CN110982056B - Method for synthesizing alkynediol block polyether - Google Patents
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
- C08G2650/24—Polymeric initiators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/60—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing acetylenic group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/62—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the nature of monomer used
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention relates to a method for synthesizing block polyether, in particular to a method for synthesizing block polyether by reacting alkyne diol serving as an initiator with ethylene oxide and/or propylene oxide under the action of a composite catalyst. Under the action of the composite catalyst, the reaction temperature and pressure are controlled, and the acetylenic diol is sequentially subjected to polymerization reaction with the epoxypropane and the epoxyethane to obtain the acetylenic diol block polyether. The composite catalyst comprises a mixture of an alkyl metal catalyst and an organic base catalyst. The alkynediol block polyether designed and synthesized by the invention has the advantages of low color and luster, no need of post-treatment, simple production process and low production cost; and secondly, the defoaming performance and static and dynamic surface tension of the product are more prominent, and the application performance is wider.
Description
Technical Field
The invention relates to a method for synthesizing block polyether, in particular to a method for synthesizing block polyether by reacting alkyne diol serving as an initiator with ethylene oxide and/or propylene oxide under the action of a composite catalyst.
Background
The alkyne diol gemini surfactant has two hydrophilic groups, the triple bond is positioned in the center of a hydrocarbon chain, and the ethoxy and the hydroxyl are symmetrically distributed on two sides of the triple bond, so that the alkyne diol gemini surfactant has good surface tension reducing capacity, defoaming and foam inhibiting capacity and the like due to the special molecular structure, and is widely applied to the fields of water-based coatings, printing ink, adhesives, building materials and the like. Patent CN102304029A discloses a method for synthesizing ethoxylated 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol by using alkali such as sodium hydroxide, trimethylamine or triethylamine as a catalyst and reacting in a solvent such as diethyl ether, benzene or toluene. The method has the advantages of reaction in a solvent, easy volatilization of the solvent or easy pollution generation, complex process and higher cost. Patent CN108517031A discloses that 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol is used as initiator, acidic ionic liquid 1-butyl-3-methylimidazole dihydrogen phosphate, 1-butyl-3-methylimidazole hydrogen sulfate or 1-butyl-3-methylimidazole trifluoromethane sulfonate is used as solvent and acidic catalyst, organic base trimethylamine, triethylamine and the like are used as basic catalyst to perform polymerization reaction, and after the reaction, ether anhydrous ether, tetrahydrofuran, methylethyl ether and the like are used as extractant to separate and obtain ethoxylated 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol. The method has the disadvantages of complicated process, high cost and difficulty in realizing industrial production.
The acetylenic diol multifunctional surfactant synthesized by the prior art mostly uses triethylamine as a catalyst, the synthesized product has high chroma, needs post-treatment or reaction and extraction in a solvent, and has complex process, high cost and easy pollution; ethylene oxide is mostly used for polymerization, and the permeability and defoaming performance of the product are different from those of silicone or fluorine surfactants; both color and performance problems limit the range of applications of acetylenic diol multifunctional surfactants, especially in demanding applications.
The invention content is as follows:
in order to overcome the defects of the prior art, the invention provides a method for synthesizing alkynediol block polyether, which comprises the following specific scheme:
the molecular formula of the alkynediol block polyether is as follows:
wherein R is 1 、R 4 Independently selected from C 3 ~C 10 Alkyl of R 2 And R 3 Is methyl or ethyl, m ranges from 1 to 6, and n ranges from 3 to 15.
A production process of alkynediol block polyether comprises the following steps:
(a) sequentially adding a composite catalyst and a preheated alkynediol initiator into a reaction kettle, discharging nitrogen for 3-4 times, and dehydrating for 1 hour at 110 ℃; controlling the reaction temperature, slowly dripping propylene oxide to carry out polyether reaction, adjusting the temperature to carry out degassing after curing, and removing unreacted propylene oxide;
(b) controlling the reaction temperature, dropwise adding ethylene oxide, carrying out polyether reaction, and curing;
(c) controlling temperature and degassing after the reaction is finished, and cooling and neutralizing (the acid selected for neutralization is at least one of phosphoric acid, hydrochloric acid, citric acid and acetic acid, preferably acetic acid) to obtain the product.
