CN104017017A - Method for synthesizing phenyl-containing organosilicon monomers - Google Patents
Method for synthesizing phenyl-containing organosilicon monomers Download PDFInfo
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- CN104017017A CN104017017A CN201410287272.4A CN201410287272A CN104017017A CN 104017017 A CN104017017 A CN 104017017A CN 201410287272 A CN201410287272 A CN 201410287272A CN 104017017 A CN104017017 A CN 104017017A
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Abstract
The invention discloses a method for synthesizing phenyl-containing organosilicon monomers. The method comprises the steps of performing one-step Grignard reaction on raw materials including methyltrimethoxy silane, magnesium and benzene halide: performing activation initiation reaction in the presence of a catalytic initiator under the condition that a solvent is added or not added, heating, continuously reacting, filtering and distilling to obtain methyl phenyl dimethoxy silane and methyl diphenyl methoxy silane. According to the method, the novel and cheap raw materials including methyltrimethoxy silane, magnesium and chlorobenzene (or bromobenzene) are used, and the raw materials react at a certain temperature by adopting the one-step Grignard method and using iodine as the catalytic initiator, are heated and then continuously react to obtain methyl phenyl dimethoxy silane and methyl diphenyl methoxy silane, thus solving the problem that the preparation of methyl phenyl dimethoxy silane with the one-step Grignard method is not realized at present and the problems of low yield, high production cost and the like when methyl triethoxysilane is used as a raw material, and meeting the requirements of modernized industrial production for high yield and low energy consumption.
Description
Technical field
The present invention relates to the field of chemical synthesis, particularly, relate to the synthetic method of a kind of environmental protection, organosilicon phenyl monomer novel material.
Background technology
aminomethyl phenyl organosilane monomer, adopts pyrocondensation legal synthetic conventionally.Pyrocondensation is legal generally to be carried out thermal condensation and reacts in fixed bed with chlorobenzene by dimethyl dichlorosilane (DMCS), generate phenyl monomer dichloromethyl phenylsilane and hydrogenchloride.The synthetic cost of this method is lower, but because the legal product composition of pyrocondensation is complicated, and raw material is approaching with product boiling point, and later stage separation difficulty, causes product purity not high, causes it to be difficult to apply in organosilicon high-end product; Owing to generating the polychlorobiphenyl etc. with carcinogenesis in this method synthetic product, be day by day subject to the pressure of environment protection, so the method will be eliminated gradually in addition.
Aminomethyl phenyl organosilane monomer, can also synthesize by prepared by sodium condensation method.By METHYL TRICHLORO SILANE or methyltrimethoxy silane or Union carbide A-162, reacted with sodium and chlorobenzene, generate dichloromethyl phenylsilane or aminomethyl phenyl dimethoxy silane or aminomethyl phenyl diethoxy silane.But due to prepared by sodium condensation method, the sodium activity of using very high, in production and application process, pay particular attention to safety etc. item.Therefore this method is not by large-scale promotion.
Aminomethyl phenyl organosilane monomer can also synthesize by Grignard except above-mentioned two methods.It is fairly simple that Grignard makes product composition, is easy to purify.Grignard is generally divided into single stage method and two-step approach, and a step Grignard is the generation of grignard reagent and completes with the step of reacting of substrate; Although for example, relevant for the report of Grignard reagent method one-step synthesis phenyl methyl diethoxy silane (but its severe reaction conditions, reaction are subject to moisture impact, the selectivity of object product is bad):
Dow Corning Corporation sets up the device of a continuous Grignard synthesis of phenyl chlorosilane, retains so far always.Useful Union carbide A-162, magnesium, chlorobenzene are raw material, by grignard reaction, make aminomethyl phenyl diethoxy silane (Xiao Lin, the synthesis technique of aminomethyl phenyl diethoxy silane and optimization, University Of Nanchang's journal, 2009. 9 31 (3): 227-229).But because Union carbide A-162 is made raw material because sterically hindered more roughly activity is lower, yield is lower is only 60.1%, and need 160 ℃ of ability reactions of high temperature, add the unfavorable factors such as cost of material height, be unfavorable for that industrialization generates.
So far do not have the report about a step Grignard synthesis of phenyl methyl dimethoxysilane.And the effect of existing two-step approach is not ideal yet, report also few.
