CN105885698B - A kind of smooth eleostearate - Google Patents

A kind of smooth eleostearate Download PDF

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Publication number
CN105885698B
CN105885698B CN201610242229.5A CN201610242229A CN105885698B CN 105885698 B CN105885698 B CN 105885698B CN 201610242229 A CN201610242229 A CN 201610242229A CN 105885698 B CN105885698 B CN 105885698B
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morpholine
deionized water
fruit
water
added
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CN105885698A (en
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樊惠昌
黄益芸
徐钱海
朱显庆
王天浩
张文兵
凌军
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SHANGHAI HUICHANG CHEMICAL FACTORY
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SHANGHAI HUICHANG CHEMICAL FACTORY
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09FNATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
    • C09F1/00Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
    • C09F1/04Chemical modification, e.g. esterification
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00Preservation or chemical ripening of fruit or vegetables
    • A23B7/16Coating with a protective layer; Compositions or apparatus therefor
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00Preservation or chemical ripening of fruit or vegetables
    • A23B7/14Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/154Organic compounds; Microorganisms; Enzymes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D295/00Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182Radicals derived from carboxylic acids
    • C07D295/185Radicals derived from carboxylic acids from aliphatic carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04Acids; Metal salts or ammonium salts thereof
    • C08F220/06Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • Microbiology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

A kind of smooth eleostearate of the present invention, by light eleostearic acid, morpholine, ethyl alcohol, ammonium hydroxide and deionized water are prepared, the light eleostearic acid, morpholine, ethyl alcohol, the weight ratio of ammonium hydroxide and deionized water is 10.0~18.0:1.93~3.95:8.0~10.0:0.5~1.2:60.0~70.0, first the deionized water of ethyl alcohol and 3 ~ 20% is added in a reaction kettle, it is preheated to 65 ~ 73 DEG C, put into light eleostearic acid, temperature is promoted to 76 ~ 83 DEG C, 70~80% morpholine is added, stir 10 ~ 30min, pressure, it is warming up to 85 ~ 93 DEG C, heat preservation 1 ~ 5 hour, it is cooled to 73 ~ 83 DEG C, remaining morpholine is added, ammonium hydroxide and remaining deionized water, continue stirring 20 ~ 35 minutes, it is cooled to 20 ~ 50 DEG C, it filters to obtain the final product Light eleostearate.

Description

A kind of smooth eleostearate
Technical field:
The invention belongs to chemical field more particularly to a kind of preservative fruit wax, specifically a kind of fruit freshness preserving fruit wax and Preparation method.
Background technique:
Fruit wax means the plastics for the surface treatment of general fruit.Due to social development, fruit is not to pick on the spot Based on eating on the spot, but large-scale popularization national market is wanted even to export, thus waxing is fresh-keeping be modern fruit picking after The merchandized handling historical link that must be handled in time.Waxing can be enhanced lustrous surface exterior quality and improve commodity value;Together When can also close fruit surface pores and reduce fruit moisture loss and reduce weightless, be reduced or avoided because the factors such as gas and water, bacterium are made The fruit of cause is rotten to protect the edible health of the mankind, is conducive to extend the fruit fresh-keeping time.Recent decades human development is developed should Class product.World's most countries and area, which have routinized to generalize, uses fruit wax.In the world, the U.S. and Spain are to be engaged in The research of fruit wax is national earlier.The nearly more than ten years, China, which has also played an active part in, to research and develop and has delivered multinomial patent, but current China Domestic market due to dog-eat-dog and the good and bad jumbled together, also once several times because caused by waxing problem citizen's phychology it is uneasy, and from the country The applicable cases in market are seen, for capability and performance, it appears that still to approve U.S.'s product 402, and its price also highest, really it is Make us sighing with feeling.How to change and improve this state, among the numerous scientific research personnel in China and unit are just actively being made great efforts.
According to market situation, the fruit wax of current most of uses is still based on fatty acid alkylbenzyldimethylasaltsum saltsum.The U.S. is in last century seven The ten's developed such fruit wax and set up corresponding FDA standard, it should recognize, design has history reason, day Right fatty acid is in conjunction with morpholine, first is that itself having the effect sense of natural material health, second is that having can be water-soluble at wax liquor, film again It is bright beautiful afterwards, be not easy to whiten, Keep the quality and freshness, third is that having carried out alkylbenzyldimethylasaltsum saltsum cracking health detection again.Generally, good fruit wax Basic main points are exactly 2 points: first is that health has evidence, second is that being not easy mutation of whitening.
