CN107936455B - Regenerated ABS/HIPS alloy material based on in-situ chain extension repair and preparation method thereof - Google Patents
Regenerated ABS/HIPS alloy material based on in-situ chain extension repair and preparation method thereof Download PDFInfo
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- CN107936455B CN107936455B CN201711126328.8A CN201711126328A CN107936455B CN 107936455 B CN107936455 B CN 107936455B CN 201711126328 A CN201711126328 A CN 201711126328A CN 107936455 B CN107936455 B CN 107936455B
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a regenerated ABS/HIPS alloy material based on in-situ chain extension repair, which mainly comprises the following components in parts by mass: 100 parts of a mixture of waste ABS and waste HIPS, 1-5 parts of an ABS-based macromolecular chain extender and 1-5 parts of a HIPS-based macromolecular chain extender. Through the in-situ chain extension, in-situ compatibilization and toughening effects of the macromolecular chain extender, chain breakage growth and repair are realized, the phase interface is improved, the compatibility is increased, the glue content is improved, the regenerated plastic alloy material with reduced flow and excellent comprehensive performance is prepared, the waste is fully utilized, and the energy conservation and emission reduction are realized. The invention also discloses a preparation method of the regenerated alloy material.
Description
Technical Field
The invention belongs to the technical field of waste plastic regeneration, and particularly relates to a regenerated ABS/HIPS alloy prepared by modifying a macromolecule chain extender with in-situ chain extension, in-situ compatibilization and toughening functions.
Background
HIPS (high impact polystyrene) and ABS (acrylonitrile-butadiene-styrene copolymer) both have excellent comprehensive properties, are widely applied to household appliances, and have more homologous applications, for example, the two materials are mainly used for shells of various electric appliances. Therefore, when the waste household appliances are disassembled, a large amount of waste ABS and waste HIPS mixed materials are inevitably generated. Because the appearance and the density of the waste HIPS and the waste ABS are similar, the mixture of the waste HIPS and the waste ABS is difficult to separate effectively or has higher separation cost; in addition, the mixture has poor compatibility and is aging material with serious performance deterioration, so that the mixture is usually used as filler with reduced cost or is subjected to modification regeneration respectively after being sorted with high cost.
Structural analysis shows that rubber phases in the waste HIPS and the waste ABS are oxidized into groups such as hydroxyl, carboxyl and the like, and the molecular structure is changed such as fracture rearrangement and the like, so that the method directly results in the following steps: 1) the main chain maintaining the main macro-mechanical properties in the waste material is broken, and the properties are seriously deteriorated; 2) the rubber phase in the waste HIPS and the waste ABS is greatly influenced, on one hand, the comprehensive mechanical property is reduced due to the reduction of the interface bonding force of the rubber phase and the matrix phase, and on the other hand, the toughness is more remarkably deteriorated due to the remarkable reduction of the rubber content; 3) the compatibility of the waste HIPS and the waste ABS is limited, and the performance of the recycled material is inevitably further reduced by directly and forcibly mixing and modifying the waste HIPS and the waste ABS.
Aiming at the problems, if hydroxyl and carboxyl active groups generated after the waste HIPS and the waste ABS are aged can be fully utilized, the chain extension of a molecular chain degraded by aging of a mixture can be directly and synchronously performed, a phase interface is improved, the compatibility is increased, the glue content is improved, a regenerated alloy material with double advantages of reduced flow (separation-free process) and high value-added regeneration can be obtained, and the application prospect of the regenerated alloy material is certainly greatly enhanced.
Disclosure of Invention
The invention aims to solve the first technical problem of providing a regenerated ABS/HIPS alloy material based on in-situ chain extension repair, wherein the regenerated alloy material improves a phase interface, increases compatibility, improves rubber content by utilizing the in-situ chain extension, in-situ compatibilization and toughening effects of a macromolecular chain extender, prepares a regenerated plastic alloy material with reduced flow and excellent comprehensive performance, fully utilizes wastes, and realizes energy conservation and emission reduction.
The second technical problem to be solved by the invention is to provide the preparation method of the regenerated ABS/HIPS alloy material based on in-situ chain extension repair.
The first technical problem of the present invention is achieved by the following technical solutions: a regenerated ABS/HIPS alloy material based on in-situ chain extension repair is mainly composed of the following components in parts by mass:
waste ABS and waste HIPS mixtures: 100
ABS-based macromolecular chain extender: 1 to 5
HIPS-based macromolecular chain extender: 1 to 5.
