CN103030767A - Degradable radiation-curable polyurethane acrylate oligomer and preparation method thereof - Google Patents
Degradable radiation-curable polyurethane acrylate oligomer and preparation method thereof Download PDFInfo
- Publication number
- CN103030767A CN103030767A CN2012105200382A CN201210520038A CN103030767A CN 103030767 A CN103030767 A CN 103030767A CN 2012105200382 A CN2012105200382 A CN 2012105200382A CN 201210520038 A CN201210520038 A CN 201210520038A CN 103030767 A CN103030767 A CN 103030767A
- Authority
- CN
- China
- Prior art keywords
- preparation
- radiation curing
- degradable
- degradable polyurethane
- origoester acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a degradable radiation-curable polyurethane acrylate oligomer and a preparation method thereof. The polyurethane acrylate oligomer is radiation-curable and is degradable above all, thus having excellent environment friendliness and being applicable to the preparation of temporary protective coatings in the field of special protective coatings. The preparation method of the polyurethane acrylate oligomer provided by the invention comprises the following steps: reacting polylactic acid polyol with a diisocyanate compound, and then blocking with hydroxyacrylate to obtain polyurethane acrylate. Thus, the operability of the whole process is high, the raw materials are abundant, the synthesis reaction is simple, and the preparation efficiency is high.
Description
Technical field
The present invention relates to a kind of macromolecule modified oligopolymer, it is strong to be specifically related to a kind of feature of environmental protection, can be used for the special protection coatings art, degradable polyurethane by radiation curing origoester acrylate of preparation temporary protective coat and preparation method thereof.
Background technology
Radiation curing technology is described as the green technology of two Pius XIs circle, and it has, and solvent-free or low solvent, curing speed are fast, low VOC, quantity discharged is low, service temperature low and the film quality advantages of higher, replaces just gradually traditional solvent based coating technology.Generally speaking, the radiation curable coating prescription generally comprises following components: oligopolymer, monomer, initiator and auxiliary agent.
Oligopolymer is one of chief component of radiation curing prescription, has determined the performance of cured film.Business-like oligopolymer is of a great variety, and is different according to its structure, can be divided into epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, amino acrylates etc.The polyvalent alcohol of preparation urethane acrylate is generally polyethers or synthesizing polyester, and the degradation property of this type of urethane acrylate is usually very poor.At present, prior art does not also have a kind of business-like degradable polyurethane by radiation curing acrylate.
Therefore, necessary on the basis of prior art, a kind of feature of environmental protection of research and development design is strong, degradable polyurethane by radiation curing origoester acrylate.
Summary of the invention
Goal of the invention: technical problem to be solved by this invention is to overcome the deficiencies in the prior art; a kind of radiation-hardenable is provided; especially can degrade; can be used for the special protection coatings art; the urethane acrylate oligomer of preparation temporary protective coat, another object of the present invention provides the preparation method of this urethane acrylate oligomer.
Technical scheme: for solving above technical problem, the present invention takes following technical scheme:
A kind of degradable polyurethane by radiation curing origoester acrylate, it has following general formula:
R wherein
1Be the initiator of polylactic acid multi-element alcohol, wherein m is 1 to 10 positive integer; N is 1 to 10 positive integer; X is CH
3Or H; R
2Be vulcabond or replacement vulcabond.
As preferred version, above-described degradable polyurethane by radiation curing origoester acrylate, described replacement vulcabond R
2Be tolylene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate.
As preferred version, above-described degradable polyurethane by radiation curing origoester acrylate, the initiator R of described polylactic acid multi-element alcohol
1Be ethylene glycol, BDO, 1,2-PD, 1,3-PD, 1,6-hexylene glycol, neopentyl glycol or glycol ether.
