CN109486131B - Efficient enhanced flame-retardant functional master batch for direct injection molding of PBT (polybutylene terephthalate) and preparation method thereof - Google Patents
Efficient enhanced flame-retardant functional master batch for direct injection molding of PBT (polybutylene terephthalate) and preparation method thereof Download PDFInfo
- Publication number
- CN109486131B CN109486131B CN201811427929.7A CN201811427929A CN109486131B CN 109486131 B CN109486131 B CN 109486131B CN 201811427929 A CN201811427929 A CN 201811427929A CN 109486131 B CN109486131 B CN 109486131B
- Authority
- CN
- China
- Prior art keywords
- master batch
- retardant
- pbt
- injection molding
- flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The invention belongs to the technical field of plastic modification and processing, and particularly relates to an efficient enhanced flame-retardant master batch capable of being directly applied to injection molding processing of PBT (polybutylene terephthalate) products and a preparation method thereof; the functional master batch is formed by combining A master batch and B master batch, wherein the A master batch comprises the following components in percentage by mass: 50.0-70.0 wt.% of glass fiber, 15.0-30.0 wt.% of high-fluidity PBT resin, 5.0-10.0 wt.% of acrylic diglycidyl ether grafted elastic ionomer 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 glass fiber and flame retardant in the processing process of the enhanced brominated flame-retardant PBT resin 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 characteristics of easy dispersion and easy processing, can be directly mixed with PBT 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 flame-retardant master batch capable of being directly applied to injection molding processing of PBT 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.
PBT is the fourth engineering plastic which is currently used in the world, and the application field of the PBT can be greatly expanded by carrying out high-performance and functional modification on the PBT. As an important PBT modified material, the reinforced flame-retardant PBT compound is widely applied to the fields of machinery, automobiles, rail efficiency, electronic and electric appliances and the like. However, in the processing and preparation process of the reinforced flame-retardant PBT special material, the inorganic reinforced fiber and the flame retardant are simultaneously added into the PBT resin for melt blending and extrusion, and the typical phenomenon of mutual loss of the modification efficiency of the additive occurs.
Disclosure of Invention
In order to solve the problem of mutual loss of modification efficiency in the preparation process of the conventional glass fiber reinforced flame-retardant PBT special material, the invention provides the high-efficiency reinforced flame-retardant functional master batch which can be directly applied to injection molding processing of PBT 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-fluidity PBT resin and acrylic acid diglycidyl ether grafted elastic ionomer, and is processed by a melt pultrusion method to prepare long fiber reinforced toughening master batch; the B master batch mainly comprises a bromine-antimony compound flame retardant and low-viscosity aliphatic copolyester super-dispersible carrier resin, and is prepared into the flame-retardant master batch through an internal mixer. The following technical advantages can be achieved by applying the method of respectively processing the two master batches: the decomposition of the halogen flame retardant caused by internal friction heat generation generated by directly blending the glass fiber and the bromine flame retardant is avoided; the great reduction of the length-diameter ratio of the fiber caused by mutual shearing and abrasion between the inorganic flame-retardant synergist (such as antimony trioxide or zinc borate) and the glass fiber is avoided; solving the problem that the processing temperature of the melt blending of two modification systems of glass fiber reinforced PBT and bromine-antimony compound flame retardant PBT is not matched; 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 the acrylic diglycidyl ether grafted elastic ionomer is used as a carrier component of the A master batch, and the reactive end group of the acrylic diglycidyl ether grafted elastic ionomer can have the largest contact opportunity with the end group of the PBT resin in the environment without interference of flame retardant powder, so that the toughening effect of the acrylic diglycidyl ether grafted elastic ionomer is exerted to the maximum extent. And the acrylic diglycidyl ether grafted elastic ionomer is used as the component of the A master batch carrier, so that the defects of poor compatibility of a general PE carrier and PBT resin and easy peeling of a composite material are overcome, the interfacial cohesiveness among organic and inorganic components in a formula can be improved, the melt fluidity of the composite is improved, and the surface smoothness and the deformation resistance of a 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 PBT 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: including but not limited to: PET resin, PC resin, 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 etching 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 PBT, 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 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, 20.0-40.0 wt% of high-fluidity PBT resin, 5.0-10.0 wt% of acrylic acid diglycidyl ether grafted elastic ionomer and 0.1-0.3 wt% of antioxidant, wherein the B master batch comprises the following components in percentage by mass: 55.0-70.0 wt% of bromine-based flame retardant, 15.0-30.0 wt% of inorganic flame retardant synergist, 5.0-10.0 wt% of acrylic acid diglycidyl ether grafted elastic ionomer, 3.0-6.0 wt% of aliphatic copolyester, 1.0-2.0 wt% of dispersant and 0.5-1.0 wt% of lubricant.
