CN104817521B - A kind of epoxy dimer (fatty acid) yl methyl ester and its preparation method and application - Google Patents
A kind of epoxy dimer (fatty acid) yl methyl ester and its preparation method and application Download PDFInfo
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- CN104817521B CN104817521B CN201510095064.9A CN201510095064A CN104817521B CN 104817521 B CN104817521 B CN 104817521B CN 201510095064 A CN201510095064 A CN 201510095064A CN 104817521 B CN104817521 B CN 104817521B
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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
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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
- 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
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
A kind of epoxy dimer (fatty acid) yl methyl ester and its preparation method and application, belongs to chemosynthesis technical field.Step of the present invention includes: employing fatty acid methyl ester is raw material, and agitating heating carries out dimerization reaction in the presence of a catalyst, it is thus achieved that intermediate product dimer (fatty acid) yl methyl ester；After intermediate product is mixed homogeneously with peroxygen source carrier and catalyst and is warmed up to uniform temperature further, dropping peroxygen source carries out epoxidation reaction, after reaction terminates, obtains epoxy dimeric acid methyl ester crude product, after stratification, neutralization and processed, obtain epoxy dimer (fatty acid) yl methyl ester finished product.Raw material sources of the present invention are extensive, renewable, are independent of oil；Preparation process by-product is few, constant product quality, and technique advantages of simple, energy consumption are low；Product asepsis environment-protecting, heat-resisting and good endurance, plasticising excellent performance, have preferable application prospect.
Description
Technical field
The present invention is the exploitation technology of preparing of the fat-based epoxy plasticiser of a kind of asepsis environment-protecting, is specifically related to one and is used as
The preparation method of the epoxy dimer (fatty acid) yl methyl ester of PVC plasticizer.
Background technology
In recent years, along with the fast development of engineering plastics industry, the demand of plasticizer is increased with the speed of annual 7-10%
Long, wherein, petroleum base phthalic ester plasticizer occupies the overwhelming majority market share.But such plasticizer has
Lasting genotoxicity, the U.S., Japan and European Union are multinational have been forbidded strictly at row such as electronics, food, article of everyday use and toys
Industry uses.China be plasticizer consume big country, current annual consumption more than 2,500,000 tons, phthalate plasticising
Agent accounts for the 86% of total quantity consumed, and national health and Environmental security are existed potential threat.Research and develop the most energetically with developed country
Comparing with the present situation of the environmental protection nontoxic plasticizer promoting alternative phthalate, domestic environment-friendly plasticizer grinds
System the most substantially lags behind the needs of engineering plastic product industry and national life.But along with taking place frequently of " plasticizing disturbance " accident,
Plasticizer safety and the pay attention to day by day of the feature of environmental protection, the market of environment-friendlyplasticizer plasticizer and consumption will be increased by domestic society day by day
Add.
At present, the environment-friendlyplasticizer plasticizer having been enter into application mainly has citric acid ester type and epoxy plasticiser etc..Wherein,
Epoxy aliphatic acid methyl ester have goods good-toughness, nontoxic contact food, lubricity good to light and thermally stable and point
Dissipate the advantage such as processing characteristics that property is excellent, can be effectively improved goods, through development for many years, become main flow bio-based
One of environment-friendlyplasticizer plasticizer.But epoxy aliphatic acid methyl ester plasticizer molecule amount is low, volatility big, and flash-point is on the low side, impact
The process operation of plastic and service life, application is the most limited.The present invention is with oils and fats derivant fatty acid methyl
Ester is raw material, by oligomerization and epoxidation modification, increases molecular weight and introduces aliphatic ring structure and epoxide group, it is thus achieved that
Multifunctional plasticizer product, has the feature of polyester plasticizer and epoxy plasticizer concurrently, alternative oil product, asepsis environment-protecting,
It it is the novel epoxy plasticiser of a class.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of epoxy dimer (fatty acid) yl acid methyl ester as PVC plasticizer,
The shortcoming such as little for conventional plasticizers molecular weight, the compatibility is poor, toxicity is single compared with big and performance, it is provided that have heat-resisting
Property good, good endurance, plasticizing efficiency is high, epoxy dimer (fatty acid) yl acid methyl ester plasticizer of asepsis environment-protecting and preparation method thereof.
