CN103570501B - Preparation method of bis-terpane-3,8-diol - Google Patents
Preparation method of bis-terpane-3,8-diol Download PDFInfo
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- CN103570501B CN103570501B CN201310577394.2A CN201310577394A CN103570501B CN 103570501 B CN103570501 B CN 103570501B CN 201310577394 A CN201310577394 A CN 201310577394A CN 103570501 B CN103570501 B CN 103570501B
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- menthane
- glycol
- reaction
- quaternary ammonium
- ammonium salt
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- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000006703 hydration reaction Methods 0.000 claims abstract description 12
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 12
- 244000165852 Eucalyptus citriodora Species 0.000 claims abstract description 10
- 235000004722 Eucalyptus citriodora Nutrition 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 claims description 10
- 229920005990 polystyrene resin Polymers 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000341 volatile oil Substances 0.000 claims description 6
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 claims description 5
- 241000134874 Geraniales Species 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 7
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 abstract 2
- 229930003633 citronellal Natural products 0.000 abstract 1
- 235000000983 citronellal Nutrition 0.000 abstract 1
- 238000007363 ring formation reaction Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LMXFTMYMHGYJEI-UHFFFAOYSA-N Menthoglycol Natural products CC1CCC(C(C)(C)O)C(O)C1 LMXFTMYMHGYJEI-UHFFFAOYSA-N 0.000 description 3
- 239000000077 insect repellent Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
- 241000255925 Diptera Species 0.000 description 2
- 244000166124 Eucalyptus globulus Species 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- LMXFTMYMHGYJEI-IWSPIJDZSA-N (1R,2R,5R)-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanol Chemical compound C[C@@H]1CC[C@@H](C(C)(C)O)[C@H](O)C1 LMXFTMYMHGYJEI-IWSPIJDZSA-N 0.000 description 1
- 241000985905 Candidatus Phytoplasma solani Species 0.000 description 1
- 241000256135 Chironomus thummi Species 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- 241000545744 Hirudinea Species 0.000 description 1
- MMOXZBCLCQITDF-UHFFFAOYSA-N N,N-diethyl-m-toluamide Chemical compound CCN(CC)C(=O)C1=CC=CC(C)=C1 MMOXZBCLCQITDF-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 241000710886 West Nile virus Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000009854 citriodiol Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000035597 cooling sensation Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 229960001673 diethyltoluamide Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003845 household chemical Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
- C07C29/05—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds with formation of absorption products in mineral acids and their hydrolysis
- C07C29/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds with formation of absorption products in mineral acids and their hydrolysis the acid being sulfuric acid
Abstract
The invention discloses a preparation method of bis-terpane-3,8-diol. According to the preparation method, eucalyptus citriodora oil and/or citronellal are/is taken as raw materials, immobilized quaternary ammonium salt is taken as a catalyst, and a cyclization hydration reaction is conducted in an acidic aqueous solution to prepare the bis-terpane-3,8-diol. The preparation method has the advantages of mild reaction conditions, short reaction time, and easy operation. The purity of prepared PMD can reach 80-98%; reaction products are easy in oil-water separation; the acidic aqueous solution can be recycled, so that the quantity of discharged waste water is small; the used raw materials are wide in source; the use amount of the catalyst is small; the raw materials are cheap and easy to obtain.
Description
Technical field
The present invention relates to the production field of p-menthane-3,8-glycol, be specifically related to a kind of production method of p-menthane-3,8-glycol.
Background technology
P-menthane-3,8-glycol, English name is p-Menthane-3,8-diol, Menthoglycol, is called for short PMD, is a kind of active ingredient for repellent, has the fragrance similar to menthol and cooling sensation.PMD has eight kinds of possible isomerss, and definite isomer seldom illustrates, and is commonly referred to be a kind of isomer mixt.
Containing a small amount of PMD in lemon-scented gum tree (Eucalyptus citriodora) essential oil, the modified PMD content that improves is for insect repellent.This modified oil is called by the U.S. " Oil of lemon eucalyptus (OLE) " or trade name is " Citriodiol ".Modification eucalyptus citriodora oil (OLE) is containing about 64%PMD (cis and trans isomers mixture), be called that " being rich in PMD vegetables oil (PMD rich botanic oil) " is announced, at the registration well afoot of safety and Health executive board of Britain (Health and Safety Executive) at European Union biocide instruction (BPD) 98/8/EC (now for European Union biocide regulation BPR Regulation (EU) No.528/212) with name.Pest management office of Canada (PMRA) is also seeking to be called that " PMD and eucalyptus citriodora oil related compound (PMD and related oil of lemon eucalyptus compounds) " is registered with name.PMD is the natural radioactivity component that unique a kind of US and European allows the insect repellent used.
