CN103894231A - Reversed micelle nanometer aluminum oxide catalytic system and method for synthesizing modified epoxy plasticizer - Google Patents
Reversed micelle nanometer aluminum oxide catalytic system and method for synthesizing modified epoxy plasticizer Download PDFInfo
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- CN103894231A CN103894231A CN201410075521.3A CN201410075521A CN103894231A CN 103894231 A CN103894231 A CN 103894231A CN 201410075521 A CN201410075521 A CN 201410075521A CN 103894231 A CN103894231 A CN 103894231A
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Abstract
The invention discloses a reversed micelle nanometer aluminum oxide catalytic system. The micelle nanometer aluminum oxide catalytic system is prepared by the method comprising the following steps: dissolving azobenzene into an organic solvent; adding sodium aluminate aqueous solution until reaching saturation; introducing carbon dioxide; then carrying out complete ultrasonic reaction under temperature of 50 to 60 DEG C to obtain the reversed micelle nanometer aluminum oxide catalytic system. The invention also discloses a method for synthesizing a modified epoxy plasticizer with the reversed micelle nanometer aluminum oxide catalytic system. Compared with the prior art, the novel plasticizer has the advantages of being high in epoxide number, and outstanding in compatibility with PVC (Polyvinyl Chloride) plastic; the flash point is high, thus the mobility is small, and overflowing is unlikely to occur; the color is relatively light, so that the novel plasticizer can be widely applied to the plastic industry; because of high electrical resistivity, the novel plasticizer is high in flame retardant performance and can be applied to the flame-retardant plastic industry to replace a chlorcosane plasticizer well; in addition, the performance is improved; the novel plasticizer is high in resistance to low temperature due to low solidifying point, and can also replace DOS (Di N Octyl Sebacate) and DOA (Di N Octyl Adipate) plasticizers well.
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 being widely used, and adds this material in plastic processing, can make its pliability strengthen, and easily processing, is widely used in industrial use.Plasticiser has aliphatic dibasic acid ester, Phthalates (comprising phthalate, terephthalate class), the many esters of gallic acid of benzene, benzoates, polyol ester class, chlorinated hydrocarbons, epoxies, citric acid ester type, polyesters etc. multiple from classification of chemical structure.
Chlorinated paraffin wax is the most frequently used flame-retardant plasticizer, but due to its color and taste not good, a lot of fields all cannot be used.Dioctyl adipate is because its cold resistance better and is extensively approved by masses, and still because its compatibility is poor, and the meeting of placement produces fuel-displaced phenomenon for a long time, therefore can only use as extender plasticizer.Epoxy plasticizer is the class plasticizer being made 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 is more and more subject to everybody welcome, because epoxy grease has good heat resistance, stability, compatibility, can play stabilizing agent and plasticizer double action.
The synthetic of traditional handicraft epoxy plasticizer added hydrogen peroxide and formic acid wherein take vegetable fat as raw material, under sulphuric acid catalysis effect, reacts and gets, and this reaction is comparatively slow and accessory substance is more.Also have for traditional handicraft and carry out improved bibliographical information at present, the patent documentation that for example publication number is CN102703225A discloses a kind of production method of Plasticizer Epoxidized Soybean Oil, load weighted soybean oil, formic acid are added to reactor, then dripping hydrogen peroxide, to carry out epoxidation synthetic, after question response, wash, finally by crossing distillation dehydration, finally make, the weight fraction of raw material system consists of: 95～100 parts of soybean oils, weight concentration are that 50～78 parts, 27～50% hydrogen peroxide, weight concentration are 8～13 parts, 85% formic acid.The method production technology is safe and reliable, still, prepares plasticizer properties of product single, and 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 deficiency separately by composite mode.The patent documentation that for example publication number is CN103483741A discloses a kind of PVC ester plasticizer, is 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, stable to photo-thermal.
But while adopting above-mentioned preparation method to prepare plasticizer, cost is higher on the one hand, technique is comparatively complicated; On the other hand, due to the complexity of raw material, the plasticizer unstable properties preparing, application is seriously limited.
