CN104478705B - The former medicine of a kind of copper rosinate, preparation method and application - Google Patents
The former medicine of a kind of copper rosinate, preparation method and application Download PDFInfo
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- CN104478705B CN104478705B CN201410633264.0A CN201410633264A CN104478705B CN 104478705 B CN104478705 B CN 104478705B CN 201410633264 A CN201410633264 A CN 201410633264A CN 104478705 B CN104478705 B CN 104478705B
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- copper rosinate
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000010949 copper Substances 0.000 title claims abstract description 129
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 129
- 239000003814 drug Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 42
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 42
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000007599 discharging Methods 0.000 claims abstract description 13
- 150000007524 organic acids Chemical class 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 45
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 229960000583 acetic acid Drugs 0.000 claims description 18
- 239000012362 glacial acetic acid Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006555 catalytic reaction Methods 0.000 claims description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 13
- 239000005750 Copper hydroxide Substances 0.000 claims description 13
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 12
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- 229960003280 cupric chloride Drugs 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 21
- 238000010992 reflux Methods 0.000 abstract description 12
- 238000009472 formulation Methods 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 12
- 238000011084 recovery Methods 0.000 description 9
- 239000004563 wettable powder Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 239000003899 bactericide agent Substances 0.000 description 4
- 230000000855 fungicidal effect Effects 0.000 description 4
- 239000000417 fungicide Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 239000000375 suspending agent Substances 0.000 description 4
- 241000193738 Bacillus anthracis Species 0.000 description 3
- 208000035143 Bacterial infection Diseases 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 208000022362 bacterial infectious disease Diseases 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- -1 polyoxyethylene Polymers 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000002566 Capsicum Nutrition 0.000 description 1
- 240000008574 Capsicum frutescens Species 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 208000031888 Mycoses Diseases 0.000 description 1
- 241000896238 Oidium Species 0.000 description 1
- 208000008469 Peptic Ulcer Diseases 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 241000952063 Polyphagotarsonemus latus Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000918585 Pythium aphanidermatum Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241001454295 Tetranychidae Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 230000001741 anti-phlogistic effect Effects 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001390 capsicum minimum Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- BCYMZMFCJMHEBD-JHZYRPMRSA-L copper;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Cu+2].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O.C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O BCYMZMFCJMHEBD-JHZYRPMRSA-L 0.000 description 1
- 238000012272 crop production Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- AKBMZGDBKBJCRQ-UHFFFAOYSA-N dodecyl naphthalene-1-sulfonate Chemical class C1=CC=C2C(S(=O)(=O)OCCCCCCCCCCCC)=CC=CC2=C1 AKBMZGDBKBJCRQ-UHFFFAOYSA-N 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000000069 prophylactic effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the former medicine of a kind of copper rosinate and preparation method, the former medicine of described copper rosinate is made up of the component of following weight part: 10-80 part rosin, 1-40 part Inorganic Copper, 1-40 part organic acid, 2-50 part organic solvent, 0.01-0.5 part catalyzer; Preparation method is: 10-80 weight part rosin, 2-50 weight parts organic solvent and 1-40 weight part organic acid are mixed, be added in the reactor of airtight band vacuum back-flow device, heated and stirred, after rosin dissolves completely, add 1-40 parts by weight of inorganic copper, then add 0.01-0.5 part by weight of catalyst, temperature rising reflux reacts, reclaim refluxer, discharging, cooling obtains the former medicine of copper rosinate.Apply the former medical instrument of copper rosinate that copper rosinate former medicine synthesizing formula involved in the present invention and preparation method obtain have content high, be applicable to prepare the advantages such as multiple formulation copper rosinate sterilant product.
Description
Technical field
The present invention relates to pesticide field, relate to the former medicine of a kind of copper rosinate, preparation method and application specifically.
Background technology
Copper agent sterilant, have the Application and Development time the earliest, duration of service is the longest, use the features such as area is maximum, sterilization effect good, purposes is wide.This series bactericidal agent can prevent and treat fungal disease, can prevent and treat bacterial disease again; Existing provide protection, has prophylactic effect again, and has certain treatment and eradicant action concurrently; Both can be used for healing wound, also may be used for bactericidal antiphlogistic.Mainly be divided into inorganic copper fungicide and organic copper sterilant.But there is a problem that can not be ignored in the long-term inorganic copper fungicide that uses continuously, namely easily brings out mite class propagation and cause mite class to cause harm.According to knowhow for many years, the angular leaf spot of life-time service inorganic copper fungicide control cotton, seedling stage anthrax, damping-off, easily cause cotton spider mites early to send out, multiple, cause cotton to fall leaves " collapse stalk "; For beans, the vegetables such as capsicum, tomato, eggplant, when using inorganic copper fungicide to prevent and treat epidemic disease, anthrax, bacterial wilt etc., easily cause yellow tea mite to lay eggs in a large number, breed, and cause that blade is withered to come off.And easily produce poisoning in the use procedure of Inorganic Copper reagent, thus affect crop production and good harvest.
