CN114621574B - Polycarbonate alloy material and preparation method and application thereof - Google Patents
Polycarbonate alloy material and preparation method and application thereof Download PDFInfo
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- CN114621574B CN114621574B CN202210288934.4A CN202210288934A CN114621574B CN 114621574 B CN114621574 B CN 114621574B CN 202210288934 A CN202210288934 A CN 202210288934A CN 114621574 B CN114621574 B CN 114621574B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a polycarbonate alloy material, which comprises the following components in parts by weight: 42-65 parts of polycarbonate resin; 30-55 parts of styrene resin; 3-8 parts of hydrogenated styrene-ethylene/butylene block copolymer resin; 8-16 parts of electromagnetic shielding master batch; 0-2 parts of auxiliary agent. According to the invention, in a polycarbonate and styrene resin material system, by adopting the electromagnetic shielding master batch with PC as a base material and containing the multi-wall carbon nanotube component and simultaneously adding the hydrogenated styrene-ethylene/butylene block copolymer resin, the multi-wall carbon nanotube can be effectively dispersed and coordinated in the material system, and meanwhile, the material system can form a more stable and consistent sea-island structure, so that the material has excellent electromagnetic shielding property and noise reduction property, the use requirement of the current automobile industry on the high-damping electromagnetic shielding material can be particularly met, and the application of the polycarbonate material in the automobile field is further widened.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polycarbonate alloy material and a preparation method and application thereof.
Background
Polycarbonate (PC) has excellent heat resistance, high strength and impact resistance, and stable size, belongs to engineering plastics with very wide application, and is widely used in the industries of automobile industry, electronic and electric industry, light industry household appliances, textile, building and the like. With the development of the automobile industry, the automobile electronic control technology has greatly advanced, more and more electronic devices are used in automobiles, and due to the increase of power and the increase of frequency of the electronic devices, the electromagnetic environment of the automobiles in the running process is increasingly complex, and a more serious electromagnetic interference phenomenon is generated, so that the problem is mainly solved by adopting electromagnetic shielding materials at present. On the other hand, the noise reduction performance of the material in the automobile industry has high attention, the noise in the automobile mainly comes from the extrusion of the combined parts in the automobile and the friction among the parts, and the physical and psychological health of a driver and passengers can be directly influenced by the high noise in the automobile, and even the driving safety can be influenced. In recent years, the requirements of the automobile industry on vibration damping, noise reduction and electromagnetic shielding materials are increasing, and the requirements are increasing. Therefore, developing a material with electromagnetic shielding and noise reduction characteristics has high application value and significance in the automobile industry.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a polycarbonate alloy material with excellent electromagnetic shielding property and noise reduction property.
Another object of the present invention is to provide a method for preparing the above polycarbonate alloy material.
The invention is realized by the following technical scheme:
the polycarbonate alloy material comprises the following components in parts by weight:
42-65 parts of polycarbonate resin;
30-55 parts of styrene resin;
3-8 parts of hydrogenated styrene-ethylene/butylene block copolymer resin;
8-16 parts of electromagnetic shielding master batch;
0-2 parts of auxiliary agent.
The electromagnetic shielding master batch is a PC master batch which takes PC as a base material and is added with 14-20wt% of multiwall carbon nanotubes. The electromagnetic shielding master batch is consistent with the polycarbonate alloy material matrix resin.
According to the invention, the PC is adopted as a base material to add the electromagnetic shielding master batch of the multiwall carbon nanotube, the compatibility of the electromagnetic shielding master batch with polycarbonate is good due to the consistency of matrix resin, the added hydrogenated styrene-ethylene/butylene block copolymer resin can be well fused with styrene resin, and meanwhile, strong hydrogen bond combination can be formed between the hydrogenated styrene-ethylene/butylene block copolymer resin and polycarbonate chain segments, so that the dispersibility of the electromagnetic shielding master batch in a material system is greatly improved, the multiwall carbon nanotube is effectively dispersed and coordinated in the material system, a stable circuit path is formed on the surface of the system, and the electromagnetic shielding characteristic of the material is remarkably improved; and due to the effect of the hydrogenated styrene-ethylene/butylene block copolymer resin, the material system forms a more stable and consistent sea-island structure, so that the absorption and internal dissipation of external energy are greatly improved, and an excellent noise reduction effect is achieved.
