CN105130800A - Preparation technology for mixed-acid neo-pentyl polyol ester - Google Patents
Preparation technology for mixed-acid neo-pentyl polyol ester Download PDFInfo
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- CN105130800A CN105130800A CN201510370754.0A CN201510370754A CN105130800A CN 105130800 A CN105130800 A CN 105130800A CN 201510370754 A CN201510370754 A CN 201510370754A CN 105130800 A CN105130800 A CN 105130800A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Abstract
The invention relates to a preparation technology for a mixed-acid neo-pentyl polyol ester. The preparation technology comprises aiming at neo-pentyl polyol and mixed acid which are purchased in different batches, determining the theoretical molar ratio demanded for a complete esterification reaction with the mixed acid according to the hydroxyl quantity of a molecule of the employed neo-pentyl polyol, or performing a plurality of small experiments according to a former experimental molar ratio of neo-pentyl polyol to the mixed acid, finishing experimentation when the acid value of a sample at a current small experiment is 1.5 mg KOH/g or less, and performing production by taking the raw material batch and the raw material ratio of the last small experiment as the raw material ratio of large-scale production. The advantages comprise that the preparation technology for a mixed-acid neo-pentyl polyol ester enables the raw materials to be fully utilized, helps to reduce product postprocessing trouble and reduce production cost.
Description
Technical field
The invention belongs to organic chemistry raw material and manufacture field, particularly a kind of preparation technology of amyl-based polyol mixed acid ester.
Background technology
In numerous fatty acid esters, a class fatty acid ester is had to have the special construction of quaternary carbon atom, also known as neopentyl structure, typical example as: pentaerythritol fatty ester, bis pentaervthritol ester, trimethylolpropane fatty acid ester, ditrimethylolpropane fatty acid ester, neopentyl glycol fatty acid ester, they enjoy the favor of people.Because the β position carbon atom of the carbonyl of these neo-pentyl fatty acid esters does not have hydrogen atom, so can not with the resonance structure of the carbon of the alcohol moiety of ester group and hydrogen evolution six atom cycloalkyl, only have high-energy could destroy such ester structure, this makes the stability of the oxidation-resistance of amyl-based polyol mixed acid ester and anti-elimination reaction fine.Thus amyl-based polyol mixed acid ester has the unrivaled superiority of other ester class, becomes the optimal selection of the high-end synthetic ester in current lubricating oil.
Not only thermal oxidation stability is good for amyl-based polyol fatty acid ester, heat decomposition temperature is high, and resistance to low temperature good, easily degrade in the environment, the lubricant in the synthetic base oil of lubricating oil, metal rolled process or the metalworking coolant in metal cutting process can be used as, so be more and more subject to people's attention.
Common amyl-based polyol fatty acid ester organic acid used is a certain acid, as: enanthic acid, 2 ethyl hexanoic acid, lauric acid, oleic acid, stearic acid etc., but these acid that purity is higher are often somewhat expensive, this can make the price of the amyl-based polyol fatty acid ester be synthesized also very high, thus has influence on the application of these esters.Thus in the occasion that ask for something is not harsh especially, can consider with the lower mixing acid of price, as cocinic acid, palm-kernel oleic acid etc., as raw material.Cocinic acid, palm-kernel oleic acid are all based on the mixing acid of the lipid acid of 12 carbon atoms (lauric acid), so also can synthesize not only good but also economic amyl-based polyol mixed acid ester with cocinic acid or palm-kernel oleic acid.
The technique document of current synthesis amyl-based polyol mixed acid ester series products is many, nothing more than employing direct esterification and ester-interchange method.Ester-interchange method owing to using basic catalyst, and can produce lower aliphatic alcohols etc. and has inflammable and byproduct that is explosion hazard, so in fact use seldom.Even employing direct esterification, be mostly adopt the excessive reaction forward of impelling of certain raw material to carry out, this will run into excessive raw material and the difficulty of product separation in follow-up purification, treating process.Even if adopt the means such as molecule rectifying to remove certain excessive raw material, even if can take off very thorough, also will inevitably cause the decline of target product yield, and the energy consumption that sepn process brings thus also can not be ignored, be thus difficult to synthesize the competitive product of price.
The current production technique display of some document reflection, in the process of synthesis amyl-based polyol mixed acid ester, adopts solvent or water entrainer to improve the efficiency of dehydration, makes esterification be unlikely to just can carry out at relatively high temperatures thoroughly.But one that adopts such technique to bring fearful effect finally will allow these solvents or water entrainer and product realize being separated thoroughly also very difficult.And the existence of a small amount of low boiling point solvent or water entrainer can cause the flash-point of product obviously to decline, at high temperature use to product and bring hidden danger.
The also current production technique display of some document reflection, in order to improve esterification yield, reduce the time of reaction, often adopts the excessive way of lipid acid to react, then carries out aftertreatment to product.To in the aftertreatment of product, mostly adopt neutralization, washing and point equal purification means.The consequence adopting such technology to bring is that the raw material of these acidity has loss, unit consumption is difficult to reach desirable level, production cost remains high.The salt produced in N-process is difficult to removing, and the process that will meet environmental requirement to the salt be in waste water is also a thing that make repeated headache.Because used alkaline matter in the process of aftertreatment, there is the situation of saponification reaction in the ester that also may occur to be synthesized, product is gone wrong again in follow-up use procedure.