The composite catalyst is a mixture of an alkyl metal catalyst and an organic base catalyst.
The alkyne diol initiator in step (a) is selected from one or more of 4, 7-dimethyl-5-decyne-4, 7-diol, 2,4,7, 9-tetramethyl-5-decyne diol, 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol, 2,3,5,8,10, 11-hexamethyl-6-dodecyne-5, 8-diol, or 7, 10-diol.
The alkynediol initiator is PO and EO =1: 1-8: 1-20.
The alkyne diol initiator is PO: EO =1: 1-6: 3-15.
The alkyl metal catalyst is nBuLi or CaEt 2 、AlEt 3 And ZnEt 3 Is one or more of dimethylamine, trimethylamine, triethylamine and N-toluidine, and a mixture thereof.
The composite catalyst is AlEt 3 And triethylamine in a weight ratio of 1: 1-8; the dosage of the composite catalyst is 0.01-2% of the quantity of the alkynediol initiator substance,
the composite catalyst is AlEt 3 And triethylamine in a weight ratio of 1: 1-6; the dosage of the composite catalyst is 0.05-1% of the quantity of the alkyne diol initiator substance.
The reaction temperature in the step (a) is 60-150 ℃, and the preferable reaction temperature is 60-130 ℃.
The reaction temperature in the step (b) is 50-120 ℃, and preferably 55-110 ℃.
The degassing temperature in the step (c) is 60-120 ℃, preferably 100-110 ℃, and the degassing time is 1 hour.
The idea of the synthetic method of the alkynediol block polyether is as follows: under the action of the composite catalyst, the reaction temperature and pressure are controlled, and the acetylenic diol is sequentially subjected to polymerization reaction with the epoxypropane and the epoxyethane to obtain the acetylenic diol block polyether. The composite catalyst comprises a mixture of an alkyl metal catalyst and an organic base catalyst.
The application of the alkynediol surfactant mainly utilizes the properties of low foam, foam inhibition and high surface activity of the alkynediol surfactant, a block copolymer is designed according to the relationship between the property of the surfactant and the structure, the introduction of a PO block increases the gaps among foam liquid membranes of a system, the liquid discharge rate is accelerated, the foamability is reduced, and meanwhile, the permeability of a PO chain with a branched chain is enhanced, so that the application performance of the alkynediol surfactant is more excellent; the problem of deep color of the alkynediol surfactant is mostly caused by triethylamine catalyst, a proper amount of alkyl metal catalyst and an organic base catalyst are compounded to be used as a composite catalyst, the activity of the alkyl metal catalyst is very low, but a stable complex can be formed after the alkyl metal catalyst and the organic base catalyst are mixed, the catalytic activity is improved, and the dosage of the catalyst is reduced, so that the synthesized alkynediol surfactant is light in color, and the problem that the alkynediol surfactant is deep in color and needs aftertreatment in the traditional synthesis process is solved. The pressures in the present invention are gauge pressures; the usage amount proportion refers to the molar ratio; in the specific implementation of the invention, the measuring method of the chromaticity adopts GB/T605-2006; the hydroxyl value test method of the product in the specific implementation of the invention adopts GB/T7383-2007 (determination of hydroxyl value of nonionic surfactant); the surface tension and dynamic surface tension of the product in the practice of the invention are by bubble compaction.
Compared with the prior art, the alkynediol block polyether designed and synthesized by the invention has the advantages of low color and luster, no need of post-treatment, simple production process and low production cost; and secondly, the defoaming performance and static and dynamic surface tension of the product are more prominent, and the application performance is wider.