Preferably, the hydrogenated styrene-ethylene/butylene block copolymer resin has a styrene content of 30 to 40wt%; more preferably, the hydrogenated styrene-ethylene/butylene block copolymer resin has a styrene content of 31 to 34wt%.
The polycarbonate resin can be prepared by adopting a phosgene method or a transesterification method in the industry, and can also be obtained in a commercially available mode.
Preferably, the melt index of the polycarbonate resin is 8-15g/10min at 300 ℃ and under 1.2 kg; more preferably, the melt index of the polycarbonate resin is 9-11g/10min at 300 ℃ under 1.2 kg. The melt index is tested against standard ISO 1133-1-2011.
The styrene resin is selected from any one or more of acrylonitrile-butadiene-styrene resin, acrylonitrile-acrylic ester-styrene resin or acrylonitrile-ethylene propylene diene monomer-styrene resin. Preferably, the styrene-based resin is selected from acrylonitrile-butadiene-styrene resins.
Preferably, the melt index of the styrene resin is 15-25 g/10min under the conditions of 220 ℃ and 10 kg; more preferably, the melt index of the styrene resin is 18-22 g/10min at 220 ℃ and 10 kg. The melt index is tested against standard ISO 1133-1-2011.
The auxiliary agent is selected from any one or more of an antioxidant, a light stabilizer, a lubricant or toner.
The proper antioxidant can be selected from any one or more of hindered phenol antioxidants or phosphite antioxidants; suitable light stabilizers are benzotriazole-based UV absorbers; a suitable lubricant is pentaerythritol stearate; a suitable toner is conductive carbon black.
The invention has no special requirements on the types and sources of various auxiliary agents, and technicians can select and add the auxiliary agents according to actual situation demands.
The invention also provides a preparation method of the polycarbonate alloy material, which comprises the following steps:
uniformly mixing the components according to the proportion, then adding the mixture into a double-screw extruder, and performing melt blending extrusion granulation to obtain a polycarbonate alloy material; wherein the melting temperature is 220-250 ℃.
The invention also provides application of the polycarbonate alloy material in the field of automobiles. In particular, the antenna can be used for the aspects of automatic cruise marks, antenna boxes and the like.
The invention has the following beneficial effects:
in the system of the polycarbonate and styrene resin materials, the electromagnetic shielding master batch which takes PC as a base material and contains the multiwall carbon nanotube component is adopted, and meanwhile, the hydrogenated styrene-ethylene/butylene block copolymer resin is added, so that the prepared polycarbonate alloy material has excellent electromagnetic shielding property and noise reduction property, can particularly meet the use requirement of the current automobile industry on the high-damping electromagnetic shielding material, and further widens the application of the polycarbonate material in the automobile field.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The raw materials used in the examples and comparative examples of the present invention are described below, but are not limited to these materials:
polycarbonate resin 1: the melt index under the conditions of 300 ℃ and 1.2kg is 10g/10min, and the PC S-2000F of Mitsubishi;
polycarbonate resin 2: the melt index under the conditions of 300 ℃ and 1.2kg is 14g/10min, LXZY1615T-11 of Shandong Luxi;
styrene resin 1: acrylonitrile-butadiene-styrene resin with a melt index of 20g/10min at 220 ℃ and 10kg, high-bridge petrochemical ABS 8434;
styrene resin 2: acrylonitrile-butyl acrylate-styrene resin, LI918 with 20g/10min melt index and LG under the condition of 220 ℃ and 10 kg;
styrene resin 3: acrylonitrile-ethylene propylene diene monomer-styrene resin with a melt index of 20g/10min at 220 ℃ and 10kg, guangzhou Jinfa AES-K300;
styrene resin 4: acrylonitrile-butadiene-styrene resin with a melt index of 25g/10min at 220 ℃ and 10kg, jilin petrochemical ABS 0215;
hydrogenated styrene-ethylene/butylene block copolymer resin 1: li Changrong chemical, trade name SEBS 9552, styrene content 33%;
hydrogenated styrene-ethylene/butylene block copolymer resin 2: li Changrong chemical, trade name SEBS 9558, styrene content 40%;
hydrogenated styrene-ethylene/butylene block copolymer resin 3: li Changrong chemical, trade name SEBS 9543, styrene content 20%;
ABS-g-GMA: self-making;
electromagnetic shielding master batch 1: PC C1508, a major in the Shandong province, with a multiwall carbon nanotube content of 15wt%;
electromagnetic shielding master batch 2: shanghai nano plastic alloy, PC NS109, multi-wall carbon nano tube content 15wt%;
electromagnetic shielding master batch 3: shandong Dada is customized, PC C1520, multi-wall carbon nano tube content is 20wt%;
electromagnetic shielding master batch 4: PC C1505, multiwall carbon nanotubes content 5wt%, shandong da;
electromagnetic shielding master batch 5: shandong is custom-made, and the content of PC C1530 multi-wall carbon nano tubes is 30wt%;
multiwall carbon nanotubes: sigmaaldrich, MWNT;
auxiliary 1: a 1:1 mixture of an antioxidant, hindered phenol antioxidant 1076 and phosphite antioxidants PEP-36, commercially available;
auxiliary 2: light stabilizers, benzotriazole UV absorbers, commercially available;
auxiliary agent 3: lubricants, pentaerythritol stearate, commercially available;
the sources of the auxiliary agents adopted in the examples and the comparative examples are the same.
