CN105037146A - Di-trimethylolpropane laurate and preparation method thereof - Google Patents
Di-trimethylolpropane laurate and preparation method thereof Download PDFInfo
- Publication number
- CN105037146A CN105037146A CN201510370842.0A CN201510370842A CN105037146A CN 105037146 A CN105037146 A CN 105037146A CN 201510370842 A CN201510370842 A CN 201510370842A CN 105037146 A CN105037146 A CN 105037146A
- Authority
- CN
- China
- Prior art keywords
- ditrimethylolpropane
- lauric acid
- lab scale
- acid
- acid number
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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 discloses a di-trimethylolpropane laurate and a preparation method thereof. The molecular formula of the di-trimethylolpropane laurate is C60H114O9, and the structural formula of the di-trimethylolpropane laurate is shown in the description. The preparation method comprises the steps that for purchased di-trimethylolpropane and lauric acid of a current batch, determining a theoretic molar ratio needed for complete esterification reaction with the lauric acid according to the quantity of hydroxyl groups in molecules of the used di-trimethylolpropane, or performing pilot tests for a plurality of times according to an experience molar ratio formed previously for the di-trimethylolpropane and the lauric acid, after a sample of the pilot test of this time meets the conditions, ending the test, and producing by taking the raw material batch and raw material ratio of the last pilot test as the raw material ratio of large scale production. The di-trimethylolpropane laurate and the preparation method have the advantage that the raw materials can be fully utilized by a preparation process of the di-trimethylolpropane laurate, and the product post-treatment trouble is reduced.
Description
Technical field
The invention belongs to organic chemistry raw material and manufacture field thereof, disclose the ditrimethylolpropane laurate that a kind of ditrimethylolpropane and lauric acid are obtained by esterification, also relate to a kind of preparation technology of ditrimethylolpropane laurate.
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 easily degrades in the environment, can be used as the lubricant in the synthetic base oil of lubricating oil and metal rolled process, so be more and more subject to people's attention.
Although people have synthesized numerous amyl-based polyol fatty acid esters, but under the effect of an acidic catalyst, carry out esterification with ditrimethylolpropane (also known as two-TriMethylolPropane(TMP), Di-trimethylolpropane) and lauric acid to carry out synthesizing bis (trihydroxy methyl propane) laurate and have not been reported.
Ditrimethylolpropane is a kind of compound having four alcoholic extract hydroxyl groups, have neopentyl structure.It is unlike tetramethylolmethane, and its alcoholic extract hydroxyl group is not connected on a carbon atom, forms the molecule of stereo structure, but is dispersed on two carbon atoms, thus can form the molecule of flush type after being unlikely to carry out esterification with acid.Because the molecular weight of ditrimethylolpropane is larger, so although there is higher viscosity with the amyl-based polyol fatty acid ester that ditrimethylolpropane synthesizes, but the steric effect in molecule is not clearly, and viscosity index is high, one of can yet be regarded as well lubricant, can be applied to the occasion needing high viscosity lubricants.
Lauric acid is a kind of common, saturated fatty acid of being easy to get.Synthesize the synthetic ester obtained with saturated fatty acid, its oxidation resistant stability also can be relatively good.The main component of common cocinic acid is also lauric acid, thus can synthesize by amyl-based polyol and lauric acid the ester obtained to compare and synthesize with corresponding amyl-based polyol and cocinic acid the ester obtained, for downstream user provide selection face wider, the amyl-based polyol fatty acid ester product of economical rationality.
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 ditrimethylolpropane laurate.
Summary of the invention
The object of the invention is to disclose the ditrimethylolpropane laurate that a kind of ditrimethylolpropane and lauric acid are obtained by esterification, also providing a kind of adopts tosic acid to be catalyzer, in conjunction with adjusting, determining rational proportioning between different batches raw material by lab scale, the preparation technology of ditrimethylolpropane laurate economically and reasonably.
