CN104892849A - Bionically designed waterborne polyacrylate modified polyurethane composite emulsion and preparation method thereof - Google Patents
Bionically designed waterborne polyacrylate modified polyurethane composite emulsion and preparation method thereof Download PDFInfo
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- CN104892849A CN104892849A CN201410075149.6A CN201410075149A CN104892849A CN 104892849 A CN104892849 A CN 104892849A CN 201410075149 A CN201410075149 A CN 201410075149A CN 104892849 A CN104892849 A CN 104892849A
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Abstract
The invention discloses a bionically designed waterborne polyacrylate modified polyurethane composite emulsion and a preparation method thereof. The method is characterized by: using acetone or butanone and acrylic monomer as the solvent, subjecting diisocyanate HDI and IPDI, mixed polyester polyol, dimethylolpropionic acid, 1, 4-butanediol, trimethylolpropane monoallyl ether, hydroxypropy, and hydroxyethyl acrylate to polymerization to obtain polyurethane with carboxyl, and conducting neutralization with tertiary amine, removing the solvent to obtain self-emulsifying waterborne polyurethane anionic emulsion containing double bonds; then taking the emulsion as seed, adding acrylate monomer, dopamine methacrylamide and a proper amount of crosslinking agent monomer to carry out pre-emulsification, then performing seeded emulsion polymerization to obtain the bionically designed waterborne polyacrylate modified polyurethane composite emulsion. The composite emulsion provided by the invention has the advantages of energy saving and environmental protection, adaptation to various material surfaces, safe and reliable process, and stable product quality.
Description
Technical field
The present invention relates to coating and adhesive for shoes technical field, more specifically design a kind of preparations and applicatio adopting the high solid content water polyacrylate modified polyurethane composite emulsion of bionic design.
Background technology
In the tissue of many biologies of occurring in nature, organ and structure, its much marvellous function designs far beyond the mankind.By the analysis and research to the special composition of natural biological, structure and function, the structure of mimic biology body, form, function and behavior, seek its inner principle and for solving the Science and Technology problem faced.Living species abundant in ocean and special chemical structure thereof, become the resource treasure-house screening various functional material.The superpower adhesion that the stickiness albumen that the biological byssus of marine mussel class is secreted shows under the water surrounding of humidity, the adhesion protein of its secretion can be attached on nearly all base material, even comprise tetrafluoroethylene (PTFE), and this natural stick do not exist synthetic adhesive in wet condition cohere the bad defect of effect, this excellent properties be at present other tamanori incomparable.
Our target to have the mussel adhesion protein functional unit (catechol) of magical adhesion effect and to have programmable, toughness, the easy polymkeric substance combination that prepare, low cost of structure, to prepare novel high-performance pasting material.Acrylic materials has that internal cohesive energy is higher, bonding strength is comparatively strong, and has the advantages such as structure can design, and performance is adjustable.Polyacrylic ester (PA) emulsion and aqueous polyurethane (WPU) emulsion with compared with traditional solvent based product, advantages such as there is safety, do not fire, be nontoxic, pollution-free, thus be widely used in coating, tackiness agent, ink, fabric finish.Pure WPU emulsion has obdurability, weathering resistance, wear resistance, chemical-resistant resistance and poor water resistance.Aqueous polyurethane/acrylate is compounded in has complementary action in nature, can overcome respective shortcoming, make the most of the advantage, and the performance of gained emulsion and glued membrane is obviously improved.
Summary of the invention
A kind of energy-conserving and environment-protective that object of the present invention is exactly deficiency in order to solve prior art and provides, process safety are reliable, the bionic design water polyacrylic acid modified polyurethane composite emulsion of constant product quality.
Another object of the present invention is to provide a kind of preparation method of bionic design water polyacrylic acid modified polyurethane composite emulsion.
