CN102942789A - High abrasion polyetherimide composite material and method for preparing same - Google Patents
High abrasion polyetherimide composite material and method for preparing same Download PDFInfo
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- CN102942789A CN102942789A CN2012104994869A CN201210499486A CN102942789A CN 102942789 A CN102942789 A CN 102942789A CN 2012104994869 A CN2012104994869 A CN 2012104994869A CN 201210499486 A CN201210499486 A CN 201210499486A CN 102942789 A CN102942789 A CN 102942789A
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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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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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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- 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
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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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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- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
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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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
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Abstract
The invention discloses a high abrasion polyetherimide composite material. The high abrasion polyetherimide composite material consists of the following materials in percentage by weight: 80-99% of polyetherimide, 0.5-20% of polytetrafluoroethylene and 0.5-2.5% of lubricating agent. The invention further discloses a method for preparing the high abrasion polyetherimide composite material. According to the high abrasion polyetherimide composite material, polytetrafluoroethylene is adopted to improve the friction performance of polyetherimide, on one hand, the friction factor of the composite material can be greatly reduced, the abrasion loss is reduced, and moreover, the other physical and mechanical performances of the composite material cannot be influenced; and on the other hand, compared with the friction materials of graphite, molybdenum disulfide and the like, polytetrafluoroethylene is white, so that the high abrasion polyetherimide composite material can be conveniently dyed into other colors.
Description
Technical field
The present invention relates to the engineering plastics technical field, be specifically related to a kind of high abrasion polyetherimide composite material and preparation method thereof.
Background technology
Polyetherimide (being called for short PEI) is a kind of thermoplastic special engineering plastics, and its Heat stability is good, second-order transition temperature are 215 ℃, and use temperature can reach 170 ℃ continuously; And (oxygen index is greater than 47 to have excellent flame retardant properties, the amount of being fuming is low), toughness, radiation resistance and chemical proofing are strong, also have in addition good dielectric properties, in the frequency of broadness and temperature range stable specific inductivity and dielectric loss value and high dielectric strength are arranged.The PEI goods are widely used in the fields such as Aeronautics and Astronautics, electrical equipment, machinery, chemical industry, microelectronics.Because its special performance often is selected to structural timber, frictional wear material and temperature-resistant material.This intensity to material, rub resistance wearing and tearing and high temperature dimensional stability have proposed high request.Yet pure PEI frictional coefficient and wear rate are bigger than normal, should not be used as lubricant.
The people such as the Wang Liqin of Harbin Institute of Technology have delivered " graphite-filled polyetherimide tribological property is analyzed " (" lubricated and sealing " the 10th phase of the 32nd volume), the document has been studied the friction and wear behavior of the graphite-filled PEI based composites of different content, adopting the wear-resisting polyetherimide composite material color of the method preparation is black, the selection needs that are unfavorable for goods, limit the range of application of product, and adopted the physical and mechanical properties of the matrix material of the method preparation also significantly to reduce than PEI.In addition, have no Research Literature and the patent report of other wear-resisting polyetherimide both at home and abroad.
Summary of the invention
The first goal of the invention of the present invention is to overcome deficiency and the defective that current techniques exists, and solves the shortcoming that the polyetherimide frictional coefficient is large, wearing and tearing are high, and the high abrasion polyetherimide composite material that a kind of frictional coefficient is low, wearing and tearing are little is provided
The second goal of the invention of the present invention is to provide the preparation method of the high abrasion polyetherimide composite material that a kind of frictional coefficient is low, wearing and tearing are little.
For realizing the present invention's the first goal of the invention, the present invention adopts following technical scheme: a kind of high abrasion polyetherimide composite material is made of by mass percentage following material:
Polyetherimide: 80～99%;
Tetrafluoroethylene: 0.5～20%;
Lubricant 0.5～2.5%.
The present invention is preferred, and described polyetherimide is to be got in 200-300 ℃ of polycondensation in dimethylacetamide solvent by bisphenol A-type dianhydride, mphenylenediamine and telogen, and its density is 1.27 ± 0.02g/cm
3, second-order transition temperature is 210-220 ℃; Preferred this polyetherimide can provide the higher resistance toheat of matrix material and physical and mechanical properties.
The present invention is preferred, and described telogen is phthalic anhydride or aniline, and described conditioning agent can effectively be controlled the molecular weight and molecualr weight distribution of polyetherimide.
The present invention is preferred, and described tetrafluoroethylene is Powdered, and relative molecular mass is 500-800 ten thousand, degree of crystallinity 92-95%, and melt temperature 320-340 ℃, preferred tetrafluoroethylene can provide the higher wear resisting property of polyetherimide composite material and processing characteristics.
The present invention is preferred, and described lubricant is one or both in pentaerythritol stearate, the silicone powder.
