CN103894231B - The method of reverse micelle nano aluminium oxide catalyst system and catalyzing and synthesis modification epoxy plasticizer - Google Patents
The method of reverse micelle nano aluminium oxide catalyst system and catalyzing and synthesis modification epoxy plasticizer Download PDFInfo
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- CN103894231B CN103894231B CN201410075521.3A CN201410075521A CN103894231B CN 103894231 B CN103894231 B CN 103894231B CN 201410075521 A CN201410075521 A CN 201410075521A CN 103894231 B CN103894231 B CN 103894231B
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Abstract
The invention discloses a kind of reverse micelle nano aluminium oxide catalyst system and catalyzing, preparation method is: be dissolved in by azobenzene in organic solvent, add sodium aluminate aqueous solution to saturated, pass into carbon dioxide, under temperature is 50 ~ 60 DEG C of conditions, ultrasonic reaction is complete, prepares reverse micelle nano aluminium oxide catalyst system and catalyzing.The invention also discloses a kind of method utilizing above-mentioned reverse micelle nano aluminium oxide catalyst system and catalyzing synthesis modification epoxy plasticizer.Compared with prior art, new plasticizer epoxide number of the present invention is higher, has good compatibility with PVC plastic.Flash-point is higher, makes its animal migration less, not easily overflows.Color is more shallow, can be used for plastic industry more widely.Resistivity is comparatively large, has good anti-flammability, can be used for, in flame retardant plastics industry, can well substituting chlorinated paraffin plasticizer, and performance more.Freezing point is lower, has good resistance to low temperature.DOS, DOA plasticizer can well be substituted.
Description
Technical field
The invention belongs to field of fine chemical, specifically relate to a kind of method of reverse micelle nano aluminium oxide catalyst system and catalyzing and synthesis modification epoxy plasticizer.
Background technology
Plasticizer is the industrial macromolecular material auxiliary agent be widely used, and adds this material in plastic processing, its pliability can be made to strengthen, easily process, be widely used in industrial use.Plasticiser chemically textural classification has aliphatic dibasic acid ester, Phthalates (comprising phthalate, terephthalic acid ester), the many esters of gallic acid of benzene, benzoates, polyol ester class, chlorinated hydrocarbons, epoxies, citric acid ester type, polyesters etc. multiple.
Chlorinated paraffin wax is the most frequently used flame-retardant plasticizer, but due to its color and taste not good, a lot of field all cannot use.Dioctyl adipate better and is extensively approved by masses due to its cold resistance, but due to its compatibility poor, and long-time placement can produce fuel-displaced phenomenon, therefore can only use as extender plasticizer.Epoxy plasticizer is the class plasticizer obtained through epoxidation by vegetable oil or unrighted acid, mainly contain epoxidised soybean oil, epoxidised linseed oil and unrighted acid epoxidised ester, as epoxyoleic acid butyl ester, epoxyoleic acid monooctyl ester, epoxyoleic acid ester in the last of the ten Heavenly stems etc.Epoxy plasticizer is a kind of novel environment-friendly plasticizer of rising in recent years, and more and more by everybody welcome, because epoxy grease has good heat resistance, stability, compatibility, can play stabilizing agent and plasticizer double action.
The synthesis of traditional handicraft epoxy plasticizer take vegetable fat as raw material, adds hydrogen peroxide and formic acid wherein, reacts and get under sulphuric acid catalysis effect, and this reaction is comparatively slow and accessory substance is more.Also have at present and carry out for traditional handicraft the bibliographical information that improves, such as publication number is the production method that patent document discloses a kind of Plasticizer Epoxidized Soybean Oil of CN102703225A, load weighted soybean oil, formic acid are added reactor, then drip hydrogen peroxide and carry out epoxidation synthesis, wash after question response, eventually pass distillation dehydration, finally make, the weight fraction of raw material consists of: soybean oil 95 ~ 100 parts, weight concentration are 50 ~ 78 parts, 27 ~ 50% hydrogen peroxide, weight concentration is 8 ~ 13 parts, 85% formic acid.The method production technology is safe and reliable, but prepare plasticizer properties of product single, structure and purposes are also comparatively single.For making up the single defect of existing plasticizer performance, some producer starts employing and makes up mutually respective deficiency by composite mode.Such as publication number be CN103483741A patent document discloses a kind of PVC ester plasticizer, be grouped into by the one-tenth of following weight portion: diethylene glycol dibenzoate 10 ~ 30; Polyvinyl chloride 10 ~ 20; Active carbon 5 ~ 10; Glycerine 3 ~ 5; Soda ash 5 ~ 8; Octyl group oxirane 1 ~ 5; Epoxidized soybean oil 1 ~ 3.The advantage of this PVC ester plasticizer is: plasticizing efficiency is high, cold-resistant, heat-resisting, anti-pollution, resistance to extraction, and animal migration is good, and electrical insulating property is good, stablizes photo-thermal.
