CN104817521A - Epoxy dimeric fatty acid methyl ester, preparation method and applications thereof - Google Patents
Epoxy dimeric fatty acid methyl ester, preparation method and applications thereof Download PDFInfo
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- CN104817521A CN104817521A CN201510095064.9A CN201510095064A CN104817521A CN 104817521 A CN104817521 A CN 104817521A CN 201510095064 A CN201510095064 A CN 201510095064A CN 104817521 A CN104817521 A CN 104817521A
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- 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
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- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
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- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
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Abstract
The invention relates to an epoxy dimeric fatty acid methyl ester, a preparation method and applications thereof, and belongs to the technical field of chemical synthesis. The preparation steps comprise: adopting fatty acid methyl ester as a raw material, carrying out stirring heating in the presence of a catalyst to carry out a dimerization reaction to obtain an intermediate product dimeric fatty acid methyl ester, uniformly mixing the intermediate product, a peroxy source carrier and a catalyst, heating to a certain temperature, adding a peroxy source in a dropwise manner to carry out an epoxidation reaction so as to obtain an epoxy dimer acid methyl ester crude product, and carrying out standing layering, neutralization and dehydration to obtain the epoxy dimeric fatty acid methyl ester finished product. According to the present invention, the preparation method has characteristics of wide raw material source, raw material recycling, no dependence on petroleum, less byproduct during the preparation process, stable product quality, simple and reasonable process, and low energy consumption, and the obtained product has characteristics of no toxicity, environmental protection, heat resistance, good durability, excellent plasticizing performance, and good application prospects.
Description
Technical field
The present invention is a kind of exploitation technology of preparing of fat-based epoxy plasticiser of asepsis environment-protecting, is specifically related to a kind of preparation method being used as the epoxy dimer (fatty acid) yl methyl esters of PVC softening agent.
Background technology
In recent years, along with the fast development of engineering plastics industry, to the demand of softening agent with the speed increment of annual 7-10%, wherein, petroleum base phthalic ester plasticizer occupies most market share.But such softening agent has lasting genotoxicity, multinational having forbidded strictly of the U.S., Japan and European Union uses in the industries such as electronics, food, daily necessities and toy.China is that softening agent consumes big country, and current annual consumption is more than 2,500,000 tons, and phthalic ester plasticizer accounts for 86% of total quantity consumed, there is potential threat to national health and environmental safety.Research and develop just energetically with developed country and compare with the present situation of the environmental protection non-toxic plasticizer promoting alternative phthalate, domestic environment-friendly plasticizer development then obviously lags behind the needs of engineering plastic product industry and national life.But along with taking place frequently of " plasticizing disturbance " accident, domestic society is to the pay attention to day by day of softening agent security and the feature of environmental protection, and the market of environment-friendlyplasticizer plasticizer and consumption will increase day by day.
At present, the environment-friendlyplasticizer plasticizer having entered Application Areas mainly contains citric acid ester type and epoxy plasticiser etc.Wherein, epoxy aliphatic acid methyl ester have goods good-toughness, nontoxic can contact food, oilness good to light and thermally stable and dispersiveness is excellent, can effectively improve the advantages such as the processing characteristics of goods, through development for many years, now become one of main flow bio-based environment-friendlyplasticizer plasticizer.But epoxy aliphatic acid methyl ester plasticizer molecule amount is low, volatility large, and flash-point is on the low side, and affect process operation and the work-ing life of plastics, Application Areas is greatly limited.The present invention with grease derivative fatty acid methyl ester for raw material, by oligomerization and epoxidation modification, increase molecular weight and introduce aliphatic ring structure and epoxide group, obtain multifunctional softening agent product, have the feature of polyester plasticizer and epoxy plasticizer concurrently, alternative petroleum products, asepsis environment-protecting is the novel epoxy plasticiser of a class.