In organic copper sterilant, modal one is copper rosinate series bactericidal agent.Copper rosinate (copperabietate), assumed name claims 1,2,3,4,4a, 9,10,10a-octahydro-Isosorbide-5-Nitrae a-dimethyl-7-(1-methylethyl)-1-phenanthrene carboxylic acid copper, and structural formula is:
Copper rosinate is the most efficient organic copper sterilant, good preventive and therapeutic action is had to fungi, bacterial disease, having good prevention effect to tens kinds of diseases such as Peptic Ulcers, epidemic disease, oidium, anthrax, blight, leaf spot, root rot, rust, is a kind of new and effective wide-spectrum bactericide.Copper rosinate has very strong tackiness, spread and perviousness, resistance of rainwater washing against, to plant safety, does not produce poisoning, nuisanceless, noresidue, low to person poultry toxicity.To plant safety, not easily producing poisoning, is a kind of new and effective sterilant having very much application value.
The former medicine of copper rosinate refers to the material medicine for the production of copper rosinate class pesticide preparation, is effective ingredient wherein.At present, not yet find Patents and the bibliographical information of copper rosinate former medicine synthesis, the former medicine content of current domestic copper rosinate is up to 35%, and formulation is emulsus, thus limits copper rosinate and make wettable powder and high-content formulation.
The former medicine of block copper rosinate of the present invention's synthesis, wherein the content of copper rosinate is up to more than 89%, is more suitable for the copper rosinate sterilant product preparing the multiple formulation of high-content, fills up blank that is international, domestic fields.Production process of the present invention is raw materials used is rosin, copper hydroxide, organic appearance agent, organic acid, catalyzer, and the water wherein having solvent and reaction to generate is recyclable to be used again.The present invention produces without waste residue, waste gas, waste water in process of production.Rosin is renewable resources, and this also ensures that resource is stablized.So product of the present invention is environmentally friendly product.
Summary of the invention
Technical problem to be solved by this invention is, in view of the single and problem that copper rosinate content is low of the former pharmaceutically dosage form of copper rosinate in prior art, the former medicine synthesizing formula of a kind of copper rosinate and preparation method are provided, improve the content of copper rosinate in the former medicine of copper rosinate by technology and control, material choice, composition of raw materials selection and prepared the former medicine of block copper rosinate.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: the former medicine of a kind of copper rosinate, is prepared by the component of following weight part: 10-80 weight part rosin, 1-40 parts by weight of inorganic copper, 1-40 weight part organic acid, 2-50 weight parts organic solvent, 0.01-0.5 part by weight of catalyst.
Described Inorganic Copper is one or more in copper hydroxide, copper sulfate, cupric chloride.
Described organic acid is one or more in glacial acetic acid, formic acid, citric acid.
Described organic solvent is one or more in dimethylbenzene, toluene, trimethylbenzene, purified petroleum benzin.
Described catalyzer is two or more in sulfuric acid, ethanol, glacial acetic acid, water, hydrochloric acid.
Apply the former medicament preparation of copper rosinate of above-mentioned copper rosinate former medicine synthesizing formula, it is characterized in that, comprise the following steps:
1) take 10-80 weight part rosin, 2-50 weight parts organic solvent, 1-40 weight part organic acid, add in the reactor with vacuum back-flow device, start reflux, 50-80 DEG C of heated and stirred, mixes, and rosin is dissolved completely;
2) add 1-40 parts by weight of inorganic copper, add 0.01-0.5 part by weight of catalyst, heated and stirred, carry out catalyzed reaction, the temperature of reaction of catalyzed reaction is 120 DEG C-170 DEG C, and the reaction times is 4-5 hour;
3) after reclaiming phlegma completely, discharging;
4) cool, obtain the former medicine of block copper rosinate.