Preparation method of polycarbonate alloy materials of examples and comparative examples:
according to the proportion in the table 1, the components are uniformly mixed, then added into a double-screw extruder, and the polycarbonate alloy material is prepared through melt blending, extrusion and granulation; wherein, the control temperature of each section of the main machine barrel (from the feed inlet to the machine head outlet) is 220 ℃, 235 ℃, 245 ℃, 250 ℃ and 245 ℃ respectively.
The related performance testing method comprises the following steps:
(1) Electromagnetic shielding effect evaluation: the effectiveness of the shield is measured by shielding effectiveness. The shielding effectiveness is tested according to GJB 6190-2008;
table 1: electromagnetic shielding effectiveness evaluation (typically, industry application standard is 30-60dB, military standard is 60-120 dB)
| Shielding effectiveness | <10 dB | 10~30 dB | 30~60 dB | 60~90 dB | >90 dB |
| Shielding effect | None (difference) | Poor quality | Medium and medium | Good quality | Excellent (excellent) |
(2) Noise risk value evaluation: the test was carried out according to the German society of automotive industries standard VDA 230-206-2005, with noise risk values divided into 10 segments, 1-3 being low risk, 4-5 being gray areas and 6-10 being high risk.
Table 2: examples 1-10 the proportions of the components (in parts by weight) and the results of the related Performance tests
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | Example 10 | |
| Polycarbonate resin 1 | 50 | 50 | 50 | 50 | 50 | 50 | 42 | 65 | 50 | |
| Polycarbonate resin 2 | 50 | |||||||||
| Styrene resin 1 | 45 | 45 | 45 | 45 | 55 | 30 | 45 | |||
| Styrene resin 2 | 45 | |||||||||
| Styrene resin 3 | 45 | |||||||||
| Styrene resin 4 | 45 | |||||||||
| Hydrogenated styrene-ethylene/butene Block copolymer resin 1 | 5 | 5 | 5 | 5 | 5 | 8 | 3 | 5 | ||
| Hydrogenated styrene-ethylene/butene Block copolymer resin 2 | 5 | |||||||||
| Hydrogenated styrene-ethylene/butene block copolymer resin 3 | 5 | |||||||||
| Electromagnetic shielding master batch 1 | 12 | 12 | 12 | 12 | 12 | 12 | 12 | 12 | ||
| Electromagnetic shielding master batch 2 | 15 | |||||||||
| Electromagnetic shielding master batch 3 | 8 | |||||||||
| Antioxidant | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | / |
| Light stabilizers | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.3 | 0.3 | / |
| Lubricant | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | / |
| Noise hazard value | 2 | 3 | 3 | 3 | 4 | 4 | 5 | 3 | 4 | 2 |
| Shielding effectiveness/dB | 72 | 69 | 69 | 68 | 65 | 66 | 63 | 68 | 62 | 61 |
Table 3: comparative examples 1 to 10 the proportions of the respective components (in parts by weight) and the results of the related property tests
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 | |
| Polycarbonate resin 1 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 60.2 |
| Styrene resin 1 | 45 | 45 | 45 | 45 | 45 | 45 | 45 | 45 | 45 | 45 |
| Hydrogenated styrene-ethylene/butene Block copolymer resin 1 | 12 | 1 | / | 5 | 5 | 5 | 5 | 5 | 5 | |
| ABS-g-GMA | 5 | |||||||||
| Electromagnetic shielding master batch 1 | 12 | 12 | 12 | 12 | 25 | 2 | / | |||
| Electromagnetic shielding master batch 4 | 12 | |||||||||
| Electromagnetic shielding master batch 5 | 12 | |||||||||
| Multiwall carbon nanotubes | 1.8 | |||||||||
| Antioxidant | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Light stabilizers | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Lubricant | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Noise hazard value | 7 | 6 | 7 | 8 | 5 | 8 | 8 | 5 | 5 | 6 |
| Shielding effectiveness/dB | 53 | 55 | 59 | 55 | 37 | 60 | 62 | 32 | 18 | 51 |
From the above examples and comparative examples, the electromagnetic shielding property and noise reduction property of the material can be remarkably improved by adopting the electromagnetic shielding master batch containing the multi-walled carbon nanotube component with PC as the base material and simultaneously adding the hydrogenated styrene-ethylene/butylene block copolymer resin in the polycarbonate and styrene resin material system.
