CN104399286B - A kind of natural fatty alcohol emulsion - Google Patents
A kind of natural fatty alcohol emulsion Download PDFInfo
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Abstract
The present invention relates to a kind of natural fatty alcohol emulsion, by natural fatty alcohol with containing propylene oxide group or have concurrently oxirane, propylene oxide group acetylenic glycols polyethers composite with alkylol polyethers with containing acetylenic glycols polyethers composite of ethylene oxide group, and with emulsion prepared by the cooling rate of 10 ~ 30 DEG C/min, not only improve the antifoaming performance of natural fatty alcohol emulsion at 25 DEG C, and under high temperature (50 DEG C), still keep good disappearing to press down bubble efficiency, also improve natural fatty alcohol emulsion intercalation method simultaneously.
Description
Technical field
The present invention relates to a kind of natural fatty alcohol emulsion, add as defoamer in paper making wet part and can play good froth breaking, degasification.Defoamer is a kind of fine chemicals additive, therefore, the invention belongs to technology of fine chemicals.
Background technology
In paper making wet part, sizing agent, retention agent, filter aid, reinforcing agent, deinking agent can be used to have surface-active auxiliary agent according to different paper kind, be easy to produce bubble in white water system process, the existence of these bubbles has a great impact paper, make that degree of sizing is poor, spot appears in paper, diaphanous spot and aperture, even cause disconnected paper, and easily make the operational efficiency of pump decline, increase energy consumption.
fatty alcohol emulsion is used for the froth breaking, degassed of paper making wet part as defoamer, and technology is very ripe.CN1295008C discloses antifoaming agent and/or the degasser of the water-bearing media for tending to formation foam, oil phase contains at least one compound, comprise the alcohol of at least 12 carbon atoms, alkoxy fatty alcohols, the list of aliphatic acid-, two-and triglyceride, the carboxylic acid of at least 12 carbon atoms and the fatty acid ester of the first alcohol of the 1-3 containing 3-22 carbon atom, boiling point is higher than the hydrocarbon of 200 DEG C, aliphatic acid containing 12-22 carbon atom, 3-thia alkane-1-alcohol, 3-thia oxo alkane-1-alcohol, the ester of 3-thia dioxo alkanol and thia alkane compound, and pass through (i) at least one polyglycerol ester, it is by obtaining the carboxylic esterification at least 20% of polyglycereol containing 12-36 carbon atom, (ii) at least one bisamide raising degasser of ethylenediamine and the carboxylic acid containing 10-36 carbon atom is higher than the efficiency of 50 DEG C, US5744066 discloses a kind of foam-killing agent in paper-making, oil phase contains: a) alcohol of at least 12 carbon atoms, it is for by oxo synthesis or prepared by Ziegler and have the mixture of obtainable bottoms or these compounds in the process of the alcohol of higher carbon atom number, b) have the sugar alcohol of ehter bond and the aliphatic acid of at least 20 carbon atoms at least 4-OH groups and at least one molecule by 1 at least 1 at least one ester that formed of molar ratio, some or all free-OH group in these esters are likely by C12-18 carboxylic esterification, c) fatty alcohol of at least 22 carbon atoms and C1-C36 carboxylic acid, the fatty acid ester of C12-22 carboxylic acid and the unit of the 1-3 containing 1-20 carbon atom alcohol, Tissuemat E, native paraffin or mixture, d) boiling point is higher than the hydrocarbon of 200 DEG C, the aliphatic acid of 12-22 carbon atom.EP-A-0322830 discloses the defoamer based on emulsion oil-in-water, wherein oil phase contains: (1) a kind of C12-26 alcohol, and if it is by oxo synthesis or prepared by Ziegler and have in the process of the alcohol of higher carbon atom number and obtain suitable bottoms that also can be alkoxylated, (2) the 1-3 unit ester that formed of alcohol of a kind of C12-22 carboxylic acid and C1-18, (3) a kind of boiling point higher than 200 DEG C hydrocarbon or there is the aliphatic acid of 12-22 carbon atom, (4) at least one is higher than the compound melted at 70 DEG C, it is selected from the fatty alcohol of at least 28 carbon atoms, the ester that C1-22 carboxylic acid is formed with the fatty alcohol of at least 28 carbon atoms, the addition product of the alcohol of C2-C4 alkylene oxide and at least 28 carbon atoms, molecular weight is at least the Tissuemat E of 2000g/mol, Brazil wax, montan wax, this invention defoamer at paper-making process higher than 35 DEG C, such as, within the scope of 50-60 DEG C also effective.