Produce aminomethyl phenyl dimethoxy silane and there is more real meaning: aminomethyl phenyl dimethoxy silane is higher than the reactive behavior of aminomethyl phenyl diethoxy silane.For example when preparing methyl phenyl silicone oil with methyl monomer cohydrolysis, reactive behavior is higher, and reaction more fully can be hydrolyzed; By suitable technique, hydrolyzable, directly prepare methyl phenyl ring siloxane in addition, save cracking link, more energy-saving consumption-reducing.Aminomethyl phenyl dimethoxy silane can also be as the important auxiliary agent of olefin polymerization catalysis.Methyldiphenyl methoxylsilane can be used for preparing high performance high vacuum diffusion pump oil, for purposes such as makeup middle-ultraviolet lamp absorption agent, aerospace high-low temperature resistant radiation hardness material, high-end damping material, high-end LED packaged materials.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of synthetic method of the organosilane monomer containing phenyl, it is raw material that the method is selected novel and cheap raw material methyltrimethoxy silane and magnesium and chlorobenzene (or bromobenzene), adopt a step Grignard, with iodine as catalysis initiator, under certain temperature condition, activate and continue reaction after heating up again after initiation reaction for some time and finally make aminomethyl phenyl dimethoxy silane and methyldiphenyl methoxylsilane, solved and also do not realized at present a step Grignard and prepare aminomethyl phenyl dimethoxy silane, and yield is lower, the problems such as production cost costliness, met the demand of the modernization industry production of high yield less energy-consumption.
The present invention addresses the above problem adopted technical scheme:
A kind of synthetic method of the organosilane monomer containing phenyl, take methyltrimethoxy silane, magnesium, benzene halide is raw material, carry out single stage method grignard reaction: add methyltrimethoxy silane, magnesium, benzene halide, under the effect of catalysis initiator, heating activates initiation reaction, after heating up again, continue reaction, filter distillation and obtain aminomethyl phenyl dimethoxy silane and methyldiphenyl methoxylsilane.Because aminomethyl phenyl dimethoxy silane reaction activity is high, can also continue to react further to make methyldiphenyl methoxylsilane with raw material.
Reaction as chemical equation below:
By weight calculating, 30 ~ 48 parts of methyltrimethoxy silanes, 1 ~ 15 part, magnesium, 5 ~ 60 parts of benzene halides, wherein benzene halide is chlorobenzene or bromobenzene.
Benzene halide adds at twice: when activation initiation reaction, add part, progressively add remaining part after intensification.Add at twice benzene halide to be, the disposable reactive behavior that adds can be very high, and reaction can be very violent on the one hand, and safety is had to impact; On the other hand, rapid reaction, can make the selectivity of product not high on the contrary, and controlling speed of response is also a kind of means that improve selectivity of product of the present invention.
Methyltrimethoxy silane, magnesium, benzene halide are first dissolved in solvent and activate initiation reaction again, and described solvent is inert solvent, and solvent ratios accounts for 0 ~ 3.5 times of reaction total raw material quality.By the benefit of inert solvent, be to avoid solvent may participate in reaction, thereby avoid the balance of whole reaction be affected and bring unfavorable result.
Solvent is toluene, 2-methyltetrahydrofuran, dimethylbenzene and/or chlorobenzene.Solvent can be a kind of in above-mentioned four kinds or their mixture.
The consumption of catalysis initiator accounts for 0.01% ~ 0.3% of total mass, and described catalysis initiator is iodine.
40 ℃ ~ 80 ℃ of activation kick off temperatures.
Temperature of reaction is 60 ℃ ~ 120 ℃.Sterically hindered little due to methyltrimethoxy silane, its activity is higher, and temperature too higher position can be reacted, and has also reduced to a certain degree energy consumption.
The time of activation initiation reaction is 0.5 ~ 2 hour.
The present invention adopts a step Grignard: select suitable catalysis initiator, suitable initial initiation reaction temperature, initial initiation reaction time and suitable temperature of reaction, making a step Grignard prepare aminomethyl phenyl dimethoxy silane can realize, start single stage method and prepared the precedent of aminomethyl phenyl dimethoxy silane, in chemosynthesis, have great importance, and the yield of the product preparing is also higher, can reach 85%, and the present invention is generating on the basis of aminomethyl phenyl dimethoxy silane, apply flexibly the active high feature of aminomethyl phenyl dimethoxy silane reaction, by demand, carry out the production of methyldiphenyl methoxylsilane, obtained reasonable result.
