CN102517157A - Rubber seed oil-based epoxy fatty acid methyl ester and preparation method and application thereof - Google Patents

Rubber seed oil-based epoxy fatty acid methyl ester and preparation method and application thereof Download PDF

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CN102517157A
CN102517157A CN2011104565712A CN201110456571A CN102517157A CN 102517157 A CN102517157 A CN 102517157A CN 2011104565712 A CN2011104565712 A CN 2011104565712A CN 201110456571 A CN201110456571 A CN 201110456571A CN 102517157 A CN102517157 A CN 102517157A
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seed oil
fatty acid
acid methyl
methyl ester
rubber seed
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蒋剑春
陈洁
聂小安
陈水根
常侠
李科
许彬
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Institute of Chemical Industry of Forest Products of CAF
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Institute of Chemical Industry of Forest Products of CAF
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Abstract

The invention relates to rubber seed oil-based epoxy fatty acid methyl ester and a preparation method and application thereof. After being degummed, rubber seed oil and methanol are subjected to pre-esterification and ester exchange reaction so that rubber seed oil-based fatty acid methyl ester rough product is obtained, the rubber seed oil-based fatty acid methyl ester rough product is subjected to crystallization and separation at low temperature so that UFAMEs (unsaturated fatty acid methyl esters) rich in polyene is obtained, products from epoxidation can be allowed to stand and delaminate, and finally the rubber seed oil-based epoxy fatty acid methyl ester is obtained after the upper oil phase is neutralized, dehydrated and adsorbed. The epoxide value is equal to or larger than 5.0%, the flash point is equal to or larger than 200 DEG C, the resistivity is equal to or larger than 1.0X109 ohmm, the tincture is smaller than or equal to 180, the acid value ranges from 0.45-0.5mgg-1, and the heating loss is smaller than or equal to 0.5. The raw materials of the rubber seed oil-based epoxy fatty acid methyl ester are easy to obtain so that the cost thereof is low. The rubber seed oil-based epoxy fatty acid methyl ester is high in performance and stable in quality and suitable for industrial production. The preparation method of the rubber seed oil-based epoxy fatty acid methyl ester is simple in process, convenient in operation, short in production cycle, low in energy consumption and low in pollution during production.

Description

A kind of rubber seed oil basic ring oxygen fatty acid methyl ester
Technical field
The present invention is a kind of preparation method of bio-based softening agent, is specifically related to a kind of rubber seed oil base high-performance epoxy aliphatic acid methyl ester and preparation method thereof and as the application of softening agent.
Background technology
China's softening agent industry has formed certain scale through the development of decades, is the maximum country of Asia plasticizer production and consumption at present.Wherein, Phthalic ester plasticizer is because of cheap, and the production and consumption amount is maximum, accounts for 90% of softening agent total quantity consumed; But not adjacent benzene class softening agent is less than 10% of ultimate production; Of less types, product specification with use the requirement can't adapt to market development, and asepsis environment-protecting and be that the renewable softening agent product of raw material is more rare with biomass; Use the environment-friendly type softening agent to account for 80% present situation with the European and American areas and compare, state internal plasticizer market still can't satisfy PVC plastic working industry to softening agent nontoxic with the high requirement of plasticization capacity.
Epoxy aliphatic acid methyl ester is one type and has nontoxic, the environmental protection of development prospect, reproducible softening agent; Except have goods good-toughness that Epoxy oil bio-based softening agent has, but consistency is good, volatility is low, transport property is little, nontoxic contact food, light and heat is had the advantages such as satisfactory stability effect; Also have more excellent oilness, consistency and dispersion performance; Can improve the adding proportion that adds man-hour at the PVC goods greatly; Can substitute DOP fully and produce PVC product nontoxic, environmental protection, be used for food product pack, medical treatment product, toy, water supply line etc.
Rubber tree is the woody oleiferous plants plant of Yunnan Province of China province and Hainan Province's establishing in large scale.The principal constituent of rubber seed oil is a fatty acid glyceryl ester, and unsaturated fatty acids accounted for more than 80% during lipid acid was formed, and iodine number is an epoxidized plasticizer ideal renewable raw materials all more than 110.According to incompletely statistics, there was about 6,000,000 hectares of rubber tree in China in 2010, can produce about 1,200,000 tons of rubber seed oil every year, and output is considerable.Pay attention to inadequately owing in the early time rubber seed oil is used, quite a few rubber seed goes out of use, and effective rate of utilization is less than 1/10 of total amount.
Summary of the invention
Single in order to change state's internal plasticizer market kind, reduce equipment corrosion and environmental pollution, the invention discloses a kind of rubber seed oil basic ring oxygen fatty acid methyl ester, have that product performance height, cost are low, production process is polluted characteristics such as few.
