CN101485990B - Solid supported heteropoly acid catalyst and preparation method thereof - Google Patents
Solid supported heteropoly acid catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an immobilization heteropoly acid catalyst and a method for preparing the same. The method comprises that: halogenating methyl polystyrene resins and compounds containing active tertiary amine radicals are dispersed in an organic solvent and react under the condition of heating, and the reaction product treated forms an immobilization quaternary ammonium salt resin; phosphotungstic acid, phosphomolybdic acid or vanadic acid is treated in an acid water solution with an oxidant, and added with the immobilization quaternary ammonium salt resin for reaction, the reaction product is washed and dried to prepare the immobilization heteropoly acid catalyst; and the weight ratio of the active heteropolyacid catalyst radicals contained in the immobilization heteropoly acid catalyst to the carrier of the active heteropoly acid catalyst radicals is 1:2-5. The catalyst and the method have the advantages of high catalytic activity, easy recovery, simple preparation method and long service life, and can effectively improve product yield and purity of the alicyclic ring epoxy resin synthesis process, simplify the synthesis process, make the synthesis process more environment friendly and safe, reduce production cost and is applied to large-scale industrialized production.
Description
Technical field
The present invention relates to a kind of catalyst that is applied in the epoxy resin synthesis technique, be specifically related to a kind of solid-carrying heteropolyacid catalyst and preparation method thereof.
Background technology
Epoxy resin is a kind of important thermosetting resin kind, and it is widely used in industrial circles such as chemical industry, light industry water conservancy, traffic, machinery, electronics, household electrical appliances, automobile and space flight and aviation.And as epoxy resin of new generation, cycloaliphatic epoxy resin is because its design feature, and has good electrical insulating property, weatherability, ultraviolet resistance and electron-irradiation resisting performance and be suitable for outdoor use, and can be widely used on the electronic products such as anti-ultraviolet paint and LED.Comparatively the preparation technology of cycloaliphatic epoxy resin commonly used is a catalytic oxidation at present, this method mainly is to adopt the homogeneous phase heteropolyacid catalyst as catalyst, and be oxygen source, thereby catalysis synthesis of alicyclic epoxide (is CN101143919, was the catalytic oxidation technology that proposes in the patent of invention on March 19th, 2008 in open day) as publication number with hydrogen peroxide or alkyl peroxide.Though recyclable the following use of homogeneous catalyst in this technology, reclaimer operation is quite numerous and diverse, and the rate of recovery is lower, and easily causes catalyst residual in product, thereby influences the purity of product.Therefore this homogeneous catalyst is unsuitable for using in suitability for industrialized production.
Summary of the invention
The method that the purpose of this invention is to provide a kind of catalysis of solid supported heteropoly acid catalyst synthesis of alicyclic epoxy resin, overcoming the cycloaliphatic epoxy resin synthesis technique poor stability that exists in the prior art, problems such as the low and catalyst residue of yield.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of preparation method of solid-carrying heteropolyacid catalyst is characterized in that, this method is:
Halogenated methyl polystyrene resin and the compound with active tertiary amine group are scattered in the organic solvent, react under heating condition, product forms immobilized quaternary ammonium resin after treatment;
With phosphotungstic acid, phosphomolybdic acid or phosphorus vanadic acid in acidic aqueous solution with oxidizer treatment, adding immobilized quaternary ammonium resin again reacts, product after treatment, make solid-carrying heteropolyacid catalyst, the weight ratio of contained active heteropolyacid catalyst group and its carrier is 1: 2～5 in this solid-carrying heteropolyacid catalyst.
Further, this method specifically comprises the steps:
The halogenated methyl polystyrene resin is scattered in the organic solvent, add compound again with active tertiary amine group, form mixed reaction solution, be to continue to stir this mixed solution to reaction under 80～100 ℃ the condition to finish in temperature, thereafter with this mixed reaction solution cooling, filtration, filter cake after cleaning and extracting processing, is inserted under the vacuum condition and is dried to constant weight successively, makes immobilized quaternary ammonium resin;
Get phosphotungstic acid, phosphomolybdic acid or phosphorus vanadic acid are soluble in water, add oxidant more in batches, form reaction solution, accompanying by under the stirring condition, the control temperature is at 20～100 ℃, make this reaction solution reaction 1～6h, while conditioned reaction liquid pH value＜2, then with the cooling of this reaction solution. and immobilized quaternary ammonium resin slowly joined in this reaction solution, behind stirring reaction 5～15h, cool off through mixed reaction solution, suction filtration, filter cake through clean and vacuum drying to constant weight, obtain solid-carrying heteropolyacid catalyst, the mass percent of contained active heteropolyacid catalyst group is 20～30% in this solid-carrying heteropolyacid catalyst.