Summary of the invention
The object of the present invention is to provide a kind of preparation method being used as the epoxy dimer (fatty acid) yl acid methyl esters of PVC softening agent, the shortcoming such as little for conventional plasticizers molecular weight, consistency is poor, toxicity is comparatively large and performance is single, provide and there is good heat resistance, good endurance, plasticizing efficiency is high, epoxy dimer (fatty acid) yl acid methyl esters softening agent of asepsis environment-protecting and preparation method thereof.This product can be used for softening agent performance and environmental protection class requirement more much higher kind of field.
Technical scheme of the present invention is: a kind of epoxy dimer (fatty acid) yl methyl esters, and the flash-point of described epoxy dimeric acid methyl ester is 210 ~ 250 DEG C, and weight loss on heating is 0.1% ~ 0.4%; Raw material composition is by n/n/n/w: dimer (fatty acid) yl methyl esters: 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 stirring heating carries out dimerization reaction in the presence of a catalyst, obtains dimer (fatty acid) yl methyl esters; Dimer (fatty acid) yl methyl esters mixes with peroxygen source carrier and epoxidation catalyst and after heating up further, drip peroxygen source and carry out epoxidation reaction, after reaction terminates, obtain epoxy dimeric acid methyl ester crude product, after stratification, neutralization and processed, obtain epoxy dimer (fatty acid) yl methyl esters finished product; .
In described dimer (fatty acid) yl methyl esters preparation, catalyzer accounts for 4 ~ 10% of fatty acid methyl ester quality.
Epoxidation catalyst is tosic acid.
Described fatty acid methyl ester is for prepared by raw material with waste grease or natural fats and oils; Described waste grease is sewer oil and soybean acidified oil; Natural fats and oils comprises soybean oil, little Oleum Verniciae fordii, coptis wood oil, Oleum Gossypii semen, rapeseed oil, shinyleaf yellowhorn oil, rubber seed oil, curcas oil, styrax tonkinensis Craib ex Hart fruit oil, tung oil.
Prepare one or more the mixture that catalyzer used in dimer (fatty acid) yl methyl esters is Aluminum chloride anhydrous, Zinc Chloride Anhydrous, atlapulgite.
Described peroxygen source carrier is formic acid or acetic acid.
Described peroxygen source is the hydrogen peroxide of tertbutyl peroxide or 50% ~ 70%wt.
The preparation method of epoxy dimer (fatty acid) yl methyl esters, step is: step one, by fatty acid methyl ester and catalyzer blended and be heated to 160 ~ 230 DEG C, reaction 3 ~ 8h, reaction mixture, through washing and underpressure distillation, obtains dimer (fatty acid) yl methyl esters; Step 2, by dimer (fatty acid) yl methyl esters, after peroxygen source carrier and epoxidation catalyst mix and blend are warming up to 50 ~ 70 DEG C, peroxygen source is added dropwise to by the speed of 15 ~ 30ml/h, continue insulation reaction 2 ~ 4h, be separated and reclaim epoxidation catalyst, obtaining epoxy dimeric acid methyl ester crude product, then obtaining epoxy dimeric acid methyl ester finished product through stratification, neutralization, processed.
Reaction mixture in described step one adopt 40 ~ 80 DEG C of mass concentrations be 2% sodium carbonate solution wash and filter, remove catalyzer; The vacuum distillation temperature of reaction mixture is between 170 ~ 220 DEG C, and vacuum tightness is 0.08MPa.
Epoxy dimer (fatty acid) yl methyl esters is as PVC softening agent or the application in preparation PVC softening agent.
Beneficial effect:
(1) containing functionalization groups such as cycloaliphatic ring, ester group and epoxy group(ing) in the molecular structure of epoxy dimer (fatty acid) yl methyl esters product, good plastification can be played in PVC product, and not containing benzene ring structure, asepsis environment-protecting.
(2) epoxy dimer (fatty acid) yl methyl esters product molecular-weight average is higher, there is high temperature resistant, the advantage such as anti-migration and resistance to extraction of polyester plasticizer, the advantage such as simultaneously also have the Heat stability is good of epoxy plasticizer and plasticizing efficiency is high, can meet softening agent performance and environmental protection class requirement more much higher kind of field.