The preparation method of degradable polyurethane by radiation curing origoester acrylate provided by the invention, it may further comprise the steps:
(1) poly(lactic acid) dibasic alcohol and vulcabond are mixed, the mol ratio that makes hydroxyl and isocyano is 1:2, drips catalyzer, is warmed up to 60 ~ 70 ℃, insulation 1 ~ 3h, and reaction prepolymer, for subsequent use;
(2) with Hydroxyethyl acrylate or hydroxyethyl methylacrylate, stopper joins in the prepolymer that step (1) prepares, the mol ratio that makes hydroxyl and isocyano is 1:1, slowly be warming up to 80 ~ 90 ℃ of insulations 2 ~ 3 hours, then use isocyano signal in the infrared spectra detection reaction system, stop insulation until isocyano group infrared signal disappears, obtain degradable urethane acrylate oligomer.
As preferred version, the preparation method of above-described degradable polyurethane by radiation curing origoester acrylate, described catalyzer is dibutyl tin laurate.
As preferred version, the preparation method of above-described degradable polyurethane by radiation curing origoester acrylate, described stopper is MEHQ.
As preferred version, the preparation method of above-described degradable polyurethane by radiation curing origoester acrylate, described step (1) temperature of reaction is 60 ℃, soaking time is 2h.
As preferred version, the preparation method of above-described degradable polyurethane by radiation curing origoester acrylate is characterized in that, described step (2) temperature of reaction is 80 ℃, and soaking time is 3h.
Beneficial effect: degradable polyurethane by radiation curing origoester acrylate provided by the invention is compared with existing technology has following advantage:
1, urethane acrylate oligomer provided by the invention; radiation-hardenable; especially degradable; the poly(lactic acid) that wherein adopts is a kind of novel biodegradable material; it has good biodegradability; can be degradable by the occurring in nature microorganism after the use; final carbonic acid gas and the water of generating; free from environmental pollution, this is highly beneficial to protection of the environment, is the environment-friendly material of generally acknowledging; two keys will be introduced in the polylactic acid molecule; crosslinked at the illumination condition curable, can be used for the special protection coatings art, the preparation temporary protective coat.
2, the preparation method of urethane acrylate oligomer provided by the invention, utilize polylactic acid multi-element alcohol and diisocyanate cpd reaction, and then through the hydroxy acrylate end-blocking, obtain urethane acrylate, whole technique is workable, abundant raw material, and building-up reactions is simple, be easy to control, the urethane acrylate oligomer for preparing can overcome the defective that the conventional polyurethanes origoester acrylate can not be degraded.
Embodiment
Below in conjunction with specific embodiment, further illustrate the present invention, should understand these embodiment only is used for explanation the present invention and is not used in and limits the scope of the invention, after having read the present invention, those skilled in the art all fall within the application's claims limited range to the modification of the various equivalent form of values of the present invention.
Embodiment 1
1, the preparation of degradable polyurethane by radiation curing origoester acrylate
(1) adding the 200g molecular weight in reflux condensing tube, drying tube and churned mechanically 500 mL three-necked bottles are housed is 2000 poly(lactic acid) dibasic alcohol (ethylene glycol is initiator), then add the 44.2g isophorone diisocyanate, two dibutyl tin laurates (DBTDL) catalyzer, stirring at room is evenly rear slowly to heat up, 60
oThen C insulation reaction 2 hours measures isocyano-content, if content be not reduced to initial concentration half, then continue insulation, until measured value be initial value half, reaction obtains polyurethane prepolymer, and is for subsequent use.
(2) 23.2g Hydroxyethyl acrylate, 0.25g MEHQ are added the polyurethane prepolymer that step (1) obtains, slowly be warming up to 80
oC insulation 3 hours, then infrared spectra detects the isocyano signal, until this group blackout stops insulation, namely obtains degradable urethane acrylate oligomer after reaction is finished.
2, urethane acrylate oligomer constitutional features, shown in the infrared spectra, 1,350 1450 cm-1 zones, peak is flexural vibration corresponding to CH2 group among the figure, and 1600 ~ 1700cm-1 zone is flexural vibration corresponding to C=O group, and 1448 ~ 1520cm-1 is that the signal of the two key groups of C=C shows; And
1A plurality of δ H 3.12 ~ 3.24 are the hydrogen signal of O-CH-among the H NMR, and δ H 6.12 ~ 6.63 is the alkene hydrogen signal of HC==CH, and 1.8 ~ 2.9 is the terminal methyl group hydrogen signal.