Described organic solvent is N, dinethylformamide or dimethyl sulfoxide (DMSO).
Described halogenated methyl polystyrene resin is at least a in chloromethyl polystyrene resin, bromomethyl polystyrene resin or the methyl fluoride polystyrene resin.
Described compound with active tertiary amine group is at least a in tertiary amine compounds, pyridine compounds and their or the piperidines.
Described oxidant is a mass percent concentration at 30～50% H
2O
2
A kind of solid-carrying heteropolyacid catalyst is characterized in that, this solid-carrying heteropolyacid catalyst prepares by following technology:
Halogenated methyl polystyrene resin and the compound with active tertiary amine group are scattered in the organic solvent, react under heating condition, product forms immobilized quaternary ammonium resin after treatment;
With phosphotungstic acid, phosphomolybdic acid or phosphorus vanadic acid in acidic aqueous solution with oxidizer treatment, then adding immobilized quaternary ammonium resin reacts, product is after cleaning, the dry processing, make solid-carrying heteropolyacid catalyst, the weight ratio of contained active heteropolyacid catalyst group and its carrier is 1: 2～5 in this solid-carrying heteropolyacid catalyst.
Described halogenated methyl polystyrene resin is at least a in chloromethyl polystyrene resin, bromomethyl polystyrene resin or the methyl fluoride polystyrene resin.
Described compound with active tertiary amine group is at least a in tertiary amine compounds, pyridine compounds and their or the piperidines.
The preparation technology of this solid-carrying heteropolyacid catalyst specifically comprises the steps:
The halogenated methyl polystyrene resin is scattered in N, in the dinethylformamide, adds tertiary amine R again
1R
2R
3N, wherein R
1, R
2, R
3It is alkyl, cycloalkyl or benzyl, form mixed reaction solution, be to continue to stir this mixed solution to reaction under 100 ℃ the condition to finish in temperature, thereafter with this mixed reaction solution cooling, filter, filter cake is successively through washing, after ethanol is washed, with behind the alcohol extract, insert under the vacuum condition and be dried to constant weight again, make immobilized quaternary ammonium resin;
Get H
3PO
40W
12.xH
2O is soluble in water, adds mass percent concentration more in batches and be 30～50% H
2O
2Form reaction solution, accompanying by under the stirring condition, the control temperature is at 20～100 ℃, make this reaction solution reaction 1～6h, simultaneously conditioned reaction liquid pH value＜2 are then with this reaction solution cooling. and immobilized quaternary ammonium resin slowly joined in this reaction solution, behind stirring reaction 5～15h, cool off through mixed reaction solution, suction filtration, filter cake through clean and vacuum drying to constant weight, obtain the immobilized phosphotungstic acid catalyst, the mass percent of contained active heteropolyacid catalyst group is 20～30% in this immobilized phosphotungstic acid catalyst.
The solid-carrying heteropolyacid catalyst that adopts among the present invention compared to prior art in homogeneous phase heteropllyacids catalyst commonly used, can make in the reaction process catalyst only promptly recyclable by modes such as filtrations, improved the service life of catalyst first, second can reduce the cost of synthesis technique, also avoid the catalyst residue problem in the product simultaneously.In addition, this case the inventor also find, the catalytic activity of the immobilized solid-carrying heteropolyacid catalyst that forms to the immobilized quaternary ammonium resin of heteropolyacid catalyst is higher than the homogeneous phase heteropolyacid catalyst.