Technical scheme of the present invention is: a kind of rubber seed oil basic ring oxygen fatty acid methyl ester; Carry out preparatory esterification and transesterification reaction obtains rubber seed oil fatty acid methyl ester bullion with rubber seed oil after coming unstuck and methyl alcohol; Separate the rubber seed oil fatty acid methyl ester that obtains being rich in polyenoid UFAMEs through low temperature crystallization; Pass through epoxidation reaction again; The product standing demix, upper oil phase obtains rubber seed oil basic ring oxygen fatty acid methyl ester through neutralization, dehydration, absorption, oxirane value>=5.0%, flash-point>=200 ℃, resistivity>=1.0*10 9Ω m, color and luster≤180, acid number are 0.45～0.5mgg -1, weight loss on heating≤0.5.
Prepare the method for described rubber seed oil basic ring oxygen fatty acid methyl ester, concrete steps are following:
Figure 2011104565712100002DEST_PATH_IMAGE002
adopts two-step approach to prepare the rubber seed oil fatty acid methyl ester through preparatory esterification and transesterification reaction: get rubber seed oil and methyl alcohol and catalyst mix after coming unstuck by stoichiometric ratio; Under 60-80 ℃ of constant temperature, carry out esterification; Treat that acid number reduces to the stopped reaction of back below the 2mg KOH/g, 90 ℃ of underpressure distillation; The oil phase product of gained adds methyl alcohol and catalyzer by stoichiometric ratio again, under 55-65 ℃ of constant temperature, carries out transesterification reaction 2h, underpressure distillation to 90 ℃ again, and standing demix reclaims lower floor's glycerine, and it is subsequent use to get upper strata rubber seed oil fatty acid methyl ester bullion;
adopts contained UFAMEs component in the crystallizing process under low temperature separate rubber seed oil fatty acid methyl esters bullion: rubber seed oil fatty acid methyl ester bullion is placed sealed vessel; Freezing after elder generation's precooling; And under freezing conditions filtration obtains clear filtrate, and the UFAMEs mass percent in the filtrating is greater than 90%;
preparation rubber seed oil basic ring oxygen fatty acid methyl ester: with filtrating, 10～30 mass parts organic acids of 100 mass parts; Mix with 1～10 mass parts epoxidation catalyst; After stirring is warming up to 50-70 ℃; In 2h, drip off 30～60 parts of ydrogen peroxide 50; Continue insulation reaction 2～5h; Through standing demix, reclaim lower floor's formic acid, get upper oil phase and obtain rubber seed oil basic ring oxygen fatty acid methyl ester through neutralization, processed;
Figure 2011104565712100002DEST_PATH_IMAGE008
decolouring: get 100 mass parts rubber seed oil basic ring oxygen fatty acid methyl esters; Add 1～3 mass parts sorbent material; After heating, stir process; Filtered while hot obtains rubber seed oil basic ring oxygen fatty acid methyl ester finished product.
The described precooling temperature of step
Figure 442297DEST_PATH_IMAGE004
is 0-5 ℃; Time is 0.5-1h; Freezing temp is-2-0 ℃, and the time is 0.5-1h.
Used catalyzer is arbitrary among tosic acid, Zeo-karb, the KOH in the step
Figure 647013DEST_PATH_IMAGE002
.
The used epoxidation catalyst of step
Figure 721280DEST_PATH_IMAGE006
is Zeo-karb, tosic acid or both mixtures.
Organic acid in the step
Figure 265525DEST_PATH_IMAGE006
is formic acid or acetate; The ydrogen peroxide 50 mass concentration is 27.5-55%.
Used sorbent material is any one or any several kinds mixture in gac, atlapulgite, the attapulgite in the step
Figure 193642DEST_PATH_IMAGE008
; Treatment temp is 80-90 ℃, and the time is 0.5-1h.
Described rubber seed oil basic ring oxygen fatty acid methyl ester is as the application of softening agent.
 
Beneficial effect:
The oxirane value of the rubber seed oil basic ring oxygen fatty acid methyl ester of preparation is high, flash-point is high, resistivity is big, lighter color, is applicable to the industry that softening agent individual event or over-all properties are had relatively high expectations.
2. simple, the production process environmental friendliness of preparation technology.Adopt SFAMEs and the UFAMEs of low temperature crystallization technical point in the fatty acid methyl ester bullion, enrichment polyenoid UFAMEs component is used to prepare the epoxyfatty acid softening agent of high epoxy ester, and is easy to operate; Avoid the use of traditional sulfuric acid or organic acid catalyst in the epoxidation process, reduced catalyzer to greatest extent, reduced wastewater discharge corrosion on Equipment.
3. utilize rubber seed oil to be raw material, wide material sources, cheap, reduce production costs; Can further drive simultaneously natural woody grease plantation industry, the high-valued development and use that realize biomass resource, the Economic development of promotion mountainous rural area, have important social benefit.
Description of drawings
The infrared analysis spectrogram of Fig. 1 epoxidezed rubber seed oil methyl esters product;
Ester carbonyl group is at 1741 cm among the figure -1The place absorbs, and the C-O stretching vibration of ester is at 1172 cm -1Absorb, the vibration of oxirane ring is at 843 and 724 cm -1The place absorbs.
Fig. 2 process flow sheet of the present invention.
Embodiment
Below be to further detailed description of the present invention through embodiment, be not limitation of the present invention.