Domestic a lot of manufacturers all use fatty acid morpholine hydrogen bond salt and fatty acid morpholino amide as preservative fruit wax, but this Although a little fruit wax prices are cheap, hidden danger can be generated to personal safety.
According to known to current data, the U.S. 402 is based on morpholine fatty acid salt, and FDA is detected also as standard Object, there is not yet other chemistry are summarized.The U.S. 402 recent decades effects of present invention affirmative, but the present invention is inquired into through chemistry and application Comparison, it is believed that should turn to improve.
Summary of the invention:
For above-mentioned technical problem in the prior art, the present invention provides a kind of fruit freshness preserving fruit wax and its preparation sides Method, described this fruit freshness preserving fruit wax and preparation method thereof to solve fruit wax in the prior art is at high cost, fresh-keeping function is weak, To the unsafe technical problem of human body.
The present invention provides a kind of morpholine fatty acid ester salts, by light eleostearic acid (bleaching shellac), abietic acid resin (PL -101, symbol Close SGS), morpholine, ethyl alcohol, ammonium hydroxide and deionized water be prepared, the light eleostearic acid (bleaching shellac), abietic acid resin (PL- 101, meet SGS), morpholine, ethyl alcohol, ammonium hydroxide and deionized water weight ratio be 10.0~18.0:5.0~15.0:1.93~ First a reaction kettle is added in the deionized water of ethyl alcohol and 3~20% by 3.95:8.0~10.0:0.5~1.2:60.0~70.0 In, 65~73 DEG C are preheated to, light eleostearic acid and abietic acid resin are put into, temperature is promoted to 76~83 DEG C, 70~80% morpholine is added, 10~30min is stirred, pressure is warming up to 85~93 DEG C, keeps the temperature 1~5 hour, is cooled to 73~83 DEG C, and remaining morpholine, ammonia is added Water and remaining deionized water, continue stirring 20~35 minutes, open kettle and are cooled to 20~50 DEG C, filter up to morpholine aliphatic ester Salt.
The present invention also provides a kind of smooth eleostearate, by light eleostearic acid (bleaching shellac), morpholine, ethyl alcohol, ammonium hydroxide and go from Sub- water is prepared, the light eleostearic acid (bleaching shellac), morpholine, ethyl alcohol, ammonium hydroxide and deionized water weight ratio be 10.0~ First the deionized water of ethyl alcohol and 3~20% is added by 18.0:1.93~3.95:8.0~10.0:0.5~1.2:60.0~70.0 In one reaction kettle, 65~73 DEG C are preheated to, puts into light eleostearic acid, temperature is promoted to 76~83 DEG C, 70~80% morpholine is added, 10~30min is stirred, pressure is warming up to 85~93 DEG C, keeps the temperature 1~5 hour, is cooled to 73~83 DEG C, and remaining morpholine, ammonia is added Water and remaining deionized water, continue stirring 20~35 minutes, open kettle and are cooled to 20~50 DEG C, filter up to light eleostearate.
The present invention also provides a kind of organosilicon acrylic resin, by acrylic acid or acrylate, propylene organosilicon, potassium peroxydisulfate, Isopropanol, ammonium hydroxide and deionized water are prepared, the acrylic acid or acrylate, propylene organosilicon, potassium peroxydisulfate, different The weight ratio of propyl alcohol, ammonium hydroxide and deionized water is 20~25:0.5~1.5:0.3~0.6:10.0~16.0:3.0~5.0: 60.0~66.0, first deionized water and isopropanol are added in a reaction kettle and heated, is preheated to 65~75 DEG C, it is added 5~ 15% K2S2O8, 76~85 DEG C are again heated to, starts that acrylic acid or acrylate, propylene organosilicon and 70~83% is added dropwise K2S2O8, 82~85 DEG C keep the temperature 2~3 hours, and dropwise reaction terminates that remaining K is added2S2O8, 85`90 DEG C keep the temperature 0.5~ 1.5 hours, 60~75 DEG C are subsequently cooled to, ammonium hydroxide is added and adjusts PH7~8, continues to be cooled to 20~50 DEG C, filters up to silicon third Resin.
The present invention also provides a kind of fruit freshness preserving fruit wax (SW-68A), by above-mentioned morpholine fatty acid ester salt and above-mentioned Organosilicon acrylic resin, deionized water composition, mass percent of the morpholine fatty acid ester salt in preservative fruit wax be 9.0%~ 12.0%, mass percent of the organosilicon acrylic resin in preservative fruit wax is 8.0%~10.0%, and surplus is deionized water.
