CN113462142B - High-weather-resistance PC/AES alloy and preparation method thereof - Google Patents
High-weather-resistance PC/AES alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high weather-resistant PC/AES alloy and a preparation method thereof, and the high weather-resistant PC/AES alloy comprises the following components: polycarbonate, acrylonitrile-styrene copolymer, AES rubber powder, modified rutile titanium dioxide and silicone master batch. In the invention, under the combined action of the acrylonitrile-styrene copolymer with specific AN content and the surface modified rutile titanium dioxide, the weather resistance of the PC/AES alloy can be obviously improved, the processing performance of the alloy material is ensured, and the application range of the PC/AES alloy in the field of automobile parts is expanded.
Description
Technical Field
The invention belongs to the field of automobile part materials, and particularly relates to a high-weather-resistance PC/AES alloy and a preparation method thereof.
Background
Polycarbonate (PC) is one of the important engineering plastics. Polycarbonates (PC) can be classified into various types, such as aliphatic, aromatic, aliphatic-aromatic, and the like, depending on the structure of the ester group. The mechanical properties of polycarbonate are relatively low, limiting its use in engineering plastics.
Acrylonitrile-ethylene propylene diene monomer-styrene copolymer (AES) is also a material with wide application, the weather resistance is better than that of acrylonitrile-butadiene-styrene copolymer (ABS), PC/AES alloy is often prepared from PC and AES in the application of engineering plastics, the PC/AES alloy is mainly applied to the field of outdoor application, and compared with high-weather-resistant materials such as ASA, AES and the like, the PC/AES alloy has more excellent physical and mechanical properties and heat resistance, but because the ester group of PC is the weak point of chain scission under light irradiation, the weather resistance is poor, so that the weather resistance of the PC/AES alloy is reduced, and the requirement of outdoor long-term use is difficult to meet.
Disclosure of Invention
The invention aims to provide a high-weather-resistance PC/AES alloy which has excellent weather resistance and fluidity, is particularly suitable for application in the field of automobile injection molding parts, and is particularly suitable for application of large-scale exterior automobile parts.
Necessarily, the invention also provides a preparation method of the high weather resistant PC/AES alloy.
A high weather-resistant PC/AES alloy comprises the following components in parts by weight:
50-75 parts by weight of polycarbonate;
14-30 parts of acrylonitrile-styrene copolymer;
10-15 parts of AES rubber powder;
1-5 parts of modified rutile titanium dioxide;
0.5-0.75 weight part of silicone master batch.
More preferably, the high weather resistant PC/AES alloy comprises the following components in parts by weight:
65 parts by weight of polycarbonate;
20 parts by weight of acrylonitrile-styrene copolymer;
12 parts of AES rubber powder;
3 parts of modified rutile titanium dioxide;
0.5 part by weight of silicone master batch.
Preferably, the acrylonitrile-styrene copolymer (SAN) with the acrylonitrile content of 26 wt% -32 wt% and the acrylonitrile-styrene copolymer (SAN) with the acrylonitrile content of more than 26 wt% has better improvement on the weather resistance of the material, but when the acrylonitrile content is more than 32 wt%, the melt index of PC/AES is low, the PC/AES cannot be processed and molded, and the comprehensive performance of the PC/AES can be better improved only when the acrylonitrile content in the acrylonitrile-styrene copolymer (SAN) is the specific content.
Preferably, the modified rutile type titanium dioxide is rutile type titanium dioxide coated with silicon dioxide, and the average thickness of the silicon dioxide coating is 5-12nm, more preferably 8 nm;
wherein, the average thickness of the silicon dioxide coating layer of the modified rutile type titanium dioxide is measured by adopting a transmission electron microscope to respectively observe the average grain diameter before and after coating, and the difference between the two is the average thickness of the coating layer.
Wherein the polycarbonate is one of phosgene method PC or ester exchange method PC.
Wherein, the AES rubber powder is acrylonitrile-EPDM rubber-styrene copolymer, the content of the EPDM rubber in the AES rubber powder is 55-70 wt%, and the content of the EPDM rubber in the AES rubber powder is more preferably 70 wt%.
Preferably, the preparation method of the modified rutile type titanium dioxide comprises the following steps:
adding rutile type titanium dioxide into a clean volumetric flask, adding deionized water to the volumetric flask to fix the volume to obtain rutile type titanium dioxide slurry, wherein the ratio of rutile type titanium dioxide to deionized water is 500g:1L, and pouring the prepared rutile type titanium dioxide slurry into a container provided with stirring equipment; adding sodium metaphosphate into the slurry to adjust the pH value to 9-10, and simultaneously controlling the stirring speed to be 150-200 r/min; uniformly dripping silicon dioxide into the reaction slurry, wherein the dosage of the silicon dioxide is 1-5 wt% of that of the rutile titanium dioxide, the dripping speed is 8-12drop/min when the silicon dioxide is dripped, simultaneously controlling the pH value of a reaction system within 9-10 by adding sodium metaphosphate, and aging for 4 hours at the water bath temperature of 70-75 ℃ after the silicon dioxide is dripped; pouring the slurry into a Buchner funnel for suction filtration, and washing with deionized water; transferring the filter cake into a ceramic crucible, and continuously drying for 12 hours in an electric heating thermostat at 90-95 ℃ to obtain blocky modified rutile titanium dioxide; and (3) primarily crushing the cooled blocky modified rutile titanium dioxide by using a high-speed crusher to prepare coarse powder, and then preparing the coarse powder into fine powder with the particle size range of 150nm-300nm by using a jet mill to obtain the modified rutile titanium dioxide.