The concrete technical scheme preparation method who adopts of the present invention may further comprise the steps:
adopts two-step approach to prepare the rubber seed oil fatty acid methyl ester.The rubber seed oil 100g that learning from else's experience comes unstuck after handling with the catalyst mix of 20-40g methyl alcohol and 0.8-1.2g, carries out esterification under 60-80 ℃ of constant temperature; Treat that acid number reduces to the stopped reaction of back below the 2mg KOH/g; When adopting solid catalyst, then divide and remove catalyzer, 90 ℃ of underpressure distillation; Remove the moisture that unnecessary methyl alcohol and esterification generate, if adopt liquid catalyst then to remove with methyl alcohol etc.; The oil phase product of gained adds the catalyzer of 10-30g methyl alcohol and 0.8-1.2g again; Under 55-65 ℃ of constant temperature, carry out transesterification reaction 2h, suitably underpressure distillation to 90 ℃ again after the cooling, standing demix; Reclaim lower floor's glycerine, it is subsequent use to get upper strata fatty acid methyl ester bullion A.
? using low temperature crystallization separation step
Figure 706903DEST_PATH_IMAGE002
SFAMEs contained in the A component and UFAMEs.Get a certain amount of A and place sealed vessel; Freezing after elder generation's precooling; And under freezing conditions filter and obtain clear filtrate B, contain mass percentage content in the liquor B greater than 90% unsaturated fatty acids methyl esters (UFAMEs), after the crystallization dissolving in the filter cake saturated fatty acid methyl ester (SFAMEs).
Figure 12114DEST_PATH_IMAGE006
is with mixture B, 10-30 part organic acid of 100 parts of steps gained; Mix with 1-10 part epoxidation catalyst; After stirring is warming up to 50-70 ℃; In 2h, drip off 30-60 part ydrogen peroxide 50; Continue insulation reaction 2-5h; If employing solid epoxidation catalyst then separates and reclaims epoxidation catalyst, handle together if adopt liquid catalyst then to be dissolved in the formic acid, through standing demix; Reclaim lower floor's formic acid, get upper oil phase and obtain rubber seed oil basic ring oxygen fatty acid methyl ester C through neutralization, processed;
Figure 341912DEST_PATH_IMAGE008
gets 100 parts of C; Add 1-3 part sorbent material; After heating, stir process; Filtered while hot gets rubber seed oil basic ring oxygen fatty acid methyl ester finished product.
Precooling temperature in the described step
Figure 860749DEST_PATH_IMAGE004
is 0-5 ℃; Time is 0.5-1h; Freezing temp is-2-0 ℃, and the time is 0.5-1h.
Described fatty acid methyl ester bullion is after the low temperature crystallization technical point leaves, and the UFAMEs component concentration is greater than 90%.
Used catalyzer is tosic acid, Zeo-karb and KOH in the described step
Figure 68352DEST_PATH_IMAGE002
; The used epoxidation catalyst of step
Figure 734957DEST_PATH_IMAGE006
is Zeo-karb, tosic acid or both mixtures.
Organic acid in the described step
Figure 689138DEST_PATH_IMAGE006
comprises formic acid and acetate; Hydrogen peroxide concentration is 27.5-55%; During oil phase carried out and the time, at first adopt the NaOH solution of 60-80 ℃ 1% concentration, transfer pH value to be about 6.5, use 60-80 ℃ of distilled water wash to neutral again.
Used sorbent material is gac, atlapulgite, attapulgite in the described step
Figure 62481DEST_PATH_IMAGE008
, and independent or mixing is used; Treatment temp is 80-90 ℃, and the time is 0.5-1h.
Used methyl alcohol, formic acid, sorbent material in the described reaction, and used solid acid, alkaline catalysts, all recyclable; Filter cake components in by-product glycerin in the step
Figure 706565DEST_PATH_IMAGE002
and the step
Figure 594886DEST_PATH_IMAGE004
; Handle through refining and reprocessing, can realize higher value application.
The preparation method of described a kind of rubber seed oil base high-performance epoxy aliphatic acid methyl ester softening agent adopts to have heat resistance (400 ℃) and good inert HT-5 high temperature chromatographic column preferably, the composition of Synchronization Analysis rubber seed oil fatty acid methyl ester.
Described rubber seed oil basic ring oxygen fatty acid methyl ester finished product has oxirane value height (>=5.0%), flash-point high (>=200 ℃), the big (>=1.0*10 of resistivity 9Ω m), Heat stability is good, lighter color, and characteristics such as stable performance.
Chemical reaction mechanism: the fatty acid component in the rubber seed oil generates fatty acid methyl ester through transesterification reaction; The UFAMEs component of gained after the crystallizing process under low temperature separating treatment; Carry out epoxidation reaction with hydrogen peroxide and organic acid cyclization reagent again; Make epoxy aliphatic acid methyl ester, its reaction principle can be represented with following chemical equation:
Embodiment 1
adopts two-step approach to prepare the rubber seed oil fatty acid methyl ester.The rubber seed oil 100g that learning from else's experience comes unstuck after handling; Mix with the catalyzer cation exchange resin catalyst of 20-40g methyl alcohol and 0.8-1.2g; Under 60-80 ℃ of constant temperature, carry out esterification, treat that acid number reduces to the stopped reaction of back below the 2mg KOH/g, divide and remove catalyzer; The moisture that unnecessary methyl alcohol and esterification generate is removed in 90 ℃ of underpressure distillation; The oil phase product of gained adds the catalyzer of 10-30g methyl alcohol and 0.8-1.2g again; Under 55-65 ℃ of constant temperature, carry out transesterification reaction 2h, suitably underpressure distillation to 90 ℃ again after the cooling, standing demix; Reclaim lower floor's glycerine, it is subsequent use to get upper strata fatty acid methyl ester bullion.