domestic and international fatty alcohol emulsion defoamer commercially available is at present mostly synthetic fatty alcohol emulsion, and a small amount of natural fatty alcohol emulsion defoamer also shows as and stores unstable, the poor problem of antifoaming performance.Compared with synthetic fatty alcohol, natural fatty alcohol can not disperse well, and the content of the natural fatty alcohol especially in fatty alcohol is greater than 20%, and the fatty alcohol emulsion so prepared is easy to retrogradation, and this uses to client and makes troubles.In addition, the plain boiled water temperature range that emulsion type defoaming agent prepared by natural fatty alcohol is suitable for is narrower, and the antifoaming performance especially under normal temperature (25 DEG C) is very poor, its market is applied limited.
Summary of the invention
The present invention by natural fatty alcohol with containing propylene oxide group or have oxirane concurrently, the composite emulsion that is prepared into of acetylenic glycols polyethers of propylene oxide group not only improves the antifoaming performance of natural fatty alcohol emulsion at 25 DEG C, and under high temperature (50 DEG C), still keeps good disappearing to press down bubble efficiency.
The present invention is by alkylol polyethers and acetylenic glycols polyethers composite containing ethylene oxide group, with be used alone alkylol polyethers or containing ethylene oxide group acetylenic glycols polyethers compared with, can form more closely, have more at natural fatty alcohol particle surface the interfacial film of intensity, thus improve natural fatty alcohol emulsion intercalation method.
Simultaneously, the discrete particles that natural fatty alcohol of the present invention is stable compared with the more difficult formation of synthetic fatty alcohol, mainly in the emulsion temperature-fall period of preparation, natural fatty alcohol particle more easily occurs assemble and cause emulsion unstable on the one hand, secondly the interfacial film strength that process of cooling more easily makes emulsifying agent be formed on natural fatty alcohol surface is damaged, thus natural fatty alcohol particle in storage process is more easily assembled and unstable.So as the necessary condition stablizing natural fatty alcohol emulsion, the present invention is by when emulsion temperature-fall period, with the cooling rate of 10 ~ 30 DEG C/min cooling emulsion, reduce the gathering of natural fatty alcohol emulsion particle, by above cooling rate, emulsion is cooled to 0 ~ 20 DEG C simultaneously, makes emulsifying agent have more intensity at the interfacial film on natural fatty alcohol surface.In addition, in order to reach above-mentioned cooling-down effect faster in the present invention, in preparation emulsion process, moisture is that two parts add, and Part I is the hot water of 70 ~ 95 DEG C, after emulsion cooling, then adds the water of Part II 20 DEG C.
technical scheme
Natural fatty alcohol emulsion defoamer of the present invention is composed of the following components:
a. natural fatty alcohol
Natural fatty alcohol of the present invention comprises the mixed alcohol containing different carbon number: be selected from C8-10 mixed alcohol, C8-14 mixed alcohol, C8-18 mixed alcohol, C12-14 mixed alcohol, C12-18 mixed alcohol, C14-16 mixed alcohol, C16-18 mixed alcohol, C18-22 mixed alcohol; Also the alcohol containing single carbon number is comprised: select C8 alcohol, C10 alcohol, C12 alcohol, C14 alcohol, C16 alcohol, C18 alcohol, C20 alcohol, C22 alcohol, C24 alcohol, C26 alcohol and C28 alcohol.These natural fatty alcohols can be used alone, also can be used in combination, and its consumption accounts for 15 ~ 25% of natural fatty alcohol emulsion gross mass.
acetylenic glycols polyethers
Acetylenic glycols polyether structure formula of the present invention is:
。
Wherein R
1, R
4for methyl or ethyl, R
2, R
3for the alkane of carbon number 3 ~ 10, p, q are the integer of 0 ~ 40, and m, n are the integer of 0 ~ 40, and are 0 when p, q, m, n are different.Acetylenic glycols is selected from 2,4,7,9-tetramethyl-5-decine-4,7-glycol, 4,7-dimethyl-5-decine-4,7-glycol, 2,5,8,11-tetramethyl-6-dodecyne-5,8-glycol.
