CN102391149B - Method for preparing benzyl hydroxyl amine antioxygen without waste water discharge - Google Patents
Method for preparing benzyl hydroxyl amine antioxygen without waste water discharge Download PDFInfo
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Abstract
The invention discloses a method for preparing benzyl hydroxyl amine antioxygen without waste water discharge, and belongs to the technical field of clean chemical synthesis. Alkyl-halogenation benzyl and oxammonium hydrochloride are taken as raw materials, organic amine compound is taken as an acid-binding agent, synthesis reaction is performed in organic solvent, and N, N-dibenzyl hydroxyl amine derivative products can be prepared. Synthesis reaction is performed in an anhydrous system, the production of waste water pollution can be effectively controlled from the source, and problems of environment pollution caused by waste water discharge in a traditional method can be fundamentally solved; in addition, by-product alkyl benzene methanol caused by alkyl-halogenation benzyl hydrolysis reaction can be prevented, and the yield of the N, N dibenzyl hydroxyl amine derivative products is improved. The method disclosed by the invention has the characteristics of simple productive technology, high product yield and good quality, and is convenient for industrial production.
Description
Technical field
The present invention relates to a kind of non-wastewater discharge and prepare N, the processing method of N-dibenzyl hydroxylamine derivative oxidation inhibitor, belongs to clean technical field of chemical synthesis.
Background technology
N, N-dibenzyl hydroxylamine derivative oxidation inhibitor refer in particular to following formula (
):
Formula (
)
Formula (
) in, R=H, C
1～C
10straight-chain paraffin or with the alkane of side chain.
The stabilization procedures of tradition oxidation inhibitor is to stop the active peroxy radical constantly producing in polymkeric substance, effective hydroperoxide decomposition.People have developed the auxiliary antioxidants such as the primary antioxidants such as Hinered phenols, phosphorous acid ester and sulphur thioether class for this reason, and obviously, this binary stable system has effectively been brought into play effect in the anti-aging process of polymkeric substance.
Carbon radicals trapping agent is suppressed under anaerobic or anoxic condition scission of link that the existence due to carbon radicals may occur, the pure thermal ageing phenomenon such as crosslinked on the one hand, plays the effect of resistant to thermal aging; Reduce on the other hand the peroxy radical quantity producing subsequently, fundamentally alleviate the burden of main and auxiliary oxidation inhibitor, carbon radicals theoretical breakthrough traditional antioxygen stable theory, carbon radicals trapping agent can be caught a large amount of carbon radicals centered by carbon that produce in the course of processing, the autoxidation process of polymkeric substance is being restricted at the very start, the use of carbon radicals trapping agent can reduce the usage quantity of Hinered phenols antioxidant, thereby can improve the colour stability of product.
N, N-dibenzyl hydroxylamine derivatives class oxidation inhibitor is similar to the mechanism of action of antioxidant of bisphenol monoacryate, aryl benzofuranone kind antioxidant, belong to carbon radicals trapping agent gang together, not only can stop living radical, hydroperoxide decomposition, the more important thing is the effect with carbon radicals trapping agent, belong to multi-functional oxidation inhibitor.N, N-dibenzyl hydroxylamine derivatives class oxidation inhibitor is in polymer stabilising process, first a reactive hydrogen atom is provided and forms a free radical with rock steady structure, then, this radical pair causes the carbon radicals of polymer degradation, alkoxy free group to be caught, thereby stops the oxidising process of polymkeric substance.Owing to comprising in azanol simultaneously, have not nitrogen, the Sauerstoffatom of shared electron, can to a plurality of free radicals, catch simultaneously, compare N, N-dibenzyl hydroxylamine derivatives class oxidation inhibitor activity is high, can in lower concentration range, show good antioxidant effect.
N, N-dibenzyl hydroxylamine derivatives class oxidation inhibitor is used together with suffocated amine antioxidant, can make polymkeric substance there is long-term thermostability, and owing to having avoided the existence of aldehydes matter, when polymkeric substance is contacted with gases such as NOx, there will not be metachromatism, thereby there is good colour stability; In addition, carry out composite with hindered amine as light stabilizer, can also improve the light stability of polymkeric substance, and add some azanol kind antioxidants in synthetic, the storage of Hinered phenols antioxidant and use procedure, can effectively stop the generation of phenolic antioxidant metachromatism.
