CN111138799B - Low-odor low-emission high-performance environment-friendly micro-foaming ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof - Google Patents
Low-odor low-emission high-performance environment-friendly micro-foaming ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-odor low-emission high-performance environment-friendly micro-foaming ABS composite material and a preparation method thereof, wherein the composite material comprises the following raw materials in percentage by weight: 65-93wt% of acrylonitrile-butadiene-styrene copolymer (ABS); 5-20wt% of heat-resistant agent; 1-15 wt% of toughening agent; 0.1-10wt% of carbon nano tube modified sodium bicarbonate master batch and 0.01-1wt% of antioxidant. The carbon nano tube modified sodium bicarbonate master batch is added in the ABS material, so that the injection molding processing temperature of the ABS material can be effectively reduced, and the energy consumption is reduced. The carbon nanotube technology with light weight and high strength characteristics and the microcellular foaming technology are combined, so that the mechanical property and the diffusion characteristic of the material are obviously improved while the light weight of the material is ensured, and the environment-friendly microcellular foaming ABS composite material with light weight, low odor and high diffusion is obtained.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a modified material based on an ABS material. The modified material is characterized by high strength and toughness, low odor and low emission.
Background
ABS and its alloy material have excellent comprehensive performance, and are widely used in automobile, household appliance, traffic and other fields. One of the current trends in the automotive industry is light weight and low odor, low emissions. On one hand, the outstanding advantage accompanied with light weight is that the oil consumption is obviously reduced, and the light weight of the automobile is very important for saving energy, reducing exhaust emission and realizing sustainable development of automobile industry in China. On the other hand, the requirement of the automobile industry on the quality of air in the automobile is continuously improved, and more host plants pay particular attention to the influence of automobile smell on the comfort level of drivers and passengers. Therefore, light-weight ABS materials with low odor and low emission become an important development direction of high polymer materials for vehicles.
The micro-foaming ABS material has a compact surface layer and a foaming core layer structure, and meanwhile, on the premise of ensuring the material performance, the weight of a finished piece is remarkably reduced, and the lightweight of an automobile is facilitated. The micro-foaming ABS material can reduce the injection molding amount to a greater extent in the injection molding process, and is beneficial to reducing the VOC content. And meanwhile, the sodium bicarbonate generates CO2 and water vapor during decomposition, so that volatile gas is diluted, and the VOC concentration is reduced. In addition, in the screw barrel at the injection molding end, the foaming agent is decomposed at high temperature to generate gas, and the polymer melt forms a homogeneous mixing system under the high-speed shearing screw, so that the viscosity of the composite material at high temperature can be greatly reduced by the presence of the gas, and the heating temperature of the screw can be reduced. The injection molding temperature is reduced, so that the energy consumption can be reduced, the injection molding beat is accelerated, the ABS is prevented from being degraded due to overheating, and the VOC is reduced to a great extent.
At present, the foaming agent for the automotive interior is mainly sodium bicarbonate, but the decomposition temperature of the sodium bicarbonate is lower. The decomposition temperature of sodium bicarbonate can be increased by modifying sodium bicarbonate, but the decomposition temperature of sodium bicarbonate is basically between 170 and 200 ℃, and the injection molding temperature of ABS is above 230 ℃. In the actual use process, the sodium bicarbonate is decomposed too early, the foam holes in the injection molding part are sparse, and the high-performance ABS material is not easy to obtain. Because the decomposition temperature of the foaming agent master batch for the automobile is low, the foaming agent master batch is added in the modification process of the polymer, and the master batch can be decomposed in advance, so that gas escapes. At present, the common process is that the master batch of the foaming agent and the polymer material are respectively added into a charging barrel of an injection molding machine in the injection molding process, thereby realizing foaming in a mold. This requires additional equipment and personnel for the injection molder, and a situation arises in which the overall cost is greatly increased.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a low-odor low-emission high-performance environment-friendly micro-foaming ABS composite material and a preparation method thereof.
