CN103724637A - Method for preparing polyvinyl alcohol master batch - Google Patents
Method for preparing polyvinyl alcohol master batch Download PDFInfo
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- CN103724637A CN103724637A CN201310750115.8A CN201310750115A CN103724637A CN 103724637 A CN103724637 A CN 103724637A CN 201310750115 A CN201310750115 A CN 201310750115A CN 103724637 A CN103724637 A CN 103724637A
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- polyvinyl alcohol
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Abstract
The invention discloses a method for preparing polyvinyl alcohol master batch. The method comprises the steps of physically mixing polyvinyl alcohol powder and a modifying additive containing ionic liquid at weight ratio of (70:30)-(90:10); injecting a mixture into extrusion equipment with a heating device, and carrying out melt extrusion at 160-180 DEG C; and cooling and dicing an extrusion melt in air to obtain the polyvinyl alcohol master batch. According to the method disclosed by the invention, the polar ionic liquid containing a hydroxyl group is uniformly mixed with polyvinyl alcohol powder which is proper in molecular structure parameter, and the hydroxyl group of the ionic liquid participates in effective interaction with hydroxyl of the polyvinyl alcohol within a proper processing temperature range, so as to prepare the polyvinyl alcohol master batch. The method, which adds triethylene glycol rich in hydroxyl and high in boiling point in the mixture, improves thermoplastic processing performance, appearance and other qualities of the granular triethylene glycol master batch.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of method of preparing particulate polyethylene alcohol masterbatch.
Background technology
Polyvinyl alcohol (PVA) is a kind of excellent performance, broad-spectrum water-soluble degradable high polymer material, owing to thering is good water-soluble, film-forming properties, cohesiveness, emulsifying property and barrier property, be widely used in the fields such as film, fiber, binding agent, paper making additive.But the melt temperature of PVA and decomposition temperature are too approaching, be difficult to carry out thermoplastic processing.The conventional machining method of PVA is solution wet moulding, as wet-spinning, solution casting film forming etc., need to experience dissolving and the drying process of resin, has the shortcomings such as complex process, cost is high, productive rate is low, wastewater discharge is large.Be subject to the limitation of solution processing molding method, PVA conventionally also can only or be used as for the preparation of low fiber products such as film, fibers and help, auxiliary material.Although China is the production and consumption big country of PVA goods, production technique still be take traditional solution machine-shaping as main, is unfavorable for industry development.Therefore the thermoplastic of, realizing PVA is processed significant.
The crucial difficult point of PVA thermoplastic processing is that its melt temperature and decomposition temperature are too approaching, and this is because PVA molecular structure contains great amount of hydroxy group, forms stronger hydrogen bond.Therefore,, in order to realize the thermoplastic processing of PVA, current known method is to add the materials such as water, alcohols, hexanolactam, reduces the fusing point of PVA by plastification.As document [polymer science and engineering, 2001,17:111] adopts water, glycerol, ethylene glycol, hexanolactam etc. as Compositional type softening agent, improved the thermoplastic processability of PVA; Publication number is that the Chinese invention patent of CN1711307A proposes take water as the technical scheme that primary plasticizer, one or more polyvalent alcohols are additional softening agent, realizes the thermoplastic processing of PVA film.Yet, as above-mentioned document, to report, the temperature of processing due to PVA thermoplastic surpasses 100 ℃, and the water adding seethes with excitement and produces bubble in the course of processing, affects the quality of PVA goods.Meanwhile, the alcohols material saturation steam adding forces down, also not good enough with the consistency of PVA, therefore in the use procedure of PVA goods, exists and separates out phenomenon to some extent.Visible, although above-mentioned known method can be realized the thermoplastic processing of PVA, also bring product property and life-time service problem.Therefore, urgently develop the new method of preparing PVA masterbatch, to meet the requirement of thermoplastic processing, and guarantee the quality that goods are good.
Summary of the invention
Object of the present invention is exactly for the above-mentioned state of the art, and a kind of method of preparing particulate polyethylene alcohol masterbatch is provided.
The inventive method comprises the following steps:
Step (1). pva powder and the modified additive that contains ionic liquid are carried out to physical mixed by 70/30～90/10 part by weight, obtain compound;
Step (2). compound is injected to the extrusion equipment with heating unit, then at 160～180 ℃ of temperature, melt extrude;
Step (3). melt extrusion is cooling in air, pelletizing, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing.