To sum up, the invention has the beneficial effects as follows:
1, the present invention adopts a step Grignard: select suitable catalysis initiator, suitable initial initiation reaction temperature, initial initiation reaction time and suitable temperature of reaction, synthesis of methyl phenyl organosilane monomer (aminomethyl phenyl dimethoxy silane and methyldiphenyl methoxylsilane), product composition is fairly simple, be easy to purify, can make highly purified aminomethyl phenyl organosilane monomer, become thus the first case that a step Grignard is successfully prepared aminomethyl phenyl dimethoxy silane;
2, the present invention selects methyltrimethoxy silane that sterically hindered little activity is large as raw material, in reaction process, can under lower temperature condition, react, reduce energy consumption, and because its activity is high, under uniform temp condition, speed of response is faster, and efficiency is higher, with Union carbide A-162, do raw material, with methyltrimethoxy silane, can make in a large number methyldiphenyl methoxylsilane, and cost of material is more cheap, makes product application performance more excellent;
3, the present invention is legal compared with pyrocondensation, not by-product polychlorobiphenyl, more environmental protection; Compared with prepared by sodium condensation method, safer;
4, the present invention adds benzene halide can control speed of response at twice, guarantees that the degree of safety of reaction and the selectivity of reaction product are good;
5, the yield of aminomethyl phenyl dimethoxy silane of the present invention, up to 85%, has significant progressive.
Embodiment
Below in conjunction with embodiment, the present invention is done to detailed description further, but embodiments of the present invention are not limited to this.
The present invention successfully uses a step Grignard to prepare aminomethyl phenyl dimethoxy silane, be achieved through the following technical solutions: select suitable catalysis initiator, suitable initial initiation reaction temperature, initial initiation reaction time and suitable temperature of reaction, first activate after initiation reaction for some time, then after heating up, continue to react finally to make aminomethyl phenyl dimethoxy silane.
The invention enables a step Grignard to prepare aminomethyl phenyl dimethoxy silane can realize, start single stage method and prepared the precedent of aminomethyl phenyl dimethoxy silane, in chemosynthesis, have great importance, and the yield of the product preparing is also higher, can reach 85%, and the present invention is generating on the basis of aminomethyl phenyl dimethoxy silane, apply flexibly the active high feature of aminomethyl phenyl dimethoxy silane reaction, by demand, carry out the production of methyldiphenyl methoxylsilane, obtained reasonable result.
Embodiment 1
In reactor, add successively 150 parts of toluene, 32 parts of methyltrimethoxy silanes, 4 parts of magnesium, 5 parts of chlorobenzenes, 0.01 part of iodine, be heated to 80 ℃ and activate initiation reaction, initiation reaction to be activated is after 1 hour, then is warming up to 120 ℃, adds gradually 55 parts of chlorobenzenes.React complete.Filtration, distillation obtain product aminomethyl phenyl dimethoxy silane, methyldiphenyl methoxylsilane.
Aminomethyl phenyl dimethoxy silane selectivity 75%, methyldiphenyl methoxylsilane selectivity 5%.
Embodiment 2
In reactor, add successively 245 parts of 2-methyltetrahydrofurans, 42 parts of methyltrimethoxy silanes, 6 parts of magnesium, 8 parts of chlorobenzenes, 0.05 part of iodine, be heated to 40 ℃ and activate initiation reaction, initiation reaction to be activated 2 hours, then be warming up to 60 ℃, add gradually 42 parts of chlorobenzenes.React complete.Filtration, distillation obtain product aminomethyl phenyl dimethoxy silane, methyldiphenyl methoxylsilane.
Aminomethyl phenyl dimethoxy silane selectivity 81%, methyldiphenyl methoxylsilane selectivity 4%.