Exploitation N, N-dibenzyl hydroxylamine derivatives class oxidation inhibitor is very meaningful.
US Patent No. 4703073 discloses that to take to tertiary butyl bromination benzyl, oxammonium hydrochloride be raw material, and anhydrous sodium carbonate is that neutralizing agent, dimethyl formamide are solvent, reaction preparation N, bis-pairs of tertiary butyl benzyl hydroxylamines of N-.The weak point of this technique is in reaction process, have water to generate, and easy generation hydrolysis reaction generation in basic solution, to tert.-butylbenzene methyl alcohol, to cause product yield to decline to tertiary butyl bromination benzyl; In addition, the product N in reaction solution, the mixture of the inorganic salt such as bis-pairs of tertiary butyl benzyl hydroxylamines of N-and sodium-chlor, the method that adopts large water gaging to rinse, result produces the trade effluent that contains in a large number dimethyl formamide, and environmental pollution is serious.
The present invention attempts take Benzyl Chloride, oxammonium hydrochloride is raw material, anhydrous sodium carbonate is neutralizing agent, industrial alcohol is solvent, reaction preparation N, N-dibenzyl hydroxylamine product, the solids component obtaining in reaction solution is N, N-dibenzyl hydroxylamine and inorganic sodium mixture, separating-purifying can only adopt massive laundering to wash, and removes inorganic sodium, produce 1 ton of product and approximately produce the trade effluent of 10～15 tons, environment is caused to very serious harm.
Summary of the invention
The present invention, for overcoming above-mentioned deficiency of the prior art, has invented a kind of non-wastewater discharge and has prepared N, the processing method of N-dibenzyl hydroxylamine.Take alkyl halide benzyl, oxammonium hydrochloride is raw material, and organic amine compound is acid binding agent, carries out building-up reactions in organic solvent, preparation N, N-dibenzyl hydroxylamine derivative product.
A kind of non-wastewater discharge of the present invention is prepared N, and the method for N-dibenzyl hydroxylamine derivative oxidation inhibitor is carried out according to following step:
(1) oxammonium hydrochloride, organic amine acid binding agent, organic solvent are added in synthesis reaction vessel in proportion, adopt two rank temperature of reaction to react, first stir and be warming up to 10～80 ℃, drip alkyl halide benzyl raw material, time for adding 0～100 min, continues insulation reaction 30～150 min; Then, rising temperature to 60～130 ℃, continue insulation reaction 180～240 min; Reaction solution contains N, N-dibenzyl hydroxylamine derivative antioxidant product and by product organic amine salt hydrochlorate;
(2) reaction solution obtaining in step (1) is added to a certain amount of organic solvent, and the abundant dissolved product that heats up; Heat filtering carries out solid-liquid separation.
(3), by the solids organic solvent washing obtaining in step (2), obtain by product organic amine salt hydrochlorate;
(4) filtrate concentrating, crystallisation by cooling, filtration, washing, the dry product that to obtain will be obtained in step (2).
Wherein the organic amine acid binding agent described in step (1) refers to Trimethylamine 99, dimethyl amine, diethyl methylamine, dimethyl propylamine, dimethyl Isopropylamine, diisopropylethylamine, triethylamine, tripropyl amine or tribenzyl amine.
Wherein the organic solvent described in step (1) refers to C
6～C
10aromatic hydrocarbon, straight-chain paraffin, isoparaffin, naphthenic hydrocarbon; C
1～C
4anhydrous fatty alcohol.
Wherein the alkyl halide benzyl described in step (1) refer to following formula (
):
Formula (
);
Formula (
) in: R=H or C
1～C
10straight-chain paraffin or with the alkane of side chain;
X=Cl or Br.