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.
The present invention also provides a kind of method that adopts self-control reverse micelle nano aluminium oxide catalyst system and catalyzing catalyzing and synthetizing modified epoxy plasticizer, both realized the recycling of vegetable oil residue material, can improve again the performance of plasticizer, expand the application of plasticizer, in original technical foundation, improve simultaneously, improve yield, reduced the generation of byproduct.
A kind of reverse micelle nano aluminium oxide catalyst system and catalyzing, utilize following method to prepare: azobenzene is dissolved in organic solvent, add sodium aluminate aqueous solution to saturated, pass into carbon dioxide, be under 50～60 ℃ of conditions in temperature, 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, for example can adopt alcohols solvent, ketones solvent etc., also can adopt the mixed solvent of alcohols solvent and alkane solvents, 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 further preferred, described normal heptane and the volume ratio of n-butanol are 10:1, experimental results show that, while adopting the mixed solvent of this ratio, the reverse micelle nano aluminium oxide catalyst system and catalyzing stability preparing is higher, and catalytic activity is high.
In the present invention, azobenzene compound, as a kind of photoswitch surfactant, under the effect of light, is controlled its surface-active variation.Its effect is mainly to provide microreactor for micella forms.Described azobenzene concentration in organic solvent can determine according to actual needs, and as preferably, described azobenzene concentration in organic solvent is 1 × 10
-6～6 × 10
-3mol/L.Add after organic solvent, for realizing the quick dissolving of azobenzene, and form constitutionally stable micellar structure, as preferably, can select ultrasonic processing 30～60min, more preferably ultrasonic processing 30min.
The concentration of described sodium aluminate aqueous solution can be adjusted according to actual needs, and as preferably, the mass percent concentration of described sodium aluminate aqueous solution is 5～10%.While adding sodium aluminate aqueous solution, add to when saturated and just muddy and finish, the amount that this muddy terminal adds when turnover changes according to solution light transmittance is terminal point determining, and dripping quantity changes according to the concentration of each configuration micellar solution.Drip sodium aluminate aqueous solution generally at room temperature.
Be added dropwise to complete after sodium aluminate aqueous solution, form for accelerating micella, and stable micellar structure, as preferably, can suitably continue sonic oscillation, the sonic oscillation time can be determined according to actual needs, be generally 30min～1h.
Passing into the time that carbon dioxide carries out ultrasonic reaction need to determine according to actual conditions, and general ultrasonic reaction 1～4 hour, gets final product to obtain required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.This catalyst system and catalyzing can change by external conditions such as illumination the catalytic performance of system, is a kind of novel catalyst.
The present invention also provides a kind of method of 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 to extract aliphatic acid wherein, removes extractant, and concentrate constant temperature in-25～15 ℃ of refrigerators is placed, and filters and obtains LCFA;
(2) LCFA step (1) being obtained is dissolved in non-proton organic solvent, under the effect of lithium aluminium hydride catalytic reduction, carries out reduction reaction, obtains corresponding long-chain fatty alcohol;
(3) long-chain fatty alcohol step (2) being obtained mixes with terephthalic acid (TPA), add the reverse micelle nano aluminium oxide catalyst system and catalyzing that utilizes said method to prepare, under ultrasound condition, 50～70 ℃ react completely, and obtain the system liquid that contains phthalic acid two long-chain fat esters;
(4) obtain adding hydrogen peroxide, formic acid to carry out epoxy reaction in system liquid to step (3), epoxy reaction completes and obtains epoxy finished fluid;
(5) in the epoxy finished fluid obtaining to step (4), pass into chlorine, 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 that contains hard soap, for example, 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 all can be used for raw material of the present invention and 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 take linoleic fatty acids sodium salt as main.
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.Add after the concentrated sulfuric acid, for guaranteeing the abundant acidifying of hard soap, as preferably, can adopt and continue to stir 3～6 hours.
