CN114621574A - Polycarbonate alloy material and preparation method and application thereof - Google Patents

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 an auxiliary agent. According to the invention, in a polycarbonate and styrene resin material system, by adopting the electromagnetic shielding master batch which takes PC as a base material and contains the multi-walled carbon nanotube component and adding hydrogenated styrene-ethylene/butylene block copolymer resin, the multi-walled carbon nanotube can be effectively dispersed and coordinated in the material system, and meanwhile, the material system can form a more stable and coherent '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

Polycarbonate alloy material and preparation method and application thereof

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, is stable in size, belongs to engineering plastics with wide application, and is widely applied to the industries such as automobile industry, electronic and electric appliance industry, light industrial and household appliances, textile, building and the like. With the development of the automobile industry, the automobile electric control technology is greatly improved, more and more electronic devices are used in automobiles, and due to the increase of the power and the increase of the 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. On the other hand, the automobile industry has a high attention to the noise reduction performance of materials, the noise in the automobile mainly comes from extrusion of combined parts in the automobile and friction among the parts, and the high noise in the automobile directly influences the physical and mental health of a driver and passengers, and even influences the driving safety. In recent years, the automobile industry has increasingly and increasingly demanded vibration reduction, noise reduction and electromagnetic shielding materials. Therefore, the development of 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 of the prior art, the invention aims to provide a polycarbonate alloy material with excellent electromagnetic shielding property and noise reduction property.

The invention also aims to provide a preparation method of the 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 an 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 multi-wall carbon nano tubes. The electromagnetic shielding master batch is consistent with the polycarbonate alloy material matrix resin.

The electromagnetic shielding master batch which takes PC as a base material and is added with the multi-walled carbon nano tube has good compatibility with polycarbonate due to the consistency of matrix resin, and the added hydrogenated styrene-ethylene/butylene block copolymer resin can be well fused with styrene resin and can form strong hydrogen bond combination with a polycarbonate chain segment, so that the dispersibility of the electromagnetic shielding master batch in a material system is greatly improved, the multi-walled carbon nano tube 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 property of the material is remarkably improved; and due to the action of the hydrogenated styrene-ethylene/butylene block copolymer resin, a material system forms a more stable and coherent '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 40 wt%; more preferably, the styrene content of the hydrogenated styrene-ethylene/butylene block copolymer resin is 31 to 34 wt%.

The polycarbonate resin can be prepared by a phosgene method or an ester exchange method in the industry, and can also be obtained by a commercial method.

Preferably, the polycarbonate resin has a melt index of 8-15g/10min at 300 ℃ and 1.2 kg; more preferably, the polycarbonate resin has a melt index of 9 to 11g/10min at 300 ℃ under 1.2 kg. The melt index is measured according to the standard ISO 1133-1-2011.

The styrene resin is selected from one or more of acrylonitrile-butadiene-styrene resin, acrylonitrile-acrylate-styrene resin or acrylonitrile-ethylene propylene diene monomer-styrene resin. Preferably, the styrenic resin is selected from the group consisting of acrylonitrile-butadiene-styrene resins.

Preferably, the styrene resin has a melt index of 15-25 g/10min at 220 ℃ under the condition of 10 kg; more preferably, the styrene-based resin has a melt index of 18 to 22 g/10min at 220 ℃ under 10 kg. The melt index is measured according to the standard ISO 1133-1-2011.

The auxiliary agent is selected from any one or more of an antioxidant, a light stabilizer, a lubricant or a toner.

The suitable antioxidant can be selected from one or more of hindered phenol antioxidants or phosphite antioxidants; suitable light stabilizers are UV absorbers of the benzotriazole type; suitable lubricants are 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 the requirements of actual conditions.

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, adding the mixture into a double-screw extruder, and performing melt blending extrusion granulation to prepare the 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 device can be used for the aspects of automatic cruise car logos, antenna boxes and the like.