13108 ~ 121 is the olefinic carbon signal of HC==CH among the C NMR, and 52.1 ~ 61.9 for containing the signal of oxygen carbon, and 152 ~ 162 is the signal of carbonyl carbon, and 28 ~ 36 is the signal of methyl carbon.
Embodiment 2
1, the preparation of degradable polyurethane by radiation curing origoester acrylate
(1) adding the 200g molecular weight in reflux condensing tube, drying tube and churned mechanically 500 mL three-necked bottles are housed is 2000 poly(lactic acid) dibasic alcohol (neopentyl glycol is initiator), 44.2g isophorone diisocyanate, two DBTDL catalyzer, stirring at room is evenly rear slowly to heat up, 60
oC is incubated 3h, then measures isocyano-content.If content be not reduced to initial concentration half, then continue insulation, until measured value be initial value half.Above-mentioned steps is finished and is obtained polyurethane prepolymer.
(2) 26.6g hydroxyethyl methylacrylate, 0.25g MEHQ are added prepolymer, slowly be warming up to 80
oC insulation 3 hours, then infrared spectra detects the isocyano signal, until this group blackout stops insulation.After finishing, reaction namely obtains the degradable polyurethane origoester acrylate.
Embodiment 3
1, the preparation of degradable polyurethane by radiation curing origoester acrylate
(1) adding the 200g molecular weight in reflux condensing tube, drying tube and churned mechanically 500 mL three-necked bottles are housed is 2000 poly(lactic acid) dibasic alcohol (1, the 6-hexylene glycol is initiator), 44.6g tolylene diisocyanate, two DBTDL catalyzer, stirring at room is evenly rear slowly to heat up, 70
oC is incubated 2h, then measures isocyano-content.If content be not reduced to initial concentration half, then continue insulation, until measured value be initial value half.Above-mentioned steps is finished and is obtained polyurethane prepolymer.
(2) 23.2g Hydroxyethyl acrylate, 0.25g MEHQ are added prepolymer, slowly be warming up to 90
oC insulation 2 hours, then infrared spectra detects the isocyano signal, until this group blackout stops insulation.After finishing, reaction namely obtains the degradable polyurethane origoester acrylate.
Embodiment 4
1, the preparation of degradable polyurethane by radiation curing origoester acrylate
(1) adding the 400g molecular weight in reflux condensing tube, drying tube and churned mechanically 500 mL three-necked bottles are housed is 4000 poly(lactic acid) dibasic alcohol (ethylene glycol is initiator), then add the 44.2g isophorone diisocyanate, two dibutyl tin laurates (DBTDL) catalyzer, stirring at room is evenly rear slowly to heat up, 60
oThen C insulation reaction 2 hours measures isocyano-content, if content be not reduced to initial concentration half, then continue insulation, until measured value be initial value half, reaction obtains polyurethane prepolymer, and is for subsequent use.
(2) 23.2g Hydroxyethyl acrylate, 0.25g MEHQ are added the polyurethane prepolymer that step (1) obtains, slowly be warming up to 80
oC insulation 3 hours, then infrared spectra detects the isocyano signal, until this group blackout stops insulation, namely obtains degradable urethane acrylate oligomer after reaction is finished.
Embodiment 5
1, the preparation of degradable polyurethane by radiation curing origoester acrylate
(1) adding the 300g molecular weight in reflux condensing tube, drying tube and churned mechanically 500 mL three-necked bottles are housed is 3000 poly(lactic acid) dibasic alcohol (ethylene glycol is initiator), then add the 44.2g isophorone diisocyanate, two dibutyl tin laurates (DBTDL) catalyzer, stirring at room is evenly rear slowly to heat up, 60
oThen C insulation reaction 2 hours measures isocyano-content, if content be not reduced to initial concentration half, then continue insulation, until measured value be initial value half, reaction obtains polyurethane prepolymer, and is for subsequent use.