The equal particle diameter of number of the pva powder described in step (1) is 0.01～0.1mm, and mean polymerisation degree is 1000～1700, and alcoholysis degree is 88 ﹪～99.8 ﹪ (mol/mol);
The modified additive that contains ionic liquid described in step (1) is the binary mixture of ionic liquid or ionic liquid and triethylene glycol, and wherein the chemical structural formula of ionic liquid is:
Or
Or
Or
Or
Or
Or
Or
In formula: Me is methyl CH
3-, Et is ethyl CH
3-CH
2-, n-Pr is n-propyl CH
3-CH
2-CH
2-, n-Bu is normal-butyl CH
3-CH
2-CH
2-CH
2-.
The weight percentage of the described modified additive intermediate ion liquid that contains ionic liquid is 50～100 ﹪.
The inventive method is passed through great many of experiments, optimize the polar that a class contains hydroxyl, its pva powder suitable with molecular structural parameter is evenly mixed, the hydroxyl generation effective interaction of the hydroxyl of this ionic liquid and polyvinyl alcohol within the scope of suitable processing temperature, significantly weaken the original hydrogen bond of polyvinyl alcohol, thereby prepare the good particulate polyethylene alcohol masterbatch of thermoplastic processability.In addition, present method also adds and is rich in hydroxyl, high boiling triethylene glycol in compound, produces beyond thought collaborative promoter action together with above-mentioned ionic liquid, has improved the qualities such as the thermoplastic processibility of particulate polyethylene alcohol masterbatch and outward appearance.Present method is not used the lower boiling softening agent such as water that adopt in routine techniques, thereby when realizing the processing of polyvinyl alcohol masterbatch thermoplastic, has effectively avoided the generation of the defects such as bubble; Present method adopts simultaneously the modified additive that contains ionic liquid and polyvinyl alcohol consistency are better, have solved the separate out problems of conventional softening agent in polyvinyl alcohol such as water, glycerol.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention and effect are further described.
Embodiment 1.
The equal particle diameter of peeking is that 70 kilograms of pva powders and the chemical structural formula that 0.01mm, mean polymerisation degree are 1000, alcoholysis degree is 99.8 ﹪ is
30 kilograms of ionic liquids in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 160 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 2.
The equal particle diameter of peeking is that 80 kilograms of pva powders and the chemical structural formula that 0.055mm, mean polymerisation degree are 1700, alcoholysis degree is 88 ﹪ is
5 kilograms of 15 kilograms of ionic liquids, triethylene glycols in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 170 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 3.
The equal particle diameter of peeking is that 90 kilograms of pva powders and the chemical structural formula that 0.1mm, mean polymerisation degree are 1350, alcoholysis degree is 93.9 ﹪ is
5 kilograms of 5 kilograms of ionic liquids, triethylene glycols in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 180 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 4.
The equal particle diameter of peeking is that 70 kilograms of pva powders and the chemical structural formula that 0.055mm, mean polymerisation degree are 1000, alcoholysis degree is 99.8 ﹪ is
30 kilograms of ionic liquids in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 160 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 5:
The equal particle diameter of peeking is that 80 kilograms of pva powders, the chemical structural formula that 0.01mm, mean polymerisation degree are 1700, alcoholysis degree is 93.9 ﹪ is
5 kilograms of 15 kilograms of ionic liquids, triethylene glycols in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 170 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 6.
The equal particle diameter of peeking is that 90 kilograms of pva powders, the chemical structural formula that 0.1mm, mean polymerisation degree are 1350, alcoholysis degree is 88 ﹪ is
5 kilograms of 5 kilograms of ionic liquids, triethylene glycols in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 180 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 7.
The equal particle diameter of peeking is that 70 kilograms of pva powders, the chemical structural formula that 0.1mm, mean polymerisation degree are 1000, alcoholysis degree is 99.8 ﹪ is
30 kilograms of ionic liquids in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 160 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 8.
The equal particle diameter of peeking is that 80 kilograms of pva powders and the chemical structural formula that 0.055mm, mean polymerisation degree are 1700, alcoholysis degree is 88 ﹪ is
5 kilograms of 15 kilograms of ionic liquids, triethylene glycols in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 170 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 9.