PMD can stop to carry west nile virus (West Ni le Virus) the uniquely a kind of of mosquito and come from natural derivative.Research shows, when PMD and the DEET consumption of natural origin is identical, both repelling mosquitoes effects are the same.PMD except there is high reactivity and long-acting mosquito repellent characteristic, to the hematophagous buges such as midge, tick and thorn fly and leech effective equally.Then research demonstrates the nontoxicity of PMD, has antibacterial, antiviral effectiveness and distinctive fragrance and cooling, expand further its household chemicals, makeup, food, hospital's antiviral agent, Household disinfectant and medicinal in range of application.As p-menthane-3,8-glycol is used as coolant agent (PMD38or Coolact by nearest Japanese STOL company
) (Shiroyama; Kenichiro; Sawano; Kiyohito; Ohta; Hideaki, Cool feeling composition, United States Patent6,328,982, December11,2001.).
Summary of the invention
The object of the present invention is to provide a kind of production method of p-menthane-3,8-glycol, it can obtain p-menthane-3,8-glycol and yield is high by single step reaction.
For achieving the above object, the present invention is by the following technical solutions:
A kind of production method of p-menthane-3,8-glycol, its be with lemon-scented gum tree essential oil and/or geranial for raw material, with immobilized quaternary ammonium salt for catalyzer, in acidic aqueous solution, carry out cyclisation hydration reaction obtain p-menthane-3,8-glycol; Described immobilized quaternary ammonium salt be brominated polystyrene resin and Tributylamine carry out quaterisation obtain; To be the obtained low crosslinking degree polystyrene resin of vinylbenzene and divinylbenzene copolyreaction with Isosorbide-5-Nitrae-dibromobutane carry out brominated polystyrene resin that bromine alkylated reaction is obtained; Tetrabutyl amonium bromide resin anion(R.A) degree of crosslinking 7% in immobilized quaternary ammonium salt.Those skilled in the art to choose according to above-mentioned immobilized quaternary ammonium salt preparation method and this area the immobilized quaternary ammonium salt that different Tetrabutyl amonium bromide resin anion(R.A) degree of crosslinking produced by corresponding material ratio and initiator for the routine operation means grasped when raw material carries out copolyreaction, bromine alkylated reaction, quaterisation with resin.
Further scheme is:
The temperature of cyclisation hydration reaction is 60 ~ 65 DEG C, the time is 12 ~ 16h.
Cyclisation hydration reaction carries out neutralizing successively, drying, vacuum fractionation, freezing and crystallizing separating treatment obtain p-menthane-3,8-glycol finished product.
First phase-transfer catalyst is placed in acidic aqueous solution, stirs and be warming up to 60 ~ 65 DEG C, then slowly add lemon-scented gum tree essential oil and/or geranial carries out cyclisation hydration reaction.
The mass ratio of phase-transfer catalyst and raw material is 0.001 ~ 0.002:0.8 ~ 1.0.
Described acidic aqueous solution is 0.3% sulphuric acid soln.
The method tool that the present invention prepares natural PMD by lemon-scented gum tree essential oil and/or geranial has the following advantages:
1, reaction conditions of the present invention is gentle, and the reaction times is shorter, easy and simple to handle, and obtained PMD purity can reach 80 ~ 98%;
2, reaction product of the present invention is easy to Oil-water separation, and acidic aqueous solution can be recycled, and wastewater discharge is few;
3, the present invention uses raw material sources wide, and catalyst levels is few, and cheap and easy to get.
Embodiment
In order to make objects and advantages of the present invention clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.Described immobilized quaternary ammonium salt be brominated polystyrene resin and Tributylamine carry out quaterisation obtain; To be the obtained low crosslinking degree polystyrene resin of vinylbenzene and divinylbenzene copolyreaction with Isosorbide-5-Nitrae-dibromobutane carry out brominated polystyrene resin that bromine alkylated reaction is obtained; Tetrabutyl amonium bromide resin anion(R.A) degree of crosslinking 7% in immobilized quaternary ammonium salt.