This product can be used for plasticizer performance and more much higher kind of field of environmental protection class requirement.
The technical scheme is that a kind of epoxy dimer (fatty acid) yl methyl ester, the flash-point of described epoxy dimeric acid methyl ester is
210～250 DEG C, heating loss is 0.1%～0.4%；Raw material forms based on n/n/n/w: dimer (fatty acid) yl methyl ester: peroxide
Source carrier: peroxygen source: epoxidation catalyst is 1:(0.5～0.8): (1～2): (0.01～0.04)；Preparation method is:
Employing fatty acid methyl ester is raw material, and agitating heating carries out dimerization reaction in the presence of a catalyst, it is thus achieved that dimer (fatty acid) yl methyl ester；
After dimer (fatty acid) yl methyl ester is mixed homogeneously with peroxygen source carrier and epoxidation catalyst and heated up further, dropping peroxygen source enters
Row epoxidation reaction, after reaction terminates, obtains epoxy dimeric acid methyl ester crude product, through stratification, neutralization and processed
After, obtain epoxy dimer (fatty acid) yl methyl ester finished product；.
In described dimer (fatty acid) yl methyl ester preparation, catalyst accounts for the 4～10% of fatty acid methyl ester quality.
Epoxidation catalyst is p-methyl benzenesulfonic acid.
Described fatty acid methyl ester is to prepare with waste grease or natural oil for raw material；Described waste grease is trench
Oil and soybean acidified oil；Natural oil includes soybean oil, little Oleum Verniciae fordii, Rhizoma Coptidis wood oil, Oleum Gossypii semen, Oleum Brassicae campestris, Wen Guan
Fruit oil, rubber seed oil, curcas oil, styrax tonkinensis Craib ex Hart fruit oil, Oleum Verniciae fordii.
Prepare in dimer (fatty acid) yl methyl ester catalyst used be anhydrous Aluminum chloride, anhydrous zinc chloride, the one of active hargil
Kind or multiple mixture.
Described peroxygen source carrier is formic acid or acetic acid.
Described peroxygen source is tert-butyl hydroperoxide or the hydrogen peroxide of 50%～70%wt.
The preparation method of epoxy dimer (fatty acid) yl methyl ester, step is: step one, is blended with catalyst by fatty acid methyl ester
And it is heated to 160～230 DEG C, and reacting 3～8h, reactant mixture is through washing and decompression distillation, it is thus achieved that dimer (fatty acid) yl first
Ester；Step 2, is warming up to 50～70 DEG C by dimer (fatty acid) yl methyl ester, peroxygen source carrier and epoxidation catalyst mix and blend
After, it is added dropwise to peroxygen source by the speed of 15～30ml/h, continues insulation reaction 2～4h, be separated and recovered from epoxidation and urge
Agent, obtains epoxy dimeric acid methyl ester crude product, then obtains epoxy dimeric acid methyl ester through stratification, neutralization, processed
Finished product.
The sodium carbonate liquor that reactant mixture 40～80 DEG C of mass concentrations of employing are 2% in described step one washs also
Filter, remove catalyst；The vacuum distillation temperature of reactant mixture is between 170～220 DEG C, and vacuum is 0.08MPa.
Epoxy dimer (fatty acid) yl methyl ester is as PVC plasticizer or the application in preparing PVC plasticizer.
Beneficial effect:
(1) containing functionalization such as cycloaliphatic ring, ester group and epoxy radicals in the molecular structure of epoxy dimer (fatty acid) yl methyl ester product
Group, can play preferable plasticization in PVC product, and without benzene ring structure, asepsis environment-protecting.
(2) epoxy dimer (fatty acid) yl methyl ester product mean molecule quantity is higher, has the high temperature resistant, anti-of polyester plasticizer and moves
Move and the advantage such as resistance to extraction, the most also there is the Heat stability is good of epoxy plasticizer and the advantage such as plasticizing efficiency is high, can meet
To plasticizer performance and more much higher kind of field of environmental protection class requirement.