And need to prove, when solid-carrying heteropolyacid catalyst of the present invention being applied in the synthesis technique of cycloaliphatic epoxy resin, also can reduce requirement to oxidant, can adopt commercially available hydrogen peroxide or alkyl peroxide to substitute the hydrogen peroxide or the anhydrous peroxyacetic acid of higher concentration in the prior art, thereby can save production cost, and make the safer environmental protection of synthesis technique, therefore be fit to very much suitability for industrialized production.
Compared with prior art, beneficial effect of the present invention is: this catalysis of solid supported heteropoly acid catalyst active high, be easy to reclaim, and the preparation method is simple, long service life, can effectively improve the product yield and the purity of cycloaliphatic epoxy resin synthesis technique, and simplify this synthesis technique, make its more Environmental Safety, and reduce production costs, be fit to large-scale industrialization production.
The specific embodiment
Embodiment 1 this immobilized phosphotungstic acid Preparation of catalysts technology is as follows:
The 2Kg chloromethyl polystyrene resin is added 61 N, and swelling 2h in the dinethylformamide (DMF) adds 8L tertiary amine R again
1R
2R
3N (R
1, R
2, R
3Be alkyl, cycloalkyl or benzyl) in 90～100 ℃ of stirring 24h, then with reactant mixture cooling, suction filtration, filter cake through washing, after ethanol is washed, is used alcohol extract 8～10h successively again, thereafter with vacuum drying to constant weight, make immobilized quaternary ammonium resin, this immobilized quaternary ammonium resin can be expressed as respectively
Wherein
Represent the chloromethyl polystyrene resin carrier.
Take by weighing the 825g phosphotungstic acid and be dissolved in the 10L water, stirring reaction, and to get the 1.5L mass percent concentration be 30% H
2O
2Divide and add for 5 times in the reaction solution, the control reaction temperature is about 60 ℃, reaction 2.5h, and with watery hydrochloric acid conditioned reaction liquid pH value＜2, then with the mixed reaction solution cool to room temperature. and get 2, the immobilized quaternary ammonium resin that the 5Kg swelling is good slowly joins in the above-mentioned mixed reaction solution. vigorous stirring reaction 10h, cooling, suction filtration, filter cake is through washing, and ethanol is washed, and vacuum drying is to constant weight, obtain the immobilized phosphotungstic acid catalyst, the weight ratio of contained heteropolyacid catalyst active group and its carrier is 1: 2 in this immobilized phosphotungstic acid catalyst.
This immobilized phosphotungstic acid catalyst can be applicable in the synthesis technique of cycloaliphatic epoxy resin, below is that example describes with the synthesis technique of epoxy resin ERL-4221.
Epoxy resin ERL-4221 is a kind of epoxy resin that specific function is arranged of U.S. associating C.-Chem AG exploitation, common and polyalcohol and anhydride curing agent use, and it has good electrical insulating property, weatherability and high heat distortion temperature.ERL-4221D is a kind of distillation body of ERL-4221, and its viscosity is low, and recommended being used in requires on the alap electrical equipment capsule of viscosity.LG-DOW company passes through intermediate 3,4-cyclohexenyl group formic acid-3, and 4-cyclohexenyl group methyl esters makes through the anhydrous peroxyacetic acid epoxidation reaction, and its course of reaction is shown below:
Wherein, intermediate (I) 3,4-cyclohexenyl group formic acid-3,4-cyclohexenyl group methyl esters can be made through the Tischenko reaction under alkyl aluminum must act on by 3-cyclohexene formaldehyde, and its reaction equation is as follows:
But there is the unmanageable defective of course of reaction in this technology, and easily causes safety problem.