The present invention adopts following technical solution to realize above-mentioned purpose: a kind of bionic design water polyacrylic acid modified polyurethane composite emulsion, it is characterized in that, it adopts acetone or butanone and acrylic monomer to make solvent, vulcabond HDI and IPDI, mixed polyester polyvalent alcohol, dimethylol propionic acid, 1, 4-butyleneglycol, TriMethylolPropane(TMP) mono allyl ether, Propylene glycol monoacrylate, Hydroxyethyl acrylate is polymerized, prepare the urethane of band carboxyl and neutralize with tertiary amine, desolvation, obtain self-emulsifying and double bond containing aqueous polyurethane anionic emulsion, again this emulsion is made seed, after adding acrylic ester monomer, Dopamine HCL Methacrylamide and appropriate crosslinkers monomers pre-emulsification, carry out the bionic design water polyacrylic acid modified polyurethane composite emulsion that seeded emulsion polymerization obtains.
Further illustrating as such scheme, described Dopamine HCL Methacrylamide (DMA) is dissolved in distilled water by dopamine hydrochloride, methacrylic anhydride to be dissolved in tetrahydrofuran (THF) and to be added drop-wise in the solution of the dopamine hydrochloride of logical nitrogen, reaction at room temperature carries out 12h, reaction solution adjusted to ph is extracted with ethyl acetate to when being less than 2, revolve steaming, hexanaphthene recrystallization, obtain after product vacuum drying.
A kind of preparation method of bionic design water polyacrylic acid modified polyurethane composite emulsion, it is characterized in that, it is the polyaminoester emulsion I first preparing double bond containing self-emulsifying, then this emulsion is made seed, add acrylic ester monomer, Dopamine HCL Methacrylamide, reactive emulsifier and linking agent and carry out seeded emulsion polymerization, obtain urethane composite emulsion II, i.e. bionic design water polyacrylic acid modified polyurethane composite emulsion.
The polyaminoester emulsion I of the described self-emulsifying containing double bond, it is by 100 weight of polyester (polyethers) polyvalent alcohol and sulfonated polyester polyol, 20-45 weight part vulcabond, 0.5-3 weight part dibasic alcohol, 1-5 weight part TriMethylolPropane(TMP) mono allyl ether, 0.5-2 weight part trivalent alcohol and 2-6 part by weight of hydrophilic monomer chainextender and 1-7 parts by weight propylene acid esters class function monomer, catalyzer and solvent, in 80-150rpm stirring velocity, reaction preparation at 70-90 DEG C, last 3000-5000rpm dispersion and emulsion half an hour.
Described urethane composite emulsion II, 10-45 parts by weight of acrylic acid esters monomer, 1-10 weight part Dopamine HCL Methacrylamide (DMA), 1-7 weight part specific functionality monomer and 0.5-3 weight part reactive emulsifier are added in the polyaminoester emulsion of the self-emulsifying containing double bond carry out pre-emulsification, get 10-30 weight part and make seed emulsion, the 0.1-1 weight part initiator of acrylic ester monomer, seeded emulsion polymerization is carried out to the polyaminoester emulsion of the self-emulsifying containing double bond, temperature of reaction 50-85 DEG C, stirring velocity 150-300rpm, time 3-8 hour.
Described vulcabond, comprises one or more in phenylmethane vulcabond (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tetramethyl-xylylene diisocyanate (TMXDI).
Described acrylic ester monomer, comprise one or more in butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, Propylene glycol monoacrylate, Hydroxyethyl acrylate, Rocryl 410, hydroxyethyl methylacrylate, 1,6 hexanediol diacrylate, Viscoat 295, butylene glycol diacrylate, glycol diacrylate, Ethylene glycol dimethacrylate, glycol ether diacrylate, Diacrylate.
The beneficial effect that the present invention adopts above-mentioned technical solution to reach is:
1, the present invention has the constitutional features of the adhesiving effect of mussel adhesion protein, adopt pre-emulsification and seeded emulsion polymerization, emulsion solid content can reach 55%, high solids content is conducive to the evaporation rate accelerating moisture, with the second-order transition temperature (Tg) of polyacrylic acid copolymerized reduction tackiness agent, thus tackiness agent film-forming temperature can be reduced to reach at room temperature film forming, introducing Dopamine HCL in addition can have outstanding adhesive power to various material surface.
2, the water-based PU emulsion used in existing market, need when being coated in material surface to use treatment agent pre-treatment just can reach good adhesion effect to material surface, do not need treatment agent pre-treatment all to have outstanding sticking power containing the urethane composite emulsion of Dopamine HCL to various material surface through bionic design synthesis, can be applicable to the use under tackiness agent and paint field and wet environment.