Further, the glass fiber is a continuous long glass fiber.
Further, the intrinsic viscosity of the high-flow PBT resin is 0.76-0.85.
Further, the aliphatic copolymer ester is one or more of poly (ethylene succinate-butylene succinate), poly (ethylene succinate-butylene methylsuccinate) and poly (ethylene succinate-butylene phenylsuccinate).
Further, the diglycidyl acrylate grafted elastomer ionomer is a diglycidyl acrylate 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 brominated flame retardant is any one or more of brominated polystyrene, polybrominated styrene, brominated epoxy resin, ethyl-bis (tetrabromobenzene-o-dicarboximide), brominated polycarbonate and decabromodiphenylethane, and preferably the brominated polystyrene and the brominated epoxy resin are used in combination.
Further, the inorganic flame-retardant synergist is one or two of antimony trioxide and zinc borate.
Further, the dispersant is one or more of stearic acid, calcium stearate or zinc stearate.
Further, the lubricant is one or more of ethylene-vinyl acetate copolymer wax, ethylene-acrylic acid copolymer wax, E wax, OP wax, pentaerythritol stearate and polydimethylsiloxane.
The preparation method of the high-efficiency enhanced flame-retardant functional master batch for the direct injection molding of the PBT 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 PBT resin, acrylic acid diglycidyl ether grafted elastomer ionomer and antioxidant according to a ratio, putting the high-flow PBT resin, the acrylic acid diglycidyl ether grafted elastomer ionomer and the antioxidant into a high-speed mixer for uniform premixing, adding the mixture into a double-screw extruder through a hopper, and performing 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.
Further, the temperature of each section from a charging barrel to a machine head of the double-screw extruder is controlled to be 230-275 ℃, 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.
The preparation method of the high-efficiency enhanced flame-retardant functional master batch for the direct injection molding of the PBT relates to a preparation method of an A master batch and a B master batch, and the preparation method of the B master batch comprises the following steps:
(1) weighing a brominated flame retardant, an inorganic flame-retardant synergist, aliphatic copolyester, an acrylic acid diglycidyl ether 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 rpm, and the barrel temperature is 155-166 ℃.
The technical scheme adopted by the invention has the beneficial effects that:
(1) aiming at the physical property characteristics of the modified additive, the method for separately processing the master batch A and the master batch B is adopted to respectively prepare the long glass fiber reinforced master batch (master batch A) and the bromine-antimony compound flame-retardant master batch (master batch B), so that the mutual loss of the reinforced modification efficiency caused by mutual shearing and abrasion between the fiber and the solid filler when the PBT, the glass fiber and the bromine flame retardant are directly melted, blended and extruded is effectively avoided, and the technical problem that the processing temperatures of two modification systems are not matched is solved, thereby obviously improving the respective modification efficiency of the two modified additives.
(2) The 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 PBT resin and the acrylic acid diglycidyl ether grafted elastic ionomer are used as the combined carrier of the glass fiber reinforced master batch, so that the interface cohesiveness of the glass fiber and the PBT matrix can be effectively improved, and the high-fluidity characteristics of the carriers can be utilized, so that the glass fiber obtains more excellent dispersion effect in the PBT resin matrix when the prepared A master batch is used for injection molding of products.
(4) In the same way, acrylic acid diglycidyl ether grafted elastic ionomer and low-viscosity aliphatic copolyester with excellent flow property are used as combined carriers for preparing the B master batch, so that different types of modified additives can obtain uniform dispersion effect in a resin matrix when the A master batch and the B master batch are jointly used for directly injection molding and processing PBT plastic products. The acrylic diglycidyl ether 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 acrylic diglycidyl ether grafted elastic ionomer can be utilized to provide excellent dispersibility for the modified additive, and the good toughening effect on the PBT resin 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 PBT resin according to a certain proportion according to the performance requirements of the PBT plastic products. Because the single-screw melt pushing mode is adopted in the injection molding machine, the shearing action on the glass fiber and the flame retardant is very weak, and the modification effects of the glass fiber and the flame retardant are basically not damaged, so that the problems of antioxidant loss, reinforcing fiber length-diameter ratio loss and matrix resin thermal cracking caused by the fact that matrix resin and modified master batch are 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 the PBT product are obviously improved.