For solving the problems of the technologies described above, technical scheme of the present invention is: ditrimethylolpropane laurate, and its innovative point is: its molecular formula is C
60h
114o
9, there is structural formula as follows:
A preparation method for above-mentioned ditrimethylolpropane laurate, its innovative point is: the corresponding reaction equation of described preparation technology is as follows:
。
For ditrimethylolpropane and the lauric acid of purchasing the present lot come, first determine the theoretical molar proportioning of carrying out with lauric acid completely needed for esterification according to the quantity of hydroxyl in ditrimethylolpropane molecule used, or select the mol ratio of current lab scale according to the former experience mol ratio formed for ditrimethylolpropane and lauric 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 gac, 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 diatomite and 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 ditrimethylolpropane and the lauric acid of purchasing the present lot come, the quantity calculating hydroxyl in ditrimethylolpropane molecule used determines the theoretical molar proportioning of carrying out with lauric acid completely needed for esterification, or according to the former experience mol ratio formed for ditrimethylolpropane and lauric acid, the hydroxyl value of a part ditrimethylolpropane is 4, so lauric acid is 4 with the theoretical molar ratio of ditrimethylolpropane;
step S2:setting ditrimethylolpropane and lauric mol ratio in this lab scale is 0.9:4 ~ 1.2:4;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into the lauric acid of 0.4 ~ 1.6mol, then the ditrimethylolpropane of 0.09 ~ 0.48mol is correspondingly dropped into, 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 lauric acid and ditrimethylolpropane 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 140 ~ 200 DEG C, heating 5 ~ 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 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 0.9:4 ~ 1.2:4 and set once the concrete mol ratio that in lab scale test, ditrimethylolpropane and lauric acid lab scale are tested; If acid number≤1.5mgKOH/g, then enter next step;
step S9:add in three-necked bottle ditrimethylolpropane and lauric acid always feed intake quality 0.5 ~ 2% gac, 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 diatomite and 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 ditrimethylolpropane and the suitable mol ratio of lauric acid, 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; If the separation property of measurement result display synthesis liquid and water is bad, then return step S2, finely tune the concrete mol ratio of lauric acid and ditrimethylolpropane in lab scale test 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 ditrimethylolpropane used and lauric mol ratio, at 1M
3reactor in, drop into lauric acid and ditrimethylolpropane, the total mass of raw material in still is made to be in the scope of 200 ~ 700kg, 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 lauric acid and ditrimethylolpropane 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 ~ 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 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 ditrimethylolpropane and lauric acid always feed intake quality 0.1 ~ 2% gac, the diatomite of 0.1 ~ 1%, 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, carry out circulation press filtration, press filtration material out turns back in reactor, till the color that circulation press filtration proceeds to the product returned has not seen that the activated carbon granule of diatomite particle and black is residual, product after press filtration being decoloured pours in pail pack.
The invention has the advantages that:
(1) ditrimethylolpropane laurate of the present invention, for the lurid thick liquid of one, owing to being adopt ditrimethylolpropane and lauric acid through esterification, and both mol ratio are close to the such theoretical molar proportioning of 1:4, infer so corresponding amyl-based polyol fatty acid ester can be synthesized according to the amyl-based polyol adopting in the industry other similar and similar fatty acid ester, the main component of such product should be ditrimethylolpropane laurate, and its molecular formula is C
60h
114o
9, this ditrimethylolpropane laurate can be used as degradable lubricant base and lubricant.
(2) 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.
(3) 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.
(4) 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.
(5) 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.
(6) gac and diatomite is adopted to combine as adsorption decolouriser, can the rational thickness of filter bed of heap, under the prerequisite of quality of guaranteeing to decolour, reduce the consumption of price greater activity charcoal, effectively reduce the cost of decolorization.
Embodiment
The invention discloses a kind of ditrimethylolpropane laurate, its molecular formula is C
60h
114o
9, there is structural formula as follows:
The corresponding reaction equation of preparation method also disclosing a kind of above-mentioned ditrimethylolpropane laurate is as follows:
For ditrimethylolpropane and the lauric acid of purchasing the present lot come, first determine the theoretical molar proportioning of carrying out with lauric acid completely needed for esterification according to the quantity of hydroxyl in ditrimethylolpropane molecule used, or select the mol ratio of current lab scale to carry out lab scale test according to the former experience mol ratio formed for ditrimethylolpropane and lauric 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 gac, 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 diatomite and 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.