Embodiment
A kind of bionic design water polyacrylic acid of the present invention modified polyurethane composite emulsion, it is characterized in that, it adopts acetone or butanone and acrylic monomer to make solvent, vulcabond HDI and IPDI, mixed polyester polyvalent alcohol, dimethylol propionic acid, 1,4-butyleneglycol, TriMethylolPropane(TMP) mono allyl ether, Propylene glycol monoacrylate, Hydroxyethyl acrylate are polymerized, prepare the urethane of band carboxyl and neutralize with tertiary amine, desolvation, obtains self-emulsifying and double bond containing aqueous polyurethane anionic emulsion; Again this emulsion is made seed, after adding acrylic ester monomer, Dopamine HCL Methacrylamide and appropriate crosslinkers monomers pre-emulsification, carry out the bionic design water polyacrylic acid modified polyurethane composite emulsion that seeded emulsion polymerization obtains.
Wherein, the synthesis of double bond containing PU emulsion: by 100 weight of polyester polyvalent alcohols, sulfonated polyester polyol or polyether glycol, 20-45 weight part vulcabond, 2-6 weight part dimethylol propionic acid, 1-5 weight part TriMethylolPropane(TMP) mono allyl ether, 0.5-5 parts by weight of acrylic acid hydroxypropyl acrylate, 0.5-5 parts by weight of acrylic acid hydroxyl ethyl ester, 1-5 weight part 1,4-butyleneglycol drops into four mouthfuls of round-bottomed flasks of reflux condensing tube, thermometer, digital display stirrer successively, drip catalyzer, constant temperature is at 80-85 DEG C, stirring velocity 80-150rpm, reaction 4-6 hour; Visual response situation adds a small amount of acetone or acrylic ester monomer to reduce viscosity, cool to 45 DEG C, add triethylamine neutralization, add water dispersed with stirring emulsification for about 15 minutes, within about ten minutes, add quadrol chain extension again, finally decompression removing acetone, self-emulsifying prepares the double bond containing anionic polyurethane emulsion of solid content 40-45%.
The PUA composite emulsion synthesis of bionic design: by 15-30 parts by weight propylene acid butyl ester, the different monooctyl ester of 10-20 parts by weight of acrylic acid, 8-15 parts by weight of methylmethacrylate, 1-10 weight part Dopamine HCL Methacrylamide (DMA), 3-8 parts by weight of acrylic acid hydroxypropyl acrylate, 1-5 parts by weight of acrylic acid hydroxyl ethyl ester, 0.5-5 weight part Ethylene glycol dimethacrylate, 0.5-3 weight part Viscoat 295, 1-6 weight part diacetone-acryloamide(DAA) or AAEM, 0.5-3 weight part reactive emulsifier and appropriate amount of deionized water add in above-mentioned water-based PU emulsion carries out pre-emulsification, get part pre-emulsion and add 0.1-0.5 weight part sodium bicarbonate at 70-80 DEG C, logical nitrogen protection, add acrylic ester monomer 0.1-1 weight part initiator, carry out seeded emulsion polymerization, stirring velocity 150-300rpm, after reaction 3-5 hour, be incubated 2 hours, be warmed up to 85-90 DEG C, be incubated 1 hour, cool to less than 40 DEG C, discharging.After filtration, namely obtain waterborne PUA composite emulsion of the present invention.Emulsion solid content is 55-60%, regulates pH value 7-8, viscosity 50-200mPas.Implement technological line:
(1) first synthesize Dopamine HCL Methacrylamide (DMA), its building-up process is as follows:
(2) containing the synthesis of double bond urethane, process is as follows:
(3) adopt the method for letex polymerization to realize the synthesis of mussel Biomimetic Polymers, building-up process is as follows:
Below in conjunction with embodiment, the present invention is described in more detail.
Embodiment 1
The waterborne PUA composite emulsion of bionic design:
The waterborne PUA composite emulsion of bionic design can replace current solvent-borne type PU and import water-based PU emulsion, and obtain film forming fast, sticking power is good, and water tolerance is ageing-resistant, and non yellowing is effective.
Prescription:
Below for weight part calculates, the molecular weight 1000-2000 of polyester polyol.