Epoxy resin ERL-4221 synthesis technique in the present embodiment is shown below:
In being equipped with the 50L reactor of reflux condenser, add toluene 20Kg under the stirring condition successively accompanying by, intermediate (I) 10Kg, immobilized phosphotungstic acid catalyst 600g and sodium carbonate 200g, reinforced finishing, mixed solution is warming up to 50 ℃, and to begin to drip mass percent concentration be 30% hydrogen peroxide 12.8Kg, the control rate of addition, and control mixed solution temperature dropwises under 65 ℃, the mixed reaction solution temperature is remained on about 55 ℃～60 ℃ reaction 5 hours, follow the tracks of reaction process with gas-chromatography simultaneously, question response finishes, and mixed reaction solution is cooled under the room temperature, and suction filtration reclaims the immobilized phosphotungstic acid catalyst, and with the filtrate standing demix, collected organic layer, after washing, decompression distillation is removed reaction dissolvent and is obtained epoxy resin ERL-4221.Intermediate (I) conversion ratio is 95%, product yield is 89%, and product purity is 96%.After the immobilized phosphotungstic acid catalyst that suction filtration reclaims among this embodiment carries out dry constant weight, be reused for catalysis synthetic epoxy resin ERL-4221 according to above-mentioned technology, its reaction result is as shown in the table:
By last table as can be known, this immobilized phosphotungstic acid catalyst is after recycling for 3 times, and catalytic effect remains unchanged substantially.The above results shows, the immobilized phosphotungstic acid catalyst that uses in the present embodiment has characteristics such as high conversion, high yield aspect the catalysis epoxidation unsaturated fat compounds of group.Simultaneously catalyst can following use, long service life, and can effectively reduce synthetic cost.
Embodiment 2 these immobilized phosphomolybdic acid Preparation of catalysts technologies are as follows:
1.5Kg bromomethyl polystyrene resin is added 5L N, swelling 3h in the dinethylformamide (DMF), add the 6L pyridine again or its homologous compound stirs 20h under 80～90 ℃ temperature, then with the reactant mixture cooling, suction filtration, filter cake are successively through washing, after ethanol is washed, use alcohol extract 9～10h again, thereafter with vacuum drying to constant weight, make immobilized quaternary ammonium resin;
Take by weighing the 30g phosphomolybdic acid and be dissolved in the 500mL water, stirring reaction, and to get the 350mL mass percent concentration be 50% H
2O
2Divide and add for 5 times in the reaction solution, the control reaction temperature is about 20 ℃, reaction 6h, and with watery hydrochloric acid conditioned reaction liquid pH value＜2, then with the mixed reaction solution cool to room temperature. take by weighing the immobilized quaternary ammonium resin of 850g thereafter and slowly join in the above-mentioned reactant liquor. vigorous stirring reaction 15h, cooling, suction filtration, filter cake is through washing, ethanol wash with vacuum drying to constant weight, obtain immobilized phosphomolybdic acid catalyst, the weight ratio of contained heteropolyacid catalyst active group and its carrier is 1: 5 in this immobilized phosphomolybdic acid catalyst.
Same, when in the synthesis technique that immobilized phosphomolybdic acid catalyst is applied to epoxy resin ERL-4221, can make the conversion ratio of intermediate (I) reach 91%, product yield is 85%, product purity is 94%
Embodiment 3 these immobilized phosphorus vanadic acid Preparation of catalysts technologies are as follows:
200g methyl fluoride polystyrene resin is added swelling 4h in the 0.5L dimethyl sulfoxide (DMSO) (DMSO), add the 0.3L piperidines again or its homologous compound stirs 18h under 100 ℃ temperature, then reactant mixture is cooled off, suction filtration, filter cake through washing, after ethanol is washed, is used alcohol extract 10h successively again, thereafter with vacuum drying to constant weight, make immobilized quaternary ammonium resin;
Take by weighing 10g phosphorus vanadic acid and be dissolved in the 150mL water, stirring reaction, and to get the 120mL mass percent concentration be 40% H
2O
2Divide and add for 5 times in the reaction solution, the control reaction temperature is about 50 ℃, reaction 3h, and with watery hydrochloric acid conditioned reaction liquid pH value＜2, then with the mixed reaction solution cool to room temperature. take by weighing the immobilized quaternary ammonium resin of 300g thereafter and slowly join in the above-mentioned reactant liquor. vigorous stirring reaction 10h, cooling, suction filtration, filter cake is through washing, ethanol wash with vacuum drying to constant weight, obtain immobilized phosphorus vanadic acid catalyst, the weight ratio of contained heteropolyacid catalyst active group and its carrier is 1: 3.2 in this immobilized phosphorus vanadic acid catalyst.
