CN102311611A - Calcium sulfate whisker modified polyformaldehyde composite material and preparation process thereof - Google Patents
Calcium sulfate whisker modified polyformaldehyde composite material and preparation process thereof Download PDFInfo
- Publication number
- CN102311611A CN102311611A CN201110104119A CN201110104119A CN102311611A CN 102311611 A CN102311611 A CN 102311611A CN 201110104119 A CN201110104119 A CN 201110104119A CN 201110104119 A CN201110104119 A CN 201110104119A CN 102311611 A CN102311611 A CN 102311611A
- Authority
- CN
- China
- Prior art keywords
- calcium sulfate
- parts
- lubricant
- mixture
- coupling agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 82
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000000314 lubricant Substances 0.000 claims abstract description 23
- 239000007822 coupling agent Substances 0.000 claims abstract description 17
- 238000001746 injection moulding Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 230000004913 activation Effects 0.000 claims abstract description 7
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 31
- -1 polyoxymethylene Polymers 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 19
- 239000004902 Softening Agent Substances 0.000 claims description 16
- 239000002351 wastewater Substances 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 9
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 239000008188 pellet Substances 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 239000003549 soybean oil Substances 0.000 claims description 6
- 235000012424 soybean oil Nutrition 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 150000004645 aluminates Chemical class 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 3
- 229940113162 oleylamide Drugs 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 abstract description 7
- 238000001125 extrusion Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 1
- 235000021355 Stearic acid Nutrition 0.000 description 3
- ULBTUVJTXULMLP-UHFFFAOYSA-N butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCC ULBTUVJTXULMLP-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 206010010219 Compulsions Diseases 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- B29C48/405—Intermeshing co-rotating screws
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a calcium sulfate whisker modified polyformaldehyde composite material and a preparation process thereof. The calcium sulfate whisker modified polyformaldehyde composite material is prepared from the following raw materials in part by weight: 80 to 90 parts of polyformaldehyde, 10 to 20 parts of calcium sulfate whiskers, 1 to 3 parts of coupling agent, 1 to 5 parts of plasticizer and 0.5 to 1.5 parts of lubricant. A preparation method of the calcium sulfate whisker modified polyformaldehyde composite material comprises the following steps of: adding the calcium sulfate whiskers and the coupling agent into a high-speed mixer to carry out activation treatment for 5 to 15 minutes; then adding the rest of raw materials into the high-speed mixer and mixing for 3 to 7 minutes; carrying out extrusion and pelleting on the obtained mixture in a co-rotating parallel double-screw extruder; and carrying out injection moulding on the obtained granules in a co-rotating parallel double-screw injection molding machine. The calcium sulfate whisker modified polyformaldehyde composite material disclosed by the invention has high impact strength and tensile strength and can be widely used for manufacturing various products with high requirement on the strength.
Description
Technical field
The present invention relates to a kind of polyformaldehyde composite material and preparation technology thereof, relate in particular to a kind of calcium sulfate whisker modified polyformaldehyde composite material and preparation technology thereof.
Background technology
Polyoxymethylene (POM) is high crystallization, highdensity linear polymer, have wear-resisting, hard, antifatigue, be prone to performances such as processing and product size are stable, but POM fragility is big, and shock resistance is poor, has limited the POM Product Application.
Summary of the invention
The technical problem that the present invention will solve is, overcomes the deficiency of existing polyformaldehyde material, provides a kind of shock strength, tensile strength high, and preparation technology is simple, calcium sulfate whisker modified polyformaldehyde composite material and preparation technology thereof that cost is low.
The present invention solve the technical problem the technical scheme that is adopted:
The present invention's calcium sulfate whisker modified polyformaldehyde composite material is processed by the raw material of following parts by weight: 80～90 parts of polyoxymethylene (POM), 10～20 parts of calcium sulfate crystal whiskers, 1～3 part of coupling agent, 1～5 part in softening agent, 0.5～1.5 part of lubricant;
Said coupling agent is one or more the mixture in silane coupling agent, maleic anhydride, the aluminate coupling agent;
Said softening agent is one or more the mixture in Witcizer 300 (DBP), DOP (DOP), the epoxy soybean oil;
Said lubricant is one or more the mixture in paraffin, Triple Pressed Stearic Acid, butyl stearate, the oleylamide.
