CN104370860A - Diepoxide vegetable oil acid acetyl glyceride and synthesis method and application thereof - Google Patents
Diepoxide vegetable oil acid acetyl glyceride and synthesis method and application thereof Download PDFInfo
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- CN104370860A CN104370860A CN201410568201.1A CN201410568201A CN104370860A CN 104370860 A CN104370860 A CN 104370860A CN 201410568201 A CN201410568201 A CN 201410568201A CN 104370860 A CN104370860 A CN 104370860A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
Abstract
The invention discloses a diepoxide vegetable oil acid acetyl glyceride plasticizer. The diepoxide vegetable oil acid acetyl glyceride plasticizer comprises a structure shown in the formula (I) or (II); the invention further discloses a synthesis method of the diepoxide vegetable oil acid acetyl glyceride. The synthesis method comprises the following steps: 1) performing transesterification on the vegetable oil and glycerin to generate vegetable oil acid diglyceride; 2) performing acetylation on the vegetable oil acid diglyceride and an acetylation reagent to synthesize vegetable oil acid acetyl diglyceride; 3) performing epoxidation reaction on the vegetable oil acid acetyl diglyceride and hydrogen peroxide to synthesize diepoxide vegetable oil acid acetyl glyceride. The diepoxide vegetable oil acid acetyl glyceride is environment-friendly and non-toxic, has the characteristics of good stability, excellent liquidity and good plastic intermiscibility, can be used as plasticizer to be added in a plastic product, and has a wide market prospect.
Description
Technical field
The present invention relates to a kind of softening agent, be specifically related to a kind of diepoxy vegetable oil acid aceto-glyceride, in addition, the invention still further relates to a kind of synthetic method and application of described diepoxy vegetable oil acid aceto-glyceride.
Background technology
In recent years, China has become Asia plasticizer production amount and the maximum country of consumption.Softening agent is mainly based on adjacent benzene-type products for a long time, but this type of softening agent is poisonous, has potential carcinogenic danger.Along with the enhancing of people's environmental consciousness, the plastic article industry such as medicine, food product pack, daily necessities, toy propose higher hygienic environment-protecting requirement to softening agent, and therefore, the softening agent of asepsis environment-protecting becomes the emphasis of global softening agent research instantly.
Because epoxidized vegetable oil has good thermotolerance, photostabilization, mutually oozing property, low malleability, and the characteristic such as volatility is low, be widely used in plastics industry in recent years, be the softening agent that uniquely can be used for instrumentation package material that united States food and drug administration (FDA) ratifies, be specially adapted to the field that food/pharmaceutical Plastic Packaging Materials, toy for children and home decoration material etc. have strict environmental requirement.But the molecular weight of epoxidized vegetable oil and viscosity are comparatively large, and poor fluidity, limits it and apply further.Glycerine ester type softening agent has lower molecular weight and higher boiling point and flash-point, and viscosity is low, good fluidity, but its low temperature plasticising performance is not as good as epoxidized vegetable oil.Therefore, exploitation one had both had the similar plasticization effect of epoxidized vegetable oil, but molecular weight is low, the material of good fluidity is very necessary as softening agent.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, there is provided that a kind of molecular weight is low, good fluidity, stability are high, the softening agent diepoxy vegetable oil acid aceto-glyceride good with plastics intermiscibility, another object of the present invention is to synthetic method and application that this softening agent a kind of is provided.
For achieving the above object, the present invention is by the following technical solutions:
The present invention with vegetables oil and glycerine for raw material, by 1) vegetables oil and glycerine carries out transesterification reaction and generates two vegetable oil acid glyceryl ester; 2) two vegetable oil acid glyceryl ester and acetylation reagent carry out acetylization reaction and synthesize two vegetable oil acid aceto-glycerides; And 3) two vegetable oil acid aceto-glycerides and hydrogen peroxide initial ring oxidizing reaction synthesize the steps such as diepoxy vegetable oil acid aceto-glyceride, synthesis obtains good stability, mobility is good, and the environment-protecting asepsis softening agent diepoxy vegetable oil acid aceto-glyceride good with plastics intermiscibility, it has such as formula the structure shown in (I) or (II):
Wherein, R
1, R
2, R
3independently of one another, be selected from the lipid acid below 20 carbon atoms in vegetables oil identical or differently.
