CN115926419A - Low-linear-expansion-coefficient flame-retardant PC/ABS alloy material and preparation method thereof - Google Patents
Low-linear-expansion-coefficient flame-retardant PC/ABS alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a low-linear expansion coefficient flame-retardant PC/ABS alloy material and a preparation method thereof, wherein the alloy material comprises the following components in parts by mass: low viscosity polycarbonate: 10-35 parts; medium viscosity polycarbonate: 25-50 parts; ABS material: 3-15 parts; flame retardant synergist: 0.1-1 part; a toughening agent A:1-10 parts; a toughening agent B:0.1-1 part; a compatilizer: 1-10 parts; coupling agent: 0.1-1 part; main antioxidant: 0.1-0.5 part; auxiliary antioxidant: 0.1-0.5 part; ultraviolet absorber: 0.1-0.3 part; hydrolysis resistance agent: 0.1-1 part; highlight black masterbatch: 0.5-3 parts; anti-dripping agent: 0.1-0.6 part; glass fiber: 10-15 parts; halogen-free flame retardant: 5-20 parts; according to the invention, through the optimization of different materials, the optimal material proportion is selected, through the arrangement of different processing technologies and double-screw extrusion equipment with different length-diameter ratios, and the optimized combination of the screw blocks combined by the screws is carried out, so that the flame-retardant PC/ABS alloy material with high melt flow rate, high impact strength, low linear expansion coefficient and small post shrinkage is obtained.
Description
Technical Field
The invention relates to the technical field of high polymer material processing, in particular to a low-linear-expansion-coefficient flame-retardant PC/ABS alloy material and a preparation method thereof.
Background
With the change of the cognition of people on plastics and the improvement of the modification technology level, the proportion of plastic products in daily life is higher, but the requirements on the appearance and the performance of the plastic are higher and higher. In general, in order to obtain a cost-effective plastic product, efforts are usually made in selecting raw materials and modifying plastic formulations, but in fact, the equipment selection of a screw extruder, the process design and the screw combination in the screw extruder are also a relatively critical ring influencing the performance of the plastic during the plastic modification process.
The screw combination is a key established by a double-screw extrusion process and is the largest influence factor influencing the material performance, the co-rotating double-screw extrusion mainly adopts mixing, and the feeding position, the sequence, the exhaust port position, the barrel temperature setting, the matching of the main machine rotating speed and the feeding rotating speed and the like are determined by considering the performance and the appearance of main materials and auxiliary materials when the screw combination is set; meanwhile, because the materials are used in various types and have complicated physical properties, the optimum screw combination needs to be allocated for each changed material combination to produce the modified material, and obviously, the combination is also diversified. At present, in the plastic modification process, as many technicians have little knowledge about screw combinations, in the formula adjustment process, people pay more attention to the components of the formula, and compared with simple material adjustment, few technicians perform series tests on the screw combinations, how to adjust the screw combinations suitable for product production is realized, so that an optimal processing mode and processing technology of one formula become a difficult problem in the current industry.
Disclosure of Invention
The invention aims to solve the problems of equipment selection, screw length-diameter ratio matching, screw combination optimization and other processing modes and processing technology optimization in the prior art except formula modification, provides a low-linear-expansion-coefficient flame-retardant PC/ABS alloy material and a preparation method thereof, and solves the problems of glossiness, tensile strength, bending strength, elongation at break, low impact, high linear expansion coefficient and large after-contraction of a glass fiber reinforced PC/ABS alloy material, so that a low-linear-expansion-coefficient halogen-free flame-retardant PC/ABS alloy product with excellent performance is obtained.
The technical scheme of the invention is as follows:
a low-linear-expansion-coefficient flame-retardant PC/ABS alloy material is composed of the following materials in parts by mass:
low viscosity polycarbonate: 10-35 parts;
medium viscosity polycarbonate: 25-50 parts;
ABS material: 3-15 parts;
flame retardant synergist: 0.1-1 part;
a toughening agent A:1-10 parts;
a toughening agent B:0.1-1 part;
a compatilizer: 1-10 parts;
coupling agent: 0.1-1 part;
main antioxidant: 0.1-0.5 part;
auxiliary antioxidant: 0.1-0.5 part;
ultraviolet light absorber: 0.1-0.3 part;
hydrolysis resistance agent: 0.1-1 part;
highlight black masterbatch: 0.5-3 parts;
anti-dripping agent: 0.1-0.6 part;
glass fiber: 10-15 parts;
halogen-free flame retardant: 5-20 parts of a solvent;
wherein the melt flow rate of the low-viscosity polycarbonate is 20g/10min, the melt flow rate of the medium-viscosity polycarbonate is 10g/10min, and the ABS material is Shanghai Gao Qiao 8391.
Preferably, the halogen-free flame retardant is bisphenol A-bis (diphenyl phosphate), and the flame retardant synergist is silsesquioxane; the toughening agent A is a terpolymer (MBS) of methyl methacrylate, butadiene and styrene, and the toughening agent B is low molecular weight polyolefin (PE 1105A); the compatibilizer is an amorphous thermoplastic random (styrene-maleic anhydride) copolymer (SMA 23110); the coupling agent is organic silicon with polarity at two ends (STAM E550); the main antioxidant is antioxidant beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester (1076); the auxiliary antioxidant is antioxidant tris [2,4-di-tert-butylphenyl]Phosphite (168); the ultraviolet absorbent is 2- (2 '-hydroxy-5' -octylphenyl) -benzotriazole (5411); the hydrolysis resistant agent is monomeric carbodiimide (A)
1010 Material); the highlight black master is cabot (2048-1); the anti-dripping agent is Polytetrafluoroethylene (PTFE).
The invention provides a preparation method of a low-linear-expansion-coefficient flame-retardant PC/ABS alloy material, which comprises the following steps:
s1, adding low-viscosity polycarbonate, medium-viscosity polycarbonate and an ABS material into a high-speed mixer in parts by mass, and carrying out primary mixing for 2min at normal temperature;
s2, adding the flame-retardant synergist, the toughening agent A, the toughening agent B, the compatilizer, the coupling agent, the main antioxidant, the auxiliary antioxidant, the ultraviolet absorbent, the hydrolysis-resistant agent, the high-gloss black master batch and the anti-dripping agent into the material mixed in the step S1 according to the parts by weight, and blending for 2 minutes by using a high-speed mixer;
and S3, adding the material mixed in the step S2 into a double-screw extruder, adding glass fiber and a halogen-free flame retardant into the screw extruder according to the mass parts, cooling the extruded material strips to room temperature through a water tank at 40 ℃, and granulating through a granulator.