Preferred weight proportion is: 82 parts of polyoxymethylene (POM), 15 parts of calcium sulfate crystal whiskers, 2 parts of coupling agents, 3 parts in softening agent, 1 part of lubricant.
The preparation technology of the present invention's calcium sulfate whisker modified polyformaldehyde composite material comprises the steps:
(1) with calcium sulfate crystal whiskers and coupling agent, join activation treatment 5～15min in the high-speed mixer (preferred 10min), get wastewaters with modified calcium sulfate whiskers; Gained wastewaters with modified calcium sulfate whiskers diameter is 10～20 μ m, length-to-diameter ratio 10～30;
(2) said polyoxymethylene, softening agent, lubricant are joined in the high-speed mixer, mix 3～7 min (preferred 5min), get the mixture of polyoxymethylene, softening agent, lubricant and wastewaters with modified calcium sulfate whiskers;
(3) with step (2) gained mixture extruding pelletization in the cocurrent and parallel twin screw extruder, extrusion temperature is 150～180 ℃ (preferred 170 ℃);
(4) with the injection moulding in cocurrent and parallel twin screw injection moulding machine of step (3) gained pellet, 160～180 ℃ of injection temperatures (preferred 175 ℃) get finished product.
Calcium sulfate crystal whiskers is claimed crystal whisker of gypsum again, is a kind of fibrous single crystal of calcium sulfate.Research shows that the wastewaters with modified calcium sulfate whiskers length-to-diameter ratio of the present invention's use is 10～30, and diameter is 10～20 μ m, and it has uniform cross-sectional area, and complete internal structure, this characteristic are given its intensity near valence link between crystal theoretical value-atom.Because it has high intensity, trickle size is prone to and the POM interfacial adhesion; Improve consistency and interface cohesive force with matrix; When receiving the foreign compulsion orientation, the unrelieved stress among the POM can pass to calcium sulfate crystal whiskers well, thereby improves the intensity of matrix material; Because calcium sulfate crystal whiskers is an inorganics, in POM matrix, be uniformly dispersed, be difficult for reuniting, make composite property stable.
The present invention's calcium sulfate whisker modified polyformaldehyde composite material, shock strength and tensile strength are high, can be widely used in the various production of products high to requirement of strength.
Embodiment
Below in conjunction with embodiment the present invention is done further explain.
Embodiment 1
Present embodiment raw material weight proportioning is: 80 parts of polyoxymethylene (POM), 18 parts of calcium sulfate crystal whiskers, 2.5 parts of aluminate coupling agents, 2 parts of Plasticizer DBP, 1.2 parts in lubricant paraffin.
The preparation method:
(1) calcium sulfate crystal whiskers and aluminate coupling agent are added in the high-speed mixer, activation treatment 10min in high-speed mixer gets wastewaters with modified calcium sulfate whiskers;
(2) said polyoxymethylene, Plasticizer DBP, lubricant paraffin are joined in the high-speed mixer, mix 5 min, get the mixture of polyoxymethylene, Plasticizer DBP, lubricant paraffin and wastewaters with modified calcium sulfate whiskers;
(3) with step (2) gained mixture extruding pelletization in the cocurrent and parallel twin screw extruder, temperature is 170 ℃;
(4) with the injection moulding in cocurrent and parallel twin screw injection moulding machine of step (3) gained pellet, 175 ℃ of temperature get finished product.
Present embodiment product mechanic property test method standard numbering and test result are listed in table 1.
Embodiment 2
Present embodiment raw material weight proportioning is: 82 parts of polyoxymethylene (POM), 15 parts of calcium sulfate crystal whiskers, 2 parts of silane coupling agents, 3 parts of plasticizer DOPs, 1 part of lubricant stearic acid.