Wherein in step (1), the mol ratio of oxammonium hydrochloride and alkyl halide benzyl is 1:0.7～3.5, and suitable mol ratio is 1:2.0～3.0; The mol ratio of oxammonium hydrochloride and organic amine acid binding agent is 1:2.5～6.0, and suitable mol ratio is 1:3.0～4.0; The mass ratio of oxammonium hydrochloride and organic solvent is 1:8～10.
Wherein in step (1), preferably first stir and be warming up to 45～60 ℃, drip alkyl halide benzyl raw material, time for adding is 30～50 min, continues insulation reaction 40～100 min; Then temperature to 70～110 ℃ raise.
Wherein described in step (2), the reaction solution obtaining in step (1) is added to organic solvent, add-on is by counting 2～10:1 with the mass ratio of oxammonium hydrochloride; Be warming up to 60～120 ℃; Stir, fully dissolve N, N-dibenzyl hydroxylamine derivative product; Heat filtering carries out solid-liquid separation.
Wherein the organic solvent described in step (2) refers to C
6～C
10aromatic hydrocarbon, straight-chain paraffin, isoparaffin, naphthenic hydrocarbon; C
1～C
4anhydrous fatty alcohol.
Wherein the solids that heat filtering in step (2) is obtained described in step (3) is further refined and is obtained by product organic amine salt hydrochlorate; Available hydrogen sodium oxide further alkalizes, generates sodium-chlor the organic amine that dissociates, and organic amine acid binding agent is reclaimed in distillation, and the building-up reactions for step (1), recycles.
Advantage of the present invention:
(1) to take alkyl halide benzyl, oxammonium hydrochloride be raw material in the present invention, and organic amine is that acid binding agent is prepared N, and N-dibenzyl hydroxylamine derivative oxidation inhibitor, has the advantages that production technique is simple, product yield is high, quality is good, be convenient to suitability for industrialized production.
(2) adopt in anhydrous system and carry out building-up reactions, can avoid alkyl halide benzyl hydrolysis reaction to generate by product alkylbenzene methyl alcohol, improved N, the yield of N-dibenzyl hydroxylamine derivative product.
(3) processing method of the present invention, adopts in anhydrous system and carries out building-up reactions, has effectively controlled the generation of Wastewater Pollutant in the source producing, and has fundamentally solved the problem of environmental pollution that traditional method waste discharge causes.
(4) the by product organic amine salt hydrochlorate generating in reaction process can be used as useful Chemicals; Or organic amine salt hydrochlorate is further alkalized, distilled, reclaim organic amine acid binding agent, be reused for building-up reactions, iterative cycles is used.
Embodiment
All raw materials used in the present invention, as: oxammonium hydrochloride, alkyl halide benzyl, organic amine acid binding agent, organic solvent are commercially available prod, and specification is industrial top grade product.
Following non-limiting example 1～9 is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change that the present invention is made, all belong to protection scope of the present invention.
embodiment 1
In the reactor with agitator, thermometer, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 256g, toluene 450g.Air in nitrogen replacement reactor, heating, stirs, and is warming up to 45 ℃, at this temperature, keeps constant, starts to drip Benzyl Chloride 230g, and 30min drips off, after dropwising, insulation reaction 40min.Then be warming up to 110 ℃, insulation reaction 180min.After reaction finishes, add toluene 450g, be warming up to 80 ℃, heat filtering obtains triethylamine hydrochloride solids, and toluene wash is refined to obtain by product triethylamine hydrochloride.Merging filtrate, washings, toluene is removed in distillation, crystallisation by cooling, crystallized product washs with 80～95% ethanolic soln, dry N, N-dibenzyl hydroxylamine white crystals product 137 g, 123.6～125.3 ℃ of the fusing points of obtaining.
embodiment 2
In the reactor with agitator, thermometer, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 240g, dimethylbenzene 450g.Air in nitrogen replacement reactor, heating, stirs, and is warming up to 45 ℃, at this temperature, keeps constant, starts to drip tertiary butyl bromination benzyl 360g, and 30min drips off, after dropwising, insulation reaction 50min.Then be warming up to 100 ℃, insulation reaction 190min.After reaction finishes, add dimethylbenzene 350g, be warming up to 70 ℃, heat filtering obtains triethylamine hydrochloride solids, the refining by product triethylamine hydrochloride that obtains of toluene wash.Merging filtrate, washings, remove removal xylene through distillation, crystallisation by cooling, and crystallized product washs with 80～95% ethanolic soln, dry N, N-bis-(the 4-tertiary butyl) benzyl hydroxylamine white crystals product 166g, 106.3～107.8 ℃ of the fusing points of obtaining.