Preferably: described R
1, R
2, R
3independently of one another, identical or differently be selected from the palmitic acid in soybean oil, stearic acid, oleic acid, cis-9,12-octadecenic acid, cis-9,12,15-octadecenic acid; Or the oleic acid, linolic acid or the palmitinic acid that independently of one another, identical or differently are selected from Rice pollard oil; Or the eicosanoic acid, oleic acid, linolic acid, erucic acid or the linolenic acid that independently of one another, identical or differently are selected from rapeseed oil.
In transesterification reaction preferably: step 1), described vegetables oil is at least one in soybean oil, Rice pollard oil, oleum lini, rapeseed oil, plam oil, Viscotrol C and sunflower seed oil, by weight percentage, the consumption of described glycerine is the 8-10.3% of vegetables oil consumption.
In transesterification reaction preferably: step 1), also add catalyzer, described catalyzer is at least one in sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium methylate and sodium ethylate, and by weight percentage, its consumption is the 0.005-0.01% of vegetables oil consumption.
Step 2) acetylization reaction in, one or more in the preferred Acetyl Chloride 98Min. of described acetylation reagent, Glacial acetic acid, diacetyl oxide, and by weight percentage, its consumption is the 16-48% of two vegetable oil acid glyceryl ester consumptions; Also acetylation catalyst can be added in described acetylization reaction; one or more in the preferred vitriol oil of described acetylation catalyst, tosic acid, acidic ion exchange resin; and by weight percentage, its consumption is the 0.02-0.04% of two vegetable oil acid glyceryl ester consumptions.
Further preferably: in described acetylization reaction, also can add water entrainer, one or more in the preferred benzene of described water entrainer, hexanaphthene, hexane, and by weight percentage, its consumption is the 20-30% of two vegetable oil acid glyceryl ester consumptions.
Preferably: in described epoxidation reaction, also add formic acid and/or acetic acid, and the mol ratio of two vegetable oil acid aceto-glycerides, hydrogen peroxide, formic acid and/or acetic acid, epoxidation catalyst is 1:0.42-0.52:0.042-0.052:0.002-0.004.
Described diepoxy vegetable oil acid aceto-glyceride as softening agent application in the plastic, has that viscosity is little, good stability, mobility are high, the feature effective with plastic plastification.
Beneficial effect of the present invention is, preparation technology of the present invention is simple, cost is low, and obtained diepoxy vegetable oil acid aceto-glyceride asepsis environment-protecting, molecular weight and viscosity less, good fluidity, stability is high, low temperature plasticising excellent performance, adds in plastics as softening agent, has wide market outlook.
Accompanying drawing explanation
Fig. 1 shows the infrared spectrum of two soybean oil acid glycerides obtained by embodiments of the invention 1;
Fig. 2 shows the infrared spectrum of two soybean oleic acid aceto-glycerides obtained by embodiments of the invention 1;
Fig. 3 shows the infrared spectrum of the diepoxy soybean oleic acid aceto-glyceride obtained by embodiments of the invention 1;
Fig. 4 shows the Temperature-viscosity curves figure of other softening agent in diepoxy soybean oleic acid aceto-glyceride obtained by embodiments of the invention 1 and prior art;
Fig. 5 shows the temperature-zero-g aircraft graphic representation according to other softening agent in diepoxy soybean oleic acid aceto-glyceride obtained in embodiments of the invention 1 and prior art.
Embodiment
Below in conjunction with specific embodiment, the specific embodiment of the present invention is described further.If no special instructions, each embodiment of the present invention is all bought can obtain by market.
Diepoxy vegetable oil acid aceto-glyceride of the present invention, its synthesis comprises the following steps:
1) vegetables oil and glycerine carry out transesterification reaction and generate two vegetable oil acid glyceryl ester
2) acetylization reaction synthesizes two vegetable oil acid aceto-glycerides
3) two vegetable oil acid aceto-glyceride epoxidation reaction synthesis diepoxy vegetable oil acid aceto-glycerides
Wherein, R
1, R
2, R
3for the lipid acid below 20 carbon atoms in vegetables oil, preferably, R
1, R
2, R
3independently of one another for being selected from palmitic acid, stearic acid, oleic acid, cis-9,12-octadecenic acid, cis-9,12, the 15-octadecenic acid in soybean oil; Or independently of one another for being selected from oleic acid, linolic acid or the palmitinic acid in Rice pollard oil; Or independently of one another for being selected from eicosanoic acid, oleic acid, linolic acid, erucic acid or the linolenic acid in rapeseed oil.
