CN104004194A - Silicon alkyne hybrid high temperature-resistant resin and preparation method thereof - Google Patents
Silicon alkyne hybrid high temperature-resistant resin and preparation method thereof Download PDFInfo
- Publication number
- CN104004194A CN104004194A CN201310300470.5A CN201310300470A CN104004194A CN 104004194 A CN104004194 A CN 104004194A CN 201310300470 A CN201310300470 A CN 201310300470A CN 104004194 A CN104004194 A CN 104004194A
- Authority
- CN
- China
- Prior art keywords
- reaction
- diacetylene
- dichlorosilane
- bromide
- silane
- 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
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a silicon alkyne hybrid high temperature-resistant resin and a preparation method thereof. The resin is prepared by a Grignard reagent method in four reaction steps, by using dichlorosilane and ethynylmagnesium bromide as raw materials. In a first reaction step, dichlorosilane reacts with ethynylmagnesium bromide to generate diethynylsilane; in a second reaction step, ethyl bromide reacts with magnesium to generate ethylmagnesium bromide; in a third reaction step, ethylmagnesium bromide reacts with diethynylsilane generated by the first reaction step to generate diethynylmagnesium bromide; and in a fourth reaction step, dichlorosilane reacts with diethynylmagnesium bromide generated by the third reaction step, and a final product can be obtained after posttreatment. The method is simple in process flow; and molding processing property, high temperature resistance and anti-oxidant property of the polymer can be increased by increasing the content of silicone element and ethynyl in the structure. The prepared resin can be used as a matrix resin of advanced composite materials and ceramic precursors, and has wide application prospects in the fields of electronics, national defense, aviation and aerospace, etc.
Description
Technical field
The present invention relates to a kind of silicon alkynes hydridization fire resistant resin and preparation method thereof, particularly on main chain, by silicon and ethynyl a kind of hybrid inorganic-organic fire resistant resin alternately, gather (diacetylene silane).
Background technology
The quick progress of aerospace industry, has higher requirement to the high temperature resistant and antioxidant property of material, and silicon-containing polymer is owing to having excellent performance, thereby has met well this requirement.In recent years, the organosilicon polymer that contains Si-C ≡ C-group in main chain has become the focus of research, in fields such as high performance composite, ceramic precursor, aerospace and missilerys, has broad application prospects.
Employing butyllithium, trieline and the dimethyldichlorosilane(DMCS)s such as Barton are main raw material, have synthesized poly-silico acetylene base resin, and this resin has good high temperature resistant and antioxidant property.Corriu etc. utilize the polycondensation of diacetylene base lithium and dichlorosilane, have synthesized the Polycarbosilane that backbone structure contains diacetylene base.Its ceramic productive rate in inert atmosphere is up to 84%.David etc. have studied the hydrosilation mechanism that two (dimethylsilyl) acetylene forms sigma-pi conjugated system.The employing dehydrogenation coupling processs such as Itoh and Grignard reagent method have been synthesized a class novel silicon alkynes hydridization high-temperature polymer (MSP resin).Its decomposition temperature is higher than 600 ℃, and the residual rate of 1000 ℃ is greater than 94%, has very high ceramic productive rate, can be used as thermal protection and ablation resistant material.A series of phenylacetylene base silane resins have been synthesized in the designs such as the Chen Qi of East China University of Science, Zhou Quan, comprise methyldiphenyl ethynyl silane (MDPES), methyl three phenylacetylene base silanes (MTPES) and four phenylacetylene base silanes (TPES).This resinoid has good solubility in ordinary organic solvents, and resin cured matter has excellent high temperature resistant and antioxidant property, is applicable to various advanced composite material moulding processs.Research is found, in polymer molecular structure, introduce Si element, can effectively improve the high temperature resistant and antioxidant property of polymkeric substance, and along with the increase of ethynyl in molecular structure and Si constituent content, the moulding processability of resin, high temperature resistant and antioxidant property improve constantly.