Preferably, the modified rutile type titanium dioxide is prepared by the following preparation method:
adding the rutile type titanium dioxide into a clean volumetric flask, adding deionized water to the volumetric flask to obtain rutile type titanium dioxide slurry, wherein the ratio of the rutile type titanium dioxide to the deionized water is 500g:1L, and pouring the prepared rutile type titanium dioxide slurry into a container provided with stirring equipment; adding sodium metaphosphate into the slurry to adjust the pH value to 9-10, and simultaneously controlling the stirring speed to be 150-200 r/min; uniformly dripping silicon dioxide into the reaction slurry, wherein the dosage of the silicon dioxide is 2 wt% of that of the rutile titanium dioxide, the dripping speed is 10drop/min when the silicon dioxide is dripped, simultaneously, the pH value of a reaction system is controlled within 9-10 by adding sodium metaphosphate, and after the silicon dioxide is dripped, aging is carried out for 4 hours at the water bath temperature; pouring the slurry into a Buchner funnel for suction filtration, and washing with deionized water; transferring the filter cake into a ceramic crucible, and continuously drying in an electric heating thermostat for 12 hours to obtain blocky modified rutile titanium dioxide; and (3) primarily crushing the cooled blocky modified rutile titanium dioxide by using a high-speed crusher to prepare coarse powder, and then preparing the coarse powder into fine powder with the particle size range of 150nm-300nm by using a jet mill to obtain the modified rutile titanium dioxide.
More preferably, after the blocky modified rutile titanium dioxide is obtained in the above steps, a high-speed pulverizer is used for primarily pulverizing the cooled blocky modified rutile titanium dioxide into coarse powder, and then an airflow pulverizer is used for pulverizing the coarse powder into fine powder with the particle size range of 200nm-250nm, so as to obtain the modified rutile titanium dioxide.
The sodium metaphosphate preferably used in the preparation of the modified rutile titanium dioxide is sodium hexametaphosphate with the structural formula of (NaPO) 3 ) 6 。
Preferably, the silicone master batch comprises silicone powder and AES resin, wherein the content of the silicone powder in the silicone master batch is 49.25-49.5 wt%.
The preparation method of the silicone master batch comprises the following steps:
adding silicone powder and a silane coupling agent into a high-speed mixer, wherein the weight ratio of the silane coupling agent to the silicone powder is (1-1.5): (98.5-99), heating to 90 ℃, performing surface treatment on the silicone powder for 20-40min at a stirring speed of 120 revolutions per minute and at 90 ℃, and then mixing the surface-treated silicone powder and AES resin in a ratio of 1: 1, adding the mixture into a double-screw extruder, performing melt extrusion in the extruder, wherein the temperature of a feeding section is 150-160 ℃, the temperature of a neck ring die is 160-170 ℃, and performing water-cooling bracing and cutting on the extruded material, and drying to obtain the silicone master batch.
A preparation method for preparing the high weather-resistant PC/AES alloy comprises the following steps:
1) weighing polycarbonate, acrylonitrile-styrene copolymer, AES rubber powder, modified rutile titanium dioxide and silicone master batch according to the weight parts, putting into a high-speed mixer, mixing for 3-4 min, and adding into a double-screw extruder at a first section after mixing uniformly;
2) and carrying out melt extrusion, granulation and drying to obtain the product.
Wherein the melt extrusion conditions of the step 2) are as follows: the temperature of the first zone is 210-230 ℃, the temperature of the second zone is 210-240 ℃, the temperature of the third zone is 220-250 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-260 ℃, the temperature of the sixth zone is 230-260 ℃, the temperature of the seventh zone is 230-260 ℃, the temperature of the eighth zone is 230-260 ℃, and the rotating speed of the host is 300-400 r/min; the length-diameter ratio of the double-screw extruder is 32:1-42: 1.
Compared with the prior art, the high weather-resistant PC/AES alloy is prepared by blending polycarbonate, acrylonitrile-styrene copolymer with specific Acrylonitrile (AN) content, AES rubber powder, modified rutile titanium dioxide and silicone master batch.
The photooxidative degradation of SAN includes the classical photooxidation of polystyrene, the oxidation of acrylonitrile units by the oxidation of adjacent styrene units, and the degradation of acrylonitrile units by the acid formed as a result of the photoproducts. Alkoxy radicals, which result from the decomposition of hydroperoxides formed in polystyrene radicals, undergo beta-scission, which generates radicals that in turn exacerbate the degradation of acrylonitrile units. The weather resistance of the material can be improved by reducing the content of styrene and increasing the content of acrylonitrile. But the too high content of acrylonitrile can reduce the fluidity of the material and influence the later injection molding processing. Therefore, the selection of SAN with an appropriate acrylonitrile content is very important to influence the overall performance of the material.
Titanium dioxide exists in nature in three crystalline forms: brookite, anatase, and rutile. The brookite type belongs to an orthorhombic crystal system, is an unstable crystal type, and can be converted into rutile type titanium dioxide at the temperature of more than 650 ℃. The anatase titanium dioxide is stable at normal temperature, but can be converted into rutile titanium dioxide at high temperature. The key performance of titanium dioxide is that light cannot penetrate through the surface of pigment particles, so that the rutile titanium dioxide is added into a high polymer material to form a natural illumination blocking agent, and the weather resistance of the material can be improved. However, rutile titanium dioxide without surface treatment is easily deprived of two electrons after being irradiated by ultraviolet rays due to its own photochemical activity, so that oxygen ions are changed into oxygen atoms, which have extremely strong photochemical activity, can oxidize a variety of adsorbed or contacted organic and inorganic substances, and is affected in weather resistance. The inorganic coated rutile type titanium dioxide can block photochemical reaction, photoactivation points on the surface of the surface-treated rutile type titanium dioxide particles are uniformly coated by an oxide film, the crystal lattice defects are few, the photocatalytic activity is low, and the oxidation reaction of free radicals of the rutile type titanium dioxide particles and organic polymers in plastics is prevented.
As a more preferable mode, under the comprehensive action of the acrylonitrile-styrene copolymer with specific AN content and the rutile titanium dioxide subjected to surface treatment, the weather resistance of the PC/AES alloy can be remarkably improved, the processing performance of the alloy material is ensured, and the application range of the PC/AES alloy in the field of automobile parts is expanded.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the technical field better understand the scheme of the present invention.
The examples and comparative examples illustrate:
polycarbonate (C): phosgene method PC, mitsubishi chemical company, japan, trade name: S-2000F; transesterification process PC, lihuayi company, brand: WY-111 BR.
