CN1252167C - Method for preparing composite material capable of forming in situ conductive microfiber network - Google Patents
Method for preparing composite material capable of forming in situ conductive microfiber network Download PDFInfo
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Abstract
The present invention discloses a method for preparing composite material capable of forming an in-situ conductive microfiber network. 70 to 95 weight portions of thermoplastic plastics with a low melting point, 5 of 30 weight portions of thermoplastic plastics with a high melting point, and 7.5 to 30 weight portions of conductive filling material added in per 100 weight portions of the mixture of the two kinds of plastics are used as raw material; the composite material is prepared by the technical steps and conditions such as raw material drying, mother material preparation, obtained produces melting, mixing together and extrusion, thermal stretching; quick cooling, granulation, etc. The inner conductive filling material of the composite material prepared by the method of the present invention is put in fiber phases with a high melting point; the fiber phases can also form the conductive network in processed and molded products; consequently, added conductive filler material is little; the conductive percolation value of the composite material is greatly reduced; the processability and the mechanical property of the composite material can not be influenced; reversely, in-situ microfiber has a certain reinforcing action to the composite material. The method of the present invention has the advantages of simple technique, easy control, and low requirements of devices; the method also has the advantages that all used devices process all plastics, and the investment is low.
Description
One, technical field
The invention belongs to the conducting polymer composite preparing technical field, be specifically related to a kind of preparation method who forms the matrix material of original position conduction fento network.
Two, background technology
The volume specific resistance of most of macromolecular material bodies is all very high, about 10
10～10
20Between the Ω cm, when using as insulating material, its performance is very good.But with scientific and technological progress, the particularly development in field such as electronic industry, information technology, people are more and more many to the demand of macromolecular material electroconductibility, and are also more and more urgent, and conducting polymer composite is transported Ying Ersheng's just under this background.Conducting polymer composite can be divided into it structure-type and compound two big classes according to raw material is different with the preparation method.The structural conductive macromolecular material is also referred to as the intrinsic conduction macromolecular material, and most typical have polyacetylene (PA), polypyrrole (PPY), polyaniline (PANI), a Polythiophene (PTH) etc.Because big, the most indissoluble of this class material molecule rigidity is separated with fusion, difficult forming, the most of toxicity of doping agent are big, cost is high, so practical value is limited.Conductive polymeric composite is meant with the macromolecular material to be matrix, adds the heterogeneous compound system with conducting function that various conducting material obtain through dispersing and mixing, moulding, the many excellent specific properties that promptly both had macromolecular material, again can be according to using needs to regulate material electricity, mechanics and other performance in a big way, cost is lower, be easy to moulding and scale operation, thereby is subjected to people and extensively payes attention to.
But conductive polymeric composite has an important feature: when conductive filler material content was low, the volume specific resistance and the straight polymer of mixture were close; When conductive filler material content was increased to a certain threshold value, volume specific resistance sharply reduced.This phenomenon is called " exceed and ooze effect " (Percolation effect).The threshold value of conductive filler material add-on is commonly referred to " exceed and ooze threshold values " (Percolation threshold).These characteristics have become the biggest obstacle of restriction conductive polymeric composite development.Because when conductive filler material content was low, mixture was non-conductive, when filler content was higher, although mixture has been conducted electricity, processing characteristics and mechanical property reduced greatly.Therefore, overcome the deficiency of conductive polymeric composite, key is will be under processing characteristics that keeps necessity and mechanical property condition, and the conduction that reduces material exceedes oozes threshold values.
The appearance of in-situ composite also causes the great interest of people." original position is compound " is meant two kinds of limited polymkeric substance of consistency in the melt blending process, makes disperse phase because of being subjected to shearing, the distortion of stretching action streamwise, orientation, and (In-situ) forms fiber on the spot in matrix.Broad research is thermoplastic polymer (TP)/thermoplastic polymer (TP) in-situ composite at present, it is compared with TP/ macroscopic fiber (as glass, carbon fibre etc.) matrix material and TP/ TLCP (TLCP) type in-situ composite, have starting material wide material sources, moderate cost, processing forming good, to advantages such as equipment attrition are little, thereby be subjected to people's attention (Zhong-Ming Li, Ming-Bo Yang, etal.Polymer-Plastics Technology Engineering, 2002,41 (1): 19; Li Zhongming, Yang Mingbo etc., Chinese patent, ZL01128896.5).