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
step S1: for ditrimethylolpropane and the lauric acid of purchasing the present lot come, have 4 hydroxyls in a ditrimethylolpropane molecule, then lauric acid is 4 with the theoretical molar ratio of ditrimethylolpropane;
step S2:set ditrimethylolpropane and lauric mol ratio in this lab scale, the theoretical molar proportioning 1:4 both first adopting
;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 0.8mol(160.256g) lauric 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 lauric acid and ditrimethylolpropane always to feed intake the 1%(2.1g of quality 210.322g) 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 180 ± 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 3.8mgKOH/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 3.5mgKOH/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, this absolute value < 0.5mgKOH/g, illustrating under such proportioning raw materials, the acid number of the product be synthesized can not reach≤level of 1.5mgKOH/g, enter next step;
step S8:due to acid number still > 1.5mgKOH/g, terminate this lab scale, and return step S2, resetting the concrete mol ratio that ditrimethylolpropane and lauric acid lab scale are tested next time is 1.05:4; Drop into 0.8mol(160.256g) lauric acid, then correspondingly drop into 0.21mol(52.569g) ditrimethylolpropane, all the other process repeats step S3, reaction 7h, sampling, the sample acid number recorded is 0.9mgKOH/g, reach the requirement of acid number≤1.5mgKOH/g, enter next step;
step S9:in three-necked bottle, add ditrimethylolpropane and lauric acid always to feed intake the 1%(2.1g of quality) gac, 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 diatomite and middling speed quantitative paper, carry out suction filtration while hot, the product in filter flask is transferred in reagent bottle;
step S10: the method specified according to GB/T7305-2003, measure the separation property of synthesis liquid and water, the result recorded be high-speed stirring terminate rear leave standstill five minutes time, namely the emulsion layer mediated is can't see between oil phase and aqueous phase, namely the volume of emulsion layer is 0mL, represent that the separation property of this synthesis liquid and water is fine, terminate this lab scale, write down this batch of ditrimethylolpropane and the suitable mol ratio of lauric acid, for 1.05:4, 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;
The concrete steps of large-scale production are:
step S111: at 1M
3reactor in, drop into 320.512g lauric acid and 105.139kg ditrimethylolpropane, the total mass of raw material in still is made to reach 425.651kg, 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 lauric acid and ditrimethylolpropane always to feed intake the 1%(4.26kg 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 180 ± 5 DEG C, heating 7.5h, 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 0.92mgKOH/g,
step S112:because the acid number of sample reaches≤the level of 1.5mgKOH/g, so reaction need not be proceeded again;
step S113:in reactor, add ditrimethylolpropane and lauric acid always to feed intake the 0.5%(2.13kg of quality) gac, diatomite 0.2%(0.85kg), 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, carry out circulation press filtration, press filtration material out turns back in reactor, after circulation press filtration carries out eight 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.
Adopt aforesaid method to synthesize in the present embodiment and obtain a kind of lurid thick liquid, owing to being adopt ditrimethylolpropane and lauric acid through esterification, and both mol ratio are close to the such theoretical molar proportioning of 1:4, infer so can synthesize corresponding amyl-based polyol fatty acid ester according to the amyl-based polyol adopting in the industry other similar and similar fatty acid ester, the main component of such product should be ditrimethylolpropane laurate.
Getting the sample of the ditrimethylolpropane laurate product that above-described embodiment obtains, be placed in reagent bottle, observe under natural light, is flaxen thick liquid.Detect above-mentioned sample, recording its kinematic viscosity 40 DEG C time is 59.4mm
2/ s, kinematic viscosity when 100 DEG C is 10.96mm
2/ s, viscosity index is 179, and its pour point is 16 DEG C, and flash-point is 250 DEG C.These data declaration ditrimethylolpropane laurates still be can yet be regarded as a kind of lubricant preferably.
