CN100367851C - Composite antistaling agent of cyclopropenes and preparation method - Google Patents
Composite antistaling agent of cyclopropenes and preparation method Download PDFInfo
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- CN100367851C CN100367851C CNB2005100450057A CN200510045005A CN100367851C CN 100367851 C CN100367851 C CN 100367851C CN B2005100450057 A CNB2005100450057 A CN B2005100450057A CN 200510045005 A CN200510045005 A CN 200510045005A CN 100367851 C CN100367851 C CN 100367851C
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Abstract
The present invention belongs to the anti-corrosive and anti-staling field of fruits and vegetables, particularly to a composite anti-staling agent of cyclopropene and a preparation method thereof. The composite anti-staling agent of cyclopropene is prepared by 1-sodium methyl cyclopropene which is mixed with a preservative agent, a bactericidal agent, a stabilizing agent, a stabilizing auxiliary agent, a retarder and an excipient according to different proportions under the conditions of low temperature and a certain pressure. The 1-sodium methyl cyclopropene of the major raw material makes 2-methyl-1-propylene as initial raw materials; 2-methyl-1.2-dibromopropane is obtained by bromination; the 2-methyl-1.2-dibromopropane takes off hydrogen bromide through sodium amide or potassium amide, and accordingly, the 1-sodium methyl cyclopropene is obtained. The composite anti-staling agent of cyclopropene which is produced by the present invention has multiple functions of anti-staling performance, sterilization and corrosion prevention, and the present invention has multiple advantages of low cost, good effects, safe and convenient storage and usage, etc.
Description
(1) technical field
The invention belongs to the antiseptic preservation of fruits and vegetables field.Be particularly related to and have anticorrosion, sterilization and multi-functional composite antistaling agent of cyclopropenes such as fresh-keeping and preparation method thereof.
(2) background technology
Cyclopropylene, especially 1-methyl cyclopropene effectively ethene suppressing to adopt the back fruits and vegetables the aging effect.Prove that now the 1-methyl cyclopropene can obviously prolong the life-span of fresh flower, delays the aging of fruits and vegetables such as garlic shoot, broccoli, apple, banana, pears, jujube, is an antistaling agent that broad prospect of application is arranged.But it can not prevent to rot, go bad by microorganism is caused well, and stores, transports, uses inconvenient.Many in addition preservatives, bactericide can prevent or reduce rotting of fruits and vegetables, but can not delay the aging of fruits and vegetables.Technical problem to be solved by this invention is: provide to have anticorrosion, sterilization and fresh-keeping multi-functional composite antistaling agent of cyclopropenes, storage, transportation, easy to use can delay fruit simultaneously and dredge old and feeble and prevent and alleviate fruit and dredge and rot.The synthetic method of 1-methyl cyclopropene has report more before this; As US.6017849; CN.1480438 (publication number) etc., the synthetic method of 1-methyl cyclopropene is different with it among the present invention; Anticorrosionly compare with prepared the having of CN.15055992 (publication number) with the cyclopropylene antistaling agent of fresh-keeping double action, the present invention have making more rationally, characteristics such as product is stable more, fresh-keeping and the scope of application is wider, effect is more lasting.
(3) summary of the invention
The objective of the invention is: in order to overcome the drawback of existing antistaling agent, provide a kind of and have the fruits and vegetables of delaying aging, anticorrosion, sterilization and multiple function such as fresh-keeping, and storage, transportation, composite antistaling agent of cyclopropenes easy to use.
Another object of the present invention provides a kind of preparation method of above-mentioned composite antistaling agent of cyclopropenes.
Technical scheme of the present invention is achieved in that
Composite antistaling agent of cyclopropenes of the present invention, it is composed of the following components to count this composite preservative by weight:
0.1～2 part of cyclopropylene
40～90 parts of stabilizing agents
2～8 parts of stabilization aids
3～20 parts of preservatives
0～15 part in bactericide
3～15 parts of sustained release agents
0.1～2 part of excipient
Cyclopropylene is the 1-methyl cyclopropene among the present invention.