Therefore, the present invention is by the content of Si element and ethynyl in raising structure, thus moulding processability, the high temperature resistant and antioxidant property of raising polymkeric substance.It is main raw material that monobromethane, ethynyl bromination magnesium and dichlorosilane are take in the present invention, adopts Grignard reagent method, the hybrid inorganic-organic fire resistant resin poly-(diacetylene silane) that contains Si-C ≡ C-group in synthetic molecule backbone structure.This resinoid has excellent high temperature resistant and antioxidant property etc., is applicable to prepare ceramic first body, high performance composite matrix and high-temperaure coating etc., has extremely broad application prospect in the high-end fields such as national defence, aerospace.
Summary of the invention
The synthetic class I organic-inorganic hybridized fire resistant resin of the present invention poly-(diacetylene silane), described polymer architecture formula is as follows:
Wherein: (1) R
1, R
2, R
3, R
4for hydrogen atom, alkyl or aryl; (2) integer that n is>=1.
The present invention is from Molecular Structure Design, design and synthesize class I organic-inorganic hybridized fire resistant resin poly-(diacetylene silane), in its repeating unit, contain a large amount of Si-C ≡ C-groups, the ethynyl containing can be under heat, irradiation or light action polymerization reaction take place, the polymkeric substance that height of formation is crosslinked; And the existence of Si element has been given again polymkeric substance and has been had higher high temperature resistant and antioxidant property.By regulating the mol ratio of ethynyl bromination magnesium and dichlorosilane, can control molecular weight and the cross-linking density of polymkeric substance, thereby realize the controllability of polymer performance.
Modest viscosity under poly-(diacetylene silane) normal temperature of silicon alkynes hydridization fire resistant resin of the present invention, be soluble in the organic solvents such as acetone, tetrahydrofuran (THF), toluene, can be used as high temperature resistant composite resin matrix, ceramic first body and fire-resistant oxidation resistant coating.
Another object of the present invention is to provide a kind of method of preparing described silicon alkynes hydridization fire resistant resin poly-(diacetylene silane).The present invention be take ethynyl bromination magnesium, dichlorosilane and is made solvent as main raw material, anhydrous tetrahydro furan, under protection of inert gas condition, by Grignard reagent method, divides four-step reaction to obtain, and preparation method is as follows:
The first step: under protection of inert gas, react with dichlorosilane and generate diacetylene silane by ethynyl bromination magnesium;
Wherein: (1) R
1, R
2for hydrogen atom, alkyl or aryl.
The invention is characterized in: the mol ratio of dichlorosilane and ethynyl bromination magnesium is 1: (2～3), the temperature of reaction of dichlorosilane and ethynyl bromination magnesium is 15～55 ℃, the reaction times is 4～12 hours.
Second step: under protection of inert gas, react with monobromethane by magnesium and generate ethylmagnesium bromide;
The invention is characterized in: the temperature of reaction of monobromethane solution in dropping process is 20～60 ℃, dropwising the rear reaction times is 1～5 hour.
The 3rd step: under protection of inert gas, ethylmagnesium bromide is reacted the diacetylene silane reaction generating and generated diacetylene silicon magnesium bromide with the first step;
Wherein: (1) R
1, R
2for hydrogen atom, alkyl or aryl.
The invention is characterized in: the mol ratio of diacetylene silane and ethylmagnesium bromide is 1: (2～4), the temperature of the reaction of diacetylene solution of silane in dropping process is 15～70 ℃, temperature of reaction after dropwising is 45～70 ℃, and the reaction times is 1～5 hour.
The 4th step: under protection of inert gas, dichlorosilane reacts with the diacetylene magnesium bromide that three-step reaction generates, and aftertreatment obtains final product.
Wherein: (1) R
1, R
2, R
3, R
4for hydrogen atom, alkyl or aryl; (2) integer that n is>=1.
The invention is characterized in: the mol ratio of the diacetylene magnesium bromide that dichlorosilane and three-step reaction generate is 1: (1～3), temperature of reaction is 45～75 ℃, the reaction times is 0.5～4 hour.