In step (1), described extractant can be selected the good solvent of long-chain fat solubility in acid, for example can adopt alcohols solvent, as preferably, described extractant is one or more in ethanol, methyl alcohol or normal propyl alcohol, isopropyl alcohol etc., as further preferred, described extractant is ethanol.The use amount of extractant is substantially to extract LCFA completely and to be as the criterion.
In step (1), remove after extractant, concentrate constant temperature in-25～15 ℃ 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, can obtain the LCFA that freezing point is lower.
In step (2), described non-proton organic solvent can be selected 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 for example reaction temperature is generally 0～30 ℃, 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, while selecting the feeding intake of this ratio, can guarantee that terephthalic acid (TPA) reacts completely substantially, can avoid again long-chain fatty alcohol wastage of material.
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 according to 0.01～0.1 times of calculating that wherein molal weight of Al is terephthalic acid (TPA).This step reaction time is generally 2～5 hours, can adopt the method for thin-layer chromatography to judge reaction end.
In step (4), epoxy reaction can adopt under ultrasound condition and carry out, and reaction temperature is generally 50～70 ℃, further selects to carry out 2～3 hours under 60～65 ℃ of constant temperature.Add the iodine number of the system liquid that the amount of hydrogen peroxide need to obtain according to step (3) to determine, calculate according to following formula: iodine number × 0.36 × system liquid weight/100 simultaneously.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, after having reacted, utilizes nitrogen that residual chlorine air-blowing in liquid is gone out, and products obtained therefrom is our needed new plasticizer, can adopt equally thin-layer chromatography to judge reaction end.
Raw material of the present invention and reagent, all can adopt commercially available prod, also can prepare voluntarily, or adopt reaction pin material of other techniques etc.
New plasticizer of the present invention has following character:
Epoxide number is greater than 6.00%; Flash-point is greater than 200 ℃; Color is less than or equal to (Pt-Co colorimetric method) No. 50; Resistivity is greater than 2 × 10
12Ω cm; Freezing point is less than or equal to-50 ℃.With 9,12-18 (carbon) dienoic acid sodium salt raw material, for example, the structure of the modified epoxy plasticizer preparing is shown below:
Compared with prior art, new plasticizer of the present invention has the following advantages:
(1) epoxide number of the modified epoxy plasticizer that the present invention prepares is higher, have good compatibility, and in molecule, benzene ring structure is comparatively stable with PVC plastics, also contributes to the improvement with the compatibility of PVC plastics.Can substitute Plasticizer Epoxidized Soybean Oil, and performance more.
(2) flash-point of the modified epoxy plasticizer that the present invention prepares is higher, makes its animal migration less, is difficult for overflowing.
(3) color of the modified epoxy plasticizer that the present invention prepares is more shallow, can be used for plastic industry more widely.
(5) resistivity of the modified epoxy plasticizer that the present invention prepares is larger, has good anti-flammability, can be used for, in flame retardant plastics industry, can well substituting chlorinated paraffin wax plasticizer, and performance more.
(6) freezing point of the modified epoxy plasticizer that the present invention prepares is lower, has good resistance to low temperature.Can well substitute DOS, DOA plasticizer.
The specific embodiment
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 modification of doing, be equal to replacement, improvement etc., within protection scope of the present invention all should be included in.
In following embodiment, the raw oil material soap stock adopting 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, and R is take 12 carbon, 14 carbon, 18 carbon, 20 carbon unsaturated alkyls as main, main component is 9,12-18 (carbon) dienoic acid sodium salt).Also can adopt as required other grease soap stocks is raw material, all can adopt method of the present invention to prepare new plasticizer, can not form limitation of the invention further.
Embodiment 1
Azobenzene is dissolved in 100ml normal heptane/n-butanol mixed solvent, and 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 add the sodium aluminate aqueous solution that the mass percent concentration that prepared is 5% with dropper, add to and finish (about 9g) when saturated and just muddy, add and finish the rear sonic oscillation 30min that continues, form to accelerate micella, and stable micellar structure, when passing into carbon dioxide wherein afterwards, continue ultrasonic reaction 1 hour, 50 ℃ of reaction temperatures, get final product to obtain required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.