Preservative is one or more in sec-butylamine, sec-butylamine hydrochloride, sec-butylamine sulphate, sec-butylamine phosphate, sec-butylamine sulphite, sec-butylamine bisulfites, sec-butylamine lactate, sodium pyrosulfite, potassium metabisulfite, sodium sulphite, potassium sulfite, sodium hydrogensulfite, potassium bisulfite, propyl isorhodanide (propyl isothiocyanate), dehydroactic acid, sodium Diacetate, the diacetic acid potassium;
Bactericide is one or more in chlorine dioxide, sodium chlorate, potassium chlorate, sodium perchlorate, potassium hyperchlorate, sodium chlorite, potassium chlorite, the ethanol;
Stabilizing agent is one or more in dextrin, active carbon, diatomite, silica gel, rosin, active polysaccharide, starch, the modified starch;
Stabilization aid is one or more water or the alcoholic solution in acetic acid, sodium acetate, potassium acetate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate, the potassium dihydrogen phosphate;
Sustained release agent is one or more in quaternary ammonium salt, quaternary ammonium base, soda lime, quicklime, calcium chloride, zinc chloride, reducing sugar alkyd, the lignin polyamide;
Excipient is one or more in stearic acid, calcium stearate, dolomol, stearyl alcohol, palmitic acid calcium, the palmitic acid magnesium etc.
In above-mentioned composite preservative, its optimum formula is:
0.1～1.5 part of cyclopropylene
45～80 parts of stabilizing agents
2～5 parts of stabilization aids
5～12 parts of preservatives
3～5 parts in bactericide
7～12 parts of sustained release agents
0.5～1 part of excipient
Wherein cyclopropylene is the 1-methyl cyclopropene.
The primary raw material 1-methyl cyclopropene system of composite antistaling agent of cyclopropenes of the present invention is an initiation material by 2-methyl isophthalic acid-propylene, generates 2-methyl isophthalic acid, 2-dibromopropane through bromination.The 2-methyl isophthalic acid, 2 moles of sodium bromides or potassium bromide are sloughed in 2-dibromopropane and Sodamide or potassamide reaction, generate the 1-methyl cyclopropene.
Its synthetic reaction formula:
The method for preparing composite antistaling agent of cyclopropenes of the present invention is made up of following steps successively:
(1) prepares the 1-methyl cyclopropene as stated above earlier;
(2) then in the blender that electric mixer, piezometer, feeder, thermometer, wireway are housed, add stabilizing agent, stabilization aid, preservative, bactericide, sustained release agent, excipient etc. and import nitrogen;
(3) chuck feeds cooling water, starts stirring;
(4) import the 1-methyl cyclopropene, make blender internal pressure 0.08-0.3Mpa, stirring 8-64 hour below 20 ℃, stop to mix;
(5) emit material, be the composite antistaling agent of cyclopropenes powder;
(6) powder is through compressing tablet, and packing can be made into the composite antistaling agent of cyclopropenes tablet.
The invention has the beneficial effects as follows: the composite antistaling agent of cyclopropenes of making, formulation can be pulvis, tablet or granule, not only have the aging effect of ethene suppressing to fruits and vegetables, prolonged the life-span of fruits and vegetables, has good preservation, and, can effectively reduce rotting of fruits and vegetables through with anticorrosion, bactericide compounded.It is easy to use that this composite antistaling agent of cyclopropenes has the transportation of storage, and adding sustained release agent can have dauer effect to the fresh-keeping, anticorrosion of fruits and vegetables, and effect is obvious.This antistaling agent is to storage fresh-keeping, the increment of agricultural product-fruits and vegetables, and the quality of life that improves people has a very important role.And the synthesis material of 1-methyl cyclopropene is cheap and easy to get among the present invention, reaction yield height, easy operating.
(4) description of drawings:
Fig. 1 is a composite antistaling agent of cyclopropenes preparation flow schematic diagram
1, is reactor 2,2-methyl isophthalic acid, 2-dibromopropane basin 3, reinforced 4, water storage tank 5, nitrogen conduit 6, condenser 7, scrubber tower 8, gas tank 9, mixing kettle 10, charge door 11, nitrogen conduit 12, pulvis storage tank 13, pulvis packing 14, tablet press machine 15, tablet packing 16, product.