As having the acetylenic glycols polyethers improving the effect of natural fatty alcohol emulsion normal temperature antifoaming performance, in its structural formula, m, n are the integer being greater than 1.Containing propylene oxide group or have oxirane concurrently, the acetylenic glycols polyethers consumption of propylene oxide group accounts for 1 ~ 6% of natural fatty alcohol emulsion total amount.
As having the acetylenic glycols polyethers of working in coordination with the effect of stable natural fatty alcohol emulsion with alkylol polyethers, in its structural formula, m, n are the integer that 0, p, q are not all 0.Acetylenic glycols polyethers consumption containing ethylene oxide group accounts for 0.1 ~ 3% of natural fatty alcohol emulsion total amount.
alkylol polyethers
Alkylol polyethers of the present invention is alkyl alcohol ethoxylates, and stablizes natural fatty alcohol emulsion containing the acetylenic glycols polyethers of ethylene oxide group is collaborative.Alkylol polyether structure formula of the present invention is: R-O-(CH
2cH
2o)
ah, wherein R is the saturated alkane of carbon number 8 ~ 18, and a is 1 ~ 60.In the present invention, the consumption of alkylol polyethers accounts for 0.1 ~ 5% of natural fatty alcohol emulsion total amount.
thickener
Thickener is used to regulate emulsion viscosity thus improve emulsion intercalation method further.Thickener in the present invention can be natural, also can be synthesis, comprise xanthan gum, guar gum, polyvinyl alcohol, carboxymethyl cellulose, hydroxyethylcellulose, methylcellulose, polyacrylic acid, polyacrylamide and polyacrylate.Acid-thickened dose of optimization polypropylene, consumption accounts for 0.5 ~ 3% of gross mass.
water
Water is decentralized medium, and its consumption determines the solid content of emulsion, preferably accounts for 60 ~ 75% of gross mass.Have requirement to the cooling rate of emulsion and cooling extent in the present invention, in order to more easily reach this requirement, moisture is that two parts add, Part I is the hot water of 70-95 DEG C, being that Part II is the water of 20 DEG C in order to prepare O/W type emulsion, is to obtain required solid content.Every part water consumption accounts for the half of total water consumption.
A preparation method for natural fatty alcohol emulsion, comprises the following steps:
(1) natural fatty alcohol, acetylenic glycols polyethers, alkylol polyethers are mixed and heated to 70-95 DEG C, stir 30min, obtain mixture M;
(2) hot water of the 70-95 of Part I DEG C is added in M in 30 ~ 60min, obtain mixture N;
(3) mixture N is passed through High shear device, obtain the mixture O of 70-95 DEG C;
(4) mixture O is cooled to 0 ~ 20 DEG C with the cooling rate of 10 ~ 30 DEG C/min, obtains mixture P;
(5) water of 20 of Part II DEG C is added in mixture P, and add thickener, namely obtain natural fatty alcohol emulsion of the present invention.
Detailed description of the invention
embodiment 1
By 20 parts of C18 natural fatty alcohols, 3 part 2,4,7,9-tetramethyl-5-decine-4,7-glycol polyoxypropylene (20) ether, 0.5 part 2,4,7,9-tetramethyl-5-decine-4,7-glycol polyoxyethylene (20) ether, 1 part of isomerous tridecanol polyoxyethylene (40) ether are heated to 75 DEG C, stir 30min, in 30min, add the hot water of 37 parts 75 DEG C, pass through High shear device, and be cooled to 0 DEG C with the speed of 10 DEG C/min, add the water of 37 parts 20 DEG C, finally add 1.5 parts of Polyacrylate thickeners, obtain the natural fatty alcohol emulsion defoamer of viscosity 345mPa.s.
embodiment 2
By 15 parts of C18-22 mixing natural fatty alcohols, 6 part 4,7-dimethyl-5-decine-4,7-glycol polyoxyethylene (10) polyoxypropylene (40) ether, 1 part 4,7-dimethyl-5-decine-4,7-glycol polyoxyethylene (40) ether, 4 parts of lauryl alcohol polyethylene glycol oxide (20) ethers are heated to 90 DEG C, stir 30min, the hot water of 36 parts 90 DEG C is added in 60min, pass through High shear device, and be cooled to 20 DEG C with the speed of 30 DEG C/min, add the water of 36 parts 20 DEG C, finally add 2 parts of Polyacrylate thickeners, obtain the natural fatty alcohol emulsion defoamer of viscosity 556mPa.s.