Step 1) in transesterification reaction, temperature of reaction is 190-260 DEG C, reaction times is 8-15 hour, and vegetables oil used is one or more in soybean oil, Rice pollard oil, oleum lini, rapeseed oil, plam oil, Viscotrol C and sunflower seed oil, and the iodine number of described vegetables oil is 120-140I
2/ 100g, acid number is 0.5-2mgKOH/g, transesterification catalyst is one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium methylate and sodium ethylate, and its consumption is the 0.005-0.01% (w/w) of vegetables oil consumption, the consumption of glycerine is the 8-10.3% (w/w) of vegetables oil consumption;
Described step 2) acetylization reaction in, described acetylation reagent is one or more in Acetyl Chloride 98Min., Glacial acetic acid, diacetyl oxide, and its consumption is the 16-48% (w/w) of two vegetable oil acid glyceryl ester consumptions; Described acetylation catalyst is one or more in the vitriol oil, tosic acid, acidic ion exchange resin, and its consumption is the 0.02-0.04% (w/w) of two vegetable oil acid glyceryl ester consumptions; Also water entrainer can be added in described acetylization reaction, to form azeotrope with the water that generates in acetylization reaction and water to be taken in time out of reaction system, reaction is impelled to carry out to the direction being conducive to two vegetable oil acid aceto-glycerides, described water entrainer is one or more in benzene, hexanaphthene, hexane, and its consumption is the 20-30% (w/w) of two vegetable oil acid glyceryl ester consumptions;
Described step 3) epoxidation reaction in, temperature of reaction is 65-78 DEG C, and the reaction times is 6-10 hour, and described epoxidation catalyst is the vitriol oil and/or strong phosphoric acid, and the concentration of described hydrogen peroxide is 30-50%; Also add in described epoxidation reaction and have formic acid and/or acetic acid, and the mol ratio of two vegetable oil acid aceto-glycerides, hydrogen peroxide, formic acid and/or acetic acid, epoxidation catalyst is 1:0.42-0.52:0.042-0.052:0.002-0.004, oxirane value>=3.0 of synthesized product diepoxy vegetable oil acid aceto-glyceride, iodine number I
2/ 100g≤3.0, acid number mgKOH/g≤3.0.
Embodiment 1
With soybean oil and glycerine for starting raw material, soybean oil belongs to triglyceride, and its lipid acid composition is as shown in table 1, and main component is 18 carbon fatty acids, the lipid acid within the scope of other non-C14-C20:
The lipid acid composition of table 1 soybean oil
With soybean oil and glycerine for Material synthesis diepoxy soybean oleic acid aceto-glyceride, comprise the following steps:
1) transesterification reaction: 912g soybean oil and 88g glycerine are joined in the there-necked flask with agitator, thermometer, reflux condensing tube, passes into nitrogen and stirring is warming up to 120 DEG C, adds calcium oxide 0.05g, is then warming up to 220 DEG C of insulation reaction 8 hours.Reaction process discontinuous feeding, when 1 increment product and 10 parts of ethanol dissolve each other, terminates reaction, give light yellow oil two soybean oil acid glyceride.Its infrared test IR (KBr) result as shown in Figure 1, wherein: 1741cm
-1for C=O stretching vibration, 1175cm
-1, 1119cm
-1be respectively asymmetrical stretching vibration and the symmetrical stretching vibration of C-O-C; 3413cm
-1(broad peak) is-OH group; 3009cm
-1for the C-H stretching vibration of unsaturated hydrocarbons C=C absorbs; 723cm
-1for the rocking vibration of methylene radical; 2925cm
-1for stable hydrocarbon CH
2c-H asymmetrical stretching vibration absorb; 2854cm
-1for stable hydrocarbon CH
2c-H symmetrical stretching vibration absorb;
2) acetylization reaction: in the four-hole bottle that agitator, thermometer, band water device and reflux condensing tube are housed; add 342g step 1) in obtained two soy acid oil glyceride, 158g Glacial acetic acid, 96g water liquid benzene and the 0.1g vitriol oil; heat up band water back flow reaction; the stopped reaction when aquifer yield reaches theoretical amount; unreacted acetic acid and benzene are extracted in decompression out, obtain grey black oily matter two soybean oleic acid aceto-glyceride.Its infrared test IR (KBr) result as shown in Figure 2, wherein: 1743cm