Three, summary of the invention
The problem that the objective of the invention is contradiction between the conductive filler material content that exists at prior art and polymer composite processing characteristics and the mechanical property, a kind of preparation method who forms the matrix material of original position conduction fento network is provided, with under processing characteristics that keeps necessity and mechanical property condition, the conduction that reduces material exceedes oozes threshold values.
Preparation provided by the invention can form the method for the matrix material of original position conduction fento network, be to be 70～95 parts of low melting point thermoplasticss, 5～30 parts of high melt point thermoplastic plastics and to add weight part by two kinds of plastics before per 100 parts be 7.5～30 parts conductive filler material, be prepared by following processing step and condition with weight part:
(1) drying is descended above-mentioned low melting point thermoplastics, high melt point thermoplastic plastics and conductive filler material dry 8～24 hours at 70～140 ℃ respectively, control water ratio＜0.01%;
(2) melting mixing was put into mill or Banbury mixer with cooled high melt point thermoplastic plastics of drying and conductive filler material by proportioning, made masterbatch at 200～290 ℃ of following melting mixing 5-25 of temperature minutes;
(3) pulverizing is broken into particulate with the cooling of melting mixing gained masterbatch, and particle diameter is 1～5mm;
(4) drying is descended gained masterbatch after the fragmentation dry 8～16 hours at 70～140 ℃, control water ratio＜0.01%;
(5) melting mixing is extruded and the dried masterbatch of fragmentation and low melting point thermoplastics are placed the forcing machine melting mixing in proportion and is extruded, and extrusion temperature is 175～295 ℃, 220～280 ℃ of die temperatures, 10～200 rev/mins of extruder screw rotating speeds;
(6) the material bar that will extrude that stretches carries out thermal stretch under normal temperature air, and hot-draw ratio is controlled to be 2～20;
(7) to force cooling that the material bar behind the drawn is immersed water temperature be to force cooling in 0～20 ℃ the cooling trough, then granulation.
High melt point thermoplastic plastics that the present invention is used and low melting point thermoplastics are meant that common processing temperature difference between the two generally should be greater than 30 ℃, and the low melting point thermoplastics should not labile plastics under high melt point thermoplastic processing of plastic temperature.
The present invention processes high melt point thermoplastic plastics, low melting point thermoplastics and conductive filler material according to a certain ratio by " masterbatch preparation-melt blending is extruded-thermal stretch-quenching " provided by the invention method, in the course of processing, the masterbatch that forms by high melt point thermoplastic plastics and conductive filler material blend shear and the drawing force field action under original position form micron or the fiber of submicron order, and fento is preserved by quick cooling.After granulation, obtain the finished product of the present invention---can form the matrix material (CEMN) of original position conduction fento network.This matrix material can extrude, in the reprocessing process such as injection moulding, mold pressing, in matrix resin, form network structure by original position conduction fento, this network structure has constituted the network path of electric transmission, and this network path is more perfect than the natural conductive path that is formed by general crystalline polymer crystallisation by cooling.Because conductive filler material only need effectively be filled in the original position fiber, make the fiber conduction can make whole system conduction.On macroscopic view, just reduce making the required filling adding amount of system conduction like this, promptly reduced system conduction excess effusion value.Owing to the minimizing of conductive filler material add-on, the processing characteristics of material itself and mechanical property just can not be affected simultaneously.
For the boundary strength that increases high melt point thermoplastic plastics and low melting point thermoplastics, the effect of stable phase form, when the present invention extrudes operation in melting mixing, also can be in per 100 parts of low melting point thermoplasticss and high melt point thermoplastic plastics, add weight part again and be 0～5 part interface modifier.Interface modifier is selected from any of ethylene vinyl acetate, ethylene methacrylate.
The low melting point thermoplastics that the present invention adds is selected from any of polyethylene, polypropylene, polystyrene and polycarbonate.Preferably polyethylene and polypropylene.
The high melt point thermoplastic plastics that the present invention adds are selected from any of polyethylene terephthalate, nylon, polybutylene terephthalate, polyphenylene sulfide.Preferred polyethylene terephthalate and nylon.
The conductive filler material that the present invention adds is selected from any of carbon black, Graphite Powder 99, carbon nanotube.Preferred carbon black, and its ultimate particle particle diameter 20～60 nanometers, DBP absorption value 50～300ml/100g.