(5) specifically prepare example;
Cyclopropylene is mainly used the 1-methyl cyclopropene among the present invention, belong to little molecule cyclic olefin, the chemism height, extremely unstable at normal temperatures, so its storage, use and all need carry out at a lower temperature, temperature is high slightly, promptly can decompose or reacts with other material, so will pay special attention to temperature during reaction, generally must not surpass room temperature.
When the 1-methyl cyclopropene mixes with stabilizing agent, also should carry out at low temperatures in addition, mix fully, make and mix back gained preparation stabilization for making, should note following some:
1, mixing kettle will seal, and mixing must be carried out under the pressure of certain 1-methyl cyclopropene, generally is advisable with 0.01～0.3Mpa;
2, mixing will have time enough, general 8～64 hours;
3, mixing temperature is generally 0～25 ℃;
4, should be full of inert nitrogen gas in the mixing kettle, not so, the 1-methyl cyclopropene is easily oxidized and lost efficacy;
5, in composite antistaling agent of cyclopropenes manufacturing process, keep low temperature, not so, not only can make product failure, also can cause danger.
Example (1):
1, in the 100L reactor, adds carbon tetrachloride 40L, bromine 20KG, start stirring, with cold water reaction cooling, make temperature in the kettle be lower than 25 ℃ in the chuck, import isobutene (2-methyl isophthalic acid-propylene) by wireway, make temperature in the kettle not be higher than 30 ℃, take off (reactant liquor is colourless) fully until the purple of bromine, continue again to stir 30 minutes, stop, steaming foreshots such as carbon tetrachloride, collect 110-120 ℃/-fraction of 0.09Mpa, get the 2-methyl isophthalic acid, 2-dibromopropane 23KG, yield 85%;
2, in the 50L reactor, use N
2Drive away air, add 60～90 ℃ dry benzinum 30L, Sodamide 5KG starts stirring, with the cold water cooling, makes temperature in the kettle about 20 ℃ in the chuck, slowly drips the 2-methyl isophthalic acid, 2-dibromopropane 13KG, and the still fixed temperature must not be above 30 ℃.After dropwising, continue to stir 30～45min;
3, stop logical N
2, the gas outlet is connected with 1-methyl cyclopropene gas tank, slowly in reactor, drip water 5KG, standby with preserving in the gas 1-methyl cyclopropene importing gas tank that produces.
4, in mixing kettle, add 50 parts in dextrin; 26 parts of active polysaccharides; 4 parts of acetic acid and sodium acetate (0.5mol) mixed solutions; Cover tight kettle cover, logical N
2Gas drive deacration, the logical cold water of chuck make below the still temperature to 20 ℃, feed 0.8 part of the 1-methylcyclopropene gas that makes, start stirring, make the still internal pressure about 0.2Mpa, stop logical 1-methyl cyclopropene, are stirring 24 hours below 20 ℃.
5, emit material, centrifugal, dry, material is poured in the comminutor, granulation.With the particle made in proportion with 4 parts of sec-butylamine bisulfites, 4 parts of quicklimes, 7 parts in calcium chloride, 1 part of mixing of stearic acid, compressing tablet, the gained tablet is composite antistaling agent of cyclopropenes;
6, composite antistaling agent of cyclopropenes (sheet) is packaged in ventilative or the air-locked packaging bag, deposits in the dry environment, hole or taking-up are pricked in packaging bag during use;
7, also compressing tablet not of gained composite antistaling agent of cyclopropenes is made pulvis and is used, and pulvis is deposited in the Air Proof Packing pack, and packaging bag is pricked the hole or taking-up is put in the vessel during use.
* this product contains 1-methyl cyclopropene 0.38% after testing
Example (2):
1, in the 100L reactor, add carbon tetrachloride 40KG, chuck cools off with frozen water, make below the still temperature drop to 10 ℃, feed the about 7KG of isobutene (2-methyl isophthalic acid-propylene) gas, slowly drip bromine, the still temperature must not be higher than 20 ℃, purple to bromine no longer takes off, and continues to stir 30min, boils off foreshots such as carbon tetrachloride, collect 110-120 ℃/-fraction of 0.09Mpa, get the 2-methyl isophthalic acid, the about 21KG of 2-dibromopropane, yield 78%;
2, in the 50L reactor, logical N
2Drive away air, add dry 60～90 ℃ benzinum 35L, Sodamide 5KG, start stirring, cool off with cold water in the chuck, make temperature in the kettle about 20 ℃, slowly drip the 2-methyl isophthalic acid, 2-dibromopropane 7KG, the still temperature remains on below 30 ℃, after dropwising, continues to stir 30min;
3, stop logical N
2, the gas outlet is connected with 1-methyl cyclopropene gas tank, slowly in reactor, drip water 5KG, standby with preserving in the gas 1-methyl cyclopropene importing gas tank that produces.
