melt obtained in the step (1) into a die cavity of an impregnation die through a die connected with a head of a double-screw extruder, simultaneously, enabling continuous long glass fibers to enter the die cavity through the other die of the impregnation die, impregnating in the melt under the traction action of a godet roller in the die cavity, drawing out glass fiber tows impregnated in the melt from the die cavity, cooling, and cutting into strip-shaped granules with the length of 8-12 mm through a granulator to obtain the master batch A.
6. The preparation method of the highly-efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of polyoxymethylene according to claim 5, wherein the preparation method comprises the following steps: the processing technology of the A master batch comprises the following steps: controlling the temperature of each section from a charging barrel to a machine head of the double-screw extruder to be 185-195 ℃, and controlling the rotating speed of the screw to be 180-250 revolutions per minute; the temperature of a die cavity of the dipping die is controlled to be 190-198 ℃, and the speed of a tractor is controlled to be 50-70 m/min.
7. The method for preparing the high-efficiency enhanced halogen-free flame-retardant functional master batch for direct injection molding of polyoxymethylene according to any one of claims 1 to 4, wherein the method comprises the following steps: the preparation method of the B master batch comprises the following steps:
(1) weighing a phosphorus flame retardant, a nitrogen flame retardant, polylactic acid and polyoxyethylene according to a ratio, putting the phosphorus flame retardant, the nitrogen flame retardant, the polylactic acid and the polyoxyethylene 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.
8. The preparation method of the highly-efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of polyoxymethylene according to claim 7, wherein the preparation method comprises the following steps: the processing technology of the B master batch comprises the following steps: the mixing temperature of the internal mixer is 120-135 ℃, 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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