SAN resin: acrylonitrile-styrene copolymer:
korean brocade lake corporation, model SAN310, with an acrylonitrile content of 21 wt%;
korea brocade lake corporation, model SAN335, with an acrylonitrile content of 26 wt%;
korea brocade lake corporation, model SAN350, with an acrylonitrile content of 32 wt%;
taiwan chemical company, model NX3400, acrylonitrile content is 38 wt%.
AES rubber powder: japanese UMG corporation, trade mark: E700N, EPDM content 70%.
Silicone powder: dow Corning, RM 4-7105;
silane coupling agent: KH-550 parts of nanjing pining;
rutile type titanium dioxide: purchased from dupont under the designation R931;
anatase type titanium dioxide: purchased from Hebei Messen, Inc. under the designation A100 (particle size 0.2-0.4 μm).
Sodium metaphosphate: (NaPO) 3 ) 6 Commercially available;
silicon dioxide: a new Shanghai bearing material;
alumina: is commercially available
The rest raw materials are commercially available.
Examples 1 to 3, example 6 and examples 9 to 10
Preparation of modified rutile titanium dioxide:
adding the rutile type titanium dioxide into a clean volumetric flask, adding deionized water to the volumetric flask to obtain titanium dioxide slurry, wherein the ratio of the rutile type titanium dioxide to the deionized water is 500g:1L, and pouring the prepared rutile type titanium dioxide slurry into a container provided with stirring equipment; adding sodium metaphosphate into the slurry to adjust the pH value to 9-10, and simultaneously controlling the stirring speed to be 200 revolutions per minute; uniformly dripping silicon dioxide into the reaction slurry, wherein the dosage of the silicon dioxide is 2 wt% of that of the rutile titanium dioxide, the dripping speed is 10drop/min when the silicon dioxide is dripped, simultaneously, the pH value of a reaction system is controlled within 9-10 by adding sodium metaphosphate, and after the silicon dioxide is dripped, aging is carried out for 4 hours at the water bath temperature of 70 ℃; pouring the slurry into a Buchner funnel for suction filtration, and washing with deionized water; transferring the filter cake into a ceramic crucible, and continuously drying in an electric heating thermostat at 90 ℃ for 12 hours; preliminarily crushing the cooled blocky modified rutile titanium dioxide by using a high-speed crusher to prepare coarse powder, and then preparing the coarse powder into fine powder with the particle size range of 150-300 nm by using a jet mill to obtain the modified rutile titanium dioxide;
the average thickness of the silicon dioxide coating layer of the modified rutile titanium dioxide is measured by adopting a transmission electron microscope, the average particle size before and after coating is respectively observed, the difference between the two is the average thickness of the coating layer, and the average thickness of the coating layer is 8nm measured by a Transmission Electron Microscope (TEM).
Silicone master batch:
adding silicone powder and a silane coupling agent into a high-speed mixer, wherein the weight ratio of the silane coupling agent to the silicone powder is 1: 99, heating to 90 ℃, performing surface treatment on the silicone powder for 30min at a stirring speed of 120 revolutions per minute and under a condition of 90 ℃, and then mixing the surface-treated silicone powder and the AES resin in a ratio of 1: 1, uniformly mixing the raw materials, adding the mixture into a double-screw extruder, carrying out melt extrusion in the extruder, wherein the temperature of a feeding section is 150-160 ℃, the temperature of a neck ring mold is 160-170 ℃, and carrying out water-cooling bracing and cutting on the extruded materials, and drying to obtain silicone master batches;
preparing a PC/AES alloy:
1) weighing polycarbonate (S-2000F), acrylonitrile-styrene copolymer, AES rubber powder, modified rutile titanium dioxide and silicone master batch according to the weight parts shown in the table 1, putting the materials into a high-speed mixer, mixing for 3min, adding the materials into a double-screw extruder at a first section after mixing uniformly;
2) carrying out melt extrusion, granulation and drying to obtain a PC/AES alloy;
wherein the melt extrusion conditions of the step 2) are as follows: the temperature of the first zone is 210-230 ℃, the temperature of the second zone is 210-240 ℃, the temperature of the third zone is 220-250 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-260 ℃, the temperature of the sixth zone is 230-260 ℃, the temperature of the seventh zone is 230-260 ℃, the temperature of the eighth zone is 230-260 ℃, and the rotating speed of the host is 300-400 r/min; the length-diameter ratio of the twin-screw extruder is 36: 1.
Example 4
Preparation of modified rutile titanium dioxide:
adding the rutile type titanium dioxide into a clean volumetric flask, adding deionized water to the volumetric flask to obtain rutile type titanium dioxide slurry, wherein the ratio of the rutile type titanium dioxide to the deionized water is 500g:1L, and pouring the prepared rutile type titanium dioxide slurry into a container provided with stirring equipment; adding sodium metaphosphate into the slurry to adjust the pH to 9-10, and simultaneously controlling the stirring speed to be 150 revolutions per minute; uniformly dripping silicon dioxide into the reaction slurry, wherein the dosage of the silicon dioxide is 5 wt% of that of the rutile titanium dioxide, the dripping speed is 8drop/min when the silicon dioxide is dripped, simultaneously, the pH value of a reaction system is controlled within 9-10 by adding sodium metaphosphate, and after the silicon dioxide is dripped, aging is carried out for 4 hours at the water bath temperature of 75 ℃; pouring the slurry into a Buchner funnel for suction filtration, and washing with deionized water; transferring the filter cake into a ceramic crucible, and continuously drying in an electric heating thermostat at 90 ℃ for 12 hours; preliminarily crushing the cooled blocky modified rutile titanium dioxide by using a high-speed crusher to prepare coarse powder, and then preparing the coarse powder into fine powder with the particle size range of 150-300 nm by using a jet mill to obtain the modified rutile titanium dioxide;
the average thickness of the silicon dioxide coating layer of the modified rutile titanium dioxide is measured by adopting a transmission electron microscope, the average particle size before and after coating is respectively observed, the difference between the two is the average thickness of the coating layer, and the average thickness of the coating layer is 12nm measured by a Transmission Electron Microscope (TEM).