4, in mixing kettle, add 30 parts in dextrin; 10 parts of active polysaccharides; 25 parts of modified starches; 5 parts of acetic acid and sodium acetate (0.5mol) mixed solutions; 5 parts of sodium chlorites; Cover tight kettle cover, logical N
2Gas drive deacration, the logical cold water of chuck make the still temperature be chilled to 0.6 part of the 1-methyl cyclopropene that 10 ℃ of importings make, and making the still internal pressure is 0.15～0.2Mpa, starts stirring, stirs 36 hours;
5, emit material, with 5 parts of material and sodium hydrogensulfites; 7 parts in sec-butylamine sulphate; 4 parts in calcium chloride; 5 parts of zinc chloride; 1 part of dolomol; Mix, pour granulation in the comminutor into, the gained particle is put into the tablet press machine compressing tablet, get composite antistaling agent of cyclopropenes (sheet);
6, cyclopropylene composite fresh-keeping sheet is packaged in ventilative or the Air Proof Packing pack in, deposit in the dry environment, hole or taking-up are pricked in packaging bag during use;
7, also compressing tablet not of gained composite antistaling agent of cyclopropenes is made pulvis and is used, and pulvis is deposited in the Air Proof Packing pack, and packaging bag is pricked the hole or taking-up is put in the vessel during use.
* this product contains 1-methyl cyclopropene 0.26% after testing
Example (3):
1, with 1,2,3 identical in the example 1;
2, in mixing kettle, add 30 parts in dextrin; 35 parts of active polysaccharides; 5 parts of acetic acid and sodium acetate (0.5mol) mixed solutions; 5 parts of sodium chlorites; Cover tight kettle cover, logical N
2Drive away air, logical cold water makes temperature in the kettle reduce to 5 ℃ in the chuck, and 0.8 part of the 1-methyl cyclopropene that importing makes starts stirring, and making the still internal pressure is 0.2～0.25Mpa, under 10 ℃ of temperature, stirs 30 hours;
3, emit material, centrifugal, dry, material is poured granulation in the comminutor into; With 8 parts in sec-butylamine sulphite; 5 parts in calcium chloride; 3 parts in sodium chlorate; 5 parts of quicklimes; 1 part of mixing of dolomol is used the tablet press machine compressing tablet, and the gained tablet is composite antistaling agent of cyclopropenes;
4, composite antistaling agent of cyclopropenes (sheet) is packaged in ventilative or the air-locked packaging bag, deposits in the dry environment, hole or taking-up are pricked in packaging bag during use;
5, also compressing tablet not of gained composite antistaling agent of cyclopropenes is made into pulvis and uses, and pulvis is deposited in air-locked packaging bag, and packaging bag is pricked the hole or taking-up is put in the vessel during use.
* this product contains 1-methyl cyclopropene 0.51% after testing
Example (4):
1, with 1,2,3 identical in the example 1;
2, in mixing kettle, add 40 parts in dextrin; 20 parts of modified starches; 10 parts of active polysaccharides cover tight kettle cover, logical N
2Drive away air, chuck lead to cold water, makes still temperature drop to 5 ℃, 0.5 part of the 1-methyl cyclopropene that importing makes, and making the still internal pressure is about 0.2Mpa, starts stirring, stirs 36 hours;
3, emit material, with 5 parts of sec-butylamines; 5 parts of sodium pyrosulfites; 5 parts in calcium chloride; 4 parts of sodium chlorites; 7 parts of zinc chloride; Stearyl alcohol mixes for 1 part, pours compressing tablet in the tablet press machine into, promptly gets composite antistaling agent of cyclopropenes (sheet);
4, cyclopropylene composite fresh-keeping sheet is packaged in ventilative or the air-locked packaging bag, deposits in the dry environment, hole or taking-up are pricked in packaging bag during use;
5, also compressing tablet not of gained composite antistaling agent of cyclopropenes is made pulvis and is used, and pulvis is deposited in the Air Proof Packing pack, and packaging bag is pricked the hole or taking-up is put in the vessel during use.
