CN102807643A - Emulsifying agent for emulsion polymerization and preparation method thereof - Google Patents
Emulsifying agent for emulsion polymerization and preparation method thereof Download PDFInfo
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- CN102807643A CN102807643A CN2012103092877A CN201210309287A CN102807643A CN 102807643 A CN102807643 A CN 102807643A CN 2012103092877 A CN2012103092877 A CN 2012103092877A CN 201210309287 A CN201210309287 A CN 201210309287A CN 102807643 A CN102807643 A CN 102807643A
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Abstract
The invention relates to an emulsifying agent for emulsion polymerization and a preparation method thereof. The emulsifying agent is an esterification derivative of a styrene-maleic anhydride (SMA) copolymer, which is obtained by performing catalytic esterification reaction of the SMA copolymer, saturated fatty alcohol and an acrylate monomer containing hydroxyl, wherein a side chain of the esterification derivative contains carbon-carbon double bonds; raw materials for the catalytic esterification reaction comprise the following component in percentage by mass: 10 to 30 percent of SMA polymer, 1 to 10 percent of saturated fatty alcohol, 0.5 to 5 percent of acrylate monomer containing hydroxyl, 0.001 to 5 percent of esterification catalyst and 40 to 70 percent of solvent; and the SMA polymer is a polymer of styrene and maleic anhydride in a molar ratio of 1:(1-3):1. According to a polymer emulsion prepared from the emulsifying agent for the emulsion polymerization, the water tolerance of a coating film is superior to that of the similar conventional emulsion, so that the emulsifying agent has an obvious effect on the aspect of enhancing the water tolerance of the coating film.
Description
Technical field
The present invention relates to a kind of emulsifier for emulsion polymerization and preparation method thereof.
Background technology
Mostly adopt emulsifying agent in the polymer emulsion building-up process, like sodium lauryl sulphate (SDS) etc., its role is to: the pattern of control latex particle reaches with size stablizes latex particle.Usually emulsifying agent all is that form with physical adsorption is distributed in the latex particle surface; But in practical application; Because the latex particle surface desorption that physical adsorption is very easily filmed from formation in the emulsifying agent on latex particle surface; Migrate to film coated surface or enrichment and form hydrophilic region, thereby influence the performances such as gloss, water tolerance, physical strength of paint film.In recent ten years, report has the novel method that much addresses the above problem both at home and abroad, comprises adopting macromole emulsifying agent or polymerisable small-molecular emulsifier and adopting the emulsifier-free emulsion polymerization method.But still there is problem more or less in these methods, adopt macromole emulsifying agent can only slow down desorb odds and speed, the problem that can not fundamentally avoid desorb to cause; Though adopt the polymerisable small-molecular emulsifier can be on principle with polymerization single polymerization monomer copolymerization together emulsion polymerization process; But the polymerization activity of emulsifying agent is Tai Gao or too low usually; If the too high meeting of activity causes the emulsifying agent autohemagglutination, be dissolved in the water thereby form polyelectrolyte, be unfavorable for the water tolerance of emulsion paint film; The too low emulsifying agent that then can cause of activity can not be with the polymerization single polymerization monomer copolymerization, and still the form with small-molecular emulsifier exists; The big multistability of the emulsion that the emulsifier-free emulsion polymerization method obtains is not fine, sometimes still need add a small amount of small-molecular emulsifier.Therefore, emulsifying agent has become the key of impact polymer quality of the emulsion, has also influenced the development of water-borne coatings.
Summary of the invention
First purpose of the present invention is: provide a kind of can with the emulsifier for emulsion polymerization of letex polymerization monomer copolymerization.