To dripping the concentrated sulfuric acid (concentrated sulfuric acid addition be soap stock weight 16%) in raw oil material soap stock, control within the scope of the about 2-3 of pH of solution, stir after 3h, extract wherein aliphatic acid as extractant with ethanol, ethanol consumption is about 500mL, get alcohol layer and remove wherein and to put it in 15 ℃ 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, under lithium aluminium hydride (weight of lithium aluminium hydride reduction be LCFA weight 0.1%) catalytic reduction effect, react, 0 ℃ of reaction temperature, in 6 hours reaction time, can obtain long-chain fatty alcohol.To adding a certain amount of self-control catalyst system and catalyzing (catalyst system and catalyzing amount according to 0.01 times of calculating that wherein the molal weight of Al is terephthalic acid (TPA)) 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 put it in ultrasonic reactor 50 ℃ of reactions 2 hours, complete through thin-layer chromatography detection reaction.By this reaction system, under 60 ℃ of thermostatic ultrasonic conditions, add hydrogen peroxide, the 5g formic acid of 50g, and continue thermostatic ultrasonic 2 hours.Stratification, washing, obtains epoxy product after dehydration.
Under normal temperature and pressure, stir to passing into chlorine in gained epoxy finished product, and with UV-irradiation approximately 3 hours, then with nitrogen, residual chlorine air-blowing in liquid is gone out, products obtained therefrom is our needed new plasticizer, adopts equally thin-layer chromatography to judge reaction end.
Products measure result is as follows:
Epoxide number: 6.07%
Flash-point: 205 ℃
Color: No. 50 (Pt-Co colorimetric method)
Resistivity: 2.04 × 10
12Ω cm
Freezing point :-50 ℃.
Embodiment 2
Azobenzene is dissolved in 100mL normal heptane/n-butanol mixed solvent, and 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 the concentration that prepared at 7% sodium aluminate aqueous solution with dropper, add to and finish (about 6g) when saturated and just muddy, add and finish the rear sonic oscillation 45min that continues, form to accelerate micella, and stable micellar structure, when passing into carbon dioxide wherein afterwards, continue ultrasonic reaction 2 hours, 55 ℃ of reaction temperatures, get final product to obtain required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.
To dripping the concentrated sulfuric acid (concentrated sulfuric acid addition be soap stock weight 16%) in raw oil material soap stock, control within the scope of the about 1-2 of pH of solution, stir after 3h, extract wherein aliphatic acid as extractant with ethanol, ethanol consumption is about 500mL, get alcohol layer and remove wherein and to put it in 5 ℃ 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, reaction (weight of lithium aluminium hydride reduction be LCFA weight 0.1%) under the effect of lithium aluminium hydride catalytic reduction, 0 ℃ of reaction temperature, in 6 hours reaction time, can obtain long-chain fatty alcohol.To adding a certain amount of self-control catalyst system and catalyzing (catalyst system and catalyzing amount according to 0.01 times of calculating that wherein the molal weight of Al is terephthalic acid (TPA)) 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 put it in ultrasonic reactor 50 ℃ of reactions 2 hours, complete through thin-layer chromatography detection reaction.By this reaction system, under 60 ℃ of thermostatic ultrasonic conditions, add hydrogen peroxide, the 15g formic acid of 50g, and continue thermostatic ultrasonic 2 hours.Stratification, washing, obtains epoxy product after dehydration.
Under normal temperature and pressure, stir to passing into chlorine in gained epoxy finished product, and with UV-irradiation approximately 3 hours, then with nitrogen, residual chlorine air-blowing in liquid is gone out, products obtained therefrom is our needed new plasticizer, adopts equally thin-layer chromatography to judge reaction end.