The present invention also provides a kind of preparation methods of above-mentioned fruit freshness preserving fruit wax, weigh morpholine rouge by mass percentage Organosilicon acrylic resin and deionized water are first added in a reaction vessel, is warming up to 45 for fat acid esters salt and organosilicon acrylic resin, deionized water It~50 DEG C, adds morpholine fatty acid ester salt, stirs 30~60min, be cooled to 25~40 DEG C, filter to obtain the final product.
The present invention also provides a kind of fruit freshness preserving fruit waxes (SW-68B), by above-mentioned light eleostearate and above-mentioned silicon third Resin, deionized water composition, mass percent of the light eleostearate in preservative fruit wax are 6.0%~10.0%, institute Mass percent of the organosilicon acrylic resin stated in preservative fruit wax is 8.0%~12.0%, and surplus is deionized water.
The present invention also provides a kind of preparation methods of above-mentioned fruit freshness preserving fruit wax, weigh light eleostearic acid by mass percentage Organosilicon acrylic resin and deionized water are first added in a reaction vessel, is warming up to 45~50 for ester salt and organosilicon acrylic resin, deionized water DEG C, it adds light eleostearate, stirs 30~60min, be cooled to 25~40 DEG C, filter to obtain the final product.
The present invention also provides a kind of fruit freshness preserving fruit waxes (SW-68C), by above-mentioned organosilicon acrylic resin and deionized water group At mass percent of the organosilicon acrylic resin in preservative fruit wax is 16.0~18.0, and surplus is deionized water.
The present invention also provides a kind of preparation methods of above-mentioned fruit freshness preserving fruit wax, weigh the third tree of silicon by mass percentage Rouge and deionized water are first added organosilicon acrylic resin in a reaction vessel, are warming up to 35~45 DEG C, add deionized water, stir Mix 20~60min, cold filtration to obtain the final product.
The present invention provides a kind of novel fruit wax bulk composition morpholine fatty acid ester salt, another kind can do auxiliary ingredients again Macromolecule resin in the water-soluble organic silicon modified acroleic acid of main component can be done, is then matched by being converted by ester salt and organosilicon acrylic resin Preservative fruit wax, not only have at after cere it is bright it is bright and new, do not whiten, ventilative control water, lasting stability, the fresh-keeping synthesis such as guarantee the quality it is excellent Different effect, and environmentally-friendly sanitary.
Specific embodiment:
Embodiment 1
The present invention provides a kind of morpholine fatty acid ester salts, by light eleostearic acid (bleaching shellac), abietic acid resin (PL -101, symbol Close SGS), morpholine, ethyl alcohol, ammonium hydroxide and deionized water be prepared, the light eleostearic acid (bleaching shellac), abietic acid resin (PL- 101, meet SGS), morpholine, ethyl alcohol, ammonium hydroxide and deionized water weight ratio be 10.0~18.0:5.0~15.0:1.93~ First a reaction kettle is added in the deionized water of ethyl alcohol and 3~20% by 3.95:8.0~10.0:0.5~1.2:60.0~70.0 In, 65~73 DEG C are preheated to, light eleostearic acid and abietic acid resin are put into, temperature is promoted to 76~83 DEG C, 70~80% morpholine is added, 10~30min is stirred, pressure is warming up to 85~93 DEG C, keeps the temperature 1~5 hour, is cooled to 73~83 DEG C, and remaining morpholine, ammonia is added Water and remaining deionized water, continue stirring 20~35 minutes, open kettle and are cooled to 20~50 DEG C, filter up to morpholine aliphatic ester Salt.
Embodiment 2
The present invention also provides a kind of smooth eleostearate, by light eleostearic acid (bleaching shellac), morpholine, ethyl alcohol, ammonium hydroxide and go from Sub- water is prepared, the light eleostearic acid (bleaching shellac), morpholine, ethyl alcohol, ammonium hydroxide and deionized water weight ratio be 10.0~ First the deionized water of ethyl alcohol and 3~20% is added by 18.0:1.93~3.95:8.0~10.0:0.5~1.2:60.0~70.0 In one reaction kettle, 65~73 DEG C are preheated to, puts into light eleostearic acid, temperature is promoted to 76~83 DEG C, 70~80% morpholine is added, 10~30min is stirred, pressure is warming up to 85~93 DEG C, keeps the temperature 1~5 hour, is cooled to 73~83 DEG C, and remaining morpholine, ammonia is added Water and remaining deionized water, continue stirring 20~35 minutes, open kettle and are cooled to 20~50 DEG C, filter up to light eleostearate.