Double the disclosed process data about synthetic ester, can find in current Technology in the selection of catalyzer, mostly the catalyzer of abandoning tradition, use load miscellaneous or composite catalyst instead.The cost in fact preparing various novel catalyzer is just higher, and the catalytic effect of these novel catalyzer is good not as good as traditional catalyst.Even if some solid catalyst can reclaim, but along with the effective constituent of in use solid-carried catalyst is constantly by wash-out, in fact these catalyzer can reusable restricted lifetime.
Because the source of raw material is different, production technique is also not quite similar, the index such as purity, foreign matter content of different batches raw material also exists trickle fluctuation, so qualified amyl-based polyol mixed acid ester will be produced, also need the feature for different batches raw material to carry out lab scale to grope, the proportioning of Reasonable adjustment raw material.
For the quality fluctuation of raw material between the deficiency of existing production amyl-based polyol mixed acid ester series products technique and different batches, be necessary the harmony considered production control cost and take into account quality product, adopt the tosic acid be easy to get as catalyzer, in conjunction with determining rational proportioning between different batches raw material by lab scale, come economical, reasonably produce amyl-based polyol mixed acid ester.
Summary of the invention
The technical problem to be solved in the present invention is to provide and a kind of adopts tosic acid to be catalyzer, economic and preparation technology that is reasonably amyl-based polyol mixed acid ester.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of preparation technology of amyl-based polyol mixed acid ester, and its innovative point is: for amyl-based polyol and the mixing acid of purchasing the present lot come,
First stratographic analysis is carried out to mixing acid, according to the content of the various lipid acid of analytical results display, calculate it and amount to molecular weight, then carry out the theoretical molar proportioning completely needed for esterification according to the quantity of hydroxyl in amyl-based polyol molecule used and corresponding mixing acid, or select the mol ratio of current lab scale according to the former experience mol ratio formed for amyl-based polyol and such mixing acid;
Adopt tosic acid as catalyzer, rely on heating to carry out esterification when logical nitrogen, and the water taken out of with nitrogen is collected by collection device, observe in collection device and no longer included after water deviates from 5 ~ 20 minutes, sampling, the acid number of working sample, makes current lab scale sample meet acid number≤1.5mgKOH/g by the adjustment of one or many lab scale mol ratio;
Add adsorption decolouriser, continue heated and stirred 0.5 ~ 2h, then heating is stopped, when being cooled to 50 ~ 70 DEG C in lab scale sample, suction filtration is carried out while hot in the Büchner funnel being covered with middling speed quantitative paper, product in filter flask is transferred in reagent bottle, the method specified according to GB/T7305-2003, measure the separation property of synthesis liquid and water; After if the result display high-speed stirring recorded terminates within three ten minutes left standstill after, the volume of emulsion layer is less than 3mL, then represent that the separation property of this synthesis liquid and water is good, terminate this lab scale;
Acid number≤1.5mgKOH/g in this lab scale and synthesis liquid and water separation property also satisfactory lab scale mol ratio carry out large-scale production as the proportioning raw materials of present lot raw material.
Further, described concrete steps are as follows:
step S1:for amyl-based polyol and the mixing acid of purchasing the present lot come, first stratographic analysis is carried out to mixing acid, according to the content of the various lipid acid of analytical results display, calculate it and amount to molecular weight, the quantity calculating hydroxyl in amyl-based polyol molecule used determines the theoretical molar proportioning of carrying out with such mixing acid completely needed for esterification, or carried out lab scale test according to the former experience mol ratio formed for amyl-based polyol and such mixing acid, if the hydroxyl value of amyl-based polyol used is n, then mixing acid and the theoretical molar of amyl-based polyol are than being n,
step S2:the mol ratio setting amyl-based polyol and mixing acid in this lab scale is 0.9:n ~ 1.3:n;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into the mixing acid of 0.4 ~ 1.6mol, then the amyl-based polyol of respective amount is dropped into according to the mol ratio set in step S2, open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 ± 4 DEG C, add mixing acid and amyl-based polyol used always feed intake quality 0.5 ~ 2% tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 10 ~ 100mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 120 ~ 250 DEG C, heating 5 ~ 24h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 5 ~ 20 minutes, sampling,
step S4:the acid number of working sample, if the acid number≤1.5mgKOH/g of sample, then leaps to step S9; If the acid number > 1.5mgKOH/g of sample, then enter next step;
step S5:continue reaction 0.5 ~ 2h;
step S6:the reacted acid number of sampling and measuring, if acid number≤1.5mgKOH/g, then jumps to step S9; If acid number > is 1.5mgKOH/g, then enter next step;
step S7:judge the absolute value of acid number and the adjacent last hypo acid value difference measured in above-mentioned steps S6, if this absolute value > is 0.5mgKOH/g, then return step S5; If this absolute value≤0.5mgKOH/g, then enter next step;
