CN1833494A - Prepn. of 1-methyl cyclopropene stable inclusion compound for fresh keeping of fruits and vegetables - Google Patents
Prepn. of 1-methyl cyclopropene stable inclusion compound for fresh keeping of fruits and vegetables Download PDFInfo
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- CN1833494A CN1833494A CN 200610042683 CN200610042683A CN1833494A CN 1833494 A CN1833494 A CN 1833494A CN 200610042683 CN200610042683 CN 200610042683 CN 200610042683 A CN200610042683 A CN 200610042683A CN 1833494 A CN1833494 A CN 1833494A
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Abstract
A stable inclusion compound for the antistaling purpose of fruit, vegetable, flower, plant, etc. is prepared from 1-methyl cyclopropene, starch and alpha-cyclodextrin or its derivative by using of a reaction system, which is composed of 1-methyl cyclopropene generator, three-pass gas washing unit, inclusion reactor and tail gas absorbing unit.
Description
Technical field
The invention belongs to the preservation technique field, be specifically related to the preparation method that a kind of 1-methyl cyclopropene that is used for the fruits and vegetables flower freshness is stablized inclusion complex.
Technical background
At present China is less through the fruit and vegetable ratio of antistaling storing, because Preservation Treatment is bad, the consumption rate that causes fruit every year is 20%～25%, the proportion of goods damageds in vegetables every year then nearly 30%, the more than one hundred million tons of the waste of annual fruits and vegetables.Simultaneously, along with improving constantly of people's quality of life, common people wish can both have throughout the year fresh good to eat fruit and vegetable, with dress up oneself living environment of fresh flower, the preservation technique of fruit and vegetable fresh flower arises at the historic moment, and some preservation techniques that fall behind are difficult to satisfy the requirement in market at present.
Ethene is the ripe old and feeble hormone of generally acknowledging, it is playing the part of important role in the ripening and senescence of especially transition type of fruit fruit.Promote artificially or the biosynthesis of ethene suppressing, can quicken effectively or the ripening and senescence process of delayed fruit.Therefore, in order to prolong the preservation and freshness life-span of fruit, suppress the synthetic of its endogenous ethylene as much as possible or stop ethene to play a role just to seem very necessary.In recent years, along with silver thiosulfate (STS), 2, the discovery of ethylene receptor inhibitor such as 5-norbornadiene, diazonium cyclopentadiene, cyclopropene is for the ripe aging of controlling fruit provides new technological means.1-methyl cyclopropene (1-MCP) is a cyclopropene compound, be a kind of novel ethylene receptor inhibitor of finding recently, it can irreversibly act on ethylene receptor, thereby blocking-up combines with the normal of ethene, suppresses a series of biochemical reactions relevant with the fruit after-ripening that it is induced.Abroad, 1-MCP is used widely as flower antistaling agent, but the application on fruits and vegetables is just at the early-stage, because it has nontoxic, low amount, advantage such as efficient, can block the physiological effect of endogenous ethylene consumingly, thereby vast potential for future development is arranged on fruit storage.
The structure of 1-methyl cyclopropene is the cyclopropylene with 1 methyl, is a kind of reaction that enliven very much, easy, very unsettled colourless gas, 4.68 ℃ of boiling points.The 1-methylcyclopropene gas can be decomposed after generation immediately, generally can only exist about two hours under the normal temperature, even the stable existence time also is no more than 48 hours under the liquid nitrogen condition, and when surpassing finite concentration or pressure, it can blast, therefore, can not separate with the form of pure product or the former medicine of high concentration and handle the 1-methyl cyclopropene in manufacture process, itself can't exist as a kind of product (pure product or former medicine) separately, can not adopt conventional method to store.