Embodiment 3
The present invention also provides a kind of organosilicon acrylic resin, by acrylic acid or acrylate, propylene organosilicon, potassium peroxydisulfate, Isopropanol, ammonium hydroxide and deionized water are prepared, the acrylic acid or acrylate, propylene organosilicon, potassium peroxydisulfate, different The weight ratio of propyl alcohol, ammonium hydroxide and deionized water is 20~25:0.5~1.5:0.3~0.6:10.0~16.0:3.0~5.0: 60.0~66.0, first deionized water and isopropanol are added in a reaction kettle and heated, is preheated to 65~75 DEG C, it is added 5~ 15% K2S2O8, 76~85 DEG C are again heated to, starts that acrylic acid or acrylate, propylene organosilicon and 70~83% is added dropwise K2S2O8, 82~85 DEG C keep the temperature 2~3 hours, and dropwise reaction terminates that remaining K is added2S2O8, 85`90 DEG C keep the temperature 0.5~ 1.5 hours, 60~75 DEG C are subsequently cooled to, ammonium hydroxide is added and adjusts PH7~8, continues to be cooled to 20~50 DEG C, filters up to silicon third Resin.
Embodiment 4
The present invention also provides a kind of fruit freshness preserving fruit wax (SW-68A), by above-mentioned morpholine fatty acid ester salt and above-mentioned Organosilicon acrylic resin, deionized water composition, mass percent of the morpholine fatty acid ester salt in preservative fruit wax be 9.0%~ 12.0%, mass percent of the organosilicon acrylic resin in preservative fruit wax is 8.0%~10.0%, and surplus is deionized water.
The present invention also provides a kind of preparation methods of above-mentioned fruit freshness preserving fruit wax, weigh morpholine rouge by mass percentage Organosilicon acrylic resin and deionized water are first added in a reaction vessel, is warming up to 45 for fat acid esters salt and organosilicon acrylic resin, deionized water It~50 DEG C, adds morpholine fatty acid ester salt, stirs 30~60min, be cooled to 25~40 DEG C, filter to obtain the final product.
Embodiment 5
The present invention also provides a kind of fruit freshness preserving fruit waxes (SW-68B), by above-mentioned light eleostearate and above-mentioned silicon third Resin, deionized water composition, mass percent of the light eleostearate in preservative fruit wax are 6.0%~10.0%, institute Mass percent of the organosilicon acrylic resin stated in preservative fruit wax is 8.0%~12.0%, and surplus is deionized water.
The present invention also provides a kind of preparation methods of above-mentioned fruit freshness preserving fruit wax, weigh light eleostearic acid by mass percentage Organosilicon acrylic resin and deionized water are first added in a reaction vessel, is warming up to 45~50 for ester salt and organosilicon acrylic resin, deionized water DEG C, it adds light eleostearate, stirs 30~60min, be cooled to 25~40 DEG C, filter to obtain the final product.
Embodiment 6
The present invention also provides a kind of fruit freshness preserving fruit waxes (SW-68C), by above-mentioned organosilicon acrylic resin and deionized water group At mass percent of the organosilicon acrylic resin in preservative fruit wax is 15.0~18.0, and surplus is deionized water.
The present invention also provides a kind of preparation methods of above-mentioned fruit freshness preserving fruit wax, weigh the third tree of silicon by mass percentage Rouge and deionized water are first added organosilicon acrylic resin in a reaction vessel, are warming up to 35~45 DEG C, add deionized water, stir Mix 20~60min, cold filtration to obtain the final product.
Next the present invention mainly proves in terms of three:
7 sanitary considerations of embodiment
Fruit wax bulk composition natural fat hydrochlorate demonstration: natural acid such as lac (light eleostearic acid class), rosin (abietic acid class), Palmitinic acid (palmitic acid) etc. and ammonium hydroxide (NH3-H2O), morpholineChemical combination.Chemically principle is inferred, main It to be following four big reaction species.
1, fatty acid ammonium salt: R-COOH+NH3·H2O→R-COO·NH4+H2O
Reaction condition: lower >=30 DEG C of i.e. dissolvable reactions, activity are maximum.
Performance effect: it is water-soluble good, it can machine spray effect on very effective raising fruit wax storage stability and fruit wax.Other It is auxiliary element in fruit wax without very positive interaction.
Environmentally-friendly sanitary: being easier to decompose, and is reduced into organic acid and volatilization ammonia, poisons very small, discussion summary.