The equal particle diameter of peeking is that 90 kilograms of pva powders and the chemical structural formula that 0.01mm, mean polymerisation degree are 1350, alcoholysis degree is 93.9 ﹪ is
5 kilograms of 5 kilograms of ionic liquids, triethylene glycols in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 180 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 10.
The equal particle diameter of peeking is that 70 kilograms of pva powders, the chemical structural formula that 0.01mm, mean polymerisation degree are 1000, alcoholysis degree is 99.8 ﹪ is
30 kilograms of ionic liquids in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 160 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 11.
The equal particle diameter of peeking is that 80 kilograms of pva powders and the chemical structural formula that 0.055mm, mean polymerisation degree are 1700, alcoholysis degree is 88 ﹪ is
5 kilograms of 15 kilograms of ionic liquids, triethylene glycols in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 170 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 12.
The equal particle diameter of peeking is that 90 kilograms of pva powders and the chemical structural formula that 0.1mm, mean polymerisation degree are 1350, alcoholysis degree is 93.9 ﹪ is
5 kilograms of 5 kilograms of ionic liquids, triethylene glycols in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 180 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 13.
The equal particle diameter of peeking is that 70 kilograms of pva powders and the chemical structural formula that 0.01mm, mean polymerisation degree are 1000, alcoholysis degree is 99.8 ﹪ is
30 kilograms of ionic liquids in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 160 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 14.
The equal particle diameter of peeking is that 80 kilograms of pva powders and the chemical structural formula that 0.055mm, mean polymerisation degree are 1700, alcoholysis degree is 88 ﹪ is
5 kilograms of 15 kilograms of ionic liquids, triethylene glycols in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 170 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 15.
The equal particle diameter of peeking is that 90 kilograms of pva powders and the chemical structural formula that 0.1mm, mean polymerisation degree are 1350, alcoholysis degree is 93.9 ﹪ is
5 kilograms of 5 kilograms of ionic liquids, triethylene glycols in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 180 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 16.
The equal particle diameter of peeking is that 70 kilograms of pva powders, the chemical structural formula that 0.055mm, mean polymerisation degree are 1000, alcoholysis degree is 99.8 ﹪ is
30 kilograms of ionic liquids in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 160 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 17.
The equal particle diameter of peeking is that 80 kilograms of pva powders, the chemical structural formula that 0.01mm, mean polymerisation degree are 1700, alcoholysis degree is 93.9 ﹪ is
5 kilograms of 15 kilograms of ionic liquids, triethylene glycols in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 170 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 18.
The equal particle diameter of peeking is that 90 kilograms of pva powders and the chemical structural formula that 0.1mm, mean polymerisation degree are 1350, alcoholysis degree is 88 ﹪ is
5 kilograms of 5 kilograms of ionic liquids, triethylene glycols in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 180 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 19.
The equal particle diameter of peeking is that 70 kilograms of pva powders, the chemical structural formula that 0.1mm, mean polymerisation degree are 1000, alcoholysis degree is 99.8 ﹪ is
30 kilograms of ionic liquids in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 160 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 20.
The equal particle diameter of peeking is that 80 kilograms of pva powders and the chemical structural formula that 0.055mm, mean polymerisation degree are 1700, alcoholysis degree is 88 ﹪ is
5 kilograms of 15 kilograms of ionic liquids, triethylene glycols in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 170 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 21.
The equal particle diameter of peeking is that 90 kilograms of pva powders and the chemical structural formula that 0.01mm, mean polymerisation degree are 1350, alcoholysis degree is 93.9 ﹪ is
5 kilograms of 5 kilograms of ionic liquids, triethylene glycols in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 180 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 22.
The equal particle diameter of peeking is that 70 kilograms of pva powders, the chemical structural formula that 0.01mm, mean polymerisation degree are 1000, alcoholysis degree is 99.8 ﹪ is
30 kilograms of ionic liquids in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 160 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 23.
The equal particle diameter of peeking is that 80 kilograms of pva powders and the chemical structural formula that 0.055mm, mean polymerisation degree are 1700, alcoholysis degree is 88 ﹪ is
5 kilograms of 15 kilograms of ionic liquids, triethylene glycols in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 170 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Embodiment 24.