(3) split reduction is utilized to distill, the content of monounsaturated fatty acid methyl ester in regulation and control intermediate product, preparation series
Change epoxy dimer (fatty acid) yl methyl ester plasticizer product, meet the different application field pliability to goods and the difference of durability
Requirement, improves the competitiveness of product in market.
(4) preparation process by-product is few, constant product quality, and technique advantages of simple, energy consumption are low, low raw-material cost,
It it is the preparation method of a kind of environmental protection and economy.
Accompanying drawing explanation
Dimer (fatty acid) yl methyl ester prepared by Fig. 1 present invention and the gel chromatography analysis of spectra of epoxy dimer (fatty acid) yl methyl ester product.Two
The Mn=475 of polyglycerol fatty acid methyl ester, Mw=533, Mw/Mn=1.11；The Mn=539 of epoxy dimer (fatty acid) yl methyl ester,
Mw=661, Mw/Mn=1.23.
Epoxy dimer (fatty acid) yl methyl ester prepared by Fig. 2 present invention, and commercially available octyl phthalate and epoxy aliphatic acid methyl ester
The thermogravimetic analysis (TGA) spectrogram of the PVC product of institute's plasticising.Result shows, epoxy dimer (fatty acid) yl methyl ester is remarkably improved PVC
The heat stability of goods.
Detailed description of the invention
Following example are to further illustrate the present invention, are not limitations of the present invention.
A kind of preparation method of epoxy dimer (fatty acid) yl methyl ester, step is:
Step one, is blended fatty acid methyl ester with catalyst (accounting for the 4～10% of fatty acid methyl ester quality) and is heated to
160～230 DEG C, reacting 3～8h, reactant mixture is through washing and decompression distillation staged care, it is thus achieved that intermediate product dimerization
Fatty acid methyl ester；Step 2, according to dimer (fatty acid) yl methyl ester: peroxygen source carrier: peroxygen source: epoxidation catalyst (n/n/n/w)
For 1:(0.5～0.8): (1～2): (0.01～0.04) proportional sampling.By dimer (fatty acid) yl methyl ester, peroxy-radical carries
After body and epoxidation catalyst mix and blend are warming up to 50～70 DEG C, it is added dropwise to peroxygen source by the speed of 15～30ml/h,
Continue insulation reaction 2～4h, be separated and recovered from epoxidation catalyst, obtain epoxy dimeric acid methyl ester crude product, then through standing
Layering, neutralization, processed obtain epoxy dimeric acid methyl ester finished product.
Described fatty acid methyl ester is to prepare with waste grease or natural oil for raw material.
Described waste grease is waste oil and soybean acidified oil；Natural oil includes soybean oil, little Oleum Verniciae fordii, Chinese pistache
Oil, Oleum Gossypii semen, Oleum Brassicae campestris, shinyleaf yellowhorn oil, rubber seed oil, curcas oil, styrax tonkinensis Craib ex Hart fruit oil, Oleum Verniciae fordii etc..
Catalyst used in described step one be anhydrous Aluminum chloride, anhydrous Aluminum chloride, active hargil one or more
Mixture.
The sodium carbonate liquor that reactant mixture 40～80 DEG C of mass concentrations of employing are 2% in described step one washs also
Filter, remove catalyst.
The vacuum distillation temperature of the reactant mixture in described step one is between 170～220 DEG C, and vacuum is 650Pa.
Described peroxygen source carrier is formic acid or acetic acid.
Described peroxygen source is hydrogen peroxide (50%～70%) or tert-butyl hydroperoxide.
Described peroxygen source uses the mode of dropping to add reaction system, and rate of addition is 15～50ml/h.
The flash-point of described epoxy dimeric acid methyl ester is 210～250 DEG C, and heating loss is 0.1%～0.4%.