Embodiment 3
To reactor, add successively 250 parts of toluene, 100 parts, 48 parts methyltrimethoxy silanes of 2-methyltetrahydrofuran, 7 parts of magnesium, 8 parts of chlorobenzenes, 0.1 part of iodine, be heated to 60 ℃ and activate initiation reaction, initiation reaction to be activated 1.5 hours, then be warming up to 110 ℃, add gradually 40 parts of chlorobenzenes.React complete.Filtration, distillation obtain product aminomethyl phenyl dimethoxy silane, methyldiphenyl methoxylsilane.
Aminomethyl phenyl dimethoxy silane selectivity 85%, methyldiphenyl methoxylsilane selectivity 3%.
Embodiment 4
To reactor, add successively 150 parts of toluene, 60 parts of 2-methyltetrahydrofurans, 30 parts, 38 parts methyltrimethoxy silanes of dimethylbenzene, 15 parts of magnesium, 2 parts of bromobenzenes, 0.08 part of iodine, be heated to 60 ℃ and activate initiation reaction, initiation reaction to be activated 1 hour, be warming up to again 100 ℃, add gradually 3 parts of bromobenzenes.React complete.Filtration, distillation obtain product aminomethyl phenyl dimethoxy silane, methyldiphenyl methoxylsilane.
Aminomethyl phenyl dimethoxy silane selectivity 75%, methyldiphenyl methoxylsilane selectivity 6%.
Embodiment 5
To reactor, add successively 150 parts of toluene, 100 parts, 42 parts methyltrimethoxy silanes of 2-methyltetrahydrofuran, 5 parts of magnesium, 2 parts of bromobenzenes, 0.08 part of iodine, be heated to 60 ℃ and activate initiation reaction, initiation reaction to be activated 1 hour, then be warming up to 100 ℃, add gradually 30 parts of bromobenzenes.React complete.Filtration, distillation obtain product aminomethyl phenyl dimethoxy silane, methyldiphenyl methoxylsilane.
Aminomethyl phenyl dimethoxy silane selectivity 71%, methyldiphenyl methoxylsilane selectivity 4%.
Embodiment 6
To reactor, add successively 30 parts of methyltrimethoxy silanes, 12 parts of magnesium, 5 parts of bromobenzenes, 0.3 part of iodine, be heated to 80 ℃ and activate initiation reaction, initiation reaction to be activated 0.5 hour, then be warming up to 120 ℃, add gradually 20 parts of bromobenzenes.React complete.Filtration, distillation obtain product aminomethyl phenyl dimethoxy silane, methyldiphenyl methoxylsilane.
Aminomethyl phenyl dimethoxy silane selectivity 56%, methyldiphenyl methoxylsilane selectivity 18%(is greater than 70% by aminomethyl phenyl dimethoxy silane).
Embodiment 7
To reactor, add successively 40 parts of methyltrimethoxy silanes, 1 part of magnesium, 6 parts of bromobenzenes, 0.2 part of iodine, be heated to 80 ℃ and activate initiation reaction, initiation reaction to be activated 0.5 hour, then be warming up to 120 ℃, add gradually 24 parts of bromobenzenes.React complete.Filtration, distillation obtain product aminomethyl phenyl dimethoxy silane, methyldiphenyl methoxylsilane.
Aminomethyl phenyl dimethoxy silane selectivity 54%, methyldiphenyl methoxylsilane selectivity 12%(is greater than 70% by aminomethyl phenyl dimethoxy silane).
As mentioned above, can realize preferably the present invention.
Claims (9)
1. the synthetic method containing the organosilane monomer of phenyl, it is characterized in that, take methyltrimethoxy silane, magnesium, benzene halide is raw material, carry out single stage method grignard reaction: add methyltrimethoxy silane, magnesium, benzene halide, under the effect of catalysis initiator, heating activates initiation reaction, after heating up again, continue reaction, filter distillation and obtain aminomethyl phenyl dimethoxy silane and methyldiphenyl methoxylsilane.
2. according to the synthetic method of a kind of organosilane monomer containing phenyl of claim 1, it is characterized in that, by weight calculating, 30 ~ 48 parts of methyltrimethoxy silanes, 1 ~ 15 part, magnesium, 5 ~ 60 parts of benzene halides, wherein benzene halide is chlorobenzene or bromobenzene.
3. according to the synthetic method of a kind of organosilane monomer containing phenyl of claim 1, it is characterized in that, benzene halide adds at twice: when activation initiation reaction, add part, progressively add remaining part after intensification.
