CN111410807A - Low-temperature water-soluble PVA composition capable of being melt and cast into film, particles and preparation method thereof - Google Patents
Low-temperature water-soluble PVA composition capable of being melt and cast into film, particles and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of biodegradable materials, and discloses a low-temperature water-soluble PVA composition capable of being melted and cast into a film, particles thereof and a preparation method thereof. The low-temperature water-soluble PVA composition capable of being melt casted into a film comprises: PVA, small molecule plasticizer, macromolecule plasticizer, thermal decomposition inhibitor, thermal oxidation aging resistant agent and lubricant; relative to 100 parts by weight of PVA, the content of the small-molecule plasticizer is 15-55 parts by weight, the content of the large-molecule plasticizer is 1-15 parts by weight, the content of the thermal decomposition inhibitor is 1-8 parts by weight, the content of the thermal oxidation aging resistant agent is 0.5-6 parts by weight, and the content of the lubricant is 2-6 parts by weight. The low-temperature water-soluble PVA particles capable of being subjected to melt casting film forming realize the melt casting film forming of the low-temperature water-soluble PVA.
Description
Technical Field
The invention relates to the field of biodegradable materials, in particular to a low-temperature water-soluble PVA composition capable of being melted and casted into a film, particles thereof and a preparation method thereof.
Background
In the field of packaging, plastics are the most widely used packaging materials, but with the growing environmental problems, energy depletion and food safety threats, people aim at biodegradable materials. The polyvinyl alcohol (PVA) has the performance and the characteristics of the traditional plastic, can be split and degraded in water with different water temperatures or under natural conditions, is finally biodegraded into carbon dioxide and water, returns to the natural environment in a form, and is a biodegradable environment-friendly material.
The PVA high-temperature water-soluble film is a film which begins to dissolve in water at a higher temperature (80 ℃) and is made of a completely alcoholysis type PVA; the PVA low-temperature water-soluble film is a film which begins to dissolve in water at a lower temperature (23 ℃), is also called a normal-temperature water-soluble film and is made of partial alcoholysis type PVA.
The PVA water-soluble film is mostly produced and prepared by a solution casting method, the processing cost is extremely high, the productivity is low, and a melt casting film forming method using the traditional plastic film bag is a processing mode with low energy consumption and high productivity.
Disclosure of Invention
The invention aims to overcome the problem that PVA raw materials are easy to decompose and carbonize in the thermoplastic processing process, and provides a low-temperature water-soluble PVA composition capable of being melted, casted and formed into a film, particles and a preparation method thereof. The low-temperature water-soluble PVA composition capable of being subjected to melt casting film formation and the particles do not decompose in the preparation process, the produced particles are smooth in surface, the melt flow rate of the particles is high, the film formation by a melt casting method is facilitated, and the continuous granulation of the low-temperature water-soluble PVA raw material and the film formation by the melt casting method are realized.
In order to achieve the above object, a first aspect of the present invention provides a low temperature water-soluble PVA composition which is melt-castable into a film, comprising: PVA, small molecule plasticizer, macromolecule plasticizer, thermal decomposition inhibitor, thermal oxidation aging resistant agent and lubricant;
relative to 100 parts by weight of PVA, the content of the small-molecule plasticizer is 15-55 parts by weight, the content of the large-molecule plasticizer is 1-15 parts by weight, the content of the thermal decomposition inhibitor is 1-8 parts by weight, the content of the thermal oxidation aging resistant agent is 0.5-6 parts by weight, and the content of the lubricant is 2-6 parts by weight.
Preferably, the content of the small molecule plasticizer is 25 to 45 parts by weight, the content of the large molecule plasticizer is 2 to 10 parts by weight, the content of the thermal decomposition inhibitor is 3 to 6 parts by weight, the content of the thermal aging resistant agent is 1 to 4 parts by weight, and the content of the lubricant is 2 to 4 parts by weight, relative to 100 parts by weight of PVA.
Preferably, the degree of polymerization of the PVA is 500-2400.
Preferably, the degree of alcoholysis of the PVA is 88%.