The invention has the beneficial effects as follows:
1) the present invention uses rosin for raw material, and rosin belongs to renewable resources, produces in process of production without waste residue, waste gas, waste gas;
2) formulation of the former medicine of the copper rosinate prepared by the present invention is blocks of solid and copper rosinate content is high, the former medicine of copper rosinate of the present invention can be passed through, prepare the copper rosinate series bactericidal agent of the high-content of any formulation, such as utilize copper rosinate of the present invention former medicine quality of production mark 35% copper rosinate suspension agent, massfraction 20% copper rosinate wettable powder, massfraction 20% copper rosinate missible oil;
3) to plant safety, not easily there is poisoning in the former medicine of the copper rosinate prepared by the present invention, can also make micro-fertilizer simultaneously and mend copper effect, be conducive to the high yield of crop to plant.
On the basis of technique scheme, the present invention can also do following improvement.
Further, the former medicine of described copper rosinate can make suspension agent, aqueous emulsion, water dispersible granules, microemulsion or wettable powder.
Adopt the beneficial effect of above-mentioned further scheme to be that former for copper rosinate medicine is prepared into organic copper sterilant, be widely used in the prevention and therapy to fungi, bacterial disease.
Embodiment
Be described principle of the present invention and feature below, example, only for explaining the present invention, is not intended to limit scope of the present invention.
The former medicine of a kind of copper rosinate, is prepared by the component of following weight part: 10-80 weight part rosin, 1-40 parts by weight of inorganic copper, 1-40 weight part organic acid, 2-50 weight parts organic solvent, 0.01-0.5 part by weight of catalyst; Described Inorganic Copper is one or more in copper hydroxide, copper sulfate, cupric chloride; Described organic acid is one or more in glacial acetic acid, formic acid, citric acid; Described organic solvent is one or more in dimethylbenzene, toluene, trimethylbenzene, purified petroleum benzin; Described catalyzer is two or more in sulfuric acid, ethanol, glacial acetic acid, water, hydrochloric acid.
The former medicament preparation of a kind of copper rosinate, is characterized in that, comprise the following steps:
1) take 10-80 weight part rosin, 2-50 weight parts organic solvent, 1-40 weight part organic acid, mix, add in the reactor with vacuum back-flow device, start reflux, 50-80 DEG C, heated and stirred, makes rosin dissolve completely;
2) add 1-40 parts by weight of inorganic copper, add 0.01-0.5 part by weight of catalyst, heated and stirred, carry out catalyzed reaction, 120 DEG C-170 DEG C, the reaction times is 4-5 hour;
3) after reclaiming phlegma completely, discharging;
4) cool, obtain the former medicine of block copper rosinate.
Kilogram corresponding with embodiment of parts by weight wherein described above.
Embodiment 1
The former medicine of a kind of copper rosinate, is prepared by the raw material of following weight: 10kg rosin, 30kg formic acid, 20kg purified petroleum benzin, 10kg dimethylbenzene, 29.9kg copper sulfate, 0.1kg catalyzer (according to volume ratio, ethanol: water=12: 80 preparations).
The former medicament preparation of a kind of copper rosinate, comprises the following steps:
1) take 10kg rosin, 20kg purified petroleum benzin, 10kg dimethylbenzene, 30kg formic acid, mix, add in the reactor with vacuum back-flow device, start reflux, heated and stirred, makes rosin dissolve completely to 80 DEG C;
2) add 29.9kg copper sulfate, add 0.1kg catalyzer, heated and stirred, carry out catalyzed reaction, 120 DEG C, the reaction times is 5 hours;
3) phlegma is reclaimed with the recovery speed of 3kg/h, discharging;
4) cool, obtain the former medicine 12kg of block copper rosinate, wherein the massfraction of copper rosinate is 96%.
Embodiment 2
The former medicine of a kind of copper rosinate, is prepared by the raw material of following weight: 40kg rosin, 20kg glacial acetic acid, 10kg formic acid, 20kg toluene, 9.95kg copper hydroxide, 0.05kg catalyzer (according to volume ratio, sulfuric acid: water=2: 80 preparations).
The former medicament preparation of a kind of copper rosinate, comprises the following steps:
1) take 40kg rosin, 20kg glacial acetic acid, 10kg formic acid, 20kg toluene, mix, add in the reactor with vacuum back-flow device, start reflux, heated and stirred, makes rosin dissolve completely to 80 DEG C;
2) add 9.95kg copper hydroxide, 0.05kg catalyzer, heated and stirred, carry out catalyzed reaction, 150 DEG C, the reaction times is 4.5 hours;
3) phlegma is reclaimed with the recovery speed of 3kg/h, discharging;
4) cool, obtain the former medicine 50kg of block copper rosinate, wherein the massfraction of copper rosinate is 95.8%.