(2) 23.2g Hydroxyethyl acrylate, 0.25g MEHQ are added the polyurethane prepolymer that step (1) obtains, slowly be warming up to 80
oC insulation 3 hours, then infrared spectra detects the isocyano signal, until this group blackout stops insulation, namely obtains degradable urethane acrylate oligomer after reaction is finished.
Embodiment 6
Urethane acrylate oligomer with preparation among embodiment 1, enforcement 2, enforcement 3 and the embodiment 4 is mixed with the light trigger Irgacure 1173 of 4% weight respectively, stirring mixes it, on sheet glass, paint the film of 200 micron thickness with spreader, medium pressure mercury lamp F300S-6 irradiation with the U.S. (Fusion UV Systems company) production, place 10 centimetres of lamps apart from the place in sample, obtain at last the solidified coating of hard transparent.And compare with the CN965 of U.S. Sartomer company, its curing membrane performance detected result is as shown in table 1.
The cured film hardness of table 1 urethane acrylate oligomer and snappiness detected result
Can find out that from the test result of table 1 urethane acrylate oligomer that the present invention prepares is identical with the cured film snappiness of commercialization CN965, but hardness is higher, has more superior performance.
Embodiment 5
Urethane acrylate with preparation among embodiment 1, enforcement 2 and the embodiment 4 mixes with the light trigger Irgacure 1173 of 4% weight respectively, stirring mixes it, on sheet glass, paint the film of 200 micron thickness with spreader, medium pressure mercury lamp F300S-6 irradiation with the U.S. (Fusion UV Systems company) production, place 10 centimetres of lamps apart from the place in sample, obtain at last the solidified coating of hard transparent.Cured film is cut into the 2cm*2cm square sheet, and with thin slice as in phosphate dihydrate disodium hydrogen (1M) buffered soln, keep 37 ℃ of constant temperature, after carrying out the period of time of degradation test, take out sample, distilled water flushing twice, drying under reduced pressure is stable to weight, the calculated weight conservation rate, weight/pleurodiaphragmatic in terspace beginning gross weight after weight conservation rate=100%* degraded.And compare with the CN965 of U.S. Sartomer company, its cured film degradation property detected result is as shown in table 2.
The degraded detected result of table 2 urethane acrylate oligomer
Test result by table 2 can find out that the urethane acrylate oligomer that the present invention prepares is compared with commercialization CN965, and degradation speed obviously is better than CN965 under the same terms.Show that urethane acrylate oligomer provided by the invention is under high temperature and high humidity; hydrolysis reaction can be finished easily, and the speed of decomposition can be used and a lot of special protection coatings art; the preparation temporary protective coat can overcome the deficiencies in the prior art.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. degradable polyurethane by radiation curing origoester acrylate is characterized in that it has following general formula:
R wherein
1Be the initiator of polylactic acid multi-element alcohol, wherein m is 1 to 10 positive integer; N is 1 to 10 positive integer; X is CH
3Or H; R
2Be vulcabond or replacement vulcabond.
2. degradable polyurethane by radiation curing origoester acrylate according to claim 1 is characterized in that, described replacement vulcabond is tolylene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate.
3. degradable polyurethane by radiation curing origoester acrylate according to claim 1 and 2 is characterized in that, the initiator of described polylactic acid multi-element alcohol is ethylene glycol, 1, the 4-butyleneglycol, 1,2-PD, 1, ammediol, 1,6-hexylene glycol, neopentyl glycol or glycol ether.