(3) reclaim liquid is utilized, the content of monounsaturated fatty acids methyl esters in regulation and control intermediate product, preparation seriation epoxy dimer (fatty acid) yl methyl esters softening agent product, meets the different requirements of different application field to the snappiness of goods and weather resistance, improves the competitiveness of product in market.
(4) few, the constant product quality of preparation process by product, technique advantages of simple, energy consumption are low, low raw-material cost, are a kind of preparation methods of environmental protection and economy.
Accompanying drawing explanation
The gel chromatography analysis of spectra of dimer (fatty acid) yl methyl esters prepared by Fig. 1 the present invention and epoxy dimer (fatty acid) yl methyl esters product.The Mn=475 of dimer (fatty acid) yl methyl esters, Mw=533, Mw/Mn=1.11; The Mn=539 of epoxy dimer (fatty acid) yl methyl esters, Mw=661, Mw/Mn=1.23.
Epoxy dimer (fatty acid) yl methyl esters prepared by Fig. 2 the present invention, and the thermogravimetic analysis (TGA) spectrogram of the PVC product of commercially available octyl phthalate and the plasticising of epoxy aliphatic acid methyl ester institute.Result shows, epoxy dimer (fatty acid) yl methyl esters can significantly improve the thermostability of PVC product.
Embodiment
Following examples further illustrate of the present invention, is not limitation of the present invention.
A preparation method for epoxy dimer (fatty acid) yl methyl esters, step is:
Step one, by fatty acid methyl ester and catalyzer (accounting for 4 ~ 10% of fatty acid methyl ester quality) blended and be heated to 160 ~ 230 DEG C, reaction 3 ~ 8h, reaction mixture, through washing and underpressure distillation stage treatment, obtains intermediate product dimer (fatty acid) yl methyl esters; Step 2, according to dimer (fatty acid) yl methyl esters: peroxygen source carrier: peroxygen source: epoxidation catalyst (n/n/n/w) is 1:(0.5 ~ 0.8): (1 ~ 2): (0.01 ~ 0.04) proportional sampling.By dimer (fatty acid) yl methyl esters, after peroxy-radical carrier and epoxidation catalyst mix and blend are warming up to 50 ~ 70 DEG C, peroxygen source is added dropwise to by the speed of 15 ~ 30ml/h, continue insulation reaction 2 ~ 4h, be separated and reclaim epoxidation catalyst, obtain epoxy dimeric acid methyl ester crude product, then obtain epoxy dimeric acid methyl ester finished product through stratification, neutralization, processed.
Described fatty acid methyl ester is for prepared by raw material with waste grease or natural fats and oils.
Described waste grease is sewer oil and soybean acidified oil; Natural fats and oils comprises soybean oil, little Oleum Verniciae fordii, coptis wood oil, Oleum Gossypii semen, rapeseed oil, shinyleaf yellowhorn oil, rubber seed oil, curcas oil, styrax tonkinensis Craib ex Hart fruit oil, tung oil etc.
Catalyzer used in described step one is one or more mixtures of Aluminum chloride anhydrous, Aluminum chloride anhydrous, atlapulgite.
Reaction mixture in described step one adopt 40 ~ 80 DEG C of mass concentrations be 2% sodium carbonate solution wash and filter, remove catalyzer.
The vacuum distillation temperature of the reaction mixture in described step one is between 170 ~ 220 DEG C, and vacuum tightness is 650Pa.
Described peroxygen source carrier is formic acid or acetic acid.
Described peroxygen source is hydrogen peroxide (50% ~ 70%) or tertbutyl peroxide.
Described peroxygen source adopts the mode dripped 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 weight loss on heating is 0.1% ~ 0.4%.
