CN100367851C - Cyclopropene composite preservative and preparation method thereof - Google Patents

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

Cyclopropene composite preservative and preparation method thereof

(1) Technical field

The invention belongs to the field of anti-corrosion and fresh-keeping of fruits and vegetables. In particular, it relates to a cyclopropene composite antistaling agent with functions of anticorrosion, sterilization and freshness preservation, and a preparation method thereof.

(2) Background technology

Cyclopropene, especially 1-methylcyclopropene, can effectively inhibit the senescence effect of ethylene on harvested fruits and vegetables. It has been proven that 1-methylcyclopropene can significantly prolong the life of flowers and delay the aging of fruits and vegetables such as garlic moss, broccoli, apples, bananas, pears, dates, etc. It is a preservative with broad application prospects. But it can't prevent rot and deterioration caused by microorganisms well, and it is inconvenient to store, transport and use. In addition, many preservatives and bactericides can prevent or reduce the rot of fruits and vegetables, but they cannot delay the aging of fruits and vegetables. The technical problem to be solved by the present invention is to provide a cyclopropene composite preservative with antiseptic, sterilizing and fresh-keeping functions, which is convenient for storage, transportation and use, and can simultaneously delay the aging of fruit thinning and prevent and reduce the decay of fruit thinning. Before this, the synthetic method of 1-methylcyclopropene has many reports; As US.6017849; CN.1480438 (publication number) etc., the synthetic method of 1-methylcyclopropene among the present invention is different with it; With CN.15055992 ( Publication No.) compared with the cyclopropene antistaling agent with anti-corrosion and fresh-keeping dual functions, the present invention has features such as making more reasonable, more stable product, wider range of fresh-keeping and application, and more lasting effect.

(3) Contents of the invention

The purpose of the present invention is to provide a cyclopropene composite antistaling agent which has multiple functions such as delaying fruit and vegetable aging, anticorrosion, sterilization and freshness preservation, and is convenient for storage, transportation and use in order to overcome the drawbacks of existing preservatives.

Another object of the present invention is to provide a method for preparing the above-mentioned cyclopropene composite preservative.

Technical scheme of the present invention is realized like this:

The cyclopropene composite antistaling agent of the present invention, the composite antistaling agent is composed of the following components in parts by weight:

Cyclopropene 0.1～2 parts

Stabilizer 40～90 parts

Stabilizing agent 2-8 parts

Preservatives 3 to 20 parts

Fungicide 0～15 parts

Sustained release agent 3～15 parts

Excipient 0.1～2 parts

The cyclopropene in the present invention is 1-methylcyclopropene.

Preservatives are sec-butylamine, sec-butylamine hydrochloride, sec-butylamine sulfate, sec-butylamine phosphate, sec-butylamine sulfite, sec-butylamine bisulfite, sec-butylamine lactate, sodium pyrosulfite , one or more of potassium metabisulfite, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, propyl isothiocyanate, dehydroacetic acid, sodium diacetate, potassium diacetate;

The bactericide is one or more of chlorine dioxide, sodium chlorate, potassium chlorate, sodium perchlorate, potassium perchlorate, sodium chlorite, potassium chlorite, ethanol;

The stabilizer is one or more of dextrin, activated carbon, diatomaceous earth, silica gel, rosin, active polysaccharide, starch, and modified starch;

The stabilizing aid is one or more water or alcohol solutions of acetic acid, sodium acetate, potassium acetate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, and potassium dihydrogen phosphate;

The slow-release agent is one or more of quaternary ammonium salt, quaternary ammonium alkali, soda lime, quicklime, calcium chloride, zinc chloride, reducing sugar alkyd acid, lignin polyamide;

The excipient is one or more of stearic acid, calcium stearate, magnesium stearate, stearyl alcohol, calcium palmitate, magnesium palmitate and the like.

Among the above compound preservatives, the best formula is:

Cyclopropene 0.1～1.5 parts

Stabilizer 45～80 parts

Stabilizing agent 2~5 parts

Preservatives 5 to 12 parts

Fungicide 3 to 5 parts

Sustained release agent 7～12 parts

Excipient 0.5～1 part

Wherein cyclopropene is 1-methylcyclopropene.