Preferably, the small molecule plasticizer is one or more of sorbitol, mannitol, glycerol, diethanolamine, triethanolamine, diglycerol, triglycerol, decapolypropylene triol, and diethylene glycol.
Preferably, the macromolecular plasticizer is a polyether polyol.
More preferably, the macromolecular plasticizer is one or more of PEG-2000, PEG-3000, PEG-4000, PEG-6000, PEG-8000 and PEO.
Preferably, the thermal decomposition inhibitor is one or more of an organic tin stabilizer, a rare earth stabilizer, zinc stearate, cerium stearate, barium stearate, aluminum distearate and calcium stearate.
Preferably, the anti-thermal oxidative aging agent is two or more of antioxidants 565, 1024, 1076, 1098, 1010, 626, 168, D L TP and DSTP.
Preferably, the lubricant is one or more of erucamide, oleamide, myristic acid, hardened oil, glycerol monostearate and pentaerythritol stearate.
In a second aspect, the present invention provides a method for preparing low temperature water soluble PVA particles capable of being melt cast into a film, the method comprising:
the low-temperature water-soluble PVA composition which can be melt cast into a film is subjected to mixing, granulation and molding.
In a third aspect, the present invention provides low temperature water soluble PVA particles that can be melt cast into films made by the method of the present invention.
Preferably, the melt flow rate of the low-temperature water-soluble PVA particles capable of being melt-casted into a film at 220 ℃ under the load of 2.16kg is 15-20g/10 min.
Compared with the prior art, the invention has the following beneficial effects:
1. the low-temperature water-soluble PVA composition capable of being melted, casted and formed into a film overcomes the problem that a part of alcoholysis type low-temperature water-soluble PVA raw material is easy to decompose and carbonize in the thermoplastic processing process, and realizes the thermoplastic processing of the low-temperature water-soluble PVA;
2. the low-temperature water-soluble PVA composition capable of being melted, casted and formed into a film overcomes the problem that a part of alcoholysis type low-temperature water-soluble PVA raw material has poor fluidity in the thermoplastic processing process, and realizes the melting, casting and film formation of the low-temperature water-soluble PVA;
3. when the partial alcoholysis type low-temperature water-soluble PVA composition for melt casting film forming is used for preparing a film, compared with the film forming by a solution casting method, the partial alcoholysis type low-temperature water-soluble PVA composition has the characteristics of small investment, high productivity, low energy consumption and the like, and is beneficial to the industrial production of the PVA melt casting film forming;
4. the low-temperature water-soluble PVA composition capable of being subjected to melt casting film formation and the PVA capable of being subjected to particle film formation have excellent plastic properties; is suitable for packaging products, in particular for various packaging films, packaging bags and/or sealing bags.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention will be described in detail below by way of examples. In the following examples, each material used was commercially available unless otherwise specified, and the method used was a conventional method in the art unless otherwise specified.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a low temperature water soluble PVA composition which is melt cast into a film, said low temperature water soluble PVA composition comprising: PVA, small molecule plasticizer, macromolecule plasticizer, thermal decomposition inhibitor, thermal oxidation aging resistant agent and lubricant;
relative to 100 parts by weight of PVA, the content of the small-molecule plasticizer is 15-55 parts by weight, the content of the large-molecule plasticizer is 1-15 parts by weight, the content of the thermal decomposition inhibitor is 1-8 parts by weight, the content of the thermal oxidation aging resistant agent is 0.5-6 parts by weight, and the content of the lubricant is 2-6 parts by weight.
By optimizing the components and the proportion of the low-temperature water-soluble PVA composition capable of being subjected to melt casting film forming, the addition amount of the plasticizer is increased, the addition amounts of the thermal decomposition inhibitor, the anti-thermal oxidation aging agent and the lubricant are increased, the melting point of the PVA is reduced, the melt flow rate is increased and the difficulty of melt casting processing is further reduced on the premise that the melt casting film forming is possible.
In order to further realize the melt casting processing possibility, preferably, the content of the small molecule plasticizer is 25 to 45 parts by weight, the content of the large molecule plasticizer is 2 to 10 parts by weight, the content of the thermal decomposition inhibitor is 3 to 6 parts by weight, the content of the thermal aging resistant agent is 1 to 4 parts by weight, and the content of the lubricant is 2 to 4 parts by weight, relative to 100 parts by weight of PVA.