Working method provided by the invention can adopt general device of plastic processing to implement, and employed major equipment is Banbury mixer or mill, crusher, single screw extrusion machine or twin screw extruder, flat and mouth mould and towing mechanism that runner seamlessly transits.
The various products of plastic shaping method moulding conductions such as the matrix material of the formed original position conduction fento network of the present invention preparation can be by injection moulding, extrude, compacting, as electric elements, communication device, mine transport pipe, auto-parts etc., but when forming process, need satisfy the electrical property that following primary condition just can not reduce material:
1, need before the forming process material is carried out drying, drying temperature is 70～120 ℃, and the time is 8～18 hours.If adopt vacuum drying oven (vacuum tightness be-0.04～-0.08MPa), then get lower bound time of drying, but need 8 hours at least;
2, the top temperature of forming process can only be controlled at the processing temperature of low melting point thermoplastics, and guaranteeing in molding process, established high melt point thermoplastic plastics/conductive filler material fento still can be present in the material with fibre shape and is not melted.
The present invention has the following advantages:
1, since with conductive filler material in the matrix material of the inventive method preparation be present in dystectic fiber mutually in, these fibers can form conductive network again mutually in the goods of post-treatment moulding, therefore the conductive filler material amount that adds is few, both greatly reduced the conduction excess effusion value of matrix material, can not influence the processibility and the mechanical property of matrix material again, also opposite because the existence of in-situ micro-fibril has certain enhancement to matrix material.
2, since conductive filler material of the present invention be present in dystectic fiber mutually in, so the matrix material of the formed original position of the inventive method preparation conduction fento network in from common use temperature to this temperature range of matrix fusing point electrical property and thermostability far above ordinary hot thermoplastic plastic/conductive filler material matrix material.
3, it is extensive to adopt method preparation of the present invention can form the raw material sources of matrix material of original position conduction fento network, selects widely, is easy to apply.
4, it is simple to form the composite technology of original position conduction fento network with the inventive method preparation, is easy to control, less demanding to equipment, and employed equipment is general device of plastic processing, reduced investment.
Four, description of drawings
Fig. 1 be the matrix material of embodiment 2 through reprocessing, and the molten electron scanning micrograph that removes the matrix material that forms original position conduction fento network of gained behind the matrix component of top layer.
Fig. 2 be the matrix material of embodiment 6 through reprocessing, and the molten electron scanning micrograph that removes the matrix material that forms original position conduction fento network of gained behind the matrix component of top layer.
Fig. 3 be the matrix material of embodiment 9 through reprocessing, and the molten electron scanning micrograph that removes the matrix material that forms original position conduction fento network of gained behind the matrix component of top layer.
Fig. 4 be the matrix material of embodiment 18 through reprocessing, and the molten electron scanning micrograph that removes the matrix material that forms original position conduction fento network of gained behind the matrix component of top layer.
Fig. 5 be the matrix material of embodiment 24 through reprocessing, and the molten electron scanning micrograph that removes the matrix material that forms original position conduction fento network of gained behind the matrix component of top layer.
Fig. 6 be the matrix material of embodiment 10 through reprocessing, and the molten matrix material brittle failure profile scanning electron micrograph that forms original position conduction fento network that removes gained behind the matrix component of top layer.
Five, embodiment
Embodiment given below is to specific descriptions of the present invention; be necessary to be pointed out that at this following examples only are used for that the present invention is further illustrated; can not be interpreted as limiting the scope of the invention, this art skilled person still belongs to protection scope of the present invention according to the invention described above content to nonessential improvement and the adjustment that the present invention makes.
Embodiment 1～22:
(1) drying was descended dry 8～24 hours control water ratio＜0.01% by the proportional quantity that table 1 provides respectively with low melting point thermoplastics, high melt point thermoplastic plastics and conductive filler material at 70～140 ℃;
(2) melting mixing was put into mill or Banbury mixer with cooled high melt point thermoplastic plastics of drying and conductive filler material by proportioning, made masterbatch at 200～290 ℃ of following melting mixing 5-25 of temperature minutes;
(3) pulverizing is broken into particulate with the cooling of melting mixing gained masterbatch, and particle diameter is 1～5mm;
(4) drying is descended gained masterbatch after the fragmentation dry 8～16 hours at 70～140 ℃, control water ratio＜0.01%;
(5) melting mixing is extruded and the dried masterbatch of fragmentation and low melting point thermoplastics are placed the forcing machine melting mixing in proportion and is extruded, and extrusion temperature is 175～295 ℃, 220～280 ℃ of die temperatures, 10～200 rev/mins of extruder screw rotating speeds;
(6) the material bar that will extrude that stretches carries out thermal stretch under normal temperature air, and hot-draw ratio is controlled to be 2～20;
(7) to force cooling that the material bar behind the drawn is immersed water temperature be to force cooling in 0～20 ℃ the cooling trough, then granulation.