step S8:if acid number is > 1.5mgKOH/g still, then terminate this lab scale, and return step S2, again adjust in the scope of 0.9:n ~ 1.3:n and set once the concrete mol ratio that amyl-based polyol and mixing acid lab scale test; If acid number≤1.5mgKOH/g, then enter next step;
step S9:add in three-necked bottle amyl-based polyol used and mixing acid always feed intake quality 0.5 ~ 5%, particle diameter is the adsorption decolouriser of 65 ~ 80 μm, continue heated and stirred 0.5 ~ 2h, then heating is stopped, when being cooled to 50 ~ 70 DEG C in lab scale sample, in the Büchner funnel being covered with middling speed quantitative paper, carry out suction filtration while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T7305-2003 specify, synthesis liquid in mensuration reagent bottle and the separation property of water, if be less than 3mL at the volume of the three ten minutes internal emulsification layers left standstill after the result display high-speed stirring recorded terminates, then represent that the separation property of this synthesis liquid and water is good, terminate this lab scale, write down this batch of mixing acid used and the suitable mol ratio of amyl-based polyol, using the mol ratio of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot; If the separation property of measurement result display synthesis liquid and water is bad, then return step S2
,in the test of fine setting lab scale, the concrete mol ratio of mixing acid and amyl-based polyol, then carries out lab scale next time;
step S11:large-scale production;
Further, the step of described large-scale production is specially:
step S111:the mol ratio of the present lot obtained with lab scale amyl-based polyol used and mixing acid, at 1M
3reactor in, drop into mixing acid and amyl-based polyol, the total mass of raw material in still is made to be in the scope of 300 ~ 800kg, open and stir, during beginning, rotating speed maintains 5 ~ 50rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 ± 5 DEG C, add mixing acid and amyl-based polyol used always feed intake quality 0.5 ~ 2% tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 1 ~ 100L/min, the rotating speed of stirring is brought up to 50 ~ 300rpm, timing from now, material in still is warmed up to 120 ~ 250 DEG C, heating 5 ~ 24h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 5 ~ 20 minutes, sampling, the acid number of working sample,
step S112:if the acid number of sample can not reach≤level of 1.5mgKOH/g, then carry out reaction 0.5 ~ 2h, resampling detects acid number, until the acid number≤1.5mgKOH/g of sample;
step S113:add in reactor amyl-based polyol used and mixing acid always feed intake quality 0.1 ~ 2% adsorption decolouriser, continue heated and stirred 0.5 ~ 3h, then heating is stopped, when being cooled to 50 ~ 70 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, order number is adopted to be 250 ~ 300 object filter screens, carry out circulation press filtration, press filtration material out turns back in reactor, the color that circulation press filtration proceeds to the product returned do not seen adsorption decolouriser particle residual till, product after press filtration being decoloured pours in pail pack.
Further, described amyl-based polyol is the one in TriMethylolPropane(TMP), ditrimethylolpropane, dipentaerythritol, neopentyl glycol.
Further, described adsorption decolouriser can be gac, atlapulgite, attapulgite, diatomite.
Further, when described adsorption decolouriser is gac, can use together in conjunction with diatomite, attapulgite, atlapulgite.
The invention has the advantages that:
(1) each batch of raw material owing to buying has trickle fluctuation in purity, the cocinic acid of especially each batch, the content of each component of palm-kernel oleic acid is allow fluctuation in certain scope, the result that thus can detect according to means such as each chromatograms, determine each batch amount to after molecular weight, then in the theoretical molar proportioning of corresponding raw material or the basis of experience mol ratio, the raw material of each batch is first adjusted to their proportioning by lab scale, until the acid number of amyl-based polyol mixed acid ester that lab scale is synthesized both met the requirements, also after meeting the requirements with the separation property of water, the feed molar proportioning adopting this suitable again goes to carry out large-scale production, raw material can be made to be fully utilized, ensure the quality of product, eliminate the highly energy-consuming that molecule rectifying is such, the lossy post-processing step of product, make production process economy, rationally, product has the market competitiveness.
(2) need not as current some processes, high, the not poisonous organic solvent of the boiling point such as toluene, dimethylbenzene is adopted to go as water entrainer, avoid the Dangerous and Harmful Factors in operating process, there is not the residual of low-boiling-point substance in product, thus ensure that the amyl-based polyol mixed acid ester be synthesized can at high temperature use.
(3) lipid acid owing to not adopting some traditional technologys to adopt is excessive, and then the technique that neutralizes is carried out with alkaline solution, eliminate washing and point equal post-processing step, and reluctant salts substances can not be produced, make that production process seems succinctly, environmental protection, avoid the product that is synthesized in the basic conditions again by the risk of saponification, hydrolysis.
(4) adopt traditional tosic acid as catalyzer, conveniently be easy to get, not exist batch between the discrepant problem of catalytic activity, it also has a benefit, be exactly that its fusing point is about 106 DEG C, after reaction end product cools down, in the process of decolorization filtering, the tosic acid of separating out from system can be filtered out together, realize being separated of catalyzer and product.
