CN113462026A - Composite calcium-zinc heat stabilizer composition and preparation method and application thereof - Google Patents
Composite calcium-zinc heat stabilizer composition and preparation method and application thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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Abstract
The invention discloses a composite calcium-zinc heat stabilizer composition, a preparation method and application thereof. The composite calcium-zinc heat stabilizer composition comprises the following components in parts by weight: 10 parts of calcium-zinc heat stabilizer, 0.2-2 parts of modified fumed silica and 0.2-2 parts of hydroxyl-terminated pentaerythritol adipate; the modified fumed silica is fumed silica modified by a silane coupling agent. The hydroxyl-terminated pentaerythritol adipate has good compatibility with PVC, and the precipitation of a heat stabilizer is reduced while the heat stability is improved; the surface of the modified fumed silica modified by the silane coupling agent has silanol groups, so that the modified fumed silica is very easy to adsorb substances capable of forming hydrogen bonds with the silanol groups. According to the invention, the composite calcium-zinc heat stabilizer composition with excellent heat stability is obtained through the cooperative use and synergistic interaction of the modified fumed silica, the hydroxyl-terminated pentaerythritol adipate and the calcium-zinc heat stabilizer.
Description
Technical Field
The invention relates to the technical field of PVC (polyvinyl chloride) heat stabilizers, and particularly relates to a composite calcium-zinc heat stabilizer composition and a preparation method and application thereof.
Background
The PVC pipeline has the advantages of excellent flame retardance, wear resistance, chemical corrosion resistance, mechanical property, electrical insulation and the like, and is widely applied to the fields of industry, building, municipal administration, agriculture and the like. The PVC molecular chain has a tertiary chlorine and tertiary hydrogen structure, the bond energy is low, HCl is very easy to remove to generate free radicals, so that the PVC molecular chain is unstable and is O-reactive2And can degrade and age under high temperature and illumination conditions. The decomposition temperature of the PVC resin is about 130 ℃, but the molding temperature of the PVC resin is 180 ℃ or higher, and therefore, in order to realize the processability of the PVC resin, a thermal stabilizer needs to be added to the PVC material system.
The calcium-zinc stabilizer is a well-known nontoxic and environment-friendly heat stabilizer, and can improve the thermal stability of PVC resin and slow down the degradation and discoloration processes of the PVC resin by adding the calcium-zinc heat stabilizer in the actual production process of the PVC pipeline. Chinese patent application CN1624040A discloses granules of UPVC pipe fittings for water supply, which are composed of PVC resin, calcium-zinc heat stabilizer, processing aid, lubricant, impact modifier and the like, and improve the heat stability of PVC-U material.
However, although the calcium-zinc heat stabilizer can effectively inhibit the initial degradation and coloring of the PVC material, the following defects still exist: the calcium-zinc heat stabilizer is easy to separate out under long-time hot processing, so that scaling and sizing sleeve frosting of a mold runner are formed, the appearance and the physical and mechanical properties of a pipe are seriously influenced, and the thermal stability of the PVC material is further degraded; ZnCl generated by calcium-zinc heat stabilizer in later stage of thermal processing2Has strong catalytic HCl removal effect, so that PVC molecular chains are unstable and easy to degrade, and the color of the material is dark. Therefore, the improvement of the long-acting thermal stability of PVC by using the calcium-zinc heat stabilizer alone is limited, and a composite calcium-zinc heat stabilizer composition needs to be developed, so that the thermal stability time of the PVC pipeline material can be effectively prolonged.
Disclosure of Invention
The composite calcium-zinc heat stabilizer composition comprises modified fumed silica, hydroxyl-terminated pentaerythritol adipate and a calcium-zinc heat stabilizer, can effectively prolong the heat stabilization time of a PVC pipeline material, and has an excellent long-acting heat stabilization effect on PVC.
The invention also aims to provide a preparation method of the composite calcium-zinc heat stabilizer composition.