2, morpholine fatty acid salt (hydrogen bond salt):
Reaction condition: it is moderate, it can be reacted for 60~80 DEG C after fatty acid dissolution, activity is larger.
Performance effect: good water solubility is stablized.It can effectively improve fruit wax glue film levelability, adhesive force, brightness, vivid Property etc. a series of effects, and because glue film absorb water it is moderate, i.e., largely absorb water it is readily soluble be not easy to whiten, can also be extensive after a small amount of water suction whiting It is multiple, therefore can be used as the main component of fruit wax, there is preferable fresh-keeping effect, is most earlier than last century the seventies by the U.S. 402 succeed in developing the main body fruit wax ingredient being developed so far.
Environmentally-friendly sanitary: it can decompose.Morpholine and corresponding fatty acid are resolved into after into human body.U.S. testing result rat LD50 of passing through mouth is 1600mg/kg, and morpholine fatty acid salt is classified as GRAS substance by 1977 U.S. FDA.
3, morpholine fatty acid ester salt:
(the ester salt is one of subject matter, and ester salt is fruit wax bulk composition of the invention)
Reaction condition: slightly higher.For suitable fatty acid in alcohol water after completely dissolution in 80~90 DEG C, a few hours reaction is active moderate.
Performance effect: good water solubility, stabilization.Waxing effect equally can effectively improve fruit wax levelability, attached with hydrogen bond salt Put forth effort, brightness, a series of effects such as vibrancy, and because ester bond salt because steady chemical structure is not easy to crack, therefore can be inhaled Water and be not easy to return it is white, protect light fresh-keeping effect time ester salt certainly will be better than hydrogen bond salt.
Environmentally-friendly sanitary: it is not easy to crack.It can be still discharged substantially with esters state into human body, even if cracking, also than hydrogen bond salt Generated morpholine much less.Clearly, morpholine belongs to a kind of organic amine being harmful to the human body, though U.S. FDA is through rat entrance It is classified as GRAS substance after test, indicates the boundary that can not be poisoned immediately.Nevertheless, when if human body is few or when long Micro intake morpholine organic amine, harmful consequences is uncertain.In brief, human body had better not take in the substance, It is at least more fewer more non-hazardous.
4, morpholine fatty acid amide:
Reaction condition: higher, it is necessary in high temperature dehydration state response.It is active little.
Performance effect: poorly water-soluble, nontransparent stabilization.Upper machine sprayability, quick-drying are better than ester salt and hydrogen bond salt, but attached Put forth effort, brightness, other aspects such as freshness are not as good as ester salt and hydrogen bond salt, be particularly susceptible water suction whiting be difficult to recover it is even de- Glue cannot function as fruit wax bulk composition at all.Both at home and abroad there is not yet such report, but the author it is reported that, some domestic Guo La manufacturers Because considering that dissolution hard fat sour (lac class etc.) needs, heating (mostly at 110~130 DEG C) is pressed with dissolved fat to water body Acid react with morpholine converts wax again, it is possible some do not know that at this point in the reaction, the probability of generation morpholine fatty acid amide mentions significantly Height, so that this sequelae such as whiting dewaxing often occurs in the market.
Environmentally-friendly sanitary: being difficult to crack, and toxicity is not surveyed, and is easy excretion not as good as ester salt and hydrogen bond salt certainly into human body, does not answer As fruit wax ingredient.
Morpholine fatty acid salt class (ester salt and hydrogen bond salt) comparison demonstration:
According to the acid value of natural acid, the compound molecular weight in conjunction with morpholine may infer that, to judge that morpholine accounts for The number of components of its compound by solid content comparison weightless after original solid content after film forming and baking, and then is inferred because of cracking The fatty acid salt structure component of weightless composition.
Lac resin: acid value is mostly 70 or so, and single moles of carboxylic acids molecular weight is 800 or so, in conjunction with molecular weight after morpholine It is 887, wherein morpholine occupancy volume is 9.81%.Rosin resin: acid value is mostly 100~130, and single moles of carboxylic acids molecular weight is 560 ~430, in conjunction with molecular weight 647~517 after morpholine, wherein morpholine occupancy volume is 13.44~16.82%.Palmitinic acid: acid value 218.8, single moles of carboxylic acids molecular weight 256, in conjunction with molecular weight 343 after morpholine, wherein morpholine occupancy volume is 25.36%.
The present invention has specially respectively done one group of comparative test using lac and rosin, be formulated it is identical (especially fatty acid with Quinoline ratio is consistent), main difference is reaction controlling condition.