Preferably, the twin-screw extruder comprises two mutually-meshed screws, and the screw combination is divided into a feeding conveying section, a melting plasticizing section, a side feeding section (liquid oiling section), a mixing homogenizing section, an air exhaust section (glass fiber opening), a mixing homogenizing section, a vacuum exhaust section and an extrusion section from a material conveying section to a material extrusion end in sequence, wherein:
the types of the thread elements adopted by the feeding conveying section comprise: 32/32A;48/48SK and 48/24SK-N;
the type of the thread element adopted by the melting and plasticizing section comprises: 48/48;48/24;32/32;22/11L; k is 30 DEG/7/48; k45 DEG/5/32; k45 DEG/5/22; k45 degrees/5/22L; k60 DEG/4/22; k90 °/5/32;
the type of the thread element adopted by the side feeding section (liquid refueling section) comprises the following steps: 48/48;32/32;
the types of the screw elements adopted by the mixing and homogenizing section comprise: 48/48;32/32;22/22;22/11L; ZME 8/16; k30 DEG/7/48; k45 degree/5/32; k45 degrees/5/32L; k45 degree/5/22; k45 degrees/5/22L; k45 DEG/5/16; k60 DEG/4/22; k90 °/5/32;
the model of the screw element that the air exhaust section (glass fiber mouth) adopted includes: 48/48;32/32;
the types of the thread elements adopted by the vacuum exhaust section comprise: 48/48;32/32;
the types of the thread elements adopted by the extrusion section comprise: 32/32 and 22/22.
Among them, ZME8/16 is a dispersive thread block which mainly plays a role of dispersive distributive mixing in the screw combination. 32/32 denotes a screw element having a lead of 32mm and a length of 32mm, 32/32A denotes a hollow screw element having a lead (axial length of one revolution around a screw block) of 32mm and a master length (master axial length) of 32mm, and there are two types of kneading elements currently used on the market, i.e., a "K" series and an "M" series (teeth), where "K" series of kneading masters are all used, wherein the expression: for example, "K90 °/5/32" belongs to a cutout (meshing block), the belt "K" refers to a sheet-shaped cutout, "90 °" refers to an angle formed by splicing sheets, "5" refers to 5 sheets in total, "32" refers to a length of 32mm, and a spiral width of 32/5=6.4mm. The rotation angle of the thread block is divided into 30 degrees, 45 degrees, 60 degrees and 90 degrees, such as: "K30 °/7/48", "K60 °/4/22", "K90 °/5/32", etc.
In addition, the thread block has a positive and negative division, wherein the expression is as follows: if "K45 °/5/32" is positive thread shear block, "K45 °/5/32L", "K45 °/5/22L", "22/11L" adds "L" letter at the end to represent left-hand thread block, and is reverse thread block, its positive and negative thread blocks play the following roles in the screw:
A. the reverse thread block has a barrier effect on the conveying of materials, and plays a role in prolonging the retention time of the materials in the screw, increasing the internal pressure of the screw barrel and improving the mixing effect of the materials, but simultaneously also increases the shearing strength of the materials in the screw barrel and increases the internal shearing heat, and the larger the angle of the thread block is, the smaller the pressure of the polymer in the screw is;
B. the forward thread block has the advantages that the larger the stagger angle is between 0 and 45 degrees, the conveying capacity is increased, the maximum dispersion distribution capacity is realized at 45 degrees, the conveying capacity is the strongest, the larger the stagger angle is between 45 and 90 degrees, the conveying capacity is reduced, the maximum shearing capacity is realized at 90 degrees, the conveying capacity is the lowest and almost no, the residence time of materials in a screw is prolonged while the shearing capacity is enhanced, and the mixing effect of the materials in a double-screw extruder is improved.
The different screw edge widths are one of the most important parameters for measuring the combined shearing size and the mixing size of the screw, and the larger the width is, the larger the shearing is, the smaller the distribution mixing is; smaller width the smaller shear the greater the distributive mixing. For distributive mixing and dispersive mixing, distributive mixing, the effectiveness decreases with increasing width and dispersive mixing increases with increasing width; the smaller the width is, the larger the ratio of the axial effective flow rate to the radial effective flow rate of the material is.
Generally, the meshing block (shear block) with the staggered angle within 90 degrees has stronger shearing capability when the angle is larger, the shearing capability of the thick meshing block is stronger than that of the thin meshing block, the positive meshing block has two functions of shearing and conveying simultaneously except for the staggered angle of 90 degrees, the thickness of the common meshing block has larger thermal influence on shearing, and the thick meshing block is beneficial to enhancing plasticizing dispersion through shearing heat.
Further preferably, in the present invention, the screw length-diameter ratio of the screw combination is one of 40/1, 44/1 and 48/1; and the screw rotating speed of the double-screw extruder is one of 400 revolutions per minute and 450 revolutions per minute.
Further preferably, in the present invention, the temperatures of the sections of the twin-screw extruder are: the head is 240-250 ℃; a first stage: 240-250 ℃; and (2) second stage: 245 to 255 ℃; and (3) three stages: 255-265 ℃; and a fourth stage: 235 to 245 ℃; five stages: 245 to 255 ℃; six sections: 245 to 255 ℃; seven sections: 245 to 255 ℃; eight sections: 245 to 255 ℃; nine sections: 245 to 255 ℃; ten sections: 245 to 255 ℃; four sections of the double-screw extruder are liquid halogen-free flame retardant BDP charging openings, six sections of the double-screw extruder are glass fiber charging openings, and nine sections of the double-screw extruder are vacuum openings.
Further preferably, in the present invention, the screw length-diameter ratio in the optimum screw combination is 40/1; and the screw rotating speed of the double-screw extruder is 450 revolutions per minute.
The invention has the beneficial effects that:
1. setting a feeding conveying section: the thread leads used large lead thread elements at the feed port and thereafter gradually decreased to the middle of the melting section. The use has the advantages that the depth of the screw groove of the co-rotating twin-screw is not changed, the lead is gradually reduced to reduce the volume of the screw groove, and the compression effect on materials is realized in the process of melting; meanwhile, the screw groove at the feeding port has larger volume, so that the feeding is smooth.
2. Setting a screw of a melting plasticizing section: the heat required for melting the material is the heat of shearing in the material in addition to the external heating of the apparatus, and the melting is preferably promoted by providing kneading blocks in appropriate places to enhance shearing, i.e., the first group of kneading blocks for promoting melting is placed in the middle and rear part of the melting zone. This has the advantage that the material delivered to this location is already nearly completely molten and, once the kneading blocks are encountered, is completely molten. The end point of the melting can be controlled by adjusting the position of the kneading blocks within a certain region. However, if the kneading blocks are too close to the feed port, the feed port is blocked or the screw torque is increased, and the service life of the screw is shortened;
3. the arrangement of the air exhaust section (glass fiber port) and the vacuum exhaust section: the section is a channel for outward emission and exhaust of small molecular substances in the whole screw combination, mainly conveying, in order to increase the emission of the small molecular substances and redundant gas in the material, a conveying original with a large lead is required to be arranged at the beginning of the section to spread the material to the maximum extent so as to volatilize the small molecular substances, an engaging block is used to fully mix the material before the beginning of the section, and a reverse threaded block with an L shape is used to increase the pressure inside the screw before the beginning of the section so as to increase the density of the material and prevent the material from overflowing out of the double-screw extruder through an open port;
4. side-feed section (liquid refueling section): in the stage, because the liquid flame retardant is pressed into the high-speed rotating twin-screw extruder by the liquid pressurizing device from the outside, a conveying block with large lead is arranged, if a meshing block or a conveying block with small lead is added, the pressure in the screw is increased, and the liquid flame retardant is difficult to be added into the twin-screw extruder;
5. setting a mixing and homogenizing section: this section requires a compromise between mixing homogenization and transport capabilities, two interrelated aspects that should be addressed in the design of the mixing section. The mixing and homogenizing include dispersive mixing and distributive mixing, and the dispersive mixing of the material in a screw can fine the filling components, such as inorganic stuffing, glass fiber, etc. and this fining is realized with shearing stress or shearing rate. Distributive mixing, which is the reduction of the non-uniformity of the distribution of the fractional fill in the fractional multi-component, depends on shear strain. As the kneading blocks increase, both the dispersive and distributive mixing effects increase. Therefore, in order to improve the mixing capability of the kneading section, a multi-head kneading block should be selected as much as possible, which is also the reason for increasing the distribution and dispersion capability of the equipment by using ZME type porous screw elements in some screw combinations; the section is positioned in front of and behind a glass fiber feeding port, the glass fiber port can be used for adding glass fibers, meanwhile, the section is an air exhaust section, in order to better convey the glass fibers and better disperse, distribute and mix the glass fibers, firstly, a resistance element, namely a kneading block (a shearing block) or a reverse threaded element (a threaded block with an L-shaped tail) is required to be arranged in front of the exhaust port (the glass fiber port), then, a large-lead threaded element is arranged at the exhaust port, and secondly, the threaded elements are arranged at intervals in the mixing section where more kneading blocks are arranged to strengthen the conveying capacity;
6. setting an extrusion section: the lead is gradually reduced from the part to the machine head, the conveying function and the pressure building function are achieved, and the material is compacted continuously, so that the compact and less-hole material appearance is achieved.