At present mainly adopt the inclusion method that this material is settled out to the use of 1-methyl cyclopropene.And the inclusion process also is one of difficult point of 1-methyl cyclopropene inclusion body formation.It is the inclusion material with modified starch and molecular sieve that Gao Rongtao etc. disclose a kind of, adopts complex coacervation to prepare the patent (Chinese patent, publication number CN1711836A) that microcapsules are used for 1-methylcyclopropene gas inclusion.United States Patent (USP) has reported that the employing alpha-cyclodextrin carries out inclusion as the inclusion material to the 1-methyl cyclopropene: for example U.S. Pat 20020043730 patents are not stop drench in the gathering unit of the alpha-cyclodextrin aqueous solution by one the 1-methylcyclopropene gas, the alpha-cyclodextrin aqueous solution that gas is gone into by pouring in this device absorbs and produces inclusion complex, outstanding thick liquid after the inclusion recycles after filtering, the time of contact of the aqueous solution and gas is short in this method, a large amount of 1-methylcyclopropene gas promptly are discharged from without inclusion, inclusion efficient is low, and along with the consumption of alpha-cyclodextrin in the solution, inclusion efficient also can obviously descend.
U.S. Pat 20050261131 is that the 1-methylcyclopropene gas is fed in the airtight pressurizing vessel, add alpha-cyclodextrin solution in the container by buffer preparation, balance obtains the inclusion product more than 24 hours under pressurized conditions, whole inclusion system complex and inclusion reaction time are long, and production efficiency is low.
There is the inclusion overlong time equally in the method that U.S. Pat 6017849 is mentioned, and along with the carrying out of inclusion process, the dividing potential drop of 1-methyl cyclopropene can reduce along with the carrying out of reaction, and then causes reducing of inclusion rate.
At present at home as yet not relevant for adopting the alpha-cyclodextrin or derivatives thereof to be used for the pertinent literature report that 1-methylcyclopropene gas inclusion is produced the fruits and vegetables flower antistaling agent.
Summary of the invention
The objective of the invention is to provide the preparation method that a kind of new 1-methyl cyclopropene that is used for the fruits and vegetables flower freshness is stablized inclusion complex.
In order to realize above-mentioned task, the present invention takes following technical solution:
A kind of 1-methyl cyclopropene that is used for the fruits and vegetables flower freshness is stablized the preparation method of inclusion complex, the inclusion complex of this method preparation is a kind of fruit vegetable flower antistaling agent, it is characterized in that, adopt 1-methyl cyclopropene generator, the reaction system of three road gas cleaning units and inclusion reactor and device for absorbing tail gas, the real-world effectiveness preparation, after 1-methyl cyclopropene active ingredient forms, use alpha-cyclodextrin or derivatives thereof inclusion under auxiliary material effects such as starch immediately, the active ingredient of the inclusion complex after the inclusion is the 1-methylcyclopropene gas, and the percentage by weight of shared antistaling agent is 1.0%～4.5%.
Its inclusion mechanism is to utilize the space ring-type hollow structure of alpha-cyclodextrin molecule that the 1-methylcyclopropene gas is packaged into microcapsules, makes 1-methylcyclopropene gas stable existence for a long time, thereby obtains a kind of novel fruit and vegetable flower antistaling agent.Greatly improve the stability of 1-methylcyclopropene gas by the inclusion technology, prolonged the life-span of this gas.This inclusion complex is mainly used in the fruit and vegetable flower freshness field with transition type ripening and senescence, can reduce fresh-keeping cost greatly, improves fresh-keeping quality, and fresh-keeping a kind of new antistaling agent and the preparation method of providing of fruit, vegetables, flowers is provided.
The mechanism that the present invention improves inclusion efficient also is, by adopting bubbling device, make the bubble diameter of the gaseous mixture that contains 1-methyl cyclopropene available gas by the alpha-cyclodextrin or derivatives thereof aqueous solution be not more than 1mm, can prolong like this its in the aqueous solution holdup time and with haptoreaction time of inclusion material, has the attached material that helps of bigger serface and strong characterization of adsorption by adding starch etc. simultaneously, utilize its characterization of adsorption make the bubble of gaseous mixture be adsorbed on for a long time its surface and do not overflow, thereby greatly prolonged the haptoreaction time of 1-methyl cyclopropene and alpha-cyclodextrin or derivatives thereof, by above two kinds of methods, what can make the 1-methylcyclopropene gas is connect the efficient raising more than 2 times by bag.Adopt normal pressure preparation technology simultaneously, simplified production procedure, greatly reduced production cost.