The main raw material 1-methylcyclopropene of the cyclopropene composite antistaling agent of the present invention is 2-methyl-1-propene as a starting material, which is brominated to generate 2-methyl-1,2-dibromopropane. 2-methyl-1,2-dibromopropane reacts with sodium amide or potassium amide to remove 2 moles of sodium bromide or potassium bromide to generate 1-methylcyclopropene.

Its synthetic reaction formula:

The method for preparing cyclopropene composite antistaling agent of the present invention is made up of following steps successively:

(1) prepare 1-methylcyclopropene earlier by the above-mentioned method;

(2) Then add stabilizers, stabilizing aids, preservatives, bactericides, slow-release agents, excipients, etc. to introduce nitrogen into the mixer equipped with electric stirrer, pressure gauge, feeder, thermometer, and air duct ;

(3) Cooling water is passed into the jacket, and stirring is started;

(4) Introduce 1-methylcyclopropene, make the pressure in the mixer 0.08-0.3Mpa, stir for 8-64 hours below 20°C, and stop mixing;

(5) emit material, be cyclopropene composite antistaling agent powder;

(6) The powder can be made into cyclopropene composite antistaling agent tablets after being pressed into tablets and packaged.

The beneficial effects of the present invention are: the cyclopropene composite antistaling agent produced can be in the form of powder, tablet or granule, which not only inhibits the aging effect of ethylene on fruits and vegetables, prolongs the life of fruits and vegetables, has good freshness preservation effect, but also has Compounded with preservatives and fungicides, it can effectively reduce the rot of fruits and vegetables. The cyclopropene composite antistaling agent has the advantages of convenient storage, transportation and use, and the addition of a slow-release agent can have a lasting effect on the preservation and preservation of fruits and vegetables, and the effect is obvious. The antistaling agent plays a very important role in the storage, preservation and value-added of agricultural products-fruits and vegetables, and in improving people's quality of life. Moreover, the synthetic raw materials of 1-methylcyclopropene in the present invention are cheap and easy to obtain, the reaction yield is high, and the operation is easy.

(4) Description of drawings:

Fig. 1 is a schematic diagram of the preparation process of cyclopropene composite preservative

1. Reactor 2, 2-methyl-1,2-dibromopropane storage tank 3, feeding 4, water storage tank 5, nitrogen conduit 6, condenser 7, gas washing tank 8, gas storage tank 9, mixing Kettle 10, feeding port 11, nitrogen conduit 12, powder storage tank 13, powder packaging 14, tablet press 15, tablet packaging 16, product.

(5) Specific preparation examples;

In the present invention, cyclopropene mainly uses 1-methylcyclopropene, which belongs to small molecule cyclic olefin, has high chemical activity, and is extremely unstable at normal temperature, so its storage and use all need to be carried out at a lower temperature, and the temperature is slightly higher. That is, it will decompose or react with other substances, so special attention should be paid to the temperature during the reaction, generally not exceeding room temperature.

In addition, when 1-methylcyclopropene is mixed with a stabilizer, it should also be carried out at low temperature. In order to make the mixture fully and stabilize the preparation obtained after mixing, the following points should be noted:

1. The mixing kettle should be sealed, and the mixing must be carried out under a certain pressure of 1-methylcyclopropene, generally 0.01-0.3Mpa is appropriate;

2. There should be sufficient time for mixing, generally 8 to 64 hours;

3. The mixing temperature is generally 0-25°C;

4. The mixing kettle should be filled with inert gas nitrogen, otherwise, 1-methylcyclopropene is easily oxidized and becomes invalid;

5. During the production process of cyclopropene composite preservative, keep low temperature, otherwise, not only will the product fail, but also danger will occur.