The present invention adopts the hybrid inorganic-organic fire resistant resin poly-(diacetylene silane) that contains Si-C ≡ C-group in the synthetic molecule backbone structure of Grignard reagent method.By the content of Si element and ethynyl in raising structure, thus moulding processability, the high temperature resistant and antioxidant property of raising polymkeric substance.This synthesis technique is simple, easy to operate; Required raw material sources are abundant, and product has satisfactory stability at normal temperatures, high temperature resistant and antioxidant property is excellent, possess industrial applicibility.Be applicable to prepare ceramic first body, high performance composite matrix and high-temperaure coating etc., in the high-end fields such as national defence, aerospace, have extremely broad application prospect.
Embodiment:
Further illustrate technical solution of the present invention, but it does not limit the scope of the invention in conjunction with the embodiments:
Embodiment 1: prepare poly-(diacetylene silane) (wherein, the R of silicon alkynes hydridization fire resistant resin
1, R
2, R
3, R
4be respectively H, CH
3, H, CH
3)
Under high pure nitrogen protective condition; 150ml ethynyl bromination magnesium is added in 250ml there-necked flask; then by constant pressure funnel, slowly drip the solution that 14ml tetrahydrofuran (THF) and 10ml methyl hydrogen dichlorosilane are made into, after dropwising, holder ties up under 25 ℃ of conditions reacts 5 hours.Meanwhile, under high pure nitrogen protective condition, 3.5g magnesium chips and 10ml tetrahydrofuran (THF) are added in the four-hole boiling flask of another 500ml; control temperature at 25～40 ℃; with constant pressure funnel, drip the solution being made into by 7ml monobromethane and 30ml THF, after dropwising, reacting by heating 2 hours.After reactant is cooling, control temperature at 25～30 ℃, drip the methyl hydrogen diacetylene silane that the first step reaction generates, after dropwising, reheat reaction 3 hours.After question response is cooling, control temperature at 25～30 ℃, continue the solution that dropping 10ml methyl hydrogen dichlorosilane and 18ml tetrahydrofuran (THF) are made into, after dropwising, reacting by heating 2 hours.Then question response thing is cooled to after room temperature, in condition of ice bath downhill reaction system, drips 5% dilute hydrochloric acid.After dropwising, fully stir, separatory, gets upper oil phase, with deionized water wash, until the pH value of water and oil phase is all neutral, collects upper strata oily matter, and underpressure distillation obtains product after eliminating solvent.
FTIR:2173cm
-1(Si-H), 2043cm
-1(C ≡ C-), 1255cm
-1(Si-CH
3);
1h-NMR (CDCl
3, TMS) δ: 4.34 (Si-H), 0.41～0.55 (Si-CH
3);
13c-NMR (CDCl
3, TMS) δ: 82.4 (C ≡ C-)-2.47 (CH
3); TGA: resin cured matter is at N
2be respectively 641 ℃ and 628 ℃ with the temperature of mass loss in air atmosphere 5%, the quality retention rate of 1000 ℃ is respectively 88.9% and 86.5%.
Embodiment 2: prepare poly-(diacetylene silane) (wherein, the R of silicon alkynes hydridization fire resistant resin
1, R
2, R
3, R
4be respectively H, CH
3,
Under high pure nitrogen protective condition; 150ml ethynyl bromination magnesium is added in 250ml there-necked flask; then by constant pressure funnel, slowly drip the solution that 14ml tetrahydrofuran (THF) and 10ml methyl hydrogen dichlorosilane are made into, after dropwising, holder ties up under 25 ℃ of conditions reacts 5 hours.Meanwhile, under high pure nitrogen protective condition, 3.5g magnesium chips and 10ml tetrahydrofuran (THF) are added in the four-hole boiling flask of another 500ml; control temperature at 25～40 ℃; with constant pressure funnel, drip the solution being made into by 7ml monobromethane and 30ml THF, after dropwising, reacting by heating 2 hours.After reactant is cooling, control temperature at 25～30 ℃, drip the methyl hydrogen diacetylene silane that the first step reaction generates, after dropwising, reheat reaction 3 hours.After question response is cooling, control temperature at 25～30 ℃, continue the solution that dropping 10ml diphenyl dichlorosilane and 18ml tetrahydrofuran (THF) are made into, after dropwising, reacting by heating 2 hours.Question response thing is cooled to after room temperature, in condition of ice bath downhill reaction system, drips 5% dilute hydrochloric acid.After dropwising, fully stir, separatory, gets upper oil phase, with deionized water wash, until the pH value of water and oil phase is all neutral, collects upper strata oily matter, and underpressure distillation obtains product after eliminating solvent.