Products measure result is as follows:
Epoxide number: 6.14%
Flash-point: 217 ℃
Color: No. 50 (Pt-Co colorimetric method)
Resistivity: 3.25 × 10
12Ω cm
Freezing point :-50 ℃.
Embodiment 3
Azobenzene is dissolved in 100ml normal heptane/n-butanol mixed solvent, and 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 the concentration that prepared at 10% sodium aluminate aqueous solution with dropper, add to and finish (about 6g) when saturated and just muddy, add and finish the rear sonic oscillation 60min that continues, form to accelerate micella, and stable micellar structure, when passing into carbon dioxide wherein afterwards, continue ultrasonic reaction 3 hours, 60 ℃ of reaction temperatures, get final product to obtain required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.
To dripping the concentrated sulfuric acid (concentrated sulfuric acid addition be soap stock weight 16%) in raw oil material soap stock, control within the scope of the about 2-3 of pH of solution, stir after 3h, extract wherein aliphatic acid as extractant with ethanol, ethanol consumption is about 500mL, get alcohol layer and remove wherein and after ethanol, put it in-5 ℃ of refrigerators constant temperature 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, reaction (weight of lithium aluminium hydride reduction be LCFA weight 0.1%) under the effect of lithium aluminium hydride catalytic reduction, 0 ℃ of reaction temperature, in 6 hours reaction time, can obtain long-chain fatty alcohol.To adding a certain amount of self-control catalyst system and catalyzing (catalyst system and catalyzing amount according to 0.01 times of calculating that wherein the molal weight of Al is terephthalic acid (TPA)) 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 put it in ultrasonic reactor 50 ℃ of reactions 2 hours, complete through thin-layer chromatography detection reaction.By this reaction system, under 60 ℃ of thermostatic ultrasonic conditions, add hydrogen peroxide, the 15g formic acid of 50g, and continue thermostatic ultrasonic 2 hours.Stratification, washing, obtains epoxy product after dehydration.
Under normal temperature and pressure, stir to passing into chlorine in gained epoxy finished product, and with UV-irradiation approximately 3 hours, then with nitrogen, residual chlorine air-blowing in liquid is gone out, products obtained therefrom is our needed new plasticizer, adopts equally thin-layer chromatography to judge reaction end.
Products measure result is as follows:
Epoxide number: 6.32%
Flash-point: 230 ℃
Color: No. 50 (Pt-Co colorimetric method)
Resistivity: 5.23 × 10
12Ω cm
Freezing point :-63 ℃.
Embodiment 4
Azobenzene is dissolved in 100ml normal heptane/n-butanol mixed solvent, and 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 the concentration that prepared at 10% sodium aluminate aqueous solution with dropper, add to and finish (about 8g) when saturated and just muddy, add and finish the rear sonic oscillation 60min that continues, form to accelerate micella, and stable micellar structure, when passing into carbon dioxide wherein afterwards, continue ultrasonic reaction 3 hours, 60 ℃ of reaction temperatures, get final product to obtain required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.
To dripping the concentrated sulfuric acid (concentrated sulfuric acid addition be soap stock weight 20%) in raw oil material soap stock, control within the scope of the about 2-3 of pH of solution, stir after 4h, extract wherein aliphatic acid as extractant with ethanol, ethanol consumption is about 500mL, get alcohol layer and remove wherein and after ethanol, put it in-15 ℃ of refrigerators constant temperature 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, reaction (weight of lithium aluminium hydride reduction be LCFA weight 0.05%) under the effect of lithium aluminium hydride catalytic reduction, 10 ℃ of reaction temperatures, in 7 hours reaction time, can obtain long-chain fatty alcohol.To adding a certain amount of self-control catalyst system and catalyzing (catalyst system and catalyzing amount according to 0.05 times of calculating that wherein the molal weight of Al is terephthalic acid (TPA)) 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 put it in ultrasonic reactor 60 ℃ of reactions 3 hours, complete through thin-layer chromatography detection reaction.By this reaction system, under 60 ℃ of thermostatic ultrasonic conditions, add hydrogen peroxide, the 15g formic acid of 50g, and continue thermostatic ultrasonic 2 hours.Stratification, washing, obtains epoxy product after dehydration.