Detailed Description
Example 1
1mol (226 g) of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and 0.113g of AlEt are introduced into a 2.5L pressure reactor 3 A composite catalyst consisting of triethylamine (1: 3); starting stirring, replacing gas in the kettle with nitrogen for 3 times, heating to about 110 ℃, and dehydrating in vacuum for 1 hour; controlling the temperature between 100 ℃ and 105 ℃, slowly dripping 9mol of ethylene oxide, controlling the pressure below 0.35Mpa, curing for about 0.5 hour until the reaction pressure is basically unchanged; then controlling the reaction temperature between 65 ℃ and 70 ℃, slowly dripping 1mol of propylene oxide, controlling the pressure below 0.35Mpa, and curing for about 3 hours until the reaction pressure is basically unchanged; after the reaction is finished, controlling the temperature to be about 100 ℃, degassing for 1 hour in vacuum, and removing unreacted ethylene oxide and propylene oxide or partial catalyst; and (3) reducing the temperature to 65 ℃, neutralizing with acetic acid, cooling to obtain an alkynediol block polyether product, and sampling for performance test.
Examples 2 to 10
The rest of the steps are the same as the setting of the example 1, the differences are the type, the proportion and the addition amount of the catalyst, the proportion of PO/EO, the reaction sequence and the reaction temperature in corresponding time periods, and specific relevant parameters are shown in the table 1.
Table 1: table for setting Process parameters of examples 1 to 10
To further illustrate the effects, the static surface tension, dynamic surface tension, color and hydroxyl number of examples 1-10 were measured and are listed in Table 2 for comparison.
Table 2: EXAMPLES 1 to 10 index test charts
Comparative examples 1 to 5
Comparative examples 1 to 5 were set up in the same manner as in example 1, except that the catalyst was different in type, and the specific test indexes were as shown in Table 3.
Table 3: index test meter for comparative examples 1 to 5
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Claims (6)
1. The alkynediol block polyether is characterized in that the molecular formula of the alkynediol block polyether is as follows:
wherein R is 1 、R 4 Independently selected from C 3 ～C 10 Alkyl of R 2 And R 3 Is methyl or ethyl, m ranges from 1 to 6, and n ranges from 3 to 15; the production process of the alkynediol block polyether comprises the following steps:
(a) sequentially adding a composite catalyst and a preheated alkynediol initiator into a reaction kettle, discharging nitrogen, and dehydrating; controlling the reaction temperature, slowly dripping propylene oxide to carry out polyether reaction, adjusting the temperature to carry out degassing after curing, and removing unreacted propylene oxide;
(b) controlling the reaction temperature, dropwise adding ethylene oxide, carrying out polyether reaction, and curing;
(c) after the reaction is finished, heating and degassing, and cooling and neutralizing to obtain a product;
the composite catalyst is AlEt 3 And triethylamine in a weight ratio of 1: 1-8; the dosage of the composite catalyst is 0.01-2% of the quantity of the alkynediol initiator substance; the reaction temperature of the step (a) is 60-150 ℃, and the reaction temperature of the step (b) is 50-120 ℃.
2. An acetylenic diol block polyether according to claim 1 wherein: the alkyne diol initiator in step (a) is selected from one or more of 4, 7-dimethyl-5-decyne-4, 7-diol, 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol, 2,3,5,8,10, 11-hexamethyl-6-dodecyne-5, 8 diol, or 7, 10-diol.
3. An acetylenic diol block polyether according to claim 1 wherein: the alkynediol initiator is PO and EO, wherein the PO and EO are 1: 1-8: 1-20.
4. An acetylenic diol block polyether according to claim 1 wherein: the alkynediol initiator is PO and EO is 1: 1-6: 3-15.
5. An acetylenic diol block polyether according to claim 1 characterised in that: the composite catalyst is AlEt 3 And triethylamine in a weight ratio of 1: 1-6; the dosage of the composite catalyst is 0.05-1% of the amount of the alkynediol initiator substance.