The equal particle diameter of peeking is that 90 kilograms of pva powders and the chemical structural formula that 0.1mm, mean polymerisation degree are 1350, alcoholysis degree is 93.9 ﹪ is
5 kilograms of 5 kilograms of ionic liquids, triethylene glycols in homogenizer, carry out physical mixed, then compound is injected to conical double screw extruder, at the temperature of 180 ℃, melt extrude, extrusion pressure is normal, melt extrusion is cooling in air, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing after pelletizing, its smooth surface, without defects such as bubble, jaundice.
Above-described embodiment is not that the present invention is not limited only to above-described embodiment for restriction of the present invention, as long as meet requirement of the present invention, all belongs to protection scope of the present invention.
Claims (3)
1. a method of preparing polyvinyl alcohol masterbatch, is characterized in that the method comprises the following steps:
Step (1). pva powder and the modified additive that contains ionic liquid are carried out to physical mixed by 70/30～90/10 part by weight, obtain compound;
Step (2). compound is injected to the extrusion equipment with heating unit, then at 160～180 ℃ of temperature, melt extrude;
Step (3). melt extrusion is cooling in air, pelletizing, prepare the particulate polyethylene alcohol masterbatch that can be used for thermoplastic processing.
2. a kind of method of preparing polyvinyl alcohol masterbatch in step as claimed in claim 1 (1), the equal particle diameter of number that it is characterized in that pva powder in step (1) is 0.01～0.1mm, mean polymerisation degree is 1000～1700, and alcoholysis degree is 88 ﹪～99.8 ﹪.
3. a kind of method of preparing polyvinyl alcohol masterbatch in step as claimed in claim 1 (1), it is characterized in that the modified additive that contains ionic liquid in step (1) is the binary mixture of ionic liquid or ionic liquid and triethylene glycol, wherein the chemical structural formula of ionic liquid is:
Or
Or
Or
Or
Or
Or
Or
In formula: Me is methyl CH
3-, Et is ethyl CH
3-CH
2-, n-Pr is n-propyl CH
3-CH
2-CH
2-, n-Bu is normal-butyl CH
3-CH
2-CH
2-CH
2-;
The weight percentage of the described modified additive intermediate ion liquid that contains ionic liquid is 50～100 ﹪.
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| CN201310750115.8A CN103724637B (en) | 2013-12-30 | 2013-12-30 | A kind of method of preparing polyvinyl alcohol masterbatch |
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| CN201310750115.8A CN103724637B (en) | 2013-12-30 | 2013-12-30 | A kind of method of preparing polyvinyl alcohol masterbatch |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832705A (en) * | 2017-02-27 | 2017-06-13 | 四川大学 | Can thermoplasticity processing polyvinyl alcohol resin and its preparation method and application |
| CN110294910A (en) * | 2019-07-08 | 2019-10-01 | 秦皇岛祥祺新材料科技有限公司 | A kind of high temperature water-soluble polyvinyl alcohol master batch and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164251A (en) * | 1994-08-05 | 1997-11-05 | 艾索利塞有限公司 | Method of manufacturing monolithic structures from polyvinyl alcohol |
| US7888412B2 (en) * | 2004-03-26 | 2011-02-15 | Board Of Trustees Of The University Of Alabama | Polymer dissolution and blend formation in ionic liquids |
| CN102603954B (en) * | 2012-02-17 | 2013-07-31 | 四川大学 | Modified polyvinyl alcohol capable of being processed by melting and preparation method of modified polyvinyl alcohol |
| CN103059486B (en) * | 2012-12-03 | 2016-03-02 | 云南云天化股份有限公司 | The manufacture method of water-resistant polyvinyl alcohol film |
-
2013
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832705A (en) * | 2017-02-27 | 2017-06-13 | 四川大学 | Can thermoplasticity processing polyvinyl alcohol resin and its preparation method and application |
| CN106832705B (en) * | 2017-02-27 | 2020-03-17 | 四川大学 | Thermoplastic processable polyvinyl alcohol resin and preparation method and application thereof |
| CN110294910A (en) * | 2019-07-08 | 2019-10-01 | 秦皇岛祥祺新材料科技有限公司 | A kind of high temperature water-soluble polyvinyl alcohol master batch and preparation method thereof |
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Denomination of invention: A method for preparing polyvinyl alcohol Masterbatch Effective date of registration: 20210910 Granted publication date: 20160518 Pledgee: Agricultural Bank of China Limited Yong'an sub branch Pledgor: YONGAN SYF WATER SOLUBLE FILMS Co.,Ltd. Registration number: Y2021350000108 |
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