PU emulsion
The PUA composite emulsion of bionic design
Above-described is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art, and without departing from the concept of the premise of the invention, can also make some distortion and improvement, these all belong to protection scope of the present invention.
Claims (7)
1. a bionic design water polyacrylic acid modified polyurethane composite emulsion, it is characterized in that, it adopts acetone or butanone and acrylic monomer to make solvent, vulcabond HDI and IPDI, mixed polyester polyvalent alcohol, dimethylol propionic acid, 1,4-butyleneglycol, TriMethylolPropane(TMP) mono allyl ether, Propylene glycol monoacrylate, Hydroxyethyl acrylate are polymerized, prepare the urethane of band carboxyl and neutralize with tertiary amine, desolvation, obtains self-emulsifying and double bond containing aqueous polyurethane anionic emulsion; Again this emulsion is made seed, after adding acrylic ester monomer, Dopamine HCL Methacrylamide and appropriate crosslinkers monomers pre-emulsification, carry out the bionic design water polyacrylic acid modified polyurethane composite emulsion that seeded emulsion polymerization obtains.
2. bionic design water polyacrylic acid modified polyurethane composite emulsion according to claim 1, it is characterized in that, described Dopamine HCL Methacrylamide (DMA) is dissolved in distilled water by dopamine hydrochloride, methacrylic anhydride to be dissolved in tetrahydrofuran (THF) and to be added drop-wise in the solution of the dopamine hydrochloride of logical nitrogen, reaction at room temperature carries out 12h, and reaction solution adjusted to ph is extracted with ethyl acetate to when being less than 2, revolves steaming, hexanaphthene recrystallization, obtains after product vacuum drying.
3. the preparation method of bionic design water polyacrylic acid modified polyurethane composite emulsion as claimed in claim 1 or 2, it is characterized in that, it is the polyaminoester emulsion I first preparing double bond containing self-emulsifying, then this emulsion is made seed, add acrylic ester monomer, Dopamine HCL Methacrylamide, reactive emulsifier and linking agent and carry out seeded emulsion polymerization, obtain urethane composite emulsion II, i.e. bionic design water polyacrylic acid modified polyurethane composite emulsion.
4. the preparation method of bionic design water polyacrylic acid modified polyurethane composite emulsion according to claim 3, it is characterized in that, the polyaminoester emulsion I of the described self-emulsifying containing double bond, it is by 100 weight of polyester (polyethers) polyvalent alcohol and sulfonated polyester polyol, 20-45 weight part vulcabond, 0.5-3 weight part dibasic alcohol, 1-5 weight part TriMethylolPropane(TMP) mono allyl ether, 0.5-2 weight part trivalent alcohol and 2-6 part by weight of hydrophilic monomer chainextender and 1-7 parts by weight propylene acid esters class function monomer, catalyzer and solvent, in 80-150rpm stirring velocity, reaction preparation at 70-90 DEG C, last 3000-5000rpm dispersion and emulsion half an hour.
5. the preparation method of bionic design water polyacrylic acid modified polyurethane composite emulsion according to claim 3, it is characterized in that, described urethane composite emulsion II, by 10-45 parts by weight of acrylic acid esters monomer, 1-10 weight part Dopamine HCL Methacrylamide, 1-7 weight part specific functionality monomer and 0.5-3 weight part reactive emulsifier add in the polyaminoester emulsion of the self-emulsifying containing double bond and carry out pre-emulsification, get 10-30 weight part and make seed emulsion, the 0.1-1 weight part initiator of acrylic ester monomer, seeded emulsion polymerization is carried out to the polyaminoester emulsion of the self-emulsifying containing double bond, temperature of reaction 50-85 DEG C, stirring velocity 150-300rpm, time 3-8 hour.
6. the preparation method of bionic design water polyacrylic acid modified polyurethane composite emulsion according to claim 3, it is characterized in that, described vulcabond, comprises one or more in phenylmethane vulcabond, isophorone diisocyanate, hexamethylene diisocyanate, tetramethyl-xylylene diisocyanate.