-1for C=O stretching vibration, 1169cm
-1, 1119cm
-1be respectively asymmetrical stretching vibration and the symmetrical stretching vibration of C-O-C; 3469cm
-1(broad peak) is-OH group; 3009cm
-1for the C-H stretching vibration of unsaturated hydrocarbons C=C absorbs; 723cm
-1for the rocking vibration of methylene radical; 2926cm
-1for stable hydrocarbon CH
2c-H asymmetrical stretching vibration absorb; 2854cm
-1for stable hydrocarbon CH
2c-H symmetrical stretching vibration absorb;
3) epoxidation reaction: to agitator is housed, thermometer, dropping funnel, in the four-hole bottle of reflux condensing tube, add 500g step 2 successively) in obtained two soybean oleic acid aceto-glycerides, 2g formic acid, the 0.2g vitriol oil, stirring is warming up to 45 DEG C, the hydrogen peroxide of 30g concentration 50% is slowly instilled under agitation condition, be added dropwise to complete rear system to react 6 hours at 75 DEG C, separate lower floor's sour water, upper strata grease priority buck, clear water is washed to neutrality, when acid number is below 0.6, underpressure distillation dewaters and filters give light yellow oil diepoxy soybean oleic acid aceto-glyceride, its oxirane value is 3.5, acid number is 1.2, iodine number is 1.7.Infrared test IR (KBr) result of product as shown in Figure 3, wherein: IR (KBr): 1746cm
-1for C=O stretching vibration; 1166cm
-1, 1102cm
-1be respectively asymmetrical stretching vibration and the symmetrical stretching vibration of C-O-C; 843cm
-1for the asymmetric stretching vibration of ternary cyclic ethers C-O-C; 725cm
-1for the rocking vibration of methylene radical; 2927cm
-1for stable hydrocarbon CH
2c-H asymmetrical stretching vibration absorb; 2856cm
-1for stable hydrocarbon CH
2c-H symmetrical stretching vibration absorb.
Embodiment 2
With soybean oil and glycerine for Material synthesis diepoxy soybean oleic acid aceto-glyceride, comprise the following steps:
1) transesterification reaction: add 897g soybean oil and 88g glycerine in the there-necked flask that agitator, thermometer, reflux condensing tube be housed, passes into nitrogen and stirs and be warming up to 120 DEG C, adds calcium hydroxide 0.05g, is warming up to 230 DEG C and insulation reaction 9 hours.Reaction process discontinuous feeding, when the ethanol of the sample of 1 part and 10 parts dissolves each other, terminates reaction, give light yellow oil two soybean oil acid glyceride.Through infrared test IR (KBr), it has the structure similar to the spectrogram shown in Fig. 1;
2) acetylization reaction: in the four-hole bottle that agitator, thermometer, band water device and reflux condensing tube are housed; add 330g step 1) in obtained two soybean oil acid glycerides, 150g Acetyl Chloride 98Min., 98g water liquid benzene and the 0.1g vitriol oil; heat up band water back flow reaction; the stopped reaction when aquifer yield reaches theoretical amount; unreacted Acetyl Chloride 98Min. and benzene are extracted in decompression out, obtain grey black oily matter two soybean oleic acid aceto-glyceride.Through infrared test IR (KBr), it has the structure similar to the spectrogram shown in Fig. 2;
3) epoxidation reaction: to agitator is housed, thermometer, dropping funnel, in the four-hole bottle of reflux condensing tube, add 500g step 2 successively) in obtained two soybean oleic acid aceto-glycerides, 2.2g formic acid, the 0.2g vitriol oil, stirring is warming up to 45 DEG C, the hydrogen peroxide of 35g concentration 50% is slowly instilled under agitation condition, be added dropwise to complete rear system to react 8 hours at 70 DEG C, separate lower floor's sour water, upper strata grease priority buck, clear water is washed to neutrality, when acid number is below 0.6, underpressure distillation dewaters and filters give light yellow oil diepoxy soybean oleic acid aceto-glyceride, its oxirane value is 3.56, acid number is 1.2, iodine number is 2.44.Through infrared test IR (KBr), it has the structure similar to the spectrogram shown in Fig. 3.