embodiment 3
By 25 parts of C22 natural fatty alcohols, 6 part 2, 5, 8, 11-tetramethyl-6-dodecyne-5, 8-glycol polyoxyethylene (5) polyoxypropylene (20) ether, 3 part 2, 5, 8, 11-tetramethyl-6-dodecyne-5, 8-glycol polyoxyethylene (10) ether, 2 parts of stearyl alcohol polyoxyethylene (60) ethers are heated to 95 DEG C, stir 30min, the hot water of 31.75 parts 95 DEG C is added in 30min, pass through High shear device, and be cooled to 15 DEG C with the speed of 15 DEG C/min, add the water of 31.75 parts 20 DEG C, finally add 0.5 part of Polyacrylate thickeners, obtain the natural fatty alcohol emulsion defoamer of viscosity 356mPa.s.
embodiment 4
By 5 parts of C16 natural fatty alcohols, 20 parts of C18-22 mixing natural fatty alcohols, 1 part 2, 4, 7, 9-tetramethyl-5-decine-4, 7-glycol polyoxyethylene (20) polyoxypropylene (40) ether, 1.5 part 2, 4, 7, 9-tetramethyl-5-decine-4, 7-glycol polyoxyethylene (20) ether, 1 part of C12-13 secondary alcohol polyoxyethylene (30) ether is heated to 90 DEG C, stir 30min, the hot water of 34.25 parts 90 DEG C is added in 40min, pass through High shear device, and be cooled to 15 DEG C with the speed of 30 DEG C/min, add the water of 34.25 parts 20 DEG C, finally add 3 parts of Polyacrylate thickeners, obtain the natural fatty alcohol emulsion defoamer of viscosity 602mPa.s.
comparative example 1
By 23 parts of C18 natural fatty alcohols, 0.5 part 2,4,7,9-tetramethyl-5-decine-4,7-glycol polyoxyethylene (20) ether, 1 part of isomerous tridecanol polyoxyethylene (40) ether are heated to 75 DEG C, stir 30min, in 30min, add the hot water of 37 parts 75 DEG C, pass through High shear device, and be cooled to 0 DEG C with the speed of 10 DEG C/min, add the water of 37 parts 20 DEG C, finally add 1.5 parts of Polyacrylate thickeners, obtain the natural fatty alcohol emulsion defoamer of viscosity 442mPa.s.
comparative example 2
23 parts of C18 natural fatty alcohols, 1.5 parts of isomerous tridecanol polyoxyethylene (40) ethers are heated to 75 DEG C, stir 30min, the hot water of 37 parts 75 DEG C is added in 30min, pass through High shear device, and be cooled to 0 DEG C with the speed of 10 DEG C/min, add the water of 37 parts 20 DEG C, finally add 1.5 parts of Polyacrylate thickeners, obtain the natural fatty alcohol emulsion defoamer of viscosity 345mPa.s.
comparative example 3
By 15 parts of C18-22 mixing natural fatty alcohols, 6 part 4,7-dimethyl-5-decine-4,7-glycol polyoxyethylene (10) polyoxypropylene (40) ether, 5 parts of lauryl alcohol polyethylene glycol oxide (20) ethers are heated to 90 DEG C, stir 30min, in 60min, add the hot water of 36 parts 90 DEG C, pass through High shear device, and be cooled to 20 DEG C with the speed of 30 DEG C/min, add the water of 36 parts 20 DEG C, finally add 2 parts of Polyacrylate thickeners, obtain the natural fatty alcohol emulsion defoamer of viscosity 656mPa.s.
comparative example 4
By 25 parts of C22 natural fatty alcohols, 6 part 2,5,8,11-tetramethyl-6-dodecyne-5,8-glycol polyoxyethylene (5) polyoxypropylene (20) ether, 3 part 2,5,8,11-tetramethyl-6-dodecyne-5,8-glycol polyoxyethylene (10) ether, 2 parts of stearyl alcohol polyoxyethylene (60) ethers are heated to 95 DEG C, stir 30min, in 30min, add the hot water of 31.75 parts 95 DEG C, pass through High shear device, and be cooled to 15 DEG C more than 4h, add the water of 31.75 parts 20 DEG C, finally add 0.5 part of Polyacrylate thickeners, obtain the natural fatty alcohol emulsion defoamer of viscosity 856mPa.s.