Embodiment 1
Step one, is separately added into 50g fatty acid methyl ester and 2g anhydrous Aluminum chloride in the four-hole boiling flask of 250mL, logical
Entering nitrogen, reduce the generation of side reaction in reaction system, be heated with stirring to 180 DEG C, react 5h, reactant mixture is used
50 DEG C of mass concentrations are sodium carbonate liquor washing the Filtration of catalyst of 2%, and at 190 DEG C, 0.08MPa condition
Under carry out decompression distillation, it is thus achieved that intermediate product dimer (fatty acid) yl methyl ester；
Step 2, weighs 20g dimer (fatty acid) yl methyl ester, 0.9g formic acid and 0.4g p-methyl benzenesulfonic acid, adds and is furnished with condensation
In the there-necked flask of pipe, stirring rod and thermometer, stirring is warming up to 50 DEG C, drips 4.3g by the speed of 15ml/h double
Oxygen water (50%), after dripping, rises to reaction temperature 65 DEG C and continues reaction 4h；After reaction terminates, thick product warp
Stratification obtains organic facies, the most neutralized alkali cleaning and washing, moisture is distilled off by decompression, has both obtained environment-friendly type ring
Oxygen Fructus anacardii phenolic group glycidyl ether plasticizer finished product.Product epoxide number (%): 3.2, heating loss (125 DEG C × 3h, %):
0.2, open flash point (DEG C): 237.
Embodiment 2
Step one, is separately added into 50g fatty acid methyl ester and 3g anhydrous Aluminum chloride in the four-hole boiling flask of 250mL, logical
Entering nitrogen, reduce the generation of side reaction in reaction system, be heated with stirring to 210 DEG C, react 4h, reactant mixture is used
70 DEG C of mass concentrations are sodium carbonate liquor washing the Filtration of catalyst of 2%, and at 190 DEG C, 0.08MPa condition
Under carry out decompression distillation, it is thus achieved that intermediate product dimer (fatty acid) yl methyl ester；
Step 2, weighs 20g dimer (fatty acid) yl methyl ester, 0.95g formic acid and 0.5g p-methyl benzenesulfonic acid, and addition is furnished with cold
In the there-necked flask of solidifying pipe, stirring rod and thermometer, stirring is warming up to 50 DEG C, drips 4.3g by the speed of 20ml/h
Hydrogen peroxide (50%), after dripping, rises to reaction temperature 65 DEG C and continues reaction 3h；After reaction terminates, thick product
Obtain organic facies, the most neutralized alkali cleaning and washing through stratification, moisture is distilled off by decompression, both obtain environment-friendly type
Epoxy Fructus anacardii phenolic group glycidyl ether plasticizer finished product.Product epoxide number (%): 3.0, heating loss (125 DEG C × 3h, %):
0.3, open flash point (DEG C): 234.
Embodiment 3
Step one, is separately added into 50g fatty acid methyl ester and 4g anhydrous zinc chloride in the four-hole boiling flask of 250mL, logical
Entering nitrogen, reduce the generation of side reaction in reaction system, be heated with stirring to 210 DEG C, react 4h, reactant mixture is used
70 DEG C of mass concentrations are sodium carbonate liquor washing the Filtration of catalyst of 2%, and at 180 DEG C, 0.08MPa condition
Under carry out decompression distillation, it is thus achieved that intermediate product dimer (fatty acid) yl methyl ester；
Step 2, weighs 20g dimer (fatty acid) yl methyl ester, 0.92g formic acid and 0.4g p-methyl benzenesulfonic acid, and addition is furnished with cold
In the there-necked flask of solidifying pipe, stirring rod and thermometer, stirring is warming up to 50 DEG C, drips 4.0g by the speed of 15ml/h
Hydrogen peroxide (70%), after dripping, rises to reaction temperature 60 DEG C and continues reaction 4h；After reaction terminates, thick product
Obtain organic facies, the most neutralized alkali cleaning and washing through stratification, moisture is distilled off by decompression, both obtain environment-friendly type
Epoxy Fructus anacardii phenolic group glycidyl ether plasticizer finished product.Product epoxide number (%): 3.1, heating loss (125 DEG C × 3h, %):
0.3, open flash point (DEG C): 235.