Silicone master batch:
adding silicone powder and a silane coupling agent into a high-speed mixer, wherein the weight ratio of the silane coupling agent to the silicone powder is 1.5: 98.5, heating to 90 ℃, performing surface treatment on the silicone powder for 20min at a stirring speed of 120 revolutions per minute and at 90 ℃, and then mixing the surface-treated silicone powder and AES resin in a ratio of 1: 1, uniformly mixing the raw materials in a weight ratio of 150-160 ℃, adding the mixture into a double-screw extruder, carrying out melt extrusion in the extruder, wherein the temperature of a feeding section is 150-160 ℃, the temperature of a neck ring mold is 160-170 ℃, and carrying out water-cooling bracing and cutting on the extruded materials, and drying to obtain silicone master batches;
preparing a PC/AES alloy:
1) weighing polycarbonate (S-2000F), acrylonitrile-styrene copolymer, AES rubber powder, modified rutile titanium dioxide and silicone master batch according to the weight parts shown in Table 1, putting into a high-speed mixer, mixing for 4min, and adding into a double-screw extruder at a first section after mixing uniformly;
2) carrying out melt extrusion, granulation and drying to obtain a PC/AES alloy;
wherein the melt extrusion conditions of the step 2) are as follows: the temperature of the first zone is 210-230 ℃, the temperature of the second zone is 210-240 ℃, the temperature of the third zone is 220-250 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-260 ℃, the temperature of the sixth zone is 230-260 ℃, the temperature of the seventh zone is 230-260 ℃, the temperature of the eighth zone is 230-260 ℃, and the rotating speed of the host is 300-400 r/min; the length-diameter ratio of the twin-screw extruder is 32: 1.
Example 5
Preparation of modified rutile titanium dioxide:
adding rutile type titanium dioxide into a clean volumetric flask, adding deionized water to the volumetric flask to fix the volume to obtain rutile type titanium dioxide slurry, wherein the ratio of rutile type titanium dioxide to deionized water is 500g:1L, and pouring the prepared rutile type titanium dioxide slurry into a container provided with stirring equipment; adding sodium metaphosphate into the slurry to adjust the pH to 9-10, and simultaneously controlling the stirring speed to be 150 revolutions per minute; uniformly dripping silicon dioxide into the reaction slurry, wherein the dosage of the silicon dioxide is 1 wt% of that of the rutile titanium dioxide, the dripping speed is 12drop/min when the silicon dioxide is dripped, simultaneously, the pH value of a reaction system is controlled within 9-10 by adding sodium metaphosphate, and after the silicon dioxide is dripped, aging is carried out for 4 hours at the water bath temperature of 70 ℃; pouring the slurry into a Buchner funnel for suction filtration, and washing with deionized water; transferring the filter cake into a ceramic crucible, and continuously drying in an electric heating thermostat at 95 ℃ for 12 hours; preliminarily crushing the cooled blocky modified rutile titanium dioxide by using a high-speed crusher to prepare coarse powder, and then preparing the coarse powder into fine powder with the particle size range of 150-300 nm by using a jet mill to obtain the modified rutile titanium dioxide;
the average thickness of the silicon dioxide coating layer of the modified rutile titanium dioxide is measured by adopting a transmission electron microscope, the average particle size before and after coating is respectively observed, the difference between the two is the average thickness of the coating layer, and the average thickness of the coating layer is 5nm measured by a Transmission Electron Microscope (TEM).
Silicone master batch:
adding silicone powder and a silane coupling agent into a high-speed mixer, wherein the weight ratio of the silane coupling agent to the silicone powder is 1: 99, heating to 90 ℃, performing surface treatment on the silicone powder for 30min at a stirring speed of 120 revolutions per minute and under a condition of 90 ℃, and then mixing the surface-treated silicone powder and the AES resin in a ratio of 1: 1, uniformly mixing the raw materials in a weight ratio of 150-160 ℃, adding the mixture into a double-screw extruder, carrying out melt extrusion in the extruder, wherein the temperature of a feeding section is 150-160 ℃, the temperature of a neck ring mold is 160-170 ℃, and carrying out water-cooling bracing and cutting on the extruded materials, and drying to obtain silicone master batches;
preparing a PC/AES alloy:
1) weighing polycarbonate (S-2000F), acrylonitrile-styrene copolymer, AES rubber powder, modified rutile titanium dioxide and silicone master batch according to the weight parts shown in Table 1, putting into a high-speed mixer, mixing for 3min, and adding into a double-screw extruder at a first section after mixing uniformly;
2) carrying out melt extrusion, granulation and drying to obtain a PC/AES alloy;
wherein the melt extrusion conditions of the step 2) are as follows: the temperature of the first zone is 210-230 ℃, the temperature of the second zone is 210-240 ℃, the temperature of the third zone is 220-250 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-260 ℃, the temperature of the sixth zone is 230-260 ℃, the temperature of the seventh zone is 230-260 ℃, the temperature of the eighth zone is 230-260 ℃, and the rotating speed of the main engine is 300-400 r/min; the length-diameter ratio of the twin-screw extruder is 42: 1.
Example 7
Preparation of modified rutile titanium dioxide:
adding the rutile type titanium dioxide into a clean volumetric flask, adding deionized water to the volumetric flask to obtain rutile type titanium dioxide slurry, wherein the ratio of the rutile type titanium dioxide to the deionized water is 500g:1L, and pouring the prepared rutile type titanium dioxide slurry into a container provided with stirring equipment; adding sodium metaphosphate into the slurry to adjust the pH to 9-10, and simultaneously controlling the stirring speed to be 200 revolutions per minute; uniformly dripping silicon dioxide into the reaction slurry, wherein the dosage of the silicon dioxide is 2 wt% of that of the rutile titanium dioxide, when the silicon dioxide is dripped, the dripping speed is 10drop/min, meanwhile, the pH value of a reaction system is controlled within 9-10 by adding sodium metaphosphate, and after the silicon dioxide is dripped, aging is carried out for 4 hours at the water bath temperature of 70 ℃; pouring the slurry into a Buchner funnel for suction filtration, and washing with deionized water; transferring the filter cake into a ceramic crucible, and continuously drying in an electric heating thermostat at 90 ℃ for 12 hours; preliminarily crushing the cooled blocky modified rutile titanium dioxide by using a high-speed crusher to prepare coarse powder, and then preparing the coarse powder into fine powder with the particle size range of 200nm-250nm by using a jet mill to obtain the modified rutile titanium dioxide;
the average thickness of the silicon dioxide coating layer of the modified rutile titanium dioxide is measured by adopting a transmission electron microscope, the average particle size before and after coating is respectively observed, the difference between the two is the average thickness of the coating layer, and the average thickness of the coating layer is 8nm measured by a Transmission Electron Microscope (TEM).