The technical scheme that realizes first purpose of the present invention is: a kind of emulsifier for emulsion polymerization is the esterified derivative that the acrylate monomer of styrene-maleic anhydride copolymer and saturated fatty alcohol and hydroxyl carries out the styrene-maleic anhydride copolymer of the side chain carbon-carbon double bonds that catalytic esterification obtains; In the raw materials used total mass of catalytic esterification; Styrene-maleic anhydride copolymer accounts for 10%～30%, saturated fatty alcohol accounts for 1～10%, the acrylate monomer of hydroxyl accounts for 0.5%～5%, esterifying catalyst accounts for 0.001%～5%, solvent accounts for 40%～70%, and the percentage ratio sum of above-mentioned each raw material consumption is 100%;
Said styrene-maleic anhydride copolymer is that mol ratio is vinylbenzene and two kinds of monomeric multipolymers of maleic anhydride of 1:1～3:1; The number-average molecular weight that its gel permeation chromatography records is 1000～10000g/mol; The MWD coefficient is 1.1～3.0, and acid number is 200～500mg KOH/g;
Said saturated fatty alcohol is one or more in propyl carbinol, Pentyl alcohol, n-Octanol, isooctyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol, the stearyl alcohol;
The acrylate monomer of said hydroxyl is a kind of in Hydroxyethyl acrylate, Rocryl 400, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester, the methylacrylic acid hydroxy butyl ester.
Second purpose of the present invention is: a kind of operation of being convenient to is provided, be used to prepare can with the method for the emulsifying agent of letex polymerization monomer copolymerization.
The technical scheme that realizes second purpose of the present invention is: a kind of preparation method of mentioned emulsifier, and its concrete steps are following:
1. prepare raw material
Press above-mentioned emulsifier ratio and prepare acrylate monomer, esterifying catalyst and the solvent of the styrene-maleic anhydride copolymer of catalytic esterification use, saturated fatty alcohol, hydroxyl;
2. preparation
In reaction vessel; Be sequentially added into the acrylate monomer and the esterifying catalyst of styrene-maleic anhydride copolymer that 1. step prepare, solvent, saturated fatty alcohol, hydroxyl and stir, be warming up to 60～150 ℃, insulation reaction is after 2～20 hours; The gained material is cooled to 40 ℃; Pour under stirring then and generate throw out in the container that water is housed, leach throw out, oven dry is emulsifier for emulsion polymerization.
Among the above-mentioned preparation method; Said styrene-maleic anhydride copolymer is that mol ratio is vinylbenzene and two kinds of monomeric multipolymers of maleic anhydride of 1:1～3:1; The number-average molecular weight that its gel permeation chromatography records is 1000～10000g/mol; The MWD coefficient is 1.1～3.0, and acid number is 200～500mg KOH/g;
Said saturated fatty alcohol is one or more in propyl carbinol, Pentyl alcohol, n-Octanol, isooctyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol, the stearyl alcohol;
The acrylate monomer of said hydroxyl is a kind of in Hydroxyethyl acrylate, Rocryl 400, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester, the methylacrylic acid hydroxy butyl ester;
Described esterifying catalyst is a kind of in tosic acid, Dimethylamino pyridine, the dibutyl tin dilaurate;
Said solvent is acetone, butanone, THF, N, dinethylformamide and 1, one or more in the 4-dioxane.
Technique effect of the present invention is: the emulsifying agent of technical scheme of the present invention has made full use of that each maleic anhydride unit all contains a characteristic with anhydride group of good reactive behavior in styrene-maleic anhydride copolymer (hereinafter to be referred as the SMA multipolymer) molecule; Select the suitable and suitable SMA multipolymer of molecular weight of ratio of maleic anhydride and styrene units for use; The saturated fatty alcohol that usefulness is suitable and the acrylate monomer of hydroxyl carry out esterification, the side chain carbon-carbon double bonds of the esterified derivative of the SMA multipolymer that obtains after the esterification to the part anhydride group of SMA multipolymer.With the esterified derivative of the SMA multipolymer of this side chain carbon-carbon double bonds during as the emulsifying agent of letex polymerizations such as benzene emulsion, organosilicon crylic acid latex, acrylate and vinyl acetate emulsion; Form micella earlier at letex polymerization initial stage emulsifying agent of the present invention; Vinylbenzene, vinylformic acid monomer polymerizations in micella such as (esters) subsequently; Polymerization process or polymerization latter stage; The contained carbon-carbon double bond of emulsifying agent side chain of the present invention just can with the vinylbenzene that is used for synthetic emulsion, vinylformic acid monomer copolymerizations such as (esters), emulsifying agent just is combined in the emulsion particle surface through chemical bonded refractory like this, has avoided using emulsifying agent migration that conventional small-molecular emulsifier and macromole emulsifying agent bring and from the problem of latex particle surface desorption; Solved the unmanageable problem of reactive behavior of polymerizable small-molecular emulsifier again; Thereby improved film behind the emulsion film forming long-term water tolerance and mechanical property, accelerate coating Water-borne modification process, compliance with environmental protection requirements.