S-49: after alcohol hydrolysis, 80~85 DEG C are reacted three hours;S-50: after alcohol hydrolysis, 75~80 DEG C are reacted one hour, pine It is fragrant;(formulation weight percentage: abietic acid: morpholine: ammonium hydroxide: ethyl alcohol: deionized water=18.0~19.0:3.0~3.2:2.8~ 3.0:8.0~10.0:65.0~68.0)
After C-410:80 DEG C of hydrolysis, >=90 DEG C are reacted three hours;After C-425:65 DEG C of alcohol hydrolysis, >=90 DEG C of reactions three are small When, lac;(formulation weight percentage: eleostearic acid: morpholine: ammonium hydroxide: ethyl alcohol: deionized water=18.0~19.0:3.6~3.8:2.0 ~2.5:8.0~10.0:65.0~68.0)
Test is imagined, and same reaction is formulated different control conditions, and rosin group should be more with S-49 ester salt composition, and weightlessness should be less than S-50;Lac should be more with C-425 ester salt composition, and weightlessness should be less than C-410.
Experimental Comparison result: original solid content (0) [100 DEG C of * 2hr] is toasted solid content (1) [130 DEG C of * 3hr], weight-loss ratio Weight loss accounts for the percentage of original solid content after as toasting.Test result is determined for compliance with test and imagines, and S-50 and C-410 are weightless Rate is obviously higher than S-49 and C-425, see Table 1 for details
Meanwhile the present invention has carried out tens groups times to SW-68 and the U.S. 402 and the multiple groups country waxy product of fruit and has test repeatedly Weight-loss ratio is toasted, see Table 2 for details.
Table 1
Table 2
Deduction, above-mentioned fruit wax main component can be inquired into.
SW-68A: natural acid morpholine ester salt, silicone-acrylic water-soluble resin;
SW-68B: silicone-acrylic water-soluble resin, light eleostearic acid morpholine ester salt;
SW-68C: silicone-acrylic water-soluble resin, (lysate is mainly NH3);
U.S. 402: fatty acid morpholine hydrogen bond salt --- masterpiece, FDA author;
Beautiful 402D:402 improves object, it is clear that ester salt composition has improved, and hydrogen bond salt composition obviously lowers perhaps added with modification Resin is the maximum imported product of the current dosage in China, and reaction is good;
State sample A: approximate 402D, ester salt hydrogen bond salt equilibrium, concentrated expression is normal, is increasingly becoming a domestic brand;
State sample B: it will be apparent that main body is palmitic acid morpholine hydrogen bond salt, low in cost, Market reaction is fine, but because of easily water Molten delustring, therefore fresh-keeping and other effects too late domestic sample A;
State sample C: fatty acid morpholino amide is more, therefore muddy not durable, and is easy water suction whiting, and it is high temperature height that future trouble, which is not surveyed, Suppress it is standby, currently improve in;
State sample D: similar domestic sample C, there are morpholino amide composition, but (translucent and long this point of susceptible of proof of storage) fewer than C, applies Fruit also hygroscopic whiting.
Integration test result sees, SW-68 high temperature weight-loss ratio is significantly lower than 402D (being more more than 402), then finally can be with Infer, on the one hand SW-68 had both met current FDA standard, on the other hand it is not surveyed harmfulness and is less than 402D yet.From the perspective of from this point, Whether related hygiene department should revised sanitary standard: improve ester salt composition, reduce hydrogen bond salt composition, prevent amide at Part.From the perspective of from another point --- for the hygienic angle point of i.e. permanently effective science, the direction of fruit wax development should be SW-68C class product, Without morpholine organic amine, even if stable is not easy cracking fission and the polymer waterborne object without other bad sequelae --- accidentally Food is also easily normally mediated.
It is presently believed that develop fruit wax class food contact class product even other direct foodstuff products, it must abundant benefit It is inquired into chemical basis mechanism and speculates and then make a decision, just meet the scientific development of human survival in this way.
Machine effect in embodiment 8
Any industrial products, if supreme machine operability, even if environmentally-friendly sanitary, performance are good again again, all are futile effort.Fruit Wax, which is operated the computer, to be had become China and waxes now the actual state of industry, therefore upper machine controllability must be paid attention to, and the present invention is according to existing Experimental observation as a result, being summarized as follows.