The PVA raw material is not particularly specified, and can be various commercially available PVAs, preferably, the PVA is a partial alcoholysis type PVA, for example, the partial alcoholysis type PVA is specified in the most extensive naming mode currently used in domestic industry-GB 12010.1-89, and other naming modes currently on the market, such as the naming mode specified in GBT 12010.1-2008 and the naming mode not used domestically, can be converted into the naming mode specified in GB 12010.1-89 according to corresponding technical indexes.
In the present invention, it is preferable that the PVA has a degree of alcoholysis of 88% and a degree of polymerization of 2400-500 ℃ as specified in GB 12010.1-89.
More preferably, the PVA is one or more of 0388, 0588, 1788, 2088, 2288, and 2488 as specified in GB 12010.1-89.
The small molecule plasticizer is not particularly limited, and may be various small molecule plasticizers commonly used in the art, and may be determined by those skilled in the art according to the actual use requirement, and may be, for example, a small molecule polyol, a polyol ether, a fatty alcohol amine, or the like. In the present invention, preferably, the small molecule plasticizer is one or more of sorbitol, mannitol, glycerol, diethanolamine, triethanolamine, diglycerol, triglycerol, decapolypropylene triol and diethylene glycol.
The macromolecular plasticizer is not particularly limited, and may be various macromolecular plasticizers commonly used in the art, and those skilled in the art can determine the macromolecular plasticizer according to the actual use requirement, and for example, the macromolecular plasticizer may be polyether polyol having a relatively large molecular weight, polyester-based macromolecular compound, or the like.
In the present invention, in order to ensure that the macromolecular plasticizer has water solubility, it is preferable that the macromolecular plasticizer is polyether polyol.
More preferably, the macromolecular plasticizer is one or more of PEG-2000, PEG-3000, PEG-4000, PEG-6000, PEG-8000 and PEO.
The thermal decomposition inhibitor is not particularly limited, and may be various thermal decomposition inhibitors or stabilizers commonly used in the art, and in order to further ensure that the PVA is not decomposed and carbonized during the twin-screw granulation process, and to inhibit the decomposition of the PVA and provide a certain internal and external lubrication effect, in the present invention, it is preferable that the thermal decomposition inhibitor is one or more of an organic tin stabilizer, a rare earth stabilizer, zinc stearate, cerium stearate, barium stearate, aluminum distearate, and calcium stearate.
The antioxidant is not particularly limited, and may be various single-component antioxidants or antioxidants commonly used in the art, and in order to further ensure that the PVA eliminates generated radicals, promotes decomposition of hydroperoxides, prevents chain reaction, and retards or inhibits polymer oxidation during twin-screw granulation and particle storage and use, in the present invention, preferably, the antioxidant is two or more of antioxidants 565, 1024, 1076, 1098, 1010, 626, 168, D L TP, and DSTP.
The lubricant is not particularly limited, and in the present invention, the low-temperature water-soluble PVA which can be melt-cast into a film is improved in the processability in granulation, and the melt flow rate of the particles is improved to some extent. Preferably, the lubricant is one or more of erucamide, oleamide, myristic acid, hardened oil, glycerol monostearate and pentaerythritol stearate.
In a second aspect, the present invention provides a method for preparing low temperature water soluble PVA particles capable of being melt cast into a film, the method comprising:
and mixing the low-temperature water-soluble PVA composition which can be melt cast into a film, and granulating and forming.
In the method of the present invention, the method for preparing the low-temperature water-soluble PVA particles that can be melt-cast into a film is not particularly limited, and may be various preparation methods that are conventionally employed by those skilled in the art, and will not be described again. In a specific embodiment of the invention, the preparation is carried out according to the following steps:
(1) stirring all the compositions in a high-speed mixer at normal temperature for 5-20 minutes;
(2) and extruding and granulating by using a parallel double-screw granulator set to obtain the low-temperature water-soluble PVA particles capable of being melted and cast into films.
In the specific embodiment of the invention, the temperature of each section of the double-screw granulator unit is 45-200 ℃, and the screw rotating speed is 200-450 rpm.