Embodiment 1
Step one, 50g fatty acid methyl ester and 2g Aluminum chloride anhydrous is added respectively in the four-hole boiling flask of 250mL, pass into nitrogen, reduce the generation of side reaction in reaction system, be heated with stirring to 180 DEG C, reaction 5h, reaction mixture is the sodium carbonate solution washing also Filtration of catalyst of 2% by 50 DEG C of mass concentrations, and at 190 DEG C, under 0.08MPa condition, carry out underpressure distillation, obtain intermediate product dimer (fatty acid) yl methyl esters;
Step 2, take 20g dimer (fatty acid) yl methyl esters, 0.9g formic acid and 0.4g tosic acid, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stirring is warming up to 50 DEG C, 4.3g hydrogen peroxide (50%) is dripped by the speed of 15ml/h, after dripping, temperature of reaction is risen to 65 DEG C and continue reaction 4h; Reaction terminate after, thick product obtains organic phase through stratification, then through in and alkali cleaning and washing, remove moisture by underpressure distillation, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product oxirane value (%): 3.2, weight loss on heating (125 DEG C × 3h, %): 0.2, open flash point (DEG C): 237.
Embodiment 2
Step one, 50g fatty acid methyl ester and 3g Aluminum chloride anhydrous is added respectively in the four-hole boiling flask of 250mL, pass into nitrogen, reduce the generation of side reaction in reaction system, be heated with stirring to 210 DEG C, reaction 4h, reaction mixture is the sodium carbonate solution washing also Filtration of catalyst of 2% by 70 DEG C of mass concentrations, and at 190 DEG C, under 0.08MPa condition, carry out underpressure distillation, obtain intermediate product dimer (fatty acid) yl methyl esters;
Step 2, take 20g dimer (fatty acid) yl methyl esters, 0.95g formic acid and 0.5g tosic acid, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stirring is warming up to 50 DEG C, 4.3g hydrogen peroxide (50%) is dripped by the speed of 20ml/h, after dripping, temperature of reaction is risen to 65 DEG C and continue reaction 3h; Reaction terminate after, thick product obtains organic phase through stratification, then through in and alkali cleaning and washing, remove moisture by underpressure distillation, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product oxirane value (%): 3.0, weight loss on heating (125 DEG C × 3h, %): 0.3, open flash point (DEG C): 234.
Embodiment 3
Step one, 50g fatty acid methyl ester and 4g Zinc Chloride Anhydrous is added respectively in the four-hole boiling flask of 250mL, pass into nitrogen, reduce the generation of side reaction in reaction system, be heated with stirring to 210 DEG C, reaction 4h, reaction mixture is the sodium carbonate solution washing also Filtration of catalyst of 2% by 70 DEG C of mass concentrations, and at 180 DEG C, under 0.08MPa condition, carry out underpressure distillation, obtain intermediate product dimer (fatty acid) yl methyl esters;
Step 2, take 20g dimer (fatty acid) yl methyl esters, 0.92g formic acid and 0.4g tosic acid, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stirring is warming up to 50 DEG C, 4.0g hydrogen peroxide (70%) is dripped by the speed of 15ml/h, after dripping, temperature of reaction is risen to 60 DEG C and continue reaction 4h; Reaction terminate after, thick product obtains organic phase through stratification, then through in and alkali cleaning and washing, remove moisture by underpressure distillation, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product oxirane value (%): 3.1, weight loss on heating (125 DEG C × 3h, %): 0.3, open flash point (DEG C): 235.
Embodiment 4
Step one, 50g fatty acid methyl ester and 5g atlapulgite is added respectively in the four-hole boiling flask of 250mL, pass into nitrogen, reduce the generation of side reaction in reaction system, be heated with stirring to 200 DEG C, reaction 5h, reaction mixture is the sodium carbonate solution washing also Filtration of catalyst of 2% by 70 DEG C of mass concentrations, and at 180 DEG C, under 0.08MPa condition, carry out underpressure distillation, obtain intermediate product dimer (fatty acid) yl methyl esters;
Step 2, take 20g dimer (fatty acid) yl methyl esters, 0.92g formic acid and 0.4g tosic acid, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stirring is warming up to 50 DEG C, 4.5g hydrogen peroxide (50%) is dripped by the speed of 25ml/h, after dripping, temperature of reaction is risen to 65 DEG C and continue reaction 3h; Reaction terminate after, thick product obtains organic phase through stratification, then through in and alkali cleaning and washing, remove moisture by underpressure distillation, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product oxirane value (%): 3.2, weight loss on heating (125 DEG C × 3h, %): 0.4, open flash point (DEG C): 221.