But when adopting above-mentioned preparation method to prepare plasticizer, cost is higher on the one hand, and technique is comparatively complicated; On the other hand, due to the complexity of raw material, the plasticizer unstable properties prepared, application critical constraints.
Summary of the invention
The invention provides a kind of reverse micelle nano aluminium oxide catalyst system and catalyzing, utilize this catalyst system and catalyzing can the good modified epoxy plasticizer of processability, and preparation technology be simple.
Present invention also offers a kind of method adopting self-control reverse micelle nano aluminium oxide catalyst system and catalyzing catalyzing and synthetizing modified epoxy plasticizer, both the recycling of vegetable oil residue material had been achieved, the performance of plasticizer can be improve again, expand the application of plasticizer, improve in original technical foundation simultaneously, improve yield, decrease the generation of byproduct.
A kind of reverse micelle nano aluminium oxide catalyst system and catalyzing, following method is utilized to prepare: to be dissolved in by azobenzene in organic solvent, add sodium aluminate aqueous solution to saturated, pass into carbon dioxide, under temperature is 50 ~ 60 DEG C of conditions, ultrasonic reaction is complete, prepares reverse micelle nano aluminium oxide catalyst system and catalyzing.
Prepare in reverse micelle nano aluminium oxide catalyst system and catalyzing process, described organic solvent can select antithesis pyridine to have better deliquescent neat solvent or mixed solvent, such as alcohols solvent can be adopted, ketones solvent etc., also the mixed solvent of alcohols solvent and alkane solvents can be adopted, as preferably, described organic solvent is the mixed solvent of normal heptane and n-butanol, wherein the volume ratio of normal heptane and n-butanol is 5 ~ 30:1, as preferred further, described normal heptane and the volume ratio of n-butanol are 10:1, experiment proves, when adopting the mixed solvent of this ratio, the reverse micelle nano aluminium oxide catalyst system and catalyzing stability prepared is higher, and catalytic activity is high.
In the present invention, azobenzene compound, as a kind of photoswitch surfactant, under the effect of light, controls its surface-active change.Its effect is mainly for micelle forma-tion provides microreactor.Described azobenzene in organic solvent concentration can be determined according to actual needs, and as preferably, described azobenzene in organic solvent concentration is 1 × 10
-6~ 6 × 10
-3mol/L.After adding organic solvent, for realizing the rapid solution of azobenzene, and forming constitutionally stable micellar structure, as preferably, ultrasonic process 30 ~ 60min can be selected, more preferably ultrasonic process 30min.
The concentration of described sodium aluminate aqueous solution can adjust according to actual needs, and as preferably, the mass percent concentration of described sodium aluminate aqueous solution is 5 ~ 10%.When adding sodium aluminate aqueous solution, add to saturated and just muddy time terminate, this muddy terminal is terminal point determining according to the amount of adding during solution light transmittance transition variation, and dripping quantity changes according to the concentration of each configuration micellar solution.Drip sodium aluminate aqueous solution generally at room temperature to carry out.
After being added dropwise to complete sodium aluminate aqueous solution, being accelerate micelle forma-tion, and stablizing micellar structure, as preferably, suitably can carry out continuation sonic oscillation, the sonic oscillation time can be determined according to actual needs, is generally 30min ~ 1h.
Passing into the time that carbon dioxide carries out ultrasonic reaction needs to determine according to actual conditions, general ultrasonic reaction 1 ~ 4 hour, required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.This catalyst system and catalyzing can change the catalytic performance of system by external conditions such as illumination, be a kind of novel catalyst.