The invention provides a low-linear-expansion-coefficient flame-retardant PC/ABS alloy material and a preparation method thereof.
Drawings
FIG. 1 is a schematic view of the arrangement of screw assemblies in example 1 of the present invention;
FIG. 2 is a schematic view of the arrangement of the screw assemblies in example 2 of the present invention;
FIG. 3 is a schematic view of the screw assembly arrangement according to example 3 of the present invention;
FIG. 4 is a schematic view of the screw assembly arrangement according to example 4 of the present invention;
FIG. 5 is a schematic view showing the arrangement of screws in comparative example 1 of the present invention;
FIG. 6 is a schematic view showing the arrangement of screw combinations of comparative example 2 of the present invention;
FIG. 7 is a schematic view showing the arrangement of screw combinations in comparative example 3 of the present invention;
FIG. 8 is a schematic view showing the screw combination arrangement of comparative example 4 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The invention provides a low-linear-expansion-coefficient flame-retardant PC/ABS alloy material which is prepared from the following materials in parts by mass:
low viscosity polycarbonate: 10-35 parts;
medium viscosity polycarbonate: 25-50 parts;
ABS material: 3-15 parts;
flame retardant synergist: 0.1-1 part;
a toughening agent A:1-10 parts;
a toughening agent B:0.1-1 part;
a compatilizer: 1-10 parts;
coupling agent: 0.1-1 part;
main antioxidant: 0.1-0.5 part;
auxiliary antioxidant: 0.1-0.5 part;
ultraviolet absorber: 0.1-0.3 part;
hydrolysis resistance agent: 0.1-1 part;
highlight black masterbatch: 0.5-3 parts;
anti-dripping agent: 0.1-0.6 part;
glass fiber: 10-15 parts;
halogen-free flame retardant: 5-20 parts of a solvent;
wherein the melt flow rate of the low-viscosity polycarbonate is 20g/10min, the melt flow rate of the medium-viscosity polycarbonate is 10g/10min, and the ABS material is Shanghai Gao Qiao 8391; the halogen-free flame retardant is bisphenol A-bis (diphenyl phosphate), and the flame retardant synergist is silsesquioxane; the toughening agent A is terpolymer (MBS) of methyl methacrylate, butadiene and styrene, and the toughening agent B is low molecular weight polyolefin (PE 1105A); the compatibilizer is an amorphous thermoplastic random (styrene-maleic anhydride) copolymer (SMA 23110); the coupling agent is organic silicon with polarity at two ends (STAM E550); the main antioxidant is antioxidant beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester (1076); the auxiliary antioxidant is antioxidant tris [2,4-di-tert-butylphenyl]Phosphite (168); the ultraviolet absorbent is 2- (2 '-hydroxy-5' -octylphenyl) -benzotriazole(s) ((5411 ); the hydrolysis resistant agent is monomeric carbodiimide (C)
1010 Material); the highlight black master is cabot (2048-1); the anti-dripping agent is Polytetrafluoroethylene (PTFE).
A preparation method of a low-linear-expansion-coefficient flame-retardant PC/ABS alloy material comprises the following steps:
s1, adding low-viscosity polycarbonate, medium-viscosity polycarbonate and an ABS material into a high-speed mixer in parts by mass, and carrying out primary mixing for 2min at normal temperature;
s2, adding the flame-retardant synergist, the toughening agent A, the toughening agent B, the compatilizer, the coupling agent, the main antioxidant, the auxiliary antioxidant, the ultraviolet absorbent, the hydrolysis-resistant agent, the high-gloss black master batch and the anti-dripping agent into the material mixed in the step S1 according to the parts by weight, and blending for 2 minutes by using a high-speed mixer;
and S3, adding the material mixed in the step S2 into a double-screw extruder, adding glass fiber and a halogen-free flame retardant into the screw extruder according to the mass parts, cooling the extruded material strips to room temperature through a water tank at 40 ℃, and granulating through a granulator.
It should be noted that, in some embodiments, the optimal mixture ratio of the materials in the flame-retardant PC/ABS alloy material is as follows:
low viscosity polycarbonate: 20 parts of (1);
medium viscosity polycarbonate: 40 parts of a mixture;
ABS material: 6 parts of (1);
flame retardant synergist: 0.3 part;
a toughening agent A:3 parts of a mixture;
a toughening agent B:0.3 part;
a compatilizer: 2.5 parts;
coupling agent: 0.5 part;
main antioxidant: 0.2 part;
auxiliary antioxidant: 0.2 part;
ultraviolet absorber: 0.2 part;
hydrolysis resistance agent: 0.2 part;
highlight black masterbatch: 2 parts of (1);
anti-dripping agent: 0.3 part;
glass fiber: 12 parts of (1);
halogen-free flame retardant: 7 parts.
According to the application, through compounding of low-viscosity polycarbonate (melt flow rate: 20g/10 min) and medium-viscosity polycarbonate (melt flow rate: 10g/10 min), different molecular weights and different melt flow rates can form a certain viscosity gradient in the modification process, so that the high-molecular-weight and low-molecular-weight molecules of the material in the modification process can be uniformly distributed, and unstable performance of the modified material due to cliff type physical property matching cannot occur. With the widening of molecular weight distribution, the internal lubricity of the polymer can be increased, and various materials, additives and glass fiber groups can be well dispersed, so that the modified PC/ABS flame-retardant alloy material with more excellent performance is obtained.
In addition, metaphosphoric acid generated in the combustion process of the phosphorus flame retardant bisphenol A bis (diphenyl phosphate) can form a stable polymer, promote the dehydration and carbonization of combustible materials and prevent or reduce the generation of combustible gas. The metaphosphoric acid also forms a glass-like melt to cover the surface of combustible materials during pyrolysis, so that the metaphosphoric acid is oxidized into carbon dioxide to play a role in flame retardance. However, in the production process of the liquid bisphenol A bis (diphenyl phosphate) flame retardant, hydraulic high-pressure injection is used, the addition is not easy, the impact property and the heat resistance of the material are greatly reduced after the addition, and in order to improve the processing efficiency and increase the mechanical property of the product, a part of silsesquioxane flame retardant is used for synergistic flame retardance, so that the addition of the bisphenol A bis (diphenyl phosphate) flame retardant is reduced. The impact strength, the heat distortion temperature, the bending strength and the bending modulus of the obtained alloy product are greatly improved.