In the regenerated ABS/HIPS alloy material based on in-situ chain extension repair:
as a preferred embodiment in the present invention, the ABS-based macromolecular chain extender according to the present invention is preferably acrylonitrile-butadiene-styrene copolymer (ABS) grafted oxazoline (ABS-g-OZ), which is preferably prepared by the following method: the ABS-based macromolecular chain extender is prepared by taking ABS high-rubber powder, ethanolamine and zinc acetate as raw materials and 2, 6-dichlorotoluene as a solvent, placing the raw materials in a reaction vessel, carrying out condensation reflux reaction for 2-3 h (preferably 3h) at 170-180 ℃ (preferably 170 ℃), and then freezing, precipitating, filtering, and drying.
In the preparation method of the ABS-based macromolecular chain extender:
the mass part ratio of the ABS high rubber powder, the ethanolamine and the zinc acetate is preferably 100: (30-50): (2-3), more preferably 100: 50: 3.
the dosage of the 2, 6-dichlorotoluene is preferably 7-10 times of the total mass of the raw material ABS high rubber powder.
The freeze precipitation is preferably carried out in ethanol.
The HIPS-based macromolecular chain extender is preferably one of high impact polystyrene grafted maleic anhydride (HIPS-g-MAH) and styrene-ethylene-butadiene-styrene copolymer grafted maleic anhydride (SEBS-g-MAH).
The mixture of the waste ABS and the waste HIPS is preferably a flaky material obtained by crushing and homogenizing the mixture of the waste ABS and the waste HIPS.
The second technical problem to be solved by the present invention is realized by the following technical solutions: the preparation method of the regenerated ABS/HIPS alloy material based on in-situ chain extension repair comprises the following steps: and mixing the mixture of the waste ABS and the waste HIPS and the HIPS-based macromolecular chain extender according to the dosage relation to obtain a mixed material, adding the mixed material from a main feeding device of a double-screw extruder to melt, controlling the rotating speed of a screw to be 25-30 rpm, adding the ABS-based macromolecular chain extender from a processing fourth area of the double-screw extruder according to the dosage relation to be mixed with the melted mixed material, and extruding, drawing, cooling and granulating to obtain the regenerated ABS/HIPS alloy material based on in-situ chain extension repair.
In the preparation method of the regenerated ABS/HIPS alloy material based on in-situ chain extension repair, the steps of:
the processing temperature area of the double-screw extruder is preferably 210-235 ℃.
Further, the temperature of the six processing zones of the double-screw extruder is set as follows in sequence: 210 ℃, 215 ℃, 225 ℃, 235 ℃, 235 ℃ and 220 ℃.
The ABS-based macromolecular chain extender added in the invention can play the following three key roles simultaneously:
(1) active oxazoline groups on a molecular chain can react with carboxyl groups generated on an aged chain of the waste ABS and the waste HIPS under an extrusion condition to carry out in-situ chain extension reaction, so that the compatibility of the waste ABS and the waste HIPS base material is improved while chain scission growth and restoration are realized;
(2) the ABS main chain of the ABS-based macromolecular chain extender is similar to the structure of the waste ABS main chain, so that the problem of weakened interfacial force after the waste ABS is aged is greatly improved, and the interface repair is realized;
(3) the ABS-based macromolecular chain extender is also a functionalized ABS high-rubber powder, and the addition of the ABS-based macromolecular chain extender is equivalent to the improvement of the overall rubber content of the regenerated alloy material, thereby playing a toughening role.
The HIPS-based macromolecular chain extender added in the invention has the following key functions besides the functions of chain extending the waste ABS and the waste HIPS in situ, compatibilization, improving the aged interface of the waste HIPS to improve the interface adhesive force and introducing new materials to improve the glue content to toughen the waste HIPS, which are similar to the functions of the ABS-based macromolecular chain extender:
under the extrusion processing condition, oxazoline is a carboxyl reaction type chain extender, so that in order to further improve the chain extension modification effect of the ABS-based macromolecular chain extender, the anhydride type HIPS-based macromolecular chain extender is added from the main feeding device, and can react with hydroxyl in an aged molecular chain of a mixed system to supplement and generate new carboxyl, thereby increasing the chain extension potential of the oxazoline type ABS-based macromolecular chain extender used subsequently; then, ABS-based macromolecular chain extender is added into a charging opening in the middle of the machine barrel in the fourth area, and stepped reaction is realized by feeding materials respectively, so that in-situ chain extension repair can be fully and effectively carried out, and excessive consumption caused by direct reaction of anhydride and oxazoline groups when HIPS-based macromolecular chain extender and ABS-based macromolecular chain extender are directly blended is avoided, and the influence on the chain extension repair of waste HIPS and waste ABS is avoided.