Embodiment 4
Step one, is separately added into 50g fatty acid methyl ester and 5g active hargil in the four-hole boiling flask of 250mL, is passed through
Nitrogen, reduces the generation of side reaction in reaction system, is heated with stirring to 200 DEG C, react 5h, and reactant mixture is with 70 DEG C
Mass concentration is sodium carbonate liquor washing the Filtration of catalyst of 2%, and at 180 DEG C, enters under the conditions of 0.08MPa
Row decompression distillation, it is thus achieved that intermediate product dimer (fatty acid) yl methyl ester；
Step 2, weighs 20g dimer (fatty acid) yl methyl ester, 0.92g formic acid and 0.4g p-methyl benzenesulfonic acid, and addition is furnished with cold
In the there-necked flask of solidifying pipe, stirring rod and thermometer, stirring is warming up to 50 DEG C, drips 4.5g by the speed of 25ml/h
Hydrogen peroxide (50%), after dripping, rises to reaction temperature 65 DEG C and continues reaction 3h；After reaction terminates, thick product
Obtain organic facies, the most neutralized alkali cleaning and washing through stratification, moisture is distilled off by decompression, both obtain environment-friendly type
Epoxy Fructus anacardii phenolic group glycidyl ether plasticizer finished product.Product epoxide number (%): 3.2, heating loss (125 DEG C × 3h, %):
0.4, open flash point (DEG C): 221.
Embodiment 5
Step one, be separately added in the four-hole boiling flask of 250mL 50g fatty acid methyl ester, 2g active hargil and 2g without
Water zinc chloride, is passed through nitrogen, reduces the generation of side reaction in reaction system, is heated with stirring to 210 DEG C, reacts 4h,
Reactant mixture the sodium carbonate liquor washing that 60 DEG C of mass concentrations are 2% Filtration of catalyst, and at 185 DEG C,
Decompression distillation is carried out, it is thus achieved that intermediate product dimer (fatty acid) yl methyl ester under the conditions of 0.08MPa；
Step 2, weighs 20g dimer (fatty acid) yl methyl ester, 0.95g formic acid and 0.4g p-methyl benzenesulfonic acid, and addition is furnished with cold
In the there-necked flask of solidifying pipe, stirring rod and thermometer, stirring is warming up to 50 DEG C, drips 5.0g by the speed of 25ml/h
Tert-butyl hydroperoxide, after dripping, rises to reaction temperature 65 DEG C and continues reaction 3h；After reaction terminates, thick product
Obtain organic facies, the most neutralized alkali cleaning and washing through stratification, moisture is distilled off by decompression, both obtain environment-friendly type
Epoxy Fructus anacardii phenolic group glycidyl ether plasticizer finished product.Product epoxide number (%): 3.3, heating loss (125 DEG C × 3h, %):
0.35, open flash point (DEG C): 229.
Embodiment 6
Step one, be separately added in the four-hole boiling flask of 250mL 50g fatty acid methyl ester, 3g active hargil and 1g without
Water aluminum chloride, is passed through nitrogen, reduces the generation of side reaction in reaction system, is heated with stirring to 210 DEG C, reacts 6h,
Reactant mixture the sodium carbonate liquor washing that 70 DEG C of mass concentrations are 2% Filtration of catalyst, and at 205 DEG C,
Decompression distillation is carried out, it is thus achieved that intermediate product dimer (fatty acid) yl methyl ester under the conditions of 0.08MPa；
Step 2, weighs 20g dimer (fatty acid) yl methyl ester, 0.90g formic acid and 0.6g p-methyl benzenesulfonic acid, and addition is furnished with cold
In the there-necked flask of solidifying pipe, stirring rod and thermometer, stirring is warming up to 50 DEG C, drips 5.0g by the speed of 15ml/h
Hydrogen peroxide (70%), after dripping, rises to reaction temperature 65 DEG C and continues reaction 2h；After reaction terminates, thick product
Obtain organic facies, the most neutralized alkali cleaning and washing through stratification, moisture is distilled off by decompression, both obtain environment-friendly type
Epoxy Fructus anacardii phenolic group glycidyl ether plasticizer finished product.Product epoxide number (%): 3.5, heating loss (125 DEG C × 3h, %):
0.24, open flash point (DEG C): 238.