Meanwhile, the grain sizes of different toughening agents are not consistent, the effects obtained in the alloy materials are not consistent, and the hole effect is easily formed due to the different grain sizes, wherein the compounding of MBS with a large-grain powder core-shell structure and 1105A with polar groups of wax with a small grain size and a dispersing effect can enable the toughening agents to play a role in filling large grain sizes in a molten substance, and the ideal effect of hole supplement of small grain sizes can greatly improve the notch impact strength of the glass fiber reinforced flame retardant PC/ABS alloy.
In addition, because the interfacial bonding force between the polycarbonate and the ABS and the glass fiber is poor, and the functional group in the compatilizer has extremely high chemical reaction activity, the functional group can react with the surface hydroxyl of the glass fiber in the extrusion blending process of the polycarbonate and the ABS to enhance the interfacial coupling effect, thereby improving the mechanical properties such as the impact strength, the tensile strength and the like of the fiber-added product, simultaneously preventing the glass fiber from leaking outwards and increasing the surface smoothness of the product. Because of having better compatibility, the resin composition can well promote the compatibility of PC/ABS, improve the interface associativity of products and the glossiness of the surfaces of the products, improve the surface connection and the adhesive force of resin products, has better heat resistance, has smaller influence on the heat resistance of the alloy and has the function of slightly improving. Meanwhile, the coupling agent with polarity at two ends is compounded, so that the interface adhesion between the glass fiber and the material is assisted to be enhanced, the interface affinity in different materials is increased, the lubricating property among molecules can be enhanced due to the small molecular silicon compatilizer, and the coupling agent is compounded with the toughening agent to play a role in dispersing the black master, the glass fiber and the auxiliary agent, so that the mechanical property of the whole alloy material is improved.
Polycarbonate (PC) has excellent performance, is colorless and transparent, has good heat resistance and impact resistance, and has self-extinguishing property, so that the PC is often modified into flame-retardant and alloy PC in daily life due to the excellent performance and appearance, and is widely applied to shells of automobiles, household appliances and electronic products. Meanwhile, when the polycarbonate PC is exposed to a damp and hot environment for a long time, ester bonds in PC molecular chains are easy to generate hydrolysis reaction with carboxylic acid or water under the damp and hot condition, so that the molecular chains are broken, and hydrolysis yellowing and aging are caused, thereby causing the reduction of comprehensive performance and the shortening of service life. Therefore, it is an important research and development direction to maintain a stable physical property of PC and its modified products during the manufacturing process and long-term use, and to reduce aging, in which a monomeric carbodiimide is reacted with the carboxyl end groups of polycarbonate and the carboxylic acid generated by decomposition to form a ureido compound. Thereby slowing down the hydrolysis of the polymer, prolonging the service life of the polymer and simultaneously solving the problem of the reduction of the comprehensive performance of the PC material caused by hydrolysis.
In addition, a halogen-free flame retardant is required to be added in the production process of the halogen-free flame-retardant PC/ABS alloy product, organic sulfonic acid metal salt (KSS), perfluorobutyl potassium sulfonate (PPFBS), bisphenol A bis (diphenyl phosphate) (BDP) and triphenyl phosphate (TPP) are flame retardants frequently used, wherein the BDP is a liquid flame retardant with the largest use amount, the flame retardant has high flame-retardant efficiency and low price, but the BDP is liquid and cannot be added in the processing process according to a conventional mode, so that the BDP needs to be added into a double-screw extruder in a side-feeding hydraulic mode, and the added uniformity and the influence on the physical performance of the material are large, so that the PC/ABS alloy product is difficult to be uniformly mixed, the processing technology is not properly controlled, the material is not well dispersed, and the stable flame-retardant effect is difficult to ensure. In addition, higher temperature is needed in the processing process, once the control is not good, the material is easy to decompose, the mechanical property is reduced, and the flame retardance is not good, the optimal formula combination is selected after the optimal combination is carried out on the formula in the application, and the process is also accurately controlled, so that better mechanical property and attractive appearance are achieved, and in order to achieve the purpose, a more effective solution is provided in the patent.
Compared with a single-screw extruder, the meshed co-rotating double-screw extruder used in plastic modification has the advantages of strong mixing capability, good exhaust performance, short retention time of materials in screws and the like. Therefore, the thermoplastic resin is widely applied to filling, reinforcing and toughening modification of thermoplastic resin. The screw combination of the screw rod adopts modularization, the screw rod elements can be flexibly disassembled, and the screw elements with different shapes and functions are organically combined according to the formula of the processed material and the processing technology conditions (feeding amount, processing temperature, main machine rotating speed, feeding rotating speed, main machine current and the like), so that the processed material achieves the best comprehensive performance.
The screw combination is the key established by a double-screw extrusion process and is the largest influence factor influencing the material performance, the co-rotating double-screw extrusion is mainly mixing, and the performance and the shape of main materials and auxiliary materials are considered when the screw combination is arranged, so that the feeding position, the sequence, the exhaust port position, the barrel temperature setting and the like are determined. Meanwhile, because the materials are used in various types and have complicated physical properties, the optimum screw combination needs to be allocated for each changed material combination to produce the modified material, and obviously, the combination is also diversified.
In this application production process, what the optimal ratio of screw combination was used is meshing syntropy twin-screw extrusion testing machine, and the barrel has two gas vents except a charge door, and one is to the air vent (glass mouth), and another is the vacuum vent. The screw configuration can be divided into a feeding and conveying section, a melting and plasticizing section, a side feeding section (liquid oiling section), a mixing and homogenizing section, an air exhaust section (glass fiber port), a mixing and homogenizing section, a vacuum exhaust section and an extrusion section (homogenizing and pressure-building material discharge section). The feeding section, the air exhaust section and the vacuum exhaust section are all composed of forward large-lead screw elements; the melting section consists of a conveying block and an engaging block, and a section of reverse threaded element is adopted at the end part of the melting section and is close to the front of the proximal feeding section (liquid refueling section); the mixing section consists of kneading discs and screw elements; the homogenizing and pressure-building discharge section consists of screw elements.
The screw combination actually arranges and combines various screw elements with different properties along the axial direction of the screw aiming at different extrusion functions. In the feeding and conveying section, because of the difference of the polymer raw material form and the difference of the filling agent or additive form, the conveying section is required to have a larger material containing space to adapt to the adjustment of the feeding amount so as to prevent the material from accumulating at the feeding port to generate flash. The screw combination should be such that the material in the conveying zone is partially filled so that the gas discharged during compression of the material before melting is discharged smoothly without affecting the solids conveying, which requires a large conveying capacity and free volume percentage of the combination in this section. In the melting section, the materials start to melt and mix after solid conveying and compression. The initial position of this stage requires that the material be subjected to some shear, producing sufficient shear heat to facilitate the melting process. According to the experiment, the material melted very quickly within a very short axial distance and mixing began to occur; in the mixing section, the material is in a molten state after undergoing a melting process, and in the process, all components of the material must be homogenized and refined, so that the section is required to combine certain dispersive mixing and distributive mixing capabilities, but at the same time, the generation of excessive shear heat and large temperature rise in the section must be prevented; in the exhaust section, in order to ensure that volatile matters and moisture in the homogenized material are easy to remove, the material is required to be in a negative pressure state, and the section combination requires a large material containing space to ensure that the material is in a full state; in the machine barrel of the melt conveying section, a certain pressure must be built up by the material so as to ensure that the material at the outlet of the die has a certain density. Generally, the mixing requirements are low and shearing of the material should be avoided. This section is closely related to the vent section throughout the extrusion process and if the melt conveying section builds up a low pressure, i.e., insufficient forward conveying capacity, the screw channel fill length can be too long, resulting in vent flash.