Embodiment
Below in conjunction with embodiment the present invention is done to further describe, but be not limited to this.
Embodiment and comparative example be raw materials used unless otherwise indicated to be commercially available industrial goods, can buy through the commercial channel.
Embodiment 1～3 preparation emulsifying agent A, B, C
The main chemical reactions that preparation emulsifying agent A, B, C relate to:
Wherein:
M:n is 1:1～3:1
R
1For carbonatoms 20 with interior alkyl;
R
2Be hydrogen or methyl;
R
3For carbonatoms 4 with interior alkyl or polyoxyethylene group.
1. prepare raw material
Each raw material consumption of emulsion of the present invention is following: in the raw materials used total mass of catalytic esterification; Styrene-maleic anhydride copolymer accounts for 10%～30%, saturated fatty alcohol accounts for 1～10%, the acrylate monomer of hydroxyl accounts for 0.5%～5%, esterifying catalyst accounts for 0.001%～5%, solvent accounts for 40%～70%, and the percentage ratio sum of above-mentioned each raw material consumption is 100%.
Embodiment 1～3 each raw material consumption is seen table 1, and table 2 seen in the chemical structural formula of each raw material.
Table 1
Annotate: 1, data are this raw material shared percentage ratio in raw materials used total mass in the bracket;
2, SMA1000P is the trade name of Satomer company; It is that mol ratio is vinylbenzene and two kinds of monomeric multipolymers of maleic anhydride of 1:1; The number-average molecular weight that its gel permeation chromatography records is 2060g/mol, and the MWD coefficient is 2.0, and acid number is 480mgKOH/g;
SMA2000 is the trade name of Satomer company; It is that mol ratio is vinylbenzene and two kinds of monomeric multipolymers of maleic anhydride of 2:1; The number-average molecular weight that its gel permeation chromatography records is 3000g/mol, and the MWD coefficient is 2.2, and acid number is 350mgKOH/g;
SMA3000 is the trade name of Satomer company; It is that mol ratio is vinylbenzene and two kinds of monomeric multipolymers of maleic anhydride of 3:1; The number-average molecular weight that its gel permeation chromatography records is 3800g/mol, and the MWD coefficient is 2.3, and acid number is 280mgKOH/g.
2. preparation
Respectively in the 500ml reaction flask, be sequentially added into the acrylate monomer and the esterifying catalyst of styrene-maleic anhydride copolymer that 1. step prepare, solvent, saturated fatty alcohol, hydroxyl and stir, be warming up to 65 ℃; After the insulation reaction 9～10 hours; The gained material is cooled to 40 ℃, stirs then to pour into down to generate throw out in the container that 500g water is housed, and leaches throw out; Oven dry is emulsifier for emulsion polymerization A, B, C, and table 2 seen in its chemical structural formula.
Embodiment 4 preparation polymer emulsion A
In the 500mL reaction flask, be sequentially added into emulsifying agent A, 220g deionized water and 8g ammoniacal liquor that 20g embodiment 1 makes, be warming up to 70 ℃, keep stirring and dissolve fully until emulsifying agent A.At this moment, under the situation of stirring and logical nitrogen, temperature is risen to 85 ℃; With the mixture of 60g vinylbenzene and 30g Bing Xisuandingzhi and at the solution of forming by 50g deionized water and 0.6g ammonium persulphate, be added drop-wise in the reaction flask then, after in 3 hours, dropwising; Continue stirring after 2 hours at 85 ℃, under stirring at low speed, be cooled to room temperature, obtain polymer emulsion A; Outward appearance is translucent, no condensation prod.
The median size that records the emulsion particle of polymer emulsion A through the nano particle size analyser is about 41nm, and the actual measurement solids content of polymer emulsion A is 29.4wt%, and it is 118mPas that rotational viscosimeter records viscosity.
Embodiment 5 preparation polymer emulsion B
In the 500mL reaction flask, be sequentially added into emulsifying agent B, 190g deionized water and 5g ammoniacal liquor that 15g embodiment 2 makes, be warming up to 70 ℃, keep stirring and dissolve fully until emulsifying agent B.At this moment, under the situation of stirring and logical nitrogen, temperature is risen to 85 ℃; Then the mixture of 20g TEB 3K and 40g Bing Xisuandingzhi and the drips of solution of being made up of 30g deionized water and 0.4g ammonium persulphate are added in the reaction flask, after in 3 hours, dropwising, continue stirring after 2 hours at 85 ℃; Under stirring at low speed, be cooled to room temperature; Obtain polymer emulsion B, outward appearance is translucent, no condensation prod.
