CN104945247A - Preparation process of neopentyl polyol oleate - Google Patents
Preparation process of neopentyl polyol oleate Download PDFInfo
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- CN104945247A CN104945247A CN201510370471.6A CN201510370471A CN104945247A CN 104945247 A CN104945247 A CN 104945247A CN 201510370471 A CN201510370471 A CN 201510370471A CN 104945247 A CN104945247 A CN 104945247A
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- 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
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Abstract
The invention relates to a preparation process of neopentyl polyol oleate. The preparation process comprises the following steps: by aiming at different batches of purchased neopentyl polyol and oleic acid, firstly determining a theoretical molar ratio required by a complete esterification reaction between neopentyl polyol and oleic acid according to the number of hydroxide radicals in molecules of utilized neopentyl polyol or mixed neopentyl polyol, or carrying out multiple small experiments according to a previous experience molar ratio of neopentyl polyol or mixed neopentyl polyol to oleic acid, ending the experiment when the acid value of a small experiment sample is less than or equal to 1.5mgKOH/g and synthetic liquid and water is well separated, and producing by taking the raw material batch and raw material ratio of the last small experiment as the raw material ratio for large-scale production. The preparation process has the advantages that the raw materials can be adequately utilized, and troubles in after-treatment of products are reduced.
Description
Technical field
The invention belongs to organic chemistry raw material and manufacture field, particularly a kind of preparation technology of amyl-based polyol oleic 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 fatty acid ester and anti-elimination reaction fine.Thus amyl-based polyol fatty 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 and metal rolled process can be used as, so be more and more subject to people's attention.
Oleic acid is a kind of common unsaturated fatty acids, although the existence of unsaturated link(age) can produce certain impact to the oxidative stability of product, but but can make to have the lipid acid of the macromolecule of 18 carbon atoms and amyl-based polyol, high fatty alcohol etc. to synthesize the synthetic ester obtained there is lower pour point with this, still very popular in the application of general base oil.
The technique document of current synthesis amyl-based polyol fatty 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 fatty 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 fatty 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 fatty acid ester Product Process 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 oleic 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 oleic 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 oleic acid ester, and its innovative point is: for amyl-based polyol and the oleic acid of purchasing the present lot come,
First determine the theoretical molar proportioning of carrying out with oleic acid completely needed for esterification according to amyl-based polyol used or the quantity that mixes hydroxyl in new penta season polyol molecule, or according to former for amyl-based polyol or mix new penta season polyvalent alcohol and the experience mol ratio that formed of oleic acid select the mol ratio of current lab scale;
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/T 7305-2003, 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 oleic acid of purchasing the present lot come, the quantity calculating amyl-based polyol used or mix hydroxyl in new penta season polyol molecule determines the theoretical molar proportioning of carrying out with oleic acid completely needed for esterification, according to former for amyl-based polyol or mix new penta season polyvalent alcohol and oleic acid formed experience mol ratio carry out lab scale test, if the quantity of amounting to hydroxyl of the hydroxyl value of amyl-based polyol used or mixing amyl-based polyol is n, then oleic acid and amyl-based polyol or mix amyl-based polyol theoretical molar than being n,
step S2:the mol ratio setting amyl-based polyol and oleic acid in this lab scale is 0.9:n ~ 1.2:n;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into the oleic acid of 0.4 ~ 1.2mol, then according to the mol ratio that sets in step S2 drop into respective amount amyl-based polyol or mix new penta season polyvalent alcohol, 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 oleic acid and amyl-based polyol used or mix new penta season polyvalent alcohol 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 and again adjust in the scope of 0.9:n ~ 1.2:n and set once the concrete mol ratio that amyl-based polyol and oleic acid lab scale test; If acid number≤1.5mgKOH/g, then enter next step;
step S9:in three-necked bottle, add amyl-based polyol used or mix new penta season polyvalent alcohol and oleic 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/T 7305-2003 specifies, 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 oleic 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 measurement result display synthesis liquid and the separation property of water bad, then return step S2, in the test of fine setting lab scale oleic acid and amyl-based polyol or mix new penta season polyvalent alcohol concrete mol ratio, then carry out lab scale next time;
step S11:large-scale production;
Further, the step of described large-scale production is specially:
step S111:the present lot obtained with lab scale amyl-based polyol used or mix new penta season polyvalent alcohol and the mol ratio of oleic acid, at 5M
3reactor in, drop into oleic acid and amyl-based polyol or mix new penta season polyvalent alcohol, the total mass of raw material in still is made to be in the scope of 1000 ~ 4000kg, 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 oleic acid and amyl-based polyol used or mix new penta season polyvalent alcohol 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:in reactor, add amyl-based polyol used or mix new penta season polyvalent alcohol and oleic 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 or mix new penta season polyvalent alcohol be one or more in TriMethylolPropane(TMP), ditrimethylolpropane, tetramethylolmethane, 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, so adopt 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 fatty 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 fatty 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.