Silicone master batch:
adding silicone powder and a silane coupling agent into a high-speed mixer, wherein the weight ratio of the silane coupling agent to the silicone powder is 1: 99, heating to 90 ℃, performing surface treatment on the silicone powder for 30min at a stirring speed of 120 revolutions per minute and under a condition of 90 ℃, and then mixing the surface-treated silicone powder and the AES resin in a ratio of 1: 1, uniformly mixing the raw materials in a weight ratio of 150-160 ℃, adding the mixture into a double-screw extruder, carrying out melt extrusion in the extruder, wherein the temperature of a feeding section is 150-160 ℃, the temperature of a neck ring mold is 160-170 ℃, and carrying out water-cooling bracing and cutting on the extruded materials, and drying to obtain silicone master batches;
preparing a PC/AES alloy:
1) weighing polycarbonate (S-2000F), acrylonitrile-styrene copolymer, AES rubber powder, modified rutile titanium dioxide and silicone master batch according to the weight parts shown in the table 1, putting the materials into a high-speed mixer, mixing for 3min, adding the materials into a double-screw extruder at a first section after mixing uniformly;
2) carrying out melt extrusion, granulation and drying to obtain a PC/AES alloy;
wherein the melt extrusion conditions of the step 2) are as follows: the temperature of the first zone is 210-230 ℃, the temperature of the second zone is 210-240 ℃, the temperature of the third zone is 220-250 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-260 ℃, the temperature of the sixth zone is 230-260 ℃, the temperature of the seventh zone is 230-260 ℃, the temperature of the eighth zone is 230-260 ℃, and the rotating speed of the host is 300-400 r/min; the length-diameter ratio of the twin-screw extruder is 36: 1.
Example 8
Preparation of modified rutile titanium dioxide:
adding the rutile type titanium dioxide into a clean volumetric flask, adding deionized water to the volumetric flask to obtain titanium dioxide slurry, wherein the ratio of the rutile type titanium dioxide to the deionized water is 500g:1L, and pouring the prepared rutile type titanium dioxide slurry into a container provided with stirring equipment; adding sodium metaphosphate into the slurry to adjust the pH to 9-10, and simultaneously controlling the stirring speed to be 200 revolutions per minute; uniformly dripping silicon dioxide into the reaction slurry, wherein the dosage of the silicon dioxide is 2 wt% of that of the rutile titanium dioxide, when the silicon dioxide is dripped, the dripping speed is 10drop/min, meanwhile, the pH value of a reaction system is controlled within 9-10 by adding sodium metaphosphate, and after the silicon dioxide is dripped, aging is carried out for 4 hours at the water bath temperature of 70 ℃; pouring the slurry into a Buchner funnel for suction filtration, and washing with deionized water; transferring the filter cake into a ceramic crucible, and continuously drying in an electric heating thermostat at 90 ℃ for 12 hours; preliminarily crushing the cooled blocky modified rutile titanium dioxide by using a high-speed crusher to prepare coarse powder, and then preparing the coarse powder into fine powder with the particle size range of 150-300 nm by using a jet mill to obtain the modified rutile titanium dioxide;
the average thickness of the silicon dioxide coating layer of the modified rutile titanium dioxide is measured by adopting a transmission electron microscope, the average particle size before and after coating is respectively observed, the difference between the two is the average thickness of the coating layer, and the average thickness of the coating layer is 8nm measured by a Transmission Electron Microscope (TEM).
Silicone master batch:
adding silicone powder and a silane coupling agent into a high-speed mixer, wherein the weight ratio of the silane coupling agent to the silicone powder is 1: 99, heating to 90 ℃, performing surface treatment on the silicone powder for 30min at a stirring speed of 120 revolutions per minute and under a condition of 90 ℃, and then mixing the surface-treated silicone powder and the AES resin in a ratio of 1: 1, uniformly mixing the raw materials in a weight ratio of 150-160 ℃, adding the mixture into a double-screw extruder, carrying out melt extrusion in the extruder, wherein the temperature of a feeding section is 150-160 ℃, the temperature of a neck ring mold is 160-170 ℃, and carrying out water-cooling bracing and cutting on the extruded materials, and drying to obtain silicone master batches;
preparing a PC/AES alloy:
1) weighing polycarbonate (WY-111BR), acrylonitrile-styrene copolymer, AES rubber powder, modified rutile titanium dioxide and silicone master batch according to the weight parts shown in Table 1, putting into a high-speed mixer, mixing for 3min, and adding into a double-screw extruder at a first stage after mixing uniformly;
2) carrying out melt extrusion, granulation and drying to obtain a PC/AES alloy;
wherein the melt extrusion conditions of the step 2) are as follows: the temperature of the first zone is 210-230 ℃, the temperature of the second zone is 210-240 ℃, the temperature of the third zone is 220-250 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-260 ℃, the temperature of the sixth zone is 230-260 ℃, the temperature of the seventh zone is 230-260 ℃, the temperature of the eighth zone is 230-260 ℃, and the rotating speed of the main engine is 300-400 r/min; the length-diameter ratio of the twin-screw extruder is 36: 1.