Embodiment 3
Be basic raw material with rapeseed oil, containing eicosanoic acid 0.4-1.0%, oleic acid 14-19%, linolic acid 12-24%, erucic acid 31-35%, linolenic acid 1-10% in rapeseed oil.
With rapeseed oil and glycerine for Material synthesis diepoxy vegetable seed oleic acid aceto-glyceride, comprise the following steps:
1) transesterification reaction: 912g rapeseed oil and 88g glycerine are joined in the there-necked flask with agitator, thermometer, reflux condensing tube, pass into nitrogen and stir and be warming up to 110 DEG C, add sodium hydroxide 0.05g, be then warming up to 250 DEG C of insulation reaction 12 hours.Reaction process discontinuous feeding, when 1 increment product and 10 parts of ethanol dissolve each other, terminates reaction, give light yellow oil two rapeseed oil acid glyceride.Through infrared test IR (KBr), it has the similar structure of spectrogram as shown in Figure 1;
2) acetylization reaction: in the four-hole bottle that agitator, thermometer, band water device and reflux condensing tube are housed; add 342g step 1) in obtained two rapeseed oil acid glycerides, 158g tosic acid, 96g water liquid benzene and the 0.12g vitriol oil; heat up band water back flow reaction; the stopped reaction when aquifer yield reaches theoretical amount; unreacted acetic acid and benzene are extracted in decompression out, obtain grey black oily matter two soybean oleic acid aceto-glyceride.Through infrared test IR (KBr), it has the similar structure of spectrogram as shown in Figure 2;
3) epoxidation reaction: to agitator is housed, thermometer, dropping funnel, in the four-hole bottle of reflux condensing tube, add 500g step 2 successively) in obtained two vegetable seed oleic acid aceto-glycerides, 3g acetic acid, the 0.2g vitriol oil, stirring is warming up to 45 DEG C, the hydrogen peroxide of 50g concentration 30% is slowly instilled under agitation condition, be added dropwise to complete rear system to react 6 hours at 75 DEG C, separate lower floor's sour water, upper strata grease priority buck, clear water is washed to neutrality, when acid number is below 0.6, underpressure distillation dewaters and filters give light yellow oil diepoxy vegetable seed oleic acid aceto-glyceride, its oxirane value is 3.5, acid number is 1.2, iodine number is 1.7.Through infrared test IR (KBr), it has the similar structure of spectrogram as shown in Figure 2.
Embodiment 4
Fig. 4 shows the Temperature-viscosity curves figure of other softening agent on diepoxy soybean oleic acid aceto-glyceride obtained in the embodiment of the present invention 1 and existing market, in figure: 1 is plasticizer DOTP, 2 be diepoxy soybean oleic acid aceto-glyceride, 3 obtained in the embodiment of the present invention 1 is plasticizer DOP, 4 be softening agent DINP, as can be seen from Figure, diepoxy soybean oleic acid aceto-glyceride viscosity of the present invention is less, has good mobility.
The high volatile volatile of softening agent is one of reason causing the public to worry in recent years, but minimizing volatility needs the molecular weight increasing softening agent usually, and this often also can reduce the efficiency of product reprocessing.Fig. 5 shows the temperature-zero-g aircraft graphic representation of other softening agent on diepoxy soybean oleic acid aceto-glyceride obtained in the embodiment of the present invention 1 and existing market, in figure: 1 is softening agent TOTM, 2 be diepoxy soybean oleic acid aceto-glyceride, 3 obtained in the embodiment of the present invention 1 is softening agent DEHP, as can be seen from Figure, relative to conventional plasticizers, the diepoxy soybean oleic acid aceto-glyceride obtained by the present invention has lower volatility.
