CN106967015A - A kind of contracting fatty acid ester of epoxy two and its preparation method and application - Google Patents
A kind of contracting fatty acid ester of epoxy two and its preparation method and application Download PDFInfo
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- CN106967015A CN106967015A CN201710202478.6A CN201710202478A CN106967015A CN 106967015 A CN106967015 A CN 106967015A CN 201710202478 A CN201710202478 A CN 201710202478A CN 106967015 A CN106967015 A CN 106967015A
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- contracting
- epoxy
- ester
- fatty acid
- acid ester
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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
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
-
- 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
-
- 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
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
-
- 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
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
-
- 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 present invention relates to a kind of contracting fatty acid ester plasticizer of epoxy two and preparation method thereof, using the ester of vegetable oil, aliphatic acid, fatty acid ester containing lower alcohols such as methyl esters, ethyl esters, peroxide as raw material, by ester exchange of common alkali with contracting ester catalyst, acid is that esterification and epoxidation catalyst catalyze and synthesize a kind of contracting fatty acid ester novel environment-friendly fat-based plasticizer of epoxy two.It is intended to need the reactions such as experience ester exchange, ester condensation, epoxidation by the product that vegetable oil prepares the present invention, the reaction of contracting ester can suitably use solvent as needed with epoxidation reaction.The twice epoxy aliphatic ester of this product molecular weight, is less than epoxy grease again, low with volatility, is difficult migration, good endurance, the features such as flash-point is high.
Description
Technical field
The present invention relates to a kind of contracting fatty acid ester of epoxy two and its preparation method and application, category Lipid use and plasticizer are opened
Hair field, product mainly applies to plastic processing industry.
Background technology
It is to increase its mobility, plasticity and make finished product when plasticizer is the high polymer processing and forming such as rubber, plastics, coating
The lower-molecular substance added with pliability, is one of essential additive in plastic processing, and consumption is huge, accounts for institute
Have the 54% of plastic additive consumption, China is the first in the world production and consumption state, production capacity has reached annual 2 more than 800kt, and
Sustainable growth year by year.It must especially be added in the processing of polyvinyl chloride, its addition reaches as high as 40-50%, but wherein adjacent
Phthalates account for exhausted vast scale.But research shows that O-phthalic acids plasticizer has potential carcinogenicity and imitative female
Hormone function, the developed country such as America and Europe has disabled.This promotes the exploitation of novel environment-friendly plasticizer more and more active, wherein both
The research of environmentally friendly and reproducible fat-based plasticizer is also more protruded, its yield cumulative year after year, but major product only has epoxy
Grease type (epoxidized soybean oil etc.), epoxyfatty acid esters, C22Few in number several such as-three esters of gallic acid.And epoxy grease is deposited
With the defect such as low, the resistance to extractable difference of the flash-point of PVC poor compatibilities, epoxy aliphatic acid methyl ester, market in urgent need improvement or substitute production
Product.Further to improve the flash-point and resistance to extractable of epoxy aliphatic acid methyl ester, a kind of epoxy dimer (fatty acid) yl methyl esters is occurred in that
Naturally the shortcomings of its epoxide number is low and viscosity increases is caused after product, but polymerization, the degree of polymerization and epoxide number are into can not make up
Conflict body.So the not enough of epoxyfatty acid esters plasticizer is badly in need of solving！
The content of the invention
In order to solve many deficiencies that existing fat-based epoxy plasticiser is present, the present invention proposes a kind of contracting of epoxy two
Fatty acid ester and its preparation method and application, the twice epoxy aliphatic ester of this product molecular weight is less than epoxy grease, had again
Volatility is low, is difficult migration, good endurance, the features such as flash-point is high.
The technical scheme is that：A kind of contracting fatty acid ester of epoxy two, structural formula is as follows：
Wherein：R1、R2For the identical or different saturation of C atomicities or unrighted acid carbon-chain structure, C total atom numbers are
10~20；R3For C1~C3 carbochain；It is monocyclic oxygen or bicyclic oxide structure at a, b.