Under normal temperature and pressure, stir to passing into chlorine in gained epoxy finished product, and with UV-irradiation approximately 3 hours, then with nitrogen, residual chlorine air-blowing in liquid is gone out, products obtained therefrom is our needed new plasticizer, adopts equally thin-layer chromatography to judge reaction end.
Products measure result is as follows:
Epoxide number: 6.55%
Flash-point: 243 ℃
Color: No. 50 (Pt-Co colorimetric method)
Resistivity: 7.06 × 10
12Ω cm
Freezing point :-75 ℃
Embodiment 5
Azobenzene is dissolved in 150ml normal heptane/n-butanol mixed solvent, and 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 the concentration that prepared at 10% sodium aluminate aqueous solution with dropper, add to and finish (about 10g) when saturated and just muddy, add and finish the rear sonic oscillation 60min that continues, form to accelerate micella, and stable micellar structure, when passing into carbon dioxide wherein afterwards, continue ultrasonic reaction 3 hours, 60 ℃ of reaction temperatures, get final product to obtain required catalyst system and catalyzing-reverse micelle nano aluminium oxide catalyst system and catalyzing.
To dripping the concentrated sulfuric acid (concentrated sulfuric acid addition be soap stock weight 32%) in raw oil material soap stock, control within the scope of the about 1-2 of pH of solution, stir after 6h, extract wherein aliphatic acid as extractant with ethanol, ethanol consumption is about 600mL, get alcohol layer and remove wherein and after ethanol, put it in-25 ℃ of refrigerators constant temperature 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, reaction (weight of lithium aluminium hydride reduction be LCFA weight 0.1%) under the effect of lithium aluminium hydride catalytic reduction, 20 ℃ of reaction temperatures, in 10 hours reaction time, can obtain long-chain fatty alcohol.To adding a certain amount of self-control catalyst system and catalyzing (catalyst system and catalyzing amount according to 0.10 times of calculating that wherein the molal weight of Al is terephthalic acid (TPA)) 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 put it in ultrasonic reactor 70 ℃ of reactions 5 hours, complete through thin-layer chromatography detection reaction.By this reaction system, under 60 ℃ of thermostatic ultrasonic conditions, add hydrogen peroxide, the 15g formic acid of 50g, and continue thermostatic ultrasonic 2 hours.Stratification, washing, obtains epoxy product after dehydration.
Under normal temperature and pressure, stir to passing into chlorine in gained epoxy finished product, and with UV-irradiation approximately 3 hours, then with nitrogen, residual chlorine air-blowing in liquid is gone out, products obtained therefrom is our needed new plasticizer, adopts equally thin-layer chromatography to judge reaction end.
Products measure result is as follows:
Epoxide number: 6.75%
Flash-point: 258 ℃
Color: No. 50 (Pt-Co colorimetric method)
Resistivity: 6.45 × 10
12Ω cm
Freezing point :-75 ℃.
From above-described embodiment, utilize the epoxide number of the modified epoxy plasticizer that the inventive method prepares higher, all, more than 6%, there is good compatibility with PVC plastics, and benzene ring structure is comparatively stable in molecule, also contribute to the improvement with the compatibility of PVC plastics.Can substitute Plasticizer Epoxidized Soybean Oil, and performance more.Utilize the flash-point of the modified epoxy plasticizer that the inventive method prepares higher, all, more than 200 ℃, make its animal migration less, be difficult for overflowing.The color of the modified epoxy plasticizer being prepared by the inventive method is more shallow, can be used for plastic industry more widely.The resistivity of the modified epoxy plasticizer being prepared by the inventive method is larger, all 2 × 10
12more than Ω cm, there is good anti-flammability, can be used for, in flame retardant plastics industry, can well substituting chlorinated paraffin wax plasticizer, and performance more.The freezing point of the modified epoxy plasticizer that the present invention prepares is lower, all, below-50 ℃, has good resistance to low temperature.Can well substitute DOS, DOA plasticizer.
