CN104645876A - Ternary surface active agent adopting 1,1,1-tri(hydroxymethyl) ethane as link group, and preparation method of ternary surface active agent - Google Patents
Ternary surface active agent adopting 1,1,1-tri(hydroxymethyl) ethane as link group, and preparation method of ternary surface active agent Download PDFInfo
- Publication number
- CN104645876A CN104645876A CN201410585810.8A CN201410585810A CN104645876A CN 104645876 A CN104645876 A CN 104645876A CN 201410585810 A CN201410585810 A CN 201410585810A CN 104645876 A CN104645876 A CN 104645876A
- Authority
- CN
- China
- Prior art keywords
- reaction
- ethane
- tri
- acid
- add
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Detergent Compositions (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invenetion relates to a preparation method of a ternary surface active agent adopting 1,1,1-tri(hydroxymethyl) ethane as a link group. A structural formula of the ternary surface active agent is as follows (described in specifications). The synthesis method includes a synthesis step of alpha-bromo-carboxylic acid, an esterification reaction step of the link group 1,1,1-tri(hydroxymethyl) ethane and an esterolysis reaction step. The synthesis process condition of the ternary surface active agent is as follows: 30% NaOH and tetrahydrofuran are used as a solvent to be subjected to reflux reaction for 5 to 7 hours.
Description
Technical field
The present invention relates to a kind of preparation method of three sub-surface activating agents.
Background technology
The research of anionic gemini surfactant is existing for many years, and little to the report of anion three sub-surface activating agent.2004; after three (2-aminoethyl) amine, the reaction of long-chain acylated with acid chloride; three sub-anionic carboxylic acid salt surfactants are synthesized with after Lithium Aluminium Hydride reducing amide with after anhydride reaction; this achievement in research is published in Journal of Surfactants And Detergents (2004,7:67-73).2008, with glycerine, epoxychloropropane, lauryl alcohol, chlorosulfonic acid etc. for primary raw material, through etherificate, open loop, sulfating reaction, three sulfuric acid ester type anion surfactants are synthesized, this achievement in research is published in (Southern Yangtze University, 2008.7) in Master's thesis.At present, little to the research report of three sub-surface activating agents both at home and abroad, due to the property that three sub-surface activating agents have, attract a lot of researchers and constantly carry out more research.We synthesize, and a kind of what have no report is the three sub-surface activating agents connecting base with 1,1,1-tri-(methylol) ethane, and the synthesis of this product adds the kind of three sub-surface activating agents, simultaneously for the research of this aspect provides some references.
Summary of the invention
The object of the invention is the preparation method in order to provide with 1,1,1-tri-(methylol) ethane the three sub-surface activating agents being connection base.This surfactant has good surface-active, wetability, foaming and foam stability.This preparation method's raw material is easy to get, and easy being easy to of operation controls, and product is easily separated.
Synthesized by the present invention is be connect three sub-surface activating agents of base with 1,1,1-tri-(methylol) ethane.Its structural formula is:
n=5、7、9
The concrete synthetic method of three sub-surface activating agents comprises following three steps:
(1) synthesis of alpha-brominated carboxylic acid
Under nitrogen protection; in the dry there-necked flask of 100 mL that reflux condensing tube, dropping funel, rotor and emission-control equipment are housed; add aliphatic acid and be slowly heated to solid thawing; then slowly thionyl chloride is dripped under stirring at 55-60 DEG C; aliphatic acid acid is 1.0:1.3 with the mol ratio of thionyl chloride, is heated to 80 DEG C after mixing, reaction 1 ~ 2 h; till not having waste gas to release, reduce pressure away excessive thionyl chloride.Then under agitation slowly drip bromine (about 4 h dropwise) in 80 DEG C, under remaining on 80 DEG C of conditions, continue reaction 12 h.Poured in frozen water by reactant liquor after reaction terminates, then add extraction into ethyl acetate, organic phase uses anhydrous magnesium sulfate drying 5-6 h with after distilled water washing, and decompression distillation removing low boiling component obtains crude product.Crude product can be collected through decompression distillation and obtain the alpha-brominated carboxylic acid of clear yellow viscous liquid.