Using the diepoxy soybean oleic acid aceto-glyceride that obtains in the present invention as softening agent, by the standard of adding 40 parts of softening agent in every 100 portions of plastics, product in embodiment of the present invention 1-3 is added in plastics, contrast with conventional adjacent benzene class softening agent on market and epoxidized vegetable oil class softening agent, its result is as shown in table 2 simultaneously:
Table 2 diepoxy vegetable oil acid aceto-glyceride plasticization effect contrasts
Table 3 shows the precipitation performance comparison that diepoxy soybean oleic acid aceto-glyceride of the present invention (adds 40 parts of softening agent in every 100 portions of plastics) with softening agent existing on market under identical addition:
Table 3 diepoxy vegetable oil acid aceto-glyceride separates out performance comparison
| 3% aqueous acetic acid | 15% aqueous ethanolic solution | Sunflower seed oil | |
| Comparative example 1 (plasticizer DOTP) | 2.83 | 1.31 | 466 |
| Comparative example 2 (softening agent DINP) | / | / | 420 |
| Embodiment 1 | 0.0058 | 0.0055 | 368 |
As known from Table 3, diepoxy soybean oleic acid aceto-glyceride of the present invention adds in plastics as softening agent, relative to softening agent traditional on market, its amount of precipitation in aqueous solvent will low 50-100 doubly, and it also significantly reduces the amount of precipitation of sunflower seed oil.
From Fig. 4-Fig. 5 and table 2-table 3, relative to existing adjacent benzene class and epoxidized vegetable oil class softening agent, diepoxy vegetable oil acid aceto-glyceride of the present invention is derived from plant completely, nontoxic pollution-free, biodegradable, viscosity is little, good fluidity, plasticization effect is good, conventional plasticizers can be substituted completely, as DOP, DINP etc., be applicable to the material with Food Contact, as food packaging film, the production of preservative film etc., and phthalate can be replaced completely be applied in medicine equipment, also can substitute the production that conventional plasticizers is applied to plastisol completely, there is market application foreground widely.
The present invention is by preferred embodiment having carried out detailed explanation.But, by studying carefully above, to the change of each embodiment with to increase also be that one of ordinary skill in the art institute is apparent.Being intended that all these changes and increasing of applicant has dropped in the protection domain of the claims in the present invention.Term used herein is only and is illustrated specific embodiment, and it is also not intended to limit the invention.Unless otherwise defined, all terms used herein (comprising technical term and scientific terminology) are all identical with the understanding of one of ordinary skill in the art of the present invention.Any modification of carrying out this product and improvement, the substituting and using of similar or close material in the scope of the claims or category, all belongs to scope of patent protection of the present invention.
Claims (10)
1. diepoxy vegetable oil acid aceto-glyceride, has such as formula the structure shown in (I) or (II):
Wherein, R
1, R
2, R
3independently of one another, be selected from the lipid acid below 20 carbon atoms in vegetables oil identical or differently.
2. diepoxy vegetable oil acid aceto-glyceride according to claim 1, is characterized in that: described R
1, R
2, R
3independently of one another, identical or differently be selected from the palmitic acid in soybean oil, stearic acid, oleic acid, cis-9,12-octadecenic acid, cis-9,12,15-octadecenic acid; Or the oleic acid, linolic acid or the palmitinic acid that independently of one another, identical or differently are selected from Rice pollard oil; Or the eicosanoic acid, oleic acid, linolic acid, erucic acid or the linolenic acid that independently of one another, identical or differently are selected from rapeseed oil.
3. the synthetic method of diepoxy vegetable oil acid aceto-glyceride as claimed in claim 1, is characterized in that: comprise the following steps:
1) vegetables oil and glycerine carry out transesterification reaction and generate two vegetable oil acid glyceryl ester
2) acetylization reaction synthesizes two vegetable oil acid aceto-glycerides
3) two vegetable oil acid aceto-glyceride epoxidation reaction synthesis diepoxy vegetable oil acid aceto-glycerides
Wherein, R
1, R
2, R
3independently of one another, be selected from the lipid acid below 20 carbon atoms in vegetables oil identical or differently.