comparative example 5
By 5 parts of C16 natural fatty alcohols, 20 parts of C18-22 mixing natural fatty alcohols, 1 part 2, 4, 7, 9-tetramethyl-5-decine-4, 7-glycol polyoxyethylene (20) polyoxypropylene (40) ether, 1.5 part 2, 4, 7, 9-tetramethyl-5-decine-4, 7-glycol polyoxyethylene (20) ether, 1 part of C12-13 secondary alcohol polyoxyethylene (30) ether is heated to 90 DEG C, stir 30min, the hot water of 34.25 parts 90 DEG C is added in 40min, pass through High shear device, and be cooled to 25 DEG C with the speed of 30 DEG C/min, add the water of 34.25 parts 20 DEG C, finally add 3 parts of Polyacrylate thickeners, obtain the natural fatty alcohol emulsion defoamer of viscosity 478mPa.s.
comparative example 6
By 5 parts of C16 natural fatty alcohols, 20 parts of C18-22 mixing natural fatty alcohols, 1 part 2, 4, 7, 9-tetramethyl-5-decine-4, 7-glycol polyoxyethylene (20) polyoxypropylene (40) ether, 2.5 part 2, 4, 7, 9-tetramethyl-5-decine-4, 7-glycol polyoxyethylene (20) ether is heated to 90 DEG C, stir 30min, the hot water of 34.25 parts 90 DEG C is added in 40min, pass through High shear device, and be cooled to 15 DEG C with the speed of 30 DEG C/min, add the water of 34.25 parts 20 DEG C, finally add 3 parts of Polyacrylate thickeners, obtain the natural fatty alcohol emulsion defoamer of viscosity 378mPa.s.
antifoaming performance is tested
Method of testing: add 600ml plain boiled water in circulation bubbling device, be heated to temperature required, turn-on flow rate pump, under the flow of 8L/min, being circulated to foam volume is 300ml, then adds 6ul defoamer, record foam volume rule over time.In same time, foam volume is less, and antifoaming performance is better.
The antifoaming performance of table 1 natural fatty alcohol emulsion at 25 DEG C
The antifoaming performance of table 2 natural fatty alcohol emulsion at 50 DEG C
Natural fatty alcohol emulsion in the present invention, at adding the defoamer 25 DEG C of acetylenic glycols polyethers, antifoaming performance improves, and at 50 DEG C, still keep identical disappearing to press down bubble effect.
stability is tested
Method of testing: natural fatty alcohol emulsion is placed and carries out viscosity tracking and testing in 1 month.Concrete method of testing adopts NDJ-8 type digital display viscosity apparatus, and 2# rotor, tests under 30rpm condition.
The viscosity B coefficent situation of table 3 natural fatty alcohol emulsion (---represent that viscosity test exceedes range)
In the present invention by alkylol polyethers and acetylenic glycols polyethers composite and with 10 ~ 30 DEG C/min be cooled to 0 ~ 20 DEG C preparation natural fatty alcohol emulsion place 1 month more stable viscosity.The natural fatty alcohol emulsion viscosity prepared of independent alkylol polyethers or independent acetylenic glycols polyethers rises obviously, lowers the temperature to be slower than natural fatty alcohol emulsion viscosity prepared by 10 DEG C/min more than 20 DEG C or cooling rate and to rise also obvious.
Claims (4)
1. a natural fatty alcohol emulsion, is characterized in that, composed of the following components:
A. natural fatty alcohol
Described natural fatty alcohol comprises the mixed alcohol containing different carbon number and the alcohol containing single carbon number, the mixed alcohol of different carbon number is selected from C8-10 mixed alcohol, C8-14 mixed alcohol, C8-18 mixed alcohol, C12-14 mixed alcohol, C12-18 mixed alcohol, C14-16 mixed alcohol, C16-18 mixed alcohol, C18-22 mixed alcohol, and the alcohol containing single carbon number is selected from C8 alcohol, C10 alcohol, C12 alcohol, C14 alcohol, C16 alcohol, C18 alcohol, C20 alcohol, C22 alcohol, C24 alcohol, C26 alcohol and C28 alcohol; Be used alone or used in combination, its consumption accounts for 15 ~ 25% of natural fatty alcohol emulsion gross mass;
B. acetylenic glycols polyethers
Described acetylenic glycols polyether structure formula is:
Wherein R
1, R
4for methyl or ethyl, R
2, R
3for the alkane of carbon number 3 ~ 10, p, q are the integer of 0 ~ 40, and m, n are the integer of 0 ~ 40, and are 0 when p, q, m, n are different, and acetylenic glycols is selected from 2,4,7,9-tetramethyl-5-decine-4,7-glycol, 4,7-dimethyl-5-decine-4,7-glycol, 2,5,8,11-tetramethyl-6-dodecyne-5,8-glycol;
C. alkylol polyethers
The general formula of described alkylol polyethers is R-O-(CH
2cH
2o)
ah, wherein R is the saturated alkane of carbon number 8 ~ 18, and a is 1 ~ 60, and the consumption of alkylol polyethers accounts for 0.1 ~ 5% of natural fatty alcohol emulsion total amount;
D. thickener
Described thickener is natural or synthesis, be selected from xanthan gum, guar gum, polyvinyl alcohol, carboxymethyl cellulose, hydroxyethylcellulose, methylcellulose, polyacrylic acid, polyacrylamide and polyacrylate, consumption accounts for 0.5 ~ 3% of natural fatty alcohol emulsion total amount;
E. water
Water is decentralized medium, and consumption accounts for 60 ~ 75% of gross mass.