(2) esterification
Under nitrogen protection, sodium hydride is added in 100 mL there-necked flasks of drying, the oxolane that 5 mL are dried, after stirred at ambient temperature 10 min, then in there-necked flask, 1 is dripped, 1, the oxolane mixed liquor of 1-tri-(methylol) ethane and 10 mL dryings, 1, 1, the mol ratio of 1-tri-(methylol) ethane and sodium hydride is 1.0:3.3, at room temperature continue stirring reaction 1 h, reaction unit is moved in ice-water bath, the oxolane mixed liquor of the alpha-brominated acid of fast drop and 5 mL dryings in reaction bulb, the mol ratio of alpha-brominated acid and sodium hydride is 1.0:1.0, stirring 0.5 h is continued under ice-water bath, then reaction unit is moved in oil bath and be warming up to 65 DEG C, backflow 23-25 h, question response liquid is cooled to room temperature, add distilled water to rock in reactant liquor and make it mix, revolve steaming removing tetrahydrofuran solvent and obtain remaining liq, surplus solution pH to 1 ~ 2 are regulated with watery hydrochloric acid, be extracted with ethyl acetate, merge organic phase and use anhydrous magnesium sulfate drying 5-6 h, filter, except desolventizing, obtain clear yellow viscous liquid intermediate compound I.Obtained clear yellow viscous liquid intermediate compound I joined in 100mL there-necked flask, then add 15 mL methyl alcohol, the concentrated sulfuric acid makes catalyst, is heated to 65 DEG C under stirring, and reaction stopped after reaction 14-16 h, reaction bulb moves in ice-water bath, adds NaHCO
3solid neutralisation of sulphuric acid, revolve and steam the excessive methyl alcohol of removing, add distilled water, be extracted with ethyl acetate, merge organic phase dried over mgso 3-4 h, filtration, except desolventizing, gained crude on silica gel column chromatography for separation, eluant, eluent is V (ethyl acetate): V (benzinum), collects after merging same composition concentrated, can obtain colorless viscous liquid intermediate II.
(3) ester hydrolysis reaction
Intermediate is added in 100mL there-necked flask
, then add the oxolane of 10 mL dryings, add the sodium hydrate aqueous solution of a certain amount of 30%, after back flow reaction 5-8 h, except desolventizing, in crude product, add distilled water, and use washed with dichloromethane water layer, decompression distillation, except after anhydrating, is placed in refrigerator crystallization, centrifugation, solid, in 60 DEG C of vacuum drying 5-7 h, obtains white solid, and namely 1,1,1-tri-(methylol) ethane is for connecting base three sub-surface activating agent.
Below the building-up process (for n=7) of the present invention three sub-surface activating agent:
(1) synthesis of alpha-brominated capric acid
(2) esterification
(3) ester hydrolysis reaction
Compared with prior art, the present invention has following beneficial effect:
(1) surfactant of the present invention is connect three sub-surface activating agents of base with 1,1,1-tri-(methylol) ethane, and the three sub-surface activating agents at present with this structure there is not yet bibliographical information.
(2) this product has water-soluble, wetability, foaming and foam stability preferably.
(3) building-up process of the present invention, has the synthesis of alpha-brominated carboxylic acid, esterification and ester hydrolysis reaction to form.Easy being easy to of operation controls, and post processing is simple, and product is easy to separating-purifying.