The present invention is preferred, and described lubricant is decomposition temperature greater than 375 ℃ silicone powder.
For realizing the present invention's the second goal of the invention, the following technical scheme of the bright employing of way: a kind of preparation method of high abrasion polyetherimide composite material may further comprise the steps:
(1) polyetherimide is positioned in 150-180 ℃ the vacuum drying oven dry 4-6 hour, then according to a certain ratio accurately weighing polyetherimide, tetrafluoroethylene, lubricant join and stir 5～20 minutes in the homogenizer;
The above-mentioned material that (2) will stir joins in the hopper of parallel double-screw extruder, setting each from the hopper to the die head of forcing machine section temperature is respectively: 260～290 ℃, 310～320 ℃, 330～350 ℃, 330～350 ℃, 330～350 ℃, 340～360 ℃, the screw speed of main frame is 250～330r/min, and the rotating speed of hopper feed screw rod is 24～35r/min, and then the material blended melting is extruded a bar;
(3) carry by the steel transport tape through extruding dies grain bar out above-mentioned, be provided with 3-6 fan above transport tape the grain bar is cooled off, the bar after air-dry enters dicing machine and carries out pelletizing.
Beneficial effect of the present invention:
(1) tetrafluoroethylene is the minimum a kind of plastics of frictional coefficient in the plastics, and has high temperature resistant, a corrosion-resistant and excellent electric property, adopt tetrafluoroethylene to improve the frictional behaviour of polyetherimide, can greatly reduce on the one hand the frictional coefficient of matrix material, the amount of reducing wear, and can not affect other physical and mechanical properties of matrix material; On the other hand, compare the friction materialss such as graphite, molybdenumdisulphide, tetrafluoroethylene can be dyed other color easily originally as white;
(2) polyetherimide composite material of the present invention adopts conveying belt to carry when extruding pelletization, first the grain bar is passed through the tank water-cooled with traditional, and then air-dry tractive manner is compared, the method can effectively reduce the water ratio of matrix material, thereby reduce the oven dry cost of material before injection molding, improve over-all properties and the job efficiency of material;
(3) composite material preparation process of the present invention is simple, cost is lower, can process at the twin screw extruder of routine, prepared high abrasion polyetherimide composite material has high lubricated, low characteristic of wearing and tearing, the comprehensive physical mechanical property is excellent, can be applied to as a kind of solid self-lubricant material the fields such as Aeronautics and Astronautics, machinery, chemical industry.
Embodiment
A kind of high abrasion polyetherimide composite material disclosed by the invention and preparation method thereof, by mass percentage cubage comprises: polyetherimide 80～99%, tetrafluoroethylene 0.5～20%, lubricant 0.5～2.5%.Wherein, tetrafluoroethylene can effectively reduce the frictional coefficient of polyetherimide as lubricant, improve its polishing machine, on the other hand, tetrafluoroethylene can not cause on the color of matrix material too large impact as a kind of white powder, can dye easily other color; The adding of lubricant will effectively improve material in the course of processing with the friction of machinery equipment, reduce energy consumption, and the flowability and the release property that improve matrix material.
In following examples, used polyetherimide is the Ultem 1000-1000 of Saudi Arabia radical innovations company, and used tetrafluoroethylene is the M-33 of Daikin company, and lubricant is the silicone powder ST-LS100 that the star shellfish reaches (Beijing) chemical materials company limited.
Embodiment 1
Carry out proportioning by following mass percent composition: polyetherimide 98.5%, tetrafluoroethylene 1%, lubricant 0.5%.
At first polyetherimide is positioned in 150 ℃ the vacuum drying oven dry 4 hours, then with polyetherimide, tetrafluoroethylene, the lubricant of accurate weighing, joins in the homogenizer and stirred 5 minutes.
The above-mentioned material that stirs is joined in the hopper of parallel double-screw extruder, set each from the hopper to the die head of forcing machine section temperature and be respectively (totally six districts): 260 ℃, 310 ℃, 330 ℃, 350 ℃, 350 ℃, 340 ℃, the screw speed of main frame is 280r/min, and the rotating speed of hopper feed screw rod is 26r/min, and then the material blended melting is extruded;
Above-mentionedly be transported to dicing machine by the steel transport tape and carry out pelletizing through an extruding dies grain bar out, can obtain length is the high abrasion polyetherimide composite material of 3～5mm.
Embodiment 2
Carry out proportioning by following mass percent composition: polyetherimide 96.5%, tetrafluoroethylene 3%, lubricant 0.5%.