Embodiment 3
The former medicine of a kind of copper rosinate, is prepared by the raw material of following weight: 80kg rosin, 1kg citric acid, 5kg dimethylbenzene, 13.5kg cupric chloride, 0.5kg catalyzer (according to volume ratio, hydrochloric acid: water=15: 80 preparations).
The former medicament preparation of a kind of copper rosinate, comprises the following steps:
1) take 80kg rosin, 1kg citric acid, 5kg dimethylbenzene, mix, add in the reactor with vacuum back-flow device, start reflux, heated and stirred, makes rosin dissolve completely to 80 DEG C;
2) add 13.5kg cupric chloride, 0.5kg catalyzer, heated and stirred, carry out catalyzed reaction, 170 DEG C, the reaction times is 4 hours;
3) phlegma is reclaimed with the recovery speed of 3kg/h, discharging;
4) cool, obtain the former medicine 90kg of block copper rosinate, wherein the massfraction of copper rosinate is 92%.
Embodiment 4
The former medicine of a kind of copper rosinate, prepared by the raw material of following weight: 51.7kg rosin, 8kg citric acid, 10kg glacial acetic acid, 1kg dimethylbenzene, 1kg toluene, 28.26kg copper sulfate, 0.04kg catalyzer (according to volume ratio, sulfuric acid: water: ethanol=10: 40: 10 preparations).
The former medicament preparation of a kind of copper rosinate, comprises the following steps:
1) take 51.7kg rosin, 8kg citric acid, 10kg glacial acetic acid, 1kg dimethylbenzene, 1kg toluene, mix, add in the reactor with vacuum back-flow device, start reflux, heated and stirred, makes rosin dissolve completely to 80 DEG C;
2) add 28.26kg copper sulfate, add 0.04kg catalyzer, heated and stirred, carry out catalyzed reaction, 120 DEG C, the reaction times is 5 hours;
3) phlegma is reclaimed with the recovery speed of 3kg/h, discharging;
4) cool, obtain the former medicine 60kg of block copper rosinate, wherein the massfraction of copper rosinate is 90%.
Embodiment 5
The former medicine of a kind of copper rosinate, prepared by the raw material of following weight: 31.7kg rosin, 20kg citric acid, 20kg glacial acetic acid, 20kg dimethylbenzene, 8.26kg copper hydroxide, 0.04kg catalyzer (according to volume ratio, sulfuric acid: water: glacial acetic acid=2: 80: 8 preparations).
The former medicament preparation of a kind of copper rosinate, comprises the following steps:
1) take 51.7kg rosin, 20kg citric acid, 20kg glacial acetic acid, 20kg dimethylbenzene, mix, add in the reactor with vacuum back-flow device, start reflux, heated and stirred, makes rosin dissolve completely to 80 DEG C;
2) add 8.26kg copper hydroxide, 0.04kg catalyzer, heated and stirred, carry out catalyzed reaction, 120 DEG C, the reaction times is 5 hours;
3) phlegma is reclaimed with the recovery speed of 3kg/h, discharging;
4) cool, obtain the former medicine 60kg of block copper rosinate, wherein the massfraction of copper rosinate is 89%.
Embodiment 6
The former medicine of a kind of copper rosinate, prepared by the raw material of following weight: 45kg rosin, 20kg citric acid, 20kg dimethylbenzene, 6.7kg purified petroleum benzin, 8.29kg copper hydroxide, 0.01kg catalyzer (according to volume ratio, hydrochloric acid: water: ethanol=10: 50: 10 preparations).
The former medicament preparation of a kind of copper rosinate, comprises the following steps:
1) take 45kg rosin, 20kg citric acid, 20kg dimethylbenzene, 6.7kg purified petroleum benzin, mix, add in the reactor with vacuum back-flow device, start reflux, heated and stirred, makes rosin dissolve completely to 80 DEG C;
2) add 8.29kg copper hydroxide, 0.01kg catalyzer, heated and stirred, carry out catalyzed reaction, 120 DEG C, the reaction times is 5 hours;
3) phlegma is reclaimed with the recovery speed of 3kg/h, discharging;
4) cool, obtain the former medicine 50kg of block copper rosinate, wherein the massfraction of copper rosinate is 96%.