1, upper machine spraying (predominantly fruit wax sprayability): SW-68A, SW-68B are bordering on 402D, and current machine performance can be grasped Make;SW-68C atomization shortcoming (Polymer Systems, though water-soluble good, viscosity is slightly higher);
2, aridity (predominantly quick-drying and non-stick): SW-68A, SW-68B, SW-68C are significantly better than that 402D;
3, brightness (predominantly performance aesthetics): due to the factor containing natural acid, so SW-68A, SW-68B The vibrancy same 402D of fruit is applied, though SW-68C bright property is good, and it is vivid to spend not as good as SW-68A, SW-68B, 402D;
4, smoothness (performance handling property): SW-68 is superior to 402D, tack-free viscous bag packet splicing dress;
5, store long property: current Tu Guo enterprise is mostly open place, and fruiting period is mostly early autumn to the early spring out, different places or areas, Influencing the most heavy phase is the severe winter, and fruit wax necessarily affects as having thick change or not freeze-resistant to the cold and applies fruit efficiency and performance, so item is wanted Attention must be given by asking.SW-68 and 402 stores long resistance to jelly, even if defrosting can be extensive rapidly in subzero 10 degree~20 degree of fully charges Restore state.
In terms of sprayability, ester salt is micro- to be inferior to hydrogen bond salt (hydrogen bond water-soluble is slightly higher than ester salt);In bright and new degree and storage In terms of long property, the two is consistent;In terms of aridity and smoothness, ester salt is substantially better than hydrogen bond salt.Here it is machine effects in the two Comparison.
9 fresh keeping property of embodiment
Fruit film function: first is that appearance looks elegant;Second is that persistently fresh-keeping.It should be the latter in terms of primary efficacy, but the two is in fact It is consistent.Inventor arrives through experimental observation over the years, if often applying wax fruit appearance has mutation --- water suction, delustring or coloured different, It is final that just easily mildew is rotted.
Fruit is anhydrous to have no result, and water has basic biotic factor for fruit growth and storage, however exactly water pair The destructive degree of fruit is also maximum most easy.For tangerine orange mandarin orange, the not processing in time after soaking water soon i.e. can be mould It is rotten., also can daily weightless (namely dehydration in fact) from being saved naturally from fruit, weightless to a certain extent that is, mildew and rot, institute With, the at all fresh-keeping element of fruit waxing is exactly to safeguard water balance in sporocarp, extends equilibration time, weight-loss ratio is reduced, Element is exactly to control chemical balance in fact.For in this way: fruit wax fruit wax, should can be water-soluble --- be first can at water-based system, Even if followed by eating by mistake can excrete after being fully hydrolyzed, these are environmentally-friendly sanitary requirements;Also want that water can be controlled --- at cere Not hygroscopic afterwards, thermal change is not easy cracking variation to the cold, these are fresh-keeping requirements.How the performance chemical balance of water is studied well, It at all will be here it is develop fruit wax.
For fatty acid, potassium, sodium salt should be not only stable water soluble but also preferably, but due to potassium, sodium salt water suction i.e. easily it is general It is white, die on selected without producer with this, amide it is water-soluble it is good is not easy to whiten again, so numerous manufacturers also all select its adapted.? Quinoline is not only water-soluble to be had corresponding adhesive force simultaneously not only but also is not easy to whiten relatively stable, therefore the U.S. has started such fruit wax and continued into the present.But It is modern from that discussed above in for known chemically structure, ester salt is more stable than hydrogen bond salt and water-soluble also good, after cere, ester salt It is better than hydrogen bond salt in water-fast anti-whiting, brightness, fresh-keeping duration.
The author in recent years from China's market Guo La site observation and repeatedly learnt by comparison sampling test, water-fast in the market now Fresh-keeping effect is really best with U.S. 402D.
Table 3 (fruit wax applies tangerine submerging test):
Chemical analysis structural factor discussion: 68A combines natural acid morpholine ester salt and organosilicon acrylic resin;68B group light combination paulownia Sour morpholine ester salt and organosilicon acrylic resin;The pure organosilicon acrylic resin of 68C.The big mutability relatively easy to crack of the small activity of abietate's molecules of salt amount, light eleostearic acid Ester salt is relatively stable, the no mutation the most stable of silicon third.Immersion failure test exactly adds clear this point.
Table 4 (the weightless comparison of fruit wax immersion mildew) A (SW-68A) D (402D)
Table 5 (comparison of fruit wax Tu Guohou natural storage weightlessness)
Illustrate: the present invention has that SW-68A structural constituent is similar with 402D only, therefore the comparison taken.The result shows that broken in immersion Bad property test aspect, the two contrast is larger, and SW-68A is substantially better than 402D, and in terms of natural storage, the two is very nearly the same, but still Right SW-68A will be better than 402D slightly.