Through the nano particle size analyser record polymer emulsion B the median size of emulsion particle be 47nm, the actual measurement solid content of polymer emulsion B is 24.3wt%, it is 82mPas that rotational viscosimeter records viscosity.
Embodiment 6 preparation polymer emulsion C
In the 500mL reaction flask, be sequentially added into emulsifying agent C, 160g deionized water and 5g ammoniacal liquor that 15g embodiment 3 makes, be warming up to 70 ℃, keep stirring and dissolve fully until emulsifying agent C.At this moment, under the situation of stirring and logical nitrogen, temperature is risen to 85 ℃; With the mixture of 10g TEB 3K, 20g vinylbenzene and 35g Bing Xisuandingzhi and the solution of forming by 40g deionized water and 0.4g ammonium persulphate, be added drop-wise in the reaction flask, after in 3 hours, dropwising then; Continue stirring after 2 hours at 85 ℃; Under stirring at low speed, be cooled to room temperature, obtain polymer emulsion C, outward appearance is translucent.
The median size that records the emulsion particle of polymer emulsion C through the nano particle size analyser is 55nm, and the actual measurement solids content of polymer emulsion C is 29.3wt%, and it is 107mPas that rotational viscosimeter records viscosity
Reference examples 1 adopts conventional small-molecular emulsifier sodium lauryl sulphate to prepare emulsion
In the 500mL reaction flask, be sequentially added into 0.45g emulsifier sodium lauryl sulfate, 170g deionized water, be warming up to 70 ℃, keep stirring until the whole dissolution system clears of emulsifying agent.At this moment, under the situation of stirring and logical nitrogen, temperature is risen to 85 ℃; With the mixture of 60g vinylbenzene and 30g Bing Xisuandingzhi and the solution of forming by 40g deionized water and 0.4g ammonium persulphate, be added drop-wise in the reaction flask, after in 3 hours, dropwising then; Continue stirring after 2 hours at 85 ℃; Under stirring at low speed, be cooled to room temperature, obtain reference examples 1 polymer emulsion, outward appearance is an oyster white.
The median size that records the emulsion particle of reference examples 1 polymer emulsion through the nano particle size analyser is 112nm, and the actual measurement solid content of emulsion is 29.8wt%, and it is 208mPas that rotational viscosimeter records viscosity.
Reference examples 2 adopts commercially available SMA1000 (not containing polymerizable double bond) to prepare emulsion as macromole emulsifying agent
In the 500mL reaction flask, be sequentially added into 5g emulsifying agent SMA1000P, 160g deionized water and 3g ammoniacal liquor, be warming up to 70 ℃, keep stirring and dissolve fully until emulsifying agent.At this moment, under the situation of stirring and logical nitrogen, temperature is increased to 85 ℃; With the mixture of 5g TEB 3K and 12g Bing Xisuandingzhi and the solution of forming by 40g deionized water and 0.08g ammonium persulphate, be added drop-wise in the reaction flask, after in 3 hours, dropwising then; Continue stirring after 2 hours at 85 ℃; Under stirring at low speed, be cooled to room temperature, obtain reference examples 2 polymer emulsions, outward appearance is translucent; Wherein emulsifying agent SMA1000P is a Satomer Company products title, and it is that mol ratio is the vinylbenzene of 1:1 and the SMA multipolymer that maleic anhydride is formed;
The median size that records the emulsion particle of reference examples 1 polymer emulsion through the nano particle size analyser is 52nm, and the actual measurement solids content of emulsion is 9.6wt%, and it is 34mPas that rotational viscosimeter records viscosity.
After film coalescence aid (the 12 carbon alcohol ester) high-speed stirring that the polymer emulsion that embodiment 4～6 and reference examples 1～2 are made adds mass ratio 0.1%～1% is processed varnish, be coated on the ABS plastic plate, process to detect and use model, and detect correlated performance as follows:
Sticking power is tested according to standard GB/T9286-98; Pencil hardness is tested according to standard GB/T6739-96; Water resistance test is tested according to standard GB/T1733-93 (first method).The performance of respectively filming that records is listed in table 3.