When the glass fiber is modified by a meshing co-rotating twin-screw extruder, the strength and weakness of the screw combination and the dispersion and distribution combination are one of the most critical problems for affecting the quality of the glass fiber in length and dispersion of the glass fiber in the material. Because the glass fiber contains alkali or medium alkali, the glass fiber is different in length and dispersity under the condition of the same glass fiber addition due to the strength and brittleness of the glass fiber, and the glass fiber is not properly distributed under the condition of different screw combinations with the same formula, so that the glass fiber is leaked in the injection molding process of the material, the surface defects of products are easily caused, and in some products easy to crystallize, the glass fiber is not uniformly distributed, and the products are easily warped and deformed. Improper screw combinations can result in entrained air and some released volatiles during production, with the potential for backflow along the screw towards the feed port, causing fluidization of the material at the feed port, which can limit the amount of material added to the feed port, affect throughput, and limit the use of neutral or reverse screw elements that push the entrained air back into the feed port, so appropriate flights and methods should be selected to address these problems.
The present invention is further described in detail with reference to the following specific embodiments, it is understood that the material ratios in the following embodiments are all the optimum material ratios, and the differences are only the arrangement and combination of the screw elements in the screw combination.
Example 1
The technological parameters of the double-screw extruder are that the temperature of each section is as follows: a first stage: 240-250 ℃; and a second stage: 245 to 255 ℃; and (3) three stages: 245 to 255 ℃; and a fourth stage: 235 to 245 ℃; five stages: 245 to 255 ℃; six sections: 245 to 255 ℃; seven sections: 250 to 265 ℃; eight sections: 245 to 255 ℃; nine sections: 245 to 255 ℃; ten sections: 245 to 255 ℃; the head is 240-250 ℃. The four sections of the double-screw extruder are hydraulic fire retardant adding oil ports, the seven sections are glass fibers, and the nine sections are vacuum ports.
Further, the screw rotating speed of the double-screw extruder is 400 revolutions per minute; the total length of the screw is: 1447mm, the length-diameter ratio L/D of the screw is as follows: 40/1, wherein the arrangement sequence of each section of thread elements in the screw combination is shown as the following figure:
in example 1, 4 shear blocks are arranged in the plasticizing section, 11 shear blocks are arranged in the mixing and homogenizing section, and 15 shear blocks are arranged in total, because 4 shear blocks are arranged in the plasticizing section, the melting effect of the material at the plasticizing section is stronger than that of the design without the shear blocks, the 11 shear blocks are further used for producing the alloy in the mixing and homogenizing section, the internal shearing of the material is stronger, the degradation is stronger, and therefore the relatively lower screw rotating speed is set to be 400 revolutions per minute.
Example 2
The technological parameters of the double-screw extruder are that the temperature of each section is as follows: a first stage: 240-250 ℃; and (2) second stage: 245 to 255 ℃; and (3) three stages: 255-265 ℃; and a fourth stage: 235 to 245 ℃; five stages: 245 to 255 ℃; six sections: 245 to 255 ℃; seven sections: 245 to 255 ℃; eight sections: 245 to 255 ℃; nine sections: 245 to 255 ℃; ten sections: 245 to 255 ℃; the head is 240-250 ℃. The four sections of the double-screw extruder are hydraulic fire retardant adding oil ports, the six sections are glass fibers, and the nine sections are vacuum ports.
Further, the screw rotating speed of the double-screw extruder is 450 revolutions per minute; the total length of the screw is: 1447mm, the length-diameter ratio L/D of the screw is as follows: 40/1, wherein the arrangement sequence of each section of thread elements in the screw combination is shown as the following figure:
in the embodiment 2, 5 shear blocks are arranged in the plasticizing section, 9 shear blocks are arranged in the mixing homogenizing section, 2 dispersing blocks ZME8/16 are additionally added, and 14 shear blocks are totally added, so that the melting effect of the material in the mixing homogenizing section is stronger than that in the embodiment 1, 9 shear blocks are further used for dispersing and mixing in the mixing homogenizing section, and 2 dispersing blocks ZME8/16 are used for distributing and mixing, therefore, the distributing and mixing capability is enhanced on the basis of the embodiment 1, the material is well dispersed, distributed and mixed in the double-screw extruder, and the material is processed at the screw rotating speed of 450 revolutions per minute, so that the retention time of the material in the double-screw extruder is shortened, the thermal degradation degree of the alloy material is reduced, and the low-linear expansion coefficient flame-retardant PC/ABS alloy material with very good performance and appearance is obtained.
Example 3
The technological parameters of the double-screw extruder are that the temperature of each section is as follows: a first stage: 240-250 ℃; and (2) second stage: 245 to 255 ℃; and (3) three stages: 245 to 255 ℃; and a fourth stage: 235 to 245 ℃; and a fifth stage: 245 to 255 ℃; six sections: 245 to 255 ℃; seven sections: 245 to 255 ℃; eight sections: 245 to 255 ℃; nine sections: 245 to 255 ℃; ten sections: 245 to 255 ℃; the head is 240-250 ℃. The four sections of the double-screw extruder are hydraulic fire retardant adding oil ports, the six sections are glass fibers, and the nine sections are vacuum ports.
Further, the screw rotating speed of the double-screw extruder is 400 revolutions per minute; the total length of the screw is: 1450mm, the length-diameter ratio L/D of the screw is as follows: 40/1, wherein the arrangement sequence of each section of thread elements in the screw combination is shown as the following figure:
in example 3,5 shear blocks are arranged in the plasticizing section, 10 shear blocks are arranged in the mixing and homogenizing section, the total number of the shear blocks is 15, the plasticizing section is added with one shear block compared with example 1 and comparative example 1, the shearing effect is stronger than that of example 1 and comparative example 1, the material is melted with stronger effect, and the 10 shear blocks are further used for alloy production in the mixing and homogenizing section, the degradation of the material is stronger, so the screw rotating speed is set to be 400 r/min.
Example 4
The technological parameters of the double-screw extruder are that the temperatures of all sections are as follows: a first stage: 240-250 ℃; and (2) second stage: 250 to 260 ℃; and (3) three stages: 250 to 260 ℃; and a fourth stage: 235 to 245 ℃; five stages: 245 to 255 ℃; six sections: 245-250 ℃; seven sections: 240-250 ℃; eight sections: 240-250 ℃; nine sections: 240-250 ℃; ten sections: 240-250 ℃; eleven sections: 240-250 ℃; the head is 240-250 ℃. The four sections of the double-screw extruder are hydraulic fire retardant adding oil ports, the six sections are glass fibers, and the eight sections and the ten sections are vacuum ports.