(5) when adopting gac as adsorption decolouriser, when gac price is higher, be combined the porousness sorbent material that diatomite, attapulgite, atlapulgite etc. are inexpensive, can the rational thickness of filter bed of heap, both be enough to play good filtration decolorizing effect in suction filtration or circulation pressure-filtering process, and effectively can have reduced again the cost of decolorization.
(6) adopt mixing acid as raw material, the structure of the amyl-based polyol mixed acid ester be synthesized can be made asymmetric, uneven, when such ester is tending towards crystallization at low temperatures, it will be caused to be not easy crystallization because lattice is uneven, this will make the amyl-based polyol mixed acid ester obtained with such mixing acid compare to reinstate the molecular weight amyl-based polyol fatty acid ester that close single fat acid is synthesized of amounting to of molecular weight and mixing acid to have lower pour point, may be used for the occasion that temperature is lower.
Embodiment
The following examples can make the present invention of professional and technical personnel's comprehend, but therefore do not limit the present invention among described scope of embodiments.
embodiment 1
A preparation method for amyl-based polyol mixed acid ester, adopt TriMethylolPropane(TMP) and palm-kernel oleic acid to be raw material, concrete steps are as follows:
step S1:for certain batch of palm-kernel oleic acid that buying comes, first carry out the content analysis of each component by gas-chromatography, the result obtained is as follows:
Calculate the molecular weight of amounting to of this batch of palm-kernel oleic acid is 214.62.Have 3 hydroxyls in a TriMethylolPropane(TMP) molecule, then such palm-kernel oleic acid is 3 with the theoretical molar ratio of TriMethylolPropane(TMP);
step S2:set the mol ratio of mixing acid and TriMethylolPropane(TMP) in this lab scale, synthesize according to front the experience drawn several times, TriMethylolPropane(TMP) and the proper mol ratio of such palm-kernel oleic acid are 1.03:3;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 0.9mol(193.158g) palm-kernel oleic acid, then correspondingly drop into 0.309mol(41.459g) TriMethylolPropane(TMP), open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 DEG C, add palm-kernel oleic acid and TriMethylolPropane(TMP) always to feed intake the 1%(2.35g of quality 234.617g) tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 30mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 200 ± 5 DEG C, heating 12h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling,
step S4:the acid number of working sample is 0.73mgKOH/g, because the acid number of sample reaches≤the level of 1.5mgKOH/g, subsequently jumps to conventional steps S9;
step S9:in three-necked bottle, adding TriMethylolPropane(TMP) and palm-kernel oleic acid always to feed intake the 2%(4.69g of quality) particle diameter is the atlapulgite of 75 μm, continue heated and stirred 1h, then heating is stopped, when being cooled to 60 DEG C in lab scale sample, in the Büchner funnel being covered with middling speed quantitative paper, carry out suction filtration while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T7305-2003 specify, measure the separation property of synthesis liquid and water, the result recorded is when leaving standstill ten minutes after high-speed stirring terminates, the volume of the emulsion layer between oil phase and aqueous phase is 0mL, represent that the separation property of this synthesis liquid and water is fine, so need not adjust the mol ratio of this batch of TriMethylolPropane(TMP) relative to palm-kernel oleic acid again; Terminate this lab scale, write down this batch of TriMethylolPropane(TMP) used and the suitable mol ratio 1.03:3 of palm-kernel oleic acid;
step S11:large-scale production;
Be specially:
Step S111: the suitable mol ratio 1.03:3 adopting the TriMethylolPropane(TMP) for present lot and the palm-kernel oleic acid obtained in above-mentioned steps, at 1M
3reactor in, drop into 643.86kg mixing acid and 138.20kg TriMethylolPropane(TMP), the total mass of raw material in still is made to reach 782.06kg, open and stir, during beginning, rotating speed maintains 15rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 DEG C, add palm-kernel oleic acid and TriMethylolPropane(TMP) always to feed intake the 1%(7.82kg of quality) tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 15L/min, the rotating speed of stirring is brought up to 150rpm, timing from now, material in still is warmed up to 200 ± 5 DEG C, heating 13h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling, the acid number of working sample, for 0.80mgKOH/g,
Step S112: because the acid number of sample reaches≤the level of 1.5mgKOH/g, so need not proceed reaction again;
Step S113: add TriMethylolPropane(TMP) and palm-kernel oleic acid and always feed intake the 0.5%(3.91kg of quality in reactor) particle diameter is the atlapulgite of 75 μm, continue heated and stirred 1.5h, then heating is stopped, when being cooled to 60 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, order number is adopted to be 270 object filter screens, carry out circulation press filtration, press filtration material out turns back in reactor, after circulation press filtration carries out 11 minutes, the color of the product returned has not seen the residual of atlapulgite particle, product after press filtration being decoloured pours in pail pack.