Table 3
| The emulsion title | Sticking power, level | Pencil hardness, H | Water tolerance |
| Polymer emulsion A | 0 | 2 | 72h does not whiten, and is non-foaming |
| Polymer emulsion B | 0 | 2 | 72h does not whiten, and is non-foaming |
| Polymer emulsion C | 0 | 2 | 72h does not whiten, and is non-foaming |
| Reference examples 1 polymer emulsion | 0 | 1 | 48h slightly whitens, and is non-foaming |
| Reference examples 2 polymer emulsions | 1 | 2 | The 24h whiting comes off |
Can find out from table 3; The polymer emulsion that makes with emulsifying agent of the present invention; Its water-resistance property of coating all is superior to conventional emulsion (reference examples 1 and 2); Particularly use not contain the reference examples 2 of the SMA multipolymer of polymerizable double bond as emulsifying agent, its water-resistance property of coating is the poorest, has proved that more emulsifying agent of the present invention (esterified derivative of the SMA multipolymer of side chain carbon-carbon double bonds) is having positive effect aspect the enhancing water-resistance property of coating ability.
Practical application shows that emulsion of the present invention all can make the water-resistance property of coating of the polymer emulsion that makes be significantly improved as the emulsifying agent of letex polymerizations such as benzene emulsion, organosilicon crylic acid latex, acrylate and vinyl acetate emulsion, repeats no more at this.
Claims (3)
1. emulsifier for emulsion polymerization; It is characterized in that; It is the esterified derivative that the acrylate monomer of styrene-maleic anhydride copolymer and saturated fatty alcohol and hydroxyl carries out the styrene-maleic anhydride copolymer of the side chain carbon-carbon double bonds that catalytic esterification obtains; In the raw materials used total mass of catalytic esterification; Styrene-maleic anhydride copolymer accounts for 10%～30%, saturated fatty alcohol accounts for 1～10%, the acrylate monomer of hydroxyl accounts for 0.5%～5%, esterifying catalyst accounts for 0.001%～5%, solvent accounts for 40%～70%, and the percentage ratio sum of above-mentioned each raw material consumption is 100%;
Said styrene-maleic anhydride copolymer is that mol ratio is vinylbenzene and two kinds of monomeric multipolymers of maleic anhydride of 1:1～3:1; The number-average molecular weight that its gel permeation chromatography records is 1000～10000g/mol; The MWD coefficient is 1.1～3.0, and acid number is 200～500mgKOH/g;
Said saturated fatty alcohol is one or more in propyl carbinol, Pentyl alcohol, n-Octanol, isooctyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol, the stearyl alcohol;
The acrylate monomer of said hydroxyl is a kind of in Hydroxyethyl acrylate, Rocryl 400, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester, the methylacrylic acid hydroxy butyl ester.
2. the preparation method of claim 1 emulsifying agent is characterized in that, concrete steps are following:
1. prepare raw material
The proportioning of pressing claim 1 is prepared acrylate monomer, esterifying catalyst and the solvent of the styrene-maleic anhydride copolymer of catalytic esterification use, saturated fatty alcohol, hydroxyl;
2. preparation
In reaction vessel; Be sequentially added into the acrylate monomer and the esterifying catalyst of styrene-maleic anhydride copolymer that 1. step prepare, solvent, saturated fatty alcohol, hydroxyl and stir, be warming up to 60～150 ℃, insulation reaction is after 2～20 hours; The gained material is cooled to 40 ℃; Pour under stirring then and generate throw out in the container that water is housed, leach throw out, oven dry is emulsifier for emulsion polymerization.
3. preparation method according to claim 2; It is characterized in that; Said styrene-maleic anhydride copolymer is that mol ratio is vinylbenzene and two kinds of monomeric multipolymers of maleic anhydride of 1:1～3:1; The number-average molecular weight that its gel permeation chromatography records is 1000～10000g/mol, and the MWD coefficient is 1.1～3.0, and acid number is 200～500mg KOH/g;
Said saturated fatty alcohol is one or more in propyl carbinol, Pentyl alcohol, n-Octanol, isooctyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol, the stearyl alcohol;
The acrylate monomer of said hydroxyl is a kind of in Hydroxyethyl acrylate, Rocryl 400, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester, the methylacrylic acid hydroxy butyl ester;
Described esterifying catalyst is a kind of in tosic acid, Dimethylamino pyridine, the dibutyl tin dilaurate;
Said solvent is acetone, butanone, THF, N, dinethylformamide and 1, one or more in the 4-dioxane.
