CN105085442A - Diacid bismonoacetyl epoxy vegetable oil ester and synthetic method thereof - Google Patents

Diacid bismonoacetyl epoxy vegetable oil ester and synthetic method thereof Download PDF

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CN105085442A
CN105085442A CN201510439440.1A CN201510439440A CN105085442A CN 105085442 A CN105085442 A CN 105085442A CN 201510439440 A CN201510439440 A CN 201510439440A CN 105085442 A CN105085442 A CN 105085442A
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acid
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vegetable oil
oil
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CN105085442B (en
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邓健能
李道斌
曹志亮
毋婷婷
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Nantong Haierma Technology Co ltd
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HAIRMA CHEMICALS (GZ) Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
    • C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses diacid bismonoacetyl epoxy vegetable oil ester with a structure as shown in a formula (I) or (II). The diacid bismonoacetyl epoxy vegetable oil ester can be used as a plasticizer and applied in plastic. The diacid bismonoacetyl epoxy vegetable oil ester is synthesized by comprising the following steps: 1) subjecting vegetable oil and alcohol to transesterification reaction so as to synthesize vegetable oil monoester; 2) subjecting the vegetable oil monoester and dibasic acid to esterification reaction so as to synthesize diacid bis vegetable oil ester; 3) subjecting the diacid bis vegetable oil ester and an acetylation reagent to reaction so as to synthesize diacid bismonoacetyl vegetable oil ester; and 4) subjecting the diacid bismonoacetyl vegetable oil ester and hydrogen peroxide to epoxidation reaction so as to synthesize the diacid bismonoacetyl epoxy vegetable oil ester. The diacid bismonoacetyl epoxy vegetable oil ester provided by the invention has simple preparation process and low cost, can be used as the plasticizer and applied in wire and cable materials, has good product ageing resistance, good low-temperature impact embrittlement property and better release and migration resistant capabilities, is a non-toxic plastic plasticizer with more excellent properties, and has broad market prospects.

Description

Two acetyl epoxidized vegetable oil ester and the synthetic method thereof of diprotic acid
Technical field
The present invention relates to a kind of softening agent, be specifically related to the two acetyl epoxidized vegetable oil ester of a kind of diprotic acid, in addition, the invention still further relates to the synthetic method of the two acetyl epoxidized vegetable oil ester of this diprotic acid a kind of.
Background technology
In recent years, along with the enhancing of people's environmental protection consciousness, the plastics such as medicine, food product pack, daily necessities, toy propose higher hygienic requirements to softening agent.Softening agent is mainly based on adjacent benzene-type products for a long time, but it is found that such softening agent has some toxic side effect to human body, for this reason, food safety mechanism of European Union (EFSA) defines dioctyl phthalate (DOP) (DOP), Octyl adipate (DOA) isocyatic limitation, so the softening agent of asepsis environment-protecting becomes the emphasis of global softening agent research instantly.
Because epoxidized vegetable oil has good thermotolerance, photostabilization, mutually oozing property, low temperature flexibility, and the characteristic such as volatility is low, be widely used in plastics industry in recent years, be the softening agent that uniquely can be used for instrumentation package material that united States food and drug administration (FDA) ratifies, be specially adapted to the field that food/pharmaceutical Plastic Packaging Materials, toy for children and home decoration material etc. have strict environmental requirement.But the molecular weight of epoxidized vegetable oil and viscosity are comparatively large, and poor fluidity, limits it and apply further.Glycerine ester type softening agent has lower molecular weight and higher boiling point and flash-point, and viscosity is low, good fluidity, but its low temperature plasticising performance is not as good as epoxidized vegetable oil.
In the authorized patent of invention CN102285946B of applicant; applicant is in conjunction with the characteristic sum character of both epoxy soybean oil and glycerine triacetate structure; synthesize a kind of novel environment-friendlyplasticizer plasticizer diacetyl epoxidized vegetable oil acid glyceride; its plastification and effect similar to epoxy soybean oil; and molecular weight is low, good fluidity.But in the subsequent applications research of diacetyl epoxidized vegetable oil acid glyceride; applicant finds; when being applied in the higher wires and cables industry of requirement, the brittle performance of its low-temperature impact and aging after break-draw strain maximum velocity of variation and do not reach industry requirement.Therefore, exploitation one had both had plasticization effect similar to epoxidized vegetable oil, but molecular weight is low, the material of good fluidity is very necessary as softening agent.
Therefore; applicant improves diacetyl epoxidized vegetable oil acid glyceride; novel process is utilized to synthesize the two acetyl epoxidized vegetable oil ester of a kind of diprotic acid; be applied in wire cable material; its goods are better than the ageing resistance of diacetyl epoxidized vegetable oil acid glyceride goods; the brittle performance of low-temperature impact is good, and more anti-precipitation and migration, be the non-toxic plastic softening agent that a kind of character is more excellent.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art; there is provided a kind of ageing resistance good; the brittle performance of low-temperature impact is good, and anti-precipitation and the good two acetyl epoxidized vegetable oil ester of softening agent diprotic acid of transport property, another object of the present invention is to the synthetic method providing this softening agent a kind of.
For achieving the above object, the present invention is by the following technical solutions:
The present invention with vegetables oil and alcohol for starting raw material, by 1) transesterification reaction: vegetables oil and alcohol carry out transesterification reaction and synthesize vegetables oil monoesters; 2) esterification: by step 1) in the vegetables oil monoesters and the diprotic acid that generate carry out esterification and synthesize diprotic acid pair vegetable oil esters; 3) acetylization reaction: by step 2) in the two vegetable oil esters of diprotic acid that generates and an acetylation reagent Reactive Synthesis diprotic acid pair acetyl vegetable oil esters; And step 4) epoxidation reaction: by step 3) in the two acetyl vegetable oil esters of diprotic acid that generates carry out epoxidation reaction with hydrogen peroxide and synthesize the steps such as diprotic acid pair acetyl epoxidized vegetable oil esters; it is good that synthesis obtains ageing resistance; the brittle performance of low-temperature impact is good; anti-precipitation and the two acetyl epoxidized vegetable oil ester of the good softening agent diprotic acid of transport property, it has as shown in the formula the structure shown in (I) or formula (II):
Wherein: described R 1, R 2, R 3independently of one another, be selected from the lipid acid below 20 carbon atoms in vegetables oil identical or differently; R is aliphatic radical or aryl.
Preferably: described R 1, R 2, R 3independently of one another, identical or differently be selected from the palmitic acid in soybean oil, stearic acid, oleic acid, cis-9,12-octadecenic acid, cis-9,12,15-octadecenic acid; Or the oleic acid, linolic acid or the palmitinic acid that independently of one another, identical or differently are selected from Rice pollard oil; Or the eicosanoic acid, oleic acid, linolic acid, erucic acid or the linolenic acid that independently of one another, identical or differently are selected from rapeseed oil.
Transesterification reaction preferably: step 1), temperature of reaction is 150-260 DEG C, and the reaction times is 1.5-20 hour.
In transesterification reaction preferably: step 1), described vegetables oil is one or more in soybean oil, Rice pollard oil, oleum lini, rapeseed oil, plam oil, Viscotrol C and sunflower seed oil.
In transesterification reaction preferably: step 1), described alcohol is at least one in BDO, glycerine, tetramethylolmethane, TriMethylolPropane(TMP), neopentyl glycol, and its consumption is the 16-33% of vegetables oil consumption.
In transesterification reaction preferably: step 1), catalyzer is one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium methylate and sodium ethylate, and its consumption is the 0.01-0.04% of vegetables oil consumption.
Esterification preferably: step 2), temperature of reaction is 180-250 DEG C, and the reaction times is 3-12 hour.
In esterification preferably: step 2), described diprotic acid is at least one in hexanodioic acid, Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, oxalic acid, terephthalic acid, and its consumption is the 1-10% of vegetables oil monoesters consumption.
In esterification preferably: step 2), described catalyzer is at least one in tetrabutyl titanate, phosphoric acid, sodium phosphate, and its consumption is the 0.1-0.4% of vegetables oil monoesters consumption.
Add siccative in esterification preferably: step 2), described siccative is at least one in calcium chloride, calcium sulfate, silica gel, activated alumina, and its consumption is the 20-30% of vegetables oil monoesters consumption.
Acetylization reaction preferably: step 3), temperature of reaction is 60-150 DEG C, and the reaction times is 5-10 hour.
In acetylization reaction preferably: step 3), described acetylation reagent is at least one in Acetyl Chloride 98Min., Glacial acetic acid, diacetyl oxide, and its consumption is the 40-50% of diprotic acid pair vegetable oil esters consumption.
In acetylization reaction preferably: step 3), described catalyzer is at least one in the vitriol oil, tosic acid, acidic ion exchange resin, and its consumption is the 0.3-0.6% of diprotic acid pair vegetable oil esters consumption.
Add water entrainer in acetylization reaction preferably: step 3), described water entrainer is at least one in benzene, hexanaphthene, hexane, and its consumption is the 35-40% of diprotic acid pair vegetable oil esters consumption.
In epoxidation reaction preferably: step 4), temperature of reaction is 50-80 DEG C, and the reaction times is 4-10 hour.
In epoxidation reaction preferably: step 4), described catalyzer is sulfuric acid or phosphoric acid.
Add formic acid and/or acetic acid in epoxidation reaction preferably: step 4), and the mol ratio of diprotic acid two an acetyl vegetable oil esters, hydrogen peroxide, formic acid and/or acetic acid, catalyzer is 1:0.4-0.7:0.04-0.08:0.001-0.003
The two acetyl epoxidized vegetable oil ester of the diprotic acid that the present invention obtains can be used as softening agent and is applied in plastics, especially electric wire, and has that viscosity is little, good stability, mobility are high, the feature effective with plastic plastification.
Beneficial effect of the present invention is; by improving diacetyl epoxidized vegetable oil acid glyceride softening agent in prior art; novel process is utilized to synthesize the two acetyl epoxidized vegetable oil ester of a kind of diprotic acid; softening agent is it can be used as to be applied in wire cable material; its goods are better than the ageing resistance of diacetyl epoxidized vegetable oil acid glyceride goods; the brittle performance of low-temperature impact is good; and better anti-precipitation and migration; be the non-toxic plastic softening agent that a kind of character is more excellent, there are wide market outlook.
Accompanying drawing explanation
Fig. 1 shows the infrared spectrum of the soybean monoesters obtained by embodiments of the invention 1;
Fig. 2 shows the infrared spectrogram of the two soybean grease of diprotic acid obtained by embodiments of the invention 1;
Fig. 3 shows the infrared spectrogram of the two acetyl soybean grease of diprotic acid obtained by embodiments of the invention 1;
Fig. 4 shows the infrared spectrogram of the two acetyl epoxy soybean grease of diprotic acid obtained by embodiments of the invention 1;
Fig. 5 shows the infrared spectrogram of the Rice pollard oil monoesters obtained by embodiments of the invention 3;
Fig. 6 shows the infrared spectrogram of the two rice bran grease of diprotic acid obtained by embodiments of the invention 3;
Fig. 7 shows the infrared spectrogram of the two acetyl rice bran grease of diprotic acid obtained by embodiments of the invention 3;
Fig. 8 shows the infrared spectrogram of the two acetyl nontoxic plasticizer ester of diprotic acid obtained by embodiments of the invention 3.
Embodiment
Below in conjunction with specific embodiment, the specific embodiment of the present invention is described further.If no special instructions, the raw material adopted in various embodiments of the present invention is all bought can obtain by market.
The two acetyl epoxidized vegetable oil ester of diprotic acid of the present invention, its building-up process comprises the following steps:
1) transesterification reaction: vegetables oil and alcohol carry out transesterification reaction and synthesizes vegetables oil monoesters, in this reactions steps, temperature of reaction is 150-260 DEG C, and the reaction times is 1.5-20 hour, and described alcohol is for glycerine, and its reaction principle is as follows:
2) esterification: by step 1) in the vegetables oil monoesters and the diprotic acid that generate carry out esterification and synthesize diprotic acid pair vegetable oil esters, in this reactions steps, temperature of reaction is 180-250 DEG C, and the reaction times is 3-12 hour, and its reaction principle is as follows:
3) acetylization reaction: by step 2) in the two vegetable oil esters of diprotic acid that generates and an acetylation reagent Reactive Synthesis diprotic acid pair acetyl vegetable oil esters; in this reactions steps; temperature of reaction is 60-150 DEG C; reaction times is 5-10 hour; described acetylation reagent is for Glacial acetic acid, and its reaction principle is as follows:
4) epoxidation reaction: by step 3) in the two acetyl vegetable oil esters of diprotic acid that generates carry out epoxidation reaction with hydrogen peroxide and synthesize a diprotic acid pair acetyl epoxidized vegetable oil ester; in this step; temperature of reaction is 50-80 DEG C, reaction times 4-10 hour, and its reaction principle is as follows:
Wherein: R 1, R 2, R 3for the lipid acid below 20 carbon atoms in vegetables oil, preferably, R 1, R 2, R 3independently of one another for being selected from palmitic acid, stearic acid, oleic acid, cis-9,12-octadecenic acid, cis-9,12, the 15-octadecenic acid in soybean oil; Or independently of one another for being selected from oleic acid, linolic acid or the palmitinic acid in Rice pollard oil; Or independently of one another for being selected from eicosanoic acid, oleic acid, linolic acid, erucic acid or the linolenic acid in rapeseed oil.
Step 1) described in transesterification reaction in, described alcohol is 1, one or more in 4-butyleneglycol, glycerine, tetramethylolmethane, TriMethylolPropane(TMP), neopentyl glycol, and its consumption is the 16-33% (w/w) of vegetables oil consumption, vegetables oil used is one or more in soybean oil, Rice pollard oil, oleum lini, rapeseed oil, plam oil, Viscotrol C and sunflower seed oil, and the iodine number of described vegetables oil is 120-140I 2/ 100g, acid number is 0.5-2mgKOH/g; Catalyzer in transesterification reaction is one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium methylate and sodium ethylate, and its consumption is the 0.01-0.04% (w/w) of vegetables oil consumption;
Step 2) described in esterification in, described diprotic acid is one or more in hexanodioic acid, phthalic anhydride, MALEIC ANHYDRIDE (cis-butenedioic anhydride), oxalic acid, terephthalic acid, and its consumption is the 1-10% (w/w) of vegetables oil monoesters consumption, in described esterification, catalyzer can be one or more in tetrabutyl titanate, phosphoric acid, sodium phosphate, and its consumption is the 0.1-0.4% (w/w) of vegetables oil monoesters consumption; Also can add siccative in described esterification, described siccative is one or more in calcium chloride, calcium sulfate, silica gel, activated alumina, and its consumption is the 20-30% (w/w) of vegetables oil monoesters consumption;
Step 3) described in acetylization reaction in, described acetylation reagent is one or more in Acetyl Chloride 98Min., Glacial acetic acid, diacetyl oxide, and the 40-50% (w/w) of its consumption two vegetable oil esters consumption that is diprotic acid; In described acetylization reaction, catalyzer is one or more in the vitriol oil, tosic acid, acidic ion exchange resin, and its consumption is the 0.3-0.6% (w/w) of diprotic acid pair vegetable oil esters consumption; Also water entrainer can be added in described acetylization reaction, to form azeotrope with the water that generates in acetylization reaction and water to be taken in time out of reaction system, reaction is impelled to carry out to the direction being conducive to the two acetyl vegetable oil esters of diprotic acid, described water entrainer is one or more in benzene, hexanaphthene, hexane, and its consumption is the 35-40% (w/w) of diprotic acid pair vegetable oil esters consumption;
Step 4) described in epoxidation reaction in, catalyzer is the vitriol oil and/or strong phosphoric acid, and the concentration of described hydrogen peroxide is 30-50%; Also add in described epoxidation reaction and have formic acid and/or acetic acid, wherein, the concentration of described formic acid is 80-85%, and the mol ratio of diprotic acid two an acetyl vegetable oil esters, hydrogen peroxide, formic acid and/or acetic acid, catalyzer is 1:0.4-0.7:0.04-0.08:0.001-0.003.
The present invention synthesizes the oxirane value (%)>=3.0 of the two acetyl epoxidized vegetable oil ester of the product diprotic acid obtained by above-mentioned steps, iodine number (I 2/ 100g)≤3.0, acid number (mgKOH/g)≤3.0, flash-point (opening, DEG C)>=240 DEG C, moisture (%)≤0.2, resistance (Ω)>=1.4 × 10 11.
Embodiment 1
With soybean oil and glycerine for the two acetyl epoxy soybean grease of Material synthesis diprotic acid, its synthesis step comprises:
1) transesterification reaction: 800g soybean oil, 140g glycerine are joined in three mouthfuls of round-bottomed flasks with whipping appts, thermometer, reflux condensing tube successively, pass into nitrogen and stir when being warming up to 155 DEG C, add calcium oxide catalyst 0.2g, and in 200 DEG C of insulation reaction 2 hours.Batch take-off, when the ethanol of the sample of 1 part and 10 parts dissolves each other, terminates reaction, obtains light yellow oil soya-bean oil monoester.Survey infrared spectra, its result as shown in Figure 1, wherein, IR (KBr): 3414cm -1broad peak is-OH peak; 3009cm -1for the C-H stretching vibration of unsaturated hydrocarbons CH=CH absorbs; 2924cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2854cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1741cm -1for the C=O stretching vibration of ester absorbs; 1464cm -1for the C-H asymmetric bending of methyl is vibrated; 1380cm -1for the C-H symmetric curvature of methyl is vibrated; 1173cm -1for the asymmetric stretching vibration of C-O-C; 1119cm -1for C-O-C symmetrical stretching vibration; 723cm -1for the rocking vibration of methylene radical;
2) esterification: in three mouthfuls of round-bottomed flasks that whipping appts, thermometer, reflux condensing tube are housed, add step 1 successively) in obtained soya-bean oil monoester 357g, adipic acid 7.5g, catalyzer tetrabutyl titanate 0.40g, siccative calcium chloride 90g, be warming up to 180 DEG C of insulation reaction 4 hours.Batch take-off, when sample acid number is less than 2.0, terminates reaction, obtains the two soybean grease of light yellow oil diprotic acid.Survey infrared spectra, its result as shown in Figure 2, wherein, IR (KBr): 3470cm -1broad peak is-OH peak; 3008cm -1for the C-H stretching vibration of unsaturated hydrocarbons CH=CH absorbs; 2926cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2855cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1742cm -1for the C=O stretching vibration of ester absorbs; 1463cm -1for the C-H asymmetric bending of methyl is vibrated; 1380cm -1for the C-H symmetric curvature of methyl is vibrated; 1170cm -1for the asymmetric stretching vibration of C-O-C; 1100cm -1for C-O-C symmetrical stretching vibration; 723cm -1for the rocking vibration of methylene radical;
3) acetylization reaction: in three mouthfuls of round-bottomed flasks that whipping appts, thermometer, de-watering apparatus are housed; add step 2 successively) in obtained diprotic acid two soybean grease 300g, Glacial acetic acid 136g, benzene 110g and catalyzer vitriol oil 1.5g; be warming up to 80 DEG C of back flow reaction 7 hours; the stopped reaction when aquifer yield reaches theoretical amount, unreacted Glacial acetic acid and water liquid benzene are extracted in decompression out.Obtain the two acetyl soybean grease of grey black oily matter diprotic acid.Survey infrared spectra, its result as shown in Figure 3, wherein, IR (KBr): 3008cm -1for the C-H stretching vibration of unsaturated hydrocarbons CH=CH absorbs; 2926cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2855cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1746cm -1for the C=O stretching vibration of ester absorbs; 1463cm -1for the C-H asymmetric bending of methyl is vibrated; 1370cm -1for the C-H symmetric curvature of methyl is vibrated; 1166cm -1for the asymmetric stretching vibration of C-O-C; 1100cm -1for C-O-C symmetrical stretching vibration; 724cm -1for the rocking vibration of methylene radical;
4) epoxidation reaction: by step 3) in the obtained two acetyl soybean grease 275g of diprotic acid, formic acid 20g, catalyzer vitriol oil 0.7g adds with whipping appts, thermometer, separating funnel, in four mouthfuls of round-bottomed flasks of reflux condensing tube, stirring is warming up to 60-65 DEG C, 50% hydrogen peroxide 180g is slowly instilled under stirring, 75-80 DEG C of reaction 4 hours after adding, separate lower floor's sour water, upper strata grease priority buck, be washed to neutrality, acid number underpressure distillation can dewater and filter the two acetyl epoxy soybean grease of give light yellow oil diprotic acid below 3, after testing: its oxirane value is 3.58, acid number is 1.25, iodine number is 2.28.Survey infrared spectra, its result as shown in Figure 4, wherein, IR (KBr): 2927cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2856cm -1for the C-H symmetrical stretching vibration of stable hydrocarbon CH2 absorbs; 1744cm -1for the C=O stretching vibration of ester absorbs; 1463cm -1for the C-H asymmetric bending of methyl is vibrated; 1371cm -1for the C-H symmetric curvature of methyl is vibrated; 1167cm -1for the asymmetric stretching vibration of C-O-C; 1102cm -1for C-O-C symmetrical stretching vibration; 843cm -1for the asymmetric stretching vibration of ternary cyclic ethers (epoxy bond) C-O-C, 726cm -1for the rocking vibration of methylene radical.
Embodiment 2
With soybean oil and glycerine for the two acetyl epoxy soybean grease of Material synthesis diprotic acid, its synthesis step comprises:
1) transesterification reaction: 750g soybean oil, 150g glycerine are joined in three mouthfuls of round-bottomed flasks with whipping appts, thermometer, reflux condensing tube successively, pass into nitrogen and stir and be warming up to 170 DEG C, add sodium hydroxide catalyst 0.25g, 220 DEG C of insulation reaction 4 hours.Batch take-off, when the ethanol of the sample of 1 part and 10 parts dissolves each other, terminates reaction, obtains light yellow oil soya-bean oil monoester.Survey infrared spectra (spectrogram is not shown), wherein: IR (KBr): 3420cm -1broad peak is-OH peak; 3010cm -1for the C-H stretching vibration of unsaturated hydrocarbons CH=CH absorbs; 2923cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2853cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1738cm -1for the C=O stretching vibration of ester absorbs; 1462cm -1for the C-H asymmetric bending of methyl is vibrated; 1380cm -1for the C-H symmetric curvature of methyl is vibrated; 1171cm -1for the asymmetric stretching vibration of C-O-C; 1112cm -1for C-O-C symmetrical stretching vibration; 723cm -1for the rocking vibration of methylene radical;
2) esterification: in three mouthfuls of round-bottomed flasks that whipping appts, thermometer, reflux condensing tube are housed, add step 1 successively) in obtained soya-bean oil monoester 426g, adipic acid 12.50g, catalyzer phosphoric acid 0.60g, siccative calcium sulfate 95g, be warming up to 200 DEG C of insulation reaction 7 hours.Batch take-off, when sample acid number is less than 2.0, terminates reaction, obtains the two soybean grease of light yellow oil diprotic acid.Survey infrared spectra (spectrogram is not shown), wherein: IR (KBr): 3465cm -1broad peak is-OH peak; 3009cm -1for the C-H stretching vibration of unsaturated hydrocarbons CH=CH absorbs; 2925cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2852cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1740cm -1for the C=O stretching vibration of ester absorbs; 1462cm -1for the C-H asymmetric bending of methyl is vibrated; 1376cm -1for the C-H symmetric curvature of methyl is vibrated; 1168cm -1for the asymmetric stretching vibration of C-O-C; 1108cm -1for C-O-C symmetrical stretching vibration; 724cm -1for the rocking vibration of methylene radical;
3) acetylization reaction: in three mouthfuls of round-bottomed flasks that whipping appts, thermometer, de-watering apparatus are housed; add step 2 successively) in obtained diprotic acid two soybean grease 300g, Glacial acetic acid 122g, hexanaphthene 120g and catalyzer tosic acid 1.2g; be warming up to 100 DEG C of back flow reaction 5 hours; the stopped reaction when aquifer yield reaches theoretical amount; unreacted Glacial acetic acid and water entrainer hexanaphthene are extracted in decompression out, obtain the two acetyl soybean grease of grey black oily matter diprotic acid.Survey infrared spectra (spectrogram is not shown), wherein: IR (KBr): 3009cm -1for the C-H stretching vibration of unsaturated hydrocarbons CH=CH absorbs; 2925cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2850cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1742cm -1for the C=O stretching vibration of ester absorbs; 1465cm -1for the C-H asymmetric bending of methyl is vibrated; 1372cm -1for the C-H symmetric curvature of methyl is vibrated; 1165cm -1for the asymmetric stretching vibration of C-O-C; 1100cm -1for C-O-C symmetrical stretching vibration; 724cm -1for the rocking vibration of methylene radical;
4) epoxidation reaction: by step 3) in the obtained two acetyl soybean grease 220g of diprotic acid, formic acid 16g, catalyzer strong phosphoric acid 0.60g adds with whipping appts, thermometer, separating funnel, in four mouthfuls of round-bottomed flasks of reflux condensing tube, 50-55 DEG C is warming up under stirring, 50% hydrogen peroxide 150g is slowly instilled under stirring, 75-80 DEG C of reaction 8 hours after adding, separate lower floor's sour water, upper strata grease priority buck, be washed to neutrality, acid number underpressure distillation can dewater and filter the two acetyl epoxy soybean grease of give light yellow oil diprotic acid below 3, after testing, its oxirane value is 3.75, acid number is 1.85, iodine number is 2.32.Survey infrared spectra (spectrogram is not shown), wherein: IR (KBr): 2927cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2852cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1742cm -1for the C=O stretching vibration of ester absorbs; 1466cm -1for the C-H asymmetric bending of methyl is vibrated; 1370cm -1for the C-H symmetric curvature of methyl is vibrated; 1167cm -1for the asymmetric stretching vibration of C-O-C; 1102cm -1for C-O-C symmetrical stretching vibration; 840cm -1for the asymmetric stretching vibration of ternary cyclic ethers (epoxy bond) C-O-C, 726cm -1for the rocking vibration of methylene radical.
Embodiment 3
With Rice pollard oil and BDO for the two acetyl nontoxic plasticizer ester of starting raw material synthesis diprotic acid, its synthesis step comprises:
1) transesterification reaction: by 800g Rice pollard oil, 162g1,4-butyleneglycol joins in three mouthfuls of round-bottomed flasks with whipping appts, thermometer, reflux condensing tube successively, pass into nitrogen and stir and be warmed up to 150 DEG C, add calcium hydroxide catalyzer 0.30g, 230 DEG C of insulation reaction 10 hours.Batch take-off, when the ethanol of the sample of 1 part and 10 parts dissolves each other, terminates reaction, obtains light yellow oil Rice pollard oil monoesters.Survey infrared spectra, its result as shown in Figure 5, wherein: IR (KBr): 3415cm -1broad peak is-OH peak; 3008cm -1for the C-H stretching vibration of unsaturated hydrocarbons CH=CH absorbs; 2926cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2855cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1742cm -1for the C=O stretching vibration of ester absorbs; 1463cm -1for the C-H asymmetric bending of methyl is vibrated; 1380cm -1for the C-H symmetric curvature of methyl is vibrated; 1173cm -1for the asymmetric stretching vibration of C-O-C; 1118cm -1for C-O-C symmetrical stretching vibration; 725cm -1for the rocking vibration of methylene radical;
2) esterification: in three mouthfuls of round-bottomed flasks that whipping appts, thermometer, reflux condensing tube are housed, add step 1 successively) in obtained Rice pollard oil monoesters 625g, oxalic acid 43.75g, catalyzer sodium phosphate 2.10g, siccative activated alumina 160g, be warming up to 220 DEG C of insulation reaction 8 hours.Batch take-off, when sample acid number is less than 2.0, terminates reaction, obtains the two rice bran grease of light yellow oil diprotic acid.Survey infrared spectra, its result as shown in Figure 6, wherein: IR (KBr): 3430cm -1broad peak is-OH peak; 3009cm -1for the C-H stretching vibration of unsaturated hydrocarbons CH=CH absorbs; 2923cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2855cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1740cm -1for the C=O stretching vibration of ester absorbs; 1464cm -1for the C-H asymmetric bending of methyl is vibrated; 1372cm -1for the C-H symmetric curvature of methyl is vibrated; 1166cm -1for the asymmetric stretching vibration of C-O-C; 1105cm -1for C-O-C symmetrical stretching vibration; 725cm -1for the rocking vibration of methylene radical;
3) acetylization reaction: in three mouthfuls of round-bottomed flasks that whipping appts, thermometer, de-watering apparatus are housed; add step 2 successively) in obtained diprotic acid two soybean grease 500g, Glacial acetic acid 225g, hexane 185g and catalyzer vitriol oil 2.5g; be warming up to 120 DEG C of back flow reaction 8 hours; the stopped reaction when aquifer yield reaches theoretical amount, unreacted Glacial acetic acid and water entrainer hexane are extracted in decompression out.Obtain the two acetyl rice bran grease of grey black oily matter diprotic acid.Survey infrared spectra, its result as shown in Figure 7, wherein: IR (KBr): 3007cm -1for the C-H stretching vibration of unsaturated hydrocarbons CH=CH absorbs; 2926cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2855cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1743cm -1for the C=O stretching vibration of ester absorbs; 1462cm -1for the C-H asymmetric bending of methyl is vibrated; 1376cm -1for the C-H symmetric curvature of methyl is vibrated; 1172cm -1for the asymmetric stretching vibration of C-O-C; 1118cm -1for C-O-C symmetrical stretching vibration; 726cm -1for the rocking vibration of methylene radical;
4) epoxidation reaction: by step 3) in the obtained two acetyl rice bran grease 375g of diprotic acid, formic acid 23g, catalyzer vitriol oil 1.05g adds with whipping appts, thermometer, separating funnel, in four mouthfuls of round-bottomed flasks of reflux condensing tube, 50-55 DEG C is warming up under stirring, 50% hydrogen peroxide 225g is slowly instilled under stirring, 75-80 DEG C of reaction 6 hours after adding, separate lower floor's sour water, upper strata grease priority buck, be washed to neutrality, acid number underpressure distillation can dewater and filter the two acetyl nontoxic plasticizer ester of give light yellow oil diprotic acid below 3, after testing, its oxirane value is 3.27, acid number is 2.23, iodine number is 1.58.Survey infrared spectra, its result as shown in Figure 8, wherein: IR (KBr): 2927cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2855cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1742cm -1for the C=O stretching vibration of ester absorbs; 1463cm -1for the C-H asymmetric bending of methyl is vibrated; 1377cm -1for the C-H symmetric curvature of methyl is vibrated; 1174cm -1for the asymmetric stretching vibration of C-O-C; 1113cm -1for C-O-C symmetrical stretching vibration; 825cm -1for the asymmetric stretching vibration of ternary cyclic ethers (epoxy bond) C-O-C, 725cm -1for the rocking vibration of methylene radical.
Embodiment 4
With plam oil and tetramethylolmethane for the two acetyl epoxy palm oil ester of Material synthesis diprotic acid, its synthesis step comprises:
1) transesterification reaction: 725g plam oil, 220g tetramethylolmethane are joined in three mouthfuls of round-bottomed flasks with whipping appts, thermometer, reflux condensing tube successively, pass into nitrogen and stir intensification, during to 180 DEG C, add sodium methoxide catalyst 0.25g, 250 DEG C of insulation reaction 12 hours.Batch take-off, when the ethanol of the sample of 1 part and 10 parts dissolves each other, terminates reaction, obtains light yellow oil plam oil monoesters.Survey infrared spectra (spectrogram is not shown), wherein: IR (KBr): 3420cm -1broad peak is-OH peak; 3009cm -1for the C-H stretching vibration of unsaturated hydrocarbons CH=CH absorbs; 2926cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2854cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1741cm -1for the C=O stretching vibration of ester absorbs; 1464cm -1for the C-H asymmetric bending of methyl is vibrated; 1378cm -1for the C-H symmetric curvature of methyl is vibrated; 1177cm -1for the asymmetric stretching vibration of C-O-C; 1119cm -1for C-O-C symmetrical stretching vibration; 724cm -1for the rocking vibration of methylene radical;
2) esterification: in three mouthfuls of round-bottomed flasks that whipping appts, thermometer, reflux condensing tube are housed, add step 1 successively) in obtained plam oil monoesters 550g, adipic acid 49.50g, catalyzer tetrabutyl titanate 1.65g, siccative silica gel 155g, be warming up to 250 DEG C of insulation reaction 6 hours.Batch take-off, when sample acid number is less than 2.0, terminates reaction, obtains the two palm grease of light yellow oil diprotic acid.Survey infrared spectra (spectrogram is not shown), wherein: IR (KBr): 3417cm -1broad peak is-OH peak; 3009cm -1for the C-H stretching vibration of unsaturated hydrocarbons CH=CH absorbs; 2925cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2852cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1736cm -1for the C=O stretching vibration of ester absorbs; 1466cm -1for the C-H asymmetric bending of methyl is vibrated; 1370cm -1for the C-H symmetric curvature of methyl is vibrated; 1168cm -1for the asymmetric stretching vibration of C-O-C; 1102cm -1for C-O-C symmetrical stretching vibration; 723cm -1for the rocking vibration of methylene radical;
3) acetylization reaction: in three mouthfuls of round-bottomed flasks that whipping appts, thermometer, de-watering apparatus are housed; add step 2 successively) in obtained diprotic acid two palm grease 400g, Glacial acetic acid 195g, benzene 155g and catalyzer vitriol oil 2.0g; be warming up to 140 DEG C of back flow reaction 9 hours; the stopped reaction when aquifer yield reaches theoretical amount, unreacted Glacial acetic acid and water liquid benzene are extracted in decompression out.Obtain the two acetyl palm grease of grey black oily matter diprotic acid.Survey infrared spectra (spectrogram is not shown), wherein: IR (KBr): 3009cm -1for the C-H stretching vibration of unsaturated hydrocarbons CH=CH absorbs; 2927cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2855cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1748cm -1for the C=O stretching vibration of ester absorbs; 1462cm -1for the C-H asymmetric bending of methyl is vibrated; 1371cm -1for the C-H symmetric curvature of methyl is vibrated; 1169cm -1for the asymmetric stretching vibration of C-O-C; 1100cm -1for C-O-C symmetrical stretching vibration; 723cm -1for the rocking vibration of methylene radical;
4) epoxidation reaction: by step 3) in the obtained two acetyl palm grease 300g of diprotic acid, formic acid 20g, catalyzer strong phosphoric acid 0.60g adds with whipping appts, thermometer, separating funnel, in four mouthfuls of round-bottomed flasks of reflux condensing tube, 60-65 DEG C is warming up under stirring, 50% hydrogen peroxide 200g is slowly instilled under stirring, 75-80 DEG C of reaction 8 hours after adding, separate lower floor's sour water, upper strata grease priority buck, be washed to neutrality, acid number underpressure distillation can dewater and filter the two acetyl epoxy palm oil ester of give light yellow oil diprotic acid below 3, after testing, its oxirane value is 3.20, acid number is 2.18, iodine number is 1.75.Survey infrared spectra (spectrogram is not shown), wherein: IR (KBr): 2930cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2855cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1745cm -1for the C=O stretching vibration of ester absorbs; 1463cm -1for the C-H asymmetric bending of methyl is vibrated; 1376cm -1for the C-H symmetric curvature of methyl is vibrated; 1165cm -1for the asymmetric stretching vibration of C-O-C; 1102cm -1for C-O-C symmetrical stretching vibration; 822cm -1for the asymmetric stretching vibration of ternary cyclic ethers (epoxy bond) C-O-C, 725cm -1for the rocking vibration of methylene radical.
Embodiment 5
With rapeseed oil and TriMethylolPropane(TMP) for the two acetyl epoxy rapeseed oil ester of Material synthesis diprotic acid, its synthesis step comprises:
1) transesterification reaction: 600g rapeseed oil, 180g TriMethylolPropane(TMP) are joined in three mouthfuls of round-bottomed flasks with whipping appts, thermometer, reflux condensing tube successively, pass into nitrogen and stir when being warmed up to 170 DEG C, add potassium hydroxide catalyst 0.22g, 250 DEG C of insulation reaction 10 hours.Batch take-off, when the ethanol of the sample of 1 part and 10 parts dissolves each other, terminates reaction, obtains light yellow oil rapeseed oil monoesters.Survey infrared spectra (spectrogram is not shown), wherein: IR (KBr): 3412cm -1broad peak is-OH peak; 3007cm -1for the C-H stretching vibration of unsaturated hydrocarbons CH=CH absorbs; 2925cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2852cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1740cm -1for the C=O stretching vibration of ester absorbs; 1462cm -1for the C-H asymmetric bending of methyl is vibrated; 1380cm -1for the C-H symmetric curvature of methyl is vibrated; 1176cm -1for the asymmetric stretching vibration of C-O-C; 1108cm -1for C-O-C symmetrical stretching vibration; 723cm -1for the rocking vibration of methylene radical;
2) esterification: in three mouthfuls of round-bottomed flasks that whipping appts, thermometer, reflux condensing tube are housed, add step 1 successively) in obtained rapeseed oil monoesters 450g, terephthalic acid 40g, catalyzer sodium phosphate 1.70g, siccative calcium chloride 130g, be warming up to 250 DEG C of insulation reaction 10 hours.Batch take-off, when sample acid number is less than 2.0, terminates reaction, obtains the two vegetable seed grease of light yellow oil diprotic acid.Survey infrared spectra (spectrogram is not shown), wherein: IR (KBr): 3420cm -1broad peak is-OH peak; 3009cm -1for the C-H stretching vibration of unsaturated hydrocarbons CH=CH absorbs; 2926cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2855cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1738cm -1for the C=O stretching vibration of ester absorbs; 1465cm -1for the C-H asymmetric bending of methyl is vibrated; 1372cm -1for the C-H symmetric curvature of methyl is vibrated; 1172cm -1for the asymmetric stretching vibration of C-O-C; 1106cm -1for C-O-C symmetrical stretching vibration; 725cm -1for the rocking vibration of methylene radical;
3) acetylization reaction: in three mouthfuls of round-bottomed flasks that whipping appts, thermometer, de-watering apparatus are housed; add step 2 successively) in obtained diprotic acid two vegetable seed grease 300g, Glacial acetic acid 144g, hexanaphthene 105g and catalyzer tosic acid 1.74g; be warming up to 150 DEG C of back flow reaction 7 hours; the stopped reaction when aquifer yield reaches theoretical amount, unreacted Glacial acetic acid and water entrainer hexanaphthene are extracted in decompression out.Obtain the two acetyl vegetable seed grease of grey black oily matter diprotic acid.Survey infrared spectra (spectrogram is not shown), wherein: IR (KBr): 3009cm -1for the C-H stretching vibration of unsaturated hydrocarbons CH=CH absorbs; 2927cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2855cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1748cm -1for the C=O stretching vibration of ester absorbs; 1462cm -1for the C-H asymmetric bending of methyl is vibrated; 1371cm -1for the C-H symmetric curvature of methyl is vibrated; 1169cm -1for the asymmetric stretching vibration of C-O-C; 1100cm -1for C-O-C symmetrical stretching vibration; 725cm -1for the rocking vibration of methylene radical;
4) epoxidation reaction: by step 3) in the obtained two acetyl vegetable seed grease 200g of diprotic acid, formic acid 15g, catalyzer strong phosphoric acid 0.60g adds with whipping appts, thermometer, separating funnel, in four mouthfuls of round-bottomed flasks of reflux condensing tube, 50-55 DEG C is warming up under stirring, 50% hydrogen peroxide 136g is slowly instilled under stirring, 75-80 DEG C of reaction 9 hours after adding, separate lower floor's sour water, upper strata grease priority buck, be washed to neutrality, acid number underpressure distillation can dewater and filter the two acetyl epoxy rapeseed oil ester of give light yellow oil diprotic acid below 3, after testing: its oxirane value is 3.35, acid number is 2.08, iodine number is 2.12.Survey infrared spectra (spectrogram is not shown), wherein: IR (KBr): 2927cm -1for stable hydrocarbon CH 2c-H asymmetrical stretching vibration absorb; 2852cm -1for stable hydrocarbon CH 2c-H symmetrical stretching vibration absorb; 1742cm -1for the C=O stretching vibration of ester absorbs; 1463cm -1for the C-H asymmetric bending of methyl is vibrated; 1376cm -1for the C-H symmetric curvature of methyl is vibrated; 1162cm -1for the asymmetric stretching vibration of C-O-C; 1108cm -1for C-O-C symmetrical stretching vibration; 826cm -1for the asymmetric stretching vibration of ternary cyclic ethers (epoxy bond) C-O-C, 726cm -1for the rocking vibration of methylene radical.
Embodiment 6
Two for diprotic acid obtained in a embodiment of the present invention 1 acetyl epoxidized vegetable oil ester (product code: HM-830) is applied to wires and cables industry polyvinyl chloride cable material J-105; specifically formula is as shown in table 1 for it; simultaneously be parallel contrast experiment synthesize conventional commercially available softening agent TOTM in the diacetyl epoxidized vegetable oil acid glyceride (product code: HM-828) and prior art that obtain in prior art by CN102285946B, table 1 and table 2 respectively illustrate formula and form and test result:
Table 1J-105 different tests formula
Note: other powder comprises calcium carbonate, high resistance powder etc.
Table 2 detected result
Note: impact-4/30 in brittle performance and represent that sample radical is 30, break 4 after impacting.
Can be found out by the detected result of table 2; relative to softening agent of the prior art; two for a diprotic acid of the present invention acetyl epoxidized vegetable oil ester is applied in electric wire as softening agent; its low-temperature impact catalytic performance, ageing-resistant performance are obtained for obvious improvement, and meet corresponding index request.Therefore, the two acetyl epoxidized vegetable oil ester of asepsis environment-protecting class softening agent diprotic acid has wide market outlook.
Embodiment 7
Detected result according to embodiment 6: use the aging rear break-draw of wire cable material that the two acetyl epoxidized vegetable oil ester (product code HM-830) of TOTM, diprotic acid is softening agent to strain maximum velocity of variation qualified, and defective when using diacetyl epoxidized vegetable oil acid glyceride (product code HM-828).Cause this existing reason to be: the anti-precipitation of different softening agent is different with migration performance, in the present embodiment, characterize its anti-precipitation with the thermal ageing mass loss of different softening agent sheet material.
Test recipe: PVC100 part, 40 parts, softening agent, thermo-stabilizer 2 parts, mill temperature 180 DEG C, time 5min, experimental result is as shown in table 3:
The thermal ageing mass loss of several softening agent of table 3
Can be found out by table 3, the mass loss of TOTM, HM-828, HM-830 thermal ageing is all qualified, but the mass loss of HM-830 thermal ageing is minimum.This is because TOTM can not form chemical bond with PVC, and the epoxy bond of HM-830 can react with the HCl in PVC, and its side's of reaction principle is as follows:
Because the epoxy bond of HM-830 can react with the HCl in PVC, thus decrease the volatile quantity of softening agent, slow down the katalysis of HCl to PVC thermal destruction simultaneously, extend the long-term thermal stability of goods.
The present invention is by preferred embodiment having carried out detailed explanation.But, by studying carefully above, to the change of each embodiment with to increase also be that one of ordinary skill in the art institute is apparent.Being intended that all these changes and increasing of applicant has dropped in the protection domain of the claims in the present invention.Term used herein is only and is illustrated specific embodiment, and it is also not intended to limit the invention.Unless otherwise defined, all terms used herein (comprising technical term and scientific terminology) are all identical with the understanding of one of ordinary skill in the art of the present invention.Any modification of carrying out this product and improvement, the substituting and using of similar or close material in the scope of the claims or category, all belongs to scope of patent protection of the present invention.