A kind of method for preparing the described contracting fatty acid ester of epoxy two, the first step prepares fatty acid ester：With vegetable oil and C1
~C3 acid or alcohol is that raw material strongly alkaline compound is catalyst, and fatty acid ester is prepared by ester exchange or esterification；
Second step, prepares two contracting fatty acid esters：Using strongly alkaline compound as contracting ester catalyst, the reaction of contracting ester is carried out in organic solvent；
Described organic solvent is non-alcohol organic solvent of ketone；3rd step, epoxidation：Acid catalyst is that esterification and epoxidation catalyst exist
The contracting fatty acid ester of epoxidation synthesizing epoxy two in the presence of peroxide.
Described vegetable oil includes any one in soybean oil, rapeseed oil, cottonseed oil, tung oil, gutter oil.
Described strongly alkaline compound includes sodium methoxide, caustic alcohol, potassium tert-butoxide, trityl sodium, Sodamide, hydrogenation
Any one or a few mixture in sodium, sodium hydroxide, potassium hydroxide.
Described acid catalyst includes the mixed of any one or a few in sulfuric acid, p-methyl benzenesulfonic acid, ionic liquid, formic acid
Compound.
Described peroxide includes peroxyformic acid, Peracetic acid, 3- chloroperoxybenzoic acids, tertbutanol peroxide, dioxygen
Any one in water.
Described C1~C3 acid or alcohol includes any one in formic acid, methanol, acetic acid, ethanol.
Described organic solvent includes methanol, ether, dimethyl sulfoxide (DMSO), tetrahydrofuran, dimethylformamide, ethylene glycol two
Any one or a few mixture in methyl ether, dichloromethane.
The described contracting fatty acid ester of epoxy two as fat-based plasticizer application.
The described contracting fatty acid ester of epoxy two as PVC plasticizer application.
Beneficial effect：
The present invention uses strong base catalyst that for the contracting fatty acid ester of a molecule two, two molecules of fatty acids ester condensations are made into monomer molecule
Amount not only effectively improves the flash-point and resistance to extractable of product between fatty-acid monoester and grease, and does not interfere with double bond, protects
The epoxide number of plasticizer is demonstrate,proved.
Brief description of the drawings
Fig. 1 is the infrared spectrum of the contracting fatty acid methyl ester of product epoxy two prepared by embodiment 1.
Embodiment
A kind of contracting fatty acid ester structure plasticizer of epoxy two and preparation method thereof.Vegetable oil, aliphatic acid are passed through into ester exchange
Or esterification is prepared into fatty acid ester (ester containing lower alcohols such as methyl esters, ethyl esters), reaction temperature is at 55~75 DEG C；Again in highly basic
Synthetically prepared two contractings fatty acid ester under effect, reaction temperature is at 90~120 DEG C；Then (peroxyformic acid, mistake are contained using peroxide
Fluoroacetic acid, metachloroperbenzoic acid, tertbutanol peroxide, hydrogen peroxide etc.) its double bond epoxidation can be prepared into the contracting of epoxy two
Fatty acid ester, it is that can obtain final products that reaction temperature passes through the processes such as alkali cleaning rinse dehydration again at -5~70 DEG C, finally, finally
Both contain monocyclic oxide structure in the contracting fatty acid ester of product epoxy two or contain bicyclic oxide structure.
Described raw material is the grease that soybean oil, rapeseed oil, cottonseed oil, tung oil, gutter oil etc. have unrighted acid
Or its aliphatic acid, fatty acid methyl ester, ethyl ester, propyl ester.
Described epoxidation reagent is peroxyformic acid, Peracetic acid, metachloroperbenzoic acid, tertbutanol peroxide, dioxygen
Water etc..