On the other hand, the temperature and the screw rotation speed have great influence on the comprehensive performance of the regenerated alloy. Longer extrusion residence times and higher temperatures are advantageous to promote in situ chain extension reactions during extrusion, but too long processing times and too high temperatures may in turn lead to decomposition of the recycled material. By controlling the rotation speed of the screw to be 25-30 rpm and the processing temperature zone to be 210-235 ℃, the regenerated material can be prevented from being decomposed on the premise of not influencing the in-situ chain extension effect.
The invention has the following advantages:
(1) the invention simultaneously uses two different types of macromolecular chain extenders to carry out in-situ chain extension repair on the mixture of the waste ABS and the waste HIPS for the first time to prepare the regenerated alloy, and the macromolecular chain extender simultaneously plays roles of in-situ chain extension, in-situ compatibilization and toughening in the preparation process of the regenerated alloy, thereby obtaining the high value-added regenerated material with wide application prospect;
(2) aiming at the characteristics of the waste ABS and HIPS mixed waste which is difficult to sort, the high-performance polymer alloy is directly prepared from the mixed plastic by analyzing the microscopic morphology and the interfacial compatibility and based on the reaction selectivity of the chain extension functional group, and the high-performance polymer alloy has the dual advantages of reduced flow (no sorting process) and high added value regeneration;
(3) the whole processing process of the invention uses conventional plastic processing equipment, and the reaction type extrusion is carried out by an optimized process, so that the invention can be conveniently popularized and applied;
(4) the invention provides a brand-new solution for the high-valued utilization of mixed waste plastics, also drives the development of the recycled plastic industry, simultaneously related products have strong market competitiveness, accord with the national policy of energy conservation and emission reduction, and have good social and economic benefits.
Detailed Description
Example 1
The regenerated ABS/HIPS alloy material based on in-situ chain extension repair provided by the embodiment mainly comprises the following components in parts by mass:
waste ABS and waste HIPS mixtures: 100
ABS-based macromolecular chain extender: 5
HIPS-based macromolecular chain extender: 5.
wherein the macromolecular chain extender is ABS grafted oxazoline which is prepared by the following method: ABS high rubber powder, ethanolamine and zinc acetate are used as raw materials, 2, 6-dichlorotoluene is used as a solvent, the raw materials are placed in a reaction vessel, the temperature is adjusted to 170 ℃, the reaction vessel is subjected to cold reflux reaction for 3 hours, and then freezing, precipitation, suction filtration and drying are carried out, so that the macromolecular chain extender ABS grafted oxazoline is obtained.
The mass part ratio of the ABS high rubber powder, the ethanolamine and the zinc acetate is 100: 50: 3.
the dosage of the 2, 6-dichlorotoluene is 10 times of the total mass of the ABS high rubber powder.
Freezing the precipitate in ethanol.
The HIPS-based macromolecular chain extender is high impact polystyrene grafted maleic anhydride (HIPS-g-MAH), which can be referred to as: the HIPS/MA grafted copolymer is used for preparing HIPS/PA1010 blending system, and the commercial products can also be directly purchased.
The mixture of the waste ABS and the waste HIPS is a flaky material obtained by crushing and homogenizing the mixture of the waste ABS and the waste HIPS.
The preparation method of the regenerated ABS/HIPS alloy material based on in-situ chain extension repair comprises the following steps: and mixing the mixture of the waste ABS and the waste HIPS and the HIPS-based macromolecular chain extender according to the dosage relation to obtain a mixed material, adding the mixed material from a main feeding device of a double-screw extruder for melting, controlling the rotating speed of a screw to be 30rpm, adding the ABS-based macromolecular chain extender from a processing fourth area of the double-screw extruder according to the dosage relation to be mixed with the melted mixed material, and extruding, drawing, cooling and granulating to obtain the regenerated ABS/HIPS alloy material based on in-situ chain extension repair.
The temperature of the six processing areas of the double-screw extruder is set as follows in sequence: 210 ℃, 215 ℃, 225 ℃, 235 ℃, 235 ℃ and 220 ℃.