Claims (19)

1. the two acetyl epoxidized vegetable oil ester of diprotic acid, has such as formula the structure shown in (I) or (II):
Wherein, R 1, R 2, R 3independently of one another, be selected from the lipid acid below 20 carbon atoms in vegetables oil identical or differently; R is aliphatic radical or aryl.
2. the two acetyl epoxidized vegetable oil ester of diprotic acid according to claim 1, is characterized in that: described R 1, R 2, R 3independently of one another, identical or differently be selected from the palmitic acid in soybean oil, stearic acid, oleic acid, cis-9,12-octadecenic acid, cis-9,12,15-octadecenic acid; Or the oleic acid, linolic acid or the palmitinic acid that independently of one another, identical or differently are selected from Rice pollard oil; Or the eicosanoic acid, oleic acid, linolic acid, erucic acid or the linolenic acid that independently of one another, identical or differently are selected from rapeseed oil.
3. the synthetic method of diprotic acid one acetyl epoxidized vegetable oil ester as claimed in claim 1 or 2, is characterized in that: comprise the following steps:
1) transesterification reaction: vegetables oil and alcohol carry out transesterification reaction and synthesizes vegetables oil monoesters:
2) esterification: by step 1) in the vegetables oil monoesters and the diprotic acid that generate carry out esterification and synthesize diprotic acid pair vegetable oil esters:
3) acetylization reaction: by step 2) in the two vegetable oil esters of diprotic acid that generates and an acetylation reagent Reactive Synthesis diprotic acid pair acetyl vegetable oil esters:
4) epoxidation reaction: by step 3) in the two acetyl vegetable oil esters of diprotic acid that generates carry out epoxidation reaction with hydrogen peroxide and synthesize a diprotic acid pair acetyl epoxidized vegetable oil ester:
Wherein, R 1, R 2, R 3for the lipid acid below 20 carbon atoms in vegetables oil, R is aliphatic radical or aryl.
4. synthetic method according to claim 3, is characterized in that: R 1, R 2, R 3independently of one another for being selected from palmitic acid, stearic acid, oleic acid, cis-9,12-octadecenic acid, cis-9,12, the 15-octadecenic acid in soybean oil; Or independently of one another for being selected from oleic acid, linolic acid or the palmitinic acid in Rice pollard oil; Or independently of one another for being selected from eicosanoic acid, oleic acid, linolic acid, erucic acid or the linolenic acid in rapeseed oil.
5. synthetic method according to claim 3, is characterized in that: step 1) described in transesterification reaction, temperature of reaction is 150-260 DEG C, and the reaction times is 1.5-20 hour.
6. the synthetic method according to claim 3 or 5, is characterized in that: step 1) described in transesterification reaction in, described vegetables oil is one or more in soybean oil, Rice pollard oil, oleum lini, rapeseed oil, plam oil, Viscotrol C and sunflower seed oil.
7. the synthetic method according to claim 3 or 5, it is characterized in that: step 1) described in transesterification reaction in, described alcohol is at least one in BDO, glycerine, tetramethylolmethane, TriMethylolPropane(TMP), neopentyl glycol, and its consumption is the 16-33% of vegetables oil consumption.
8. the synthetic method according to claim 3 or 5, it is characterized in that: step 1) described in transesterification reaction in, catalyzer is one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium methylate and sodium ethylate, and its consumption is the 0.01-0.04% of vegetables oil consumption.
9. synthetic method according to claim 3, is characterized in that: step 2) described in esterification, temperature of reaction is 180-250 DEG C, and the reaction times is 3-12 hour.
10. the synthetic method according to claim 3 or 9, it is characterized in that: step 2) described in esterification in, described diprotic acid is at least one in hexanodioic acid, Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, oxalic acid, terephthalic acid, and its consumption is the 1-10% of vegetables oil monoesters consumption.
11. building-up reactionss according to claim 3 or 9, is characterized in that: step 2) described in esterification in, described catalyzer is at least one in tetrabutyl titanate, phosphoric acid, sodium phosphate, and its consumption is the 0.1-0.4% of vegetables oil monoesters consumption.
12. building-up reactionss according to claim 3 or 9, it is characterized in that: step 2) described in esterification in add siccative, described siccative is at least one in calcium chloride, calcium sulfate, silica gel, activated alumina, and its consumption is the 20-30% of vegetables oil monoesters consumption.
13. synthetic methods according to claim 3, is characterized in that: step 3) described in acetylization reaction, temperature of reaction is 60-150 DEG C, and the reaction times is 5-10 hour.
14. synthetic methods according to claim 3 or 13; it is characterized in that: step 3) described in acetylization reaction in; described acetylation reagent is at least one in Acetyl Chloride 98Min., Glacial acetic acid, diacetyl oxide, and its consumption is the 40-50% of diprotic acid pair vegetable oil esters consumption.
15. synthetic methods according to claim 3 or 13; it is characterized in that: step 3) described in acetylization reaction in; described catalyzer is at least one in the vitriol oil, tosic acid, acidic ion exchange resin, and its consumption is the 0.3-0.6% of diprotic acid pair vegetable oil esters consumption.
16. synthetic methods according to claim 3 or 13; it is characterized in that: step 3) described in acetylization reaction in add water entrainer; described water entrainer is at least one in benzene, hexanaphthene, hexane, and its consumption is the 35-40% of diprotic acid pair vegetable oil esters consumption.
17. synthetic methods according to claim 3, is characterized in that: step 4) described in epoxidation reaction in, temperature of reaction is 50-80 DEG C, and the reaction times is 4-10 hour.
18. synthetic methods according to claim 3 or 17, is characterized in that: step 4) described in epoxidation reaction in, described catalyzer is sulfuric acid or phosphoric acid.
19. synthetic methods according to claim 3 or 17, it is characterized in that: step 4) described in epoxidation reaction in add formic acid and/or acetic acid, and the mol ratio of diprotic acid two an acetyl vegetable oil esters, hydrogen peroxide, formic acid and/or acetic acid, catalyzer is 1:0.4-0.7:0.04-0.08:0.001-0.003.
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