Example (1):

1. In a 100L reaction kettle, add 40L of carbon tetrachloride and 20KG of bromine, start stirring, and cool down with cold water in the jacket to make the temperature in the kettle lower than 25°C, and introduce isobutylene (2-methyl- 1-propene), so that the temperature in the kettle is not higher than 30 ° C, until the purple color of bromine completely fades (the reaction solution is colorless), and then continue to stir for 30 minutes, stop, distill out the former fractions such as carbon tetrachloride, and collect 110- 120°C/-0.09Mpa fraction, 23KG of 2-methyl-1,2-dibromopropane was obtained, with a yield of 85%;

2. In the 50L reaction kettle, use _N2 to drive out the air, add 30L of dry petroleum ether at 60-90℃, 5KG of sodium amide, start stirring, cool with cold water in the jacket, keep the temperature in the kettle at about 20℃, slowly Slowly add 13KG of 2-methyl-1,2-dibromopropane dropwise, and the constant temperature of the kettle should not exceed 30°C. After the dropwise addition, continue to stir for 30-45 minutes;

3. Stop the flow of N ₂ , connect the gas outlet to the 1-methylcyclopropene gas storage tank, slowly add 5KG of water to the reactor, and import the generated gas 1-methylcyclopropene into the gas storage tank for future use.

4. Add 50 parts of dextrin to the mixing kettle; 26 parts of active polysaccharides; 4 parts of mixed solution of acetic acid and sodium acetate (0.5mol); close the lid of the kettle, ventilate _N gas to drive out the air, and let cold water through the jacket to bring the temperature of the kettle to Below 20°C, feed 0.8 parts of the prepared 1-methylcyclopropene gas, start stirring, keep the pressure in the kettle at about 0.2Mpa, stop passing 1-methylcyclopropene, and stir at below 20°C for 24 hours.

5. Release the material, centrifuge, dry, and pour the material into the granulator for granulation. Mix the prepared granules with 4 parts of sec-butylamine bisulfite, 4 parts of quicklime, 7 parts of calcium chloride, and 1 part of stearic acid in proportion, and press into tablets. The obtained tablets are cyclopropene composite preservatives;

6. Pack the cyclopropylene composite antistaling agent (tablet) in an air-permeable or air-impermeable packaging bag, store in a dry environment, and pierce the packaging bag or take it out when in use;

7. The obtained cyclopropene composite antistaling agent can also be used without tableting. The powder is stored in an airtight packaging bag. When used, the packaging bag is punched or taken out and placed in a container.

*After testing, this product contains 0.38% of 1-methylcyclopropene

Example (2):

1. In a 100L reaction kettle, add 40KG of carbon tetrachloride, and cool the jacket with ice water to lower the temperature of the kettle to below 10°C, and introduce about 7KG of isobutene (2-methyl-1-propylene) gas, slowly drop Add bromine, the temperature of the kettle should not be higher than 20°C, until the purple color of bromine no longer fades, continue to stir for 30 minutes, evaporate the previous fractions such as carbon tetrachloride, collect the fractions at 110-120°C/-0.09Mpa, and obtain 2 - About 21KG of methyl-1,2-dibromopropane, yield 78%;

2. In the 50L reaction kettle, pass _N2 to drive out the air, add 35L of dry petroleum ether at 60-90℃, 5KG of sodium amide, start stirring, cool with cold water in the jacket, keep the temperature in the kettle at about 20℃, slowly Slowly add 7KG of 2-methyl-1,2-dibromopropane dropwise, keep the temperature of the kettle below 30°C, and continue stirring for 30 minutes after the dropwise addition;

3. Stop the flow of N ₂ , connect the gas outlet to the 1-methylcyclopropene gas storage tank, slowly add 5KG of water to the reactor, and import the generated gas 1-methylcyclopropene into the gas storage tank for future use.

4. Add 30 parts of dextrin to the mixing kettle; 10 parts of active polysaccharide; 25 parts of modified starch; 5 parts of mixed solution of acetic acid and sodium acetate (0.5mol); 5 parts of sodium chlorite; ₂ Gas to drive out the air, pass cold water through the jacket to cool the temperature of the kettle to 10°C, and introduce 0.6 parts of the prepared 1-methylcyclopropene, so that the pressure in the kettle is 0.15-0.2Mpa, start stirring, and stir for 36 hours;

5. Release the material, mix the material with 5 parts of sodium bisulfite; 7 parts of sec-butylamine sulfate; 4 parts of calcium chloride; 5 parts of zinc chloride; 1 part of magnesium stearate; mix well and pour into the granulator During the granulation, the gained granules are put into a tablet press and pressed into tablets to obtain a cyclopropene composite antistaling agent (tablet);

6. Pack the cyclopropylene composite fresh-keeping sheet in an air-permeable or air-impermeable packaging bag, store in a dry environment, and pierce the packaging bag or take it out when using;

7. The obtained cyclopropene composite antistaling agent can also be used without tableting. The powder is stored in an airtight packaging bag. When used, the packaging bag is punched or taken out and placed in a container.