4. according to the method for a kind of synthetic organosilane monomer containing phenyl of claim 1, it is characterized in that, methyltrimethoxy silane, magnesium, benzene halide are first dissolved in solvent and activate initiation reaction again, and described solvent is inert solvent, and solvent ratios accounts for 0 ~ 3.5 times of reaction total raw material quality.
5. according to the synthetic method of a kind of organosilane monomer containing phenyl of claim 4, it is characterized in that, solvent is toluene, 2-methyltetrahydrofuran, dimethylbenzene and/or chlorobenzene.
6. according to the synthetic method of a kind of organosilane monomer containing phenyl of claim 1, it is characterized in that, the consumption of catalysis initiator accounts for 0.01% ~ 0.3% of total mass, and described catalysis initiator is iodine.
7. according to the synthetic method of a kind of organosilane monomer containing phenyl described in claim 1-6 any one, it is characterized in that, activation kick off temperature is 40 ℃ ~ 80 ℃.
8. according to the synthetic method of a kind of organosilane monomer containing phenyl of claim 7, it is characterized in that, the temperature of reaction after intensification is 60 ℃ ~ 150 ℃.
9. the synthetic method of a kind of organosilane monomer containing phenyl according to Claim 8, is characterized in that, the time of activation initiation reaction is 0.5 ~ 2 hour.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107794112A (en) * | 2017-10-28 | 2018-03-13 | 德清云偶新材料科技有限公司 | A kind of high abrasion aluminium alloy silicone release and preparation method |
| CN110964051A (en) * | 2019-12-04 | 2020-04-07 | 湖北华邦化学有限公司 | Method for industrially producing dialkyl dialkoxy silane |
| CN114605887A (en) * | 2022-04-19 | 2022-06-10 | 宁波宣威彩色世界涂料有限公司 | Smooth, clean and odor-free super-scrubbing water paint for skin |
| CN115010746A (en) * | 2022-07-20 | 2022-09-06 | 江苏八巨药业有限公司 | Preparation method of tert-butyldimethylsilyl chloride |
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| US4309557A (en) * | 1981-02-12 | 1982-01-05 | Nusil Research | Process for the preparation of alkyl and aryl substituted oligosiloxanes suitable for use as diffusion pump oils |
| CN102702248A (en) * | 2011-03-28 | 2012-10-03 | 苏州百灵威超精细材料有限公司 | A preparation method for methyl phenyl siloxane unit-containing organosilicone ring bodies |
| CN102863465A (en) * | 2012-10-11 | 2013-01-09 | 威海新元化工有限公司 | Preparation method for methyl phenyl di-alkoxy silane |
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2014
- 2014-06-25 CN CN201410287272.4A patent/CN104017017A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4309557A (en) * | 1981-02-12 | 1982-01-05 | Nusil Research | Process for the preparation of alkyl and aryl substituted oligosiloxanes suitable for use as diffusion pump oils |
| CN102702248A (en) * | 2011-03-28 | 2012-10-03 | 苏州百灵威超精细材料有限公司 | A preparation method for methyl phenyl siloxane unit-containing organosilicone ring bodies |
| CN102863465A (en) * | 2012-10-11 | 2013-01-09 | 威海新元化工有限公司 | Preparation method for methyl phenyl di-alkoxy silane |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107794112A (en) * | 2017-10-28 | 2018-03-13 | 德清云偶新材料科技有限公司 | A kind of high abrasion aluminium alloy silicone release and preparation method |
| CN110964051A (en) * | 2019-12-04 | 2020-04-07 | 湖北华邦化学有限公司 | Method for industrially producing dialkyl dialkoxy silane |
| CN110964051B (en) * | 2019-12-04 | 2023-03-14 | 湖北华邦化学有限公司 | Method for industrially producing dialkyl dialkoxy silane |
| CN114605887A (en) * | 2022-04-19 | 2022-06-10 | 宁波宣威彩色世界涂料有限公司 | Smooth, clean and odor-free super-scrubbing water paint for skin |
| CN115010746A (en) * | 2022-07-20 | 2022-09-06 | 江苏八巨药业有限公司 | Preparation method of tert-butyldimethylsilyl chloride |
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Application publication date: 20140903 |