embodiment 3
In the reactor with agitator, thermometer, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 304g, benzene 500g.Air in nitrogen replacement reactor, heating, stirs, and is warming up to 45 ℃, at this temperature, keeps constant, starts to drip tertiary butyl chlorination benzyl 404g, and 40min drips off, after dropwising, insulation reaction 60min.Then be warming up to 90 ℃, insulation reaction 200min.After reaction finishes, add benzene 100g, be warming up to 100 ℃, heat filtering obtains triethylamine hydrochloride solids, and benzene detergent makes by product triethylamine hydrochloride.Merging filtrate, washings, remove benzene through distillation, crystallisation by cooling, and crystallized product washs with 80～95% ethanolic soln, dry N, N-bis-(the 4-tertiary butyl) benzyl hydroxylamine white crystals product 170g, 107.9～109.4 ℃ of the fusing points of obtaining.
embodiment 4
In the reactor with agitator, thermometer, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 320g, toluene 550g.Air in nitrogen replacement reactor, heating, stirs, and is warming up to 50 ℃, at this temperature, keeps constant, starts to drip tertiary butyl bromination benzyl 539g, and 50min drips off, after dropwising, insulation reaction 70min.Then be warming up to 110 ℃, insulation reaction 240min.After reaction finishes, add toluene 200g, be warming up to 120 ℃, heat filtering obtains triethylamine hydrochloride solids, the refining by product triethylamine hydrochloride that obtains of toluene wash.Merging filtrate, washings, remove toluene through distillation, crystallisation by cooling, and crystallized product washs with 80～95% ethanolic soln, dry N, N-bis-(the 4-tertiary butyl) benzyl hydroxylamine white crystals product 175g, 107.2～109.1 ℃ of the fusing points of obtaining.
embodiment 5
In the reactor with agitator, thermometer, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 272g, hexanaphthene 450g.Air in nitrogen replacement reactor, heating, stirs, and is warming up to 45 ℃, at this temperature, keeps constant, starts to drip Benzyl Chloride 220g, and 30min drips off, after dropwising, insulation reaction 80min.Then be warming up to 80 ℃, insulation reaction 200min.After reaction finishes, add hexanaphthene 450g, be warming up to 80 ℃, heat filtering obtains triethylamine hydrochloride solids, and hexanaphthene detergent makes by product triethylamine hydrochloride.Merging filtrate, washings, remove hexanaphthene through distillation, crystallisation by cooling, and crystallized product washs with 80～95% ethanolic soln, dry N, N-dibenzyl hydroxylamine white crystals product 140g, 123.1～125.6 ℃ of the fusing points of obtaining.
embodiment 6
In the reactor with agitator, thermometer, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 288g, toluene 500g.Air in nitrogen replacement reactor, heating, stirs, and is warming up to 50 ℃, at this temperature, keeps constant, starts to drip tertiary butyl bromination benzyl 413g, and 50min drips off, after dropwising, insulation reaction 100min.Then be warming up to 80 ℃, insulation reaction 230min.After reaction finishes, add toluene 400g, be warming up to 60 ℃, heat filtering obtains triethylamine hydrochloride solids, the refining by product triethylamine hydrochloride that obtains of toluene wash.Merging filtrate, washings, remove toluene through distillation, crystallisation by cooling, and crystallized product washs with 80～95% ethanolic soln, dry N, N-bis-(the 4-tertiary butyl) benzyl hydroxylamine white crystals product 175g, 108.1～109.6 ℃ of the fusing points of obtaining.