Immersion failure test 4 minutes SW-68A, 402D uniform week is out of control, but comparative test SW-68B of the present invention soaks 5 points Clock one or two weeks also normal, and SW-68C soaks 15 minutes or more January, there are no different.It has been known that there is chemical analysis master control institutes at no longer more It states.
Embodiment 10 integrates explanation
The ultimate constituent (including other by-products of novel fruits preservative fruit wax SW-68A, SW-68B, SW-68C of the invention Or leave composition) it is detailed in following table 6 (percentage).
Table 6
Novel fruits preservative fruit wax SW-68A, SW-68B and SW-68C of the invention is full water-soluble system;SW-68A, SW-68B appearance is purplish red as clear as crystal, and SW-68C appearance pure water color is colourless as clear as crystal;Its master control water-soluble components is fat Barbiturates and middle polyphosphazene polymer ester ammonium salt.
Complete water-soluble system wax liquor in stability, carefully knot property, film forming various aspects are better than emulsifying or floating type wax liquor, Also just due to the water soluble natural sex for combining salt, be also highly advantageous to environmentally-friendly sanitary control --- after especially being eaten by mistake at cere It can normally excrete, so the main points are the primary starting point of the present invention.
Design synthesis fruit wax composition based on fatty acid morpholine ester salt, can not only substantially reduce morpholine lysate to subtract Human factor is endangered less and improves hygiene and health effect, and it is water-soluble similar with morpholine fatty acid hydrogen bond salt.Its comprehensive preservation Effect is also better than hydrogen bond salt, this is one of main points of the invention.
Design synthesis using macromolecule resin in the polymerization of the aqueous solution of organosilicon-modified acrylic as fruit wax auxiliary ingredients or Main component, reduce or completely Chu fatty acid morpholine salt composition.Such technical products should become the controllable environmental protection of the mankind and defend Raw and cheap and good-quality novel fruit wax (or other similar amenities) developing direction.This is the two of main points of the present invention.
Pure acrylic acid is although water-soluble good and stablizes, but is extremely short of in terms of adhesive force, water-resistance, cold-and-heat resistent, draws It is copolymerized therewith to enter active organosilicon, this respect can be overcome to be short of completely, can extremely efficient reach not only molten water but also controls water Advantage.
By-product (unreacting propylene acid esters, potassium sulfate): one of future trouble factor of high molecular polymerization, it is necessary to control.This hair Bright to utilize special process (especially adding initiator, such as potassium peroxydisulfate) to reduce or eliminate, current unreacted monomer is micro, adds Upper toxicity itself is very small, and more upper film almost volatilizees nothing left, so without very hidden danger.For potassium peroxydisulfate dosage in this this formula compared with More, effect is first is that cause macromolecule, second is that closing macromolecule, remaining person become K in this system2SO4Potassium sulfate is people Class edibility salt, it is harmless.
Auxiliary ingredients: fatty acid ammonium salt, auxiliary body improve water-soluble;Ammonium hydroxide adjusts finished product PH;Ethyl alcohol, isopropanol are Controllability food grade solvent.Such solvent facilitates fatty acid dissolution reaction and high molecular weight reactive in a word, is also highly advantageous to and is applying Fruit plays table bactericidal effect at the beginning, volatilizees after achievement wax;Deionized water is the pure water specially handled, is the main body of aqueous wax liquor Solvent.

Claims (1)

1. a kind of smooth eleostearate, it is characterised in that: be prepared by light eleostearic acid, morpholine, ethyl alcohol, ammonium hydroxide and deionized water, institute The weight ratio of light eleostearic acid, morpholine, ethyl alcohol, ammonium hydroxide and the deionized water stated is 10.0~18.0:1.93~3.95:8.0~10.0: The deionized water of ethyl alcohol and 3 ~ 20% is first added in a reaction kettle, is preheated to 65 ~ 73 DEG C by 0.5~1.2:60.0~70.0, Light eleostearic acid is put into, temperature is promoted to 76 ~ 83 DEG C, 70~80% morpholine is added, stirs 10 ~ 30min, pressure is warming up to 85 ~ 93 DEG C, 1 ~ 5 hour is kept the temperature, is cooled to 73 ~ 83 DEG C, remaining morpholine, ammonium hydroxide and remaining deionized water is added, continues stirring 20 ~ 35 Minute, 20 ~ 50 DEG C are cooled to, is filtered up to light eleostearate.
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