The invention has the following beneficial effects:

in a polycarbonate and styrene resin material system, the polycarbonate alloy material prepared by adopting the electromagnetic shielding master batch taking PC as a base material and containing the multi-wall carbon nano tube component and simultaneously adding the hydrogenated styrene-ethylene/butylene block copolymer resin has excellent electromagnetic shielding property and noise reduction property, can particularly meet the use requirement of the current automobile industry on high-damping electromagnetic shielding materials, 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 invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling 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: melt index at 300 deg.C under 1.2kg is 10g/10min, PC S-2000F of Mitsubishi;

polycarbonate resin 2: melt index at 300 deg.C under 1.2kg of 14g/10min, LXZY1615T-11 of Shandong Luxi;

styrene-based resin 1: acrylonitrile-butadiene-styrene resin with a melt index of 20g/10min at 220 ℃ under 10kg, high petrochemical ABS 8434;

styrene-based resin 2: an acrylonitrile-butylacrylate-styrene resin having a melt index of 20g/10min, LG LI918 at 220 ℃ under 10 kg;

styrene-based resin 3: acrylonitrile-ethylene propylene diene monomer-styrene resin with a melt index of 20g/10min at 220 ℃ under 10kg, AES-K300 of Guangzhou golden hair;

styrene-based resin 4: acrylonitrile-butadiene-styrene resin having a melt index of 25g/10min at 220 ℃ under 10kg, Jilin petrochemical ABS 0215;

hydrogenated styrene-ethylene/butene block copolymer resin 1: li Changrong chemical, brand SEBS 9552, styrene content 33%;

hydrogenated styrene-ethylene/butene block copolymer resin 2: li Changrong chemical, No. SEBS 9558, styrene content 40%;

hydrogenated styrene-ethylene/butene block copolymer resin 3: li Changrong chemical, trade mark SEBS 9543, styrene content 20%;

ABS-g-GMA: self-making;

electromagnetic shielding master batch 1: shandong Dazhan, PC C1508, multiwalled carbon nanotube content 15 wt%;

electromagnetic shielding master batch 2: shanghai nano plastic alloy, PC NS109, and the content of the multi-walled carbon nano tube is 15 wt%;

electromagnetic shielding master batch 3: custom made by Shandong Dachang, PC C1520, multi-walled carbon nanotubes content 20 wt%;

electromagnetic shielding master batch 4: shandong Dazhao, PC C1505, multiwalled carbon nanotubes content 5 wt%;

electromagnetic shielding master batch 5: the PC C1530 multi-wall carbon nano tube is prepared by Shandong Dachang, and the content is 30 wt%;

multi-walled carbon nanotubes: sigmaaldrich, MWNT;

auxiliary agent 1: 1:1 mixture of antioxidant, hindered phenol antioxidant 1076 and phosphite ester antioxidant PEP-36, commercially available;

auxiliary agent 2: light stabilizers, benzotriazole-based UV absorbers, commercially available;

and (3) auxiliary agent: lubricants, pentaerythritol stearate, commercially available;

the auxiliary agents used in the examples of the invention and the comparative examples have the same source.

The preparation methods of the polycarbonate alloy materials of the examples and the comparative examples:

according to the proportion shown in the table 1, the components are uniformly mixed, then the mixture is added into a double-screw extruder, and the polycarbonate alloy material is prepared through melt blending, extrusion and granulation; wherein, the temperature of each section of the main machine cylinder (from the feed inlet to the outlet of the machine head) is controlled to be 220 ℃, 235 ℃, 245 ℃, 250 ℃ and 245 ℃.

The related performance test method comprises the following steps:

(1) and (3) evaluating the electromagnetic shielding effect: the effectiveness of the shield is measured by the shielding effectiveness. The shielding effectiveness is tested according to the standard GJB 6190-2008;

table 1: evaluation of electromagnetic Shielding effectiveness (generally, the standard of industrial application is 30-60dB, and the standard of military is 60-120 dB)

Shielding effectiveness	<10 dB	10~30 dB	30~60 dB	60~90 dB	>90 dB
						Shielding effect	Nothing (Difference)	Is poor	Medium and high grade	Is good	Superior food

(2) Evaluation of noise hazard value: the test was conducted according to the German society for automotive industries standard VDA 230-.