Example 2
The regenerated ABS/HIPS alloy material based on in-situ chain extension repair provided by the embodiment comprises the following components in parts by mass:
waste ABS and waste HIPS mixtures: 100
ABS-based macromolecular chain extender: 3
HIPS-based macromolecular chain extender: 5.
wherein the macromolecular chain extender is ABS grafted oxazoline which is prepared by the following method: ABS high rubber powder, ethanolamine and zinc acetate are used as raw materials, 2, 6-dichlorotoluene is used as a solvent, the raw materials are placed in a reaction vessel, the temperature is adjusted to be 180 ℃, after the cold reflux reaction is carried out for 2 hours, freezing, precipitating, filtering, and drying are carried out, and the macromolecular chain extender ABS grafted oxazoline is obtained.
The mass part ratio of the ABS high rubber powder, the ethanolamine and the zinc acetate is 100: 30: 2.
the dosage of the 2, 6-dichlorotoluene is 8 times of the total mass of the ABS high rubber powder as the raw material.
Freezing the precipitate in ethanol.
The HIPS-based macromolecular chain extender is styrene-ethylene-butadiene-styrene copolymer grafted maleic anhydride (SEBS-g-MAH), American Keteng FG1901
The mixture of waste ABS and waste HIPS was the same as in example 1.
The preparation method of the regenerated ABS/HIPS alloy material based on in-situ chain extension repair comprises the following steps: and mixing the mixture of the waste ABS and the waste HIPS and the HIPS-based macromolecular chain extender according to the dosage relation to obtain a mixed material, adding the mixed material from a main feeding device of a double-screw extruder for melting, controlling the rotating speed of a screw to be 25rpm, adding the ABS-based macromolecular chain extender from a processing fourth area of the double-screw extruder according to the dosage relation to be mixed with the melted mixed material, and extruding, drawing, cooling and granulating to obtain the regenerated ABS/HIPS alloy material based on in-situ chain extension repair.
The temperature of the six processing areas of the double-screw extruder is set as follows in sequence: 210 ℃, 215 ℃, 225 ℃, 235 ℃, 235 ℃ and 220 ℃.
Example 3
The regenerated ABS/HIPS alloy material based on in-situ chain extension repair provided by the embodiment mainly comprises the following components in parts by mass:
waste ABS and waste HIPS mixtures: 100
ABS-based macromolecular chain extender: 5
HIPS-based macromolecular chain extender: 3.
the ABS-based macromolecular chain extender was the same as in example 1.
HIPS-based macromolecular chain extender was the same as in example 1.
The mixture of waste ABS and waste HIPS was the same as in example 1.
The preparation method of the regenerated ABS/HIPS alloy material based on in-situ chain extension repair comprises the following steps: and mixing the mixture of the waste ABS and the waste HIPS and the HIPS-based macromolecular chain extender according to the dosage relation to obtain a mixed material, adding the mixed material from a main feeding device of a double-screw extruder for melting, controlling the rotating speed of a screw to be 30rpm, adding the ABS-based macromolecular chain extender from a processing fourth area of the double-screw extruder according to the dosage relation to be mixed with the melted mixed material, and extruding, drawing, cooling and granulating to obtain the regenerated ABS/HIPS alloy material based on in-situ chain extension repair.
The temperature of the six processing areas of the double-screw extruder is set as follows in sequence: 210 ℃, 215 ℃, 225 ℃, 235 ℃, 235 ℃ and 220 ℃.
The mechanical properties of the recycled ABS/HIPS alloy materials prepared in examples 1-3 are summarized in Table 1 below.
TABLE 1 summary of mechanical Properties of the recycled ABS/HIPS alloy materials prepared in examples 1-3
In table 1 above:
① the preparation method and steps are the same as example 1, but the ABS-based macromolecular chain extender and HIPS-based macromolecular chain extender are not added in the materials.
From the specific experimental data, the regenerated ABS/HIPS alloy directly prepared by the trinity effect of in-situ chain extension, in-situ compatibilization and toughening improves the mechanical property of the waste material comprehensively, and particularly improves the impact strength which is more sensitive to the molecular weight of the main chain, the molecular chain structure and the phase interface effect by 4.5-5.6 times greatly. The regenerated alloy product with the comprehensive mechanical property can be applied to the fields of various electrical appliances, building materials and the like, and the process reduction has the environmental protection property, so that the product has good market prospect not only from the national policy support level but also from the market competitiveness level.
The embodiment is a preferred embodiment of the invention, and the HIPS-based macromolecular chain extenders HIPS-g-MAH and SEBS-g-MAH selected in the embodiment are obtained from commercially available existing products.