Further, the screw rotating speed of the double-screw extruder is 450 revolutions per minute; the total length of the screw is: 1590mm, the length-diameter ratio L/D of the screw is as follows: 44/1, wherein the arrangement sequence of each section of thread elements in the screw combination is shown as the following figure:
in example 4, there were 3 blocks in the plasticizing zone and 11 blocks in the mixing homogenization zone, for a total of 14 blocks, and two vacuum evacuations were designed after addition of the liquid BDP flame retardant, compared to comparative example 4, where 2 blocks were reduced and the shear weakened, but where the material could be completely melted, but the compatibility dispersion was lower than in comparative example 4. In the mixing and homogenizing section, one more shearing block is added, K90 degree/5/32 is removed, the K45 degree/5/32 meshing block with better dispersing effect is replaced, and simultaneously 2 blocks of ZMW 8/16 dispersing blocks are added to enhance the shearing and dispersing capability of the whole screw,
compared with the examples 1, 2, 3 and 3, the screw used here has a length-diameter ratio of 44/1, and the screw speed set here is 450 rpm because the length-diameter ratio is longer and the degradation is reduced in order to reduce the residence time of the alloy material in the screw.
Comparative example 1
The technological parameters of the double-screw extruder are that the temperature of each section is as follows: a first stage: 240-250 ℃; and (2) second stage: 245 to 255 ℃; and (3) three stages: 245 to 255 ℃; and a fourth stage: 235 to 245 ℃; five stages: 245 to 255 ℃; six sections: 245 to 255 ℃; seven sections: 240-250 ℃; eight sections: 245 to 255 ℃; nine sections: 245 to 255 ℃; ten sections: 245 to 255 ℃; the head is 240-250 ℃. The four sections of the double-screw extruder are hydraulic fire retardant adding oil ports, the six sections are glass fibers, and the nine sections are vacuum ports.
Further, the screw rotating speed of the double-screw extruder is 400 revolutions per minute; the total length of the screw is: 1446mm, the length-diameter ratio L/D of the screw is as follows: 40/1, wherein the arrangement sequence of each section of thread elements in the screw combination is shown as the following figure:
in comparative example 1, 4 blocks were used in the plasticizing zone, 10 blocks were used in the mixing and homogenizing zone, and 14 blocks were used in total, and the shearing in the plasticizing zone was weaker than that in example 1, i.e., in this part, the alloy material in example 1 was melted more strongly and the material was melted earlier, and in the mixing and homogenizing zone, 10 blocks were further used to disperse the alloy while setting the screw rotation speed at 400 rpm.
Comparative example 2
The technological parameters of the double-screw extruder are that the temperature of each section is as follows: a first stage: 240-250 ℃; and (2) second stage: 245 to 255 ℃; and (3) three stages: 245 to 255 ℃; and a fourth stage: 235 to 245 ℃; five stages: 245 to 255 ℃; six sections: 245 to 255 ℃; seven sections: 245 to 255 ℃; eight sections: 245 to 255 ℃; nine sections: 245 to 255 ℃; ten sections: 245 to 255 ℃; the head is 240-250 ℃. The four sections of the double-screw extruder are hydraulic fire retardant feeding ports, the six sections are glass fibers, and the nine sections are vacuum ports.
Further, the screw rotating speed of the double-screw extruder is 450 revolutions per minute; the total length of the screw is: 1452mm, the length-diameter ratio L/D of the screw is as follows: 40/1, wherein the arrangement sequence of each section of thread elements in the screw combination is shown as the following figure:
in comparative example 2,4 shear blocks are provided in the plasticizing zone, 8 shear blocks are provided in the mixing and homogenizing zone, and 12 shear blocks are provided in total, and 2 dispersed blocks ZME8/16 are used for distributive mixing, compared with example 2, the screw combination has 1 shear block in the plasticizing zone at the front section and 1 shear block in the mixing and homogenizing zone, and the shear blocks are K30 DEG/7/48 and K45 DEG/5/32, and the shear blocks are K45 DEG/5/32, K90 DEG/5/32 and K60 DEG/4/22 in example 2, and the shear dispersion function of example 2 is stronger than that of example 2, so that the shear dispersion capability of comparative example 2 is weaker than that of example 2. However, from the appearance alone, since 4 conveying blocks of 22/22 are used at the very front end of the extrusion section, the screw set is denser than the other 5 screw sets, and the screw set is finer at the same screw rotation speed and drawing speed.
Comparative example 3
The technological parameters of the double-screw extruder are that the temperatures of all sections are as follows: a first stage: 240-250 ℃; and (2) second stage: 245 to 255 ℃; and (3) three stages: 245 to 255 ℃; and a fourth stage: 235 to 245 ℃; five stages: 245 to 255 ℃; six sections: 245 to 255 ℃; seven sections: 245 to 255 ℃; eight sections: 245 to 255 ℃; nine sections: 245 to 255 ℃; ten sections: 245 to 255 ℃; the head is 240-250 ℃. The four sections of the double-screw extruder are hydraulic fire retardant adding oil ports, the six sections are glass fibers, and the nine sections are vacuum ports.
Further, the screw rotating speed of the double-screw extruder is 400 revolutions per minute; the total length of the screw is: 1447mm, and the length-diameter ratio L/D of the screw is as follows: 40/1, wherein the arrangement sequence of each section of thread elements in the screw combination is shown as the following figures:
in comparative example 3, there were 2 blocks in the plasticization zone and 11 blocks in the mixing homogenization zone, and 13 blocks in total, and the plasticization zone was reduced in 2 blocks compared to example 2, and the ZME8/16 type dispersed blocks in the mixing homogenization zone were reduced, but in this case, the K90 °/5/32 blocks were increased compared to example 2, so that the shear in the mixing homogenization zone of example 2 was weaker than that of comparative example 3.
Comparative example 4
The technological parameters of the double-screw extruder are that the temperatures of all sections are as follows: a first stage: 240-250 ℃; and (2) second stage: 245 to 255 ℃; and (3) three stages: 245 to 255 ℃; and a fourth stage: 235 to 245 ℃; five stages: 245 to 255 ℃; six sections: 245-250 ℃; seven sections: 240-250 ℃; eight sections: 240-250 ℃; nine sections: 240-250 ℃; ten sections: 240-250 ℃; eleven sections: 240-250 ℃; the head is 240-250 ℃. The four sections of the double-screw extruder are hydraulic fire retardant adding oil ports, the six sections are glass fibers, and the eight sections and the ten sections are vacuum ports.
Further, the screw rotating speed of the double-screw extruder is 450 revolutions per minute; the total length of the screw is: 1590mm, the length-diameter ratio L/D of the screw is as follows: 44/1, wherein the arrangement sequence of each section of thread elements in the screw combination is shown as the following figures:
in comparative example 4, which has 5 shear blocks in the plasticizing zone and is designed to perform two-stage vacuum degassing after the addition of the liquid BDP flame retardant, compared with comparative example 2, where the shear becomes stronger due to the addition of K90 DEG/4/32 shear blocks, the material melts earlier at this point, and in the mixing and homogenizing zone, the shear dispersion function is enhanced, and the mixing and homogenizing zone has 10 shear blocks, and 15 shear blocks in total, compared with examples 1 to 3, where the screw used has a length-to-diameter ratio of 44/1, and since the length-to-diameter ratio is longer, the screw speed is set at 450 rpm in order to reduce the residence time of the alloy material in the screw and to reduce degradation.