Embodiment 5
Step one, 50g fatty acid methyl ester, 2g atlapulgite and 2g Zinc Chloride Anhydrous is added respectively in the four-hole boiling flask of 250mL, pass into nitrogen, reduce the generation of side reaction in reaction system, be heated with stirring to 210 DEG C, reaction 4h, reaction mixture is the sodium carbonate solution washing also Filtration of catalyst of 2% by 60 DEG C of mass concentrations, and at 185 DEG C, under 0.08MPa condition, carry out underpressure distillation, obtain intermediate product dimer (fatty acid) yl methyl esters;
Step 2, take 20g dimer (fatty acid) yl methyl esters, 0.95g formic acid and 0.4g tosic acid, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stirring is warming up to 50 DEG C, 5.0g tertbutyl peroxide is dripped by the speed of 25ml/h, after dripping, temperature of reaction is risen to 65 DEG C and continue reaction 3h; Reaction terminate after, thick product obtains organic phase through stratification, then through in and alkali cleaning and washing, remove moisture by underpressure distillation, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product oxirane value (%): 3.3, weight loss on heating (125 DEG C × 3h, %): 0.35, open flash point (DEG C): 229.
Embodiment 6
Step one, 50g fatty acid methyl ester, 3g atlapulgite and 1g Aluminum chloride anhydrous is added respectively in the four-hole boiling flask of 250mL, pass into nitrogen, reduce the generation of side reaction in reaction system, be heated with stirring to 210 DEG C, reaction 6h, reaction mixture is the sodium carbonate solution washing also Filtration of catalyst of 2% by 70 DEG C of mass concentrations, and at 205 DEG C, under 0.08MPa condition, carry out underpressure distillation, obtain intermediate product dimer (fatty acid) yl methyl esters;
Step 2, take 20g dimer (fatty acid) yl methyl esters, 0.90g formic acid and 0.6g tosic acid, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stirring is warming up to 50 DEG C, 5.0g hydrogen peroxide (70%) is dripped by the speed of 15ml/h, after dripping, temperature of reaction is risen to 65 DEG C and continue reaction 2h; Reaction terminate after, thick product obtains organic phase through stratification, then through in and alkali cleaning and washing, remove moisture by underpressure distillation, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product oxirane value (%): 3.5, weight loss on heating (125 DEG C × 3h, %): 0.24, open flash point (DEG C): 238.
Embodiment 7
Step one, 50g fatty acid methyl ester, 3g Aluminum chloride anhydrous is added respectively in the four-hole boiling flask of 250mL, pass into nitrogen, reduce the generation of side reaction in reaction system, be heated with stirring to 200 DEG C, reaction 8h, reaction mixture is the sodium carbonate solution washing also Filtration of catalyst of 2% by 60 DEG C of mass concentrations, and at 220 DEG C, under 0.08MPa condition, carry out underpressure distillation, obtain intermediate product dimer (fatty acid) yl methyl esters;
Step 2, take 20g dimer (fatty acid) yl methyl esters, 0.92g formic acid and 0.4g tosic acid, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stirring is warming up to 50 DEG C, 5.0g hydrogen peroxide (50%) is dripped by the speed of 15ml/h, after dripping, temperature of reaction is risen to 65 DEG C and continue reaction 4h; Reaction terminate after, thick product obtains organic phase through stratification, then through in and alkali cleaning and washing, remove moisture by underpressure distillation, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product oxirane value (%): 2.9, weight loss on heating (125 DEG C × 3h, %): 0.20, open flash point (DEG C): 241.