FTIR:2174cm
-1(Si-H), 2041cm
-1(C ≡ C-), 1256cm
-1(Si-CH
3), 1429cm
-1(Si-Ph), 3070cm
-1(Ph-H);
1h-NMR (CDCl
3, TMS) δ: 4.46 (Si-H), 0.53 (Si-CH
3), 7.34～7.69 (Ph-H);
13c-NMR (CDCl
3, TMS) δ: 87.1 (C ≡ C-) ,-2.39 (CH
3), 123～136 (Ph); TGA: resin cured matter is at N
2be respectively 526 ℃ and 517 ℃ with the temperature of mass loss in air atmosphere 5%, the quality retention rate of 1000 ℃ is respectively 83.5% and 52.3%.
Embodiment 3: prepare poly-(diacetylene silane) (wherein, the R of silicon alkynes hydridization fire resistant resin
1, R
2, R
3, R
4be
Under high pure nitrogen protective condition; 150ml ethynyl bromination magnesium is added in 250ml there-necked flask; then by constant pressure funnel, slowly drip the solution that 14ml tetrahydrofuran (THF) and 10ml diphenyl dichlorosilane are made into, after dropwising, holder ties up under 25 ℃ of conditions reacts 5 hours.Meanwhile, under high pure nitrogen protective condition, 3.5g magnesium chips and 10ml tetrahydrofuran (THF) are added in the four-hole boiling flask of another 500ml; control temperature at 25～40 ℃; with constant pressure funnel, drip the solution being made into by 7ml monobromethane and 30ml THF, after dropwising, reacting by heating 2 hours.After reactant is cooling, control temperature at 25～30 ℃, drip the phenylbenzene diacetylene silane that the first step reaction generates, after dropwising, reheat reaction 3 hours.After question response is cooling, control temperature at 25～30 ℃, continue the solution that dropping 10ml diphenyl dichlorosilane and 18ml tetrahydrofuran (THF) are made into, after dropwising, reacting by heating 2 hours.Question response thing is cooled to after room temperature, in condition of ice bath downhill reaction system, drips 5% dilute hydrochloric acid.After dropwising, fully stir, separatory, gets upper oil phase, with deionized water wash, until the pH value of water and oil phase is all neutral, collects upper strata oily matter, and underpressure distillation obtains product after eliminating solvent.
FTIR:2040cm
-1(C ≡ C-), 1429cm
-1(Si-Ph), 3070cm
-1(Ph-H);
1h-NMR (CDCl
3, TMS) δ: 7.31～7.72 (Ph-H);
13c-NMR (CDCl
3, TMS) δ: 90.1 (C ≡ C-), 124～136 (Ph); TGA: resin cured matter is at N
2be respectively 483 ℃ and 454 ℃ with the temperature of mass loss in air atmosphere 5%, the quality retention rate of 1000 ℃ is respectively 70.8% and 46.9%.
Claims (7)
1. a silicon alkynes hydridization fire resistant resin gathers (diacetylene silane), it is characterized in that described silicon alkynes hydridization fire resistant resin has following structural formula:
Wherein: (1) R
1, R
2, R
3, R
4for hydrogen atom, alkyl or aryl; (2) integer that n is>=1.