The preparation method of the antistaling agent that the present invention provides, technology is simple, and the normal pressure preparation is safe and reliable, the productive rate height, cost is low, has higher economic results in society.
The product that the present invention provides has antistaling agent active constituent content height, freshness height, is difficult for oxidation, is easy to accumulating, advantage such as easy to use, fresh-keeping a kind of new antistaling agent and the preservation method of providing for fruit, vegetables, flowers etc., can obviously reduce the cost of preservation technique, improve fresh-keeping quality, prolong fresh keeping time.And noresidue is the good assistant of numerous fruiterers, fruit and vegetable farming, vegetables merchant increasing both production and income, is the good antistaling agent that hundreds of millions consumers realize the safe green environmental protection.
Embodiment
Below the present invention is described in further detail.
The present invention is a kind of novel fruits and vegetables flower antistaling agent by inclusion complex, is the white solid product, mainly forms by the inclusion material with by inclusion complex, and composition is the 1-methylcyclopropene gas.Promptly after 1-methyl cyclopropene active ingredient forms, use alpha-cyclodextrin or derivatives thereof inclusion under auxiliary material effects such as starch immediately, make it to form a kind of very stable inclusion body, the percentage by weight that the inclusion complex after the inclusion accounts for antistaling agent is 1.0%～4.5%.
The 1-methyl cyclopropene is a kind of very active, very easily reaction, very unsettled gas; when surpassing finite concentration or pressure is to blast; therefore; in manufacture process, can not separate and handle its form with pure product or the former medicine of high concentration; itself can't exist as a kind of product separately, can not store.So the applicant adopts the method for alpha-cyclodextrin or derivatives thereof inclusion, promptly after 1-methyl cyclopropene active ingredient forms, form the inclusion body with alpha-cyclodextrin or derivatives thereof molecule inclusion immediately, to guarantee the validity of 1-methyl cyclopropene.
The fruits and vegetables flower antistaling agent that the present invention provides prepares by following method: set up a reaction system that comprises a 1-methyl cyclopropene generate reactor, three air-washers, 1-methyl cyclopropene inclusion reactor and device for absorbing tail gas, connect with pipeline between each device.
1-methylcyclopropene gas that will real-world effectiveness prepares in 1-methyl cyclopropene generate reactor at inert gas (as nitrogen, helium, argon gas etc.) carry down successively by after three air-washer washings, feeding is equipped with in the inclusion reactor of the alpha-cyclodextrin or derivatives thereof aqueous solution, and under auxiliary material effects such as starch, stirring condition generates white solid inclusion product down, after filtration, promptly obtain solid fruit-vegetable flower antistaling agent of the present invention after the natural seasoning.