Embodiment 7
The former medicine of a kind of copper rosinate, prepared by the raw material of following weight: 46kg rosin, 20kg citric acid, 20kg dimethylbenzene, 5kg cupric chloride, 8.7kg copper hydroxide, 0.3kg catalyzer (according to volume ratio, sulfuric acid: water: glacial acetic acid=2: 80: 8).
The former medicament preparation of a kind of copper rosinate, comprises the following steps:
1) take 46kg rosin, 20kg citric acid, 20kg dimethylbenzene, mix, add in the reactor with vacuum back-flow device, start reflux, heated and stirred, makes rosin dissolve completely to 80 DEG C;
2) add 5kg cupric chloride, 8.7kg copper hydroxide, 0.3kg catalyzer, heated and stirred, carry out catalyzed reaction, 120 DEG C, the reaction times is 5 hours;
3) phlegma is reclaimed with the recovery speed of 3kg/h, discharging;
4) cool, obtain the former medicine 55kg of block copper rosinate, wherein the massfraction of copper rosinate is 85%.
Embodiment 8
The former medicine of a kind of copper rosinate, is prepared by the raw material of following weight: 29.97kg rosin, 20kg glacial acetic acid, 10kg trimethylbenzene, 40kg copper sulfate, 0.03kg catalyzer (according to volume ratio, sulfuric acid: water: ethanol=10: 40: 10 preparations).
The former medicament preparation of a kind of copper rosinate, comprises the following steps:
1) take 29.97kg rosin, 20kg glacial acetic acid, 10kg trimethylbenzene, mix, add in the reactor with vacuum back-flow device, start reflux, heated and stirred, makes rosin dissolve completely to 80 DEG C;
2) add 40kg copper sulfate, add 0.03kg catalyzer, heated and stirred, carry out catalyzed reaction, 120 DEG C, the reaction times is 5 hours;
3) phlegma is reclaimed with the recovery speed of 3kg/h, discharging;
4) cool, obtain the former medicine 50kg of block copper rosinate, wherein the massfraction of copper rosinate is 94%.
Embodiment 9
The former medicine of a kind of copper rosinate, prepared by the raw material of following weight: 30.75kg rosin, 8kg citric acid, 10kg glacial acetic acid, 50kg dimethylbenzene, 1kg copper hydroxide, 0.25kg catalyzer (according to volume ratio, sulfuric acid: water: ethanol=10: 40: 10 preparations).
The former medicament preparation of a kind of copper rosinate, comprises the following steps:
1) take 30.75kg rosin, 8kg citric acid, 10kg glacial acetic acid, 50kg dimethylbenzene, mix, add in the reactor with vacuum back-flow device, start reflux, heated and stirred, makes rosin dissolve completely to 80 DEG C;
2) add 1kg copper sulfate, add 0.25kg catalyzer, heated and stirred, carry out catalyzed reaction, 120 DEG C, the reaction times is 5 hours;
3) phlegma is reclaimed with the recovery speed of 3kg/h, discharging;
4) cool, obtain the former medicine 32kg of block copper rosinate, wherein the massfraction of copper rosinate is 85%.
Embodiment 10: with obtained copper rosinate former medicine preparation quality mark 35% copper rosinate suspension agent
Take the former medicine of 37kg95% copper rosinate (massfraction of copper rosinate is 95%), 1kg calcium lignin sulphonate, 2kg aliphatic acid polyethenoxy base ester, 1kg urea, 1kg ethylene glycol, 4kg polyvinyl alcohol, 0.3kgC8-10 fatty alcohol, 51.7kg water, mix, stirring and dissolving adds 2kg dodecyl polyoxyethylene sulfonic acid sodium salt and carry out high speed shear emulsification, make massfraction 35% copper rosinate suspension emulsion, obtain massfraction 35% copper rosinate suspension agent 100kg.
Embodiment 11: with obtained copper rosinate former medicine preparation quality mark 20% copper rosinate wettable powder
Take the former medicine of 22kg copper rosinate (massfraction of copper rosinate is 95%), 8kg poly carboxylic acid sodium, 0.1kg dodecyl naphthalene sulfonate salt, 1kg pull open powder, 7kg starch, 31.9kg kaolin, 30kg white carbon black, mix, and carry out micronizing and make massfraction 20% copper rosinate wettable powder, obtain massfraction 20% copper rosinate wettable powder 100kg.