(6) The invention effectively improves the PBT reinforced flame-retardant modification efficiency, simplifies the plastic modification processing steps, reduces the processing period, reduces the energy consumption, improves the production efficiency and really realizes the green chemical development concept. The combined functional master batch can flexibly adjust the combination mode of the master batch A and the master batch B and the proportion of the master batch A and the master batch B to 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 PBT plastic products. The method and the technology can be widely applied to injection molding and high-performance and functional modification integrated processing of various PBT 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 flame-retardant functional master batch for direct injection molding of PBT resin 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:
| glass fiber | 70.0kg |
| High-flow PBT resin | 20.0kg |
| Acrylic acid diglycidyl ether grafted sodium ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer | 9.7kg |
| Antioxidant agent | 300.0g |
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:
| brominated polystyrene | 35.0kg |
| Brominated epoxy resins | 35.0kg |
| Antimony trioxide | 15.0kg |
| Acrylic acid diglycidyl ether grafted sodium ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer | 8.0kg |
| Poly (ethylene succinate-butylene succinate) | 5.0kg |
| Stearic acid | 1.0kg |
| Pentaerythritol stearate | 1.0kg |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting all the raw materials except the glass fiber into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder through a hopper, carrying 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 230-275 ℃, 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 ring connected with the machine head of the double-screw extruder, simultaneously, feeding continuous long glass fiber (direct yarn) into the die cavity through another die ring of the impregnation die, impregnating in the melt under the traction action of a godet roller in the die cavity, controlling the temperature of the die cavity of the impregnation die to be 285 ℃, controlling the speed of a traction machine to be 70 meters per minute, drawing the glass fiber strand impregnated by the melt from the die cavity and cooling, cutting the mixture 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 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 175 revolutions per minute, and the temperature of the machine barrel is controlled to be 155-165 ℃ in sections.
Example 2
A high-efficiency enhanced flame-retardant functional master batch for direct injection molding of PBT resin 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:
| glass fiber | 50.0kg |
| High-flow PBT resin | 40.0kg |
| Acrylic acid diglycidyl ether grafted zinc ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer | 9.7kg |
| Antioxidant agent | 300.0g |
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:
| brominated polystyreneAlkene(s) | 35.0kg |
| Brominated epoxy resins | 20.0kg |
| Antimony trioxide | 20.0kg |
| Zinc borate | 10.0kg |
| Acrylic acid diglycidyl ether grafted zinc ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer | 10.0kg |
| Poly (ethylene succinate-butylene methylsuccinate) | 3.0kg |
| Stearic acid calcium salt | 1.5kg |
| E wax | 500.0g |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting all the raw materials except the glass fiber into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder through a hopper, carrying 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 230-275 ℃, controlling the rotating speed of a screw to be 200 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 fiber (direct yarn) into the die cavity through the other die ring of the impregnation die, impregnating in the melt under the traction action of a godet roller in the die cavity, controlling the die cavity temperature of the impregnation die to be 280 ℃, controlling the speed of a traction machine to be 70 m/min, drawing the glass fiber strand impregnated by the melt from the die cavity and cooling, 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 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 155-165 ℃ in sections.
Example 3
A high-efficiency enhanced flame-retardant functional master batch for direct injection molding of PBT resin 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:
| glass fiber | 60.0kg |
| High-flow PBT resin | 30.7kg |
| Acrylic acid diglycidyl ether grafted barium ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer | 9.0kg |
| Antioxidant agent | 300.0g |
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:
| ethyl-bis (tetrabromophthalimide) | 65.0kg |
| Antimony trioxide | 20.0kg |
| Acrylic acid diglycidyl ether grafted barium ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer | 9.5kg |
| Poly (ethylene succinate-butylene phenyl succinate) | 3.0kg |
| Zinc stearate | 2.0kg |
| Polydimethylsiloxane | 500.0g |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio, putting all the raw materials except the glass fiber into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder through a hopper, carrying 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 230-275 ℃, controlling the rotating speed of a screw to be 190 revolutions per minute, directly extruding the compound melt into a die cavity of an impregnation die through a die ring connected with the machine head of the double-screw extruder, simultaneously, feeding continuous long glass fiber (direct yarn) into the die cavity through the other die ring of the impregnation die, impregnating in the melt under the traction action of a godet roller in the die cavity, controlling the die cavity temperature of the impregnation die to be 283 ℃, controlling the speed of a tractor to be 70 meters per minute, drawing out a glass fiber strand impregnated by the melt from the die cavity, cooling, and cutting the mixture 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 155-165 ℃ in sections.