embodiment 2
A preparation method for amyl-based polyol mixed acid ester, adopt ditrimethylolpropane and cocinic acid to be raw material, concrete steps comprise:
step S1:for certain batch of cocinic acid that first time buying comes, first carry out the content analysis of each component by gas-chromatography, the result obtained is as follows:
Calculate the molecular weight of amounting to of this batch of mixing acid is have 4 hydroxyls in 206.54, ditrimethylolpropane molecule, then cocinic acid is 4 with the theoretical molar ratio of ditrimethylolpropane;
step S2:set the mol ratio of cocinic acid and ditrimethylolpropane in this lab scale, the theoretical molar proportioning 1:4 of both employings carries out lab scale test;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 0.8mol(165.232g) cocinic acid, then correspondingly drop into 0.2mol(50.066g) ditrimethylolpropane, open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 DEG C, add cocinic acid and ditrimethylolpropane always to feed intake the 1%(2.15g of quality 215.298g) tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 30mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 185 ± 5 DEG C, heating 10h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling,
step S4:the acid number of working sample is 2.9mgKOH/g, due to the acid number > 1.5mgKOH/g of sample, enters next step S5;
step S5:continue reaction 1h;
step S6:sampling, the acid number of working sample is 2.5mgKOH/g, due to acid number > 1.5mgKOH/g, enters next step S7;
step S7:judge the absolute value of acid number and the adjacent last hypo acid value difference measured in above-mentioned steps S6, in the present embodiment, due to the acid number of one-time detection after sample and adjacent last hypo acid value difference absolute value≤0.5mgKOH/g, enter next step;
step S8:due to the level of current acid number still > 1.5mgKOH/g, terminate this lab scale, and return step S2, the mol ratio of ditrimethylolpropane and cocinic acid is adjusted to 1.04:4, drop into 0.8mol(160.256g) cocinic acid, then correspondingly drop into 0.208mol(52.069g) ditrimethylolpropane, all the other process repeats step S3, reaction 11h, sampling, the sample acid number recorded is 0.8mgKOH/g, has reached the requirement of acid number≤1.5mgKOH/g, subsequently enters step S9;
step S9:in three-necked bottle, adding ditrimethylolpropane and cocinic acid always to feed intake the 0.8%(1.74g of quality) particle diameter is the gac of 75 μm, continue heated and stirred 1h, then heating is stopped, when being cooled to 60 DEG C in lab scale sample, be carry out suction filtration in the Büchner funnel of the diatomite of 75 μm and middling speed quantitative paper being covered with particle diameter while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T7305-2003 specify, measure the separation property of synthesis liquid and water, the result recorded is when leaving standstill ten minutes after high-speed stirring terminates, between oil phase and aqueous phase, the volume of emulsion layer is 1mL, represent that the separation property of this synthesis liquid and water is fine, terminate this lab scale, write down the raw material for this batch buied, suitable ditrimethylolpropane and the mol ratio of cocinic acid are 1.04:4, using the proportioning raw materials of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot;
step S11:large-scale production;
Be specially:
Step S111: the suitable mol ratio 1.04:4 adopting the ditrimethylolpropane for present lot and the cocinic acid obtained in above-mentioned steps, at 1M
3reactor in, drop into 330.464kg cocinic acid and 104.14kg ditrimethylolpropane, the total mass of raw material in still is made to reach 434.60kg, open and stir, during beginning, rotating speed maintains 15rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 DEG C, add cocinic acid and ditrimethylolpropane always to feed intake the 1.0%(4.35kg of quality) tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 10L/min, the rotating speed of stirring is brought up to 150rpm, timing from now, material in still is warmed up to 185 ± 5 DEG C, heating 11.5h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling, the acid number of working sample, for 0.84mgKOH/g,
Step S112: because the acid number of sample reaches≤the level of 1.5mgKOH/g, so need not proceed reaction again;
Step S113: add ditrimethylolpropane and cocinic acid and always feed intake the 0.5%(2.17kg of quality in reactor) particle diameter is the gac of 75 μm, 0.2%(0.87kg) particle diameter is the diatomite of 75 μm, continue heated and stirred 1.5h, then heating is stopped, when being cooled to 60 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, order number is adopted to be 270 object filter screens, carry out circulation press filtration, press filtration material out turns back in reactor, after circulation press filtration carries out nine minutes, the color of the product returned has not seen that the activated carbon granule of diatomite particle and black remains, product after press filtration being decoloured pours in pail pack.