The carbon nano tube is selected to modify and modify the sodium bicarbonate, so that the decomposition temperature of the sodium bicarbonate is increased, nano dispersion is realized in an ABS system due to the existence of a small amount of carbon nano tubes, and the physical and mechanical properties of the ABS are improved. Meanwhile, the carbon nano tube can form physical crosslinking in an ABS system, which is beneficial to improving the melt strength of the ABS material, is beneficial to generating uniform and fine foam holes, and greatly reduces the mechanical property loss after ABS foaming.
In order to achieve the purpose, the invention adopts the following technical scheme:
a low-odor low-emission high-performance environment-friendly micro-foaming ABS composite material is composed of the following raw materials in percentage by weight:
65-93wt% of acrylonitrile-butadiene-styrene copolymer (ABS); 5-20wt% of heat-resistant agent; 1-15 wt% of toughening agent; 0.1-10wt% of carbon nano tube modified sodium bicarbonate foaming master batch and 0.01-1wt% of antioxidant.
The ABS resin is produced by a continuous bulk polymerization process, wherein the percentage content of the rubber phase is 8-20%.
The heat-resistant agent is any one or a composition of N-phenyl maleimide, N-cyclohexyl maleimide and N-tertiary butyl maleimide.
The toughening agent is any one or a composition of ethylene-vinyl acetate-hydroxyl, ethylene-n-butyl acrylate-glycidyl ester and high rubber powder.
The carbon nano tube modified sodium bicarbonate foaming master batch is prepared from the following raw materials in percentage by weight:
acidifying the carbon nano tube: 0.01-30wt%;
0.01-40wt% of sodium bicarbonate;
0.01-20wt% of inorganic salt modifier;
10-99wt% of polyethylene;
0.01-2wt% of other auxiliary agents.
In the carbon nanotube modified sodium bicarbonate foaming masterbatch:
the acidified carbon nanotube is a potassium permanganate acidified multi-arm carbon nanotube, the purity of the carbon nanotube is more than or equal to 95%, the diameter is 8-40nm, and the length is less than 30 mu m.
The inorganic salt modifier is one or a mixture of two of sodium citrate, sodium stearate and the like.
The other auxiliary agents are equivalent mixtures of nucleating agents, dispersing agents, antioxidants and the like.
The preparation method of the carbon nanotube modified sodium bicarbonate foaming master batch comprises the following steps:
(1) Weighing the acidified carbon nano tube, the sodium bicarbonate, the inorganic acid salt modifier and other auxiliary agents in percentage by weight, adding into a high-speed stirrer, and stirring for 15-30 min;
(2) Adding the materials in the high-speed stirrer and the polyethylene resin in percentage by weight into a main feeding bin of a single-screw extruder, adding the materials into a machine barrel of the extruder through a feeding screw, wherein the diameter of the screw of the extruder is 30mm, the length-diameter ratio L/D is 25, and the temperature of each subarea of the main machine barrel from a feeding port to a machine head outlet is set as follows: the carbon nano tube modified sodium bicarbonate foaming agent master batch is prepared by melt extrusion, cooling and granulation at the temperature of 70 ℃, 90 ℃, 100 ℃ and the rotating speed of a main engine of 40 r/min.
A preparation method of a low-odor low-emission high-performance environment-friendly micro-foaming ABS composite material comprises the following steps:
(1) Weighing ABS, a heat-resistant agent, a toughening agent and an antioxidant according to the weight percentage, uniformly mixing to obtain a mixed raw material, and then weighing the carbon nanotube modified sodium bicarbonate master batch according to the weight percentage;
(2) Drying the mixed raw materials, placing the dried mixed raw materials into a main feeding bin of a meshing co-rotating double-screw extruder, adding the dried mixed raw materials into a machine barrel of the extruder through a feeding screw, adding the carbon nano tube modified sodium bicarbonate master batch into the extruder from a melting section feeding port, wherein the diameter of the screw of the extruder is 35mm, the length-diameter ratio L/D is 40, and the temperature of each subarea of the main machine barrel from the feeding port to a machine head outlet is set as follows: the low-odor low-emission high-performance environment-friendly micro-foaming ABS composite material is prepared by melt extrusion, cooling, granulation and drying at the temperature of 180 ℃, 190 ℃, 200 ℃ and the rotating speed of a main engine of 250 revolutions per minute.