Described catalyst is strong acid catalyst and sodium methoxide, caustic alcohol, the uncles such as sulfuric acid, p-methyl benzenesulfonic acid, ionic liquid
The alkali catalysts such as butanol potassium, trityl sodium, Sodamide, sodium hydride, sodium hydroxide, potassium hydroxide.
Embodiment 1：
Raw material：Soybean oil, methanol, potassium hydroxide, dimethylformamide, sodium methoxide, 3- chloroperoxybenzoic acids, dichloromethane
Alkane；
Soybean oil is put into reactor, the methanol of 20% mass (relative to grease, similarly hereinafter) and urging for 1% mass is added
Agent potassium hydroxide, is heated to 60 DEG C, is stirred at reflux reaction 4 hours, stratification removing lower floor raw glycerin phase after cooling, then 90
Methanol in DEG C vacuum distillation removing upper oil phase produces fatty acid methyl ester；The fatty acid methyl ester of half quality is taken out, to reaction
The dimethylformamide of remaining 2 times of methyl esters quality is put into kettle and the sodium methoxide of remaining methyl esters 22% is accounted for, 30 DEG C of temperature control is simultaneously stirred,
Remaining half fatty acid methyl ester is added dropwise and enters kettle.110 DEG C are warming up to after being added dropwise to complete to react 2 hours, vacuum distillation to 90 DEG C it is de-
Except methanol etc., it is 2 to be down to room temperature and watery hydrochloric acid is added dropwise to pH, is stirred 3 hours, point liquid is washed to neutral dehydration and just obtains two contracting methyl esters；
Room temperature such as is added dropwise at the dichloromethane solution of the 3- chloroperoxybenzoic acids of the amount of material again, and 30 DEG C are reacted 4 hours after completion of dropping, most
Product is that can obtain the contracting methyl esters of epoxy two by PROCESS FOR TREATMENTs such as alkali cleaning-washing-dehydrations afterwards, and product is light yellow clear liquid.
Embodiment 2：
Raw material：Fatty acid methyl ester, sodium methoxide, formic acid, hydrogen peroxide, sulfuric acid；
Quantitative fatty acid methyl ester is put into reactor, the dimethylformamide of 1.5 times of its quality is added and accounts for fat
The sodium methoxide of sour methyl esters quality 23%, is stirred at room temperature dissolving, then the fatty acid methyl ester of equivalent is added dropwise enters kettle.Heated up after being added dropwise to complete
Reacted 3 hours to 90-120 DEG C, vacuum distillation to 90 DEG C of methanol removals etc., be down to room temperature be added dropwise watery hydrochloric acid to pH be 2, stirring 2
Hour, point liquid is washed to neutral dehydration and just obtains two contracting methyl esters；Into reactor, input accounts for two contracting methyl esters quality 10%-50% first
Acid and the concentrated sulfuric acid for accounting for two contracting methyl esters quality 0.5%-1%, are heated to the hydrogen peroxide of 40-60 DEG C of 0.9-1.4 times of dropwise addition, at 40 points
Dripped off in clock, then be warming up to 60-65 DEG C and reacted 3-5 hours.Point liquid water removal is located after the routines such as alkali cleaning washing distillation again after cooling
Reason both obtains the contracting fatty acid methyl ester of product epoxy two, and product is light yellow clear liquid.
Embodiment 3：
Raw material：Rapeseed oil, ethanol, sodium methoxide, dimethylformamide, tertbutanol peroxide, ionic liquid；
Rapeseed oil is put into reactor, the ethanol of 20-30% mass and the catalyst methanol of 0.6-1.6% mass is added
Sodium, is heated to 60-75 DEG C, is stirred at reflux reaction 3-5 hours, and 60-90 DEG C of vacuum distillation removes unreacted ethanol after cooling, quiet
Put insulation layering and remove lower floor's raw glycerin phase and produce fatty-acid ethyl ester；The fatty-acid ethyl ester of half quality is taken out, to reactor
The dimethylformamide and 22% sodium methoxide of middle remaining 1.5 times of the ethyl ester quality of input, are stirred at room temperature, remaining half fat are added dropwise
Fat acetoacetic ester enters kettle.It is added dropwise to complete rear room temperature and reacts 3 hours to 110 DEG C, vacuum distillation is down to room temperature to 90 DEG C of removing ethanol etc.