Present invention also offers a kind of method utilizing above-mentioned reverse micelle nano aluminium oxide catalyst system and catalyzing synthesis modification epoxy plasticizer, comprising:
(1) in raw oil material soap stock, add acid, hierarchy of control pH value is 1 ~ 3, utilizes extractant extraction aliphatic acid wherein, removes extractant, and concentrate constant temperature in-25 ~ 15 DEG C of refrigerators is placed, and filters and obtains LCFA;
(2) LCFA that step (1) obtains is dissolved in non-proton organic solvent, under the effect of lithium aluminium hydride catalytic reduction, carries out reduction reaction, obtain corresponding long-chain fatty alcohol;
(3) long-chain fatty alcohol that step (2) obtains is mixed with terephthalic acid (TPA), add the reverse micelle nano aluminium oxide catalyst system and catalyzing utilizing said method to prepare, under ultrasound condition, 50 ~ 70 DEG C react completely, and obtain the system liquid containing phthalic acid two long-chain fat ester;
(4) obtain adding hydrogen peroxide in system liquid to step (3), formic acid carries out epoxy reaction, epoxy reaction completes and obtains epoxy finished fluid;
(5) pass into chlorine in the epoxy finished fluid obtained to step (4), UV-irradiation carries out chlorination reaction simultaneously, and the complete post processing of chlorination reaction obtains modified epoxy plasticizer.
In step (1), byproduct when grease soap stock is alkali refining animal and plant fat, can select the multiple soap stock material containing hard soap, such as, can adopt rapeseed oil soapstock, soybean oil soap stock, peanut oil soap stock, wheat malt oil soap stock or animal oil soap stock etc.Wherein grease soap stock active ingredient fatty acid sodium salt general formula is: RCOONa.Wherein the content of hard soap is not strict with, and raw material all used in the present invention uses.As preferably, described raw oil material soap stock is soybean oil grease soap stock, and iodine number is 110 ~ 130%, is mainly the mixing-in fat acid sodium-salt of the unsaturated hydrocarbons such as 12 carbon, 14 carbon, 18 carbon, 20 carbon, wherein based on linoleic fatty acids sodium salt.
In step (1), as preferably, described acid is the concentrated sulfuric acid, and the addition of the concentrated sulfuric acid is 16 ~ 32% of grease soap stock weight.After adding the concentrated sulfuric acid, for ensureing the abundant acidifying of hard soap, as preferably, can adopt and continue stirring 3 ~ 6 hours.
In step (1), described extractant can be selected the good solvent of long-chain fat solubility in acid, such as alcohols solvent can be adopted, as preferably, described extractant is one or more in ethanol, methyl alcohol or normal propyl alcohol, isopropyl alcohol etc., as preferred further, described extractant is ethanol.The use amount of extractant is as the criterion completely substantially to be extracted by LCFA.
In step (1), after removing extractant, concentrate constant temperature in-25 ~ 15 DEG C of refrigerators is placed, and high-solidification point LCFA is separated out from concentrate, filters and obtains low-freezing LCFA.Constant temperature is placed and can be determined according to actual needs, is generally 10 ~ 24 hours, and as preferably, described constant temperature time of repose is 12 hours.After constant temperature has left standstill, the LCFA that freezing point is lower can be obtained.
In step (2), described non-proton organic solvent can select ether, oxolane etc., and as preferably, described non-proton organic solvent is ether.The volume ratio of LCFA and non-proton organic solvent is generally 1:2 ~ 3.The addition of lithium aluminium hydride is 0.01 ~ 0.1% of LCFA weight, and reaction is generally carried out under room temperature or low temperature, and such as reaction temperature is generally 0 ~ 30 DEG C, and the reaction time is generally 6 ~ 10 hours.
In step (3), described long-chain fatty alcohol and the mol ratio of terephthalic acid (TPA) are 2 ~ 4:1, when selecting the feeding intake of this ratio, can ensure that terephthalic acid (TPA) reacts completely substantially, can avoid long-chain fatty alcohol wastage of material again.
In step (3), the addition of reverse micelle nano aluminium oxide catalyst system and catalyzing can be determined according to actual needs, as preferably, the addition of described reverse micelle nano aluminium oxide catalyst system and catalyzing is 0.01 ~ 0.1 times of calculating of terephthalic acid (TPA) according to the molal weight of wherein Al.This step reaction time is generally 2 ~ 5 hours, and the method for thin-layer chromatography can be adopted to judge reaction end.
In step (4), epoxy reaction can adopt and carry out under ultrasound condition, and reaction temperature is generally 50 ~ 70 DEG C, carries out 2 ~ 3 hours under selecting 60 ~ 65 DEG C of constant temperature further.The iodine number of the system liquid that the amount needs adding hydrogen peroxide obtain according to step (3) is determined, simultaneously according to following formulae discovery: iodine number × 0.36 × system liquid weight/100.The addition of formic acid calculates according to quality × 0.12 of hydrogen peroxide.After having reacted, need to leave standstill, layering, organic layer can obtain epoxy product after washing and drying.