Example 4
A high-efficiency enhanced flame-retardant functional master batch for direct injection molding of PBT resin 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:
| glass fiber | 65.0kg |
| High flowPBT resin | 29.7kg |
| Acrylic acid diglycidyl ether grafted calcium ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer | 5.0kg |
| Antioxidant agent | 300.0g |
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:
| decabromodiphenylethane | 63.0kg |
| Antimony trioxide | 22.0kg |
| Acrylic acid diglycidyl grafted calcium ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer | 7.0kg |
| Poly (ethylene succinate-butylene methylsuccinate) | 6.0kg |
| Stearic acid calcium salt | 1.0kg |
| Montan wax | 1.0kg |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting all the raw materials except the glass fiber into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder through a hopper, carrying 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 230-275 ℃, 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 ring connected with the machine head of the double-screw extruder, simultaneously, feeding continuous long glass fiber (direct yarn) into the die cavity through another die ring of the impregnation die, impregnating in the melt under the traction action of a godet roller in the die cavity, controlling the die cavity temperature of the impregnation die to be 275 ℃, controlling the speed of a traction machine to be 70 meters per minute, drawing the glass fiber strand impregnated by the melt out of the die cavity and cooling, and cutting the mixture into strip-shaped granules with the length of 9mm 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 115 ℃, the mixing time is 20 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the B master batch; the screw rotating speed of the single-screw extruder is 170 revolutions per minute, and the temperature of the machine barrel is controlled to be 155-165 ℃ in sections.
Example 5
A high-efficiency enhanced flame-retardant functional master batch for direct injection molding of PBT resin 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:
| glass fiber | 70.0kg |
| High-flow PBT resin | 21.7kg |
| Acrylic acid diglycidyl grafted magnesium ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer | 8.0kg |
| Antioxidant agent | 300.0g |
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:
| decabromodiphenylethane | 33.0kg |
| Brominated polycarbonate | 30.0kg |
| Oxide of two carbon atomsAntimony (Sb) | 22.0kg |
| Acrylic acid diglycidyl grafted magnesium ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer | 8.0kg |
| Poly (ethylene succinate-butylene succinate) | 5.0kg |
| Zinc stearate | 1.0kg |
| Ethylene-vinyl acetate copolymer wax | 1.0kg |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting all the raw materials except the glass fiber into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder through a hopper, carrying 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 230-275 ℃, 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 die ring connected with the machine head of the double-screw extruder, simultaneously, feeding continuous long glass fiber (direct yarn) into the die cavity through another die ring of the impregnation die, impregnating in the melt under the traction action of a godet roller in the die cavity, controlling the die cavity temperature of the impregnation die to be 275 ℃, controlling the speed of a traction machine to be 70 meters per minute, drawing the glass fiber strand impregnated by the melt out of the die cavity and cooling, cutting the mixture 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 15 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and carrying out melt extrusion and granulation to obtain the B master batch; the screw rotating speed of the single-screw extruder is 180 revolutions per minute, and the temperature of the machine barrel is controlled to be 155-165 ℃ in sections.