Figure 580608DEST_PATH_IMAGE004
gets 100g fatty acid methyl ester bullion in 5 ℃ of precooling 1h; 0 ℃ of freezing 1h also filters; Filtering SFAMEs crystallization 17.12g; Through synchronous gas phase analysis, calculate by area normalization method that the UFAMEs component concentration is 92.43% in the filtrating.
Figure 460839DEST_PATH_IMAGE006
gets 100g filtrating, 30g formic acid; The 2g cation exchange resin catalyst; After mixing is stirred and is warming up to 50 ℃; Be controlled at and drip ydrogen peroxide 50 (30%) 60g in 2 h, continue insulation reaction 3 h; After the reaction end, separate and also reclaim catalyzer, bullion is removed lower floor's water through standing demix and is also reclaimed, and upper oil phase is extremely neutral with sodium hydroxide solution and distilled water wash; 90 ℃ of underpressure distillation dehydrations get rubber seed oil basic ring oxygen fatty acid methyl ester;
Figure 771210DEST_PATH_IMAGE008
gets 100 g rubber seed oil basic ring oxygen fatty acid methyl esters; Add 1 g gac; Handle 1h for 80 ℃; After the filtered while hot, get rubber seed oil basic ring oxygen fatty acid methyl ester finished product.Quality index is: outward appearance: yellow oily liquid, and color and luster (platinum-cobalt) :≤No. 180, oxirane value (%): 6.52%, acid number (mgg -1): 0.50, flash-point (℃): 201, weight loss on heating ((125 ℃ * 3 hours) %) :≤0.5, resistivity (Ω m): 1.56 * 10 9
Embodiment 2
Figure 67194DEST_PATH_IMAGE002
adopts two-step approach to prepare the rubber seed oil fatty acid methyl ester.The rubber seed oil 100g that learning from else's experience comes unstuck after handling; Mix with the catalyzer tosic acid of 20-40g methyl alcohol and 0.8-1.2g; Under 60-80 ℃ of constant temperature, carry out esterification; Treat that acid number reduces to the stopped reaction of back below the 2mg KOH/g, the moisture that unnecessary methyl alcohol, tosic acid and esterification generate is removed in 90 ℃ of underpressure distillation; The oil phase product of gained adds the catalyzer of 10-30g methyl alcohol and 0.8-1.2g again; Under 55-65 ℃ of constant temperature, carry out transesterification reaction 2h, suitably underpressure distillation to 90 ℃ again after the cooling, standing demix; Reclaim lower floor's glycerine, it is subsequent use to get upper strata fatty acid methyl ester bullion.
Figure 415130DEST_PATH_IMAGE004
gets 100g fatty acid methyl ester bullion in 3 ℃ of precooling 0.5h;-1 ℃ of freezing 1h also filters; Filtering SFAMEs crystallization 17.25g; Through synchronous gas phase analysis, calculate by area normalization method that the UFAMEs component concentration is 93.87% in the filtrating.
Figure 466262DEST_PATH_IMAGE006
gets 100g filtrating, 30g formic acid; The agent of 2g Catalyzed by p-Toluenesulfonic Acid; After mixing is stirred and is warming up to 50 ℃; Be controlled at and drip ydrogen peroxide 50 (27.5%) 60g in 2 h, continue insulation reaction 3 h; After the reaction end, separate and also reclaim catalyzer, bullion is removed lower floor's water through standing demix and is also reclaimed, and upper oil phase is extremely neutral with sodium hydroxide solution and distilled water wash; 90 ℃ of underpressure distillation dehydrations get rubber seed oil basic ring oxygen fatty acid methyl ester;
Figure 266859DEST_PATH_IMAGE008
gets 100 g rubber seed oil basic ring oxygen fatty acid methyl esters; Add 1.5 g atlapulgites; Handle 1h for 80 ℃; After the filtered while hot, get rubber seed oil basic ring oxygen fatty acid methyl ester finished product.Quality index is: outward appearance: yellow oily liquid, and color and luster (platinum-cobalt) :≤No. 180, oxirane value (%): 5.85%, acid number (mgg -1): 0.46, flash-point (℃): 196, weight loss on heating ((125 ℃ * 3 hours) %) :≤0.5, resistivity (Ω m): 1.72 * 10 9
Embodiment 3
Figure 199541DEST_PATH_IMAGE002
adopts two-step approach to prepare the rubber seed oil fatty acid methyl ester.The rubber seed oil 100g that learning from else's experience comes unstuck after handling; Catalyst mix with 20-40g methyl alcohol and 0.8-1.2g; Under 60-80 ℃ of constant temperature, carry out esterification, treat that acid number reduces to the stopped reaction of back below the 2mg KOH/g, divide and remove catalyzer; The moisture that unnecessary methyl alcohol and esterification generate is removed in 90 ℃ of underpressure distillation; The oil phase product of gained adds the catalyzer of 10-30g methyl alcohol and 0.8-1.2g again; Under 55-65 ℃ of constant temperature, carry out transesterification reaction 2h, suitably underpressure distillation to 90 ℃ again after the cooling, standing demix; Reclaim lower floor's glycerine, it is subsequent use to get upper strata fatty acid methyl ester bullion.