Embodiment 8
Step one, 50g fatty acid methyl ester, 3g Zinc Chloride Anhydrous is added respectively in the four-hole boiling flask of 250mL, pass into nitrogen, reduce the generation of side reaction in reaction system, be heated with stirring to 220 DEG C, reaction 4h, reaction mixture is the sodium carbonate solution washing also Filtration of catalyst of 2% by 50 DEG C of mass concentrations, and at 175 DEG C, under 0.08MPa condition, carry out underpressure distillation, obtain intermediate product dimer (fatty acid) yl methyl esters;
Step 2, take 20g dimer (fatty acid) yl methyl esters, 0.92g formic acid and 0.4g tosic acid, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stirring is warming up to 50 DEG C, 4.3g hydrogen peroxide (50%) is dripped by the speed of 30ml/h, after dripping, temperature of reaction is risen to 65 DEG C and continue reaction 3h; Reaction terminate after, thick product obtains organic phase through stratification, then through in and alkali cleaning and washing, remove moisture by underpressure distillation, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product oxirane value (%): 3.4, weight loss on heating (125 DEG C × 3h, %): 0.37, open flash point (DEG C): 231.
Embodiment 9
Step one, 50g fatty acid methyl ester, 4g atlapulgite is added respectively in the four-hole boiling flask of 250mL, pass into nitrogen, reduce the generation of side reaction in reaction system, be heated with stirring to 220 DEG C, reaction 5h, reaction mixture is the sodium carbonate solution washing also Filtration of catalyst of 2% by 40 DEG C of mass concentrations, and at 190 DEG C, under 0.08MPa condition, carry out underpressure distillation, obtain intermediate product dimer (fatty acid) yl methyl esters;
Step 2, take 20g dimer (fatty acid) yl methyl esters, 1.0g formic acid and 0.6g tosic acid, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stirring is warming up to 50 DEG C, 4.2g hydrogen peroxide (70%) is dripped by the speed of 15ml/h, after dripping, temperature of reaction is risen to 65 DEG C and continue reaction 3h; Reaction terminate after, thick product obtains organic phase through stratification, then through in and alkali cleaning and washing, remove moisture by underpressure distillation, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product oxirane value (%): 3.0, weight loss on heating (125 DEG C × 3h, %): 0.37, open flash point (DEG C): 228.
Embodiment 10
Step one, 50g fatty acid methyl ester, 4g Aluminum chloride anhydrous is added respectively in the four-hole boiling flask of 250mL, pass into nitrogen, reduce the generation of side reaction in reaction system, be heated with stirring to 210 DEG C, reaction 4h, reaction mixture is the sodium carbonate solution washing also Filtration of catalyst of 2% by 60 DEG C of mass concentrations, and at 180 DEG C, under 0.08MPa condition, carry out underpressure distillation, obtain intermediate product dimer (fatty acid) yl methyl esters;
Step 2, take 20g dimer (fatty acid) yl methyl esters, 0.93g formic acid and 0.4g tosic acid, add in the there-necked flask being furnished with prolong, stirring rod and thermometer, stirring is warming up to 50 DEG C, 4.6g hydrogen peroxide (50%) is dripped by the speed of 15ml/h, after dripping, temperature of reaction is risen to 65 DEG C and continue reaction 3h; Reaction terminate after, thick product obtains organic phase through stratification, then through in and alkali cleaning and washing, remove moisture by underpressure distillation, both environment-friendly epoxy cashew nut phenolic group glycidyl ether softening agent finished product.Product oxirane value (%): 3.4, weight loss on heating (125 DEG C × 3h, %): 0.33, open flash point (DEG C): 237.
By the application of prepared softening agent with PVC, according to mass ratio PVC: softening agent: thermo-stabilizer is after mixture is stirred 3min by the formula of 100:50:2 in high-speed mixer, certain thickness PVC sheet is made, for heat stability testing by two roller mill.Thermal weight loss result in Fig. 1 shows, compared with conventional petroleum base plasticizer phthalic acid dibutyl ester and commercially available epoxy aliphatic acid methyl ester, epoxy dimer (fatty acid) yl methyl esters softening agent can significantly improve the thermostability of PVC product.Result in table 1 shows, compared with two kinds of commodity softening agent, the incipient degradation maximum temperature range of decrease of epoxy dimer (fatty acid) yl methyl esters/PVC product is close to 10%.