Through the analysis of the performance and the production process of the low-linear expansion coefficient flame-retardant PC/ABS alloy material produced under the combination of 8 screws, the screw blocks with longer lead and deeper screw grooves are arranged at a feed opening, a glass fiber opening and a vacuum opening, and a section of reverse threaded element is arranged at the end of an oil filling opening and the vacuum opening; more continuous shearing blocks are arranged in the melting section; the mixing section is provided with a screw combination with dispersedly distributed shearing blocks. The combination can better plasticize and mix materials, thereby finding a screw combination suitable for producing the low-linear expansion coefficient flame-retardant PC/ABS alloy material and being applied in production.
By using the optimal formula under different screw combinations, modified alloy materials with different properties are obtained, so that materials with different linear expansion coefficients under different screw combinations are compared, and the low-linear expansion coefficient flame-retardant PC/ABS alloy material is modified.
According to the 8 sets of embodiments in the above table, the properties of the finally prepared material are shown in the following table:
by using the optimal formula under different screw combinations, modified alloy materials with different properties are obtained, so that materials with different linear expansion coefficients under different screw combinations are obtained by comparison, the modified flame-retardant PC/ABS alloy material with low shrinkage and low linear expansion coefficient is obtained, and the modified flame-retardant PC/ABS alloy material has higher physical properties in glossiness, tensile strength, bending modulus, impact strength and glow wire temperature, so that the modified flame-retardant PC/ABS alloy material can be widely applied to television frames.
From the above examples 1-4 and comparative examples 1-4, it can be seen that example 2 gives the best overall performance of the material in all screw combinations, using a screw combination with a length to diameter ratio of 40/1, with a shorter residence time of the material in the screw, a much lower internal shear heat and less degradation than comparative example 4. Example 2 compared with other examples, the screw has less shearing engaged blocks, so that the internal shearing of the alloy material in the screw is weakened, the length-diameter ratio of the glass fiber after being added into the screw is larger, and in order to better disperse the glass fiber and the material components, the screw is added with 2 ZME8/16 type dispersible tablets with stronger dispersion effect in the mixing and dispersing stage, so that the dispersion distribution capability of the screw combination is stronger. Meanwhile, in the processing process, in order to better ensure that the material can be completely melted and pre-dispersed as much as possible before adding the glass fibers and the halogen-free flame retardant in the melting and plasticizing section, the internal shear heat of the whole screw is reduced, and the processing temperature of 10 ℃ is increased in the region 1 before the glass fiber opening compared with that of the region 3 before the glass fiber opening, so that the whole screw still has better shear dispersion capability even under the condition of not being very strong, the produced modified product has lower post-shrinkage and linear expansion coefficients, and the glass fibers have better dispersion effect in the modified product and better compatibility among the components, except for higher physical property, the product has higher surface gloss under the same condition.
Example 2 compared with comparative example 2, comparative example 2 has a screw combination shearing weaker than example 2, wherein comparative example 2 has 2 engaging blocks less than example 2, under the same process conditions, the shearing dispersing ability of example 2 is stronger, and comparative example 2 has weaker shearing dispersing ability even though the dispersible tablets are added because shearing is too weak, and various materials can not be well compatibly dispersed in the shearing dispersing ability, so that the overall performance of the data is weaker and the flame retardant efficiency is lower.
Meanwhile, in the case of the same screw length-diameter ratio of example 2 compared with example 1, although example 2 has 3 meshed blocks reduced, 2 dispersed blocks are added, the screw rotation speed is increased from 400 rpm/min in example 1 to 450 rpm, the processing temperature of 3 zones is higher than that of other examples by 10 degrees, the internal shear heat is smaller in example 2 compared with example 1, the length-diameter ratio of the added glass fiber is longer due to weak internal shear, and the dispersing distribution capacity of the added ZME8/16 type dispersing tablet to the glass fiber is stronger, so that the physical property of the material is better.
Comparative example 1 in comparison with example 1, in comparative example 1, K45 °/5/22, K45 °/5/32, K60 °/4/22 were used; the engaged blocks of K45 DEG/5/22 type are used in example 1, while those of K45 DEG/5/16, K45 DEG/5/32, K90 DEG/5/32 and K60 DEG/4/22 type are used in example 1, and the engaged blocks in example 1 are more than those in comparative example 1, and the internal shear example 1 as a whole is higher than that in comparative example 1, so that the tensile strength, flexural modulus and heat distortion temperature are higher than those in comparative example 1, while the impact strength is lower than that in comparative example 1, and the linear thermal expansion coefficient of the material is lower than that in comparative example 1 because of the high shear and the relatively high melt flow rate.
Compared with the comparative example 1, the shear dispersion effect of the example 1 is the best, the shear dispersion effect of the example 3 is the next, and the comparative example 1 is the worst, according to experimental data, under the condition of proper screw combination arrangement, the stronger screw combination can better mix and homogenize various materials on the basis of ensuring the materials to be melted, and the stronger screw combination before an air exhaust section is more likely to melt the materials, so that the problems that the glass fibers are too short to be sheared in the screws and are not well dispersed due to the fact that the materials are not uniformly melted before glass fiber openings, the premixing is not good, the internal shear heat formed by the material particles is larger, and the glass fibers, the compatilizer and the toner assistant are agglomerated to influence the performance of products are reduced.
Comparative example 4 in comparison with example 4, two screws were combined with a screw having a length/diameter ratio of 44/1, and since the alloy material was sensitive to shear and the product was added with a wave form and a liquid flame retardant, the residence time of the alloy material in the screw was required to be short in order to reduce the internal shear heat of the material, so that the screw rotation speed was set at 450 rpm. Meanwhile, the shear setting in the melting section in comparative example 4 is stronger than that in example 4, so the material can be better melted when liquid BDP is added into the screw, but the mixing dispersion capability of comparative example 4 in the mixing homogenization section is weaker than that in example 4, and the shear capability of example 4 is weaker than that of comparative example 4 after the glass fiber opening, so the glass fiber length is longer, and further, because 2 ZMW 8/16-shaped dispersible tablets are added, the glass fiber can be better dispersed in example 4, and because the length-diameter ratio of the whole screw is longer, the weak force of the melting section in example 4 can supplement the shear dispersion capability after the BDP oil opening and before the glass fiber inlet opening, so the physical combination property and the post-shrinkage and linear expansion coefficient in example 4 are better than those in comparative example 4 in the whole screw.
According to the material performance data table and analysis comparison, the material prepared by the screw combination in the embodiment 2 has the most excellent performance, and the problems that the glass fiber reinforced PC/ABS has better flame retardance, higher tensile strength, elongation at break, bending strength, bending modulus, impact strength and thermal deformation performance and higher glow wire temperature in the production process are solved, and more importantly, the halogen-free flame retardant PC/ABS alloy material with lower post-shrinkage and linear expansion coefficient is obtained by controlling the length of glass fiber and the dispersion condition of BDP added with a flame retardant. And through the analysis of the performance and the production process of the low-linear expansion coefficient flame-retardant PC/ABS alloy material produced under the combination of 8 screws, the screw blocks with longer lead and deeper screw grooves are arranged at the feed opening, the glass fiber opening and the vacuum opening, and a section of reverse screw element is arranged at the end of the glass fiber opening and the vacuum opening; more continuous shearing blocks are arranged in the melting section; the mixing section is provided with a screw combination with the shearing blocks distributed dispersedly. The combination can better plasticize and mix materials, so that a screw combination suitable for production is found and is applied to production.