Figure 198721DEST_PATH_IMAGE004
gets 100g fatty acid methyl ester bullion in 0 ℃ of precooling 0.5h; 0 ℃ of freezing 1h also filters; Filtering SFAMEs crystallization 17.84g; Through synchronous gas phase analysis, calculate by area normalization method that the UFAMEs component concentration is 95.61% in the filtrating.
Figure 358438DEST_PATH_IMAGE006
gets 100g filtrating, 30g acetate; The 2g cation exchange resin catalyst; After mixing is stirred and is warming up to 55 ℃; Be controlled at and drip ydrogen peroxide 50 (30%) 60g in 2 h, continue insulation reaction 3 h; After the reaction end, separate and also reclaim catalyzer, bullion is removed lower floor's water through standing demix and is also reclaimed, and upper oil phase is extremely neutral with sodium hydroxide solution and distilled water wash; 90 ℃ of underpressure distillation dehydrations get rubber seed oil basic ring oxygen fatty acid methyl ester;
Figure 584014DEST_PATH_IMAGE008
gets 100 g rubber seed oil basic ring oxygen fatty acid methyl esters; Add 1.0 g attapulgites; Handle 0.5h for 80 ℃; After the filtered while hot, get rubber seed oil basic ring oxygen fatty acid methyl ester finished product.Quality index is: outward appearance: yellow oily liquid, and color and luster (platinum-cobalt) :≤No. 180, oxirane value (%): 5.36%, acid number (mgg -1): 0.49, flash-point (℃): 196, weight loss on heating ((125 ℃ * 3 hours) %) :≤0.5, resistivity (Ω m): 1.67 * 10 9
Embodiment 4
Figure 546767DEST_PATH_IMAGE002
adopts two-step approach to prepare the rubber seed oil fatty acid methyl ester.The rubber seed oil 100g that learning from else's experience comes unstuck after handling; Catalyst mix with 20-40g methyl alcohol and 0.8-1.2g; Under 60-80 ℃ of constant temperature, carry out esterification, treat that acid number reduces to the stopped reaction of back below the 2mg KOH/g, divide and remove catalyzer; The moisture that unnecessary methyl alcohol and esterification generate is removed in 90 ℃ of underpressure distillation; The oil phase product of gained adds the catalyzer of 10-30g methyl alcohol and 0.8-1.2g again; Under 55-65 ℃ of constant temperature, carry out transesterification reaction 2h, suitably underpressure distillation to 90 ℃ again after the cooling, standing demix; Reclaim lower floor's glycerine, it is subsequent use to get upper strata fatty acid methyl ester bullion.
gets 100g fatty acid methyl ester bullion in 5 ℃ of precooling 1h;-2 ℃ of freezing 0.5h also filter; Filtering SFAMEs crystallization 17.33g; Through synchronous gas phase analysis, calculate by area normalization method that the UFAMEs component concentration is 93.11% in the filtrating.
Figure 668754DEST_PATH_IMAGE006
gets 100g filtrating, 20g formic acid; The agent of 2g Catalyzed by p-Toluenesulfonic Acid; After mixing is stirred and is warming up to 50 ℃; Be controlled at and drip ydrogen peroxide 50 (33%) 55g in 2 h, continue insulation reaction 3 h; After the reaction end, separate and also reclaim catalyzer, bullion is removed lower floor's water through standing demix and is also reclaimed, and upper oil phase is extremely neutral with sodium hydroxide solution and distilled water wash; 90 ℃ of underpressure distillation dehydrations get rubber seed oil basic ring oxygen fatty acid methyl ester;
Figure 443944DEST_PATH_IMAGE008
gets 100 g rubber seed oil basic ring oxygen fatty acid methyl esters; Add 1.0 g gacs and 1.0 g attapulgites; Handle 1h for 90 ℃; After the filtered while hot, get rubber seed oil basic ring oxygen fatty acid methyl ester finished product.Quality index is: outward appearance: yellow oily liquid, and color and luster (platinum-cobalt) :≤No. 180, oxirane value (%): 5.28%, acid number (mgg -1): 0.45, flash-point (℃): 198, weight loss on heating ((125 ℃ * 3 hours) %) :≤0.5, resistivity (Ω m): 1.60 * 10 9
Embodiment 5
adopts two-step approach to prepare the rubber seed oil fatty acid methyl ester.The rubber seed oil 100g that learning from else's experience comes unstuck after handling; Catalyst mix with 20-40g methyl alcohol and 0.8-1.2g; Under 60-80 ℃ of constant temperature, carry out esterification, treat that acid number reduces to the stopped reaction of back below the 2mg KOH/g, divide and remove catalyzer; The moisture that unnecessary methyl alcohol and esterification generate is removed in 90 ℃ of underpressure distillation; The oil phase product of gained adds the catalyzer of 10-30g methyl alcohol and 0.8-1.2g again; Under 55-65 ℃ of constant temperature, carry out transesterification reaction 2h, suitably underpressure distillation to 90 ℃ again after the cooling, standing demix; Reclaim lower floor's glycerine, it is subsequent use to get upper strata fatty acid methyl ester bullion.