Adopted the real-world effectiveness preparation by inclusion complex 1-methyl cyclopropene, the step of concrete inclusion process is:
1) add the reactant that generates the 1-methyl cyclopropene in 1-methyl cyclopropene generator, reactant is made of following raw materials by weight percentage: Sodamide 16%, metering system chlorine 32%, oxolane 2%, normal octane 50%; Reaction temperature is controlled at 50～55 ℃, and under electromagnetism or electronic stirring, the 1-methylcyclopropene gas of generation and other inert gas are together successively through entering the inclusion reactor behind three air-washers;
2) in first air-washer, fill deionized water, regulate its pH value less than 5; In second air-washer, add neutral deionized water, and add the extraordinary chemical reagent that is used to indicate the deionized water effect, in the 3rd air-washer, add the solution of following volume ratio preparation: monoethanolamine 20%, isopropyl alcohol 40%, deionized water 40%;
3) saturated aqueous solution and the auxiliary material that are equivalent to alpha-cyclodextrin or derivatives thereof consumption 10% of adding alpha-cyclodextrin or derivatives thereof in the inclusion reactor; Before the inclusion process begins,, remove the air in the system, and in course of reaction, remain the feeding of inert gas the logical inert gas 5min～10min of whole reaction system;
4) in the inclusion reactor with 1-methyl cyclopropene and inert gas mist under mechanical agitation or magnetic agitation condition, adopt the bubbling mode by in the saturated aqueous solution of alpha-cyclodextrin or derivatives thereof, produce white depositions, it is excessive not by the 1-methylcyclopropene gas of inclusion to absorb that the tail gas in the inclusion reactor feeds in the device for absorbing tail gas that fills benzinum;
5) the muddy liquid that will have white depositions filters, and natural seasoning 24 hours obtains the white solid product, is the fruits and vegetables flower antistaling agent.
In the inclusion process, the purpose that adopts three road gas cleaning units is that alkalescence and the organic impurities in the 1-methylcyclopropene gas that course of reaction is generated removed, to guarantee to wrap the practice midwifery stability and the inclusion efficient of thing.Simultaneously in cleaning solution, add indicator, to guarantee the validity of cleaning solution.
In the inclusion process, can also be arranged on bubbling device in the reactor by employing, make the bubble diameter of the gaseous mixture that contains 1-methyl cyclopropene available gas by the alpha-cyclodextrin or derivatives thereof aqueous solution be not more than 1mm, prolonged bubble in the inclusion reactor holdup time and with haptoreaction time of inclusion material, simultaneously by adding starch, modified starch, the attached material that helps such as natural polysaccharide or talcum powder, utilize its characterization of adsorption to make the bubble of gaseous mixture be adsorbed on its surface for a long time and do not overflow, thereby greatly prolonged haptoreaction time of 1-methyl cyclopropene and alpha-cyclodextrin or derivatives thereof.
By above two kinds of methods, can make the bag of 1-methylcyclopropene gas connect the efficient raising more than 2 times.Adopt normal pressure preparation technology simultaneously, simplified production procedure, greatly reduced production cost.
A specific embodiment of the present invention is as follows:
Set up a reaction system that comprises 1-methyl cyclopropene generate reactor, three air-washers, 1-methyl cyclopropene inclusion reactor and device for absorbing tail gas, connect with pipeline between each device.
In 1-methyl cyclopropene generator, add the reactant of the raw material of following percentage quality, Sodamide, 16% as the 1-methyl cyclopropene; Metering system chlorine, 32%; Oxolane, 2%; Normal octane, 50%; In first air-washer, add deionized water, regulate its pH value less than 5; In second air-washer, add neutral deionized water and add the extraordinary chemical reagent (as a kind of or several mixtures of methyl orange, phenolphthalein, bromine cresol orchid, methyl red) that is used to indicate the deionized water effect, in the 3rd air-washer, add monoethanolamine, 20%; Isopropyl alcohol, the solution of 40% and deionized water, 40% preparation; In the inclusion reactor, add the saturated alpha-cyclodextrin or derivatives thereof aqueous solution and the auxiliary material (, can be a kind of or several mixtures wherein) such as grade that are equivalent to alpha-cyclodextrin or derivatives thereof consumption 10% as starch, modified starch, natural polysaccharide, talcum powder etc.; In the device for absorbing tail gas, add benzinum.
Before beginning, the inclusion process, removes the air in the system, in order to avoid the 1-methylcyclopropene gas that generates is oxidized to logical inert gas (as nitrogen, helium, the argon gas etc.) 5～10min of whole reaction system.And in course of reaction, remain the feeding of inert gas.
According to following mass percent, in 1-methyl cyclopropene generating means, add reactant: Sodamide 16%, metering system chlorine 32%, oxolane 2%, normal octane 50%.Reaction temperature is controlled at 50～55 ℃.