The invention also aims to provide application of the composite calcium-zinc heat stabilizer composition in PVC pipeline materials.
In order to solve the technical problems, the invention adopts the technical scheme that:
a composite calcium-zinc heat stabilizer composition comprises the following components in parts by weight:
10 parts of calcium-zinc heat stabilizer, 0.2-2 parts of modified fumed silica and 0.2-2 parts of hydroxyl-terminated pentaerythritol adipate;
the modified fumed silica is fumed silica modified by a silane coupling agent.
Pentaerythritol is an excellent auxiliary heat stabilizer, and the mechanism for improving the thermal stability of a PVC material system is as follows: oxygen atoms in hydroxyl groups of pentaerythritol have lone electrons, and zinc chloride generated by zinc salts in the calcium-zinc heat stabilizer is easy to complex, so that the catalytic decomposition effect of the zinc chloride on PVC is delayed. Although the pentaerythritol and the calcium-zinc heat stabilizer are used simultaneously, a certain synergistic effect can be generated, so that a better heat stability effect is obtained; but because pentaerythritol has poor compatibility with PVC and is easy to precipitate, the addition of pentaerythritol alone to a PVC system can limit the synergistic effect of pentaerythritol on the thermal stability of PVC materials.
In the invention, the hydroxyl-terminated adipic acid and pentaerythritol are used for introducing an ester group through esterification reaction, on one hand, after the pentaerythritol is esterified, the compatibility with PVC is obviously improved, and the ester group is not easy to separate out in the thermal processing process; on the other hand, through esterification reaction, hydroxyl in hydroxyl-terminated adipic acid is reserved, the reacted hydroxyl in pentaerythritol molecules is compensated, oxygen atoms in the hydroxyl can also promote complexing zinc chloride, and the synergistic effect of the composite calcium-zinc heat stabilizer composition on the PVC heat stability is further improved.
The surface of the modified fumed silica is modified by a silane coupling agent and has silanol groups, so that the modified fumed silica can easily adsorb substances capable of forming hydrogen bonds with the silanol groups. Therefore, the modified fumed silica has a rapid adsorption effect on HCl degraded and removed from PVC, and is not easy to desorb. HCl is adsorbed and removed in time through the modified fumed silica, so that the autocatalytic degradation effect of the HCl on PVC molecules is blocked, and the modified fumed silica has an important effect of slowing down the degradation of the PVC molecules.
Therefore, the modified fumed silica in the composite calcium-zinc heat stabilizer composition provided by the invention is cooperated with hydroxyl-terminated pentaerythritol adipate to realize synergistic interaction, so that an excellent heat stabilization effect is achieved.
The composite calcium-zinc heat stabilizer composition with excellent long-acting heat stabilization effect on PVC materials can be obtained through the synergistic effect of the modified fumed silica, the hydroxyl-terminated pentaerythritol adipate and the calcium-zinc heat stabilizer.
The hydroxyl-terminated adipic acid pentaerythritol ester is obtained by esterification reaction of hydroxyl-terminated adipic acid and pentaerythritol.
Preferably, the molar ratio of the hydroxyl-terminated adipic acid to the pentaerythritol is (1-1.5) to 2.
Preferably, the acid value of the hydroxyl-terminated pentaerythritol adipate is less than or equal to 0.5mgKOH/g, and the hydroxyl value is 70-90 mgKOH/g.
Preferably, the preparation method of the modified fumed silica comprises the following steps:
dispersing the fumed silica and a silane coupling agent in an organic solvent, carrying out reflux reaction for 2-4 h at the temperature of 60-80 ℃, and carrying out post-treatment to obtain the modified fumed silica.
Preferably, the mass ratio of the fumed silica to the silane coupling agent is (40-50): (20-30).
Preferably, the organic solvent is one or more of acetone, methanol, ethanol and ethyl acetate.
Preferably, the silane coupling agent is one or more of KH570, KH560 and KH 171.