* this product contains 1-methyl cyclopropene 0.22% after testing
Example (5):
1, with 1,2,3 identical in the example 1;
2, in mixing kettle, add 40 parts in dextrin; 20 parts of modified starches; 5 parts of acetic acid and sodium acetate (0.5mol) mixed solutions; Cover tight kettle cover, use N
2Drive away air, chuck cools off with cold water, makes still temperature drop to 10 ℃, feeds 1.1 parts of the 1-methyl cyclopropenes that make, and making the still internal pressure is 0.15～0.2Mpa, starts stirring, stirs 28 hours.Emit material, centrifugal, dry, pour material in comminutor granulation.Add 8 parts of zinc chloride in proportion; 0.5 part of zinc stearate, mixing, compressing tablet get composite antistaling agent of cyclopropenes (sheet) A;
3, in proportion with 10 parts of sec-butylamine hydrochlorides; 5 parts of sodium sulphites; 5 parts in calcium chloride; 5 parts of sodium chlorites; 8 parts in calcium chloride; Zinc stearate is poured in the mixing kettle for 0.5 part, and normal temperature mixes, and adds granulation in the comminutor, adds in the tablet press machine, compressing tablet, composite antistaling agent of cyclopropenes (sheet) B;
4, composite antistaling agent of cyclopropenes A and B be packaged in ventilative respectively or the Air Proof Packing pack in, deposit in respectively in the dry environment, hole or taking-up are pricked in packaging bag during use;
5, also compressing tablet not of composite antistaling agent of cyclopropenes A and B is made as pulvis, is packaged in respectively in the Air Proof Packing pack, and packaging bag is pricked the hole or taking-up is put in the vessel during use.
* this product A sheet contains 1-methyl cyclopropene 0.83% after testing
Example (6):
1, with 1,2,3 identical in the example 1;
2, in mixing kettle, add 40 parts in dextrin; 10 parts of active polysaccharides; 10 parts in calcium chloride; 0.5 part of dolomol; Cover tight kettle cover, logical N
2Drive away air, the logical cold water cooling of chuck makes still temperature drop to 15 ℃, feeds 0.6 part of the 1-methyl cyclopropene that makes, and making the still internal pressure is about 0.2Mpa, starts stirring, stirs 40 hours; Emit material, pour granulation in the comminutor, compressing tablet into, get composite antistaling agent of cyclopropenes (sheet) A;
3, in mixing kettle, add 10 parts of sodium pyrosulfites; 2 parts of sodium Diacetates; 4 parts of sodium chlorites; 30 parts of modified starches; 0.5 part of stirring and evenly mixing of stearyl alcohol, granulation, compressing tablet get composite antistaling agent of cyclopropenes (sheet) B;
4, composite antistaling agent of cyclopropenes A and B are packaged in respectively in ventilative or the air-locked packaging bag, deposit in respectively in the dry environment, and hole or taking-up are pricked in packaging bag during use;
5, also compressing tablet not of composite antistaling agent of cyclopropenes A and B is made into pulvis, is packaged in respectively in air-locked packaging bag, and packaging bag is pricked the hole or taking-up is put in the vessel during use.
* this product A sheet contains 1-methyl cyclopropene 0.38% after testing
Example (7):
1,1,2,3 identical in the example 2;
2, in mixing kettle, add 40 parts in dextrin; 30 parts of active polysaccharides; 4 parts of acetic acid and sodium acetate (0.5mol) mixed solutions; Cover tight kettle cover, logical N
2Drive away air, the logical cold water cooling of chuck makes still temperature drop to 10 ℃.1.2 parts of the 1-methyl cyclopropenes that feeding makes, making still pressure is 0.08～0.12Mpa, starts stirring, stirs 30 hours;
3, emit material, centrifugal, dry, add 12 parts in sec-butylamine sulphite; 10 parts in calcium chloride; 1 part of dolomol is poured granulation in the comminutor, compressing tablet into, gets composite antistaling agent of cyclopropenes (sheet);
4, composite antistaling agent of cyclopropenes (sheet) can be packaged in ventilative or the air-locked packaging bag, deposits in the dry environment, and hole or taking-up are pricked in packaging bag during use;
5, also compressing tablet not of composite antistaling agent of cyclopropenes is made pulvis, deposits in air-locked packaging bag, and packaging bag is pricked the hole or taking-up is put in the vessel during use.