Under electromagnetism or electronic stirring, the 1-methylcyclopropene gas of generation and inert gas are together successively through entering the inclusion reactor behind three air-washers.
In the inclusion reactor with 1-methyl cyclopropene and inert gas mist under mechanical agitation or magnetic agitation condition, in the bubbling mode by in the saturated aqueous solution of alpha-cyclodextrin or derivatives thereof, to produce white precipitate.Can in the inclusion reactor, add fillers such as porcelain ring or porcelain bead in case of necessity and be used to improve inclusion efficient.
Above-mentioned bubbling mode realizes by bubbling device, and this device is provided with the breather pipe of porous sand plate or waffle slab for port, and to guarantee being not more than 1mm through the bubble diameter of breather pipe, this device is installed in the inclusion reactor, controls from the outside.
The muddy liquid that will have white precipitate filters, and sediment natural seasoning 24 hours obtains the white solid product, is fruits and vegetables flower antistaling agent product of the present invention.
It is excessive not by the 1-methylcyclopropene gas of inclusion to absorb that tail gas in the inclusion reaction response device feeds in the container that fills benzinum.
When preparing antistaling agent product according to the method described above, adopt the method for thermogravimetric analysis, the inclusion complex that obtains is detected, recording 1-methyl cyclopropene shared mass percent in inclusion complex is 1.0%～4.5%.
The alpha-cyclodextrin or derivatives thereof that the present invention uses, comprise alpha-cyclodextrin, hydroxypropyl-alpha-cyclodextrin, ethoxy-alpha-cyclodextrin, sulfonic group-alpha-cyclodextrin, sulphur butyl-alpha-cyclodextrin, carboxymethyl-alpha-cyclodextrin and alkyl replace alpha-cyclodextrin (alkyl that alkyl replaces alpha-cyclodextrin comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl etc.), wherein a kind of or several.Employed auxiliary material are: glucose, starch and derivative thereof, modified starch, natural polysaccharide, talcum powder etc. can be a kind of or several mixtures wherein.
No matter above-mentioned alpha-cyclodextrin or derivatives thereof and auxiliary material adopt one or more mixing, all can reach purpose of the present invention, do not enumerate one by one at this.
The inclusion complex that the present invention makes is the inclusion complex antistaling agent for a class water-soluble solid material, its using method is as follows: postharvest fruit and vegetable is removed sick and wounded residual, be positioned in sealing storehouse or sealed plastic account or other closed containers, 50 extraordinarily entry or add acid about 10 times or the weak solution of alkali by inclusion complex antistaling agent usage amount, the alpha-cyclodextrin or derivatives thereof is dissolved, the 1-methyl cyclopropene is discharged, encapsulation process was by fresh-keeping fruits and vegetables 6-8 hour more than 15 ℃, below 15 ℃ 12-16 hour, take out the raffinate depressurization.
Inclusion complex antistaling agent of the present invention can be kept about 2 years effective at ambient temperature.It is obvious to seal treatment effect fast up for safekeeping after vegetable or flower is plucked, and as delay process, the time, late more effect was not obvious more.Must guard against to surpass and re-used by the climacteric after date of fruit and vegetable preservation.
A large number of experiments show that, use inclusion complex antistaling agent of the present invention, be applicable to the fresh-keeping of fruit and vegetable flowers, have the following advantages:
1. easy to use, processing ease. If seal cavity, regardless of different kinds of, fill according to volume, namely Available antistaling agent of the present invention is processed.
2. effect is remarkable, applied widely. Multiple exhaling such as apple, pears, Kiwi berry, banana, hawthorn Inhale to use in the transition type fruit positive effect is all arranged.
3. consumption is few, and is with low cost. Per kilogram use cost on the big fruit of the respiratory capacities such as apple, pears 2-4 divides money (deciding according to storage time length, application concentration and processing space and dress fruit density), perfume (or spice) Any of several broadleaf plants, title monkey peach use cost per kilogram 1-2 divide money.