embodiment 3
A preparation method for amyl-based polyol mixed acid ester, adopt dipentaerythritol and cocinic acid to be raw material, concrete steps are as follows:
step S1:for the cocinic acid that buying comes, first carry out the content analysis of each component by gas-chromatography, the result obtained is as follows:
Can calculate the molecular weight of amounting to of this batch of cocinic acid is have 6 hydroxyls in 206.54, dipentaerythritol molecule, for dipentaerythritol and cocinic acid, its theoretical molar proportioning is 1:6;
step S2:set the mol ratio of cocinic acid and amyl-based polyol in this lab scale, this lab scale first adopts the theoretical molar proportioning 1:6 of dipentaerythritol and such cocinic acid;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 1.2mol(247.848g) cocinic acid, then correspondingly drop into 0.2mol(50.856g) dipentaerythritol, open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 DEG C, add cocinic acid and dipentaerythritol always to feed intake the 1%(2.99g of quality 298.704g) tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 30mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 205 ± 5 DEG C, heating 14h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling,
step S4:the acid number of working sample is 0.25mgKOH/g, because the acid number of sample reaches≤the level of 1.5mgKOH/g, leaps to the S9 of conventional steps so subsequent;
step S9:in three-necked bottle, adding dipentaerythritol and cocinic acid always to feed intake the 2%(5.97g of quality) particle diameter is the attapulgite of 75 μm, continue heated and stirred 1h, then heating is stopped, when being cooled to 60 DEG C in lab scale sample, in the Büchner funnel being covered with middling speed quantitative paper, carry out suction filtration while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T7305-2003 specify, measure synthesis liquid and the separation property of water, it is rear when leaving standstill 30 minutes that the result recorded is that high-speed stirring terminates, and between oil phase and aqueous phase, the volume of emulsion layer is 5mL, represents that the separation property of this synthesis liquid and water is bad;
The separation property of synthesizing liquid and water due to the result display recorded is bad, so for this batch of dipentaerythritol of buying and cocinic acid, its mol ratio is adjusted to 0.94:6, drop into 1.2mol(257.544g) cocinic acid, then correspondingly drop into 0.188mol(47.805g) dipentaerythritol, the rapid S3 of all the other course synchronization of lab scale synthesis, to the product sampling synthesized, recording its acid number is 0.75mgKOH/g, proceed decolouring, filter, then the separation property of synthesis liquid and water is measured, the result recorded is that high-speed stirring terminates rear leaving standstill after 20 minutes, between oil phase and aqueous phase, the volume of emulsion layer is 1mL, represent that the separation property of this synthesis liquid and water can accept, write down the raw material for this batch buied, suitable dipentaerythritol and the mol ratio of cocinic acid are 0.94:6, using the proportioning raw materials of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot,
step S11:large-scale production;
Be specially:
Step S111: the suitable mol ratio 0.94:6 adopting the dipentaerythritol for present lot and the cocinic acid obtained in above-mentioned steps, at 1M
3reactor in, drop into 619.62kg cocinic acid and 119.512kg dipentaerythritol, the total mass of raw material in still is made to reach 739.132kg, open and stir, during beginning, rotating speed maintains 15rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 DEG C, add cocinic acid and mixing amyl-based polyol always to feed intake the 1%(7.391kg of quality) tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 10L/min, the rotating speed of stirring is brought up to 150rpm, timing from now, material in still is warmed up to 205 ± 5 DEG C, heating 15h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling, the acid number of working sample, for 0.81mgKOH/g,
Step S112: because the acid number of sample reaches≤the level of 1.5mgKOH/g, so need not proceed reaction again;
Step S113: add the mixing amyl-based polyol of preparation and cocinic acid and always feed intake the 0.6%(4.43kg of quality in reactor) attapulgite, continue heated and stirred 2h, then heating is stopped, when being cooled to 60 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, employing order number is the filter screen of 270 μm, carry out circulation press filtration, press filtration material out turns back in reactor, after circulation press filtration carries out ten minutes, the color of the product returned has not seen the residual of the attapulgite particle of brown, product after press filtration being decoloured pours in pail pack.
embodiment 4
A preparation method for amyl-based polyol mixed acid ester, adopt neopentyl glycol and palm-kernel oleic acid to be raw material, concrete steps are as follows:
step S1:for certain batch of palm-kernel oleic acid that buying comes, first carry out the content analysis of each component by gas-chromatography, the result obtained is as follows:
Calculate the molecular weight of amounting to of this batch of palm-kernel oleic acid is have 2 hydroxyls in 214.62, neopentyl glycol molecule, the theoretical molar of palm-kernel oleic acid and neopentyl glycol is than being 2:1;
step S2:set the mol ratio of palm-kernel oleic acid and neopentyl glycol in this lab scale, synthesize according to front the experience drawn several times, neopentyl glycol and the proper mol ratio of such palm-kernel oleic acid are 1.02:2;
step S3:in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 1mol(214.62g) palm-kernel oleic acid, then correspondingly drop into 0.51mol(53.117g) neopentyl glycol, open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 DEG C, add palm-kernel oleic acid and neopentyl glycol always to feed intake the 1%(2.68g of quality 267.737g) tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 30mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 190 ± 5 DEG C, heating 7h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling,