Preferably, the density of silanol groups on the surface of the modified fumed silica is 3-5 SiOH/nm2。
Preferably, the specific surface area of the modified fumed silica is 250-350 m2/g。
Preferably, the calcium zinc heat stabilizer is a mixture of calcium stearate and zinc stearate salts.
More preferably, the mass ratio of the calcium stearate salt to the zinc stearate salt is (15-30) to (10-20).
Preferably, the composite calcium-zinc heat stabilizer composition consists of the following components in parts by weight:
8-10 parts of calcium-zinc heat stabilizer, 0.4-0.8 part of modified fumed silica and 0.3-0.6 part of hydroxyl-terminated pentaerythritol adipate.
The invention also provides a preparation method of the composite calcium-zinc heat stabilizer composition, which comprises the following steps:
and uniformly mixing the calcium-zinc heat stabilizer, the modified fumed silica and the hydroxyl-terminated adipic acid pentaerythritol ester to obtain the composite calcium-zinc heat stabilizer composition.
The invention also protects the application of the composite calcium-zinc heat stabilizer composition in PVC composite materials.
Preferably, the PVC composite material comprises the following components in parts by weight:
80-100 parts of polyvinyl chloride, 5-30 parts of inorganic filler, 1-3 parts of titanium dioxide and 5-12 parts of the composite calcium-zinc heat stabilizer composition.
Preferably, the PVC composite material also comprises 6.5-17 parts by weight of other auxiliary agents.
Preferably, the other additives include lubricants, impact modifiers, processing aids.
Preferably, the other auxiliary agents comprise 1-5 parts of lubricant, 5-10 parts of impact modifier and 0.5-2 parts of processing auxiliary agent.
Optionally, the lubricant is PE wax and/or monoglycerides.
Optionally, the impact modifier is Chlorinated Polyethylene (CPE) and/or methyl methacrylate-butadiene-styrene terpolymer (MBS).
Optionally, the processing aid is an acrylate copolymer.
The processing aid can promote the plasticizing effect of the PVC-U material to be better.
Compared with the prior art, the invention has the beneficial effects that:
the composite calcium-zinc heat stabilizer composition with excellent long-acting heat stabilization effect on PVC materials is developed through the synergistic effect of the modified fumed silica, the hydroxyl-terminated pentaerythritol adipate and the calcium-zinc heat stabilizer.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The starting materials in the examples and comparative examples are all commercially available, wherein:
the calcium zinc heat stabilizer A is prepared from calcium stearate and zinc stearate according to the weight ratio of 20: 12 with a solvent;
the calcium zinc heat stabilizer B is calcium stearate and zinc stearate, and the weight ratio of the calcium zinc heat stabilizer B is 15: 20, a mixture of;
the calcium zinc heat stabilizer C is calcium stearate and zinc stearate, and the weight ratio of calcium stearate to zinc stearate is 30: 10, a mixture of;
the calcium-zinc heat stabilizer D is purchased from a new Jiashan Yiqi material, W520.