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 (4)
1.
a kind ofditrimethylolpropane laurate, is characterized in that: its molecular formula is C
60h
114o
9, there is structural formula as follows:
.
2. a preparation method for ditrimethylolpropane laurate according to claim 1, is characterized in that: the corresponding reaction equation of described preparation technology is as follows:
For ditrimethylolpropane and the lauric acid of purchasing the present lot come, first determine the theoretical molar proportioning of carrying out with lauric acid completely needed for esterification according to the quantity of hydroxyl in ditrimethylolpropane molecule used, or select the mol ratio of current lab scale according to the former experience mol ratio formed for ditrimethylolpropane and lauric 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 gac, 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 diatomite and 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.
3. the preparation method of ditrimethylolpropane laurate according to claim 2, is characterized in that described concrete steps are as follows:
step S1:for ditrimethylolpropane and the lauric acid of purchasing the present lot come, the quantity calculating hydroxyl in ditrimethylolpropane molecule used determines the theoretical molar proportioning of carrying out with lauric acid completely needed for esterification, or according to the former experience mol ratio formed for ditrimethylolpropane and lauric acid, the hydroxyl value of a part ditrimethylolpropane is 4, so lauric acid is 4 with the theoretical molar ratio of ditrimethylolpropane;
step S2:setting ditrimethylolpropane and lauric mol ratio in this lab scale is 0.9:4 ~ 1.2:4;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into the lauric acid of 0.4 ~ 1.6mol, then the ditrimethylolpropane of 0.09 ~ 0.48mol is correspondingly dropped into, 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 lauric acid and ditrimethylolpropane 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 140 ~ 200 DEG C, heating 5 ~ 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 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 0.9:4 ~ 1.2:4 and set once the concrete mol ratio that in lab scale test, ditrimethylolpropane and lauric acid lab scale are tested; If acid number≤1.5mgKOH/g, then enter next step;
step S9:add in three-necked bottle ditrimethylolpropane and lauric acid always feed intake quality 0.5 ~ 2% gac, 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 diatomite and 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 ditrimethylolpropane and the suitable mol ratio of lauric acid, 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; If the separation property of measurement result display synthesis liquid and water is bad, then return step S2, finely tune the concrete mol ratio of lauric acid and ditrimethylolpropane in lab scale test next time;
step S11:large-scale production.
4. the preparation method of ditrimethylolpropane laurate according to claim 3, is characterized in that the step of described large-scale production is specially:
step S111:the present lot obtained with lab scale ditrimethylolpropane used and lauric mol ratio, at 1M
3reactor in, drop into lauric acid and ditrimethylolpropane, the total mass of raw material in still is made to be in the scope of 200 ~ 700kg, 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 lauric acid and ditrimethylolpropane 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 ~ 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 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 ditrimethylolpropane and lauric acid always feed intake quality 0.1 ~ 2% gac, the diatomite of 0.1 ~ 1%, 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, carry out circulation press filtration, press filtration material out turns back in reactor, till the color that circulation press filtration proceeds to the product returned has not seen that the activated carbon granule of diatomite particle and black is residual, product after press filtration being decoloured pours in pail pack.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510370842.0A CN105037146A (en) | 2015-06-30 | 2015-06-30 | Di-trimethylolpropane laurate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510370842.0A CN105037146A (en) | 2015-06-30 | 2015-06-30 | Di-trimethylolpropane laurate and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105037146A true CN105037146A (en) | 2015-11-11 |