*After testing, this product contains 0.26% of 1-methylcyclopropene

Example (3):

1. Same as 1, 2, and 3 in Example 1;

2. Add 30 parts of dextrin to the mixing kettle; 35 parts of active polysaccharide; 5 parts of mixed solution of acetic acid and sodium acetate (0.5mol); ₅ parts of sodium chlorite; Pass cold water through the inside to reduce the temperature in the kettle to 5°C, introduce 0.8 parts of the prepared 1-methylcyclopropene, start stirring, make the pressure inside the kettle be 0.2-0.25Mpa, and stir for 30 hours at a temperature of 10°C;

3. Release the material, centrifuge, dry, and pour the material into the granulator to granulate; with 8 parts of sec-butylamine sulfite; 5 parts of calcium chloride; 3 parts of sodium chlorate; 5 parts of quicklime; stearic acid 1 part of magnesium is mixed evenly, and the tablets are compressed with a tablet machine, and the resulting tablets are cyclopropene composite preservatives;

4. Pack the cyclopropylene composite antistaling agent (tablet) in an air-permeable or air-impermeable packaging bag, store in a dry environment, and pierce the packaging bag or take it out when in use;

5. The obtained cyclopropene composite antistaling agent can also be made into a powder for use without tableting, and the powder is stored in an airtight packaging bag. When used, the packaging bag is punched or taken out and placed in a container.

*After testing, this product contains 0.51% of 1-methylcyclopropene

Example (4):

1. Same as 1, 2, and 3 in Example 1;

2. Add 40 parts of dextrin, 20 parts of modified starch, and 10 parts of active polysaccharide to the mixing kettle. Close the lid of the kettle, pass _N2 to drive out the air, and pass cold water through the jacket to reduce the temperature of the kettle to 5°C. 0.5 part of 1-methylcyclopropene, so that the pressure in the kettle is about 0.2Mpa, start stirring, and stir for 36 hours;

3. Release the material, mix well with 5 parts of sec-butylamine; 5 parts of sodium metabisulfite; 5 parts of calcium chloride; 4 parts of sodium chlorite; 7 parts of zinc chloride; Press into tablets to obtain cyclopropene composite antistaling agent (tablet);

4. Pack the cyclopropylene composite fresh-keeping sheet in an air-permeable or air-impermeable packaging bag, store it in a dry environment, and pierce the packaging bag or take it out when using;

5. The obtained cyclopropene composite antistaling agent can also be made into a powder without being pressed into tablets. The powder is stored in an airtight packaging bag. When used, the packaging bag is punched or taken out and placed in a container.

*After testing, this product contains 0.22% of 1-methylcyclopropene

Example (5):

1. Same as 1, 2, and 3 in Example 1;

2. Add 40 parts of dextrin to the mixing kettle; 20 parts of modified starch; 5 parts of mixed solution of acetic acid and _sodium acetate (0.5 mol); Cool down to 10°C, feed 1.1 parts of the prepared 1-methylcyclopropene to make the pressure inside the kettle 0.15-0.2Mpa, start stirring, and stir for 28 hours. Release the material, centrifuge, dry, and pour the material into the granulator for granulation. Add 8 parts of zinc chloride in proportion; 0.5 part of zinc stearate, mix evenly, and press into tablets to obtain cyclopropene composite antistaling agent (tablet) A;

3. Pour 10 parts of sec-butylamine hydrochloride; 5 parts of sodium sulfite; 5 parts of calcium chloride; 5 parts of sodium chlorite; 8 parts of calcium chloride; Mix evenly, add in the granulator to granulate, add in the tablet press, and compress into tablets to obtain cyclopropene composite antistaling agent (tablet) B;

4. Cyclopropene composite preservatives A and B are packaged in air-permeable or air-impermeable packaging bags, respectively, and stored in a dry environment, and the packaging bags are punched or taken out when used;

5. Cyclopropene composite preservatives A and B can also be made into powder without tableting, and packed in airtight packaging bags respectively. When used, the packaging bags are punched or taken out and placed in a container.