The modified fumed silica A is prepared by the following method:
mixing the components in a mass ratio of 50:20, dispersing the fumed silica and a silane coupling agent KH570 in acetone, carrying out reflux heating reaction at the reaction temperature of 70 ℃ for 2h, and separating and drying to obtain modified fumed silica A; the modified fumed silica A has a silanol group density of 3.1SiOH/nm2(ii) a The specific surface area of the modified fumed silica is 258m2/g；
The modified fumed silica B is prepared by the following method:
and (3) mixing the components in a mass ratio of 40: 30 of fumed silica and a silane coupling agent KH560 are dispersed in ethanol and subjected to reflux heating reactionThe reaction temperature is 70 ℃, the reaction time is 2 hours, and the modified gas-phase silicon dioxide B is obtained after separation and drying; the modified fumed silica B has a silanol group density of 4.8SiOH/nm2(ii) a The specific surface area of the modified fumed silica is 277m2/g；
The modified fumed silica C is prepared by the following method:
dispersing fumed silica and a silane coupling agent KH171 in a mass ratio of 45:25 in xylene, carrying out reflux heating reaction at a reaction temperature of 70 ℃ for 2h, and separating and drying to obtain modified fumed silica C; the modified fumed silica C has a silanol group density of 4.1SiOH/nm2(ii) a The specific surface area of the modified fumed silica is 302m2/g；
The modified fumed silica D is prepared by the following method:
dispersing gas-phase silicon dioxide and an aluminate coupling agent in a mass ratio of 50:20 into dimethylbenzene, carrying out reflux heating reaction at the reaction temperature of 70 ℃ for 2 hours, and separating and drying to obtain modified gas-phase silicon dioxide D;
the hydroxyl-terminated pentaerythritol adipate is prepared by the following method:
under the action of concentrated sulfuric acid catalyst, adding hydroxyl-terminated adipic acid and pentaerythritol into a round-bottom flask with a stirring device, and carrying out esterification reaction under the vacuum-pumping condition to obtain hydroxyl-terminated adipic acid pentaerythritol ester;
in the preparation method of the hydroxyl-terminated pentaerythritol adipate A, the molar ratio of the hydroxyl-terminated adipic acid to pentaerythritol is 1:2, the esterification reaction temperature is 150 ℃, the reaction time is 4 hours, the acid value of the prepared hydroxyl-terminated pentaerythritol adipate A is 0.2mgKOH/g, and the hydroxyl value is 90 mgKOH/g;
in the preparation method of the hydroxyl-terminated pentaerythritol adipate B, the molar ratio of the hydroxyl-terminated adipic acid to pentaerythritol is 1.5:2, the esterification reaction temperature is 150 ℃, the reaction time is 4 hours, the acid value of the prepared hydroxyl-terminated pentaerythritol adipate B is 0.35mgKOH/g, and the hydroxyl value is 70 mgKOH/g;
in the preparation method of the hydroxyl-terminated pentaerythritol adipate C, the molar ratio of the hydroxyl-terminated adipic acid to pentaerythritol is 1:2, the esterification reaction temperature is 170 ℃, the reaction time is 2 hours, the acid value of the prepared hydroxyl-terminated pentaerythritol adipate C is 0.31mgKOH/g, and the hydroxyl value is 80 mgKOH/g;
in the preparation method of the hydroxyl-terminated pentaerythritol adipate D, the molar ratio of the hydroxyl-terminated adipic acid to pentaerythritol is 1:2, the esterification reaction temperature is 130 ℃, the reaction time is 5 hours, and the prepared hydroxyl-terminated pentaerythritol adipate D has an acid value of 0.25mgKOH/g and a hydroxyl value of 86 mgKOH/g.
Pentaerythritol stearate purchased from Sandan bioscience, Inc., has an acid value of not more than 0.5mgKOH/g and a hydroxyl value of 20-37 mgKOH/g.
The pentaerythritol oleate is purchased from biological processes in Anqing, and has an acid value of less than or equal to 1mgKOH/g and a hydroxyl value of less than or equal to 15 mgKOH/g.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Examples 1 to 13
Embodiments 1 to 13 respectively provide a composite calcium-zinc heat stabilizer composition, the contents of each component are shown in table 1, and the preparation method comprises: the components are uniformly mixed according to the table 1 to obtain the composite calcium-zinc heat stabilizer composition.
TABLE 1 component content (parts by weight) of the composite calcium-zinc heat stabilizer compositions of examples 1 to 13
Comparative examples 1 to 8
Comparative examples 1 to 8 respectively provide a composite calcium-zinc heat stabilizer composition, the contents of the components are shown in table 2, and the preparation method comprises the following steps: the components are uniformly mixed according to the table 1 to obtain the composite calcium-zinc heat stabilizer composition.