Example 11
Preparation of modified rutile titanium dioxide:
adding the rutile type titanium dioxide into a clean volumetric flask, adding deionized water to the volumetric flask to obtain titanium dioxide slurry, wherein the ratio of the rutile type titanium dioxide to the deionized water is 500g:1L, and pouring the prepared rutile type titanium dioxide slurry into a container provided with stirring equipment; adding sodium metaphosphate into the slurry to adjust the pH value to 9-10, and simultaneously controlling the stirring speed to be 200 revolutions per minute; uniformly dripping silicon dioxide into the reaction slurry, wherein the dosage of the silicon dioxide is 8 wt% of that of the rutile titanium dioxide, the dripping speed is 10drop/min when the silicon dioxide is dripped, simultaneously, the pH value of a reaction system is controlled within 9-10 by adding sodium metaphosphate, and after the silicon dioxide is dripped, aging is carried out for 4 hours at the water bath temperature of 70 ℃; pouring the slurry into a Buchner funnel for suction filtration, and washing with deionized water; transferring the filter cake into a ceramic crucible, and continuously drying in an electric heating thermostat at 90 ℃ for 12 hours; preliminarily crushing the cooled blocky modified rutile titanium dioxide by using a high-speed crusher to prepare coarse powder, and then preparing the coarse powder into fine powder with the particle size range of 150-300 nm by using a jet mill to obtain the modified rutile titanium dioxide;
the average thickness of the silicon dioxide coating layer of the modified rutile titanium dioxide is measured by adopting a transmission electron microscope, the average particle size before and after coating is respectively observed, the difference between the two is the average thickness of the coating layer, and the average thickness of the coating layer is 15nm measured by a Transmission Electron Microscope (TEM).
Silicone master batch:
adding silicone powder and a silane coupling agent into a high-speed mixer, wherein the weight ratio of the silane coupling agent to the silicone powder is 1: 99, heating to 90 ℃, performing surface treatment on the silicone powder for 30min at a stirring speed of 120 revolutions per minute and under a condition of 90 ℃, and then mixing the surface-treated silicone powder and the AES resin in a ratio of 1: 1, uniformly mixing the raw materials in a weight ratio of 150-160 ℃, adding the mixture into a double-screw extruder, carrying out melt extrusion in the extruder, wherein the temperature of a feeding section is 150-160 ℃, the temperature of a neck ring mold is 160-170 ℃, and carrying out water-cooling bracing and cutting on the extruded materials, and drying to obtain silicone master batches;
preparing a PC/AES alloy:
1) weighing polycarbonate (S-2000F), acrylonitrile-styrene copolymer, AES rubber powder, modified rutile titanium dioxide and silicone master batch according to the weight parts shown in Table 1, putting into a high-speed mixer, mixing for 3min, and adding into a double-screw extruder at a first section after mixing uniformly;
2) carrying out melt extrusion, granulation and drying to obtain a PC/AES alloy;
wherein the melt extrusion conditions of the step 2) are as follows: the temperature of the first zone is 210-230 ℃, the temperature of the second zone is 210-240 ℃, the temperature of the third zone is 220-250 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-260 ℃, the temperature of the sixth zone is 230-260 ℃, the temperature of the seventh zone is 230-260 ℃, the temperature of the eighth zone is 230-260 ℃, and the rotating speed of the host is 300-400 r/min; the length-diameter ratio of the twin-screw extruder is 36: 1.
Example 12
Preparation of modified rutile titanium dioxide:
adding the rutile type titanium dioxide into a clean volumetric flask, adding deionized water to the volumetric flask to obtain rutile type titanium dioxide slurry, wherein the ratio of the rutile type titanium dioxide to the deionized water is 500g:1L, and pouring the prepared rutile type titanium dioxide slurry into a container provided with stirring equipment; adding sodium metaphosphate into the slurry to adjust the pH to 9-10, and simultaneously controlling the stirring speed to be 200 revolutions per minute; uniformly dripping silicon dioxide into the reaction slurry, wherein the dosage of the silicon dioxide is 0.5 wt% of that of the rutile titanium dioxide, the dripping speed is 10drop/min when the silicon dioxide is dripped, meanwhile, the pH value of a reaction system is controlled within 9-10 by adding sodium metaphosphate, and after the silicon dioxide is dripped, aging is carried out for 4 hours at the water bath temperature of 70 ℃; pouring the slurry into a Buchner funnel for suction filtration, and washing with deionized water; transferring the filter cake into a ceramic crucible, and continuously drying in an electric heating thermostat at 90 ℃ for 12 hours; preliminarily crushing the cooled blocky modified rutile titanium dioxide by using a high-speed crusher to prepare coarse powder, and then preparing the coarse powder into fine powder with the particle size range of 150-300 nm by using a jet mill to obtain the modified rutile titanium dioxide;
the average thickness of the silicon dioxide coating layer of the modified rutile titanium dioxide is measured by adopting a transmission electron microscope, the average particle size before and after coating is respectively observed, the difference between the two is the average thickness of the coating layer, and the average thickness of the coating layer is 3nm measured by a Transmission Electron Microscope (TEM).
Silicone master batch:
adding silicone powder and a silane coupling agent into a high-speed mixer, wherein the weight ratio of the silane coupling agent to the silicone powder is 1: 99, heating to 90 ℃, performing surface treatment on the silicone powder for 30min at a stirring speed of 120 revolutions per minute and under a condition of 90 ℃, and then mixing the surface-treated silicone powder and the AES resin in a ratio of 1: 1, uniformly mixing the raw materials in a weight ratio of 150-160 ℃, adding the mixture into a double-screw extruder, carrying out melt extrusion in the extruder, wherein the temperature of a feeding section is 150-160 ℃, the temperature of a neck ring mold is 160-170 ℃, and carrying out water-cooling bracing and cutting on the extruded materials, and drying to obtain silicone master batches;
preparing a PC/AES alloy:
1) weighing polycarbonate (S-2000F), acrylonitrile-styrene copolymer, AES rubber powder, modified rutile titanium dioxide and silicone master batch according to the weight parts shown in the table 1, putting the materials into a high-speed mixer, mixing for 3min, adding the materials into a double-screw extruder at a first section after mixing uniformly;
2) carrying out melt extrusion, granulation and drying to obtain a PC/AES alloy;
wherein the melt extrusion conditions of the step 2) are as follows: the temperature of the first zone is 210-230 ℃, the temperature of the second zone is 210-240 ℃, the temperature of the third zone is 220-250 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-260 ℃, the temperature of the sixth zone is 230-260 ℃, the temperature of the seventh zone is 230-260 ℃, the temperature of the eighth zone is 230-260 ℃, and the rotating speed of the host is 300-400 r/min; the length-diameter ratio of the twin-screw extruder is 36: 1.