Example 6
A high-efficiency enhanced flame-retardant functional master batch for direct injection molding of PBT resin 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:
| glass fiber | 67.0kg |
| High-flow PBT resin | 26.0kg |
| Acrylic acid diglycidyl grafted sodium ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer | 6.7kg |
| Antioxidant agent | 300.0g |
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:
| polybrominated styrenes | 35.0kg |
| Ethyl-bis (tetrabromophthalimide) | 30.0kg |
| Antimony trioxide | 20.0kg |
| Acrylic acid diglycidyl grafted sodium ion crosslinked ethylene-octene-acrylic acid copolymerized elastic ionomer | 7.0kg |
| Poly (ethylene succinate-butylene succinate) | 6.0kg |
| Stearic acid | 1.2kg |
| Ethylene-acrylic acid copolymer wax | 800.0g |
The preparation method of the A master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting all the raw materials except the glass fiber into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder through a hopper, carrying 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 230-275 ℃, controlling the rotating speed of a screw to be 175 r/min, directly extruding the compound melt into a die cavity of an impregnation die through a die ring connected with the machine head of the double-screw extruder, simultaneously, feeding continuous long glass fiber (direct yarn) into the die cavity through the other die ring of the impregnation die, impregnating in the melt under the traction action of a wire guide roller in the die cavity, controlling the temperature of the die cavity of the impregnation die to be 278 ℃, controlling the speed of a traction machine to be 65 m/min, drawing the glass fiber strand impregnated by the melt from the die cavity, cooling, cutting the mixture into 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 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 155-165 ℃ in sections.
The glass fibers in examples 1-6 were continuous long glass fibers, and the intrinsic viscosity of the high flow PBT resin was 0.76 to 0.85.
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 the PBT resin, the A master batch and the B master batch prepared in the embodiments 1 to 6 are mixed with the PBT resin according to the respective mass percentage of 25wt.%, and are directly injected to mold a test sample strip, and then various performance tests are carried out; meanwhile, the test specimens obtained in examples 1 to 6 were injection-molded with the same components and compounding ratios by blending with a twin-screw extruder as a control, and the properties were measured. All the results of the property tests are shown in Table 1 (wherein comparative examples 1 to 6 are the same compositions and compounding ratios as those in examples 1 to 6, respectively, and the properties of the specimens were measured by injection molding after processing with a twin-screw extruder).
The data in table 1 show that the tensile strength, notch impact strength and flame retardant property of the plastic product of the high-efficiency reinforced flame retardant master batch for direct injection molding of the PBT resin prepared by the embodiment of the invention are obviously superior to those of the plastic product which is processed by a double-screw extruder and then injection molded under the condition that the components and the proportion are completely the same after the high-efficiency reinforced flame retardant master batch is applied to direct injection molding of the PBT resin. By utilizing the functional master batch, the PBT resin modification processing steps 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 PBT resin test specimens directly injection molded from the master batches prepared in examples 1 to 6 with the PBT resin test specimens injection molded from the same raw material formulation after processing 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 (10)
1. The high-efficiency enhanced flame-retardant master batch for the direct injection molding of the PBT 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, 20.0-40.0 wt.% of high-fluidity PBT resin, 5.0-10.0 wt.% of acrylic diglycidyl ether grafted elastomer ionomer, 0.1-0.3 wt.% of antioxidant,
the B master batch comprises the following components in percentage by mass: 55.0-70.0 wt% of bromine-based flame retardant, 15.0-30.0 wt% of inorganic flame retardant synergist, 5.0-10.0 wt% of acrylic diglycidyl ether grafted elastomer ionomer, 3.0-6.0 wt% of aliphatic copolyester, 1.0-2.0 wt% of dispersant and 0.5-1.0 wt% of lubricant.
2. The high-efficiency reinforced flame-retardant master batch for the direct injection molding of the PBT according to claim 1, which is characterized in that: the glass fiber is a continuous long glass fiber, the intrinsic viscosity of the high-flow PBT resin is 0.76-0.85, and the aliphatic copolymer is one or more of poly (ethylene succinate-butylene succinate), poly (ethylene succinate-butylene methylsuccinate) and poly (ethylene succinate-butylene phenylsuccinate).
3. The high-efficiency reinforced flame-retardant master batch for the direct injection molding of the PBT according to claim 1, which is characterized in that: the acrylic acid diglycidyl ether grafted elastomer ionomer is an acrylic acid diglycidyl ether grafted ethylene-octene-acrylic acid copolymerized elastomer ionomer crosslinked by sodium, calcium, magnesium, barium or zinc ions.
4. The high-efficiency reinforced flame-retardant master batch for the direct injection molding of the PBT 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 high-efficiency reinforced flame-retardant master batch for the direct injection molding of the PBT according to claim 1, which is characterized in that: the brominated flame retardant is any one or more of brominated polystyrene, polybrominated styrene, brominated epoxy resin, ethyl-bis (tetrabromophthalimide), brominated polycarbonate and decabromodiphenylethane, and the inorganic flame retardant synergist is any one or two of antimony trioxide and zinc borate.