embodiment 7
In the reactor with agitator, thermometer, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 240g, hexanaphthene 450g.Air in nitrogen replacement reactor, heating, stirs, and is warming up to 55 ℃, at this temperature, keeps constant, starts to drip cylite 311g, and 45min drips off, after dropwising, insulation reaction 90min.Then be warming up to 70 ℃, insulation reaction 200min.After reaction finishes, add hexanaphthene 450g, be warming up to 80 ℃, heat filtering obtains triethylamine hydrochloride solids, and hexanaphthene detergent makes by product triethylamine hydrochloride.Merging filtrate, washings, remove hexanaphthene through distillation, crystallisation by cooling, and crystallized product washs with 80～95% ethanolic soln, dry N, N-dibenzyl hydroxylamine white crystals product 143g, 123.1～125.6 ℃ of the fusing points of obtaining.
embodiment 8
In the reactor with agitator, thermometer, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 256g, toluene 500g.Air in nitrogen replacement reactor, heating, stirs, and is warming up to 60 ℃, at this temperature, keeps constant, starts to drip tertiary butyl chlorination benzyl 361g, and 50min drips off, after dropwising, insulation reaction 70min.Then be warming up to 100 ℃, insulation reaction 220min.After reaction finishes, add toluene 500g, be warming up to 80 ℃, heat filtering obtains triethylamine hydrochloride solids, the refining by product triethylamine hydrochloride that obtains of toluene wash.Merging filtrate, washings, remove toluene through distillation, crystallisation by cooling, and crystallized product washs with 80～95% ethanolic soln, dry N, N-bis-(the 4-tertiary butyl) benzyl hydroxylamine white crystals product 176g, 108.0～109.8 ℃ of the fusing points of obtaining.
embodiment 9
In the reactor with agitator, thermometer, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 240g, dehydrated alcohol 500g.Air in nitrogen replacement reactor, heating, stirs, and is warming up to 45 ℃, at this temperature, keeps constant, starts to drip tertiary butyl bromination benzyl 360g, and 30min drips off, after dropwising, insulation reaction 100min.Then be warming up to 70 ℃, insulation reaction 200min.After reaction finishes, be cooled to 5～10 ℃, crystallization, crystallized product washs with 80～95% ethanolic soln, dry N, N-bis-(the 4-tertiary butyl) benzyl hydroxylamine white crystals product 169g, 107.1～108.7 ℃ of the fusing points of obtaining.
Claims (6)
1. non-wastewater discharge is prepared a N, and the method for N-dibenzyl hydroxylamine derivative oxidation inhibitor, is characterized in that carrying out according to following step:
(1) oxammonium hydrochloride, organic amine acid binding agent, organic solvent are added in synthesis reaction vessel in proportion, adopt two rank temperature of reaction to react, first stir and be warming up to 10～80 ℃, drip alkyl halide benzyl raw material, time for adding 0～100 min, continues insulation reaction 30～150 min; Then, rising temperature to 60～130 ℃, continue insulation reaction 180～240 min; Reaction solution contains N, N-dibenzyl hydroxylamine derivative antioxidant product and by product organic amine salt hydrochlorate;
(2) reaction solution obtaining in step (1) is added to a certain amount of organic solvent, and the abundant dissolved product that heats up; Heat filtering carries out solid-liquid separation;
(3), by the solids organic solvent washing obtaining in step (2), obtain by product organic amine salt hydrochlorate;
(4) filtrate concentrating, crystallisation by cooling, filtration, washing, the dry product that to obtain will be obtained in step (2).
2. a kind of non-wastewater discharge claimed in claim 1 is prepared N, the method of N-dibenzyl hydroxylamine derivative oxidation inhibitor, is characterized in that wherein the organic amine acid binding agent described in step (1) refers to Trimethylamine 99, dimethyl amine, diethyl methylamine, dimethyl propylamine, dimethyl Isopropylamine, diisopropylethylamine, triethylamine, tripropyl amine or tribenzyl amine;
Wherein the organic solvent described in step (1) refers to C
6～C
10aromatic hydrocarbon, straight-chain paraffin, isoparaffin, naphthenic hydrocarbon; C
1～C
4anhydrous fatty alcohol;
Wherein the alkyl halide benzyl described in step (1) refer to following formula (
):
Formula (
);
Formula (
) in: R=C
1～C
10straight-chain paraffin or with the alkane of side chain;
X=Cl or Br;
Wherein described in step (2), the reaction solution obtaining in step (1) is added to organic solvent, add-on is by counting 2～10:1 with the mass ratio of oxammonium hydrochloride; Be warming up to 60～120 ℃; Stir, fully dissolve N, N-dibenzyl hydroxylamine derivative product; Heat filtering carries out solid-liquid separation;
Wherein the organic solvent described in step (2) refers to C
6～C
10aromatic hydrocarbon, straight-chain paraffin, isoparaffin, naphthenic hydrocarbon; C
1～C
4anhydrous fatty alcohol.