Comparative example 1
Preparing silicone master batch according to the method of the embodiment 1, and then preparing PC/AES alloy according to the following method;
1) weighing polycarbonate (S-2000F), acrylonitrile-styrene copolymer, AES rubber powder, unmodified rutile type titanium dioxide and silicone master batch according to the weight parts of 1) and 1) shown in the table 1, putting the materials into a high-speed mixer, mixing for 3min, and adding the materials into a double-screw extruder at a first section after uniformly mixing;
2) carrying out melt extrusion, granulation and drying to obtain a PC/AES alloy;
wherein the melt extrusion conditions of the step 2) are as follows: the temperature of the first zone is 210-230 ℃, the temperature of the second zone is 210-240 ℃, the temperature of the third zone is 220-250 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-260 ℃, the temperature of the sixth zone is 230-260 ℃, the temperature of the seventh zone is 230-260 ℃, the temperature of the eighth zone is 230-260 ℃, and the rotating speed of the host is 300-400 r/min; the length-diameter ratio of the twin-screw extruder is 36: 1.
Comparative example 2
Respectively preparing modified rutile titanium dioxide and silicone master batch according to the method of example 1, and then preparing PC/AES alloy according to the following method;
1) weighing polycarbonate (S-2000F), AES rubber powder, modified rutile titanium dioxide and silicone master batch according to the weight parts of 1) and 1) shown in the table 1, putting the materials into a high-speed mixer, mixing for 3min, and adding the materials into a double-screw extruder at a first section after mixing uniformly;
2) carrying out melt extrusion, granulation and drying to obtain a PC/AES alloy;
wherein the melt extrusion conditions of the step 2) are as follows: the temperature of the first zone is 210-230 ℃, the temperature of the second zone is 210-240 ℃, the temperature of the third zone is 220-250 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-260 ℃, the temperature of the sixth zone is 230-260 ℃, the temperature of the seventh zone is 230-260 ℃, the temperature of the eighth zone is 230-260 ℃, and the rotating speed of the host is 300-400 r/min; the length-diameter ratio of the twin-screw extruder is 36: 1.
Comparative example 3
Preparing modified anatase titanium dioxide:
adding the anatase titanium dioxide into a clean volumetric flask, adding deionized water to a constant volume to prepare anatase titanium dioxide slurry, wherein the proportion of the anatase titanium dioxide to the deionized water is 500g to 1L, and pouring the prepared anatase titanium dioxide slurry into a container provided with stirring equipment; adding sodium metaphosphate into the slurry to adjust the pH to 9-10, and simultaneously controlling the stirring speed to be 200 revolutions per minute; uniformly dripping silicon dioxide into the reaction slurry, wherein the dosage of the silicon dioxide is 2 wt% of that of the anatase titanium dioxide, the dripping speed is 10drop/min when the silicon dioxide is dripped, simultaneously, the pH value of the reaction system is controlled within 9-10 by adding sodium metaphosphate, and after the silicon dioxide is dripped, aging is carried out for 4 hours at the water bath temperature of 70 ℃; pouring the slurry into a Buchner funnel for suction filtration, and washing with deionized water; transferring the filter cake into a ceramic crucible, and continuously drying in an electric heating thermostat at 90 ℃ for 12 hours; primarily crushing the cooled blocky modified anatase titanium dioxide into coarse powder by using a high-speed crusher, and then preparing the coarse powder into fine powder with the particle size range of 150-300 nm by using a jet mill to obtain the modified anatase titanium dioxide;
silicone master batch:
adding silicone powder and a silane coupling agent into a high-speed mixer, wherein the weight ratio of the silane coupling agent to the silicone powder is 1: 99, heating to 90 ℃, performing surface treatment on the silicone powder for 30min at a stirring speed of 120 revolutions per minute and under a condition of 90 ℃, and then mixing the surface-treated silicone powder and the AES resin in a ratio of 1: 1, uniformly mixing the raw materials, adding the mixture into a double-screw extruder, carrying out melt extrusion in the extruder, wherein the temperature of a feeding section is 150-160 ℃, the temperature of a neck ring mold is 160-170 ℃, and carrying out water-cooling bracing and cutting on the extruded materials, and drying to obtain silicone master batches;
preparing a PC/AES alloy:
1) weighing polycarbonate (S-2000F), acrylonitrile-styrene copolymer, AES rubber powder, anatase titanium dioxide and silicone master batch according to the weight parts shown in Table 1, putting into a high-speed mixer, mixing for 3min, and adding into a double-screw extruder at a first section after mixing uniformly;
2) carrying out melt extrusion, granulation and drying to obtain a PC/AES alloy;
wherein the melt extrusion conditions of the step 2) are as follows: the temperature of the first zone is 210-230 ℃, the temperature of the second zone is 210-240 ℃, the temperature of the third zone is 220-250 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-260 ℃, the temperature of the sixth zone is 230-260 ℃, the temperature of the seventh zone is 230-260 ℃, the temperature of the eighth zone is 230-260 ℃, and the rotating speed of the host is 300-400 r/min; the length-diameter ratio of the twin-screw extruder is 36: 1.
TABLE 1 EXAMPLES AND COMPARATIVE EXAMPLES ingredient tables (unit: parts by weight)
The materials obtained in examples and comparative examples were subjected to the following performance tests, and the test results are shown in table 2.
And (3) wet light aging resistance test: SAE J2527 material exterior decoration weather resistance test, illumination stage: blackboard temperature: 70 ℃; the temperature of the box body is as follows: 47 ℃; relative humidity: 50 percent; and (3) a dark stage: blackboard temperature: 38 ℃; the temperature of the box body is as follows: 38 ℃, relative humidity: 95 percent; the time was 2000 hours, and the tensile strength, impact strength and gloss before and after photoaging were recorded, respectively.