Comparative example 1～9:
(1) set of dispense that provides by comparative example in the table 1 1～9 is put into mill than with conductive filler material and plastics, 160～200 ℃ of following melting mixing of temperature 10 minutes, takes off material, treats to be broken into after the material cooling granular.
(2) the granular matrix material of gained is placed press, pressing process condition routinely is pressed into sheet material, and is cut into test sample, is of a size of 4 * 10 * 30mm and carries out performance test, and performance test project and method are together down.
Electrical property and physical and mechanical properties for the original position composite conducting material of investigating the present invention preparation, the matrix material of gained is placed press, pressing process condition routinely is pressed into sheet material, and is cut into test sample, is of a size of 4 * 10 * 30mm and carries out following performance test:
Volume specific resistance: volume resistance is greater than 10
8Ω, with the test of ZC36 type high resistant instrument, volume resistance is less than 10
8Ω is with the test of DT-9205B type numerical value formula volt ohm-milliammeter;
Tensile strength and modulus: press the test of GB1040-79 regulation, rate of extension is 50 millimeters/minute; 25 ± 2 ℃ of temperature.
Table 2 is the common matrix material of the conducing composite material CEMN of the present invention preparation and conductive filler material/plastics some performance comparison according to above-mentioned testing method test.As shown in Table 2, the matrix material of the more common conductive filler material/plastics of electrical property of CEMN has increased significantly, and the CB content of the common matrix material of conductive filler material/plastics exceedes and oozes the about 15phr of threshold values, and only 7.5phr of threshold values is oozed in exceeding of CEMN.When CB content was all 10phr, the volume specific resistance of CEMN system was 4.36 * 10
4Ω cm, and common conducing composite material is up to 7.61 * 10
16Ω cm.
Form for the conducing composite material of observing the present invention preparation has adopted scanning electronic microscope to observe.The sample that is used for morphologic observation divides two kinds, and a kind of is to adopt hot dimethylbenzene (120 ℃) dissolving 2 hours, and the surface that makes after washing with pure dimethylbenzene; Another kind is to use cooled with liquid nitrogen 1 hour, the section that impact fracture obtains.Adopt the sample form of sem observation, see accompanying drawing 1～6, acceleration voltage 20KV.From Fig. 1～5 as can be seen, with the matrix material of the inventive method preparation really after reprocessing, formed original position conduction fento network.As can be seen from Figure 6, in the matrix material with the inventive method preparation, conductive filler material only is distributed in the in-situ micro-fibril, does not have conductive filler material in the matrix.
Table 1
| Embodiment | Component (weight part) | |||||||
| PET | PA6 | PE | PP | CB | GP | EVA | EAA | |
| 1 | 5 | 95 | 7.5 | |||||
| 2 | 10 | 90 | 15 | |||||
| 3 | 15 | 85 | 20 | |||||
| 4 | 20 | 80 | 16 | |||||
| 5 | 25 | 75 | 30 | |||||
| 6 | 30 | 70 | 7.5 | |||||
| 7 | 30 | 70 | 10 | |||||
| 8 | 30 | 70 | 15 | |||||
| 9 | 30 | 70 | 20 | |||||
| 10 | 15 | 85 | 7.5 | 2 | ||||
| 11 | 30 | 70 | 10 | 5 | ||||
| 12 | 10 | 90 | 15 | 2 | ||||
| 13 | 25 | 75 | 25 | 5 | ||||
| 14 | 5 | 95 | 7.5 | 3 | ||||
| 15 | 15 | 85 | 10 | |||||
| 16 | 30 | 70 | 25 | |||||
| 17 | 5 | 95 | 7.5 | |||||
| 18 | 15 | 85 | 15 | |||||
| 19 | 30 | 70 | 25 | 5 | ||||
| 20 | 5 | 95 | 7.5 | |||||
| 21 | 20 | 80 | 15 | |||||
| 22 | 30 | 70 | 30 | 4 | ||||
| Comparative example 1 | 100 | 5 | ||||||
| Comparative example 2 | 100 | 15 | ||||||
| Comparative example 3 | 100 | 30 | ||||||
| Comparative example 4 | 100 | 5 | ||||||
| Comparative example 5 | 100 | 10 | ||||||
| Comparative example 6 | 100 | 15 | ||||||
| Comparative example 7 | 100 | 5 | ||||||
| Comparative example 8 | 100 | 10 | ||||||
| Comparative example 9 | 100 | 15 | ||||||
Annotate: PET is a polyethylene terephthalate; PA6 is a nylon 6; PE is a polyethylene; PP is a polypropylene; CB is a carbon black; GP is a graphite; EVA is an ethylene vinyl acetate copolymer; EAA is an ethylene acrylic acid co polymer.