The preparation method:
(1) calcium sulfate crystal whiskers and silane coupling agent are added in the high-speed mixer, activation treatment 10min in high-speed mixer gets wastewaters with modified calcium sulfate whiskers;
(2) said polyoxymethylene, plasticizer DOP, lubricant stearic acid are joined in the high-speed mixer, mix 5 min, get the mixture of polyoxymethylene, plasticizer DOP, lubricant stearic acid and wastewaters with modified calcium sulfate whiskers;
(3) with step (2) gained mixture extruding pelletization in the cocurrent and parallel twin screw extruder, temperature is 170 ℃;
(4) with the injection moulding in cocurrent and parallel twin screw injection moulding machine of step (3) gained pellet, 175 ℃ of temperature get finished product.
Present embodiment product mechanic property test method standard numbering and test result are listed in table 1.
Embodiment 3
Present embodiment raw material weight proportioning is: 84 parts of polyoxymethylene (POM), 20 parts of calcium sulfate crystal whiskers, 2 parts of maleic anhydrides, 3 parts of softening agent epoxy soybean oils, 1 part of lubricant stearic acid butyl ester.
The preparation method:
(1) calcium sulfate crystal whiskers and maleic anhydride are added in the high-speed mixer, activation treatment 10min in high-speed mixer gets wastewaters with modified calcium sulfate whiskers;
(2) said polyoxymethylene, softening agent epoxy soybean oil, lubricant stearic acid butyl ester are joined in the high-speed mixer, mix 5 min, get the mixture of polyoxymethylene, softening agent epoxy soybean oil, lubricant stearic acid butyl ester and wastewaters with modified calcium sulfate whiskers;
(3) with step (2) gained mixture extruding pelletization in the cocurrent and parallel twin screw extruder, temperature is 170 ℃;
(4) with the injection moulding in cocurrent and parallel twin screw injection moulding machine of step (3) gained pellet, 175 ℃ of temperature get finished product.
Present embodiment product mechanic property test method standard numbering and test result are listed in table 1.
Claims (5)
1. a calcium sulfate whisker modified polyformaldehyde composite material is characterized in that, is processed by the raw material of following parts by weight: 80～90 parts of polyoxymethylene, 10～20 parts of calcium sulfate crystal whiskers, 1～3 part of coupling agent, 1～5 part in softening agent, 0.5～1.5 part of lubricant;
Said coupling agent is one or more the mixture in silane coupling agent, maleic anhydride, the aluminate coupling agent;
Said softening agent is one or more the mixture in Witcizer 300, DOP, the epoxy soybean oil;
Said lubricant is one or more the mixture in paraffin, Triple Pressed Stearic Acid, butyl stearate, the oleylamide.
2. calcium sulfate whisker modified polyformaldehyde composite material according to claim 1 is characterized in that, is processed by the raw material of following parts by weight: 82 parts of polyoxymethylene, 15 parts of calcium sulfate crystal whiskers, 2 parts of coupling agents, 3 parts in softening agent, 1 part of lubricant;
Said coupling agent is one or more the mixture in silane coupling agent, maleic anhydride, the aluminate coupling agent;
Said softening agent is one or more the mixture in Witcizer 300, DOP, the epoxy soybean oil;
Said lubricant is one or more the mixture in paraffin, Triple Pressed Stearic Acid, butyl stearate, the oleylamide.
3. the preparation technology of a calcium sulfate whisker modified polyformaldehyde composite material according to claim 1 or claim 2 is characterized in that, may further comprise the steps:
(1) calcium sulfate crystal whiskers and coupling agent are joined in the high-speed mixer, activation treatment 5～15min in high-speed mixer gets wastewaters with modified calcium sulfate whiskers;
(2) said polyoxymethylene, softening agent, lubricant are joined in the high-speed mixer, mix 3～7 min, get the mixture of polyoxymethylene, softening agent, lubricant and wastewaters with modified calcium sulfate whiskers;
(3) with step (2) gained mixture extruding pelletization in the cocurrent and parallel twin screw extruder, temperature is 150～180 ℃;
(4) with the injection moulding in cocurrent and parallel twin screw injection moulding machine of step (3) gained pellet, 160～180 ℃ of temperature get finished product.