4. the energy is saved in long term storage, improves quality. As long as processing in time, the storage effect can improve shelves Inferior, common freezer can reach the controlled atmosphere effect, and upper kiln, big account storehouse can reach the effect in common storehouse, and storage Depositing temperature can relax, and saves the energy more than 20～30%.
5. normal temperature uses Shelf-life. Apple, pears 50～60 days, Kiwi berry, banana etc. are the longest can Reach 58 days, freezer stores can reach 210 days, earth kiln 160 days.
6. to the basic simlarity of the preservation methods of flowers and vegetables, fruit. Collecting period in flowers can have Effect protection flowers prevent that it from rotting to reach withered.
Claims (8)
1. a 1-methyl cyclopropene that is used for the fruits and vegetables flower freshness is stablized the preparation method of inclusion complex, the inclusion complex of this method preparation is a kind of fruit vegetable flower antistaling agent, it is characterized in that, adopt 1-methyl cyclopropene generator, the reaction system of three road gas cleaning units and inclusion reactor and device for absorbing tail gas, the real-world effectiveness preparation, after 1-methyl cyclopropene active ingredient forms, use alpha-cyclodextrin or derivatives thereof inclusion under the auxiliary material effect immediately, the active ingredient of the inclusion complex after the inclusion is the 1-methylcyclopropene gas, and the percentage by weight of shared antistaling agent is 1.0%～4.5%.
2. the method for claim 1 is characterized in that, described real-world effectiveness prepares concrete inclusion process and comprises the following steps:
1) add the reactant that generates the 1-methyl cyclopropene in 1-methyl cyclopropene generator, reactant is made of following raw materials by weight percentage: Sodamide 16%, metering system chlorine 32%, oxolane 2%, normal octane 50%; Reaction temperature is controlled at 50～55 ℃, and under electromagnetism or electronic stirring, the 1-methylcyclopropene gas of generation and other inert gas are together successively through entering the inclusion reactor behind three air-washers;
2) in first air-washer, fill deionized water, regulate its pH value less than 5; In second air-washer, add neutral deionized water, and add the extraordinary chemical reagent that is used to indicate the deionized water effect, in the 3rd air-washer, add the solution of following volume ratio preparation: monoethanolamine 20%, isopropyl alcohol 40%, deionized water 40%;
3) saturated aqueous solution and the auxiliary material that are equivalent to alpha-cyclodextrin or derivatives thereof consumption 10% of adding alpha-cyclodextrin or derivatives thereof in the inclusion reactor; Before the inclusion process begins,, remove the air in the system, and in course of reaction, remain the feeding of inert gas the logical inert gas 5min～10min of whole reaction system;
4) in the inclusion reactor with 1-methyl cyclopropene and inert gas mist under mechanical agitation or magnetic agitation condition, adopt the bubbling mode by in the saturated aqueous solution of alpha-cyclodextrin or derivatives thereof, produce white depositions, it is excessive not by the 1-methylcyclopropene gas of inclusion to absorb that the tail gas in the inclusion reactor feeds in the device for absorbing tail gas that fills benzinum;
5) the muddy liquid that will have white depositions filters, and natural seasoning 24 hours obtains the white solid product, is the fruits and vegetables flower antistaling agent.
3. method as claimed in claim 1 or 2, it is characterized in that, described alpha-cyclodextrin or derivatives thereof is an alpha-cyclodextrin, hydroxypropyl-alpha-cyclodextrin, ethoxy-alpha-cyclodextrin, sulfonic group-alpha-cyclodextrin, sulphur butyl-alpha-cyclodextrin, carboxymethyl-alpha-cyclodextrin, alkyl replace a kind of of alpha-cyclodextrin or several.
4. method as claimed in claim 3 is characterized in that, the alkyl that described alkyl replaces in the alpha-cyclodextrin is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, can be wherein a kind of or several.