The process of epoxidation technique that this immobilized phosphorus vanadic acid catalyst is applied to dicyclopentadiene is as follows
Getting the 0.25mol dicyclopentadiene is dissolved among the 60mL DCM, and adding 3.4g immobilized phosphorus vanadic acid catalyst and 2g NaOH, form mixed solution, thereafter temperature is that slowly to drip the 1mol mass percent concentration under 40 ℃ the condition in this mixed solution be 30% hydrogen peroxide, then keep temperature of reaction system about 70 ℃, to react 6h, after reaction finishes, mixed reaction solution is cooled under the room temperature, the immobilized phosphorus vanadic acid of suction filtration catalyst, and with the filtrate standing demix, collected organic layer, after washing, decompression distillation is removed reaction dissolvent and is obtained the bicyclopentadiene dioxide crystal.In this technology, the conversion ratio 100% of raw material dicyclopentadiene, bicyclopentadiene dioxide yield are 95%.More than reaction is shown below:
It is pointed out that the foregoing description only is explanation technical conceive of the present invention and characteristics, its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit essence is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (8)
1. the preparation method of a solid-carrying heteropolyacid catalyst is characterized in that, this method is:
Halogenated methyl polystyrene resin and the compound with active tertiary amine group are scattered in the organic solvent, react under heating condition, product forms immobilized quaternary ammonium resin after treatment;
With H
3PO
4OM
12.xH
2O in acidic aqueous solution with oxidizer treatment, adding immobilized quaternary ammonium resin again reacts, wherein M is tungsten, molybdenum or vanadium, product after treatment, make solid-carrying heteropolyacid catalyst, the weight ratio of contained active heteropolyacid catalyst group and its carrier is 1: 2～5 in this solid-carrying heteropolyacid catalyst;
Say that further this method specifically comprises the steps:
The halogenated methyl polystyrene resin is scattered in the organic solvent, add compound again with active tertiary amine group, form mixed reaction solution, be to continue to stir this mixed solution to reaction under 80～100 ℃ the condition to finish in temperature, thereafter with this mixed reaction solution cooling, filtration, filter cake after cleaning and extracting processing, is inserted under the vacuum condition and is dried to constant weight successively, makes immobilized quaternary ammonium resin;
Get phosphotungstic acid, phosphomolybdic acid or phosphorus vanadic acid are soluble in water, add oxidant more in batches, form reaction solution, accompanying by under the stirring condition, the control temperature is at 20～100 ℃, make this reaction solution reaction 1～6h, conditioned reaction solution pH value＜2 slowly join in this reaction solution then with this reaction solution cooling, and with immobilized quaternary ammonium resin simultaneously, behind stirring reaction 5～15h, through mixed reaction solution cooling, suction filtration, filter cake through clean and vacuum drying to constant weight, obtain solid-carrying heteropolyacid catalyst, the mass percent of contained active heteropolyacid catalyst group is 20～30% in this solid-carrying heteropolyacid catalyst.
2. the preparation method of solid-carrying heteropolyacid catalyst according to claim 1 is characterized in that described organic solvent is N, dinethylformamide or dimethyl sulfoxide (DMSO).
3. the preparation method of solid-carrying heteropolyacid catalyst according to claim 1 is characterized in that described halogenated methyl polystyrene resin is at least a in chloromethyl polystyrene resin, bromomethyl polystyrene resin and the methyl fluoride polystyrene resin.
4. the preparation method of solid-carrying heteropolyacid catalyst according to claim 1 is characterized in that described compound with active tertiary amine group is at least a in tertiary amine compounds, pyridine compounds and their and the piperidines.