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Cited By (6)
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| CN105506643A (en) * | 2015-12-20 | 2016-04-20 | 中国海洋石油总公司 | Polymerized imidazoline corrosion inhibitor and preparation method thereof |
| CN105693944A (en) * | 2014-11-27 | 2016-06-22 | 合众（佛山）化工有限公司 | Preparation method of high-temperature-resistant modified styrene acrylic emulsion |
| CN110698579A (en) * | 2019-09-18 | 2020-01-17 | 中科院广州化学有限公司 | Alcohol-resistant water-based resin emulsion binder for quick-drying ink and preparation method thereof |
| CN113881003A (en) * | 2021-09-27 | 2022-01-04 | 万华化学(四川)有限公司 | ABS graft polymerizable emulsifier, preparation method and application thereof, and preparation method of ABS graft latex |
| WO2022018510A1 (en) * | 2020-07-23 | 2022-01-27 | Arkema France | (meth)acrylate functional dispersant |
| CN115197381A (en) * | 2022-09-16 | 2022-10-18 | 广州鹿山新材料股份有限公司 | Unsaturated SMA resin modified polypropylene and preparation method thereof |
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| CN105693944A (en) * | 2014-11-27 | 2016-06-22 | 合众（佛山）化工有限公司 | Preparation method of high-temperature-resistant modified styrene acrylic emulsion |
| CN105693944B (en) * | 2014-11-27 | 2019-01-29 | 合众（佛山）化工有限公司 | A kind of preparation method of heat resist modification styrene-acrylic emulsion |
| CN105506643A (en) * | 2015-12-20 | 2016-04-20 | 中国海洋石油总公司 | Polymerized imidazoline corrosion inhibitor and preparation method thereof |
| CN110698579A (en) * | 2019-09-18 | 2020-01-17 | 中科院广州化学有限公司 | Alcohol-resistant water-based resin emulsion binder for quick-drying ink and preparation method thereof |
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| CN113881003A (en) * | 2021-09-27 | 2022-01-04 | 万华化学(四川)有限公司 | ABS graft polymerizable emulsifier, preparation method and application thereof, and preparation method of ABS graft latex |
| CN113881003B (en) * | 2021-09-27 | 2024-02-27 | 万华化学(四川)有限公司 | ABS grafted polymerizable emulsifier, preparation method and application thereof, and preparation method of ABS grafted latex |
| CN115197381A (en) * | 2022-09-16 | 2022-10-18 | 广州鹿山新材料股份有限公司 | Unsaturated SMA resin modified polypropylene and preparation method thereof |
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Address after: 100010 Dongcheng District, Chaoyangmen, North Street, No. 4705, No. 25, box office, Beijing Patentee after: China National Offshore Oil Corporation Patentee after: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE CO., LTD. Patentee after: CNOOC Energy Development Co., Ltd. Patentee after: CNOOC Changzhou EP Coating Co., Ltd. Address before: 100010 Dongcheng District, Chaoyangmen, North Street, No. 4705, No. 25, box office, Beijing Patentee before: China National Offshore Oil Corporation Patentee before: CNOOC Changzhou Paint & Coatings Industry Research Institute Patentee before: CNOOC Energy Development Co., Ltd. Patentee before: CNOOC Changzhou EP Coating Co., Ltd. |
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Effective date of registration: 20161020 Address after: 213016 Changzhou Zhong Road, Jiangsu Province, No. 22 Longjiang Road Patentee after: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE CO., LTD. Patentee after: CNOOC Energy Development Co., Ltd. Patentee after: CNOOC Changzhou EP Coating Co., Ltd. Address before: 100010 Dongcheng District, Chaoyangmen, North Street, No. 4705, No. 25, box office, Beijing Patentee before: China National Offshore Oil Corporation Patentee before: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE CO., LTD. Patentee before: CNOOC Energy Development Co., Ltd. Patentee before: CNOOC Changzhou EP Coating Co., Ltd. |