Embodiment 12: with obtained copper rosinate former medicine preparation quality mark 20% copper rosinate missible oil
Take the former medicine of 22kg copper rosinate (massfraction of copper rosinate is 95%), 5kg alkylpolyoxyethylene, 2kg polyoxyethylene aliphatic alcohol ether, 43kg solvent oil, 15kg turps, 7kg dimethylbenzene, mix and blend dissolves, add 6kg656T emulsifying agent again, make massfraction 20% copper rosinate missible oil, obtain massfraction 20% copper rosinate missible oil 100kg.
The foregoing is only section Example of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. the former medicament preparation of copper rosinate, is characterized in that, comprise the following steps:
1) take 10-80 weight part rosin, 2-50 weight parts organic solvent, 1-40 weight part organic acid, mix, heated and stirred, react, rosin is dissolved completely;
2) add 1-40 parts by weight of inorganic copper and 0.01-0.5 part by weight of catalyst, heated and stirred, carry out catalyzed reaction; Described catalyzer is the two or more mixing in sulfuric acid, ethanol, glacial acetic acid, water, hydrochloric acid;
3) refluxer is reclaimed, discharging;
4) cool, obtain the former medicine of copper rosinate.
2. the former medicament preparation of a kind of copper rosinate according to claim 1, is characterized in that, step 1) in, described reaction is carried out in the reactor with vacuum back-flow device.
3. the former medicament preparation of a kind of copper rosinate according to claim 1, is characterized in that, step 1) in, the temperature of described heating is 50 DEG C-80 DEG C.
4. the former medicament preparation of a kind of copper rosinate according to claim 1, is characterized in that, step 2) in, the temperature of reaction of described catalyzed reaction is 120 DEG C-170 DEG C, and the reaction times is 4-5 hour.
5. the former medicament preparation of a kind of copper rosinate according to any one of claim 1-4, is characterized in that, described Inorganic Copper is the mixing of one or more in copper hydroxide, copper sulfate, cupric chloride.
6. the former medicament preparation of a kind of copper rosinate according to any one of claim 1-4, is characterized in that, described organic acid is the mixing of one or more in glacial acetic acid, formic acid, citric acid.
7. the former medicament preparation of a kind of copper rosinate according to any one of claim 1-4, is characterized in that, described organic solvent is the mixing of one or more in dimethylbenzene, toluene, trimethylbenzene, purified petroleum benzin.
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Citations (4)
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|---|---|---|---|---|
| US3262846A (en) * | 1962-11-06 | 1966-07-26 | Tennessee Corp | Stable copper emulsion for controlling plant diseases |
| CN1034471A (en) * | 1988-01-26 | 1989-08-09 | 山西省运城地区夹马口管理局化工厂 | The production method of desinsection, plant growth regulator |
| CN1161780A (en) * | 1996-10-16 | 1997-10-15 | 黄迪辉 | High-effective copploid liquid and preparation method thereof |
| CN1241358A (en) * | 1999-02-16 | 2000-01-19 | 胡功卓 | Copper resinate bactericidal acaricide and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03229806A (en) * | 1990-02-06 | 1991-10-11 | Harima Chem Inc | Manufacture of metal fine particles |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3262846A (en) * | 1962-11-06 | 1966-07-26 | Tennessee Corp | Stable copper emulsion for controlling plant diseases |
| CN1034471A (en) * | 1988-01-26 | 1989-08-09 | 山西省运城地区夹马口管理局化工厂 | The production method of desinsection, plant growth regulator |
| CN1161780A (en) * | 1996-10-16 | 1997-10-15 | 黄迪辉 | High-effective copploid liquid and preparation method thereof |
| CN1241358A (en) * | 1999-02-16 | 2000-01-19 | 胡功卓 | Copper resinate bactericidal acaricide and preparation method thereof |
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Inventor after: Lan Hongyan Inventor after: He Lilian Inventor after: Tan Renjing Inventor after: Wei Qingshu Inventor after: Liang Yongxing Inventor after: Wei Wei Inventor after: Tan Renwei Inventor after: Deng Xinyi Inventor before: Lan Hongyan Inventor before: He Lilian Inventor before: Tan Renjing Inventor before: Wei Qingshu Inventor before: Liang Yongxing Inventor before: Wei Wei Inventor before: Tan Renwei Inventor before: Deng Xinyi |
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Denomination of invention: A copper turpentine raw material, preparation method and application Granted publication date: 20160427 Pledgee: Bank of China Limited Liuzhou Branch Pledgor: LIUZHOU HUINONG CHEMICALS CO.,LTD. Registration number: Y2024980042701 |