5. the preparation method of solid-carrying heteropolyacid catalyst according to claim 1 is characterized in that described oxidant is a mass percent concentration at 30～50% H
2O
2
6. a solid-carrying heteropolyacid catalyst is characterized in that, this solid-carrying heteropolyacid catalyst prepares by following technology:
Halogenated methyl polystyrene resin and the compound with active tertiary amine group are scattered in the organic solvent, react under heating condition, product forms immobilized quaternary ammonium resin after treatment;
With H
3PO
4OM
12.xH
2O in acidic aqueous solution with oxidizer treatment, adding immobilized quaternary ammonium resin again reacts, wherein M is tungsten, molybdenum or vanadium, product after treatment, make solid-carrying heteropolyacid catalyst, the weight ratio of contained active heteropolyacid catalyst group and its carrier is 1: 2～5 in this solid-carrying heteropolyacid catalyst;
Say that further this technology specifically comprises the steps:
The halogenated methyl polystyrene resin is scattered in the organic solvent, add compound again with active tertiary amine group, form mixed reaction solution, be to continue to stir this mixed solution to reaction under 80～100 ℃ the condition to finish in temperature, thereafter with this mixed reaction solution cooling, filtration, filter cake after cleaning and extracting processing, is inserted under the vacuum condition and is dried to constant weight successively, makes immobilized quaternary ammonium resin;
Get phosphotungstic acid, phosphomolybdic acid or phosphorus vanadic acid are soluble in water, add oxidant more in batches, form reaction solution, accompanying by under the stirring condition, the control temperature is at 20～100 ℃, make this reaction solution reaction 1～6h, while conditioned reaction solution pH value＜2, then with the cooling of this reaction solution. and immobilized quaternary ammonium resin slowly joined in this reaction solution, behind stirring reaction 5～15h, cool off through mixed reaction solution, suction filtration, filter cake through clean and vacuum drying to constant weight, obtain solid-carrying heteropolyacid catalyst, the mass percent of contained active heteropolyacid catalyst group is 20～30% in this solid-carrying heteropolyacid catalyst.
7. solid-carrying heteropolyacid catalyst according to claim 6 is characterized in that, described halogenated methyl polystyrene resin is at least a in chloromethyl polystyrene resin, bromomethyl polystyrene resin and the methyl fluoride polystyrene resin.
8. solid-carrying heteropolyacid catalyst according to claim 6 is characterized in that, described compound with active tertiary amine group is at least a in tertiary amine compounds, pyridine compounds and their and the piperidines.
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| CN102941123B (en) * | 2012-11-13 | 2015-03-04 | 山东大学 | Ion exchanging resin load-type heteropoly compound as well as preparation method and application thereof |
| CN103288783A (en) * | 2013-06-08 | 2013-09-11 | 南通豪锦化工有限公司 | Novel synthesis method of glycidyl amine epoxy resin |
| CN104987457A (en) * | 2015-06-25 | 2015-10-21 | 沈阳化工大学 | Functional monomer doubling reactive diluent and preparation method thereof |
| CN106693997B (en) * | 2017-01-10 | 2019-05-31 | 中国石油大学(华东) | A kind of diesel hydrogenation for removal sulphur catalyst and its preparation method and application |
| CN107321391A (en) * | 2017-04-06 | 2017-11-07 | 东北林业大学 | A kind of method for preparing magnetic coupling bio-based Catalyzed By Immobilized Phosphotungstic agent |
| CN109046452B (en) * | 2018-05-29 | 2022-02-08 | 南京大学 | Immobilized heteropolyacid catalyst and preparation method and application thereof |
| CN111097525A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Solid acid catalyst for olefin epoxidation reaction, preparation method and application |
| CN110563884B (en) * | 2019-04-10 | 2021-06-29 | 江苏扬农化工集团有限公司 | Preparation method of supported heteropolyacid catalyst |
| CN113429544A (en) * | 2021-03-19 | 2021-09-24 | 南通新纳希新材料有限公司 | Method for synthesizing epoxy resin by olefin oxidation |
| CN114345382B (en) * | 2022-01-14 | 2023-08-04 | 中原工学院 | Biochar covalent immobilized phosphoric acid catalyst and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1781598A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Method for preparing resin assembled heteropoly acid salt catalyst |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
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Non-Patent Citations (1)
| Title |
|---|
| 王振兴.双氧水环氧化环己烯合成环氧环己烷的关键技术研究.郑州大学硕士学位论文.2006,47. * |
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Effective date of registration: 20160825 Address after: 226500 Jiangsu, Nantong City, Rugao Province town of Hong Kong Road No. 59 Patentee after: NANTONG SYNASIA NEW MATERIAL CO., LTD. Address before: 215163 No. 115 Yang Pu Road, Suzhou Industrial Park, Jiangsu, China Patentee before: Synasia (Suzhou) Co., Ltd. |