The ABS composite material is prepared into the low-odor low-emission high-performance environment-friendly ABS product under the condition of secondary mold opening or under the condition of short injection by adopting an injection molding method.
The invention has the beneficial effects that: the carbon nano tube is used for modifying the modified sodium bicarbonate, so that the decomposition temperature of the sodium bicarbonate is obviously increased, the sodium bicarbonate can be used as an auxiliary agent to directly participate in ABS modification, the injection molding beat can be increased, the injection molding equipment cost and the labor input can be reduced, and the efficiency can be improved. In addition, the existence of a small amount of carbon nano tubes can easily realize nano dispersion in an ABS system, improve the physical and mechanical properties and melt strength of the ABS, contribute to the generation of uniform and fine foam holes and improve the mechanical properties of the ABS after foaming. The carbon nano tube modified sodium bicarbonate is added into an ABS system, so that the ABS foaming injection molding temperature can be reduced, the odor and the emission are obviously improved, the ABS dosage is reduced, and the cost is reduced.
Detailed Description
The invention will be further illustrated by the following preferred embodiments, but these examples are given by way of illustration only and do not limit the scope of the invention.
In the composite formulations of the examples and comparative examples, the ABS resin used was a model 3453 resin supplied by DOW corporation; the acidified carbon nanotube is obtained by acidifying carbon nanotube potassium permanganate, and has a purity of not less than 95%, a diameter of 8-40nm and a length of less than 30 μm; sodium bicarbonate was supplied by Weifangjiejia new materials Limited, particle size: 1600 meshes; the inorganic salt modifier is sodium citrate provided by Dongyang auxiliary agent factory in Li of Wujiang; polyethylene is supplied by the famous petrochemical company and has the trade mark of 2520D; the heat-resistant agent is supplied by the Japanese electric chemical company (Denka), under the brand name MS-NIP; tougheners are high rubber powder supplied by BASF corporation (BASF), designation VLK; other adjuvants are antioxidants available from BASF corporation and ICE corporation, UK under the trade designations Irganox 168 and Negonox DSTP.
Example 1
Firstly weighing 20wt% of acidified carbon nanotube and sodium bicarbonate according to the following weight percentage: 30wt%, sodium citrate: 15wt%, other auxiliaries: 1wt%; putting the mixture into a high-speed mixer to mix for 15 to 30min. After uniform mixing, placing the mixture and 34wt% of polyethylene in a main feeding bin of a meshing homodromous single-screw extruder, adding the mixture into a machine barrel of the extruder through a feeding screw, wherein the diameter of the screw of the extruder is 30mm, the length-diameter ratio L/D is 25, and the temperature of each subarea of the main machine barrel from a feeding port to a machine head outlet is set as follows: the master batch is prepared by melt extrusion, cooling and granulation at the host rotation speed of 40 r/min at the temperature of 70 ℃, 90 ℃, 100 ℃ and 100 ℃ to obtain the carbon nano tube modified sodium bicarbonate foaming agent master batch.
And weighing ABS:79wt%; heat-resistant agent: 10wt%; toughening agent: 10wt%; antioxidant: 0.5wt% mixing homogeneously: obtaining mixed raw materials, then placing the mixed raw materials in a main feeding bin of a meshing co-rotating double-screw extruder, and adding the mixed raw materials into a machine barrel of the extruder through a feeding screw; then 0.5wt% of carbon nano tube modified sodium bicarbonate master batch is weighed; and adding the sodium bicarbonate master batch into the extruder from a feeding port of the melting section. The diameter of the screw of the extruder is 35mm, the length-diameter ratio L/D is 40, and the temperature of each subarea from the feed inlet to the head outlet of the main machine cylinder is set as follows: 180 ℃, 190 ℃, 200 ℃ and the rotation speed of a main engine is 250 r/min, and the ABS composite material is prepared by melt extrusion, cooling, granulation and drying.