4. the preparation method of degradable polyurethane by radiation curing origoester acrylate claimed in claim 1 is characterized in that, may further comprise the steps:
(1) poly(lactic acid) dibasic alcohol and vulcabond are mixed, the mol ratio that makes hydroxyl and isocyano is 1:2, drips catalyzer, is warmed up to 60 ~ 70 ℃, insulation 1 ~ 3h, and reaction prepolymer, for subsequent use;
(2) with Hydroxyethyl acrylate or hydroxyethyl methylacrylate, stopper joins in the prepolymer that step (1) prepares, the mol ratio that makes hydroxyl and isocyano is 1:1, slowly be warming up to 80 ~ 90 ℃ of insulations 2 ~ 3 hours, then use isocyano signal in the infrared spectra detection reaction system, stop insulation until isocyano group infrared signal disappears, obtain degradable urethane acrylate oligomer.
5. the preparation method of degradable polyurethane by radiation curing origoester acrylate according to claim 4 is characterized in that, described catalyzer is dibutyl tin laurate.
6. the preparation method of degradable polyurethane by radiation curing origoester acrylate according to claim 4 is characterized in that, described stopper is MEHQ.
7. the preparation method of degradable polyurethane by radiation curing origoester acrylate according to claim 4 is characterized in that, described step (1) temperature of reaction is 60 ℃, and soaking time is 2h.
8. the preparation method of degradable polyurethane by radiation curing origoester acrylate according to claim 4 is characterized in that, described step (2) temperature of reaction is 80 ℃, and soaking time is 3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105200382A CN103030767A (en) | 2012-12-07 | 2012-12-07 | Degradable radiation-curable polyurethane acrylate oligomer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105200382A CN103030767A (en) | 2012-12-07 | 2012-12-07 | Degradable radiation-curable polyurethane acrylate oligomer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103030767A true CN103030767A (en) | 2013-04-10 |
Family
ID=48018202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012105200382A Pending CN103030767A (en) | 2012-12-07 | 2012-12-07 | Degradable radiation-curable polyurethane acrylate oligomer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103030767A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483536A (en) * | 2013-08-27 | 2014-01-01 | 陕西科技大学 | Preparation method of solventless ultraviolet-curing polyurethane for synthetic leather |
| CN106519161A (en) * | 2016-10-25 | 2017-03-22 | 深圳光华伟业股份有限公司 | Light-cured resin prepolymer, light-cured resin and preparation methods of light-cured resin prepolymer and light-cured resin |
| CN106810670A (en) * | 2017-01-06 | 2017-06-09 | 浙江新迪在龙涂料科技有限公司 | A kind of preparation method of urethane acrylate oligomer |
| CN109400844A (en) * | 2018-09-19 | 2019-03-01 | 江苏三木化工股份有限公司 | A kind of biology base photocurable prepolymer and preparation method thereof |
| CN114835860A (en) * | 2022-03-29 | 2022-08-02 | 深圳锐沣科技有限公司 | Degradable DLP3D printing facing resin |
| EP4393987A1 (en) * | 2022-12-30 | 2024-07-03 | Swancor Innovation & Incubation Co., Ltd. | Method for degrading polyurethane acrylic resin material, polyurethane acrylic resin, composition, preparation method and composite material thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293214A (en) * | 1999-10-13 | 2001-05-02 | 中国科学院成都有机化学研究所 | Biodegradable polyester-polyester copolymer and its preparing process |
| CN102056956A (en) * | 2008-07-10 | 2011-05-11 | 氰特表面技术有限公司 | Aqueous radiation curable polyurethane compositions |
| CN102199271A (en) * | 2010-03-22 | 2011-09-28 | 湖南松井化学技术有限公司 | Adiation-hardenable polyurethane resin and preparation method thereof |
-
2012
- 2012-12-07 CN CN2012105200382A patent/CN103030767A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293214A (en) * | 1999-10-13 | 2001-05-02 | 中国科学院成都有机化学研究所 | Biodegradable polyester-polyester copolymer and its preparing process |
| CN102056956A (en) * | 2008-07-10 | 2011-05-11 | 氰特表面技术有限公司 | Aqueous radiation curable polyurethane compositions |