gets 100g fatty acid methyl ester bullion in 5 ℃ of precooling 1h;-2 ℃ of freezing 1h also filter; Filtering SFAMEs crystallization 17.62g; Through synchronous gas phase analysis, calculate by area normalization method that the UFAMEs component concentration is 94.02% in the filtrating.
Figure 357782DEST_PATH_IMAGE006
gets 100g filtrating, 30g formic acid; Agent of 1g Catalyzed by p-Toluenesulfonic Acid and 1g cation exchange resin catalyst; After mixing is stirred and is warming up to 50 ℃; Be controlled at and drip ydrogen peroxide 50 (55%) 60g in 2 h, continue insulation reaction 3 h; After the reaction end, separate and also reclaim catalyzer, bullion is removed lower floor's water through standing demix and is also reclaimed, and upper oil phase is extremely neutral with sodium hydroxide solution and distilled water wash; 90 ℃ of underpressure distillation dehydrations get rubber seed oil basic ring oxygen fatty acid methyl ester;
Figure 682585DEST_PATH_IMAGE008
gets 100 g rubber seed oil basic ring oxygen fatty acid methyl esters; Add 1.0 g atlapulgites and 1.0 g attapulgites; Handle 1h for 80 ℃; After the filtered while hot, get rubber seed oil basic ring oxygen fatty acid methyl ester finished product.Quality index is: outward appearance: yellow oily liquid, and color and luster (platinum-cobalt) :≤No. 180, oxirane value (%): 6.25%, acid number (mgg -1): 0.49, flash-point (℃): 202, weight loss on heating ((125 ℃ * 3 hours) %) :≤0.5, resistivity (Ω m): 1.27 * 10 9
Embodiment 6
Figure 927752DEST_PATH_IMAGE002
adopts two-step approach to prepare the rubber seed oil fatty acid methyl ester.The rubber seed oil 100g that learning from else's experience comes unstuck after handling; Catalyst mix with 20-40g methyl alcohol and 0.8-1.2g; Under 60-80 ℃ of constant temperature, carry out esterification, treat that acid number reduces to the stopped reaction of back below the 2mg KOH/g, divide and remove catalyzer; The moisture that unnecessary methyl alcohol and esterification generate is removed in 90 ℃ of underpressure distillation; The oil phase product of gained adds the catalyzer of 10-30g methyl alcohol and 0.8-1.2g again; Under 55-65 ℃ of constant temperature, carry out transesterification reaction 2h, suitably underpressure distillation to 90 ℃ again after the cooling, standing demix; Reclaim lower floor's glycerine, it is subsequent use to get upper strata fatty acid methyl ester bullion.
Figure 690784DEST_PATH_IMAGE004
gets 100g fatty acid methyl ester bullion in 0 ℃ of precooling 1h;-2 ℃ of freezing 1h also filter; Filtering SFAMEs crystallization 17.92g; Through synchronous gas phase analysis, calculate by area normalization method that the UFAMEs component concentration is 97.21% in the filtrating.
C) get 100g filtrating, 30g formic acid, the agent of 1g Catalyzed by p-Toluenesulfonic Acid, mixing are controlled at and drip ydrogen peroxide 50 (30%) 60g in 2 h after stirring and being warming up to 50 ℃, continue insulation reaction 3 h; After the reaction end, separate and also reclaim catalyzer, bullion is removed lower floor's water through standing demix and is also reclaimed, and upper oil phase is extremely neutral with sodium hydroxide solution and distilled water wash; 90 ℃ of underpressure distillation dehydrations get rubber seed oil basic ring oxygen fatty acid methyl ester;
D) get 100 g rubber seed oil basic ring oxygen fatty acid methyl esters, add 2.0 g atlapulgites, handle 1h for 80 ℃, after the filtered while hot, get rubber seed oil basic ring oxygen fatty acid methyl ester finished product.Quality index is: outward appearance: yellow oily liquid, and color and luster (platinum-cobalt) :≤No. 180, oxirane value (%): 6.09%, acid number (mgg -1): 0.47, flash-point (℃): 201, weight loss on heating ((125 ℃ * 3 hours) %) :≤0.5, resistivity (Ω m): 1.71 * 10 9
Embodiment 7
Figure 425522DEST_PATH_IMAGE002
adopts two-step approach to prepare the rubber seed oil fatty acid methyl ester.The rubber seed oil 100g that learning from else's experience comes unstuck after handling; Catalyst mix with 20-40g methyl alcohol and 0.8-1.2g; Under 60-80 ℃ of constant temperature, carry out esterification, treat that acid number reduces to the stopped reaction of back below the 2mg KOH/g, divide and remove catalyzer; The moisture that unnecessary methyl alcohol and esterification generate is removed in 90 ℃ of underpressure distillation; The oil phase product of gained adds the catalyzer of 10-30g methyl alcohol and 0.8-1.2g again; Under 55-65 ℃ of constant temperature, carry out transesterification reaction 2h, suitably underpressure distillation to 90 ℃ again after the cooling, standing demix; Reclaim lower floor's glycerine, it is subsequent use to get upper strata fatty acid methyl ester bullion.