The ABS composite material is subjected to injection molding by adopting an injection molding method, the thickness of a mold is 2.0mm, a fixed template is retracted by 0.5mm in the injection molding process, and the low-odor low-emission high-performance environment-friendly ABS product is prepared.
And (3) product performance testing:
tensile property: the test was carried out according to ISO527-2 standard at a rate of 50mm/min. Bending property: the test was carried out according to IS178 with a span of 64mm and a test speed of 2mm/min. Impact properties: the method is carried out on a simply supported beam impact tester according to the ISO179-1 standard, and the notch of a sample band is A type. Density: tested according to ISO1183-1 standard. Appearance and cells were primarily observed by the naked eye. Odor: testing according to the popular PV3900 standard; the VOC test results according to ISO 12219-2 are shown in tables 1 and 2.
Example 2
Firstly weighing 20wt% of acidified carbon nanotube and sodium bicarbonate according to the following weight percentage: 30wt%, sodium citrate: 15wt%, other auxiliaries: 1wt%; putting into a high-speed mixer to mix for 15-30 min. After uniform mixing, placing the mixture and 34wt% of polyethylene in a main feeding bin of a meshing homodromous single-screw extruder, adding the mixture into a machine barrel of the extruder through a feeding screw, wherein the diameter of the screw of the extruder is 30mm, the length-diameter ratio L/D is 25, and the temperature of each subarea of the main machine barrel from a feeding port to a machine head outlet is set as follows: the carbon nano tube modified sodium bicarbonate foaming agent master batch is prepared by melt extrusion, cooling and granulation at the temperature of 70 ℃, 90 ℃, 100 ℃ and the rotating speed of a main engine of 40 r/min.
And weighing ABS:78.5wt%; heat-resistant agent: 10wt%; a toughening agent: 10wt%; antioxidant: 0.5wt% mixing: obtaining mixed raw materials, then placing the mixed raw materials in a main feeding bin of a meshing co-rotating double-screw extruder, and adding the mixed raw materials into a machine barrel of the extruder through a feeding screw; then weighing 1wt% of carbon nano tube modified sodium bicarbonate master batch; and adding the sodium bicarbonate master batches into the extruder from a feeding port of the melting section. The diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, and the temperature of each subarea from a feed inlet to a machine head outlet of the main machine cylinder is set as follows: the ABS composite material is prepared by melt extrusion, cooling, granulation and drying at 180 ℃, 190 ℃, 200 ℃ and at the main engine speed of 250 revolutions per minute.
The ABS composite material is subjected to injection molding by adopting an injection molding method, the thickness of a mold is 2.0mm, a fixed template is retracted by 0.5mm in the injection molding process, and the low-odor low-emission high-performance environment-friendly ABS product is prepared.
And (3) product performance testing:
tensile property: the test was carried out according to ISO527-2 standard at a rate of 50mm/min. Bending property: the test was carried out according to IS178 with a span of 64mm and a test speed of 2mm/min. Impact properties: the method is carried out on a simple beam impact tester according to ISO179-1 standard, and a sample strip notch is of an A type. Density: tested according to ISO1183-1 standard. Appearance and cells were observed primarily by the naked eye. Odor: testing according to the popular PV3900 standard; the VOC test results according to ISO 12219-2 are shown in tables 1 and 2.
Example 3
Firstly, weighing 20wt% of acidified carbon nano tube and sodium bicarbonate according to the following weight percentage: 30wt%, sodium citrate: 15wt%, other auxiliaries: 1wt%; putting into a high-speed mixer to mix for 15-30 min. After uniform mixing, placing the mixture and 34wt% of polyethylene in a main feeding bin of a meshing homodromous single-screw extruder, adding the mixture into a machine barrel of the extruder through a feeding screw, wherein the diameter of the screw of the extruder is 30mm, the length-diameter ratio L/D is 25, and the temperature of each subarea of the main machine barrel from a feeding port to a machine head outlet is set as follows: the carbon nano tube modified sodium bicarbonate foaming agent master batch is prepared by melt extrusion, cooling and granulation at the temperature of 70 ℃, 90 ℃, 100 ℃ and the rotating speed of a main engine of 40 r/min.