4. the preparation technology of a calcium sulfate whisker modified polyformaldehyde composite material as claimed in claim 3 is characterized in that, may further comprise the steps:
(1) calcium sulfate crystal whiskers and coupling agent are joined activation treatment 10min in the high-speed mixer, get wastewaters with modified calcium sulfate whiskers;
(2) said polyoxymethylene, softening agent, lubricant are joined in the high-speed mixer, mix 5min, get the mixture of polyoxymethylene, softening agent, lubricant and wastewaters with modified calcium sulfate whiskers;
(3) with step (2) gained mixture extruding pelletization in the cocurrent and parallel twin screw extruder, temperature is 170 ℃;
(4) with the injection moulding in cocurrent and parallel twin screw injection moulding machine of step (3) gained pellet.
5. temperature is 175 ℃, gets finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110104119XA CN102311611B (en) | 2011-04-26 | 2011-04-26 | Calcium sulfate whisker modified polyformaldehyde composite material and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110104119XA CN102311611B (en) | 2011-04-26 | 2011-04-26 | Calcium sulfate whisker modified polyformaldehyde composite material and preparation process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102311611A true CN102311611A (en) | 2012-01-11 |
| CN102311611B CN102311611B (en) | 2013-03-20 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110104119XA Active CN102311611B (en) | 2011-04-26 | 2011-04-26 | Calcium sulfate whisker modified polyformaldehyde composite material and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102311611B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672775A (en) * | 2015-02-06 | 2015-06-03 | 合肥康龄养生科技有限公司 | Carbon fiber reinforced polyformaldehyde composite material with high UV resistance and preparation method thereof |
| CN104672765A (en) * | 2015-02-06 | 2015-06-03 | 合肥康龄养生科技有限公司 | Carbon fiber reinforced formaldehyde composite material with good low temperature resistance and preparation method of composite material |
| CN106479137A (en) * | 2016-10-21 | 2017-03-08 | 安徽江淮汽车集团股份有限公司 | A kind of high thermal conductivity PBT composite and preparation method thereof |
| CN106967274A (en) * | 2017-04-28 | 2017-07-21 | 东莞市耐格美塑胶制品有限公司 | A kind of enhanced POM plate material and preparation method thereof |
| CN109749349A (en) * | 2018-12-03 | 2019-05-14 | 安徽华米生物科技有限公司 | A kind of novel polyformaldehyde composite material and preparation method thereof |
| CN111471267A (en) * | 2020-05-21 | 2020-07-31 | 深州市工程塑料有限公司 | Sliding plate for friction pendulum type seismic mitigation and isolation support and preparation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672775A (en) * | 2015-02-06 | 2015-06-03 | 合肥康龄养生科技有限公司 | Carbon fiber reinforced polyformaldehyde composite material with high UV resistance and preparation method thereof |
| CN104672765A (en) * | 2015-02-06 | 2015-06-03 | 合肥康龄养生科技有限公司 | Carbon fiber reinforced formaldehyde composite material with good low temperature resistance and preparation method of composite material |
| CN106479137A (en) * | 2016-10-21 | 2017-03-08 | 安徽江淮汽车集团股份有限公司 | A kind of high thermal conductivity PBT composite and preparation method thereof |
| CN106967274A (en) * | 2017-04-28 | 2017-07-21 | 东莞市耐格美塑胶制品有限公司 | A kind of enhanced POM plate material and preparation method thereof |
| CN109749349A (en) * | 2018-12-03 | 2019-05-14 | 安徽华米生物科技有限公司 | A kind of novel polyformaldehyde composite material and preparation method thereof |
| CN111471267A (en) * | 2020-05-21 | 2020-07-31 | 深州市工程塑料有限公司 | Sliding plate for friction pendulum type seismic mitigation and isolation support and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102311611B (en) | 2013-03-20 |
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Effective date of registration: 20160816 Address after: An Industrial Park Economic Development Zone, Changde City, Hunan province Linli County 415200 Patentee after: Hunan Fu Xiang new type building material Co., Ltd. Address before: 410005, 12 floor, Haidong mansion, Furong Road, Changsha, Hunan Patentee before: Liu Liwen |