* After testing, tablet A of this product contains 0.83% of 1-methylcyclopropene

Example (6):

1. Same as 1, 2, and 3 in Example 1;

2. Add 40 parts of dextrin to the mixing kettle; 10 parts of active polysaccharide; ₁₀ parts of calcium chloride; Lower the temperature to 15°C, feed 0.6 parts of the prepared 1-methylcyclopropene, make the pressure in the kettle be about 0.2Mpa, start stirring, and stir for 40 hours; release the material, pour it into a granulator to granulate and tablet, Obtain cyclopropene composite antistaling agent (sheet) A;

3. Add 10 parts of sodium metabisulfite; 2 parts of sodium diacetate; 4 parts of sodium chlorite; 30 parts of modified starch; Antistaling agent (tablet) B;

4. Cyclopropene composite preservatives A and B are packaged in air-permeable or air-impermeable packaging bags, respectively, and stored in a dry environment. When using, the packaging bags are punched or taken out;

5. Cyclopropene composite preservatives A and B can also be made into powder without tableting, and packed in airtight packaging bags respectively. When used, the packaging bags are pierced or taken out and placed in a container.

* After testing, tablet A of this product contains 0.38% of 1-methylcyclopropene

Example (7):

1. 1, 2, and 3 are the same in Example 2;

2. Add 40 parts of dextrin to the mixing kettle; 30 parts of active polysaccharide; ₄ parts of mixed solution of acetic acid and sodium acetate (0.5mol); down to 10°C. Feed 1.2 parts of the prepared 1-methylcyclopropene, make the pressure of the kettle be 0.08-0.12Mpa, start stirring, and stir for 30 hours;

3. Release the material, centrifuge, dry, add 12 parts of sec-butylamine sulfite; 10 parts of calcium chloride; Agent (tablet);

4. Cyclopropene composite antistaling agent (tablet) can be packaged in air-permeable or air-impermeable packaging bags, stored in a dry environment, and the packaging bags are punched or taken out when used;

5. The cyclopropene composite antistaling agent can also be made into a powder without being pressed into tablets, and stored in an airtight packaging bag. When used, the packaging bag is punched or taken out and placed in a container.

*After testing, this product contains 1.03% of 1-methylcyclopropene.

Example (8):

1. Same as 1, 2, and 3 in Example 2;

2. Add 40 parts of dextrin; 40 parts of modified starch; 8 parts of active polysaccharide; 10 parts of calcium chloride; ₁ part of calcium stearate; Cool water to 0°C, feed 1.1 parts of the prepared 1-methylcyclopropene, make the pressure inside the kettle 0.08Mpa, start stirring, and stir for 24 hours;

3. Release the material, pour it into a granulator to granulate, and press into tablets to obtain a cyclopropene composite preservative (tablet);

4. Cyclopropylene composite fresh-keeping sheets can be packaged in air-permeable or air-impermeable packaging bags, stored in a dry environment, and the packaging bags are punched or taken out when used;

5. The cyclopropene composite antistaling agent can also be made into a powder without being pressed into tablets, and packed in an airtight packaging bag. When used, the packaging bag is punched or taken out and placed in a container.

*After testing, this product contains 0.88% of 1-methylcyclopropene

Embodiment (9):

1. Same as 1, 2, and 3 in Example 2;

2. Add 30 parts of active polysaccharides to the mixing kettle; 40 parts of modified starch; 5 parts of mixed solution of acetic acid and sodium acetate (0.5mol); close the lid of the kettle, pass _N to drive out the air, and cool the jacket with ice water to make the kettle The temperature was lowered to 0°C, and 1.2 parts of the prepared 1-methylcyclopropene was introduced, so that the pressure in the kettle was 0.05-0.08Mpa, and the stirring was started for 18 hours; the materials were released, centrifuged, dried, and calcium chloride 5 1 part; 1 part of zinc stearate, poured into the granulator to granulate, tableted to obtain cyclopropene composite antistaling agent (tablet) A;

3. Pour 10 parts of sec-butylamine; 30 parts of active polysaccharide; 10 parts of calcium chloride; Propylene composite preservative (tablet) B;

4. Cyclopropene composite preservative (tablets) A and B are packaged in air-permeable or air-impermeable packaging bags and stored in a dry environment. When in use, the packaging bags are punched or taken out. A and B tablets can be used separately or together .