Detailed description of the invention is as follows:
The synthesis (for n=7) of embodiment 1 three sub-surface activating agent
(1) synthesis of alpha-brominated capric acid
Under nitrogen protection; in the dry there-necked flask of 100 mL that reflux condensing tube, dropping funel, rotor and emission-control equipment are housed; 17.215 g (0.1 mol) capric acid; slowly be heated to solid melt; then slowly 9.3 mL (0.13 mol) thionyl chloride is dripped under stirring at 55-60 DEG C; the mol ratio of capric acid and thionyl chloride is 1.0:1.3; 80 DEG C are heated to after mixing; react 1.5 h; till not having waste gas to release, reduce pressure away excessive thionyl chloride.Then under agitation slowly drip 23.970 g (0.15 mol) bromine (about 4 h dropwise) in 80 DEG C, under remaining on 80 DEG C of conditions, continue reaction 12 h.After reaction terminates, reactant liquor is poured in 40mL frozen water, add (45 mL × 3) ethyl acetate again, point water-yielding stratum, organic phase is with distilled water washing (30 mL × 3) and with anhydrous magnesium sulfate drying 5-6 h, and then decompression distillation removes low boiling component and obtains crude product.Crude product can be collected through decompression distillation (boiling point 160 DEG C) and obtain the alpha-brominated capric acid of clear yellow viscous liquid, yield 86.1%.
(2) esterification
Under nitrogen protection, 0.528 g (13.2 mmol) sodium hydride is added in 100 mL there-necked flasks of drying, the oxolane that 5 mL are dried, after stirred at ambient temperature 10 min, then in there-necked flask, drip 0.240 g (2.0 mmol) 1, 1, the oxolane mixed liquor of 1-tri-(methylol) ethane and 10 mL dryings, 1, 1, the mol ratio of 1-tri-(methylol) ethane and sodium hydride is 1.0:3.3, at room temperature continue stirring 1 h, reaction unit is moved in ice-water bath, the oxolane mixed liquor of fast drop 1.658 g (6.6 mmol) alpha-brominated capric acid and 5 mL dryings in reaction bulb, the mol ratio of alpha-brominated capric acid and sodium hydride is 1.0:1.0, stirring 0.5 h is continued under ice-water bath, then reaction unit is moved in oil bath and be warming up to 65 DEG C, reflux after 24 h, question response liquid is cooled to room temperature, add 15 mL distilled water to rock in reactant liquor and make it mix, revolve steaming removing tetrahydrofuran solvent and obtain remaining liq, watery hydrochloric acid with 5% regulates surplus solution pH to 1 ~ 2, be extracted with ethyl acetate (20 mL × 3), merge organic phase and use anhydrous magnesium sulfate drying 5-6 h, filter, except desolventizing, obtain clear yellow viscous liquid intermediate compound I 1.224g, yield 97%.Obtained clear yellow viscous liquid intermediate compound I added in 100mL there-necked flask, then add 15 mL methyl alcohol and the 38.2 mg concentrated sulfuric acids, be heated to 65 DEG C under stirring, reaction stopped after reacting 15 h, reaction bulb moves in ice-water bath, adds 69.8mgNaHCO
3solid neutralisation of sulphuric acid, revolve and steam the excessive methyl alcohol of removing, add 20 mL distilled water, be extracted with ethyl acetate (20 mL × 3), merge organic phase dried over mgso 3-4 h, filtration, except desolventizing, gained crude on silica gel column chromatography for separation, eluant, eluent is V (ethyl acetate): V (benzinum)=5:95, collects after merging same composition concentrated, can obtain colorless viscous liquid intermediate II 0.741g, yield is 55.1%.
(3) ester hydrolysis reaction
By 0.672 g (1.0 mmol) intermediate
join in 100mL there-necked flask, then add the oxolane of 10 mL dryings, add the sodium hydrate aqueous solution of a certain amount of 30%, after back flow reaction 6 h, except desolventizing, in crude product, add 20mL distilled water, and with washed with dichloromethane (10 mL × 3) water layer, decompression distillation is except after anhydrating, be placed in refrigerator crystallization, centrifugation, solid is in 60 DEG C of vacuum drying 5 h, obtain white solid 0.566g, yield 81.3%.