5. method as claimed in claim 2 is characterized in that, described auxiliary material are glucose, starch and derivative thereof, modified starch, natural polysaccharide, talcum powder a kind of or several mixtures wherein.
6. method as claimed in claim 2 is characterized in that, described inert gas is that nitrogen, helium, argon gas are wherein a kind of.
7. method as claimed in claim 2 is characterized in that, described to be used to indicate the extraordinary chemical reagent of deionized water effect be methyl orange, phenolphthalein, bromine cresol orchid, methyl red a kind of or several mixtures wherein.
8. method as claimed in claim 2 is characterized in that, described bubbling mode realizes by bubbling device, and this device is provided with the breather pipe of porous sand plate or waffle slab for port, and the bubble diameter that breather pipe produces is not more than 1mm.
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| CN101971875A (en) * | 2010-10-19 | 2011-02-16 | 西安交通大学 | 1-methylcyclopropene inclusion complex for fruits, vegetables and flowers and preparation method thereof |
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| CN101990936A (en) * | 2010-10-19 | 2011-03-30 | 西安交通大学 | 1-methyl-3-(2-methyl cyclopropane)-1-cyclopropylene stable inclusion compound and preparation method thereof |
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| CN101990936A (en) * | 2010-10-19 | 2011-03-30 | 西安交通大学 | 1-methyl-3-(2-methyl cyclopropane)-1-cyclopropylene stable inclusion compound and preparation method thereof |
| CN101971875A (en) * | 2010-10-19 | 2011-02-16 | 西安交通大学 | 1-methylcyclopropene inclusion complex for fruits, vegetables and flowers and preparation method thereof |
| CN101990936B (en) * | 2010-10-19 | 2013-05-22 | 西安交通大学 | 1-methyl-3-(2-methyl cyclopropane)-1-cyclopropylene stable inclusion compound and preparation method thereof |
| CN101971875B (en) * | 2010-10-19 | 2012-11-28 | 西安交通大学 | 1-methylcyclopropene inclusion complex for fruits, vegetables and flowers and preparation method thereof |
| CN102119719A (en) * | 2010-12-10 | 2011-07-13 | 山东营养源食品科技有限公司 | Cyclopropene preservative, and preparation and packaging methods thereof |
| CN102119719B (en) * | 2010-12-10 | 2013-06-19 | 山东营养源食品科技有限公司 | Cyclopropene preservative, and preparation and packaging methods thereof |
| CN102119718B (en) * | 2010-12-10 | 2013-06-19 | 山东营养源食品科技有限公司 | Cyclopropene preservative and preparation method thereof |
| CN102119718A (en) * | 2010-12-10 | 2011-07-13 | 山东营养源食品科技有限公司 | Cyclopropene preservative and preparation method thereof |
| CN102273504A (en) * | 2011-04-21 | 2011-12-14 | 华中农业大学 | Preparation method for inclusion complex of 1-methylcyclopropene and its derivatives, and application thereof |
| CN102217671A (en) * | 2011-04-27 | 2011-10-19 | 武汉双奇科技发展有限公司 | 1-methyl cyclopropene slow release formulation and preparation method thereof |
| CN102217671B (en) * | 2011-04-27 | 2013-07-03 | 武汉双奇科技发展有限公司 | 1-methyl cyclopropene slow release formulation and preparation method thereof |
| CN105851213A (en) * | 2016-04-08 | 2016-08-17 | 广东中迅农科股份有限公司 | Pesticide composition containing 2,4-D and 1-methylcyclopropene |
| CN107307069A (en) * | 2016-04-27 | 2017-11-03 | 上海鲜锐生物科技有限公司 | 1- methyl cyclopropenes preparation and preparation and application for fruits and vegetables flower freshness |
| CN115254058A (en) * | 2022-08-02 | 2022-11-01 | 郑州郑氏化工产品有限公司 | Preparation method of 1-methylcyclopropene inclusion complex |
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