TABLE 2 component contents (parts by weight) of composite calcium-zinc heat stabilizer compositions of comparative examples 1 to 8
Performance testing
The calcium-zinc heat stabilizer prepared in the above examples and comparative examples is uniformly mixed according to the following parts by weight: 100 parts of PVC, 8 parts of a composite calcium-zinc heat stabilizer composition, 5 parts of calcium carbonate, 1 part of a lubricant, 5 parts of an impact modifier and 1 part of a processing aid to obtain a PVC pipeline material; and adding the PVC pipeline material into a double-screw extruder, performing melt extrusion, molding by a mold, performing cooling shaping by using a cooling water tank, and cutting to obtain the PVC pipeline.
The heat-resistant stability time test is carried out on the PVC pipeline material, the precipitation condition of the composite calcium-zinc heat stabilizer composition is observed, and the heat stability of the composite calcium-zinc heat stabilizer composition is evaluated, and the specific method comprises the following steps:
heat-resistant stabilization time: performing a rheological experiment on the PVC pipeline material by using a torque rheometer, sampling a sample at intervals, and testing the color change of the sample by using a color difference meter, wherein the time for changing the color from colorless to other colors is the heat-resistant stable time;
precipitation of the heat stabilizer: performing a pipe extrusion experiment on the PVC pipeline material by using an extruder, observing precipitates at a neck mold after 4 hours of continuous startup, and weighing the mass of the precipitates, wherein less than 1mg is I grade, 1-5 mg is II grade, and more than 5mg is III grade.
The test results of the examples and comparative examples are shown in Table 3.
According to the test results in the table, the composite calcium-zinc heat stabilizer composition provided by the embodiments of the invention has excellent heat stabilization effect on PVC, has long heat stabilization time which is equal to or more than 30min, and does not have a heat stabilizer precipitation condition in the PVC pipeline preparation process.
In comparative example 1, the composite calcium-zinc heat stabilizer composition does not contain modified fumed silica and hydroxyl-terminated pentaerythritol adipate, the heat resistance stability is poor, the heat resistance stabilization time is only 20min, the color of a sample piece is changed in 25min, and more precipitates exist. In comparative examples 2 and 3, the fumed silica added was not modified with a silane coupling agent, the heat-resistant stability time was only 25min, and there was a certain degree of precipitation. In comparative examples 5 and 6, when the hydroxyl-terminated pentaerythritol adipate was replaced with pentaerythritol stearate or pentaerythritol oleate in equal amounts, respectively, although pentaerythritol was added to the PVC system as an ester group in the two comparative examples, stearic acid or oleic acid, both of which are non-hydroxyl-containing acids, failed to compensate for the reacted hydroxyl groups in the pentaerythritol molecule, and thus it was difficult to achieve effective improvement of heat resistance, and some of them were precipitated during the production process. In the comparative example 7, the unesterified pentaerythritol is used to replace the pentaerythritol terminated with hydroxyl adipic acid, so that the thermal stability can not meet the requirement, and the precipitates are more and reach the III level. In comparative examples 4 and 8, in the case where the modified fumed silica or the hydroxyl-terminated pentaerythritol adipate was not added, the heat-resistant stabilization time was 25min, and the excellent effects as in the examples of the present application could not be obtained.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The composite calcium-zinc heat stabilizer composition is characterized by comprising the following components in parts by weight:
10 parts of calcium-zinc heat stabilizer, 0.2-2 parts of modified fumed silica and 0.2-2 parts of hydroxyl-terminated pentaerythritol adipate;
the modified fumed silica is fumed silica modified by a silane coupling agent.
2. The composite calcium-zinc heat stabilizer composition according to claim 1, wherein the hydroxyl-terminated adipic acid pentaerythritol ester is obtained by esterification of hydroxyl-terminated adipic acid and pentaerythritol; the molar ratio of the hydroxyl-terminated adipic acid to the pentaerythritol is (1-1.5) to 2.