And weighing ABS:77.5wt%; heat-resistant agent: 10wt%; toughening agent: 10wt%; antioxidant: 0.5wt% mixing homogeneously: obtaining mixed raw materials, then placing the mixed raw materials in a main feeding bin of a meshing co-rotating double-screw extruder, and adding the mixed raw materials into a machine barrel of the extruder through a feeding screw; then weighing 2wt% of carbon nano tube modified sodium bicarbonate master batch; and adding the sodium bicarbonate master batches into the extruder from a feeding port of the melting section. The diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, and the temperature of each subarea from a feed inlet to a machine head outlet of the main machine cylinder is set as follows: the ABS composite material is prepared by melt extrusion, cooling, granulation and drying at 180 ℃, 190 ℃, 200 ℃ and at the main engine speed of 250 revolutions per minute.
The ABS composite material is subjected to injection molding by adopting an injection molding method, the thickness of a mold is 2.0mm, a fixed template retreats by 0.5mm in the injection molding process, and a low-odor low-emission high-performance environment-friendly ABS product is prepared.
And (3) product performance testing:
tensile property: the test was carried out according to ISO527-2 standard at a test rate of 50mm/min. Bending property: the test was carried out according to IS178 with a span of 64mm and a test speed of 2mm/min. Impact properties: the method is carried out on a simply supported beam impact tester according to the ISO179-1 standard, and the notch of a sample band is A type. Density: tested according to ISO1183-1 standard. Appearance and cells were primarily observed by the naked eye. Odor: testing according to the popular PV3900 standard; the VOC test results according to ISO 12219-2 are shown in tables 1 and 2.
Example 4
Firstly weighing 20wt% of acidified carbon nanotube and sodium bicarbonate according to the following weight percentage: 30wt%, sodium citrate: 15wt%, other auxiliaries: 1wt%; putting the mixture into a high-speed mixer to mix for 15 to 30min. After uniform mixing, placing the mixture and 34wt% of polyethylene in a main feeding bin of a meshing homodromous single-screw extruder, adding the mixture into a machine barrel of the extruder through a feeding screw, wherein the diameter of the screw of the extruder is 30mm, the length-diameter ratio L/D is 25, and the temperature of each subarea of the main machine barrel from a feeding port to a machine head outlet is set as follows: the carbon nano tube modified sodium bicarbonate foaming agent master batch is prepared by melt extrusion, cooling and granulation at the temperature of 70 ℃, 90 ℃, 100 ℃ and the rotating speed of a main engine of 40 r/min.
And weighing ABS:75.5wt%; heat-resistant agent: 10wt%; toughening agent: 10wt%; antioxidant: 0.5wt% mixing: obtaining mixed raw materials, then placing the mixed raw materials in a main feeding bin of a meshing co-rotating double-screw extruder, and adding the mixed raw materials into a machine barrel of the extruder through a feeding screw; then weighing 4wt% of carbon nano tube modified sodium bicarbonate master batch; and adding the sodium bicarbonate master batch into the extruder from a feeding port of the melting section. The diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, and the temperature of each subarea from a feed inlet to a machine head outlet of the main machine cylinder is set as follows: 180 ℃, 190 ℃, 200 ℃ and the rotation speed of a main engine is 250 r/min, and the ABS composite material is prepared by melt extrusion, cooling, granulation and drying.
The ABS composite material is subjected to injection molding by adopting an injection molding method, the thickness of a mold is 2.0mm, a fixed template retreats by 0.5mm in the injection molding process, and a low-odor low-emission high-performance environment-friendly ABS product is prepared.
And (3) product performance testing:
tensile property: the test was carried out according to ISO527-2 standard at a test rate of 50mm/min. Bending property: the test was carried out according to IS178 with a span of 64mm and a test speed of 2mm/min. Impact properties: the method is carried out on a simple beam impact tester according to ISO179-1 standard, and a sample strip notch is of an A type. Density: tested according to ISO1183-1 standard. Appearance and cells were primarily observed by the naked eye. Odor: testing according to the popular PV3900 standard; the VOC was measured according to ISO 12219-2 with the results shown in tables 1 and 2.