In a third aspect, the invention provides low temperature water soluble PVA particles that can be melt cast into films made by the above method.
In consideration of practical considerations of the production equipment of the low-temperature water-soluble PVA particles for melt-cast film formation, and convenience and feasibility analysis of subsequent use, in the method of the invention, the water content of the low-temperature water-soluble PVA particles for melt-cast film formation is preferably 0.1-0.5 wt%.
For the feasibility of the low-temperature water-soluble PVA particles for melt-cast film formation in the subsequent use process, the melt flow rate of the low-temperature water-soluble PVA particles for melt-cast film formation is 15-20g/10min under the load of 2.16kg and at 220 ℃.
The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.
All the starting materials used in the examples are commercially available, except where otherwise indicated.
Performance evaluation method:
the prepared modified particles are subjected to a water content test on low-temperature water-soluble PVA particles which can be melted and cast into films according to the national standard GB/T6284-2006, and the melt flow rate of the modified particles is tested according to the national standard GB 3682-2000.
Example 1
A low temperature water soluble PVA composition that is melt castable into a film comprising:
PVA 2088100 parts, mannitol 15 parts, glycerol 20 parts, PEG-30002 parts, rare earth stabilizer 2 parts, cerium stearate 3 parts, antioxidant 5653 parts, 1680.5 part and pentaerythritol stearate 2 parts.
Example 2
A low temperature water soluble PVA composition that is melt castable into a film comprising:
PVA 1788100 weight parts, sorbitol 25 weight parts, PEG-20005 weight parts, organotin stabilizer 2 weight parts, zinc stearate 2 weight parts, antioxidant 10102 weight parts, DSTP 1 weight parts, and oleamide 2 weight parts.
Example 3
A low temperature water soluble PVA composition that is melt castable into a film comprising:
50 parts of PVA 228850 parts, 178850 parts of PVA, 15 parts of diethanolamine, 25 parts of triethanolamine, 3 parts of PEO, 2 parts of barium stearate, 1 part of aluminum distearate, 10243 parts of antioxidant, 6261 parts and 2 parts of pentaerythritol stearate.
Example 4
A low temperature water soluble PVA composition that is melt castable into a film comprising:
PVA 248850 parts by weight, PVA 058850 parts by weight, sorbitol 10 parts by weight, glycerol trimer 15 parts by weight, diethanolamine 15 parts by weight, PEG-80004 parts by weight, aluminum distearate 4 parts by weight, calcium stearate 2 parts by weight, antioxidant 10980.5 parts by weight, 1680.5 parts by weight, pentaerythritol stearate 4 parts by weight.
Example 5
A low temperature water soluble PVA composition that is melt castable into a film comprising:
PVA 248840 parts by weight, PVA 058860 parts by weight, diglycerol 15 parts by weight, sorbitol 20 parts by weight, PEG-40008 parts by weight, rare earth stabilizer 3 parts by weight, calcium stearate 2 parts by weight, antioxidant 10981.5 parts by weight, D L TP 2 parts by weight, and myristic acid 2 parts by weight.
Example 6
A low temperature water soluble PVA composition that is melt castable into a film comprising:
80 parts of PVA 178880, 20 parts of PVA 038820, 25 parts of decapolyglycerol, 10 parts of mannitol, 2 parts of PEG-80005, 3 parts of zinc stearate, 2 parts of calcium stearate, 5652 parts of antioxidant, 6261 parts of hardened oil and 2 parts of lubricating oil.
Example 7
A low temperature water soluble PVA composition that is melt castable into a film comprising:
208860 parts of PVA, 058840 parts of PVA, 15 parts of glycerol trimer, 15 parts of diethanolamine, 200010 parts of PEG, 3 parts of zinc stearate, 2 parts of aluminum distearate, 10242 parts of antioxidant, 1681 part of glycerol monostearate and 2 parts of glycerol trimer.
Example 8
A low temperature water soluble PVA composition that is melt castable into a film comprising:
PVA 208880 parts by weight, PVA 228820 parts by weight, mannitol 15 parts by weight, diglycerol 10 parts by weight, PEO 2 parts by weight, barium stearate 3 parts by weight, antioxidant 6981.5 parts by weight, 1680.5 parts by weight, and hardened oil 4 parts by weight.