Family
ID=54444194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510370842.0A Pending CN105037146A (en) | 2015-06-30 | 2015-06-30 | Di-trimethylolpropane laurate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105037146A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11752077B2 (en) | 2017-05-30 | 2023-09-12 | The Nisshin Oillio Group, Ltd. | Oily moisturizer and topical skin composition containing same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3673226A (en) * | 1968-04-10 | 1972-06-27 | Ethyl Corp | Synthetic lubricants |
| USH1536H (en) * | 1995-04-11 | 1996-06-04 | The Lubrizol Corporation | Overbased materials in ester media |
| CN102203225A (en) * | 2008-10-27 | 2011-09-28 | 佩什托普特殊化学股份公司 | Low pour point lubricant base stock |
| CN103275812A (en) * | 2013-04-26 | 2013-09-04 | 青岛中科润美润滑材料技术有限公司 | Method for preparing base oil of lubricating oil from waste animal and vegetable oil |
| CN104672085A (en) * | 2014-12-12 | 2015-06-03 | 诺泰生物科技(合肥)有限公司 | Synthesis of trimethylolpropane organic acid ester and application in special oil |
-
2015
- 2015-06-30 CN CN201510370842.0A patent/CN105037146A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3673226A (en) * | 1968-04-10 | 1972-06-27 | Ethyl Corp | Synthetic lubricants |
| USH1536H (en) * | 1995-04-11 | 1996-06-04 | The Lubrizol Corporation | Overbased materials in ester media |
| CN102203225A (en) * | 2008-10-27 | 2011-09-28 | 佩什托普特殊化学股份公司 | Low pour point lubricant base stock |
| CN103275812A (en) * | 2013-04-26 | 2013-09-04 | 青岛中科润美润滑材料技术有限公司 | Method for preparing base oil of lubricating oil from waste animal and vegetable oil |
| CN104672085A (en) * | 2014-12-12 | 2015-06-03 | 诺泰生物科技(合肥)有限公司 | Synthesis of trimethylolpropane organic acid ester and application in special oil |
Non-Patent Citations (1)
| Title |
|---|
| 宋岩等: "双三羟甲基丙烷正辛酸酯的合成", 《应用化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11752077B2 (en) | 2017-05-30 | 2023-09-12 | The Nisshin Oillio Group, Ltd. | Oily moisturizer and topical skin composition containing same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104945247A (en) | Preparation process of neopentyl polyol oleate | |
| CN104496819B (en) | A kind of method that environment-friendly plasticizer is prepared in waste resource recycling | |
| ITBO950017A1 (en) | PROCESS FOR THE PREPARATION OF BIS (2-HYDROXYETHYL) TERAPHTHALATE | |
| CN108047036A (en) | A kind of synthetic method of Ergol | |
| TWI398430B (en) | Trimethylolpropane color improvement | |
| CN101130524B (en) | Method for producing saccharin | |
| CN103450018B (en) | Preparation method of ethyl acetoacetate | |
| CN105130800A (en) | Preparation technology for mixed-acid neo-pentyl polyol ester | |
| CN101348451A (en) | Preparation of medicinal D,L-2-hydroxy-4-methylthio calcium butyrate | |
| CN105037146A (en) | Di-trimethylolpropane laurate and preparation method thereof | |
| CN101157615A (en) | Method for producing plasticizer phthalic acid dinonyl | |
| CN101774897A (en) | Method for preparing vanillin and analogue thereof | |
| CN101786949B (en) | Method for preparing 4-ethyl octanoic acid through microwave heating | |
| TWI529159B (en) | Method for continuously preparing carboxylic acid esters | |
| CN105037144A (en) | 2-ethylexanoic acid bi-trimethylolpropane ester and production method thereof | |
| CN101792387A (en) | Preparation method of 2,3,4-trimethoxybenzoic acid | |
| CN104910010A (en) | Method for producing di-trimethylolpropane heptylate | |
| CN105130799A (en) | Method for producing di(trimethylolpropane) trioleate | |
| CN105017014A (en) | Preparation method of neo-pentyl polyhydric alcohol heptanoic acid ester | |
| CN105001082A (en) | Preparation technology of neopentyl polyol laurate | |
| CN101659620B (en) | Green synthetic method of 2,5-diaminotoluene | |
| CN109734572A (en) | Zinc acetylacetonate and preparation method thereof | |
| CN104926654A (en) | 2-ethylhexoic acid neopentyl polyol ester preparation technology | |
| CN104829457B (en) | Method for Bronsted-Lewis acidic ionic liquid catalyzed synthesis of di(glycol monoalkyl ether)terephthalate | |
| CN105037145A (en) | Process for preparing neo-polyhydric alcohol aliphatic ester by adopting prepared acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151111 |