At first polyetherimide is positioned in 170 ℃ the vacuum drying oven dry 4 hours, then with polyetherimide, tetrafluoroethylene, the lubricant of accurate weighing, joins in the homogenizer and stirred 8 minutes;
The above-mentioned material that stirs is joined in the hopper of parallel double-screw extruder, set each from the hopper to the die head of forcing machine section temperature and be respectively (totally six districts): 270 ℃, 310 ℃, 330 ℃, 340 ℃, 340 ℃, 360 ℃, the screw speed of main frame is 280r/min, and the rotating speed of hopper feed screw rod is 29r/min, and then the material blended melting is extruded;
Above-mentionedly be transported to dicing machine by the steel transport tape and carry out pelletizing through an extruding dies grain bar out, can obtain length is the high abrasion polyetherimide composite material of 3～5mm.
Embodiment 3
Carry out proportioning by following mass percent composition: polyetherimide 94.2%, tetrafluoroethylene 5%, lubricant 0.8%.
At first polyetherimide is positioned in 180 ℃ the vacuum drying oven dry 4 hours, then with polyetherimide, tetrafluoroethylene, the lubricant of accurate weighing, joins in the homogenizer and stirred 5 minutes;
The above-mentioned material that stirs is joined in the hopper of parallel double-screw extruder, set each from the hopper to the die head of forcing machine section temperature and be respectively (totally six districts): 290 ℃, 320 ℃, 350 ℃, 350 ℃, 350 ℃, 360 ℃, the screw speed of main frame is 330r/min, and the rotating speed of hopper feed screw rod is 35r/min, and then the material blended melting is extruded;
Above-mentionedly be transported to dicing machine by the steel transport tape and carry out pelletizing through an extruding dies grain bar out, can obtain length is the high abrasion polyetherimide composite material of 3～5mm.
Embodiment 4
Carry out proportioning by following mass percent composition: polyetherimide 98.2%, tetrafluoroethylene 1%, lubricant 0.8%.
At first polyetherimide is positioned in 160 ℃ the vacuum drying oven dry 6 hours, then with polyetherimide, tetrafluoroethylene, the lubricant of accurate weighing, joins in the homogenizer and stirred 10 minutes;
The above-mentioned material that stirs is joined in the hopper of parallel double-screw extruder, set each from the hopper to the die head of forcing machine section temperature and be respectively (totally six districts): 280 ℃, 320 ℃, 340 ℃, 350 ℃, 350 ℃, 360 ℃, the screw speed of main frame is 310r/min, and the rotating speed of hopper feed screw rod is 30r/min, and then the material blended melting is extruded;
Above-mentionedly be transported to dicing machine by the steel transport tape and carry out pelletizing through an extruding dies grain bar out, can obtain length is the high abrasion polyetherimide composite material of 3～5mm.
Embodiment 5
Carry out proportioning by following mass percent composition: polyetherimide 79%, tetrafluoroethylene 20%, lubricant 1%.
At first polyetherimide is positioned in 180 ℃ the vacuum drying oven dry 4 hours, then with polyetherimide, tetrafluoroethylene, the lubricant of accurate weighing, joins in the homogenizer and stirred 15 minutes;
The above-mentioned material that stirs is joined in the hopper of parallel double-screw extruder, set each from the hopper to the die head of forcing machine section temperature and be respectively (totally six districts): 260 ℃, 310 ℃, 330 ℃, 350 ℃, 350 ℃, 360 ℃, the screw speed of main frame is 300r/min, and the rotating speed of hopper feed screw rod is 29r/min, and then the material blended melting is extruded;
Above-mentionedly be transported to dicing machine by the steel transport tape and carry out pelletizing through an extruding dies grain bar out, can obtain length is the high abrasion polyetherimide composite material of 3～5mm.
Comparative Examples 1
Carry out proportioning by following mass percent composition: polyetherimide 99.5%, lubricant 0.5%.
At first polyetherimide is positioned in 150 ℃ the vacuum drying oven dry 4 hours, then with polyetherimide, the lubricant of accurate weighing, joins in the homogenizer and stirred 5 minutes.
The above-mentioned material that stirs is joined in the hopper of parallel double-screw extruder, set each from the hopper to the die head of forcing machine section temperature and be respectively (totally six districts): 260 ℃, 310 ℃, 330 ℃, 350 ℃, 350 ℃, 340 ℃, the screw speed of main frame is 280r/min, and the rotating speed of hopper feed screw rod is 26r/min, and then the material blended melting is extruded;
Above-mentionedly be transported to dicing machine by the steel transport tape and carry out pelletizing through an extruding dies grain bar out, can obtain the polyetherimide composite material that length is 3～5mm.
The physical and mechanical property of resulting materials and wear resisting property are as shown in the table in above-described embodiment:
Claims (7)
1. high abrasion polyetherimide composite material is made of by mass percentage following material:
Polyetherimide: 80～99%;
Tetrafluoroethylene: 0.5～20%;
Lubricant 0.5～2.5%.