7. the preparation method of bionic design water polyacrylic acid modified polyurethane composite emulsion according to claim 3, it is characterized in that, described acrylic ester monomer, comprise butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, Propylene glycol monoacrylate, Hydroxyethyl acrylate, Rocryl 410, hydroxyethyl methylacrylate, 1, 6-hexanediyl ester, Viscoat 295, butylene glycol diacrylate, glycol diacrylate, Ethylene glycol dimethacrylate, glycol ether diacrylate, one or more in Diacrylate.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085814A (en) * | 2015-09-10 | 2015-11-25 | 中国石油大学(华东) | Preparation method of air wetting reversal material based on mussel bionic principle |
| CN106046252A (en) * | 2016-06-14 | 2016-10-26 | 苏州大学 | Sugar-containing polymer with surface adsorption property and method for manufacturing sugar-containing polymer |
| CN106632898A (en) * | 2015-11-04 | 2017-05-10 | 鸿富锦精密工业（深圳）有限公司 | Spectacle lens material, and spectacle lens and preparation method thereof |
| CN107478790A (en) * | 2016-06-08 | 2017-12-15 | 中国石油化工股份有限公司 | The Polyurethane carrier of surface with poly-dopamine hydrophilic layer and preparation method and application |
| CN108822615A (en) * | 2018-07-03 | 2018-11-16 | 肇庆市华莱特复合新型材料有限公司 | A kind of abrasion-resistance water ink and preparation method thereof |
| CN109021836A (en) * | 2018-07-03 | 2018-12-18 | 肇庆市华莱特复合新型材料有限公司 | A kind of antibacterial aqueous shoe polish and preparation method thereof |
| CN109912779A (en) * | 2019-04-04 | 2019-06-21 | 陕西科技大学 | The pectination water-base polyurethane material and preparation method thereof of imitative mussel mucin structure |
| CN110066565A (en) * | 2019-05-24 | 2019-07-30 | 齐鲁工业大学 | A kind of high-adhesiveness leather finishing agent of color inhibition and preparation method thereof |
| CN110079180A (en) * | 2019-05-24 | 2019-08-02 | 齐鲁工业大学 | A kind of high-adhesiveness coating material for leather and preparation method thereof |
| CN110317558A (en) * | 2019-08-05 | 2019-10-11 | 陕西科技大学 | A kind of poly-dopamine acrylic adhesive for polyurethane and preparation method thereof |
| CN110903456A (en) * | 2019-10-24 | 2020-03-24 | 江汉大学 | Bionic polyurethane and preparation method thereof |
| CN112175147A (en) * | 2020-09-08 | 2021-01-05 | 中山大桥化工集团有限公司 | Waterborne polyurethane-polyacrylate resin and preparation method and application thereof |
| CN113244132A (en) * | 2020-02-13 | 2021-08-13 | 万华化学集团股份有限公司 | Aqueous nail polish based on dopa modified aqueous polyurethane (meth) acrylate dispersion and preparation method thereof |
| CN114085331A (en) * | 2021-12-01 | 2022-02-25 | 长兴化学工业(中国)有限公司 | Mussel biomimetic modified acrylic hybrid alkyd resin and preparation method thereof |
| CN114763395A (en) * | 2021-01-14 | 2022-07-19 | 万华化学集团股份有限公司 | Waterborne polyurethane-acrylate hybrid copolymer and preparation method thereof |
| CN115873510A (en) * | 2022-11-29 | 2023-03-31 | 烟台德邦科技股份有限公司 | High-temperature-resistant high-humidity-resistant high-bonding-strength UV adhesive for battery shell membrane and preparation method thereof |
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Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085814A (en) * | 2015-09-10 | 2015-11-25 | 中国石油大学(华东) | Preparation method of air wetting reversal material based on mussel bionic principle |
| CN106632898A (en) * | 2015-11-04 | 2017-05-10 | 鸿富锦精密工业（深圳）有限公司 | Spectacle lens material, and spectacle lens and preparation method thereof |
| CN107478790A (en) * | 2016-06-08 | 2017-12-15 | 中国石油化工股份有限公司 | The Polyurethane carrier of surface with poly-dopamine hydrophilic layer and preparation method and application |