In step (5), chlorination reaction generally can be carried out at normal temperatures and pressures, and after having reacted, utilize nitrogen residual chlorine air-blowing in liquid to be gone out, products obtained therefrom is the new plasticizer required for us, and thin-layer chromatography can be adopted equally to judge reaction end.
Raw material of the present invention and reagent, all can adopt commercially available prod, also can prepare voluntarily, or adopt the reaction pin material etc. of other techniques.
New plasticizer of the present invention has following character:
Epoxide number is greater than 6.00%; Flash-point is greater than 200 DEG C; Color is less than or equal to No. 50 (Pt-Co colorimetric methods); Resistivity is greater than 2 × 10
12Ω cm; Freezing point is less than or equal to-50 DEG C.With 9,12-18 (carbon) dienoic acid sodium salt raw material for example, the structure of the modified epoxy plasticizer prepared is shown below:
Compared with prior art, new plasticizer of the present invention has the following advantages:
(1) epoxide number of modified epoxy plasticizer for preparing of the present invention is higher, have good compatibility, and in molecule, benzene ring structure is comparatively stable, also contributes to the improvement with the compatibility of PVC plastic with PVC plastic.Plasticizer Epoxidized Soybean Oil can be substituted, and performance more.
(2) flash-point of modified epoxy plasticizer for preparing of the present invention is higher, makes its animal migration less, not easily overflows.
(3) color of modified epoxy plasticizer for preparing of the present invention is more shallow, can be used for plastic industry more widely.
(5) resistivity of modified epoxy plasticizer for preparing of the present invention is comparatively large, has good anti-flammability, can be used for, in flame retardant plastics industry, can well substituting chlorinated paraffin plasticizer, and performance more.
(6) freezing point of modified epoxy plasticizer for preparing of the present invention is lower, has good resistance to low temperature.DOS, DOA plasticizer can well be substituted.
Detailed description of the invention
For further illustrating technical scheme of the present invention, be below the preferred embodiment of the present invention, it should be pointed out that the those skilled in the art for the art, the present invention can also have various modifications and variations.Under the premise without departing from the principles of the invention, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
In following embodiment, the raw oil material soap stock adopted all derives from the byproduct of Zhejiang Province Jia'aoEnvironmental Science and Technology Co., Ltd, be mainly soybean oil grease soap stock, iodine number 115%, addition is 200g, and soap stock active ingredient fatty acid sodium salt general formula is: RCOONa, R are based on 12 carbon, 14 carbon, 18 carbon, 20 carbon unsaturated alkyls, main component is 9,12-18 (carbon) dienoic acid sodium salt).Also other grease soap stocks can be adopted as required to be raw material, method of the present invention all can be adopted to prepare new plasticizer, can not limitation of the invention further be formed.
Embodiment 1
Be dissolved in by azobenzene in 100ml normal heptane/n-butanol mixed solvent, the volume ratio of mixed solvent normal heptane/n-butanol is 10:1, is configured to concentration 1 × 10
-6the solution of mol/L, afterwards sonic oscillation 30min.
Under room temperature condition, dropwise adding with dropper the mass percent concentration prepared is the sodium aluminate aqueous solution of 5%, add to saturated and just muddy time terminate (about 9g), add after terminating and continue sonic oscillation 30min, to accelerate micelle forma-tion, and stablize micellar structure, while passing into carbon dioxide wherein afterwards, continue ultrasonic reaction 1 hour, reaction temperature 50 DEG C, required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.
The concentrated sulfuric acid (concentrated sulfuric acid addition is 16% of soap stock weight) is dripped in raw oil material soap stock, the pH controlling solution is about within the scope of 2-3, after stirring 3h, wherein aliphatic acid is extracted as extractant with ethanol, ethanol consumption is about 500mL, get alcohol layer to remove and wherein to put it in 15 DEG C of refrigerators constant temperature after ethanol 12 hours, filter and obtain the LCFA that required freezing point is lower.Be dissolved in (volume ratio of LCFA and ether is 1:2) in ether, react under lithium aluminium hydride (weight of lithium aluminium hydride reduction is 0.1% of LCFA weight) catalytic reduction effect, reaction temperature 0 DEG C, in 6 hours reaction time, can obtain long-chain fatty alcohol.A certain amount of self-control catalyst system and catalyzing (catalyst system and catalyzing amount is 0.01 times of calculating of terephthalic acid (TPA) according to the molal weight of wherein Al) is added in long-chain fatty alcohol (0.5mol) and raw material terephthalic acid (TPA) (0.25mol) (molar ratio of long-chain fatty alcohol and terephthalic acid (TPA) is 6:3), and to put it in ultrasonic reactor 50 DEG C of reactions 2 hours, complete through thin-layer chromatography detection reaction.By this reaction system, under 60 DEG C of thermostatic ultrasonic conditions, add the hydrogen peroxide of 50g, 5g formic acid, and continue thermostatic ultrasonic 2 hours.Stratification, washing, namely obtains epoxy product after dehydration.