Table 1 thermal weight loss parameter
Note: T
ifor first decomposition temperature; T
10for mass loss 10% time temperature; Temperature time T50 is mass loss 50%.
Claims (10)
1. an epoxy dimer (fatty acid) yl methyl esters, is characterized in that, the flash-point of described epoxy dimeric acid methyl ester is 210 ~ 250 DEG C, and weight loss on heating is 0.1% ~ 0.4%; Raw material composition is by n/n/n/w: dimer (fatty acid) yl methyl esters: 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 stirring heating carries out dimerization reaction in the presence of a catalyst, obtains dimer (fatty acid) yl methyl esters; Dimer (fatty acid) yl methyl esters mixes with peroxygen source carrier and epoxidation catalyst and after heating up further, drip peroxygen source and carry out epoxidation reaction, after reaction terminates, obtain epoxy dimeric acid methyl ester crude product, after stratification, neutralization and processed, obtain epoxy dimer (fatty acid) yl methyl esters finished product; .
2. epoxy dimer (fatty acid) yl methyl esters as claimed in claim 1, is characterized in that, in described dimer (fatty acid) yl methyl esters preparation, catalyzer accounts for 4 ~ 10% of fatty acid methyl ester quality.
3. epoxy dimer (fatty acid) yl methyl esters as claimed in claim 1, it is characterized in that, epoxidation catalyst is tosic acid.
4. epoxy dimer (fatty acid) yl methyl esters as claimed in claim 1, is characterized in that, described fatty acid methyl ester is for prepared by raw material with waste grease or natural fats and oils; Described waste grease is sewer oil and soybean acidified oil; Natural fats and oils comprises soybean oil, little Oleum Verniciae fordii, coptis wood oil, Oleum Gossypii semen, rapeseed oil, shinyleaf yellowhorn oil, rubber seed oil, curcas oil, styrax tonkinensis Craib ex Hart fruit oil, tung oil.
5. epoxy dimer (fatty acid) yl methyl esters as claimed in claim 1, is characterized in that, prepare one or more the mixture that catalyzer used in dimer (fatty acid) yl methyl esters is Aluminum chloride anhydrous, Zinc Chloride Anhydrous, atlapulgite.
6. epoxy dimer (fatty acid) yl methyl esters as claimed in claim 1, it is characterized in that, described peroxygen source carrier is formic acid or acetic acid.
7. epoxy dimer (fatty acid) yl methyl esters as claimed in claim 1, it is characterized in that, described peroxygen source is the hydrogen peroxide of tertbutyl peroxide or 50% ~ 70%wt.
8. the preparation method of the arbitrary described epoxy dimer (fatty acid) yl methyl esters of claim 1 ~ 7, it is characterized in that, step is: step one, by fatty acid methyl ester and catalyzer blended and be heated to 160 ~ 230 DEG C, reaction 3 ~ 8 h, reaction mixture, through washing and underpressure distillation, obtains dimer (fatty acid) yl methyl esters; Step 2, by dimer (fatty acid) yl methyl esters, after peroxygen source carrier and epoxidation catalyst mix and blend are warming up to 50 ~ 70 DEG C, peroxygen source is added dropwise to by the speed of 15 ~ 30ml/ h, continue insulation reaction 2 ~ 4 h, be separated and reclaim epoxidation catalyst, obtaining epoxy dimeric acid methyl ester crude product, then obtaining epoxy dimeric acid methyl ester finished product through stratification, neutralization, processed.
9. the preparation method of epoxy dimer (fatty acid) yl methyl esters as claimed in claim 8, is characterized in that, reaction mixture employing 40 ~ 80 DEG C of mass concentrations in described step one are that the sodium carbonate solution of 2 % washs and filters, removing catalyzer; The vacuum distillation temperature of reaction mixture is between 170 ~ 220 DEG C, and vacuum tightness is 0.08 MPa.
10. epoxy dimer (fatty acid) yl methyl esters according to claim 1 is as PVC softening agent or the application in preparation PVC softening agent.
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