Table 2: examples 1-10 composition ratios (in parts by weight) and associated Performance test results

	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/butylene block copolymer resin 1	5	5	5	5	5			8	3	5
Hydrogenated styrene-ethylene/butylene block copolymer resin 2						5
											Hydrogenated styrene-ethylene/butylene 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 agent	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 agent	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 1-10 proportion of each component (by weight) and relevant performance test results

	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/butylene 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
Multiwalled carbon nanotube										1.8
											Antioxidant agent	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 agent	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

It is seen from the above examples and comparative examples that, in the polycarbonate and styrene resin material system, the electromagnetic shielding master batch containing the multi-wall carbon nanotube component and taking the PC as the base material is added with the hydrogenated styrene-ethylene/butylene block copolymer resin, so that the electromagnetic shielding property and the noise reduction property of the material can be remarkably improved.

Comparative example 1, ABS-g-GMA was used instead of hydrogenated styrene-ethylene/butylene block copolymer resin, and it did not have good noise reduction and electromagnetic shielding effects;

comparative example 2, the hydrogenated styrene-ethylene/butylene block copolymer resin was excessively added to deteriorate noise reduction and electromagnetic shielding effects;

comparative example 3/4, too little hydrogenated styrene-ethylene/butylene block copolymer resin or no hydrogenated styrene-ethylene/butylene block copolymer resin was added, the material had a high noise risk value and the shielding effectiveness was low;

comparative example 7, the electromagnetic shielding master batch is excessively added, and although the electromagnetic shielding master batch has 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, the electromagnetic shielding master batch is added too little or not, the material shielding effectiveness is poor;

in comparative example 10, the electromagnetic shielding effect and noise reduction effect were poor when the multi-walled carbon nanotube was directly added.

Claims (9)

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 an auxiliary agent.

2. The polycarbonate alloy material of claim 1, wherein the hydrogenated styrene-ethylene/butylene block copolymer resin has a styrene content of 30 to 40 wt%; preferably, the styrene content of the hydrogenated styrene-ethylene/butylene block copolymer resin is 31 to 34 wt%.

3. The carbonate alloy material of claim 1, wherein the electromagnetic shielding master batch is a PC master batch prepared by taking PC as a base material and adding 14-20wt% of multi-walled carbon nanotubes.

4. The polycarbonate alloy material according to claim 1, wherein the polycarbonate resin has a melt index of 8 to 15g/10min at 300 ℃ under 1.2 kg; preferably, the polycarbonate resin has a melt index of 9 to 11g/10min at 300 ℃ under 1.2 kg.

5. The polycarbonate alloy material according to claim 1, wherein the styrene resin is selected from one or more of acrylonitrile-butadiene-styrene resin, acrylonitrile-acrylate-styrene resin or acrylonitrile-ethylene propylene diene monomer-styrene resin; preferably, the styrenic resin is selected from the group consisting of acrylonitrile-butadiene-styrene resins.

6. The polycarbonate alloy material of claim 6, wherein the styrenic resin has a melt index of 15 to 25g/10min at 220 ℃ under 10 kg; preferably, the styrene-based resin has a melt index of 18 to 22 g/10min at 220 ℃ under 10 kg.

7. The polycarbonate alloy material as defined in claim 1, wherein the auxiliary agent is selected from one or more of an antioxidant, a light stabilizer, a lubricant or a toner.

8. The method for preparing the polycarbonate alloy material according to any one of claims 1 to 7, comprising the steps of:

uniformly mixing the components according to the proportion, adding the mixture into a double-screw extruder, and performing melt blending extrusion granulation to prepare the polycarbonate alloy material; wherein the melting temperature is 220-250 ℃.

9. Use of the polycarbonate alloy material according to any one of claims 1-7 in the automotive field.