Example 9
A low temperature water soluble PVA composition that is melt castable into a film comprising:
PVA 248840 parts by weight, PVA 178860 parts by weight, triethanolamine 15 parts by weight, diethylene glycol 30 parts by weight, PEG-40006 parts by weight, calcium stearate 3 parts by weight, aluminum distearate 2 parts by weight, antioxidant 10760.5 parts by weight, D L TP1 parts by weight, and erucamide 2 parts by weight.
Example 10
A low temperature water soluble PVA composition that is melt castable into a film comprising:
PVA 2488100 weight parts, glycerol 15 weight parts, decapolyglycerol 15 weight parts, PEG-30005 weight parts, cerous stearate 3 weight parts, aluminum distearate 1 weight parts, antioxidant 6981.5 weight parts, antioxidant 10241 weight parts, D L TP0.5 weight parts, and hardened oil 4 weight parts.
Comparative example 1:
PVA 2088100 parts by weight, mannitol 5 parts by weight, glycerol 5 parts by weight, PEG-30000.5 parts by weight, rare earth stabilizer 6 parts by weight, cerium stearate 3 parts by weight, antioxidant 5655 parts by weight, 1683 parts by weight, and pentaerythritol stearate 1 part by weight.
Comparative example 2:
PVA 2088100 weight parts, mannitol 15 weight parts, glycerol 20 weight parts, rare earth stabilizer 2 weight parts, cerium stearate 3 weight parts, antioxidant 5653 weight parts, 1680.5 weight parts, pentaerythritol stearate 2 weight parts.
PVA particles S1 to S10 and D1 and D2 were prepared by the following steps in the above examples 1 to 10 and comparative examples 1 and 2:
(1) stirring all the components in a high-speed mixer at normal temperature for 15 minutes;
(2) extruding and granulating by using a parallel double-screw granulator set to obtain low-temperature water-soluble PVA particles which can be melted and cast into films; wherein, the temperature of each section of the double-screw granulator set is as follows: first zone 90 deg.C, second zone 130 deg.C, third zone 140 deg.C, fourth zone 150 deg.C, fifth zone 160 deg.C, sixth zone 160 deg.C, seventh zone 165 deg.C, eighth zone 165 deg.C, ninth zone 170 deg.C, tenth zone 165 deg.C, eleventh zone 160 deg.C, twelfth zone 155 deg.C, thirteenth zone 155 deg.C, and head 155 deg.C; setting the rotating speed of a screw to 300 rpm;
the low temperature water soluble PVA particles S1-S10 and D1 and D2 described above, which were melt cast into films, were tested and the results are shown in Table 1 below.
TABLE 1
As can be seen from Table 1, the low temperature water-soluble PVA particles of the present invention which are melt-castable into films have a relatively low water content, and examples S1 to S10 are in a stable range, do not affect the thermoplastic processing, and do not generate blisters. The comparative example No. D1 has a large moisture content, and a large amount of blisters may be generated during the melt-casting process to cause film breakage, which is not useful. Comparative example D2 differs from example S1 in that no macromolecular plasticizer was added, but the moisture content was not affected, indicating whether the addition of macromolecular plasticizer had no effect on the moisture content of the particles.
The melt flow rate of the examples S1-S10 is 15-20g/10min, the fluidity is higher, and the melt casting film forming is more facilitated. The comparative example No. D1 has a small melt flow rate and a large difference from those of S1 to S10, and the particles were seriously decomposed during the granulation process, which was not suitable for the melt-casting process. The difference between the comparative example D2 and the example S1 is that the melt flow rate of the added macromolecular plasticizer is smaller than that of the example S1, which shows that the macromolecular plasticizer obviously improves the melt flow rate and is more beneficial to melt casting film formation.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A low temperature water soluble PVA composition capable of being cast into a film, which is characterized by comprising: PVA, small molecule plasticizer, macromolecule plasticizer, thermal decomposition inhibitor, thermal oxidation aging resistant agent and lubricant;
relative to 100 parts by weight of PVA, the content of the small-molecule plasticizer is 15-55 parts by weight, the content of the large-molecule plasticizer is 1-15 parts by weight, the content of the thermal decomposition inhibitor is 1-8 parts by weight, the content of the thermal oxidation aging resistant agent is 0.5-6 parts by weight, and the content of the lubricant is 2-6 parts by weight.