It is 2-3 that watery hydrochloric acid, which is added dropwise, to pH, is stirred 3 hours, point liquid is washed to neutral dehydration and just obtains two contracting ethyl esters；Two contracting into reactor again
Ethyl ester amount 5-20% ionic liquid, is heated to 55 DEG C of dropwise addition 70-140% tertbutanol peroxide, was dripped off in 1 hour, then
70 DEG C are warming up to react 2-4 hours.Product is both obtained by certain conventional post processing after cooling, product is light yellow clear liquid
Body.
Embodiment 4：
Raw material：Gutter oil, methanol, potassium hydroxide, potassium tert-butoxide, formic acid, hydrogen peroxide, p-methyl benzenesulfonic acid；
Low acid number gutter oil is put into reactor, the methanol and catalyst potassium hydroxide of 20-40% mass, heating is added
To 55-70 DEG C, reaction 2-6 hours is stirred at reflux, stratification removing lower floor raw glycerin phase after cooling, then 60-90 DEG C of decompression are steamed
The methanol evaporated in removing upper oil phase produces fatty acid methyl ester；The fatty-acid ethyl ester of half quality is taken out, is put into reactor
The dimethylformamide of remaining 1.5 times of methyl esters quality and the potassium tert-butoxide with methyl esters equimolar amounts, are stirred at room temperature, and are added dropwise remaining
Half fatty acid methyl ester enters kettle.Be added dropwise to complete rear room temperature to 90-120 DEG C react 2-4 hour, vacuum distillation to 50-90 DEG C remove
Methanol etc., it is 2-3 to be down to room temperature and watery hydrochloric acid is added dropwise to pH, is stirred 3 hours, point liquid is washed to neutral dehydration and just obtains two contracting methyl esters；
Into reactor put into two contracting ethyl ester amount 10-50% formic acid and 1% to catalyst toluenesulfonic acid, be heated to 55 DEG C be added dropwise etc.
The hydrogen peroxide to 140% is measured, was dripped off in 40 minutes, then is warming up to 65 DEG C and is reacted 3-5 hours.End product passes through alkali cleaning-water
The PROCESS FOR TREATMENT such as wash-be dehydrated and can obtain the qualified contracting fatty acid methyl ester of epoxy two, product is light yellow clear liquid.
Embodiment is only to state implementation, changes wherein ratio or time but still fall into this specially using the method
The protection domain of profit.
Table 1：The contracting fatty acid methyl ester of epoxy two and epoxy aliphatic acid methyl ester performance comparison
From the data in table 1 can be seen that the epoxy methyl esters after two contractings not only molecular weight improve by about one time, and flash-point, plus
Therefore the performances such as hot decrement are also correspondingly improved.
Claims (10)
1. a kind of contracting fatty acid ester of epoxy two, it is characterised in that structural formula is as follows：
Wherein：R1、R2For the identical or different saturation of C atomicities or unrighted acid carbon-chain structure, C total atom numbers are 10~
20；R3For C1~C3 carbochain；It is monocyclic oxygen or bicyclic oxide structure at a, b.
2. a kind of method of the contracting fatty acid ester of epoxy two prepared described in claim 1, it is characterised in that the first step, prepares fat
Fat acid esters：Acid or alcohol using vegetable oil and C1~C3 be raw material strongly alkaline compound as catalyst, it is anti-by ester exchange or esterification
Fatty acid ester should be prepared；Second step, prepares two contracting fatty acid esters：Using strongly alkaline compound as contracting ester catalyst, organic
The reaction of contracting ester is carried out in solvent；Described organic solvent is non-alcohol organic solvent of ketone；3rd step, epoxidation：Acid catalyst is
Esterification and the epoxidation catalyst contracting fatty acid ester of epoxidation synthesizing epoxy two in the presence of a peroxide.