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 oleic acid ester, adopt TriMethylolPropane(TMP) and oleic acid to be raw material, concrete steps comprise:
step S1:the TriMethylolPropane(TMP) of present lot that buying is come and oleic acid, the quantity of the hydroxyl contained due to a part TriMethylolPropane(TMP) is 3, then oleic acid is 3 with the theoretical molar ratio of TriMethylolPropane(TMP);
step S2:set the mol ratio of oleic 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 oleic acid are 1.04:3;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 0.9mol(254.223g) oleic acid, then correspondingly drop into 0.312mol(41.861g) 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 oleic acid and TriMethylolPropane(TMP) always to feed intake the 1%(2.96g of quality 296.084g) 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 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,
step S4:the acid number of working sample is 0.78mgKOH/g, due to the acid number≤1.5mgKOH/g of sample, then leaps to step S9;
step S9:in three-necked bottle, adding TriMethylolPropane(TMP) and oleic acid always to feed intake the 2%(5.92g 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/T 7305-2003 specifies, measure the separation property of synthesis liquid and water, the result recorded be high-speed stirring terminate rear leave standstill 15 minutes time, between oil phase and aqueous phase, the volume of emulsion layer is 2mL, represent that the separation property of this synthesis liquid and water is good, so need not adjust the mol ratio of this batch of TriMethylolPropane(TMP) relative to oleic acid again; Terminate this lab scale, write down this batch of oleic acid used and the suitable mol ratio of TriMethylolPropane(TMP), 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;
step S11:large-scale production;
Be specially:
Step S111: the suitable mol ratio 1.04:3 adopting the TriMethylolPropane(TMP) for present lot and the oleic acid obtained in above-mentioned steps, at 5M
3reactor in, drop into 2542.23kg oleic acid and 418.61kg TriMethylolPropane(TMP), the total mass of raw material in still is made to reach 2960.84kg, open and stir, during beginning, rotating speed maintains 10rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 DEG C, add oleic acid and TriMethylolPropane(TMP) always to feed intake the 0.8%(23.69kg of quality) tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 50L/min, the rotating speed of stirring is brought up to 100rpm, timing from now, material in still is warmed up to 200 ± 5 DEG C, heating 16h, 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 0.82mgKOH/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 oleic acid and always feed intake the 0.5%(14.80kg of quality in reactor) particle diameter is the atlapulgite of 75 μm, 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 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 ten 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
Produce a method for ditrimethylolpropane oleic acid ester, adopt ditrimethylolpropane and oleic acid to be raw material, concrete steps comprise:
step S1:for ditrimethylolpropane and the oleic acid of purchasing the present lot come, have 4 hydroxyls in a ditrimethylolpropane molecule, then oleic acid is 4 with the theoretical molar ratio of ditrimethylolpropane;
step S2:set the mol ratio of oleic acid and ditrimethylolpropane in this lab scale, combine according to the front experience drawn of synthesizing several times with theoretical molar ratio, ditrimethylolpropane and the proper mol ratio of oleic acid are 1.05:4;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 0.8mol(225.976g) oleic acid, then correspondingly drop into 0.21mol(50.569g) 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 oleic acid and ditrimethylolpropane always to feed intake the 1%(2.79g of quality 278.545g) 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 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 1.38mgKOH/g, because the acid number of sample reaches≤the level of 1.5mgKOH/g, leaps to step S9 so subsequent;
step S9:in three-necked bottle, adding ditrimethylolpropane and oleic acid always to feed intake the 1.5%(4.97g 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/T 7305-2003 specifies, measure the separation property of synthesis liquid and water, the result recorded is that when leaving standstill 15 minutes after high-speed stirring terminates, between oil phase and aqueous phase, the volume of emulsion layer is 1mL, represents that the separation property of this synthesis liquid and water is good; 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 ditrimethylolpropane relative to oleic acid again; Terminate this lab scale, write down this batch of ditrimethylolpropane used and the suitable mol ratio 1.05:4 of oleic acid;
step S11:large-scale production;
Be specially:
Step S111: the suitable mol ratio 1.05:4 adopting the ditrimethylolpropane for present lot and the oleic acid obtained in above-mentioned steps, at 5M
3reactor in, drop into 2824.7kg oleic acid and 657.12kg ditrimethylolpropane, the total mass of raw material in still is made to reach 3481.82kg, open and stir, during beginning, rotating speed maintains 10rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 DEG C, add oleic acid and ditrimethylolpropane always to feed intake the 1.0%(34.82kg of quality) tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 50L/min, the rotating speed of stirring is brought up to 100rpm, timing from now, material in still is warmed up to 185 ± 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 1.42mgKOH/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 oleic acid and always feed intake the 0.4%(13.93kg of quality in reactor) particle diameter is the gac of 75 μm, 0.2%(6.96kg) particle diameter is the diatomite of 75 μm, 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, 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 oleic acid ester, adopt tetramethylolmethane and oleic acid to be raw material, concrete steps are as follows:
step S1:for tetramethylolmethane and the oleic acid of purchasing the present lot come, have 4 hydroxyls in a tetramethylolmethane molecule, then oleic acid is 4 with the theoretical molar ratio of tetramethylolmethane;
step S2:set the mol ratio of oleic acid and tetramethylolmethane in this lab scale, synthesize according to front the experience drawn several times, tetramethylolmethane and the proper mol ratio of oleic acid are 1.04:4;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 0.8mol(225.976g) oleic acid, then correspondingly drop into 0.208mol(28.319g) tetramethylolmethane, 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 oleic acid and tetramethylolmethane always to feed intake the 1%(2.54g of quality 254.30g) 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 210 ± 5 DEG C, heating 18h, 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 0.6mgKOH/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 tetramethylolmethane and oleic acid always to feed intake the 1%(2.54g 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/T 7305-2003 specifies, measure the separation property of synthesis liquid and water, the result recorded is that when leaving standstill 30 minutes after high-speed stirring terminates, between oil phase and aqueous phase, the volume of emulsion layer is 4mL, 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 reenter step S2, for this batch of tetramethylolmethane buied and oleic acid, by the fine setting of its mol ratio for 1.02:4, drop into 0.8mol(225.976g) oleic acid, then correspondingly drop into 0.204mol(27.775g) tetramethylolmethane, the rapid S3 of all the other course synchronization of lab scale synthesis, to the product sampling synthesized, recording its acid number is 0.9mgKOH/g, and acid number reaches≤1.5mgKOH/g; Then decolouring, the filtration of step S9 is carried out, re-start the separation property of synthesis liquid and water, the result recorded is that high-speed stirring terminates rear leaving standstill after 15 minutes, between oil phase and aqueous phase, the volume of emulsion layer is 2mL, represent that the separation property of this synthesis liquid and water can accept, write down the raw material for this batch buied, suitable tetramethylolmethane and the mol ratio of oleic acid are 1.02:4, 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 1.02:4 adopting the tetramethylolmethane for present lot and the oleic acid obtained in above-mentioned steps, at 5M
3reactor in, drop into 2824.7kg oleic acid and 347.183kg tetramethylolmethane, the total mass of raw material in still is made to reach 3171.883kg, open and stir, during beginning, rotating speed maintains 10rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 DEG C, add oleic acid and tetramethylolmethane always to feed intake the 0.8%(25.38kg of quality) tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 50L/min, the rotating speed of stirring is brought up to 100rpm, timing from now, material in still is warmed up to 210 ± 5 DEG C, heating 19h, 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 1.1mgKOH/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 tetramethylolmethane and oleic acid and always feed intake the 0.4%(12.69kg of quality in reactor) particle diameter is the gac of 75 μm, 0.2%(6.34kg) particle diameter is the diatomite of 75 μm, 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, 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 12 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 4
A preparation method for amyl-based polyol oleic acid ester, the mixing amyl-based polyol that employing mass percent accounts for the tetramethylolmethane of 85%, the dipentaerythritol of 15% forms and oleic acid are raw material, and concrete steps are as follows:
step S1:4 hydroxyls are had in a tetramethylolmethane molecule, 6 hydroxyls are had in a dipentaerythritol molecule, account for the tetramethylolmethane of 85% by mass percent, the molecular-weight average of mixing amyl-based polyol that the dipentaerythritol of 15% forms is 146.348, amounting to hydroxyl value is 4.173, for this mixing amyl-based polyol that the tetramethylolmethane come with buying and dipentaerythritol are mixed with, be 1:4.173 relative to the theoretical molar proportioning of oleic acid;
step S2:set the mol ratio of oleic acid and amyl-based polyol in this lab scale, this lab scale directly adopts theoretical molar proportioning;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 0.835mol(235.730g) oleic acid, then correspondingly drop into 0.2mol(29.27g) mixing amyl-based polyol, 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 oleic acid and mixing amyl-based polyol always to feed intake the 1%(2.65g of quality 265.00g) 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 245 ± 5 DEG C, heating 22h, 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 0.3mgKOH/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 mixing amyl-based polyol and oleic acid always to feed intake the 1%(2.65g of quality) particle diameter is the attapulgite of 75 μm, continue heated and stirred 1.5h, 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/T 7305-2003 specifies, measure the separation property of synthesis liquid and water, the result recorded is that high-speed stirring terminates rear leaving standstill after 30 minutes, 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;
Needs return
step S2finely tune oleic acid and this concrete mol ratio mixing amyl-based polyol in lab scale test next time; For the mixing amyl-based polyol of the tetramethylolmethane prepared according to such mass percent and dipentaerythritol, the mol ratio of itself and oleic acid is adjusted to 0.95:4.173;
Drop into 0.835mol(235.73g) oleic acid, then correspondingly drop into 0.19mol(27.806g) mixing amyl-based polyol, the rapid S3 of all the other course synchronization of lab scale synthesis, to the product sampling synthesized, recording its acid number is 0.8mgKOH/g, meet the requirements, therefore directly step 9 is entered, and then measure the separation property of synthesis liquid and water, the result recorded is that high-speed stirring terminates rear leaving standstill after 15 minutes, between oil phase and aqueous phase, the volume of emulsion layer is 2mL, represent that the separation property of this synthesis liquid and water can accept, writing down for the mixing amyl-based polyol of this batch of preparation and the suitable mol ratio of oleic acid raw material is 0.95:4.173, 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: adopt in above-mentioned steps obtain for the mixing amyl-based polyol of present lot and the suitable mol ratio 0.95:4.173 of oleic acid, at 5M
3reactor in, drop into the mixing amyl-based polyol of 2824.7kg oleic acid and 333.195kg preparation, the total mass of raw material in still is made to reach 3157.895kg, open and stir, during beginning, rotating speed maintains 10rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 DEG C, add oleic acid and mixing amyl-based polyol always to feed intake the 1%(31.579kg of quality) tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 50L/min, the rotating speed of stirring is brought up to 100rpm, timing from now, material in still is warmed up to 245 ± 5 DEG C, heating 23h, 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 0.87mgKOH/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 oleic acid and always feed intake the 0.6%(18.95kg of quality in reactor) particle diameter is the attapulgite of 75 μm, 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 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 15 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 5
A preparation method for amyl-based polyol oleic acid ester, adopt neopentyl glycol and oleic acid to be raw material, concrete steps are as follows:
step S1:have 2 hydroxyls in a neopentyl glycol molecule, then oleic acid and the theoretical molar of neopentyl glycol are than being 2:1;
step S2:set the mol ratio of 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 oleic acid are 1.03:2;
step S3:in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 1mol(282.47g) oleic acid, then correspondingly drop into 0.515mol(53.637g) 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 oleic acid and neopentyl glycol always to feed intake the 1%(3.36g of quality 336.274g) 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 160 ± 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 2.3mgKOH/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:the reacted acid number of sampling and measuring, it is 1.6mgKOH/g that sampling detects acid number; Because its acid number does not still reach≤the level of 1.5mgKOH/g, therefore continue to enter 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, if this absolute value > is 0.5mgKOH/g, then return step S5; If this absolute value≤0.5mgKOH/g, then enter next step;