Under normal temperature and pressure, in gained epoxy finished product, pass into chlorine stir, and with UV-irradiation about 3 hours, then residual chlorine air-blowing in liquid gone out with nitrogen, products obtained therefrom was the new plasticizer required for us, and the same thin-layer chromatography that adopts judges reaction end.
Products measure result is as follows:
Epoxide number: 6.07%
Flash-point: 205 DEG C
Color: No. 50 (Pt-Co colorimetric method)
Resistivity: 2.04 × 10
12Ω cm
Freezing point :-50 DEG C.
Embodiment 2
Be dissolved in by azobenzene in 100mL normal heptane/n-butanol mixed solvent, the mol ratio of mixed solvent normal heptane/n-butanol is 10:1, and being configured to mass percent concentration is 3 × 10
-5the solution of mol/L, afterwards sonic oscillation 30min.Under room temperature condition, dropwise add with dropper the concentration that prepared 7% sodium aluminate aqueous solution, add to saturated and just muddy time terminate (about 6g), add after terminating and continue sonic oscillation 45min, to accelerate micelle forma-tion, and stablize micellar structure, while passing into carbon dioxide wherein afterwards, continue ultrasonic reaction 2 hours, reaction temperature 55 DEG C, required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.
The concentrated sulfuric acid (concentrated sulfuric acid addition is 16% of soap stock weight) is dripped in raw oil material soap stock, the pH controlling solution is about within the scope of 1-2, after stirring 3h, wherein aliphatic acid is extracted as extractant with ethanol, ethanol consumption is about 500mL, get alcohol layer to remove and wherein to put it in 5 DEG C of refrigerators constant temperature after ethanol 12 hours, filter and obtain the LCFA that required freezing point is lower.Be dissolved in (volume ratio of LCFA and ether is 1:2) in ether, (weight of lithium aluminium hydride reduction is 0.1% of LCFA weight) is reacted under the effect of lithium aluminium hydride catalytic reduction, reaction temperature 0 DEG C, in 6 hours reaction time, can obtain long-chain fatty alcohol.A certain amount of self-control catalyst system and catalyzing (catalyst system and catalyzing amount is 0.01 times of calculating of terephthalic acid (TPA) according to the molal weight of wherein Al) is added in long-chain fatty alcohol (0.5mol) and raw material terephthalic acid (TPA) (0.25mol) (molar ratio of long-chain fatty alcohol and terephthalic acid (TPA) is 6:3), and to put it in ultrasonic reactor 50 DEG C of reactions 2 hours, complete through thin-layer chromatography detection reaction.By this reaction system, under 60 DEG C of thermostatic ultrasonic conditions, add the hydrogen peroxide of 50g, 15g formic acid, and continue thermostatic ultrasonic 2 hours.Stratification, washing, namely obtains epoxy product after dehydration.
Under normal temperature and pressure, in gained epoxy finished product, pass into chlorine stir, and with UV-irradiation about 3 hours, then residual chlorine air-blowing in liquid gone out with nitrogen, products obtained therefrom was the new plasticizer required for us, and the same thin-layer chromatography that adopts judges reaction end.
Products measure result is as follows:
Epoxide number: 6.14%
Flash-point: 217 DEG C
Color: No. 50 (Pt-Co colorimetric method)
Resistivity: 3.25 × 10
12Ω cm
Freezing point :-50 DEG C.
Embodiment 3
Be dissolved in by azobenzene in 100ml normal heptane/n-butanol mixed solvent, the mol ratio of mixed solvent normal heptane/n-butanol is 10:1, and being configured to mass percent concentration is 6 × 10
-3the solution of mol/L, afterwards sonic oscillation 30min.Under room temperature condition, dropwise add with dropper the concentration that prepared 10% sodium aluminate aqueous solution, add to saturated and just muddy time terminate (about 6g), add after terminating and continue sonic oscillation 60min, to accelerate micelle forma-tion, and stablize micellar structure, while passing into carbon dioxide wherein afterwards, continue ultrasonic reaction 3 hours, reaction temperature 60 DEG C, required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.