Claims (10)
1. a reverse micelle nano aluminium oxide catalyst system and catalyzing, it is characterized in that, utilize following method to prepare: azobenzene is dissolved in organic solvent, add sodium aluminate aqueous solution to saturated, pass into carbon dioxide, be that under 50～60 ℃ of conditions, ultrasonic reaction is complete in temperature, prepare reverse micelle nano aluminium oxide catalyst system and catalyzing.
2. reverse micelle nano aluminium oxide catalyst system and catalyzing according to claim 1, is characterized in that, 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.
3. reverse micelle nano aluminium oxide catalyst system and catalyzing according to claim 1, is characterized in that, described azobenzene concentration in organic solvent is 1 × 10
-6～6 × 10
-3mol/L.
4. 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%.
5. 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 to extract aliphatic acid wherein, removes extractant, and concentrate constant temperature in-25～15 ℃ of refrigerators is placed, and filters and obtains LCFA;
(2) LCFA step (1) being obtained is dissolved in non-proton organic solvent, under the effect of lithium aluminium hydride catalytic reduction, carries out reduction reaction, obtains corresponding long-chain fatty alcohol;
(3) long-chain fatty alcohol step (2) being obtained mixes with terephthalic acid (TPA), add the reverse micelle nano aluminium oxide catalyst system and catalyzing described in the arbitrary claim of claim 1-4, under ultrasound condition, 50～70 ℃ react completely, and obtain the system liquid that contains phthalic acid two long-chain fat esters;
(4) in the system liquid obtaining to step (3), add hydrogen peroxide, formic acid to carry out epoxy reaction, epoxy reaction completes and obtains epoxy finished fluid;
(5) in the epoxy finished fluid obtaining to step (4), pass into chlorine, UV-irradiation carries out chlorination reaction simultaneously, and the complete post processing of chlorination reaction obtains modified epoxy plasticizer.
6. the method for synthesis modification epoxy plasticizer according to claim 5, 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.
7. the method for synthesis modification epoxy plasticizer according to claim 5, 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.
8. the method for synthesis modification epoxy plasticizer according to claim 5, is characterized in that, in step (3), described long-chain fatty alcohol and the mol ratio of terephthalic acid (TPA) are 2～4:1.
9. the method for synthesis modification epoxy plasticizer according to claim 5, is characterized in that, in step (3), the addition of described reverse micelle nano aluminium oxide catalyst system and catalyzing is according to 0.01～0.1 times of calculating that wherein molal weight of Al is terephthalic acid (TPA).
10. the method for synthesis modification epoxy plasticizer according to claim 5, it is characterized in that, in step (4), the iodine number of the system liquid that the addition of hydrogen peroxide need to obtain according to step (3) is determined, calculates: iodine number × 0.36 × system liquid weight/100 according to following formula simultaneously; The addition of formic acid calculates according to quality × 0.12 of hydrogen peroxide.
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| CN105837631A (en) * | 2016-04-01 | 2016-08-10 | 浙江嘉澳环保科技股份有限公司 | Phosphorus-containing modified epoxy plasticizer preparation method and plasticizer prepared through method |
| CN111217769A (en) * | 2020-02-29 | 2020-06-02 | 华南理工大学 | Method for synthesizing epoxy compound by catalyzing olefin epoxidation through nano aluminum oxide |
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| CN111217769A (en) * | 2020-02-29 | 2020-06-02 | 华南理工大学 | Method for synthesizing epoxy compound by catalyzing olefin epoxidation through nano aluminum oxide |
| CN111217769B (en) * | 2020-02-29 | 2023-04-21 | 华南理工大学 | Method for synthesizing epoxy compound by catalyzing olefin epoxy by using nano alumina |
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