Table 2
| Material | Volume specific resistance (Ω .cm) | Tensile strength (MPa) | Tensile modulus (MPa) |
| Embodiment 1 | 8.60×10 9 | 20.64 | 390.78 |
| Embodiment 4 | 2.58×10 4 | 21.34 | 368.67 |
| Embodiment 6 | 4.60×10 9 | 21.68 | 376.36 |
| Embodiment 7 | 3.63×10 5 | 22.18 | 380.56 |
| Embodiment 8 | 5.94×10 3 | 24.69 | 387.07 |
| Embodiment 11 | 5.35×10 7 | 23.14 | 360.74 |
| | 3.23×10 7 | 22.43 | 346.83 |
| | 4.36×10 4 | 23.75 | 353.49 |
| Embodiment 16 | 2.66×10 3 | 25.20 | 378.45 |
| Embodiment 17 | 5.20×10 7 | 29.46 | 1005.70 |
| Embodiment 18 | 8.32×10 4 | 30.04 | 1080.23 |
| Embodiment 19 | 1.89×10 3 | 32.10 | 1150.67 |
| Embodiment 20 | 6.33×10 9 | 22.98 | 388.19 |
| Embodiment 21 | 5.32×10 5 | 24.03 | 392.25 |
| Embodiment 22 | 7.05×10 3 | 25.73 | 406.60 |
| Comparative example 1 | 2.51×10 17 | 24.28 | 221.02 |
| Comparative example 2 | 7.03×10 15 | 24.96 | 225.61 |
| Comparative example 3 | 1.29×10 9 | 25.32 | 242.52 |
| Comparative example 4 | 5.02×10 17 | 24.36 | 230.46 |
| Comparative example 5 | 4.34×10 16 | 25.10 | 238.94 |
| Comparative example 6 | 6.04×10 12 | 25.94 | 246.79 |
| Comparative example 7 | 8.20×10 17 | 30.15 | 786.50 |
| Comparative example 8 | 7.61×10 16 | 31.20 | 799.20 |
| Comparative example 9 | 6.73×10 16 | 31.48 | 803.56 |
Claims (10)
1. preparation method that can form the matrix material of original position conduction fento network, it is characterized in that with weight part be 70～95 parts of low melting point thermoplasticss, 5～30 parts of high melt point thermoplastic plastics and to add weight part by two kinds of plastics before per 100 parts be 7.5～30 parts conductive filler material, be prepared by following processing step and condition:
(1) drying is descended above-mentioned low melting point thermoplastics, high melt point thermoplastic plastics and conductive filler material dry 8～24 hours at 70～140 ℃ respectively, control water ratio＜0.01%;
(2) melting mixing was put into mill or Banbury mixer with cooled high melt point thermoplastic plastics of drying and conductive filler material by proportioning, made masterbatch at 200～290 ℃ of following melting mixing 5-25 of temperature minutes;
(3) pulverizing is broken into particulate with the cooling of melting mixing gained masterbatch, and particle diameter is 1～5mm;
(4) drying is descended gained masterbatch after the fragmentation dry 8～16 hours at 70～140 ℃, control water ratio＜0.01%;
(5) melting mixing is extruded and the dried masterbatch of fragmentation and low melting point thermoplastics are placed the forcing machine melting mixing in proportion and is extruded, and extrusion temperature is 175～295 ℃, 220～280 ℃ of die temperatures, 10～200 rev/mins of extruder screw rotating speeds;
(6) the material bar that will extrude that stretches carries out thermal stretch under normal temperature air, and hot-draw ratio is controlled to be 2～20;
(7) to force cooling that the material bar behind the drawn is immersed water temperature be to force cooling in 0～20 ℃ the cooling trough, then granulation.