Embodiment 7
Step one, is separately added into 50g fatty acid methyl ester, 3g anhydrous Aluminum chloride in the four-hole boiling flask of 250mL, logical
Entering nitrogen, reduce the generation of side reaction in reaction system, be heated with stirring to 200 DEG C, react 8h, reactant mixture is used
60 DEG C of mass concentrations are sodium carbonate liquor washing the Filtration of catalyst of 2%, and at 220 DEG C, 0.08MPa condition
Under carry out decompression distillation, it is thus achieved that intermediate product dimer (fatty acid) yl methyl ester；
Step 2, weighs 20g dimer (fatty acid) yl methyl ester, 0.92g formic acid and 0.4g p-methyl benzenesulfonic acid, and addition is furnished with cold
In the there-necked flask of solidifying pipe, stirring rod and thermometer, stirring is warming up to 50 DEG C, drips 5.0g by the speed of 15ml/h
Hydrogen peroxide (50%), after dripping, rises to reaction temperature 65 DEG C and continues reaction 4h；After reaction terminates, thick product
Obtain organic facies, the most neutralized alkali cleaning and washing through stratification, moisture is distilled off by decompression, both obtain environment-friendly type
Epoxy Fructus anacardii phenolic group glycidyl ether plasticizer finished product.Product epoxide number (%): 2.9, heating loss (125 DEG C × 3h, %):
0.20, open flash point (DEG C): 241.
Embodiment 8
Step one, is separately added into 50g fatty acid methyl ester, 3g anhydrous zinc chloride in the four-hole boiling flask of 250mL, logical
Entering nitrogen, reduce the generation of side reaction in reaction system, be heated with stirring to 220 DEG C, react 4h, reactant mixture is used
50 DEG C of mass concentrations are sodium carbonate liquor washing the Filtration of catalyst of 2%, and at 175 DEG C, 0.08MPa condition
Under carry out decompression distillation, it is thus achieved that intermediate product dimer (fatty acid) yl methyl ester；
Step 2, weighs 20g dimer (fatty acid) yl methyl ester, 0.92g formic acid and 0.4g p-methyl benzenesulfonic acid, and addition is furnished with cold
In the there-necked flask of solidifying pipe, stirring rod and thermometer, stirring is warming up to 50 DEG C, drips 4.3g by the speed of 30ml/h
Hydrogen peroxide (50%), after dripping, rises to reaction temperature 65 DEG C and continues reaction 3h；After reaction terminates, thick product
Obtain organic facies, the most neutralized alkali cleaning and washing through stratification, moisture is distilled off by decompression, both obtain environment-friendly type
Epoxy Fructus anacardii phenolic group glycidyl ether plasticizer finished product.Product epoxide number (%): 3.4, heating loss (125 DEG C × 3h, %):
0.37, open flash point (DEG C): 231.
Embodiment 9
Step one, is separately added into 50g fatty acid methyl ester, 4g active hargil in the four-hole boiling flask of 250mL, is passed through
Nitrogen, reduces the generation of side reaction in reaction system, is heated with stirring to 220 DEG C, react 5h, and reactant mixture is with 40 DEG C
Mass concentration is sodium carbonate liquor washing the Filtration of catalyst of 2%, and at 190 DEG C, enters under the conditions of 0.08MPa
Row decompression distillation, it is thus achieved that intermediate product dimer (fatty acid) yl methyl ester；
Step 2, weighs 20g dimer (fatty acid) yl methyl ester, 1.0g formic acid and 0.6g p-methyl benzenesulfonic acid, adds and is furnished with condensation
In the there-necked flask of pipe, stirring rod and thermometer, stirring is warming up to 50 DEG C, drips 4.2g by the speed of 15ml/h double
Oxygen water (70%), after dripping, rises to reaction temperature 65 DEG C and continues reaction 3h；After reaction terminates, thick product warp
Stratification obtains organic facies, the most neutralized alkali cleaning and washing, moisture is distilled off by decompression, has both obtained environment-friendly type ring
Oxygen Fructus anacardii phenolic group glycidyl ether plasticizer finished product.Product epoxide number (%): 3.0, heating loss (125 DEG C × 3h, %):
0.37, open flash point (DEG C): 228.