The concentrated sulfuric acid (concentrated sulfuric acid addition is 16% of soap stock weight) is dripped in raw oil material soap stock, the pH controlling solution is about within the scope of 2-3, after stirring 3h, wherein aliphatic acid is extracted as extractant with ethanol, ethanol consumption is about 500mL, get alcohol layer to remove and wherein to put it in-5 DEG C of refrigerators constant temperature after ethanol 12 hours, filter and obtain the LCFA that required freezing point is lower.Be dissolved in (volume ratio of LCFA and ether is 1:2) in ether, (weight of lithium aluminium hydride reduction is 0.1% of LCFA weight) is reacted under the effect of lithium aluminium hydride catalytic reduction, reaction temperature 0 DEG C, in 6 hours reaction time, can obtain long-chain fatty alcohol.A certain amount of self-control catalyst system and catalyzing (catalyst system and catalyzing amount is 0.01 times of calculating of terephthalic acid (TPA) according to the molal weight of wherein Al) is added in long-chain fatty alcohol (0.5mol) and raw material terephthalic acid (TPA) (0.25mol) (molar ratio of long-chain fatty alcohol and terephthalic acid (TPA) is 6:3), and to put it in ultrasonic reactor 50 DEG C of reactions 2 hours, complete through thin-layer chromatography detection reaction.By this reaction system, under 60 DEG C of thermostatic ultrasonic conditions, add the hydrogen peroxide of 50g, 15g formic acid, and continue thermostatic ultrasonic 2 hours.Stratification, washing, namely obtains epoxy product after dehydration.
Under normal temperature and pressure, in gained epoxy finished product, pass into chlorine stir, and with UV-irradiation about 3 hours, then residual chlorine air-blowing in liquid gone out with nitrogen, products obtained therefrom was the new plasticizer required for us, and the same thin-layer chromatography that adopts judges reaction end.
Products measure result is as follows:
Epoxide number: 6.32%
Flash-point: 230 DEG C
Color: No. 50 (Pt-Co colorimetric method)
Resistivity: 5.23 × 10
12Ω cm
Freezing point :-63 DEG C.
Embodiment 4
Be dissolved in by azobenzene in 100ml normal heptane/n-butanol mixed solvent, the mol ratio of mixed solvent normal heptane/n-butanol is 10:1, and being configured to mass percent concentration is 6 × 10
-3the solution of mol/L, afterwards sonic oscillation 30min.Under room temperature condition, dropwise add with dropper the concentration that prepared 10% sodium aluminate aqueous solution, add to saturated and just muddy time terminate (about 8g), add after terminating and continue sonic oscillation 60min, to accelerate micelle forma-tion, and stablize micellar structure, while passing into carbon dioxide wherein afterwards, continue ultrasonic reaction 3 hours, reaction temperature 60 DEG C, required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.
The concentrated sulfuric acid (concentrated sulfuric acid addition is 20% of soap stock weight) is dripped in raw oil material soap stock, the pH controlling solution is about within the scope of 2-3, after stirring 4h, wherein aliphatic acid is extracted as extractant with ethanol, ethanol consumption is about 500mL, get alcohol layer to remove and wherein to put it in-15 DEG C of refrigerators constant temperature after ethanol 12 hours, filter and obtain the LCFA that required freezing point is lower.Be dissolved in (volume ratio of LCFA and ether is 1:2) in ether, (weight of lithium aluminium hydride reduction is 0.05% of LCFA weight) is reacted under the effect of lithium aluminium hydride catalytic reduction, reaction temperature 10 DEG C, in 7 hours reaction time, can obtain long-chain fatty alcohol.A certain amount of self-control catalyst system and catalyzing (catalyst system and catalyzing amount is 0.05 times of calculating of terephthalic acid (TPA) according to the molal weight of wherein Al) is added in long-chain fatty alcohol (0.32mol) and raw material terephthalic acid (TPA) (0.12mol) (molar ratio of long-chain fatty alcohol and terephthalic acid (TPA) is 8:3), and to put it in ultrasonic reactor 60 DEG C of reactions 3 hours, complete through thin-layer chromatography detection reaction.By this reaction system, under 60 DEG C of thermostatic ultrasonic conditions, add the hydrogen peroxide of 50g, 15g formic acid, and continue thermostatic ultrasonic 2 hours.Stratification, washing, namely obtains epoxy product after dehydration.
Under normal temperature and pressure, in gained epoxy finished product, pass into chlorine stir, and with UV-irradiation about 3 hours, then residual chlorine air-blowing in liquid gone out with nitrogen, products obtained therefrom was the new plasticizer required for us, and the same thin-layer chromatography that adopts judges reaction end.