6. The high-efficiency reinforced flame-retardant master batch for the direct injection molding of the PBT according to claim 1, which is characterized in that: the dispersant is one or more of stearic acid, calcium stearate or zinc stearate; the lubricant is one or more of ethylene-vinyl acetate copolymer wax, ethylene-acrylic acid copolymer wax, E wax, OP wax, pentaerythritol stearate and polydimethylsiloxane.
7. The method for preparing the high-efficiency reinforced flame-retardant master batch for the direct injection molding of the PBT according to any one of claims 1 to 6, which is characterized by comprising the following steps: the preparation method of the A master batch comprises the following steps:
(1) weighing glass fiber, high-flow PBT resin, acrylic acid diglycidyl ether grafted elastomer ionomer and antioxidant according to a ratio, putting the high-flow PBT resin, the acrylic acid diglycidyl ether grafted elastomer ionomer and the antioxidant into a high-speed mixer for uniform premixing, adding the mixture into a double-screw extruder through a hopper, and performing 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.
8. The preparation method of the high-efficiency reinforced flame-retardant functional master batch for the direct injection molding of the PBT according to claim 7, 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 230-275 ℃, and controlling the rotating speed of a screw to be 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 reinforced flame-retardant master batch for the direct injection molding of the PBT according to any one of claims 1 to 6, which is characterized by comprising the following steps: the preparation method of the B master batch comprises the following steps:
(1) weighing a brominated flame retardant, an inorganic flame-retardant synergist, aliphatic copolyester, an acrylic acid diglycidyl ether 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 high-efficiency reinforced flame-retardant functional master batch for the direct injection molding of the PBT according to claim 9, 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 110-130 ℃, and the mixing time is 15-20 minutes; the screw rotating speed of the single-screw extruder is 150-200 rpm, and the barrel temperature is 155-165 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811427929.7A CN109486131B (en) | 2018-11-27 | 2018-11-27 | Efficient enhanced flame-retardant functional master batch for direct injection molding of PBT (polybutylene terephthalate) and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811427929.7A CN109486131B (en) | 2018-11-27 | 2018-11-27 | Efficient enhanced flame-retardant functional master batch for direct injection molding of PBT (polybutylene terephthalate) and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109486131A CN109486131A (en) | 2019-03-19 |
| CN109486131B true CN109486131B (en) | 2021-03-23 |
Family
ID=65697889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811427929.7A Active CN109486131B (en) | 2018-11-27 | 2018-11-27 | Efficient enhanced flame-retardant functional master batch for direct injection molding of PBT (polybutylene terephthalate) and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109486131B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4085086A (en) * | 1974-06-27 | 1978-04-18 | Dainippon Ink And Chemicals, Inc. | Process for preparing flame retardant thermoplastic polyesters |
| CN1810862A (en) * | 2006-02-23 | 2006-08-02 | 广州金发科技股份有限公司 | Continuous long fiber reinforced fire-retardant thermoplastic resin and its prepn |
| CN1810872A (en) * | 2006-02-23 | 2006-08-02 | 广州金发科技股份有限公司 | Continuous long fiber reinforced composite nylon/polyolefin material and its prepn |
| CN101899202A (en) * | 2010-07-30 | 2010-12-01 | 福建师范大学 | Method for preparing drainage pipe by recycled polyethylene terephthalate bottle scraps |
| CN103160080A (en) * | 2011-12-14 | 2013-06-19 | 合肥杰事杰新材料股份有限公司 | A halogen free flame retardant long glass fiber reinforced PBT composite material and a preparation method thereof |
| CN106633681A (en) * | 2015-08-04 | 2017-05-10 | 东丽先端材料研究开发（中国）有限公司 | High-toughness polyester resin alloy composition and preparation method thereof |
-
2018
- 2018-11-27 CN CN201811427929.7A patent/CN109486131B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4085086A (en) * | 1974-06-27 | 1978-04-18 | Dainippon Ink And Chemicals, Inc. | Process for preparing flame retardant thermoplastic polyesters |
| CN1810862A (en) * | 2006-02-23 | 2006-08-02 | 广州金发科技股份有限公司 | Continuous long fiber reinforced fire-retardant thermoplastic resin and its prepn |