3. The composite calcium-zinc heat stabilizer composition as claimed in claim 1, wherein the hydroxyl-terminated pentaerythritol adipate has an acid value of 0.5mgKOH/g or less and a hydroxyl value of 70 to 90 mgKOH/g.
4. The composite calcium-zinc heat stabilizer composition of claim 1, wherein the modified fumed silica is prepared by the following method:
dispersing the fumed silica and a silane coupling agent in an organic solvent, carrying out reflux reaction for 2-4 h at the temperature of 60-80 ℃, and carrying out post-treatment to obtain the modified fumed silica.
5. The composite calcium-zinc heat stabilizer composition according to claim 4, wherein the mass ratio of the fumed silica to the silane coupling agent is (40-50): (20-30).
6. The composite calcium-zinc heat stabilizer composition according to claim 1, wherein the density of silanol groups on the surface of the modified fumed silica is 3-5 SiOH/nm2。
7. The composite calcium-zinc heat stabilizer composition as claimed in claim 1, wherein the specific surface area of the modified fumed silica is 250-350 m2/g。
8. The composite calcium-zinc heat stabilizer composition of claim 1, wherein the calcium-zinc heat stabilizer is a mixture of calcium stearate and zinc stearate.
9. The preparation method of the composite calcium-zinc heat stabilizer composition of any one of claims 1 to 8, characterized by comprising the following steps:
and uniformly mixing the calcium-zinc heat stabilizer, the modified fumed silica and the hydroxyl-terminated adipic acid pentaerythritol ester to obtain the composite calcium-zinc heat stabilizer composition.
10. Use of the composite calcium-zinc heat stabilizer composition of any one of claims 1 to 8 in PVC composite materials.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093648A (en) * | 2010-12-10 | 2011-06-15 | 浙江海普顿化工科技有限公司 | Pasty calcium-zinc composite heat stabilizer and preparation method thereof |
| CN102504339A (en) * | 2011-10-25 | 2012-06-20 | 浙江海普顿新材料股份有限公司 | Powdery calcium-zinc complex heat stabilizer and preparation method and application thereof |
| CN103613884A (en) * | 2013-12-05 | 2014-03-05 | 山东慧科助剂股份有限公司 | Efficient zinc-based composite heat stabilizer for PVC (polyvinyl chloride) and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1597688A (en) * | 1977-04-22 | 1981-09-09 | Koei Chemical Co | Stabilizer for chlorine-containing resins |
| CN105237942B (en) * | 2015-10-12 | 2019-01-29 | 神华集团有限责任公司 | A kind of reinforced polyformaldehyde composite material and preparation method |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093648A (en) * | 2010-12-10 | 2011-06-15 | 浙江海普顿化工科技有限公司 | Pasty calcium-zinc composite heat stabilizer and preparation method thereof |
| CN102504339A (en) * | 2011-10-25 | 2012-06-20 | 浙江海普顿新材料股份有限公司 | Powdery calcium-zinc complex heat stabilizer and preparation method and application thereof |
| CN103613884A (en) * | 2013-12-05 | 2014-03-05 | 山东慧科助剂股份有限公司 | Efficient zinc-based composite heat stabilizer for PVC (polyvinyl chloride) and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 刘淑强著: "《聚乳酸纤维》", 30 November 2012, 东华大学出版社 * |
| 吴改红等著: "《聚乳酸纤维及其纺织品》", 31 May 2014, 东华大学出版社 * |
| 景永杰等: ""PVC辅助热稳定剂己二酸季戊四醇酯催化合成研究及应用"", 《山东化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113816842A (en) * | 2021-10-11 | 2021-12-21 | 山东键兴新材料科技有限公司 | Calcium acetylacetonate, preparation method and application thereof |
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| CN115232363B (en) | 2023-09-01 |
| CN115232363A (en) | 2022-10-25 |
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