Figure 909724DEST_PATH_IMAGE004
gets 100g fatty acid methyl ester bullion in 0 ℃ of precooling 0.5h;-2 ℃ of freezing 0.5h also filter; Filtering SFAMEs crystallization 17.20g; Through synchronous gas phase analysis, calculate by area normalization method that the UFAMEs component concentration is 93.21% in the filtrating.
C) get 100g filtrating, 30g formic acid, the 1g cation exchange resin catalyst, mixing is controlled at and drips ydrogen peroxide 50 (30%) 60g in 2 h after stirring and being warming up to 50 ℃, continues insulation reaction 3 h; After the reaction end, separate and also reclaim catalyzer, bullion is removed lower floor's water through standing demix and is also reclaimed, and upper oil phase is extremely neutral with sodium hydroxide solution and distilled water wash; 90 ℃ of underpressure distillation dehydrations get rubber seed oil basic ring oxygen fatty acid methyl ester;
D) get 100 g rubber seed oil basic ring oxygen fatty acid methyl esters, add 2.0 g atlapulgites, handle 1h for 80 ℃, after the filtered while hot, get rubber seed oil basic ring oxygen fatty acid methyl ester finished product.Quality index is: outward appearance: yellow oily liquid, and color and luster (platinum-cobalt) :≤No. 180, oxirane value (%): 6.11%, acid number (mgg -1): 0.45, flash-point (℃): 201, weight loss on heating ((125 ℃ * 3 hours) %) :≤0.5, resistivity (Ω m): 1.65 * 10 9

Claims (8)

1. rubber seed oil basic ring oxygen fatty acid methyl ester; It is characterized in that, carry out preparatory esterification and transesterification reaction obtains rubber seed oil fatty acid methyl ester bullion, separate the rubber seed oil fatty acid methyl ester that obtains being rich in polyenoid UFAMEs through low temperature crystallization with rubber seed oil after coming unstuck and methyl alcohol; Pass through epoxidation reaction again; The product standing demix, upper oil phase obtains rubber seed oil basic ring oxygen fatty acid methyl ester through neutralization, dehydration, absorption, oxirane value>=5.0%, flash-point>=200 ℃, resistivity>=1.0*10 9Ω m, color and luster≤180, acid number are 0.45～0.5mgg -1, weight loss on heating≤0.5.
2. prepare the method for the described rubber seed oil basic ring of claim 1 oxygen fatty acid methyl ester, it is characterized in that concrete steps are following:
Figure 2011104565712100001DEST_PATH_IMAGE002
adopts two-step approach to prepare the rubber seed oil fatty acid methyl ester through preparatory esterification and transesterification reaction: get rubber seed oil and methyl alcohol and catalyst mix after coming unstuck by stoichiometric ratio; Under 60-80 ℃ of constant temperature, carry out esterification; Treat that acid number reduces to the stopped reaction of back below the 2mg KOH/g; 90 ℃ of underpressure distillation; The oil phase product of gained adds methyl alcohol and catalyzer by stoichiometric ratio again; Under 55-65 ℃ of constant temperature, carry out transesterification reaction 2h, underpressure distillation to 90 ℃ again, standing demix; Reclaim lower floor's glycerine, it is subsequent use to get upper strata rubber seed oil fatty acid methyl ester bullion;
Figure 2011104565712100001DEST_PATH_IMAGE004
adopts contained UFAMEs component in the crystallizing process under low temperature separate rubber seed oil fatty acid methyl esters bullion: rubber seed oil fatty acid methyl ester bullion is placed sealed vessel; Freezing after elder generation's precooling; And under freezing conditions filtration obtains clear filtrate, and the UFAMEs mass percent in the filtrating is greater than 90%;
Figure 2011104565712100001DEST_PATH_IMAGE006
preparation rubber seed oil basic ring oxygen fatty acid methyl ester: with filtrating, 10～30 mass parts organic acids of 100 mass parts; Mix with 1～10 mass parts epoxidation catalyst; After stirring is warming up to 50-70 ℃; In 2h, drip off 30～60 parts of ydrogen peroxide 50; Continue insulation reaction 2～5h; Through standing demix, reclaim lower floor's formic acid, get upper oil phase and obtain rubber seed oil basic ring oxygen fatty acid methyl ester through neutralization, processed;
Figure 2011104565712100001DEST_PATH_IMAGE008
decolouring: get 100 mass parts rubber seed oil basic ring oxygen fatty acid methyl esters; Add 1～3 mass parts sorbent material; After heating, stir process; Filtered while hot obtains rubber seed oil basic ring oxygen fatty acid methyl ester finished product.