3. a kind of non-wastewater discharge claimed in claim 1 is prepared N, the method of N-dibenzyl hydroxylamine derivative oxidation inhibitor, is characterized in that wherein the solids that heat filtering in step (2) is obtained described in step (3) is further refined and obtained by product organic amine salt hydrochlorate; With sodium hydroxide, further alkalize, generate sodium-chlor the organic amine that dissociates, distillation, reclaims organic amine acid binding agent, and the building-up reactions for step (1), recycles.
4. a kind of non-wastewater discharge claimed in claim 1 is prepared N, the method of N-dibenzyl hydroxylamine derivative oxidation inhibitor, it is characterized in that in step (1) wherein, the mol ratio of oxammonium hydrochloride and alkyl halide benzyl is 1:0.7～3.5, the mol ratio of oxammonium hydrochloride and organic amine acid binding agent is 1:2.5～6.0; The mass ratio of oxammonium hydrochloride and organic solvent is 1:8～10.
5. a kind of non-wastewater discharge claimed in claim 1 is prepared N, the method of N-dibenzyl hydroxylamine derivative oxidation inhibitor, it is characterized in that wherein in step (1), first stirring and being warming up to 45～60 ℃, drip alkyl halide benzyl raw material, time for adding is 30～50 min, continues insulation reaction 40～100 min; Then temperature to 70～110 ℃ raise.
6. a kind of non-wastewater discharge claimed in claim 4 is prepared N, and the method for N-dibenzyl hydroxylamine derivative oxidation inhibitor is characterized in that in step (1) wherein, the mol ratio of oxammonium hydrochloride and alkyl halide benzyl is 1:2.0～3.0; The mol ratio of oxammonium hydrochloride and organic amine acid binding agent is 1:3.0～4.0.
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| CN201110287554.0A CN102391149B (en) | 2011-09-26 | 2011-09-26 | Method for preparing benzyl hydroxyl amine antioxygen without waste water discharge |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644278A (en) * | 1968-03-04 | 1972-02-22 | Ciba Geigy Corp | Substituted hydroxylamine stabilizers |
| US4703073A (en) * | 1983-10-11 | 1987-10-27 | Ciba-Geigy Corporation | Alkylated N,N-dibenzylhydroxylamines and polyolefin compositions stabilized therewith |
-
2011
- 2011-09-26 CN CN201110287554.0A patent/CN102391149B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644278A (en) * | 1968-03-04 | 1972-02-22 | Ciba Geigy Corp | Substituted hydroxylamine stabilizers |
| US4703073A (en) * | 1983-10-11 | 1987-10-27 | Ciba-Geigy Corporation | Alkylated N,N-dibenzylhydroxylamines and polyolefin compositions stabilized therewith |
Non-Patent Citations (2)
| Title |
|---|
| 赵刚等.N N-双-（苯并咪唑基甲基）羟胺的合成及其研究.《北京师范大学学报（自然科学版）》.1997 |
| 赵刚等.N,N-双-(苯并咪唑基甲基)羟胺的合成及其研究.《北京师范大学学报(自然科学版)》.1997,第33卷(第1期),第107-111页. * |
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Effective date of registration: 20191230 Address after: 213311 building 7, No. 8-2, Dutou street, Daitou Town, Liyang, Changzhou City, Jiangsu Province Patentee after: Liyang Chang Technology Transfer Center Co., Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: Changzhou University |
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