Comparative example 1
Weighing ABS:79.5wt%; heat-resistant agent: 10wt%; toughening agent: 10wt%; antioxidant: 0.5wt% mixing homogeneously: obtaining mixed raw materials, then placing the mixed raw materials in a main feeding bin of a meshing co-rotating twin-screw extruder, and adding the mixed raw materials into a machine barrel of the extruder through a feeding screw; the diameter of the screw of the extruder is 35mm, the length-diameter ratio L/D is 40, and the temperature of each subarea from the feed inlet to the head outlet of the main machine cylinder is set as follows: the ABS composite material is prepared by melt extrusion, cooling, granulation and drying at 200 ℃, 220 ℃, 2200 ℃, 230 ℃ and a main machine rotating speed of 250 r/min.
The ABS composite material is prepared into an ABS product by adopting an injection molding method and a mold with the thickness of 2.0 mm.
And (3) product performance testing:
tensile property: the test was carried out according to ISO527-2 standard at a test rate of 50mm/min. Bending property: the test was carried out according to IS178 with a span of 64mm and a test speed of 2mm/min. Impact properties: the method is carried out on a simple beam impact tester according to ISO179-1 standard, and a sample strip notch is of an A type. Density: tested according to ISO1183-1 standard. The appearance is mainly observed by naked eyes. Odor: testing according to the popular PV3900 standard; the VOC was measured according to ISO 12219-2 with the results shown in tables 1 and 2.
Comparative example 2
Firstly weighing sodium bicarbonate according to the following weight percentage: 30wt%, sodium citrate: 15wt%, other auxiliaries: 1wt%; putting the mixture into a high-speed mixer to mix for 15 to 30min. After uniform mixing, placing the mixture and 54wt% of polyethylene in a main feeding bin of a meshing homodromous single-screw extruder, adding the mixture and the polyethylene into a machine barrel of the extruder through a feeding screw, wherein the diameter of the screw of the extruder is 30mm, the length-diameter ratio L/D is 25, and the temperature of each subarea of the machine barrel from a feeding port to a machine head outlet is set as follows: the master batch of the modified sodium bicarbonate foaming agent is prepared by melt extrusion, cooling and granulation at the temperature of 70 ℃, 90 ℃, 100 ℃ and the rotating speed of a main engine of 40 r/min.
And weighing ABS:77.5wt%; heat-resistant agent: 10wt%; toughening agent: 10wt%; antioxidant: 0.5wt% mixing homogeneously: obtaining mixed raw materials, then placing the mixed raw materials in a main feeding bin of a meshing co-rotating twin-screw extruder, and adding the mixed raw materials into a machine barrel of the extruder through a feeding screw; then weighing 2wt% of sodium bicarbonate master batch; and adding the sodium bicarbonate master batch into the extruder from a feeding port of the melting section. The diameter of the screw of the extruder is 35mm, the length-diameter ratio L/D is 40, and the temperature of each subarea from the feed inlet to the head outlet of the main machine cylinder is set as follows: the ABS composite material is prepared by melt extrusion, cooling, granulation and drying at 180 ℃, 190 ℃, 200 ℃ and at the main engine speed of 250 revolutions per minute.
The ABS composite material is subjected to injection molding by adopting an injection molding method, the thickness of a mold is 2.0mm, a fixed template retreats by 0.5mm in the injection molding process, and a low-odor low-emission high-performance environment-friendly ABS product is prepared.
And (3) product performance testing:
tensile property: the test was carried out according to ISO527-2 standard at a rate of 50mm/min. Bending property: the test was carried out according to IS178 with a span of 64mm and a test speed of 2mm/min. Impact properties: the method is carried out on a simple beam impact tester according to ISO179-1 standard, and a sample strip notch is of an A type. Density: tested according to ISO1183-1 standard. The appearance is mainly observed by naked eyes. Odor: testing according to the popular PV3900 standard; the VOC was measured according to ISO 12219-2 with the results shown in tables 1 and 2.