In the present embodiment, acid number due in the acid number 1.6mgKOH/g(step S6 of one-time detection after sample) and the absolute value of difference of front one-time detection acid number 2.3mgKOH/g result more than 0.5mgKOH/g, therefore step S5 is returned, carry out reaction 1h again, and then sampling detects acid number, the acid number of sample is 1.3mgKOH/g, and the absolute value of difference of the acid number result that adjacent two sub-samplings detect is no more than 0.5mgKOH/g, subsequently enters step S8;
step S8:due to third time, the acid number of sample reaches≤the level of 1.5mgKOH/g, subsequently enters step S9;
step S9:in three-necked bottle, add neopentyl glycol and oleic acid always to feed intake the 2%(6.72g 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/T 7305-2003 specifies, 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 0mL, 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 oleic acid, is 1.03:2, 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 oleic acid again;
step S11:large-scale production;
Be specially:
Step S111: the suitable mol ratio 1.03:2 adopting the neopentyl glycol for present lot and the oleic acid obtained in above-mentioned steps, at 5M
3reactor in, drop into 2824.7kg oleic acid and 197.767kg neopentyl glycol, the total mass of raw material in still is made to reach 3022.467kg, 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 oleic acid and neopentyl glycol always to feed intake the 0.8%(24.18kg of quality) tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 50L/min, the rotating speed of stirring is brought up to 180rpm, timing from now, material in still is warmed up to 160 ± 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 1.35mgKOH/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 oleic acid and always feed intake the 0.6%(18.13kg 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 five 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 kind ofthe preparation technology of amyl-based polyol oleic acid ester, it is characterized in that: described preparation technology is amyl-based polyol and oleic acid for purchasing the present lot come, first determine the theoretical molar proportioning of carrying out with oleic acid completely needed for esterification according to amyl-based polyol used or the quantity that mixes hydroxyl in new penta season polyol molecule, or according to former for amyl-based polyol or mix new penta season polyvalent alcohol and the experience mol ratio that formed of oleic acid select the mol ratio of current lab scale; 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/T 7305-2003, 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 oleic acid ester according to claim 1, is characterized in that described concrete steps are as follows:
step S1:for amyl-based polyol and the oleic acid of purchasing the present lot come, the quantity calculating amyl-based polyol used or mix hydroxyl in new penta season polyol molecule determines the theoretical molar proportioning of carrying out with oleic acid completely needed for esterification, according to former for amyl-based polyol or mix new penta season polyvalent alcohol and oleic acid formed experience mol ratio carry out lab scale test, if the quantity of amounting to hydroxyl of the hydroxyl value of amyl-based polyol used or mixing amyl-based polyol is n, then oleic acid and amyl-based polyol or mix amyl-based polyol theoretical molar than being n,
step S2:the mol ratio setting amyl-based polyol and oleic acid in this lab scale is 0.9:n ~ 1.2:n;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into the oleic acid of 0.4 ~ 1.2mol, then according to the mol ratio that sets in step S2 drop into respective amount amyl-based polyol or mix new penta season polyvalent alcohol, 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 oleic acid and amyl-based polyol used or mix new penta season polyvalent alcohol 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 and again adjust in the scope of 0.9:n ~ 1.2:n and set once the concrete mol ratio that amyl-based polyol and oleic acid lab scale test; If acid number≤1.5mgKOH/g, then enter next step;
step S9:in three-necked bottle, add amyl-based polyol used or mix new penta season polyvalent alcohol and oleic 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/T 7305-2003 specifies, 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 oleic 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 measurement result display synthesis liquid and the separation property of water bad, then return step S2, in the test of fine setting lab scale oleic acid and amyl-based polyol or mix new penta season polyvalent alcohol concrete mol ratio, then carry out lab scale next time;
step S11:large-scale production.