| CN1810872A (en) * | 2006-02-23 | 2006-08-02 | 广州金发科技股份有限公司 | Continuous long fiber reinforced composite nylon/polyolefin material and its prepn |
| CN101899202A (en) * | 2010-07-30 | 2010-12-01 | 福建师范大学 | Method for preparing drainage pipe by recycled polyethylene terephthalate bottle scraps |
| CN103160080A (en) * | 2011-12-14 | 2013-06-19 | 合肥杰事杰新材料股份有限公司 | A halogen free flame retardant long glass fiber reinforced PBT composite material and a preparation method thereof |
| CN106633681A (en) * | 2015-08-04 | 2017-05-10 | 东丽先端材料研究开发（中国）有限公司 | High-toughness polyester resin alloy composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109486131A (en) | 2019-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109503969B (en) | Efficient enhanced flame-retardant heat-conducting shading multifunctional master batch for direct injection molding of nylon and preparation method thereof | |
| CN109486013B (en) | Efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of polypropylene and preparation method thereof | |
| CN110452502B (en) | Low-warpage good-appearance high-heat-resistance polyester composite material and preparation method thereof | |
| CN109370144B (en) | High-efficiency flame-retardant antibacterial functional master batch for direct injection molding of ABS (acrylonitrile butadiene styrene) resin and preparation method thereof | |
| CN109535701B (en) | Efficient enhanced flame-retardant functional master batch for direct injection molding of nylon 6 and preparation method thereof | |
| CN104371291B (en) | The preparation method of high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material | |
| CN108117735B (en) | High-performance halogen-free flame-retardant polycarbonate material and preparation method thereof | |
| CN103102684A (en) | Weather-proof and hydrolysis-resistant continuous glass fiber reinforced polyamide composite material and its preparation method | |
| CN109370210B (en) | Efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 and preparation method thereof | |
| CN109504078B (en) | Efficient enhanced halogen-free flame-retardant heat-conducting shading multifunctional master batch for direct injection molding of nylon resin and preparation method thereof | |
| CN104629338A (en) | Permanently antistatic PC/ABS modified alloy, and preparation method thereof | |
| CN102337029A (en) | Halogen-free flame-retardant nylon 66 composite material and preparation method thereof | |
| CN103160080A (en) | A halogen free flame retardant long glass fiber reinforced PBT composite material and a preparation method thereof | |
| CN106189126B (en) | A kind of low molding cycle flame-retardant strengthening polythylene terephthalate (PET) material of high heat distortion temperature and preparation method | |
| CN103013075A (en) | PET (polyethylene terephthalate) composite material as well as preparation method and application thereof | |
| CN107541049B (en) | Graphene-continuous glass fiber reinforced halogen-free flame-retardant weather-resistant PPO/HIPS alloy material and preparation method thereof | |
| CN109486133B (en) | Efficient enhanced flame-retardant heat-conducting shading multifunctional master batch for direct injection molding of PBT (polybutylene terephthalate) and preparation method thereof | |
| CN109535559B (en) | Efficient enhanced flame-retardant functional master batch for direct injection molding of polypropylene and preparation method thereof | |
| CN109517259B (en) | High-efficiency flame-retardant antibacterial functional master batch for direct injection molding of polypropylene and preparation method thereof | |
| CN101831171A (en) | Flame retardant reinforced polyphthalamide composite material and preparation method thereof | |
| CN109370175B (en) | Efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of PBT (polybutylene terephthalate) and preparation method thereof | |
| CN109486132B (en) | Efficient enhanced halogen-free flame-retardant heat-conducting shading multifunctional master batch for direct injection molding of PBT (polybutylene terephthalate) and preparation method thereof | |
| CN109486131B (en) | Efficient enhanced flame-retardant functional master batch for direct injection molding of PBT (polybutylene terephthalate) and preparation method thereof | |
| CN109486154B (en) | Efficient halogen-free enhanced flame-retardant functional master batch for direct injection molding of PC-ABS (polycarbonate-acrylonitrile butadiene styrene) alloy and preparation method thereof | |
| CN103387743A (en) | Polyphenylether resin alloy material used for processing spinning cans and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |