CN112029116A - Preparation method of emulsified modified asphalt based on zwitterionic Gemini emulsifier - Google Patents
Preparation method of emulsified modified asphalt based on zwitterionic Gemini emulsifier Download PDFInfo
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Abstract
The invention relates to a preparation method of emulsified modified asphalt based on a zwitterionic Gemini emulsifier, which comprises the following steps: firstly, mixing and stirring a zwitterionic Gemini emulsifier, an antifreeze, a thickening agent and water uniformly, and heating to 40-65 ℃ to obtain a soap solution; heating the modified asphalt to 125-160 ℃ to obtain softened asphalt; and (2) simultaneously and respectively conveying the soap solution and the softened asphalt into a colloid mill, uniformly dispersing and grinding the soap solution and the softened asphalt by the colloid mill to form an oil-in-water type emulsion, taking the emulsion out of the system when the temperature of the emulsion is reduced to below 60 ℃, adding alumina sol into the system, and uniformly stirring the mixture to obtain the amphoteric ion type Gemini emulsifier-based emulsified modified asphalt. The invention synthesizes the zwitterionic Gemini emulsifier with a special structure, which has high emulsification effect, anti-settling effect and high wettability on asphalt, and the emulsified modified asphalt has the advantages of good permeability and high stability.
Description
Technical Field
The invention relates to emulsified asphalt, in particular to a preparation method of emulsified modified asphalt based on a zwitterionic Gemini emulsifier, and belongs to the technical field of road engineering.
Background
Emulsified asphalt is an oily asphalt emulsion formed by dispersing asphalt in an aqueous solution containing an emulsifier in a fine particulate state through the action of mechanical shearing after the asphalt is hot-melted. When the emulsified asphalt is used, heating is not needed, and construction can be carried out at normal temperature. In road engineering, the emulsified asphalt is suitable for asphalt surface treatment pavements, asphalt penetration pavements, normal-temperature asphalt mixture pavements, permeable layers, adhesive layers, sealing layers and the like. Compared with conventional asphalt and hot asphalt, the application and comprehensive energy of the emulsified asphalt have the characteristics of no harm to human bodies, safety, no environmental pollution and the like. The polymer latex is added during the emulsification processing of the polymer modified asphalt, or the emulsified asphalt is prepared, or the polymer latex and the emulsified asphalt finished product are mixed, so that the emulsified modified asphalt finished product can be obtained.
Chinese patent 201310232879.8 relates to a method for synthesizing zwitterionic modified asphalt emulsifier, which uses alkali solution as catalyst, and the zwitterionic modified asphalt emulsifier prepared by the method has a cation center and an anion center, and can effectively improve the storage stability and permeability of emulsified modified asphalt. The addition amount of the polyoxyethylene ether surfactant in the emulsified modified asphalt is large, which shows that the wetting action of the zwitterionic modified asphalt emulsifier is poor.
The Gemini type surfactant is a novel surfactant which connects 2 or more than 2 traditional surfactant molecules together at a hydrophilic group or a position close to the hydrophilic group through a linking group, has high surface activity and the capability of reducing the interfacial tension of oil (water), and has good solubilization, anti-deposition and wetting properties on crude petroleum oil and a separation product thereof.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention mainly aims to provide emulsified modified asphalt based on a zwitterionic Gemini emulsifier.
The emulsifying modified asphalt based on the zwitterionic Gemini emulsifier comprises the following components in parts by weight: 60-65 parts of modified asphalt, 0.1-0.5 part of zwitterionic Gemini emulsifier, 3-6 parts of alumina sol, 0.1-0.2 part of thickening agent, 1-3 parts of antifreezing agent and 35-40 parts of water.
Wherein the modified asphalt is at least one of SBS modified asphalt and SBR modified asphalt, wherein the weight parts of SBS in the SBS modified asphalt is 1-3%, and the weight parts of SBR in the SBR modified asphalt is 1-3%.
The weight fraction of the alumina sol is 20-30%, the pH value is 5-7, and the median particle size of alumina in the alumina sol is 30-60 nm.
The thickening agent is at least one of carboxymethyl starch, organic bentonite and polyacrylamide.
The antifreezing agent is at least one of urea, sodium nitrite, calcium chloride and calcium nitrite.
The molecular structural formula of the zwitterionic Gemini emulsifier is as follows:
wherein, in the molecular structural formula, n: 1-7, m: 1-3.
The preparation method of the zwitterionic Gemini emulsifier comprises the following steps in parts by weight:
adding 10-15 parts of long-chain alkyl phenylamine, 50-80 parts of acetone and 0.01-0.02 part of catalyst into a reactor under the protection of nitrogen; then heating to 50-60 ℃, dropwise adding a mixed solution of 5-8 parts of binary brominated alkanes and 10-15 parts of acetone into the reactor, keeping the temperature and continuing to react for 2-4 hours after the dropwise adding is finished for 1-2 hours; dropwise adding a mixed solution of 2-4 parts of dimethyl sulfate and 5-10 parts of acetone into the reactor, keeping the temperature and continuously reacting for 2-4 hours after the dropwise adding is finished for 1-2 hours to obtain an N, N' -double long-chain alkyl phenyl alkyl di-tertiary amine solution; adding 3-6 parts of 1, 3-propane sultone into the N, N' -double-long-chain alkyl phenyl alkyl di-tertiary amine solution, heating to 80-95 ℃, performing reflux reaction for 6-12h, generating a large amount of precipitates in the reaction process, filtering the precipitates, repeating the purification steps of methanol dissolution, acetone precipitation and filtering precipitation for 3-5 times, and performing vacuum drying on the precipitates for 24h to obtain the zwitterionic Gemini emulsifier.
The long-chain alkyl phenylamine is at least one of 4-dodecyl aniline, 4-tridecyl aniline, 4-tetradecyl aniline, 4-pentadecyl aniline, 4-hexadecyl aniline, 4-heptadecyl aniline, 4-octadecyl aniline, 3-dodecyl aniline, 3-tridecyl aniline, 3-tetradecyl aniline, 3-pentadecyl aniline, 3-hexadecyl aniline, 3-heptadecyl aniline and 3-octadecyl aniline.
The catalyst is at least one of dibutyltin dilaurate, dibutyltin maleate, tin naphthenate and dibutyltin diacetate.
The binary brominated alkane is at least one of 1, 3-dibromopropane, 1, 4-dibromopropane, 1, 5-dibromopropane and 1, 6-dibromopropane.
The invention also aims to provide a preparation method of the emulsified modified asphalt based on the zwitterionic Gemini emulsifier.
The preparation method of the emulsified modified asphalt based on the zwitterionic Gemini emulsifier comprises the following steps:
firstly, mixing and stirring a zwitterionic Gemini emulsifier, an antifreeze, a thickening agent and water uniformly, and heating to 40-65 ℃ to obtain a soap solution; heating the modified asphalt to 125-160 ℃ to obtain softened asphalt; and (2) simultaneously and respectively conveying the soap solution and the softened asphalt into a colloid mill, uniformly dispersing and grinding the soap solution and the softened asphalt by the colloid mill to form an oil-in-water type emulsion, taking the emulsion out of the system when the temperature of the emulsion is reduced to below 60 ℃, adding alumina sol into the system, and uniformly stirring the mixture to obtain the amphoteric ion type Gemini emulsifier-based emulsified modified asphalt.
Compared with the prior art, the invention has the following advantages or beneficial results: (1) the amphoteric ionic Gemini emulsifier with a special structure is synthesized, has high emulsification, anti-settling and high wettability on asphalt, and has the advantages of good permeability and high stability; (2) the inorganic antifreeze agent is selected, so that the inorganic antifreeze agent is easy to dry when the pavement construction is carried out on the asphalt while the freezing point of the emulsified asphalt is reduced; (3) on one hand, the alumina sol is used as a flame retardant component of emulsified modified asphalt and solidified asphalt, and on the other hand, the alumina sol, fillers (sand and stone), ground base materials and the like are combined through aluminum-oxygen bonds after the asphalt is solidified, so that the compressive strength of the asphalt pavement is improved.
Detailed Description
The invention further describes an emulsified modified asphalt based on a zwitterionic Gemini emulsifier and a preparation method thereof by combining with the examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
The emulsified modified asphalt based on the zwitterionic Gemini emulsifier comprises the following components in parts by weight: 65 parts of modified asphalt, 0.5 part of amphoteric ion type Gemini emulsifier, 6 parts of alumina sol (the weight percentage is 20%, the pH value is 5, and the median particle size of alumina in the alumina sol is 50-60nm), 0.1 part of polyacrylamide, 1 part of calcium nitrite and 40 parts of water; wherein the modified asphalt is SBR modified asphalt, and the weight part of SBR in the SBR modified asphalt is 1 percent.
The preparation method of the modified emulsified asphalt of the zwitterionic Gemini emulsifier comprises the following steps:
firstly, mixing and stirring a zwitterionic Gemini emulsifier, an antifreeze, a thickening agent and water uniformly, and heating to 55 ℃ to obtain a soap solution; heating the modified asphalt to 138 ℃ to obtain softened asphalt; and (2) simultaneously and respectively conveying the soap solution and the softened asphalt into a colloid mill, uniformly dispersing and grinding the soap solution and the softened asphalt by the colloid mill to form an oil-in-water type emulsion, taking the emulsion out of the system when the temperature of the emulsion is reduced to below 60 ℃, adding alumina sol into the system, and uniformly stirring the mixture to obtain the amphoteric ion type Gemini emulsifier-based emulsified modified asphalt.
The preparation method of the zwitterionic Gemini emulsifier comprises the following steps of:
under the protection of nitrogen, 12 parts of 4-dodecylaniline, 62 parts of acetone and 0.015 part of stannic naphthenate are added into a reactor; then heating to 58 ℃, dropwise adding a mixed solution of 5 parts of 1, 4-dibromopropane and 10 parts of acetone into the reactor, keeping the temperature and continuing to react for 2.5 hours after dropwise adding is finished for 1.5 hours; dropwise adding a mixed solution of 2 parts of dimethyl sulfate and 5 parts of acetone into the reactor, keeping the temperature and continuously reacting for 3 hours after the dropwise adding is finished for 1.5 hours to obtain an N, N' -double-long-chain alkyl phenyl alkyl di-tertiary amine solution; adding 3 parts of 1, 3-propane sultone into the N, N' -double-long-chain alkyl phenyl alkyl di-tertiary amine solution, heating to 86 ℃, carrying out reflux reaction for 8 hours, generating a large amount of precipitates in the reaction process, filtering the precipitates, repeating the purification steps of methanol dissolution, acetone precipitation and filtering precipitation for 4 times, and then carrying out vacuum drying on the precipitates for 24 hours to obtain the zwitterionic Gemini emulsifier.
Example 2
The emulsified modified asphalt based on the zwitterionic Gemini emulsifier comprises the following components in parts by weight: 60 parts of modified asphalt, 0.1 part of zwitterionic Gemini emulsifier, 3 parts of alumina sol (the weight percentage is 30%, the pH value is 6, and the median particle size of alumina in the alumina sol is 30-40nm), 0.2 part of organic bentonite, 3 parts of calcium chloride and 35 parts of water; wherein the modified asphalt is SBS modified asphalt, and the SBS weight part in the SBS modified asphalt is 3%.
The preparation method of the modified emulsified asphalt of the zwitterionic Gemini emulsifier comprises the following steps:
firstly, mixing and stirring a zwitterionic Gemini emulsifier, an antifreeze, a thickening agent and water uniformly, and heating to 40 ℃ to obtain a soap solution; heating the modified asphalt to 125 ℃ to obtain softened asphalt; and (2) simultaneously and respectively conveying the soap solution and the softened asphalt into a colloid mill, uniformly dispersing and grinding the soap solution and the softened asphalt by the colloid mill to form an oil-in-water type emulsion, taking the emulsion out of the system when the temperature of the emulsion is reduced to below 60 ℃, adding alumina sol into the system, and uniformly stirring the mixture to obtain the amphoteric ion type Gemini emulsifier-based emulsified modified asphalt.
The preparation method of the zwitterionic Gemini emulsifier comprises the following steps of:
adding 10 parts of 3-dodecylaniline, 50 parts of acetone and 0.02 part of dibutyltin dilaurate into a reactor under the protection of nitrogen; then heating to 50 ℃, dropwise adding a mixed solution of 7 parts of 1, 3-dibromopropane and 13 parts of acetone into the reactor, keeping the temperature and continuing to react for 4 hours after dropwise adding is finished for 2 hours; dropwise adding a mixed solution of 3.5 parts of dimethyl sulfate and 8 parts of acetone into the reactor, keeping the temperature and continuously reacting for 4 hours after the dropwise adding is finished for 2 hours to obtain an N, N' -double-long-chain alkyl phenyl alkyl di-tertiary amine solution; and adding 5 parts of 1, 3-propane sultone into the N, N' -double-long-chain alkyl phenyl alkyl di-tertiary amine solution, heating to 80 ℃, carrying out reflux reaction for 12 hours, generating a large amount of precipitates in the reaction process, filtering the precipitates, repeating the purification steps of methanol dissolution, acetone precipitation and filtering precipitation for 5 times, and then carrying out vacuum drying on the precipitates for 24 hours to obtain the zwitterionic Gemini emulsifier.
Example 3
The emulsified modified asphalt based on the zwitterionic Gemini emulsifier comprises the following components in parts by weight: 62 parts of modified asphalt, 0.3 part of zwitterionic Gemini emulsifier, 4 parts of alumina sol (the weight percentage is 25%, the pH value is 7, and the median particle size of alumina in the alumina sol is 30-50nm), 0.15 part of carboxymethyl starch, 2 parts of sodium nitrite and 38 parts of water; wherein the modified asphalt is SBS modified asphalt, and the weight portion of SBS in the SBS modified asphalt is 1.53%.
The preparation method of the modified emulsified asphalt of the zwitterionic Gemini emulsifier comprises the following steps:
firstly, mixing and stirring a zwitterionic Gemini emulsifier, an antifreeze, a thickening agent and water uniformly, and heating to 65 ℃ to obtain a soap solution; heating the modified asphalt to 160 ℃ to obtain softened asphalt; and (2) simultaneously and respectively conveying the soap solution and the softened asphalt into a colloid mill, uniformly dispersing and grinding the soap solution and the softened asphalt by the colloid mill to form an oil-in-water type emulsion, taking the emulsion out of the system when the temperature of the emulsion is reduced to below 60 ℃, adding alumina sol into the system, and uniformly stirring the mixture to obtain the amphoteric ion type Gemini emulsifier-based emulsified modified asphalt.
The preparation method of the zwitterionic Gemini emulsifier comprises the following steps of:
adding 15 parts of 4-octadecylaniline, 80 parts of acetone and 0.01 part of dibutyltin maleate into a reactor under the protection of nitrogen; then heating to 60 ℃, dropwise adding a mixed solution of 8 parts of 1, 6-dibromopropane and 15 parts of acetone into the reactor, keeping the temperature and continuing to react for 2 hours after 1 hour of dropwise addition; dropwise adding a mixed solution of 4 parts of dimethyl sulfate and 10 parts of acetone into the reactor, keeping the temperature and continuing to react for 2 hours after 1 hour of dropwise addition is finished, thus obtaining an N, N' -double-long-chain alkyl phenyl alkyl di-tertiary amine solution; adding 6 parts of 1, 3-propane sultone into the N, N' -double-long-chain alkyl phenyl alkyl di-tertiary amine solution, heating to 95 ℃, carrying out reflux reaction for 6 hours, generating a large amount of precipitates in the reaction process, filtering the precipitates, repeating the purification steps of methanol dissolution, acetone precipitation and filtering precipitation for 3 times, and then carrying out vacuum drying on the precipitates for 24 hours to obtain the zwitterionic Gemini emulsifier.
Comparative example
Emulsified asphalt was prepared according to the following formulation composition (the zwitterionic Gemini emulsifier used in example 1 was changed to octadecyl trimethyl ammonium chloride and the amount of octadecyl trimethyl ammonium chloride was doubled): the formula comprises the following components in parts by weight: 65 parts of modified asphalt, 1 part of octadecyl trimethyl ammonium chloride emulsifier, 6 parts of alumina sol (the weight fraction is 20%, the pH value is 5, and the median particle size of alumina in the alumina sol is 50-60nm), 0.1 part of polyacrylamide, 1 part of calcium nitrite and 40 parts of water; wherein the modified asphalt is SBR modified asphalt, and the weight part of SBR in the SBR modified asphalt is 1 percent.
The preparation method of the above comparative example is as follows: firstly, mixing and stirring an octadecyl trimethyl ammonium chloride emulsifier, an antifreeze agent, a thickening agent and water uniformly, and heating to 55 ℃ to obtain a soap solution; heating the modified asphalt to 138 ℃ to obtain softened asphalt; and (3) simultaneously and respectively conveying the soap solution and the softened asphalt into a colloid mill, uniformly dispersing and grinding the soap solution and the softened asphalt by the colloid mill to form an oil-in-water emulsion, taking the emulsion out of the system when the temperature of the emulsion is reduced to below 60 ℃, adding alumina sol into the emulsion, and uniformly stirring the mixture to obtain the comparative example.
The emulsified modified asphalts of examples 1-3 were tested according to the relevant standards, and some of the physical and chemical parameters are shown in Table 1.
TABLE 1 emulsifying modified asphalt Properties based on zwitterionic Gemini emulsifier
As can be seen from Table 1, the normal temperature storage performance and the low temperature storage performance of the emulsified and modified asphalt based on the zwitterionic Gemini emulsifier are obviously superior to those of a comparative example, the freeze-thaw performance is not loose after the emulsified and modified asphalt is mixed with mineral aggregate at the low temperature of-25 ℃, and the emulsified and modified asphalt mainly derives from the low temperature resistance of the zwitterionic Gemini emulsifier; meanwhile, the table also shows that the Gemini emulsifier in the embodiment has better emulsifying effect and smaller particle size of the emulsified asphalt.
Claims (11)
1. A preparation method of emulsified modified asphalt based on a zwitterionic Gemini emulsifier comprises the following steps:
firstly, mixing and stirring a zwitterionic Gemini emulsifier, an antifreeze, a thickening agent and water uniformly, and heating to 40-65 ℃ to obtain a soap solution; heating the modified asphalt to 125-160 ℃ to obtain softened asphalt; and (2) simultaneously and respectively conveying the soap solution and the softened asphalt into a colloid mill, uniformly dispersing and grinding the soap solution and the softened asphalt by the colloid mill to form an oil-in-water type emulsion, taking the emulsion out of the system when the temperature of the emulsion is reduced to below 60 ℃, adding alumina sol into the system, and uniformly stirring the mixture to obtain the amphoteric ion type Gemini emulsifier-based emulsified modified asphalt.
2. The preparation method of the emulsified and modified asphalt based on the zwitterionic Gemini emulsifier according to claim 1, which is characterized by comprising the following components in parts by weight: 60-65 parts of modified asphalt, 0.1-0.5 part of zwitterionic Gemini emulsifier, 3-6 parts of alumina sol, 0.1-0.2 part of thickening agent, 1-3 parts of antifreezing agent and 35-40 parts of water.
3. The method according to claim 1, wherein the modified asphalt is at least one of SBS modified asphalt and SBR modified asphalt, wherein the SBS modified asphalt comprises 1-3 wt% of SBS and the SBR modified asphalt comprises 1-3 wt% of SBR.
4. The preparation method of the emulsified and modified asphalt based on the zwitterionic Gemini emulsifier according to claim 1, wherein the weight fraction of the alumina sol is 20-30%, the pH value is 5-7, and the median particle size of alumina in the alumina sol is 30-60 nm.
5. The method for preparing the emulsified and modified asphalt based on the zwitterionic Gemini emulsifier according to claim 1, wherein the thickener is at least one of carboxymethyl starch, organic bentonite and polyacrylamide.
6. The method for preparing the emulsified and modified asphalt based on the zwitterionic Gemini emulsifier according to claim 1, wherein the antifreezing agent is at least one of urea, sodium nitrite, calcium chloride and calcium nitrite.