2. natural fatty alcohol emulsion according to claim 1, in the structural formula of acetylenic glycols polyethers, m, n are the integer being greater than 1, then containing propylene oxide group or have oxirane concurrently, the acetylenic glycols polyethers consumption of propylene oxide group accounts for 1 ~ 6% of natural fatty alcohol emulsion total amount; In the structural formula of acetylenic glycols polyethers, m, n are the integer that 0, p, q are not all 0, then the acetylenic glycols polyethers consumption containing ethylene oxide group accounts for 0.1 ~ 3% of natural fatty alcohol emulsion total amount.
3. natural fatty alcohol emulsion according to claim 1, the acid of thickener optimization polypropylene.
4. a preparation method for the natural fatty alcohol emulsion in claim 1-3 described in any one, is characterized in that comprising the following steps:
natural fatty alcohol, acetylenic glycols polyethers, alkylol polyethers are mixed and heated to 70-95 DEG C, stir 30min, obtain mixture M;
the hot water of the 70-95 of Part I DEG C is added in M in 30 ~ 60min, obtains mixture N;
by mixture N by High shear device, obtain the mixture O of 70-95 DEG C;
mixture O is cooled to 0 ~ 20 DEG C with the cooling rate of 10 ~ 30 DEG C/min, obtains mixture P;
the water of 20 of Part II DEG C is added in mixture P, and adds thickener, namely obtain natural fatty alcohol emulsion of the present invention.
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| CN113512901B (en) * | 2020-04-09 | 2023-03-10 | 江苏四新科技应用研究所股份有限公司 | Preparation method of fatty alcohol emulsion defoaming agent |
| CN112870773A (en) * | 2021-01-14 | 2021-06-01 | 江苏赛欧信越消泡剂有限公司 | Aqueous emulsion type non-silicon defoaming agent and preparation method thereof |
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| JPH09242A (en) * | 1995-06-23 | 1997-01-07 | Kao Corp | Defoaming agent for fermentation and fermentative production using the same |
| US6717019B2 (en) * | 2002-01-30 | 2004-04-06 | Air Products And Chemicals, Inc. | Glycidyl ether-capped acetylenic diol ethoxylate surfactants |
| CN100408138C (en) * | 2006-07-28 | 2008-08-06 | 南京四新科技应用研究所有限公司 | Prepn process of active defoaming agent composition |
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| CN100547158C (en) * | 2007-09-27 | 2009-10-07 | 南京四新科技应用研究所有限公司 | A kind of paper making wet part defoamer |
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Free format text: CORRECT: APPLICANT; FROM: SIXIN SCIENCE + TECHNOLOGY APPLIED INST. CO., LTD., NANJING CITY TO: JIANGSU INSTITUTE OF FOUR NEW TECHNOLOGYAPPLICATIONS |
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| C14 | Grant of patent or utility model | ||
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Address after: 210027 A22, 199 shogundong Road, Gulou District, Nanjing, Jiangsu. Patentee after: JIANGSU SIXIN SCIENTIFIC-TECHNOLOGICAL APPLICATION RESEARCH INSTITUTE CO., LTD. Address before: 210027 Nanjing, Jiangsu, Gulou District, No. 199 shogundong Road, purple gold (Xiaguan) technology entrepreneurship special community D11 Patentee before: JIANGSU SIXIN SCIENTIFIC-TECHNOLOGICAL APPLICATION RESEARCH INSTITUTE CO., LTD. |