* this product contains 1-methyl cyclopropene 1.03% after testing.
Example (8):
1, with 1,2,3 identical in the example 2;
2, in mixing kettle, add 40 parts in dextrin; 40 parts of modified starches; 8 parts of active polysaccharides; 10 parts in calcium chloride; 1 part of calcium stearate; Cover tight kettle cover, logical N
2Drive away air, the logical cold water of chuck is cooled to 0 ℃, 1.1 parts of the 1-methyl cyclopropenes that feeding makes, and making the still internal pressure is 0.08Mpa, starts stirring, stirs 24 hours;
3, emit material, pour granulation in the comminutor into, compressing tablet gets composite antistaling agent of cyclopropenes (sheet);
4, cyclopropylene composite fresh-keeping sheet can be packaged in ventilative or the air-locked packaging bag, deposits in the dry environment, and hole or taking-up are pricked in packaging bag during use;
5, also compressing tablet not of composite antistaling agent of cyclopropenes is made pulvis, is packaged in air-locked packaging bag, and packaging bag is pricked the hole or taking-up is put in the vessel during use.
* this product contains 1-methyl cyclopropene 0.88% after testing
Embodiment (9):
1, with 1,2,3 identical in the example 2;
2, in mixing kettle, add 30 parts of active polysaccharides; 40 parts of modified starches; 5 parts of acetic acid and sodium acetate (0.5mol) mixed solutions; Cover tight kettle cover, logical N
2Drive away air, chuck cools off with frozen water, makes still temperature drop to 0 ℃, feeds 1.2 parts of the 1-methyl cyclopropenes that make, and making the still internal pressure is 0.05～0.08Mpa, starts stirring, stirs 18 hours; Emit material, centrifugal, dry, add 5 parts in calcium chloride; 1 part of zinc stearate,, pour granulation in the comminutor into, compressing tablet gets composite antistaling agent of cyclopropenes (sheet) A;
3, with 10 parts of sec-butylamines; 30 parts of active polysaccharides; 10 parts in calcium chloride; Zinc stearate is poured in the mixing kettle for 1 part, and stirring and evenly mixing is poured granulation in the comminutor, compressing tablet into, gets composite antistaling agent of cyclopropenes (sheet) B;
4, composite antistaling agent of cyclopropenes (sheet) A and B are packaged in respectively in ventilative or the air-locked packaging bag, deposit in the dry environment, and hole or taking-up are pricked in packaging bag during use, and A, B sheet can use separately or together.
5, also compressing tablet not of above-mentioned composite antistaling agent of cyclopropenes A and B is made pulvis, is packaged in respectively in air-locked packaging bag, and packaging bag is pricked the hole or taking-up is put in the vessel during use, and A, B powder can use separately or together.
* this product A sheet contains 1-methyl cyclopropene 1.27% after testing.