5. The above-mentioned cyclopropene composite preservatives A and B can also be made into powder without tableting, and packed in airtight packaging bags respectively. When used, the packaging bags are punched or taken out and placed in a container. use together.

* After testing, tablet A of this product contains 1.27% of 1-methylcyclopropene.

Example (10):

Stability of 1-methylcyclopropene in compound preservatives

The content of 1-methylcyclopropene in the composite preservative made by this patent at 0-5°C for different time

Composite preservative serial number content (%) original content Leave it for 7 days Hold for 30 days Hold for 90 days 180 days Hold for 360 days Example 1 Composite preservative (tablet) 0.38 0.36 0.36 0.35 0.30 0.29 Example 2 Composite preservative (tablet) 0.26 0.26 0.25 0.23 0.20 0.20 Example 7 Composite preservative (tablet) 1.03 1.01 0.96 0.96 0.93 0.87 Example 9 Composite preservative A (tablet) 1.20 1.16 1.12 1.10 1.06 0.98

As can be seen from the above table, in the composite antistaling agent made by this patent, the content of 1-methylcyclopropene is relatively stable. After calculation, place 360 days at 0-5 ℃, the content loss rate is 15.5-23.7%

In sunny weather, after the dew dries up in the morning or in the evening, harvest broccoli bulbs that are all green in color, with small buds not open, and 13-16 cm in diameter. Within 2 hours after the broccoli is harvested, put it in a food-grade polyvinyl chloride plastic tent, then weigh the compound preservative of Example 2 according to the volume of the plastic tent, and pour it into a small dry beaker according to the amount of 0.96 g/m3 middle. Put the beaker in the tent, add 10ml of water/gram of preservative, and quickly seal it for 12 hours. The broccoli is taken out for storage, transportation or circulation sale. For the broccoli treated in this way, the opening of flower buds and senility and yellowing at room temperature can be delayed by 1 time. Under the condition of 0-1 ℃, use 4 silk food-grade polyvinyl chloride fresh-keeping bags for MA storage, and the fresh-keeping time can be extended by 1 month.

Example (12) Prolonging the fresh-keeping period of kiwi fruit by using cyclopropene composite preservative

Harvest 7-8 mature Qinmei kiwifruit in fine weather after the dew dries up in the morning or in the evening. Within 4 hours, put it in a polyethylene plastic tent. According to the volume of the plastic tent, take by weighing the composite preservative of Example 1 according to 0.66 g/m3, and pour it into a dry small beaker. Put the beaker in the big tent, add water 15ml/g composite preservative, and seal it quickly. After 12 hours, the kiwi fruit was taken out for storage, transportation or distribution. The kiwifruit treated in this way has a delay of 7 days in softening time at 20-25°C. 0°C--0.5°C, store in 3-filament polyethylene fresh-keeping bag MA, and the storage life will be extended by 3 months.

Example (13) Using cyclopropene compound preservative to reduce apple tiger skin disease

Fuji apples harvested according to quality standards are transported to the controlled atmosphere storage room within 24 hours, and the daily storage volume does not exceed 1/5 of the designed storage capacity. The temperature in the library was lowered to -1°C in advance. After the storage is full and the storage temperature drops to 0°C, weigh the composite preservative of Example 9 according to the storage capacity of 0.020 g/m3, and put it in a dry beaker in 3 parts. Put the beakers evenly in different parts of the warehouse, and then pour water into the beakers according to 20 ml of water/gram of composite preservative. Store airtight. Stored for 10 months, the incidence of tiger skin disease was 5% in the control group, and no tiger skin disease occurred in the treatment.

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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