From the basic physical property tests of each example and comparative example shown in table 1, it can be seen that: compared with the conventional ABS system, the carbon nanotube modified sodium bicarbonate master batch has the advantages that the material density is greatly reduced, the weight reduction in the system can reach more than 20%, and the carbon nanotube modified sodium bicarbonate master batch has great advantages in light weight and cost reduction. The flexural modulus, tensile strength and notched impact performance are varied with the amount of the sodium bicarbonate masterbatch. The tensile strength, the flexural modulus and the notch impact strength of the ABS material are all close to those of the unfoamed ABS material under the condition of the addition proportion of 2 percent of the sodium bicarbonate foaming agent master batch. The carbon nano tube is added into the sodium bicarbonate master batch, so that the decomposition temperature of the foaming agent master batch can be greatly improved, and the foaming agent master batch can be conveniently and directly added into the ABS matrix. The carbon nano tube can also improve the melt strength of the ABS material, and the foam structure of the product after injection molding foaming is better than that of a system without addition. Along with the increase of the proportion of the foaming agent master batch in the injection molding foaming, the number of foam holes is increased, and the lightweight effect is more and more obvious. However, at a high addition ratio, the number of the foam cells is too large, and the foam cells are easy to form holes, so that the mechanical property, the appearance and the weight loss are optimal at a ratio of 2wt% in the system.
Table 1 basic mechanical properties physical properties of ABS composites:
table 2ABS composite odor and emission characteristics:
| physical Properties | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 |
| Smell of rice | 4.0 | 3.5+ | 3.5 | 3.5 | 4.5 | 4.5 |
| Benzene/μ g/m3 | ND | ND | ND | ND | 40 | 20 |
| Toluene/. Mu.g/m 3 | ND | ND | ND | ND | 60 | 50 |
| Ethylbenzene/. Mu.g/m 3 | 400 | 305 | 200 | 180 | 508 | 490 |
| Xylene/. Mu.g/m 3 | ND | ND | ND | ND | 25 | ND |
| Styrene/. Mu.g/m 3 | 240 | 160 | 130 | 100 | 370 | 350 |
| Formaldehyde/. Mu.g/m 3 | ND | ND | ND | ND | ND | ND |
| Acetaldehyde/. Mu.g/m 3 | ND | ND | ND | ND | ND | ND |
| Acrolein/. Mu.g/m 3 | ND | ND | ND | ND | ND | ND |
The results of the odor and emission characteristics of the examples and comparative examples shown in table 2 are known: the odor and the diffusion characteristic of the ABS material are obviously improved along with the use of the carbon nano tube modified sodium bicarbonate master batch. The ABS resin is related to that the carbon nano tube modified sodium bicarbonate master batch can obviously reduce the ABS injection molding temperature, and is related to that the dosage of ABS is reduced and that water vapor and CO2 generated after the sodium bicarbonate is decomposed can dilute the pentacene trialdehyde. Therefore, with the increase of the consumption of the modified sodium bicarbonate master batch modified by the carbon nano tube, the odor and the diffusion characteristic of the ABS composite material are both obviously improved. Therefore, the invention obtains the microcellular foam injection molding ABS material with optimized process, light weight, fine foam holes, excellent mechanical property, low odor and low emission.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (9)
1. A low-odor low-emission high-performance environment-friendly micro-foaming ABS composite material is characterized in that: the composite material consists of the following raw materials in percentage by weight:
65-93wt% of acrylonitrile-butadiene-styrene copolymer (ABS); 5-20wt% of heat-resistant agent; 1-15 wt% of toughening agent; 0.1-10wt% of carbon nano tube modified sodium bicarbonate foaming master batch and 0.01-1wt% of antioxidant; the carbon nano tube modified sodium bicarbonate foaming master batch is prepared from the following raw materials in percentage by weight:
acidifying the carbon nano tube: 0.01-30wt%;
0.01-40wt% of sodium bicarbonate;
0.01-20wt% of inorganic salt modifier;
10-99wt% of polyethylene;
0.01-2wt% of other auxiliary agents.