2. the preparation method who forms the matrix material of original position conduction fento network according to claim 1, it is characterized in that when melting mixing is extruded, also can be in per 100 parts of low melting point thermoplasticss and high melt point thermoplastic plastics, add weight part again and be 0～5 part interface modifier.
3. the preparation method who forms the matrix material of original position conduction fento network according to claim 1 and 2 is characterized in that the low melting point thermoplastics that adds is selected from any of polyethylene, polypropylene, polystyrene, polyvinyl chloride and polycarbonate.
4. the preparation method who forms the matrix material of original position conduction fento network according to claim 1 and 2 is characterized in that the high melt point thermoplastic plastics that add are selected from any of polyethylene terephthalate, nylon, polybutylene terephthalate, polyphenylene sulfide.
5. the preparation method who forms the matrix material of original position conduction fento network according to claim 3 is characterized in that the high melt point thermoplastic plastics that add are selected from any of polyethylene terephthalate, nylon, polybutylene terephthalate, polyphenylene sulfide.
6. the preparation method who forms the matrix material of original position conduction fento network according to claim 1 and 2 is characterized in that the conductive filler material that adds is selected from any of carbon black, Graphite Powder 99, carbon nanotube.
7. the preparation method who forms the matrix material of original position conduction fento network according to claim 5 is characterized in that the conductive filler material that adds is selected from any of carbon black, Graphite Powder 99, carbon nanotube.
8. the preparation method who forms the matrix material of original position conduction fento network according to claim 2 is characterized in that the interface modifier that adds is selected from any of ethylene vinyl acetate, ethylene methacrylate.
9. the preparation method who forms the matrix material of original position conduction fento network according to claim 5 is characterized in that the interface modifier that adds is selected from any of ethylene vinyl acetate, ethylene methacrylate.
10. the preparation method who forms the matrix material of original position conduction fento network according to claim 7 is characterized in that the interface modifier that adds is selected from any of ethylene vinyl acetate, ethylene methacrylate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1294003C (en) * | 2005-01-26 | 2007-01-10 | 四川大学 | Method of preparing polymer / inorganic nanometer particle compesite |
| CN106219514B (en) * | 2009-12-11 | 2018-08-24 | 北京富纳特创新科技有限公司 | The preparation method of carbon nano tube structure |
| CN102061028A (en) * | 2010-12-13 | 2011-05-18 | 四川大学 | Preparation method of conductive polymer composite with low percolation value |
| CN102070876B (en) * | 2010-12-30 | 2013-05-22 | 桂林电子科技大学 | Epoxy resin base polynary conductive composite material with ultra-low threshold value and preparation method thereof |
| CN103255502B (en) * | 2013-05-23 | 2015-08-12 | 中原工学院 | A kind of preparation method of the light composite conducting fiber containing nano ATO |
| CN106065108A (en) * | 2016-06-06 | 2016-11-02 | 苏州市奎克力电子科技有限公司 | A kind of antistatic composite material and preparation method thereof |
| CN105837950B (en) * | 2016-06-22 | 2018-04-24 | 四川大学 | A kind of polyolefin-based conductive and dielectric composite material and preparation method thereof |
| CN111081423B (en) * | 2019-12-27 | 2021-07-27 | 暨南大学 | Oriented conductive composite material and preparation method and application thereof |
| CN111057301A (en) * | 2019-12-30 | 2020-04-24 | 贵州省材料产业技术研究院 | Conductive elastomer and preparation method thereof |
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Effective date of registration: 20080919 Address after: Institute of polymer science and engineering Sichuan University Sichuan city of Chengdu province moziqiao zip code: 610065 Co-patentee after: Yinxi Engineering Plastic (Dongguan) Co., Ltd. Patentee after: Sichuan University Address before: Institute of polymer science and engineering Sichuan University Sichuan city of Chengdu province moziqiao zip code: 610065 Patentee before: Sichuan University |
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