The infrared spectrum (for n=7) of embodiment 2 three sub-surface activating agent
The three sub-surface activating agents be obtained by reacting with capric acid are example, and adopt coating method, do infrared analysis with Fourier infrared spectrum analyzer to product, data are as follows:
2956.7 cm
-1, 2923.80 cm
-1, 2854.40 cm
-1place is-CH
3,-CH
2-symmetric and anti-symmetric stretching vibration absworption peak, 1581.40 cm
-1, 1424.80 cm
-1place is the characteristic absorption peak of carboxylate, 1109.2 cm
-1place is the stretching vibration absworption peak of C-O-C key, 723.5 cm
-1for long-chain-CH
2-stretching vibration vibration absorption peak.
Embodiment 3 three sub-surface activating agent
1hNMR (for n=7)
With CDCl
3for solvent is to three sub-surface activating agents
1h-NMR analyzes, and data are as follows:
1HNMR (600MHz, CDCl
3, ppm)
δ：0.88 (t,
J = 7.2, 9H,CH
3), 1.02 (s, 3H, CH
3), 1.26-1.31 (m, 36H, (CH
2)
6), 1.37-1.45 (m, 6H, CH
2), 1.70-1.81 (m, 6H, CH
2), 3.26 (d，
J= 8.4 Hz, 3H, CH
2), 3.65 (d,
J= 8.4 Hz, 3H, CH
2), 3.81-3.83 (m, 3H, CH)。
Claims (1)
1. be the preparation method of three sub-surface activating agents connecting base with 1,1,1-tri-(methylol) ethane, the structural formula that to it is characterized in that with 1,1,1-tri-(methylol) ethane be the three sub-surface activating agents connecting base is:
n=5、7、9
Above-mentioned is that the preparation method of three sub-surface activating agents connecting base is prepared according to the following steps with 1,1,1-tri-(methylol) ethane:
(1) synthesis of alpha-brominated carboxylic acid
Under nitrogen protection, in the dry there-necked flask of 100 mL that reflux condensing tube, dropping funel, rotor and emission-control equipment are housed, add aliphatic acid and be slowly heated to solid thawing, then slowly thionyl chloride is dripped under stirring at 55-60 DEG C, aliphatic acid acid is 1.0:1.3 with the mol ratio of thionyl chloride, is heated to 80 DEG C after mixing, reaction 1 ~ 2 h, till not having waste gas to release, reduce pressure away excessive thionyl chloride; Then under agitation slowly drip bromine (about 4 h dropwise) in 80 DEG C, under remaining on 80 DEG C of conditions, continue reaction 12 h; Poured in frozen water by reactant liquor after reaction terminates, then add extraction into ethyl acetate, organic phase uses anhydrous magnesium sulfate drying 5-6 h with after distilled water washing, and decompression distillation removing low boiling component obtains crude product; Crude product can be collected through decompression distillation and obtain the alpha-brominated carboxylic acid of clear yellow viscous liquid;
(2) esterification
Under nitrogen protection, sodium hydride is added in 100 mL there-necked flasks of drying, the oxolane that 5 mL are dried, after stirred at ambient temperature 10 min, then in there-necked flask, 1 is dripped, 1, the oxolane mixed liquor of 1-tri-(methylol) ethane and 10 mL dryings, 1, 1, the mol ratio of 1-tri-(methylol) ethane and sodium hydride is 1.0:3.3, at room temperature continue stirring reaction 1 h, reaction unit is moved in ice-water bath, the oxolane mixed liquor of the alpha-brominated acid of fast drop and 5 mL dryings in reaction bulb, the mol ratio of alpha-brominated acid and sodium hydride is 1.0:1.0, stirring 0.5 h is continued under ice-water bath, then reaction unit is moved in oil bath and be warming up to 65 DEG C, backflow 23-25 h, question response liquid is cooled to room temperature, add distilled water to rock in reactant liquor and make it mix, revolve steaming removing tetrahydrofuran solvent and obtain remaining liq, surplus solution pH to 1 ~ 2 are regulated with watery hydrochloric acid, be extracted with ethyl acetate, merge organic phase and use anhydrous magnesium sulfate drying 5-6 h, filter, except desolventizing, obtain clear yellow viscous liquid intermediate compound I, obtained clear yellow viscous liquid intermediate compound I joined in 100mL there-necked flask, then add 15 mL methyl alcohol, the concentrated sulfuric acid makes catalyst, is heated to 65 DEG C under stirring, and reaction stopped after reaction 14-16 h, reaction bulb moves in ice-water bath, adds NaHCO