| CN102199271A (en) * | 2010-03-22 | 2011-09-28 | 湖南松井化学技术有限公司 | Adiation-hardenable polyurethane resin and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483536A (en) * | 2013-08-27 | 2014-01-01 | 陕西科技大学 | Preparation method of solventless ultraviolet-curing polyurethane for synthetic leather |
| CN106519161A (en) * | 2016-10-25 | 2017-03-22 | 深圳光华伟业股份有限公司 | Light-cured resin prepolymer, light-cured resin and preparation methods of light-cured resin prepolymer and light-cured resin |
| CN106810670A (en) * | 2017-01-06 | 2017-06-09 | 浙江新迪在龙涂料科技有限公司 | A kind of preparation method of urethane acrylate oligomer |
| CN109400844A (en) * | 2018-09-19 | 2019-03-01 | 江苏三木化工股份有限公司 | A kind of biology base photocurable prepolymer and preparation method thereof |
| CN114835860A (en) * | 2022-03-29 | 2022-08-02 | 深圳锐沣科技有限公司 | Degradable DLP3D printing facing resin |
| EP4393987A1 (en) * | 2022-12-30 | 2024-07-03 | Swancor Innovation & Incubation Co., Ltd. | Method for degrading polyurethane acrylic resin material, polyurethane acrylic resin, composition, preparation method and composite material thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103030767A (en) | Degradable radiation-curable polyurethane acrylate oligomer and preparation method thereof | |
| CN105504215B (en) | A kind of aqueous polyurethane emulsion of color inhibition and preparation method thereof | |
| CN106905504B (en) | Water-based ultraviolet-curing polyurethane resin and preparation method and application thereof | |
| US8048979B2 (en) | Process for synthesis of telechelic urethane acrylate UV curable pre-polymeric materials | |
| CN108456290A (en) | A kind of dual cure polyurethane acrylate resin and preparation method thereof | |
| CN105348474A (en) | Preparation method for UV-curing self-healing polyurethane based on furan-maleimide structure | |
| CN105859584B (en) | One kind being based on the 3 degree of functionality urethane acrylates and its preparation method and application of trihydroxy methyl second (third) alkane | |
| CN102911338B (en) | Multifunctional urethane acrylate oligomer as well as synthesis method and application thereof | |
| CN103554393B (en) | A kind of preparation method of natural polymer subbase light-cured resin | |
| CN106519182A (en) | Organic silicon modified polyurethane acrylate oligomer, and preparation method thereof | |
| CN105131227B (en) | A kind of use for synthetic leather UV cured flame-retardant polyurethane and preparation method thereof | |
| CN105440260A (en) | Ultraviolet curing urethane acrylate and preparation method thereof | |
| CN106957406A (en) | A kind of calixarene type light-cured polyurethane resin and its coatings of preparation | |
| CN105505197A (en) | Ultraviolet curing coating and preparation method thereof | |
| CN1966544A (en) | Method of preparing superbranched polyurethane | |
| CN103214649B (en) | 9-functionality-degree polyurethane acrylate as well as preparation method and application thereof | |
| CN105440245A (en) | Ultraviolet curing coating and preparation method thereof | |
| CN103627305A (en) | Preparation method of modified unsaturated polyester resin coating | |
| CN103193953B (en) | Urethane acrylate with functionality of 12 as well as preparation method and application thereof | |
| CN105859585B (en) | A kind of 3 degree of functionality urethane acrylates based on glycerine and its preparation method and application | |
| CN105542121A (en) | Ultraviolet-curing polyurethane acrylate and preparation method thereof | |
| CN114213622B (en) | Preparation method of modified polyurethane acrylic ester photo-curing resin | |
| CN104211903B (en) | Core-added UV (ultraviolet) photocuring hyperbranched polyurethane acrylate resin | |
| CN110746572A (en) | Dual-curing solvent-free polyurethane resin for automobile interior leather and preparation method thereof | |
| CN105820063A (en) | 4-functionality polyurethane acrylic ester based on anhydrous citric acid as well as preparation method and application of 4-functionality polyurethane acrylic ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130410 |