Embodiment:
Take acidic aqueous solution 1 part by mass fraction listed in table 1, immobilized quaternary ammonium salt 0.001 ~ 0.002 part is mixed in the reactor of tool whipping appts; Mixing solutions is stirred and heats up, then slowly add lemon-scented gum tree essential oil by deal listed in table 1 or geranial carries out cyclisation hydration reaction, after reaction terminating, adopt component and PMD content in gc analysis reaction product, calculate PMD yield; Reaction product is separated through neutralization, drying, vacuum fractionation, freezing and crystallizing, measures purity and the yield of PMD product.Operate 15 groups as stated above, the concrete outcome of each operation is as shown in table 1:
Wherein: after 01 ~ 04 group of mixing solutions stirs and heats up, temperature is 60 DEG C, and the time of cyclisation hydration reaction is 16h; After 05 ~ 08 group of mixing solutions stirs and heats up, temperature is 65 DEG C, and the time of cyclisation hydration reaction is 12h; After 09 ~ 12 group of mixing solutions stirs and heats up, temperature is 63 DEG C, and the time of cyclisation hydration reaction is 14h; After 13 groups of mixing solutionss stir and heat up, temperature is 14 DEG C, and the time of cyclisation hydration reaction is 15h.
Table 1 is the result of above-mentioned 15 groups of operations
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles 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 (2)
1. a p-menthane-3, the production method of 8-glycol, be the ratio of 0.001 ~ 0.002: 0.8 ~ 1.0 in the mass ratio of catalyzer and raw material, first immobilized quaternary ammonium salt catalyst being placed in concentration is 0.3% sulphuric acid soln, stirring is warming up to 60 ~ 65 DEG C, then slowly adds lemon-scented gum tree essential oil and/or geranial carries out cyclisation hydration reaction, reaction 12 ~ 16h, obtained p-menthane-3,8-glycol; Described immobilized quaternary ammonium salt be brominated polystyrene resin and Tributylamine carry out quaterisation obtain; To be the obtained low crosslinking degree polystyrene resin of vinylbenzene and divinylbenzene copolyreaction with Isosorbide-5-Nitrae-dibromobutane carry out brominated polystyrene resin that bromine alkylated reaction is obtained; Tetrabutyl amonium bromide resin anion(R.A) degree of crosslinking 7% in immobilized quaternary ammonium salt.
2. the production method of p-menthane-3,8-glycol as claimed in claim 1, is characterized in that: cyclisation hydration reaction carries out neutralizing successively, drying, vacuum fractionation, freezing and crystallizing separating treatment obtain p-menthane-3,8-glycol finished product.
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|---|---|---|---|
| CN201310577394.2A CN103570501B (en) | 2013-11-19 | 2013-11-19 | Preparation method of bis-terpane-3,8-diol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310577394.2A CN103570501B (en) | 2013-11-19 | 2013-11-19 | Preparation method of bis-terpane-3,8-diol |
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| Publication Number | Publication Date |
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| CN103570501A CN103570501A (en) | 2014-02-12 |
| CN103570501B true CN103570501B (en) | 2015-07-22 |
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| CN104262108A (en) * | 2014-09-24 | 2015-01-07 | 厦门琥珀香料有限公司 | Preparation method of high-purity trans-p-menthane-3,8-diol |
| CN105052925A (en) * | 2015-07-31 | 2015-11-18 | 常州宁录生物科技有限公司 | Composition with mosquito repelling activity |
| CN105211115B (en) * | 2015-11-05 | 2019-04-26 | 厦门琥珀日化科技股份有限公司 | A kind of natural liquid and the preparation method and application thereof |
| CN106380377A (en) * | 2016-09-07 | 2017-02-08 | 张家港威胜生物医药有限公司 | Preparation method of syn-p-menthyl-3,8-diol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103193598A (en) * | 2013-03-15 | 2013-07-10 | 彭学东 | Oriented synthesis preparation process of cis-form p-menthane-3,8-diol |
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| DK2200430T3 (en) * | 2007-09-13 | 2014-06-30 | Chemian Technology Ltd | Composition containing p-menthan-3,8-diol and its use as insect repellant |
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| CN103193598A (en) * | 2013-03-15 | 2013-07-10 | 彭学东 | Oriented synthesis preparation process of cis-form p-menthane-3,8-diol |
Non-Patent Citations (2)
| Title |
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| 三相相转移催化剂催化合成N-乙基间甲苯胺的研究;谭晓军;《广东化工》;19991231(第1期);第24-25页 * |
| 固载相转移催化剂催化合成1,4-二氢-2,6-二甲基-3,5-吡啶二甲酸二乙酯;陆绍荣;《化学研究》;20030630;第14卷(第2期);第50-52页 * |
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