4. synthetic method according to claim 3, is characterized in that: described R
1, R
2, R
3independently of one another, identical or differently be selected from the palmitic acid in soybean oil, stearic acid, oleic acid, cis-9,12-octadecenic acid, cis-9,12,15-octadecenic acid; Or the oleic acid, linolic acid or the palmitinic acid that independently of one another, identical or differently are selected from Rice pollard oil; Or the eicosanoic acid, oleic acid, linolic acid, erucic acid or the linolenic acid that independently of one another, identical or differently are selected from rapeseed oil.
5. synthetic method according to claim 3, it is characterized in that: in transesterification reaction, described vegetables oil is at least one in soybean oil, Rice pollard oil, oleum lini, rapeseed oil, plam oil, Viscotrol C and sunflower seed oil, by weight percentage, the consumption of described glycerine is the 8-10.3% of vegetables oil consumption.
6. synthetic method according to claim 3, it is characterized in that: in transesterification reaction, described catalyzer is at least one in sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium methylate and sodium ethylate, and by weight percentage, its consumption is the 0.005-0.01% of vegetables oil consumption.
7. synthetic method according to claim 3, it is characterized in that: in acetylization reaction, described acetylation reagent is one or more in Acetyl Chloride 98Min., Glacial acetic acid, diacetyl oxide, and by weight percentage, its consumption is the 16-48% of two vegetable oil acid glyceryl ester consumptions; Described acetylation catalyst is one or more in the vitriol oil, tosic acid, acidic ion exchange resin, and by weight percentage, its consumption is the 0.02-0.04% of two vegetable oil acid glyceryl ester consumptions.
8. the synthetic method according to claim 3 or 7; it is characterized in that: in described acetylization reaction, also add water entrainer; described water entrainer is one or more in benzene, hexanaphthene, hexane, and by weight percentage, its consumption is the 20-30% of two vegetable oil acid glyceryl ester consumptions.
9. synthetic method according to claim 3, it is characterized in that: in described epoxidation reaction, also add formic acid and/or acetic acid, and the mol ratio of two vegetable oil acid aceto-glycerides, hydrogen peroxide, formic acid and/or acetic acid, epoxidation catalyst is 1:0.42-0.52:0.042-0.052:0.002-0.004.
10. diepoxy vegetable oil acid aceto-glyceride as claimed in claim 1 or 2 is in the application as softening agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817521A (en) * | 2015-03-03 | 2015-08-05 | 中国林业科学研究院林产化学工业研究所 | Epoxy dimeric fatty acid methyl ester, preparation method and applications thereof |
| CN105038261A (en) * | 2015-06-18 | 2015-11-11 | 张家港市大能塑料制品有限公司 | Environment-friendly plasticizer |
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| CN106146431A (en) * | 2016-06-30 | 2016-11-23 | 中国林业科学研究院林产化学工业研究所 | A kind of epoxy low calorie fats plasticizer and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817521A (en) * | 2015-03-03 | 2015-08-05 | 中国林业科学研究院林产化学工业研究所 | Epoxy dimeric fatty acid methyl ester, preparation method and applications thereof |
| CN105038261A (en) * | 2015-06-18 | 2015-11-11 | 张家港市大能塑料制品有限公司 | Environment-friendly plasticizer |
| CN105085442A (en) * | 2015-07-23 | 2015-11-25 | 广州市海珥玛植物油脂有限公司 | Diacid bismonoacetyl epoxy vegetable oil ester and synthetic method thereof |
| CN106146431A (en) * | 2016-06-30 | 2016-11-23 | 中国林业科学研究院林产化学工业研究所 | A kind of epoxy low calorie fats plasticizer and preparation method thereof |
| CN106519081A (en) * | 2016-09-22 | 2017-03-22 | 深圳立山环保材料有限公司 | Epoxy plasticizer and preparation method |
| CN106519081B (en) * | 2016-09-22 | 2018-06-26 | 深圳立山环保材料有限公司 | A kind of epoxy plasticiser and preparation method thereof |
| CN108530681A (en) * | 2018-01-23 | 2018-09-14 | 四川大学 | A method of improving epoxidized methyl acetorieinoleate plasticizer and polyvinyl chloride resin compatibility |
| CN108530681B (en) * | 2018-01-23 | 2020-05-05 | 四川大学 | Method for improving compatibility of epoxy methyl acetylricinoleate plasticizer and PVC resin |
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