The foregoing description of the specific embodiments of the present invention has been presented for purposes of illustration and description and is not intended to limit the invention to the precise form disclosed, and it will be apparent from the foregoing description that numerous modifications and variations are possible, the embodiments being chosen and described in order to explain certain principles of the invention and its practical application, to thereby enable others skilled in the art to make and use the invention in various embodiments and with various alternatives and modifications. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (7)
1. The low-linear-expansion-coefficient flame-retardant PC/ABS alloy material is characterized by comprising the following materials in parts by mass:
low viscosity polycarbonate: 10-35 parts;
medium viscosity polycarbonate: 25-50 parts;
ABS:3-15 parts;
flame retardant synergist: 0.1-1 part;
a toughening agent A:1-10 parts;
a toughening agent B:0.1-1 part;
a compatilizer: 1-10 parts;
coupling agent: 0.1-1 part;
main antioxidant: 0.1-0.5 part;
auxiliary antioxidant: 0.1-0.5 part;
ultraviolet absorber: 0.1-0.3 part;
hydrolysis resistance agent: 0.1-1 part;
highlight black masterbatch: 0.5-3 parts;
anti-dripping agent: 0.1-0.6 part;
glass fiber: 10-15 parts;
halogen-free flame retardant: 5-20 parts of a solvent;
the melt flow rate of the low-viscosity polycarbonate is 20g/10min, the melt flow rate of the medium-viscosity polycarbonate is 10g/10min, and the ABS material is Shanghai Gao Qiao 8391.
2. The low-linear-expansion-coefficient flame-retardant PC/ABS alloy material as claimed in claim 1, which is characterized by comprising the following materials in parts by mass:
low viscosity polycarbonate: 20 parts of (1);
medium viscosity polycarbonate: 40 parts of a mixture;
ABS material: 6 parts of (1);
flame retardant synergist: 0.3 part;
a toughening agent A:3 parts of a mixture;
a toughening agent B:0.3 part;
a compatilizer: 2.5 parts;
coupling agent: 0.5 part;
main antioxidant: 0.2 part;
auxiliary antioxidant: 0.2 part;
ultraviolet light absorber: 0.2 part;
hydrolysis resistance agent: 0.2 part;
highlight black masterbatch: 2 parts of (1);
anti-dripping agent: 0.3 part;
glass fiber: 12 parts of (1);
halogen-free flame retardant: 7 parts.
3. The low-linear expansion coefficient flame-retardant PC/ABS alloy material as claimed in claim 1, wherein the halogen-free flame retardant is bisphenol A-bis (diphenyl phosphate), the flame-retardant synergist is silsesquioxane; the toughening agent A is a terpolymer (MBS) of methyl methacrylate, butadiene and styrene, and the toughening agent B is low molecular weight polyolefin (PE 1105A); the compatibilizer is an amorphous thermoplastic random (styrene-maleic anhydride) copolymer (SMA 23110); the coupling agent is organic silicon with polarity at two ends (STAM E550); the main antioxidant isAntioxidant beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester (1076); the auxiliary antioxidant is antioxidant tris [2,4-di-tert-butylphenyl]Phosphite (168); the ultraviolet absorbent is 2- (2 '-hydroxy-5' -octylphenyl) -benzotriazole (5411); the hydrolysis resistant agent is monomeric carbodiimide (A)
1010 Material); the highlight black master is cabot (2048-1); the anti-dripping agent is Polytetrafluoroethylene (PTFE).
4. A method for preparing the low linear expansion coefficient flame-retardant PC/ABS alloy material of claims 1-3, characterized by comprising the following steps:
s1, adding low-viscosity polycarbonate, medium-viscosity polycarbonate and an ABS material into a high-speed mixer in parts by mass, and carrying out primary mixing for 2min at normal temperature;
s2, adding the flame-retardant synergist, the toughening agent A, the toughening agent B, the compatilizer, the coupling agent, the main antioxidant, the auxiliary antioxidant, the ultraviolet absorbent, the hydrolysis-resistant agent, the high-gloss black master batch and the anti-dripping agent into the material mixed in the step S1 according to the parts by weight, and blending for 2 minutes by using a high-speed mixer;
and S3, adding the material mixed in the step S2 into a double-screw extruder, adding glass fiber and a halogen-free flame retardant into the double-screw extruder according to the mass part, cooling the extruded material strips to the room temperature through a water tank at the temperature of 40 ℃, and then granulating through a granulator.
5. The method for preparing the low-linear expansion coefficient flame-retardant PC/ABS alloy material as claimed in claim 4, wherein the twin-screw extruder comprises two screws which are meshed with each other, and the screw combination is divided into a feeding and conveying section, a melting and plasticizing section, a side feeding section (liquid oiling section), a mixing and homogenizing section, an air exhaust section (glass fiber opening), a mixing and homogenizing section, a vacuum exhaust section and an extrusion section from a material conveying section to a material extrusion end in sequence, wherein:
the types of the thread elements adopted by the feeding conveying section comprise: 32/32A;48/48SK and 48/24SK-N;
the type of the thread element adopted by the melting and plasticizing section comprises: 48/48;48/24;32/32;22/11L; k30 DEG/7/48; k45 DEG/5/32; k45 degree/5/22; k45 degrees/5/22L; k60 DEG/4/22; k90 °/5/32;
the side feeding section (liquid refueling section) adopts the threaded elements with the types comprising: 48/48;32/32;
the types of the thread elements adopted by the mixing and homogenizing section comprise: 48/48;32/32;22/22;22/11L; ZME 8/16; k is 30 DEG/7/48; k45 DEG/5/32; k is 45 degrees/5/32L; k45 DEG/5/22; k45 degrees/5/22L; k45 DEG/5/16; k60 DEG/4/22; k90 °/5/32;
the model of the screw element that the air exhaust section (glass fiber mouth) adopted includes: 48/48;32/32;
the types of the thread elements adopted by the vacuum exhaust section comprise: 48/48;32/32;
the types of the thread elements adopted by the extrusion section comprise: 32/32 and 22/22.
6. The method for preparing the low-linear-expansion-coefficient flame-retardant PC/ABS alloy material as claimed in claim 5, wherein the length-diameter ratio of the screws in the screw combination is one of 40/1, 44/1 and 48/1; and the screw rotating speed of the double-screw extruder is one of 400 revolutions per minute and 450 revolutions per minute.
7. The preparation method of the low-linear-expansion-coefficient flame-retardant PC/ABS alloy material as claimed in claim 5, wherein the temperature of each section of the twin-screw extruder is as follows: the head is 240-250 ℃; a first stage: 240-250 ℃; and (2) second stage: 245 to 255 ℃; and (3) three stages: 245 to 265 ℃; and a fourth stage: 235 to 245 ℃; five stages: 245 to 255 ℃; six sections: 245 to 255 ℃; seven sections: 245 to 255 ℃; eight sections: 245 to 255 ℃; nine sections: 245 to 255 ℃; ten sections: 245 to 255 ℃; four sections of the double-screw extruder are liquid halogen-free flame retardant BDP charging openings, six sections of the double-screw extruder are glass fiber charging openings, and nine sections of the double-screw extruder are vacuum openings.
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