Embodiment 10
Step one, is separately added into 50g fatty acid methyl ester, 4g anhydrous Aluminum chloride in the four-hole boiling flask of 250mL, logical
Entering nitrogen, reduce the generation of side reaction in reaction system, be heated with stirring to 210 DEG C, react 4h, reactant mixture is used
60 DEG C of mass concentrations are sodium carbonate liquor washing the Filtration of catalyst of 2%, and at 180 DEG C, 0.08MPa condition
Under carry out decompression distillation, it is thus achieved that intermediate product dimer (fatty acid) yl methyl ester；
Step 2, weighs 20g dimer (fatty acid) yl methyl ester, 0.93g formic acid and 0.4g p-methyl benzenesulfonic acid, and addition is furnished with cold
In the there-necked flask of solidifying pipe, stirring rod and thermometer, stirring is warming up to 50 DEG C, drips 4.6g by the speed of 15ml/h
Hydrogen peroxide (50%), after dripping, rises to reaction temperature 65 DEG C and continues reaction 3h；After reaction terminates, thick product
Obtain organic facies, the most neutralized alkali cleaning and washing through stratification, moisture is distilled off by decompression, both obtain environment-friendly type
Epoxy Fructus anacardii phenolic group glycidyl ether plasticizer finished product.Product epoxide number (%): 3.4, heating loss (125 DEG C × 3h, %):
0.33, open flash point (DEG C): 237.
By in prepared plasticizer application and PVC, according to mass ratio PVC: plasticizer: heat stabilizer is 100:50:2
Formula mixture is stirred 3min in high-speed mixer after, make certain thickness PVC by two-roll mill
Sheet material, for heat stability testing.Thermal weight loss result in Fig. 1 shows, with conventional petroleum base plasticizer phthalic acid
Dibutyl ester and commercially available epoxy aliphatic acid methyl ester are compared, and epoxy dimer (fatty acid) yl methyl ester plasticizer is remarkably improved PVC
The heat stability of goods.Result in table 1 shows, compared with two kinds of commodity plasticizers, and epoxy dimer (fatty acid) yl methyl ester/PVC
The incipient degradation maximum temperature range of decrease of goods is close to 10%.
Table 1 thermal weight loss parameter
Note: TiFor first decomposition temperature；T10For temperature when mass loss 10%；T50 is temperature when mass loss 50%.
Claims (8)
1. an epoxy dimer (fatty acid) yl methyl ester, it is characterised in that the flash-point of described epoxy dimer (fatty acid) yl methyl ester is 210～250 DEG C, and heating loss is 0.1%～0.4%；Raw material forms based on n/n/n/w: dimer (fatty acid) yl methyl ester: peroxygen source carrier: peroxygen source: epoxidation catalyst is 1:(0.5～0.8): (1～2): (0.01～0.04)；Preparation method is: employing fatty acid methyl ester is raw material, and agitating heating carries out dimerization reaction in the presence of a catalyst, it is thus achieved that dimer (fatty acid) yl methyl ester；After dimer (fatty acid) yl methyl ester is mixed homogeneously with peroxygen source carrier and epoxidation catalyst and is heated up further, dropping peroxygen source carries out epoxidation reaction, after reaction terminates, obtains epoxy dimeric acid methyl ester crude product, after stratification, neutralization and processed, obtain epoxy dimer (fatty acid) yl methyl ester finished product；Described peroxygen source carrier is formic acid or acetic acid.
2. epoxy dimer (fatty acid) yl methyl ester as claimed in claim 1, it is characterised in that in described dimer (fatty acid) yl methyl ester preparation, catalyst accounts for the 4～10% of fatty acid methyl ester quality.
3. epoxy dimer (fatty acid) yl methyl ester as claimed in claim 1, it is characterised in that epoxidation catalyst is p-methyl benzenesulfonic acid.