2. silicon alkynes hydridization fire resistant resin claimed in claim 1 gathers the preparation method of (diacetylene silane), and its key step is:
(1) the first step reaction: under protection of inert gas, dichlorosilane and ethynyl bromination reactive magnesium generate diacetylene silane;
(2) second step reaction: under protection of inert gas, monobromethane and reactive magnesium generate ethylmagnesium bromide;
(3) three-step reactions: under protection of inert gas, ethylmagnesium bromide is reacted the diacetylene silane reaction generating and generated diacetylene magnesium bromide with the first step;
(4) four-step reactions: under protection of inert gas, dichlorosilane reacts with the diacetylene magnesium bromide that three-step reaction generates, and aftertreatment obtains final product.
3. according to the preparation method of claim 2, it is characterized in that: in the first step reaction, the mol ratio of dichlorosilane and ethynyl bromination magnesium is 1: (2～3); In three-step reaction, the mol ratio of diacetylene silane and ethylmagnesium bromide is 1: (2～4); The mol ratio of the diacetylene magnesium bromide that in four-step reaction, dichlorosilane and three-step reaction generate is 1: (1～3).
4. according to the preparation method of claim 2, it is characterized in that: in the first step reaction, the temperature of reaction of dichlorosilane and ethynyl bromination magnesium is 15～55 ℃, and the reaction times is 4～12 hours.
5. according to the preparation method of claim 2, it is characterized in that: in second step reaction, the temperature of reaction of monobromethane solution in dropping process is 20～60 ℃, and dropwising the rear reaction times is 1～5 hour.
6. according to the preparation method of claim 2, it is characterized in that: in three-step reaction, the temperature of the reaction of diacetylene solution of silane in dropping process is 15～70 ℃, and the temperature of reaction after dropwising is 45～70 ℃, and the reaction times is 1～5 hour.
7. according to the preparation method of claim 2, it is characterized in that: in four-step reaction, the temperature of the reaction of dichlorosilane solution in dropping process is 15～50 ℃, and the temperature of reaction after dropwising is 45～75 ℃, and the reaction times is 0.5～4 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310300470.5A CN104004194A (en) | 2013-07-17 | 2013-07-17 | Silicon alkyne hybrid high temperature-resistant resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310300470.5A CN104004194A (en) | 2013-07-17 | 2013-07-17 | Silicon alkyne hybrid high temperature-resistant resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104004194A true CN104004194A (en) | 2014-08-27 |
Family
ID=51365116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310300470.5A Pending CN104004194A (en) | 2013-07-17 | 2013-07-17 | Silicon alkyne hybrid high temperature-resistant resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104004194A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237772A (en) * | 2015-10-08 | 2016-01-13 | 华东理工大学 | Phenylethynyl-terminated silicon-containing polytriazole resins and preparation method thereof |
| CN105542172A (en) * | 2016-01-18 | 2016-05-04 | 华东理工大学 | Boron-silicon-alkyne polymer containing carborane in main chain and preparation method of boron-silicon-alkyne polymer |
| CN107057070A (en) * | 2016-12-01 | 2017-08-18 | 福建师范大学 | A kind of side chain Silicon Containing Hydrogen alkynes hydridization heat-resistant polymer and preparation method thereof |
| CN111548497A (en) * | 2020-05-29 | 2020-08-18 | 华东理工大学 | Silyne hybrid resin, cured product, ceramic material, composite material and preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260175A (en) * | 2008-05-08 | 2008-09-10 | 华东理工大学 | Silicon-containing copolymer with phenylacetylene end group |
| CN102010510A (en) * | 2010-10-21 | 2011-04-13 | 华东理工大学 | Novel high-temperature resistant phenylacetylene terminated poly (acetenyl-silane) and preparation method thereof |
-
2013
- 2013-07-17 CN CN201310300470.5A patent/CN104004194A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260175A (en) * | 2008-05-08 | 2008-09-10 | 华东理工大学 | Silicon-containing copolymer with phenylacetylene end group |