Products measure result is as follows:
Epoxide number: 6.55%
Flash-point: 243 DEG C
Color: No. 50 (Pt-Co colorimetric method)
Resistivity: 7.06 × 10
12Ω cm
Freezing point :-75 DEG C
Embodiment 5
Be dissolved in by azobenzene in 150ml normal heptane/n-butanol mixed solvent, the mol ratio of mixed solvent normal heptane/n-butanol is 10:1, and being configured to mass percent concentration is 6 × 10
-3the solution of mol/L, afterwards sonic oscillation 30min.Under room temperature condition, dropwise add with dropper the concentration that prepared 10% sodium aluminate aqueous solution, add to saturated and just muddy time terminate (about 10g), add after terminating and continue sonic oscillation 60min, to accelerate micelle forma-tion, and stablize micellar structure, while passing into carbon dioxide wherein afterwards, continue ultrasonic reaction 3 hours, reaction temperature 60 DEG C, required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.
The concentrated sulfuric acid (concentrated sulfuric acid addition is 32% of soap stock weight) is dripped in raw oil material soap stock, the pH controlling solution is about within the scope of 1-2, after stirring 6h, wherein aliphatic acid is extracted as extractant with ethanol, ethanol consumption is about 600mL, get alcohol layer to remove and wherein to put it in-25 DEG C of refrigerators constant temperature after ethanol 12 hours, filter and obtain the LCFA that required freezing point is lower.Be dissolved in (volume ratio of LCFA and ether is 1:2) in ether, (weight of lithium aluminium hydride reduction is 0.1% of LCFA weight) is reacted under the effect of lithium aluminium hydride catalytic reduction, reaction temperature 20 DEG C, in 10 hours reaction time, can obtain long-chain fatty alcohol.A certain amount of self-control catalyst system and catalyzing (catalyst system and catalyzing amount is 0.10 times of calculating of terephthalic acid (TPA) according to the molal weight of wherein Al) is added in long-chain fatty alcohol (0.60mol) and raw material terephthalic acid (TPA) (0.15mol) (molar ratio of long-chain fatty alcohol and terephthalic acid (TPA) is 12:3), and to put it in ultrasonic reactor 70 DEG C of reactions 5 hours, complete through thin-layer chromatography detection reaction.By this reaction system, under 60 DEG C of thermostatic ultrasonic conditions, add the hydrogen peroxide of 50g, 15g formic acid, and continue thermostatic ultrasonic 2 hours.Stratification, washing, namely obtains epoxy product after dehydration.
Under normal temperature and pressure, in gained epoxy finished product, pass into chlorine stir, and with UV-irradiation about 3 hours, then residual chlorine air-blowing in liquid gone out with nitrogen, products obtained therefrom was the new plasticizer required for us, and the same thin-layer chromatography that adopts judges reaction end.
Products measure result is as follows:
Epoxide number: 6.75%
Flash-point: 258 DEG C
Color: No. 50 (Pt-Co colorimetric method)
Resistivity: 6.45 × 10
12Ω cm
Freezing point :-75 DEG C.
From above-described embodiment, the epoxide number of the modified epoxy plasticizer utilizing the inventive method to prepare is higher, all more than 6%, has good compatibility with PVC plastic, and benzene ring structure is comparatively stable in molecule, also contribute to the improvement with the compatibility of PVC plastic.Plasticizer Epoxidized Soybean Oil can be substituted, and performance more.The flash-point of the modified epoxy plasticizer utilizing the inventive method to prepare is higher, all more than 200 DEG C, makes its animal migration less, not easily overflows.The color of the modified epoxy plasticizer prepared by the inventive method is more shallow, can be used for plastic industry more widely.The resistivity of the modified epoxy plasticizer prepared by the inventive method is comparatively large, all 2 × 10
12more than Ω cm, has good anti-flammability, can be used for, in flame retardant plastics industry, can well substituting chlorinated paraffin plasticizer, and performance more.The freezing point of the modified epoxy plasticizer that the present invention prepares is lower, all below-50 DEG C, has good resistance to low temperature.DOS, DOA plasticizer can well be substituted.