3solid neutralisation of sulphuric acid, revolve and steam the excessive methyl alcohol of removing, add distilled water, be extracted with ethyl acetate, merge organic phase dried over mgso 3-4 h, filtration, except desolventizing, gained crude on silica gel column chromatography for separation, eluant, eluent is V (ethyl acetate): V (benzinum), collects after merging same composition concentrated, can obtain colorless viscous liquid intermediate II,
(3) ester hydrolysis reaction
Intermediate is added in 100mL there-necked flask
, then add the oxolane of 10 mL dryings, add the sodium hydrate aqueous solution of a certain amount of 30%, after back flow reaction 5-8 h, except desolventizing, in crude product, add distilled water, and use washed with dichloromethane water layer, decompression distillation, except after anhydrating, is placed in refrigerator crystallization, centrifugation, solid, in 60 DEG C of vacuum drying 5-7 h, obtains white solid, and namely 1,1,1-tri-(methylol) ethane is for connecting base three sub-surface activating agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410585810.8A CN104645876B (en) | 2014-10-28 | 2014-10-28 | 1,1,1-tri-(methylol) ethane is for connecting base three sub-surface promoting agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410585810.8A CN104645876B (en) | 2014-10-28 | 2014-10-28 | 1,1,1-tri-(methylol) ethane is for connecting base three sub-surface promoting agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104645876A true CN104645876A (en) | 2015-05-27 |
| CN104645876B CN104645876B (en) | 2016-04-20 |
Family
ID=53237811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410585810.8A Expired - Fee Related CN104645876B (en) | 2014-10-28 | 2014-10-28 | 1,1,1-tri-(methylol) ethane is for connecting base three sub-surface promoting agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104645876B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019136782A1 (en) * | 2018-01-11 | 2019-07-18 | 西南石油大学 | Tri-cationic viscoelastic surfactant, preparation method therefor, application thereof and clean fracturing fluid |
| CN114773579A (en) * | 2022-06-02 | 2022-07-22 | 江西百盛精细化学品有限公司 | Solvent-free epoxy curing agent and preparation method thereof |
| CN115530133A (en) * | 2022-04-25 | 2022-12-30 | 安徽宏飞钓具有限公司 | Fishhook processing technology for improving surface glossiness of fishhook |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3860425A (en) * | 1971-08-25 | 1975-01-14 | Fuji Photo Film Co Ltd | Dispersion containing nonionic surface acting agent with units of polyoxyethylene and polyoxypropylene |
| JPH04268397A (en) * | 1991-02-25 | 1992-09-24 | Kao Corp | Detergent composition |
| CN101618300A (en) * | 2009-08-05 | 2010-01-06 | 中北大学 | Trimerization anion surface active agent |
| CN101745341A (en) * | 2009-12-18 | 2010-06-23 | 齐齐哈尔大学 | Gemini surface active agent and preparation method thereof |
| CN102389746A (en) * | 2011-10-10 | 2012-03-28 | 西南石油大学 | Sulfonate trimeric surfactant and preparation method thereof |
-
2014
- 2014-10-28 CN CN201410585810.8A patent/CN104645876B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3860425A (en) * | 1971-08-25 | 1975-01-14 | Fuji Photo Film Co Ltd | Dispersion containing nonionic surface acting agent with units of polyoxyethylene and polyoxypropylene |
| JPH04268397A (en) * | 1991-02-25 | 1992-09-24 | Kao Corp | Detergent composition |
| CN101618300A (en) * | 2009-08-05 | 2010-01-06 | 中北大学 | Trimerization anion surface active agent |