3. the method according to claim 2 for preparing the contracting fatty acid ester of epoxy two, it is characterised in that described vegetable oil bag
Include any one in soybean oil, rapeseed oil, cottonseed oil, tung oil, gutter oil.
4. the method according to claim 2 for preparing the contracting fatty acid ester of epoxy two, it is characterised in that described strong basicity
Compound is included in sodium methoxide, caustic alcohol, potassium tert-butoxide, trityl sodium, Sodamide, sodium hydride, sodium hydroxide, potassium hydroxide
Any one or a few mixture.
5. the method according to claim 2 for preparing the contracting fatty acid ester of epoxy two, it is characterised in that described acid catalyst
Including any one or a few the mixture in sulfuric acid, p-methyl benzenesulfonic acid, ionic liquid, formic acid.
6. the method according to claim 2 for preparing the contracting fatty acid ester of epoxy two, it is characterised in that described peroxide
Including any one in peroxyformic acid, Peracetic acid, 3- chloroperoxybenzoic acids, tertbutanol peroxide, hydrogen peroxide.
7. the method according to claim 2 for preparing the contracting fatty acid ester of epoxy two, it is characterised in that described C1~C3's
Acid or alcohol include any one in formic acid, methanol, acetic acid, ethanol.
8. the method according to claim 2 for preparing the contracting fatty acid ester of epoxy two, it is characterised in that described organic solvent
Including any in methanol, ether, dimethyl sulfoxide (DMSO), tetrahydrofuran, dimethylformamide, glycol dimethyl ether, dichloromethane
One or more of mixtures.
9. the contracting fatty acid ester of epoxy two described in claim 1 is used as the application of fat-based plasticizer.
10. the contracting fatty acid ester of epoxy two described in claim 1 is used as the application of PVC plasticizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710202478.6A CN106967015A (en) | 2017-03-30 | 2017-03-30 | A kind of contracting fatty acid ester of epoxy two and its preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710202478.6A CN106967015A (en) | 2017-03-30 | 2017-03-30 | A kind of contracting fatty acid ester of epoxy two and its preparation method and application |
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| CN106967015A true CN106967015A (en) | 2017-07-21 |
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| CN201710202478.6A Pending CN106967015A (en) | 2017-03-30 | 2017-03-30 | A kind of contracting fatty acid ester of epoxy two and its preparation method and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112961404A (en) * | 2020-12-24 | 2021-06-15 | 中国林业科学研究院林产化学工业研究所 | Epoxy oligoether glyceride plasticizer and preparation method thereof |
| WO2021135222A1 (en) * | 2019-12-30 | 2021-07-08 | 华南农业大学 | Multifunctional-epoxy-vegetable-oil-based uv-curable prepolymer, preparation method therefor and use thereof |
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| US3770806A (en) * | 1970-10-12 | 1973-11-06 | Shell Oil Co | Nitro substituted propyl ester |
| JPH11208122A (en) * | 1998-01-21 | 1999-08-03 | Oji Paper Co Ltd | Thermal recording body |
| 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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2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3770806A (en) * | 1970-10-12 | 1973-11-06 | Shell Oil Co | Nitro substituted propyl ester |
| JPH11208122A (en) * | 1998-01-21 | 1999-08-03 | Oji Paper Co Ltd | Thermal recording body |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 聂小安，等: "环氧脂肪酸甲酯的合成及其降凝性能初探", 《林产化学与工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021135222A1 (en) * | 2019-12-30 | 2021-07-08 | 华南农业大学 | Multifunctional-epoxy-vegetable-oil-based uv-curable prepolymer, preparation method therefor and use thereof |
| CN112961404A (en) * | 2020-12-24 | 2021-06-15 | 中国林业科学研究院林产化学工业研究所 | Epoxy oligoether glyceride plasticizer and preparation method thereof |
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