Example (10):
The rare stability of 1-methyl ring third in the composite preservative
Place different time at 0-5 ℃, the rare content of 1-methyl ring third in the composite preservative of making of this patent
| The composite preservative sequence number | Content (%) | |||||
| Original content | Placed 7 days | Placed 30 days | Placed 90 days | Placed 180 days | Placed 360 days | |
| Example 1 composite preservative (sheet) | 0.38 | 0.36 | 0.36 | 0.35 | 0.30 | 0.29 |
| Example 2 composite preservatives (sheet) | 0.26 | 0.26 | 0.25 | 0.23 | 0.20 | 0.20 |
| Example 7 composite preservatives (sheet) | 1.03 | 1.01 | 0.96 | 0.96 | 0.93 | 0.87 |
| Example 9 composite preservative A (sheet) | 1.20 | 1.16 | 1.12 | 1.10 | 1.06 | 0.98 |
As can be seen from the above table, in the composite preservative that this patent is made, 1-methyl ring third rare content still is more stable.As calculated, placed 360 days at 0-5 ℃, the content loss rate is that 15.5-23.7% example (11) utilizes the fresh-keeping broccoli of ring third rare composite preservative
Sunny weather dew in morning does the back or at dusk, the color of gathering is for green entirely, and small bud is not open, and diameter is 13-16 centimetre a broccoli bouquet.Broccoli is adopted in back 2 hours, is put in the big account of food-grade igelite, then according to the volume of the big account of plastics, takes by weighing example 2 composite preservatives according to the consumption of 0.96 gram/cubic meter, pours in the dry small beaker.Beaker is put in the big account, adds 10 ml waters/gram antistaling agent, seal 12 hours rapidly.Take out broccoli, preserve transportation or circulation sale.The broccoli of Chu Liing according to said method, open, the old and feeble flavescence of bud can postpone 1 times of time under the normal temperature, carries out the MA storage with 4 food-grade polyvinyl chloride freshness protection packages under the 0-1 ℃ of condition, fresh keeping time prolongation 1 month.
Example (12) utilizes ring third rare composite preservative to prolong the kiwi fruit freshness date
Sunny weather dew in morning is done back or dusk, the Qin Mei kiwi fruit of the 7-8 maturation of gathering.In 4 hours, be put in the big account of vinyon.According to the volume of the big account of plastics, take by weighing example 1 composite preservative according to 0.66 gram/cubic meter, pour in the dry small beaker.Beaker is put in the big account, adds 15 milliliters of entry/gram composite preservative, rapidly sealing.After 12 hours, take out kiwi fruit, preserve transportation or circulation sale.The kiwi fruit of Chu Liing like this, 20-25 ℃ of following deliquescing time delay 7 days.0 ℃--0.5 ℃, with 3 polyethylene freshness protection package MA storages, shelf-life prolongs 3 months.
Example (13) utilizes ring third rare composite preservative to reduce apple superficial scald
According to the Fuji apple that quality standard is gathered, in 24 hours, be transported between controlled atmosphere storage in, every day the warehouse-in amount be no more than the design storage capacity 1/5.Storehouse temperature is reduced to-1 ℃ in advance.The storehouse is gone into full, behind the storehouse temperature drop to 0 ℃, takes by weighing example 9 composite preservatives according to 0.020 gram/cubic meter storage capacity, divides in 3 parts of beakers that are put in drying.Beaker evenly is put in different parts in the storehouse, according to 20 ml waters/gram composite preservative water is poured in the beaker then.Airtight storage.Preserved 10 months, the contrast Scald incidence of disease 5% is handled no Scald and is taken place.
Claims (5)
1. composite antistaling agent of cyclopropenes, it is characterized in that: this composite preservative is composed of the following components by weight:
0.1～2 part of cyclopropylene
40～90 parts of stabilizing agents
2～8 parts of stabilization aids
3～20 parts of preservatives
0～15 part in bactericide
3～15 parts of sustained release agents
0.1～2 part of excipient
Wherein, cyclopropylene is the 1-methyl cyclopropene;
Preservative is one or more in sec-butylamine, sec-butylamine hydrochloride, sec-butylamine sulphate, sec-butylamine phosphate, sec-butylamine sulphite, sec-butylamine bisulfites, sec-butylamine lactate, sodium pyrosulfite, potassium metabisulfite, sodium sulphite, potassium sulfite, sodium hydrogensulfite, potassium bisulfite, propyl isorhodanide (propyl isothiocyanate), dehydroactic acid, sodium Diacetate, the diacetic acid potassium;
Bactericide is one or more in chlorine dioxide, sodium chlorate, potassium chlorate, sodium perchlorate, potassium hyperchlorate, sodium chlorite, potassium chlorite, the ethanol;
Stabilizing agent is one or more in dextrin, active carbon, diatomite, silica gel, rosin, active polysaccharide, starch, the modified starch;
Stabilization aid is one or more water or the alcoholic solution in acetic acid, sodium acetate, potassium acetate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, the sodium hydrogen phosphate;
Sustained release agent is that in quaternary ammonium salt, quaternary ammonium base, soda lime, quicklime, calcium chloride, zinc chloride, reducing sugar alkyd, the lignin polyamide one or more are mixed;
Excipient is one or more in stearic acid, calcium stearate, dolomol, stearyl alcohol, palmitic acid calcium, the palmitic acid magnesium.