7. The preparation method of the emulsified and modified asphalt based on the zwitterionic Gemini emulsifier according to claim 1, wherein the preparation method of the zwitterionic Gemini emulsifier comprises the following steps in parts by weight:
adding 10-15 parts of long-chain alkyl phenylamine, 50-80 parts of acetone and 0.01-0.02 part of catalyst into a reactor under the protection of nitrogen; then heating to 50-60 ℃, dropwise adding a mixed solution of 5-8 parts of binary brominated alkanes and 10-15 parts of acetone into the reactor, keeping the temperature and continuing to react for 2-4 hours after the dropwise adding is finished for 1-2 hours; dropwise adding a mixed solution of 2-4 parts of dimethyl sulfate and 5-10 parts of acetone into the reactor, keeping the temperature and continuously reacting for 2-4 hours after the dropwise adding is finished for 1-2 hours to obtain an N, N' -double long-chain alkyl phenyl alkyl di-tertiary amine solution; adding 3-6 parts of 1, 3-propane sultone into the N, N' -double-long-chain alkyl phenyl alkyl di-tertiary amine solution, heating to 80-95 ℃, performing reflux reaction for 6-12h, generating a large amount of precipitates in the reaction process, filtering the precipitates, repeating the purification steps of methanol dissolution, acetone precipitation and filtering precipitation for 3-5 times, and performing vacuum drying on the precipitates for 24h to obtain the zwitterionic Gemini emulsifier.
8. The preparation method of the emulsified and modified asphalt based on the zwitterionic Gemini emulsifier according to claim 1, wherein the zwitterionic Gemini emulsifier has a molecular structural formula as follows:
wherein, in the molecular structural formula, n: 1-7, m: 1-3.
9. The method of claim 7, wherein the long-chain alkylphenylamine is at least one of 4-dodecylaniline, 4-tridecylaniline, 4-tetradecylaniline, 4-pentadecylaniline, 4-hexadecylaniline, 4-heptadecylaniline, 4-octadecylaniline, 3-dodecylaniline, 3-tridecylaniline, 3-tetradecylaniline, 3-pentadecylaniline, 3-hexadecylaniline, 3-heptadecylaniline, and 3-octadecylaniline.
10. The method for preparing the emulsified and modified asphalt based on the zwitterionic Gemini emulsifier according to claim 7, wherein the catalyst is at least one of dibutyltin dilaurate, dibutyltin maleate, tin naphthenate and dibutyltin diacetate.
11. The method for preparing the emulsifying modified asphalt based on the zwitterionic Gemini emulsifier according to claim 7, wherein the binary brominated alkane is 1, 3-dibromopropane.
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| CN202010956671.0A Withdrawn CN112029302A (en) | 2018-04-05 | 2018-04-05 | Zwitterionic Gemini emulsifier and application thereof in asphalt |
| CN202010957731.0A Withdrawn CN112029116A (en) | 2018-04-05 | 2018-04-05 | Preparation method of emulsified modified asphalt based on zwitterionic Gemini emulsifier |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201810302644.4A Active CN108359256B (en) | 2018-04-05 | 2018-04-05 | Emulsified modified asphalt based on zwitterionic Gemini emulsifier and preparation method thereof |
| CN202010956671.0A Withdrawn CN112029302A (en) | 2018-04-05 | 2018-04-05 | Zwitterionic Gemini emulsifier and application thereof in asphalt |
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Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101856600B (en) * | 2010-06-25 | 2012-08-29 | 西北大学 | Amphoteric ionic Gemini surfactant and synthetic method thereof |
| CN103059581B (en) * | 2011-10-18 | 2015-05-13 | 中国石油化工股份有限公司 | Anti-freezing emulsified asphalt and preparation method thereof |
| CN102516093B (en) * | 2011-12-08 | 2014-10-08 | 江苏博特新材料有限公司 | Gemini type asphalt emulsifier and preparation method thereof |
| CN103525099B (en) * | 2012-07-03 | 2015-10-28 | 华东理工大学 | Compound asphalt emulsifier containing Gemini surface active agent |
| CN103274972B (en) * | 2013-06-13 | 2015-06-03 | 江苏苏博特新材料股份有限公司 | Synthesis method of zwitterion type modified asphalt emulsifier and modified emulsified asphalt containing emulsifier |
| CN107298725B (en) * | 2017-08-23 | 2019-07-12 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of the miscellaneous Shuangzi asphalt emulsifier of chitosan-based cationic |
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2018
- 2018-04-05 CN CN201810302644.4A patent/CN108359256B/en active Active
- 2018-04-05 CN CN202010956671.0A patent/CN112029302A/en not_active Withdrawn
- 2018-04-05 CN CN202010957731.0A patent/CN112029116A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| CN108359256B (en) | 2020-12-29 |
| CN112029302A (en) | 2020-12-04 |
| CN108359256A (en) | 2018-08-03 |
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Application publication date: 20201204 |