| CN101745341A (en) * | 2009-12-18 | 2010-06-23 | 齐齐哈尔大学 | Gemini surface active agent and preparation method thereof |
| CN102389746A (en) * | 2011-10-10 | 2012-03-28 | 西南石油大学 | Sulfonate trimeric surfactant and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YUN-PENG ZHU ET AL.: "Preparation and Properties of Glycerol-Based Double- or Triple- Chain Surfactants with Two Hydrophilic Ionic Groups", 《JAOCS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019136782A1 (en) * | 2018-01-11 | 2019-07-18 | 西南石油大学 | Tri-cationic viscoelastic surfactant, preparation method therefor, application thereof and clean fracturing fluid |
| US10870790B2 (en) | 2018-01-11 | 2020-12-22 | Southwest Petroleum University | Tri-cationic viscoelastic surfactant, preparation method and application thereof and clean fracturing fluid |
| CN115530133A (en) * | 2022-04-25 | 2022-12-30 | 安徽宏飞钓具有限公司 | Fishhook processing technology for improving surface glossiness of fishhook |
| CN115530133B (en) * | 2022-04-25 | 2024-04-02 | 安徽宏飞钓具有限公司 | Fishhook processing technology for improving glossiness of fishhook surface |
| CN114773579A (en) * | 2022-06-02 | 2022-07-22 | 江西百盛精细化学品有限公司 | Solvent-free epoxy curing agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104645876B (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hu | Nucleophilic, radical, and electrophilic (phenylsulfonyl) difluoromethylations | |
| CN100355732C (en) | Preparation of 2-Cl-5-F-nicotinate and nicotonic acid | |
| CN101502772B (en) | Colophony-based sulphonate type gemini surfactant and method for preparing the same | |
| CN103611471B (en) | One class contains carboxylate surface active agent of aromatic group and preparation method thereof | |
| CN104645876A (en) | Ternary surface active agent adopting 1,1,1-tri(hydroxymethyl) ethane as link group, and preparation method of ternary surface active agent | |
| CN106365986B (en) | Compound and preparation method thereof and the purposes in synthesis Bu Waxitan | |
| CN101585519B (en) | Method for preparing <15>N-hydroxylamine hydrochloride by hydrolyzing <15>N-nitromethane | |
| CN109824472A (en) | novel method for synthesizing gem-difluoroalkane and α -fluorocarboxylic acid | |
| CN100543004C (en) | 1,7,8-three fluoro-beta naphthals and the preparation method who utilizes its liquid crystalline cpd | |
| CN101480590A (en) | Sulphonate Gemini surfactant and preparation method thereof | |
| CN109053443A (en) | The bromo- 3- aldehyde radical-phenoxy group of 4-(4-)-benzonitrile synthetic method | |
| CN102964268A (en) | Synthesis method of menthyl amide cooling agent | |
| CN104817479A (en) | Preparation technology optimization method of biomass surfactant for oil displacement | |
| CN107674074A (en) | A kind of preparation method and application of amphipathic naphthoyl diimine gelator | |
| CN101745341B (en) | Gemini surface active agent and preparation method thereof | |
| CN103694117B (en) | Method for preparing Asiatic corn borer sex pheromone from tridecane compound | |
| CN104974017B (en) | The preparation method of (1R, 2S) 2 (3,4 difluorophenyl) cyclopropylamine D mandelates | |
| CN102827002A (en) | Chemical full-synthetic method of salvinanolic acid A | |
| CN111454315B (en) | Synthesis method of androstane-16-alkene-3 beta-alcohol | |
| CN107815321A (en) | The preparation method of lateral o-difluoro-benzene class liquid-crystal compounds containing cyclohexyl | |
| CN101792434B (en) | Preparation method of tetra-acylated puerarin | |
| CN102093257B (en) | Method for preparing 2,2-diisopropylpropionitrile | |
| CN103626649B (en) | A kind of method preparing Pelretin acid | |
| CN102531865B (en) | Preparation method of 1-(2,6,6-trimethylcyclohex-3-enyl) butyl-2-en-1-one | |
| CN1328233C (en) | Process for synthesizing 4-[2-(trans-4-alkyl-cyclohexyl)ethyl] phenol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160420 Termination date: 20161028 |