6. An acetylenic diol block polyether according to claim 1 wherein: the reaction temperature of the step (a) is 60-130 ℃, and the reaction temperature of the step (b) is 55-110 ℃.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
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| CN201911256920.9A CN110982056B (en) | 2019-12-10 | 2019-12-10 | Method for synthesizing alkynediol block polyether |
| PCT/CN2020/099059 WO2021114619A1 (en) | 2019-12-10 | 2020-06-30 | Alkynediol block polyether and synthesis method therefor |
| KR1020227023420A KR20220114004A (en) | 2019-12-10 | 2020-06-30 | Alkynediol block polyethers and methods for their synthesis |
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| CN201911256920.9A CN110982056B (en) | 2019-12-10 | 2019-12-10 | Method for synthesizing alkynediol block polyether |
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| CN110982056B (en) * | 2019-12-10 | 2022-09-27 | 浙江皇马科技股份有限公司 | Method for synthesizing alkynediol block polyether |
| CN111471180A (en) * | 2020-05-07 | 2020-07-31 | 上海麦豪新材料科技有限公司 | Organosilicon surfactant and application thereof in preparation of slow-rebound polyurethane foam |
| CN111533916A (en) * | 2020-05-11 | 2020-08-14 | 江西麦豪化工科技有限公司 | Organosilicon surfactant and application thereof in preparation of polyurethane soft foam |
| CN112898556B (en) * | 2021-03-23 | 2023-08-01 | 浙江皇马科技股份有限公司 | Alkyne diol polyether and preparation method thereof |
| CN115109246B (en) * | 2022-07-01 | 2023-07-14 | 佳化化学科技发展（上海）有限公司 | Alkynyl alcohol ether and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03163038A (en) * | 1989-08-15 | 1991-07-15 | Nisshin Kagaku Kogyo Kk | Propylene oxide adduct of acetylene glycol and production thereof |
| CN107935826A (en) * | 2017-11-21 | 2018-04-20 | 浙江皇马科技股份有限公司 | Good fatty alcohol block polyether of a kind of low-temperature stability and its preparation method and application |
| CN109970964A (en) * | 2019-03-29 | 2019-07-05 | 浙江皇马科技股份有限公司 | A kind of preparation method of tertiary alkynol polyethers |
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| US6455234B1 (en) * | 1999-05-04 | 2002-09-24 | Air Products And Chemicals, Inc. | Acetylenic diol ethylene oxide/propylene oxide adducts and their use in photoresist developers |
| US6864395B2 (en) * | 1999-05-04 | 2005-03-08 | Air Products And Chemicals, Inc. | Acetylenic diol ethylene oxide/propylene oxide adducts and processes for their manufacture |
| CN103242143A (en) * | 2013-04-18 | 2013-08-14 | 岳阳市英泰合成材料有限公司 | Production process for performing oxyalkylation on alkynol |
| CN103965462B (en) * | 2014-05-19 | 2016-07-06 | 上海多纶化工有限公司 | Catalyst for the synthesis of acetylenic glycols polyoxyethylene ether |
| CN105384926B (en) * | 2015-12-17 | 2017-05-17 | 上海多纶化工有限公司 | Alkynediol polyether crude product refining method |
| CN110982056B (en) * | 2019-12-10 | 2022-09-27 | 浙江皇马科技股份有限公司 | Method for synthesizing alkynediol block polyether |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03163038A (en) * | 1989-08-15 | 1991-07-15 | Nisshin Kagaku Kogyo Kk | Propylene oxide adduct of acetylene glycol and production thereof |
| CN107935826A (en) * | 2017-11-21 | 2018-04-20 | 浙江皇马科技股份有限公司 | Good fatty alcohol block polyether of a kind of low-temperature stability and its preparation method and application |
| CN109970964A (en) * | 2019-03-29 | 2019-07-05 | 浙江皇马科技股份有限公司 | A kind of preparation method of tertiary alkynol polyethers |
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| WO2021114619A1 (en) | 2021-06-17 |
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Effective date of registration: 20220819 Address after: 312000 Shangyu Economic and Technological Development Zone, Hangzhou Bay, Shangyu District, Shaoxing City, Zhejiang Province Applicant after: ZHEJIANG HUANGMA TECHNOLOGY Co.,Ltd. Applicant after: Zhejiang Real Madrid Shangyi New Material Co.,Ltd. Applicant after: ZHEJIANG LYUKEAN CHEMICAL Co.,Ltd. Applicant after: Zhejiang real special surfactant Research Institute Co.,Ltd. Address before: 312000 No. 8, Jingqi East Road, Shangyu economic and Technological Development Zone, Hangzhou Bay, Shangyu District, Shaoxing City, Zhejiang Province Applicant before: Zhejiang Real Madrid Shangyi New Material Co.,Ltd. Applicant before: ZHEJIANG HUANGMA TECHNOLOGY Co.,Ltd. |
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