| CN106046252A (en) * | 2016-06-14 | 2016-10-26 | 苏州大学 | Sugar-containing polymer with surface adsorption property and method for manufacturing sugar-containing polymer |
| CN106046252B (en) * | 2016-06-14 | 2018-10-30 | 苏州大学 | Sugar-containing polymer and preparation method thereof with adsorption |
| CN108822615A (en) * | 2018-07-03 | 2018-11-16 | 肇庆市华莱特复合新型材料有限公司 | A kind of abrasion-resistance water ink and preparation method thereof |
| CN109021836A (en) * | 2018-07-03 | 2018-12-18 | 肇庆市华莱特复合新型材料有限公司 | A kind of antibacterial aqueous shoe polish and preparation method thereof |
| CN109912779B (en) * | 2019-04-04 | 2021-05-18 | 陕西科技大学 | Comb-shaped waterborne polyurethane material with mussel mucin-like structure and preparation method thereof |
| CN109912779A (en) * | 2019-04-04 | 2019-06-21 | 陕西科技大学 | The pectination water-base polyurethane material and preparation method thereof of imitative mussel mucin structure |
| CN110079180B (en) * | 2019-05-24 | 2021-08-13 | 齐鲁工业大学 | High-adhesion leather coating material and preparation method thereof |
| CN110066565B (en) * | 2019-05-24 | 2021-08-13 | 齐鲁工业大学 | Yellowing-resistant high-adhesion leather finishing agent and preparation method thereof |
| CN110066565A (en) * | 2019-05-24 | 2019-07-30 | 齐鲁工业大学 | A kind of high-adhesiveness leather finishing agent of color inhibition and preparation method thereof |
| CN110079180A (en) * | 2019-05-24 | 2019-08-02 | 齐鲁工业大学 | A kind of high-adhesiveness coating material for leather and preparation method thereof |
| CN110317558A (en) * | 2019-08-05 | 2019-10-11 | 陕西科技大学 | A kind of poly-dopamine acrylic adhesive for polyurethane and preparation method thereof |
| CN110903456A (en) * | 2019-10-24 | 2020-03-24 | 江汉大学 | Bionic polyurethane and preparation method thereof |
| CN113244132A (en) * | 2020-02-13 | 2021-08-13 | 万华化学集团股份有限公司 | Aqueous nail polish based on dopa modified aqueous polyurethane (meth) acrylate dispersion and preparation method thereof |
| CN112175147A (en) * | 2020-09-08 | 2021-01-05 | 中山大桥化工集团有限公司 | Waterborne polyurethane-polyacrylate resin and preparation method and application thereof |
| CN112175147B (en) * | 2020-09-08 | 2022-12-27 | 中山大桥化工集团有限公司 | Waterborne polyurethane-polyacrylate resin and preparation method and application thereof |
| CN114763395A (en) * | 2021-01-14 | 2022-07-19 | 万华化学集团股份有限公司 | Waterborne polyurethane-acrylate hybrid copolymer and preparation method thereof |
| CN114763395B (en) * | 2021-01-14 | 2024-02-27 | 万华化学集团股份有限公司 | Water-based polyurethane-acrylic ester hybrid copolymer and preparation method thereof |
| CN114085331A (en) * | 2021-12-01 | 2022-02-25 | 长兴化学工业(中国)有限公司 | Mussel biomimetic modified acrylic hybrid alkyd resin and preparation method thereof |
| CN114085331B (en) * | 2021-12-01 | 2024-05-28 | 长兴化学工业(中国)有限公司 | Mussel bionic modified acrylic hybrid alkyd resin and preparation method thereof |
| CN115873510A (en) * | 2022-11-29 | 2023-03-31 | 烟台德邦科技股份有限公司 | High-temperature-resistant high-humidity-resistant high-bonding-strength UV adhesive for battery shell membrane and preparation method thereof |
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| C06 | Publication | ||
| PB01 | Publication | ||
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| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20171010 Address after: 528139 Guangdong province Foshan Sanshui Lubao Town Industrial Development Zone (duozheng chemical adhesive resin Research Institute) Applicant after: Guangdong multi Resin Technology Co., Ltd. Address before: 528139 Guangdong province Foshan Sanshui Lubao Town Industrial Development Zone Applicant before: Duozheng Chemical Science and Technology Co., Ltd., Guangdong |
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| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150909 |