| CN102010510A (en) * | 2010-10-21 | 2011-04-13 | 华东理工大学 | Novel high-temperature resistant phenylacetylene terminated poly (acetenyl-silane) and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237772A (en) * | 2015-10-08 | 2016-01-13 | 华东理工大学 | Phenylethynyl-terminated silicon-containing polytriazole resins and preparation method thereof |
| CN105542172A (en) * | 2016-01-18 | 2016-05-04 | 华东理工大学 | Boron-silicon-alkyne polymer containing carborane in main chain and preparation method of boron-silicon-alkyne polymer |
| CN107057070A (en) * | 2016-12-01 | 2017-08-18 | 福建师范大学 | A kind of side chain Silicon Containing Hydrogen alkynes hydridization heat-resistant polymer and preparation method thereof |
| CN107057070B (en) * | 2016-12-01 | 2020-05-08 | 福建师范大学 | Side-chain hydrogen-containing alkyne hybrid high-temperature-resistant polymer and preparation method thereof |
| CN111548497A (en) * | 2020-05-29 | 2020-08-18 | 华东理工大学 | Silyne hybrid resin, cured product, ceramic material, composite material and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102585239A (en) | Novel high temperature resistant phenylboronic acid-siloxane-imino linear polymer and preparation method thereof | |
| CN109337078B (en) | Preparation method of silicon carbide ceramic precursor polycarbosilane | |
| CN101235113A (en) | Aryne resin containing polysilicone and preparation method thereof | |
| CN106674528B (en) | A kind of preparation method of Polycarbosilane | |
| CN104004194A (en) | Silicon alkyne hybrid high temperature-resistant resin and preparation method thereof | |
| CN102660030A (en) | Preparation method of Si-C-N ceramic precursor | |
| CN104130417A (en) | High-temperature silicon alkyne resin containing nitrogen and preparation method thereof | |
| CN103333341A (en) | High-temperature-resistant hybrid silazane resin and preparation method thereof | |
| CN110423352B (en) | Preparation method of high-temperature-resistant organic silicon material containing carborane structure | |
| CN102226000B (en) | Novel boron silicon alkyne hybrid high temperature resistant resin and preparation method thereof | |
| CN102585240A (en) | Aryne resin containing boron and silicon and preparation method thereof | |
| CN107057070B (en) | Side-chain hydrogen-containing alkyne hybrid high-temperature-resistant polymer and preparation method thereof | |
| CN106957433A (en) | Can the dual crosslinking of light heat hyperbranched polycarbosilanes benzocyclobutane olefine resin and preparation method thereof | |
| CN111333844B (en) | Preparation method of high-heat-resistance silicon oxide alkyne hybrid resin | |
| CN105542172A (en) | Boron-silicon-alkyne polymer containing carborane in main chain and preparation method of boron-silicon-alkyne polymer | |
| CN101544765B (en) | Novel high temperature-resisting phenylboronic acid-silane-ethynyl polymer and preparation method thereof | |
| CN103524746B (en) | A kind of Borazine aryne resin and preparation method thereof | |
| CN101591438B (en) | Preparation method for liquid polycarbosilane precusor | |
| EP2580255B1 (en) | Polyarylacetylenes containing siloxane, silane, and carborane moieties | |
| CN101134816A (en) | Sesquialter siloxane polyaryne hybrid resin and preparation method and use thereof | |
| CN102234375B (en) | Polyphenylacetylene silicon oxide borane and preparation method thereof | |
| CN102010510A (en) | Novel high-temperature resistant phenylacetylene terminated poly (acetenyl-silane) and preparation method thereof | |
| CN101139442B (en) | Organic-inorganic hybrid resin containing sesquialter siloxane and preparation method and use thereof | |
| CN101709062A (en) | Novel silazane-diacetylene aniline silane and preparation method thereof | |
| TW201819393A (en) | Polymer with alternating phenylene and silicon siloxane framework, and method for preparing its precursor for improving the compatibility of inorganic silicon-based flame retardant and the polymer substrate, so as to prevent the properties of polymer material and the processing performance from being affected |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140827 |