Claims (8)
1. a reverse micelle nano aluminium oxide catalyst system and catalyzing, it is characterized in that, following method is utilized to prepare: to be dissolved in by azobenzene in organic solvent, add sodium aluminate aqueous solution to saturated, pass into carbon dioxide, under temperature is 50 ~ 60 DEG C of conditions, ultrasonic reaction is complete, prepares reverse micelle nano aluminium oxide catalyst system and catalyzing; Described organic solvent is the mixed solvent of normal heptane and n-butanol, and wherein the volume ratio of normal heptane and n-butanol is 5 ~ 30:1; Described azobenzene in organic solvent concentration is 1 × 10
-6~ 6 × 10
-3mol/L.
2. reverse micelle nano aluminium oxide catalyst system and catalyzing according to claim 1, is characterized in that, the mass percent concentration of described sodium aluminate aqueous solution is 5 ~ 10%.
3. a method for synthesis modification epoxy plasticizer, comprising:
(1) in raw oil material soap stock, add acid, hierarchy of control pH value is 1 ~ 3, utilizes extractant extraction aliphatic acid wherein, removes extractant, and concentrate constant temperature in-25 ~ 15 DEG C of refrigerators is placed, and filters and obtains LCFA;
(2) LCFA that step (1) obtains is dissolved in non-proton organic solvent, under the effect of lithium aluminium hydride catalytic reduction, carries out reduction reaction, obtain corresponding long-chain fatty alcohol;
(3) long-chain fatty alcohol that step (2) obtains is mixed with terephthalic acid (TPA), add the reverse micelle nano aluminium oxide catalyst system and catalyzing described in claim 1 or 2, under ultrasound condition, 50 ~ 70 DEG C react completely, and obtain the system liquid containing phthalic acid two long-chain fat ester;
(4) add hydrogen peroxide in the system liquid obtained to step (3), formic acid carries out epoxy reaction, epoxy reaction completes and obtains epoxy finished fluid;
(5) pass into chlorine in the epoxy finished fluid obtained to step (4), UV-irradiation carries out chlorination reaction simultaneously, and the complete post processing of chlorination reaction obtains modified epoxy plasticizer.
4. the method for synthesis modification epoxy plasticizer according to claim 3, is characterized in that, in step (1), described acid is the concentrated sulfuric acid, and the addition of the concentrated sulfuric acid is 16 ~ 32% of grease soap stock weight; Described extractant is ethanol.
5. the method for synthesis modification epoxy plasticizer according to claim 3, is characterized in that, in step (2), described non-proton organic solvent is ether; The addition of described lithium aluminium hydride is 0.01 ~ 0.1% of LCFA weight.
6. the method for synthesis modification epoxy plasticizer according to claim 3, is characterized in that, in step (3), described long-chain fatty alcohol and the mol ratio of terephthalic acid (TPA) are 2 ~ 4:1.
7. the method for synthesis modification epoxy plasticizer according to claim 3, it is characterized in that, in step (3), the addition of described reverse micelle nano aluminium oxide catalyst system and catalyzing is 0.01 ~ 0.1 times of calculating of terephthalic acid (TPA) according to the molal weight of wherein Al.
8. the method for synthesis modification epoxy plasticizer according to claim 3, it is characterized in that, in step (4), the addition of hydrogen peroxide needs the iodine number of the system liquid obtained according to step (3) to determine, obtains: iodine number × 0.36 × system liquid weight/100 according to following formulae discovery simultaneously; The addition of formic acid calculates according to quality × 0.12 of hydrogen peroxide.
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| US2771472A (en) * | 1956-11-20 | Epoxyoctadecyl adipates | ||
| CN101993783A (en) * | 2010-09-30 | 2011-03-30 | 浙江嘉澳环保科技股份有限公司 | Method for preparing modified aliphatic ester plasticizer |
| CN101372539B (en) * | 2008-07-31 | 2011-07-06 | 浙江嘉澳环保科技股份有限公司 | Method for producing environment-friendly type plasticiser using waste oil and oil foot |
| CN102936074A (en) * | 2012-12-03 | 2013-02-20 | 浙江嘉澳环保科技股份有限公司 | Pretreatment method of epoxy type plasticizer production wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2771472A (en) * | 1956-11-20 | Epoxyoctadecyl adipates | ||
| CN101372539B (en) * | 2008-07-31 | 2011-07-06 | 浙江嘉澳环保科技股份有限公司 | Method for producing environment-friendly type plasticiser using waste oil and oil foot |
| CN101993783A (en) * | 2010-09-30 | 2011-03-30 | 浙江嘉澳环保科技股份有限公司 | Method for preparing modified aliphatic ester plasticizer |
| CN102936074A (en) * | 2012-12-03 | 2013-02-20 | 浙江嘉澳环保科技股份有限公司 | Pretreatment method of epoxy type plasticizer production wastewater |
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