3. the method for preparing rubber seed oil basic ring oxygen fatty acid methyl ester as claimed in claim 2; It is characterized in that; The described precooling temperature of step is 0-5 ℃; Time is 0.5-1h, freezing temp is-and 2-0 ℃, the time is 0.5-1h.
4. the method for preparing rubber seed oil basic ring oxygen fatty acid methyl ester as claimed in claim 2; It is characterized in that used catalyzer is arbitrary among tosic acid, Zeo-karb, the KOH in the step .
5. the method for preparing rubber seed oil basic ring oxygen fatty acid methyl ester as claimed in claim 2; It is characterized in that the used epoxidation catalyst of step
Figure 833898DEST_PATH_IMAGE006
is Zeo-karb, tosic acid or both mixtures.
6. the method for preparing rubber seed oil basic ring oxygen fatty acid methyl ester as claimed in claim 2; It is characterized in that the organic acid in the step
Figure 104473DEST_PATH_IMAGE006
is formic acid or acetate; The ydrogen peroxide 50 mass concentration is 27.5-55%.
7. the method for preparing rubber seed oil basic ring oxygen fatty acid methyl ester as claimed in claim 2; It is characterized in that used sorbent material is any one or any several kinds mixture in gac, atlapulgite, the attapulgite in the step
Figure 856529DEST_PATH_IMAGE008
; Treatment temp is 80-90 ℃, and the time is 0.5-1h.
8. the described rubber seed oil basic ring of claim 1 oxygen fatty acid methyl ester is as the application of softening agent.
CN2011104565712A 2011-12-31 2011-12-31 Rubber seed oil-based epoxy fatty acid methyl ester and preparation method and application thereof Pending CN102517157A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102942995A (en) * 2012-12-03 2013-02-27 浙江嘉澳环保科技股份有限公司 Method for separating and modifying plant oil
CN103709125A (en) * 2013-12-31 2014-04-09 成都恒润高新科技有限公司 Method for preparing biological plasticizers-epoxidized fatty acid methyl esters from kitchen waste grease
CN104781328A (en) * 2012-11-12 2015-07-15 陶氏环球技术有限公司 Methods for making epoxidized fatty acid alkyl esters
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
EP2990470A1 (en) * 2014-08-26 2016-03-02 Evonik Degussa GmbH Mixed epoxidised fatty acid esters
CN107383417A (en) * 2017-07-21 2017-11-24 中国林业科学研究院林产化学工业研究所 A kind of binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer and preparation method thereof
CN107840800A (en) * 2016-09-19 2018-03-27 北京林氏精化新材料有限公司 A kind of cryogenic purincation separating technology of the fatty acid ester of low-carbon alcohol class plasticizer based on palm oil

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1986739A (en) * 2006-12-20 2007-06-27 西北农林科技大学 Process of preparing biodiesel oil with pricklyash seed oil in high acid value
CN101885710A (en) * 2010-07-06 2010-11-17 中国林业科学研究院林产化学工业研究所 Method for preparing epoxy fatty acid methyl ester by using magnetic catalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1986739A (en) * 2006-12-20 2007-06-27 西北农林科技大学 Process of preparing biodiesel oil with pricklyash seed oil in high acid value
CN101885710A (en) * 2010-07-06 2010-11-17 中国林业科学研究院林产化学工业研究所 Method for preparing epoxy fatty acid methyl ester by using magnetic catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
黄惠琴 等: "多价不饱和脂肪酸分离与纯化技术进展", 《中国油脂》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104781328A (en) * 2012-11-12 2015-07-15 陶氏环球技术有限公司 Methods for making epoxidized fatty acid alkyl esters
CN104781328B (en) * 2012-11-12 2017-12-05 陶氏环球技术有限公司 The method for manufacturing epoxidized fat acid alkyl ester
CN102942995A (en) * 2012-12-03 2013-02-27 浙江嘉澳环保科技股份有限公司 Method for separating and modifying plant oil
CN103709125A (en) * 2013-12-31 2014-04-09 成都恒润高新科技有限公司 Method for preparing biological plasticizers-epoxidized fatty acid methyl esters from kitchen waste grease
CN103709125B (en) * 2013-12-31 2016-05-25 成都恒润高新科技股份有限公司 The method of the biological plasticizer epoxy aliphatic acid methyl ester of kitchen castoff oil and fat preparation
EP2990470A1 (en) * 2014-08-26 2016-03-02 Evonik Degussa GmbH Mixed epoxidised fatty acid esters
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
CN107840800A (en) * 2016-09-19 2018-03-27 北京林氏精化新材料有限公司 A kind of cryogenic purincation separating technology of the fatty acid ester of low-carbon alcohol class plasticizer based on palm oil
CN107383417A (en) * 2017-07-21 2017-11-24 中国林业科学研究院林产化学工业研究所 A kind of binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer and preparation method thereof
CN107383417B (en) * 2017-07-21 2019-05-21 中国林业科学研究院林产化学工业研究所 A kind of binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer and preparation method thereof

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