However, the embodiments of the present invention are not limited by the above examples, and the raw materials such as the ABS-based macromolecular chain extender, the mixture of the waste ABS and the waste HIPS selected in the above embodiments can also be selected from commercially available products with similar properties, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent substitution modes, and all are included in the scope of the present invention.
Claims (5)
1. A regenerated ABS/HIPS alloy material based on in-situ chain extension repair is characterized by mainly comprising the following components in parts by mass:
waste ABS and waste HIPS mixtures: 100
ABS-based macromolecular chain extender: 1 to 5
HIPS-based macromolecular chain extender: 1-5;
the ABS-based macromolecular chain extender is acrylonitrile-butadiene-styrene copolymer grafted oxazoline;
the HIPS-based macromolecular chain extender is one of high impact polystyrene grafted maleic anhydride and styrene-ethylene-butadiene-styrene copolymer grafted maleic anhydride.
2. The in-situ chain extension repair-based regenerated ABS/HIPS alloy material as claimed in claim 1, wherein: the mixture of the waste ABS and the waste HIPS is a flaky material obtained by crushing and homogenizing the mixture of the waste ABS and the waste HIPS.
3. The preparation method of the regenerated ABS/HIPS alloy material based on in-situ chain extension repair as claimed in claim 1 or 2, which is characterized by comprising the following steps: and mixing the mixture of the waste ABS and the waste HIPS and the HIPS-based macromolecular chain extender according to the dosage relation to obtain a mixed material, adding the mixed material from a main feeding device of a double-screw extruder to melt, controlling the rotating speed of a screw to be 25-30 rpm, adding the ABS-based macromolecular chain extender from a processing fourth area of the double-screw extruder according to the dosage relation to be mixed with the melted mixed material, and extruding, drawing, cooling and granulating to obtain the regenerated ABS/HIPS alloy material based on in-situ chain extension repair.
4. The preparation method of the in-situ chain extension repair-based regenerated ABS/HIPS alloy material as claimed in claim 3, wherein the preparation method comprises the following steps: the processing temperature zone of the double-screw extruder is 210-235 ℃.
5. The preparation method of the in-situ chain extension repair-based regenerated ABS/HIPS alloy material as claimed in claim 4, wherein the preparation method comprises the following steps: the six processing zones of the double-screw extruder are set to be 210 ℃, 215 ℃, 225 ℃, 235 ℃, 235 ℃ and 220 ℃ in sequence.
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| CN112694702B (en) * | 2020-12-08 | 2022-09-16 | 中国电器科学研究院股份有限公司 | Regenerated HIPS/PPO alloy material and preparation method thereof |
| CN112724571B (en) * | 2020-12-08 | 2023-01-13 | 中国电器科学研究院股份有限公司 | Regenerated alloy material based on chemical and physical common modification and preparation method thereof |
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| WO2003086733A1 (en) * | 2002-04-12 | 2003-10-23 | Mba Polymers, Inc. | Multistep separation of plastics |
| CN104419108A (en) * | 2013-08-29 | 2015-03-18 | 合肥杰事杰新材料股份有限公司 | Bamboo powder/acrylonitrile-butadiene-styrene composite material and preparation method thereof |
| CN105462150A (en) * | 2015-12-09 | 2016-04-06 | 佳易容相容剂江苏有限公司 | ABS-HIPS (acrylonitrile-butadiene-styrene/high impact polystyrene) alloy and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003086733A1 (en) * | 2002-04-12 | 2003-10-23 | Mba Polymers, Inc. | Multistep separation of plastics |
| CN104419108A (en) * | 2013-08-29 | 2015-03-18 | 合肥杰事杰新材料股份有限公司 | Bamboo powder/acrylonitrile-butadiene-styrene composite material and preparation method thereof |
| CN105462150A (en) * | 2015-12-09 | 2016-04-06 | 佳易容相容剂江苏有限公司 | ABS-HIPS (acrylonitrile-butadiene-styrene/high impact polystyrene) alloy and preparation method thereof |
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Address after: 510302 No. 204 Xingang West Road, Haizhu District, Guangzhou City, Guangdong Province Applicant after: China Electrical Appliance Research Institute Co., Ltd. Address before: 510300 No. 204 Xingang West Road, Haizhu District, Guangzhou City, Guangdong Province Applicant before: China National Electric Apparatus Research Institute Co., Ltd. |
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