2. high abrasion polyetherimide composite material as claimed in claim 1, it is characterized in that: described polyetherimide is to be got in 200-300 ℃ of polycondensation in dimethylacetamide solvent by bisphenol A-type dianhydride, mphenylenediamine and telogen, and its density is 1.27 ± 0.02g/cm
3, second-order transition temperature is 210-220 ℃.
3. high abrasion polyetherimide composite material as claimed in claim 2, it is characterized in that: described telogen is phthalic anhydride or aniline.
4. high abrasion polyetherimide composite material as claimed in claim 1, it is characterized in that: described tetrafluoroethylene is Powdered, relative molecular mass is 500-800 ten thousand, degree of crystallinity 92-95%, melt temperature 320-340 ℃.
5. high abrasion polyetherimide composite material as claimed in claim 1, it is characterized in that: described lubricant is one or both mixing in pentaerythritol stearate, the silicone powder.
6. high abrasion polyetherimide composite material as claimed in claim 5 is characterized in that: described lubricant is decomposition temperature greater than 375 ℃ silicone powder.
7. such as the preparation method of the described arbitrary high abrasion polyetherimide composite material of claim 1-6, it is characterized in that may further comprise the steps:
(1) polyetherimide is positioned in 150-180 ℃ the vacuum drying oven dry 4-6 hour, then according to a certain ratio accurately weighing polyetherimide, tetrafluoroethylene, lubricant join and stir 5～20 minutes in the homogenizer;
The above-mentioned material that (2) will stir joins in the hopper of parallel double-screw extruder, setting forcing machine each heating zone temperature from the hopper to the die head is respectively: 260～290 ℃, 310～320 ℃, 330～350 ℃, 330～350 ℃, 330～350 ℃, 340～360 ℃, the screw speed of main frame is 250～330r/min, and the rotating speed of hopper feed screw rod is 24～35r/min, and then the material blended melting is extruded a bar;
(3) carry by the steel transport tape through extruding dies grain bar out above-mentioned, be provided with 3-6 fan above transport tape the grain bar is cooled off, the bar after air-dry enters dicing machine and carries out pelletizing.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104530694A (en) * | 2014-12-26 | 2015-04-22 | 广州市聚赛龙工程塑料有限公司 | Regenerated PA6 (polyamide 6)-base flame-retardant electric-insulating heat-conducting composite material, and preparation method and application thereof |
| CN105062069A (en) * | 2015-07-17 | 2015-11-18 | 中国科学院宁波材料技术与工程研究所 | Wear-resisting modified polyimide composite and preparation method thereof |
| CN110767404A (en) * | 2018-07-25 | 2020-02-07 | 南京滕达机械设备有限公司 | Ferrite magnetic material production line |
| CN111234527A (en) * | 2018-11-28 | 2020-06-05 | 合肥杰事杰新材料股份有限公司 | Wear-resistant polyetherimide composite material and preparation method thereof |
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| EP1177256B1 (en) * | 1999-04-28 | 2005-06-22 | General Electric Company | Compositions and methods for reduced food adhesion |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530694A (en) * | 2014-12-26 | 2015-04-22 | 广州市聚赛龙工程塑料有限公司 | Regenerated PA6 (polyamide 6)-base flame-retardant electric-insulating heat-conducting composite material, and preparation method and application thereof |
| CN105062069A (en) * | 2015-07-17 | 2015-11-18 | 中国科学院宁波材料技术与工程研究所 | Wear-resisting modified polyimide composite and preparation method thereof |
| CN105062069B (en) * | 2015-07-17 | 2017-09-01 | 中国科学院宁波材料技术与工程研究所 | Wear-resisting modified polyimide composite and preparation method thereof |
| CN110767404A (en) * | 2018-07-25 | 2020-02-07 | 南京滕达机械设备有限公司 | Ferrite magnetic material production line |
| CN111234527A (en) * | 2018-11-28 | 2020-06-05 | 合肥杰事杰新材料股份有限公司 | Wear-resistant polyetherimide composite material and preparation method thereof |
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| CN102942789B (en) | 2015-07-01 |
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Effective date of registration: 20151118 Address after: Conghua Ao town Guangzhou city Guangdong province 510940 Longtan Jubao industrial district (Village) Patentee after: Guangzhou Super-Dragon Engineering plastic Co., Ltd. Address before: Conghua Ao town Guangzhou city Guangdong province 510945 Longtan Jubao Industrial Zone Patentee before: Super-Dragon New Material Technology Co., Ltd. |
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Address after: Conghua Ao town Guangzhou city Guangdong province 510940 Longtan Jubao industrial district (Village) Patentee after: GUANGZHOU SUPER-DRAGON ENGINEERING PLASTICS CO., LTD. Address before: Conghua Ao town Guangzhou city Guangdong province 510940 Longtan Jubao industrial district (Village) Patentee before: Guangzhou Super-Dragon Engineering plastic Co., Ltd. |