2. The low temperature water-soluble PVA composition of claim 1, wherein the amount of said small molecule plasticizer is 25 to 45 parts by weight, the amount of said large molecule plasticizer is 2 to 10 parts by weight, the amount of said thermal decomposition inhibitor is 3 to 6 parts by weight, the amount of said thermal aging inhibitor is 1 to 4 parts by weight, and the amount of said lubricant is 2 to 4 parts by weight, relative to 100 parts by weight of PVA.
3. A melt castable film forming, low temperature water soluble PVA composition as claimed in claim 1, wherein the degree of polymerization of said PVA is 2400;
preferably, the degree of alcoholysis of the PVA is 88%.
4. A low temperature water soluble PVA composition that can be melt cast into a film according to any one of claims 1 to 3, wherein said small molecule plasticizer is one or more of sorbitol, mannitol, glycerol, diethanolamine, triethanolamine, diglycerol, triglycerol, tripropylene glycol and diethylene glycol.
5. A melt castable film forming, low temperature water soluble PVA composition according to any one of claims 1 to 3, wherein said macromolecular plasticizer is a polyether polyol;
preferably, the macromolecular plasticizer is one or more of PEG-2000, PEG-3000, PEG-4000, PEG-6000, PEG-8000 and PEO.
6. A low temperature aqueous PVA composition that can be melt cast into a film according to any one of claims 1 to 3, wherein the thermal decomposition inhibitor is one or more of an organotin stabilizer, a rare earth stabilizer, zinc stearate, cerium stearate, barium stearate, aluminium distearate and calcium stearate.
7. A melt castable film forming, low temperature water soluble PVA composition according to any one of claims 1 to 3, wherein said anti thermal oxidative aging agent is two or more of antioxidants 565, 1024, 1076, 1098, 1010, 626, 168, D L TP and DSTP.
8. A melt castable film forming, low temperature water soluble PVA composition according to any one of claims 1 to 3, wherein the lubricant is one or more of erucamide, oleamide, myristic acid, hardened oil, glycerol monostearate and pentaerythritol stearate.
9. A preparation method of low-temperature water-soluble PVA particles capable of being melted and casted into a film is characterized by comprising the following steps:
the steps of mixing, granulating and shaping the low-temperature water-soluble PVA composition which can be melt casted into a film according to any one of the claims 1 to 8.
10. Low temperature water soluble PVA particles melt castable into a film made by the method of claim 9.
11. The low temperature water soluble PVA particles of claim 10, wherein said low temperature water soluble PVA particles of melt cast film have a melt flow rate of 15-20g/10min at 220 ℃ under a load of 2.16 kg.
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| CN202010249953.7A CN111410807A (en) | 2020-04-01 | 2020-04-01 | Low-temperature water-soluble PVA composition capable of being melt and cast into film, particles and preparation method thereof |
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| CN202010249953.7A CN111410807A (en) | 2020-04-01 | 2020-04-01 | Low-temperature water-soluble PVA composition capable of being melt and cast into film, particles and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521643A (en) * | 2020-12-25 | 2021-03-19 | 洛阳金裕新材料科技有限公司 | Method for producing water-soluble film |
| CN113717484A (en) * | 2021-09-13 | 2021-11-30 | 深圳市智远隆材料科技有限公司 | Sealing rubber ring of low-temperature soluble bridge plug and preparation method thereof |
-
2020
- 2020-04-01 CN CN202010249953.7A patent/CN111410807A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521643A (en) * | 2020-12-25 | 2021-03-19 | 洛阳金裕新材料科技有限公司 | Method for producing water-soluble film |
| CN113717484A (en) * | 2021-09-13 | 2021-11-30 | 深圳市智远隆材料科技有限公司 | Sealing rubber ring of low-temperature soluble bridge plug and preparation method thereof |
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