2. The low odor, low emission, high performance, environmentally friendly, micro-foamed ABS composite of claim 1, wherein: the ABS resin is produced by a continuous bulk polymerization process, wherein the percentage content of the rubber phase is 8-20%.
3. The low odor, low emission, high performance, environmentally friendly, micro-foamed ABS composite of claim 1, wherein: the heat-resistant agent is any one or a combination of N-phenyl maleimide, N-cyclohexyl maleimide and N-tert-butyl maleimide.
4. The low odor, low emission, high performance, environmentally friendly micro-foamed ABS composite of claim 1, wherein the ABS composite comprises: the toughening agent is any one or a composition of ethylene-vinyl acetate-hydroxyl, ethylene-n-butyl acrylate-glycidyl ester and high rubber powder.
5. The low odor, low emission, high performance, environmentally friendly micro-foamed ABS composite of claim 1, wherein the ABS composite comprises: the acidified carbon nanotube is a potassium permanganate acidified multi-arm carbon nanotube, the purity of the carbon nanotube is more than or equal to 95%, the diameter is 8-40nm, and the length is less than 30 mu m.
6. The low odor, low emission, high performance, environmentally friendly micro-foamed ABS composite of claim 1, wherein the ABS composite comprises: the inorganic salt modifier is one or a mixture of sodium citrate and sodium stearate.
7. The low odor, low emission, high performance, environmentally friendly, micro-foamed ABS composite of claim 1, wherein: the other auxiliary agents are a mixture of nucleating agents, dispersing agents and antioxidants.
8. The low odor, low emission, high performance, environmentally friendly, micro-foamed ABS composite of claim 1, wherein: the preparation method of the carbon nanotube modified sodium bicarbonate foaming master batch comprises the following steps:
(1) Weighing the acidified carbon nano tube, the sodium bicarbonate, the inorganic acid salt modifier and other auxiliary agents in percentage by weight, adding into a high-speed stirrer, and stirring for 15-30 min;
(2) Adding the materials in the high-speed stirrer and the polyethylene resin in percentage by weight into a main feeding bin of a single-screw extruder, adding the materials into a machine barrel of the extruder through a feeding screw, wherein the diameter of the screw of the extruder is 30mm, the length-diameter ratio L/D is 25, and the temperature of each subarea of the main machine barrel from a feeding port to a machine head outlet is set as follows: the master batch is prepared by melt extrusion, cooling and granulation at the host rotation speed of 40 r/min at the temperature of 70 ℃, 90 ℃, 100 ℃ and 100 ℃ to obtain the carbon nano tube modified sodium bicarbonate foaming agent master batch.
9. The preparation method of the low-odor low-emission high-performance environment-friendly micro-foaming ABS composite material as claimed in any one of claims 1 to 8, which comprises the following steps:
(1) Weighing ABS, a heat-resistant agent, a toughening agent and an antioxidant according to the weight percentage, uniformly mixing to obtain a mixed raw material, and then weighing the carbon nanotube modified sodium bicarbonate foaming master batch according to the weight percentage;
(2) Drying the mixed raw materials, placing the dried mixed raw materials into a main feeding bin of a meshing co-rotating double-screw extruder, adding the dried mixed raw materials into a machine barrel of the extruder through a feeding screw, adding the carbon nano tube modified sodium bicarbonate foaming master batch into the extruder from a melting section feeding port, wherein the diameter of the screw of the extruder is 35mm, the length-diameter ratio L/D is 40, and the temperature of each subarea of the main machine barrel from the feeding port to a machine head outlet is set as follows: the low-odor low-emission high-performance environment-friendly micro-foaming ABS composite material is prepared by melt extrusion, cooling, granulation and drying at the temperature of 180 ℃, 190 ℃, 200 ℃ and 200 ℃ at the rotating speed of a main engine of 250 revolutions per minute.
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