step S4:the acid number of working sample is 2.7mgKOH/g, because the acid number of sample does not reach≤the level of 1.5mgKOH/g, therefore enters next step;
step S5:continue reaction 1h;
step S6:sampling, the acid number of working sample is 1.6mgKOH/g; Due to its acid number still > 1.5mgKOH/g, enter next step;
step S7:judge the absolute value of acid number and the adjacent last hypo acid value difference measured in above-mentioned steps S6, in the present embodiment, due to the acid number of one-time detection after sample and the absolute value still > 0.5mgKOH/g of adjacent last hypo acid value difference, react 1h again, sampling, the acid number of working sample is 1.25mgKOH/g;
step S8:because current acid number reaches≤the level of 1.5mgKOH/g, therefore enter next step;
step S9:in three-necked bottle, add neopentyl glycol and palm-kernel oleic acid always to feed intake the 2%(5.35g of quality) particle diameter be the diatomite of 75 μm, continue heated and stirred 1h, then heating is stopped, when being cooled to 60 DEG C in lab scale sample, in the Büchner funnel being covered with middling speed quantitative paper, carry out suction filtration while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T7305-2003 specify, measure the separation property of synthesis liquid and water, the result recorded be high-speed stirring terminate rear leave standstill ten minutes time, between oil phase and aqueous phase, the volume of emulsion layer is 1mL, represent that the separation property of this synthesis liquid and water is good, writing down this batch of neopentyl glycol and the suitable mol ratio of palm-kernel oleic acid, is 1.02:2, using the proportioning raw materials of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot; The separation property of synthesizing liquid and water due to the result display recorded is good, so need not adjust the mol ratio of this batch of neopentyl glycol relative to palm-kernel oleic acid again;
step S11:large-scale production;
Be specially:
Step S111: the suitable mol ratio 1.02:2 adopting the neopentyl glycol for present lot and the palm-kernel oleic acid obtained in above-mentioned steps, at 1M
3reactor in, drop into 643.86kg palm-kernel oleic acid and 77.329kg neopentyl glycol, the total mass of raw material in still is made to reach 721.189kg, open and stir, during beginning, rotating speed maintains 15rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 DEG C, add palm-kernel oleic acid and neopentyl glycol always to feed intake the 0.8%(5.77kg of quality) tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 10L/min, the rotating speed of stirring is brought up to 160rpm, timing from now, material in still is warmed up to 190 ± 5 DEG C, heating 9.5h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling, the acid number of working sample, for 1.36mgKOH/g,
Step S112: because the acid number of sample reaches≤the level of 1.5mgKOH/g, so need not proceed reaction again;
Step S113: add neopentyl glycol and palm-kernel oleic acid and always feed intake the 0.6%(4.33kg of quality in reactor) particle diameter is the diatomite of 75 μm, continue heated and stirred 1.5h, then heating is stopped, when being cooled to 60 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, employing order number is that the filter screen of 270 μm carries out circulation press filtration, press filtration material out turns back in reactor, after circulation press filtration carries out seven minutes, the color of the product returned has not seen the residual of diatomite particle, product after press filtration being decoloured pours in pail pack.
Above content shows and describes ultimate principle of the present invention and principal character.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (8)
1. a preparation technology for amyl-based polyol mixed acid ester, is characterized in that: described preparation technology is amyl-based polyol and mixing acid for purchasing the present lot come,
First stratographic analysis is carried out to mixing acid, according to the content of the various lipid acid of analytical results display, calculate it and amount to molecular weight, then carry out the theoretical molar proportioning completely needed for esterification according to the quantity of hydroxyl in amyl-based polyol molecule used and corresponding mixing acid, or select the mol ratio of current lab scale according to the former experience mol ratio formed for amyl-based polyol and such mixing acid;
Adopt tosic acid as catalyzer, rely on heating to carry out esterification when logical nitrogen, and the water taken out of with nitrogen is collected by collection device, observe in collection device and no longer included after water deviates from 5 ~ 20 minutes, sampling, the acid number of working sample, makes current lab scale sample meet acid number≤1.5mgKOH/g by the adjustment of one or many lab scale mol ratio;
Add adsorption decolouriser, continue heated and stirred 0.5 ~ 2h, then heating is stopped, when being cooled to 50 ~ 70 DEG C in lab scale sample, suction filtration is carried out while hot in the Büchner funnel being covered with middling speed quantitative paper, product in filter flask is transferred in reagent bottle, the method specified according to GB/T7305-2003, measure the separation property of synthesis liquid and water; After if the result display high-speed stirring recorded terminates within three ten minutes left standstill after, the volume of emulsion layer is less than 3mL, then represent that the separation property of this synthesis liquid and water is good, terminate this lab scale;
Acid number≤1.5mgKOH/g in this lab scale and synthesis liquid and water separation property also satisfactory lab scale mol ratio carry out large-scale production as the proportioning raw materials of present lot raw material.