Tensile strength: ISO 527-2, test speed 50mm/min, test temperature: at 23 deg.c.
Impact strength: ISO 179, test temperature: at 23 ℃.
Glossiness: the gloss values were recorded using a BYK4560 gloss instrument for 60 ° angle testing according to ISO 2813.
The values after the photo-aging and before the photo-aging were compared to calculate the retention of tensile strength, impact strength and gloss respectively.
Melt index: ISO 1133, test conditions 260 ℃, load 5 kg.
TABLE 2 Properties of materials obtained in examples and comparative examples
The data show that the PC/AES alloy prepared in the examples 1-12 is obviously superior to the PC/AES alloy prepared in the comparative example 1 in comprehensive performance, and the weather resistance of the prepared PC/AES alloy is remarkably improved after the rutile type titanium dioxide is modified. In examples 1 to 12, the PC/AES alloys obtained in examples 1 to 8 were significantly superior in weather resistance to those of comparative example 2 and examples 10 to 12, and the PC/AES alloys obtained in examples 1 to 8 were comparable in weather resistance to those of example 9, but the PC/AES alloys obtained in examples 1 to 8 had a higher melt index and better processability than those of example 9, and were more useful for applications in the field of automobile parts. The PC/AES alloys prepared in the examples 1 to 8 have better weather resistance than the PC/AES alloy prepared in the comparative example 3, which shows that the modified rutile type titanium dioxide has obviously improved weather resistance to the PC/AES alloy compared with the modified anatase type titanium dioxide.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A high weather-resistant PC/AES alloy is characterized by comprising the following components in parts by weight:
50-75 parts by weight of polycarbonate;
14-30 parts of acrylonitrile-styrene copolymer;
10-15 parts of AES rubber powder;
1-5 parts of modified rutile titanium dioxide;
0.5-0.75 weight part of silicone master batch;
the content of acrylonitrile in the acrylonitrile-styrene copolymer is 26 wt% -32 wt%;
the modified rutile type titanium dioxide is rutile type titanium dioxide coated with silicon dioxide, and the average thickness of the silicon dioxide coating layer is 5-12 nm.
2. The highly weatherable PC/AES alloy of claim 1, wherein:
the polycarbonate is one of phosgene method PC or ester exchange method PC.
3. The highly weatherable PC/AES alloy of claim 1, wherein:
the AES rubber powder is acrylonitrile-EPDM rubber-styrene copolymer, and the content of the EPDM rubber in the AES rubber powder is 55-70 wt%.
4. The highly weather-resistant PC/AES alloy as recited in claim 1, wherein the preparation method of the modified rutile titanium dioxide comprises the following steps:
adding the rutile type titanium dioxide into a clean volumetric flask, adding deionized water to the volumetric flask to obtain rutile type titanium dioxide slurry, wherein the ratio of the rutile type titanium dioxide to the deionized water is 500g:1L, and pouring the prepared rutile type titanium dioxide slurry into a container provided with stirring equipment; adding sodium metaphosphate into the slurry to adjust the pH value to 9-10, and simultaneously controlling the stirring speed to be 150-200 r/min; uniformly dripping silicon dioxide into the reaction slurry, wherein the dosage of the silicon dioxide is 1-5 wt% of that of the rutile titanium dioxide, when the silicon dioxide is dripped, the dripping speed is 8-12drop/min, meanwhile, the pH value of a reaction system is controlled within 9-10 by adding sodium metaphosphate, and after the silicon dioxide is dripped, aging is carried out for 4 hours at the water bath temperature of 70-75 ℃; pouring the slurry into a Buchner funnel for suction filtration, and washing with deionized water; transferring the filter cake into a ceramic crucible, and continuously drying for 12 hours in an electric heating thermostat at 90-95 ℃ to obtain blocky modified rutile titanium dioxide; and (3) primarily crushing the cooled blocky modified rutile titanium dioxide by using a high-speed crusher to prepare coarse powder, and then preparing the coarse powder into fine powder with the particle size range of 150nm-300nm by using a jet mill to obtain the modified rutile titanium dioxide.
5. The highly weatherable PC/AES alloy of claim 1, wherein:
the silicone master batch comprises silicone powder and AES resin, wherein the content of the silicone powder in the silicone master batch is 49.25-49.5 wt%.
6. The highly weatherable PC/AES alloy of claim 1, wherein:
the preparation method of the silicone master batch comprises the following steps:
adding silicone powder and a silane coupling agent into a high-speed mixer, wherein the weight ratio of the silane coupling agent to the silicone powder is (1-1.5): (98.5-99), heating to 90 ℃, performing surface treatment on the silicone powder for 20-40min at a stirring speed of 120 revolutions per minute and at 90 ℃, and then mixing the surface-treated silicone powder and AES resin in a ratio of 1: 1, adding the mixture into a double-screw extruder, performing melt extrusion in the extruder, wherein the temperature of a feeding section is 150-160 ℃, the temperature of a neck ring die is 160-170 ℃, and performing water-cooling bracing and cutting on the extruded material, and drying to obtain the silicone master batch.
7. The method for producing the highly weather-resistant PC/AES alloy as recited in any one of claims 1 to 6, characterized by comprising the steps of:
1) weighing polycarbonate, acrylonitrile-styrene copolymer, AES rubber powder, modified rutile titanium dioxide and silicone master batch according to the weight parts, putting into a high-speed mixer, mixing for 3-4 min, and adding into a double-screw extruder at a first section after mixing uniformly;
2) and carrying out melt extrusion, granulation and drying to obtain the product.
8. The method of claim 7, wherein:
the melt extrusion conditions of the step 2) are as follows: the temperature of the first zone is 210-230 ℃, the temperature of the second zone is 210-240 ℃, the temperature of the third zone is 220-250 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-260 ℃, the temperature of the sixth zone is 230-260 ℃, the temperature of the seventh zone is 230-260 ℃, the temperature of the eighth zone is 230-260 ℃, and the rotating speed of the host is 300-400 r/min; the length-diameter ratio of the twin-screw extruder is 32:1-42: 1.
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