2. composite antistaling agent of cyclopropenes according to claim 1 is characterized in that, its prescription is:
0.1～1.5 part of cyclopropylene
45～80 parts of stabilizing agents
2～5 parts of stabilization aids
5～12 parts of preservatives
3～5 parts in bactericide
7～12 parts of sustained release agents
0.5～1 part of excipient.
3. composite antistaling agent of cyclopropenes according to claim 1 is characterized in that: 1-methyl cyclopropene synthetic reaction is: 2-methyl isophthalic acid-propylene and bromine react in aprotic solvent, generate the 2-methyl isophthalic acid, the 2-dibromopropane; The 2-methyl isophthalic acid, 2-dibromopropane and Sodamide or potassamide reaction are sloughed sodium bromide or potassium bromide and are obtained the 1-methyl cyclopropene; 2-methyl isophthalic acid, the mol ratio of 2-dibromopropane and Sodamide or potassamide are 1: 1～3.
4. the preparation method of composite antistaling agent of cyclopropenes according to claim 1 is characterized in that:
When cyclopropylene and stabilizing agent, stabilization aid, preservative, bactericide, sustained release agent, mixed with excipients, 0～25 ℃ of temperature; Pressure 0.01～0.3Mpa in the blender; Incorporation time 8～64 hours.
5. the preparation method of composite antistaling agent of cyclopropenes according to claim 4 comprises the following steps:
(1) prepares the 1-methyl cyclopropene earlier;
(2) in the blender that electric mixer, piezometer, feeder, thermometer, wireway are housed, add stabilizing agent, stabilization aid, preservative, bactericide, sustained release agent, excipient importing nitrogen;
(3) chuck feeds cooling water, starts stirring;
(4) import the 1-methyl cyclopropene, make blender internal pressure 0.08-0.3Mpa, stirring 8-64 hour below 20 ℃, stop to mix;
(5) emit material, be the composite antistaling agent of cyclopropenes powder;
(6) powder is through compressing tablet, and packing can be made into the composite antistaling agent of cyclopropenes tablet.
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| CN1907046B (en) * | 2006-07-31 | 2010-05-12 | 山东营养源食品科技有限公司 | 1-methyl cyclopropene stable solution, preparation method thereof and preparation |
| CN101785498A (en) * | 2010-03-12 | 2010-07-28 | 国家农产品保鲜工程技术研究中心（天津） | Freshness preservative pad used for edible fungi storage and use method thereof |
| CN101810197B (en) * | 2010-04-14 | 2012-09-05 | 福州超大现代农业发展有限公司 | Pollution-free soil disinfectant and application thereof |
| CN105028619A (en) * | 2015-07-23 | 2015-11-11 | 成都市农林科学院 | Modified-atmosphere preservation method for bitter gourds |
| CN106417573A (en) * | 2016-12-07 | 2017-02-22 | 国家农产品保鲜工程技术研究中心（天津） | Double-effect freshness retaining sticker and application thereof to freshness retention of young garlic shoot |
| AU2019258844A1 (en) | 2018-04-27 | 2020-11-12 | Fresh Inset S.A. | Compositions and articles comprising complexes of 1-methylcycloproprene and alpha-cyclodextrin |
| CN109527081A (en) * | 2018-11-08 | 2019-03-29 | 华南农业大学 | A kind of 1- methyl cyclopropene sustained release adhesive and its preparation and application |
| CN109880527A (en) * | 2019-02-01 | 2019-06-14 | 西安泰鲜生物科技有限公司 | Increase the method for one layer of preservative film on packaging material and articles |
| PE20230411A1 (en) | 2020-02-03 | 2023-03-07 | Fresh Inset S A | STABLE COMPOSITIONS OF 1-METHYLCYCLOPROPENE AND USES THEREOF |
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