2. the preparation technology of amyl-based polyol mixed acid ester according to claim 1, is characterized in that described concrete steps are as follows:
step S1:for amyl-based polyol and the mixing acid of purchasing the present lot come, first stratographic analysis is carried out to mixing acid, according to the content of the various lipid acid of analytical results display, calculate it and amount to molecular weight, the quantity calculating hydroxyl in amyl-based polyol molecule used determines the theoretical molar proportioning of carrying out with such mixing acid completely needed for esterification, or carried out lab scale test according to the former experience mol ratio formed for amyl-based polyol and such mixing acid, if the hydroxyl value of amyl-based polyol used is n, then mixing acid and the theoretical molar of amyl-based polyol are than being n,
step S2:the mol ratio setting amyl-based polyol and mixing acid in this lab scale is 0.9:n ~ 1.3:n;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into the mixing acid of 0.4 ~ 1.6mol, then the amyl-based polyol of respective amount is dropped into according to the mol ratio set in step S2, open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 ± 4 DEG C, add mixing acid and amyl-based polyol used always feed intake quality 0.5 ~ 2% tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 10 ~ 100mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 120 ~ 250 DEG C, heating 5 ~ 24h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 5 ~ 20 minutes, sampling,
step S4:the acid number of working sample, if the acid number≤1.5mgKOH/g of sample, then leaps to step S9; If the acid number > 1.5mgKOH/g of sample, then enter next step;
step S5:continue reaction 0.5 ~ 2h;
step S6:the reacted acid number of sampling and measuring, if acid number≤1.5mgKOH/g, then jumps to step S9; If acid number > is 1.5mgKOH/g, then enter next step;
step S7:judge the absolute value of acid number and the adjacent last hypo acid value difference measured in above-mentioned steps S6, if this absolute value > is 0.5mgKOH/g, then return step S5; If this absolute value≤0.5mgKOH/g, then enter next step;
step S8:if acid number is > 1.5mgKOH/g still, then terminate this lab scale, and return step S2, again adjust in the scope of 0.9:n ~ 1.3:n and set once the concrete mol ratio that amyl-based polyol and mixing acid lab scale test; If acid number≤1.5mgKOH/g, then enter next step;
step S9:add in three-necked bottle amyl-based polyol used and mixing acid always feed intake quality 0.5 ~ 5%, particle diameter is the adsorption decolouriser of 65 ~ 80 μm, continue heated and stirred 0.5 ~ 2h, then heating is stopped, when being cooled to 50 ~ 70 DEG C in lab scale sample, in the Büchner funnel being covered with middling speed quantitative paper, carry out suction filtration while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T7305-2003 specify, synthesis liquid in mensuration reagent bottle and the separation property of water, if be less than 3mL at the volume of the three ten minutes internal emulsification layers left standstill after the result display high-speed stirring recorded terminates, then represent that the separation property of this synthesis liquid and water is good, terminate this lab scale, write down this batch of mixing acid used and the suitable mol ratio of amyl-based polyol, using the mol ratio of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot; If the separation property of measurement result display synthesis liquid and water is bad, then return step S2
,in the test of fine setting lab scale, the concrete mol ratio of mixing acid and amyl-based polyol, then carries out lab scale next time;
step S11:large-scale production.
3. the preparation technology of amyl-based polyol mixed acid ester according to claim 1 and 2, is characterized in that the step of described large-scale production is specially:
step S111:the mol ratio of the present lot obtained with lab scale amyl-based polyol used and mixing acid, at 1M
3reactor in, drop into mixing acid and amyl-based polyol, the total mass of raw material in still is made to be in the scope of 300 ~ 800kg, open and stir, during beginning, rotating speed maintains 5 ~ 50rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 ± 5 DEG C, add mixing acid and amyl-based polyol used always feed intake quality 0.5 ~ 2% tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 1 ~ 100L/min, the rotating speed of stirring is brought up to 50 ~ 300rpm, timing from now, material in still is warmed up to 120 ~ 250 DEG C, heating 5 ~ 24h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 5 ~ 20 minutes, sampling, the acid number of working sample,
step S112:if the acid number of sample can not reach≤level of 1.5mgKOH/g, then carry out reaction 0.5 ~ 2h, resampling detects acid number, until the acid number≤1.5mgKOH/g of sample;
step S113:add in reactor amyl-based polyol used and mixing acid always feed intake quality 0.1 ~ 2% adsorption decolouriser, continue heated and stirred 0.5 ~ 3h, then heating is stopped, when being cooled to 50 ~ 70 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, order number is adopted to be 250 ~ 300 object filter screens, carry out circulation press filtration, press filtration material out turns back in reactor, the color that circulation press filtration proceeds to the product returned do not seen adsorption decolouriser particle residual till, product after press filtration being decoloured pours in pail pack.
4. the preparation technology of amyl-based polyol mixed acid ester according to claim 1 and 2, is characterized in that: described amyl-based polyol is the one in TriMethylolPropane(TMP), ditrimethylolpropane, dipentaerythritol, neopentyl glycol.
5. the preparation technology of amyl-based polyol mixed acid ester according to claim 3, is characterized in that: described amyl-based polyol is the one in TriMethylolPropane(TMP), ditrimethylolpropane, dipentaerythritol, neopentyl glycol.
6. the preparation technology of amyl-based polyol mixed acid ester according to claim 2, is characterized in that: described adsorption decolouriser can be gac, atlapulgite, attapulgite, diatomite.
7. the preparation technology of amyl-based polyol mixed acid ester according to claim 3, is characterized in that: described adsorption decolouriser can be gac, atlapulgite, attapulgite, diatomite.
8. the preparation technology of the amyl-based polyol mixed acid ester according to claim 6 or 7, is characterized in that: when described adsorption decolouriser is gac, can use together in conjunction with diatomite, attapulgite, atlapulgite.
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