Comparative example 1, which uses ABS-g-GMA instead of hydrogenated styrene-ethylene/butylene block copolymer resin, does not have excellent noise reduction and electromagnetic shielding effects;
comparative example 2, the hydrogenated styrene-ethylene/butylene block copolymer resin was excessively added, but rather, the noise reduction and electromagnetic shielding effects were deteriorated;
comparative example 3/4, hydrogenated styrene-ethylene/butylene block copolymer resin was added too little or no hydrogenated styrene-ethylene/butylene block copolymer resin was added, the noise hazard value of the material was high, and the shielding effectiveness was low;
comparative example 7, in which the electromagnetic shielding master batch is excessively added, although having higher shielding effectiveness, the noise hazard value of the material is as high as 8, and the noise reduction performance is poor;
comparative example 8/9, electromagnetic shielding master batch added too little or no electromagnetic shielding master batch added, poor material shielding effectiveness;
in comparative example 10, the direct addition of multiwall carbon nanotubes has poor electromagnetic shielding effect and noise reduction effect.
Claims (12)
1. The polycarbonate alloy material is characterized by comprising the following components in parts by weight:
42-65 parts of polycarbonate resin;
30-55 parts of styrene resin;
3-8 parts of hydrogenated styrene-ethylene/butylene block copolymer resin;
8-16 parts of electromagnetic shielding master batch;
0-2 parts of auxiliary agent;
the electromagnetic shielding master batch takes PC as a base material, and 14-20wt% of the PC master batch of the multiwall carbon nanotube is added.
2. The polycarbonate alloy material according to claim 1, wherein the styrene content in the hydrogenated styrene-ethylene/butylene block copolymer resin is 30 to 40wt%.
3. The polycarbonate alloy material of claim 1, wherein the hydrogenated styrene-ethylene/butylene block copolymer resin has a styrene content of 31 to 34wt%.
4. The polycarbonate alloy material of claim 1, wherein the polycarbonate resin has a melt index of 8-15g/10min at 300 ℃ and 1.2 kg.
5. The polycarbonate alloy material of claim 1, wherein the polycarbonate resin has a melt index of 9-11g/10min at 300 ℃ and 1.2 kg.
6. The polycarbonate alloy material according to claim 1, wherein the styrene resin is selected from any one or more of acrylonitrile-butadiene-styrene resin, acrylonitrile-acrylate-styrene resin, and acrylonitrile-ethylene propylene diene monomer-styrene resin.
7. The polycarbonate alloy material of claim 1, wherein the styrenic resin is selected from the group consisting of acrylonitrile-butadiene-styrene resins.
8. The polycarbonate alloy material according to claim 1, wherein the styrene-based resin has a melt index of 15 to 25g/10min at 220 ℃ under 10kg conditions.
9. The polycarbonate alloy material according to claim 1, wherein the styrene-based resin has a melt index of 18 to 22 g/10min at 220 ℃ under 10kg conditions.
10. The polycarbonate alloy material according to claim 1, wherein the auxiliary agent is selected from any one or more of an antioxidant, a light stabilizer, a lubricant, and a toner.
11. The method for producing a polycarbonate alloy material according to any one of claims 1 to 10, comprising the steps of:
uniformly mixing the components according to the proportion, then adding the mixture into a double-screw extruder, and performing melt blending extrusion granulation to obtain a polycarbonate alloy material; wherein the melting temperature is 220-250 ℃.
12. Use of the polycarbonate alloy material according to any one of claims 1-10 in the automotive field.
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