4. epoxy dimer (fatty acid) yl methyl ester as claimed in claim 1, it is characterised in that described fatty acid methyl ester is to prepare with waste grease or natural oil for raw material；Described waste grease is waste oil and soybean acidified oil；Natural oil includes soybean oil, Rhizoma Coptidis wood oil, Oleum Gossypii semen, Oleum Brassicae campestris, shinyleaf yellowhorn oil, rubber seed oil, curcas oil, styrax tonkinensis Craib ex Hart fruit oil, Oleum Verniciae fordii.
5. epoxy dimer (fatty acid) yl methyl ester as claimed in claim 1, it is characterised in that prepare the mixture of one or more that catalyst is anhydrous Aluminum chloride, anhydrous zinc chloride, active hargil used in dimer (fatty acid) yl methyl ester.
6. epoxy dimer (fatty acid) yl methyl ester as claimed in claim 1, it is characterised in that described peroxygen source is the hydrogen peroxide of tert-butyl hydroperoxide or 50% ~ 70%wt.
7. the preparation method of the arbitrary described epoxy dimer (fatty acid) yl methyl ester of claim 1～6, it is characterized in that, step is: step one, fatty acid methyl ester and catalyst are blended and are heated to 160 ~ 230 DEG C, reaction 3 ~ 8 h, reactant mixture 40 ~ 80 DEG C of mass concentrations of employing are that the sodium carbonate liquor of 2 % washs and filters, and remove catalyst；The vacuum distillation temperature of reactant mixture is between 170 ~ 220 DEG C, and vacuum is 0.08 MPa, it is thus achieved that dimer (fatty acid) yl methyl ester；Step 2, by dimer (fatty acid) yl methyl ester, after peroxygen source carrier and epoxidation catalyst mix and blend are warming up to 50～70 DEG C, it is added dropwise to peroxygen source by the speed of 15 ~ 30ml/ h, continue insulation reaction 2～4 h, it is separated and recovered from epoxidation catalyst, obtains epoxy dimeric acid methyl ester crude product, then obtain epoxy dimeric acid methyl ester finished product through stratification, neutralization, processed；Described peroxygen source carrier is formic acid or acetic acid.
8. the epoxy dimer (fatty acid) yl methyl ester described in claim 1 is as PVC plasticizer or the application in preparing PVC plasticizer.
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| DE2250470A1 (en) * | 1972-10-14 | 1974-04-18 | Henkel & Cie Gmbh | PROCESS FOR DIMERIZING UNSATATURATED FATTY ACIDS AND FATTY ACID ESTERS |
| US6274750B1 (en) * | 1998-07-21 | 2001-08-14 | Cognis Corporation | Dimer and trimer acid esters from epoxidized compounds and methods for their preparation |
| CN1966497A (en) * | 2006-09-11 | 2007-05-23 | 罗春妹 | Epoxy fatty acid methyl ester |
| WO2009102592A2 (en) * | 2008-02-12 | 2009-08-20 | Polyone Corporation | Epoxidized soyate diesters and methods of using same |
| CN101293829B (en) * | 2008-06-12 | 2011-06-29 | 江苏工业学院 | Method for preparing polydiallyl itaconate and dimer acid |
| CN101613273B (en) * | 2009-07-25 | 2014-04-16 | 青岛科技大学 | Method for preparing dimeric acid methyl ester |
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| CN102517157A (en) * | 2011-12-31 | 2012-06-27 | 中国林业科学研究院林产化学工业研究所 | Rubber seed oil-based epoxy fatty acid methyl ester and preparation method and application thereof |
| EP2909261B1 (en) * | 2012-10-18 | 2019-04-03 | Dow Global Technologies LLC | Epoxidized fatty acid alkyl ester plasticizers and methods for making epoxidized fatty acid alkyl ester plasticizers |
| CN104370860B (en) * | 2014-10-22 | 2017-01-11 | 广州市海珥玛植物油脂有限公司 | Diepoxide vegetable oil acid acetyl glyceride and synthesis method and application thereof |
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