3. the preparation technology of amyl-based polyol oleic acid ester according to claim 1 and 2, is characterized in that the step of described large-scale production is specially:
step S111:the present lot obtained with lab scale amyl-based polyol used or mix new penta season polyvalent alcohol and the mol ratio of oleic acid, at 5M
3reactor in, drop into oleic acid and amyl-based polyol or mix new penta season polyvalent alcohol, the total mass of raw material in still is made to be in the scope of 1000 ~ 4000kg, 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 oleic acid and amyl-based polyol used or mix new penta season polyvalent alcohol 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:in reactor, add amyl-based polyol used or mix new penta season polyvalent alcohol and oleic 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 oleic acid ester according to claim 1 and 2, is characterized in that: described amyl-based polyol or mix new penta season polyvalent alcohol be one or more in TriMethylolPropane(TMP), ditrimethylolpropane, tetramethylolmethane, dipentaerythritol, neopentyl glycol.
5. the preparation technology of amyl-based polyol oleic acid ester according to claim 3, is characterized in that: described amyl-based polyol or mix new penta season polyvalent alcohol be one or more in TriMethylolPropane(TMP), ditrimethylolpropane, tetramethylolmethane, dipentaerythritol, neopentyl glycol.
6. the preparation technology of amyl-based polyol oleic 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 oleic 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 oleic 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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| CN108689841A (en) * | 2018-07-06 | 2018-10-23 | 湖南理工学院 | A method of preparing high-quality pentaerythritol oleate |
| CN108707074A (en) * | 2018-07-06 | 2018-10-26 | 湖南理工学院 | A method of preparing low acid value tricarboxymethyl propane oleate |
| CN112625772A (en) * | 2020-11-27 | 2021-04-09 | 山东益丰生化环保股份有限公司 | Diesel antiwear agent and preparation method thereof |
| CN114717698A (en) * | 2022-05-06 | 2022-07-08 | 张云云 | Production method of high-bulkiness textured yarn |
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| CN106748759A (en) * | 2015-11-24 | 2017-05-31 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of bio-based pentaerythritol fatty ester |
| CN108689841A (en) * | 2018-07-06 | 2018-10-23 | 湖南理工学院 | A method of preparing high-quality pentaerythritol oleate |
| CN108707074A (en) * | 2018-07-06 | 2018-10-26 | 湖南理工学院 | A method of preparing low acid value tricarboxymethyl propane oleate |
| CN112625772A (en) * | 2020-11-27 | 2021-04-09 | 山东益丰生化环保股份有限公司 | Diesel antiwear agent and preparation method thereof |
| CN114717698A (en) * | 2022-05-06 | 2022-07-08 | 张云云 | Production method of high-bulkiness textured yarn |
| CN115353919A (en) * | 2022-09-07 | 2022-11-18 | 新乡市瑞丰新材料股份有限公司 | Preparation method of flame-retardant base oil polyol oleate for hydraulic oil |
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Application publication date: 20150930 |