CN105037144A - 2-ethyl hexanoic acid ditrimethylolpropane ester and production method thereof - Google Patents
2-ethyl hexanoic acid ditrimethylolpropane ester and production method thereof Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- -1 2-ethyl hexanoic acid ditrimethylolpropane ester Chemical class 0.000 title abstract description 28
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims abstract description 81
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims abstract description 80
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 238000005886 esterification reaction Methods 0.000 claims abstract description 19
- 238000011031 large-scale manufacturing process Methods 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000012360 testing method Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims description 55
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000000047 product Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 29
- 150000002148 esters Chemical class 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 19
- 238000003786 synthesis reaction Methods 0.000 claims description 19
- 230000032050 esterification Effects 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000005070 sampling Methods 0.000 claims description 13
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 13
- 235000021050 feed intake Nutrition 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000009775 high-speed stirring Methods 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 238000012952 Resampling Methods 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 22
- 229930195729 fatty acid Natural products 0.000 description 22
- 239000000194 fatty acid Substances 0.000 description 22
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 16
- 229920005862 polyol Polymers 0.000 description 16
- 230000008569 process Effects 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000012675 alcoholic extract Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 206010019233 Headaches Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 230000001404 mediated effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses 2-ethyl hexanoic acid ditrimethylolpropane ester and a preparation method thereof, and the molecular formula of the 2-ethyl hexanoic acid ditrimethylolpropane ester is C44H82O9Having the structural formula:
Description
Technical field
The invention belongs to organic chemistry raw material and manufacture field, disclose the 2 ethyl hexanoic acid ditrimethylolpropane ester that a kind of ditrimethylolpropane and 2 ethyl hexanoic acid are obtained by esterification, also relate to a kind of preparation technology of 2 ethyl hexanoic acid ditrimethylolpropane 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.
Although people have synthesized numerous amyl-based polyol fatty acid esters, but it is little to the report synthesizing 2 ethyl hexanoic acid ditrimethylolpropane ester to carry out esterification with ditrimethylolpropane (also known as two-TriMethylolPropane(TMP), Di-trimethylolpropane) and 2 ethyl hexanoic acid under the effect of an acidic catalyst.
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, can be applied to the occasion needing high viscosity lubricants.
2 ethyl hexanoic acid is a kind of common, saturated fatty acid of being easy to get, and because it is branched acid, so not only the zero pour of itself is lower, and it is also lower with the pour point of its amyl-based polyol fatty acid ester synthesized, make product not only can be high temperature resistant, and can be low temperature resistant, be in liquid wider range.Synthesize the synthetic ester obtained with saturated fatty acid, its oxidation resistant stability also can be relatively good.
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 2 ethyl hexanoic acid ditrimethylolpropane ester.
Summary of the invention
The object of the invention is to disclose the 2 ethyl hexanoic acid ditrimethylolpropane ester that a kind of ditrimethylolpropane and 2 ethyl hexanoic 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 2 ethyl hexanoic acid ditrimethylolpropane ester economically and reasonably.
For solving the problems of the technologies described above, technical scheme of the present invention is: 2 ethyl hexanoic acid ditrimethylolpropane ester, and its innovative point is: its molecular formula is C
44h
82o
9, there is structural formula as follows:
A preparation method for above-mentioned 2 ethyl hexanoic acid ditrimethylolpropane ester, its innovative point is: the corresponding reaction equation of described preparation technology is as follows:
For ditrimethylolpropane and the 2 ethyl hexanoic acid of purchasing the present lot come, first determine the theoretical molar proportioning of carrying out with 2 ethyl hexanoic 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 2 ethyl hexanoic 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 2 ethyl hexanoic acid of purchasing the present lot come, the quantity calculating hydroxyl in ditrimethylolpropane molecule used determines the theoretical molar proportioning of carrying out with 2 ethyl hexanoic acid completely needed for esterification, or the mol ratio of current lab scale was selected according to the former experience mol ratio formed for ditrimethylolpropane and 2 ethyl hexanoic acid, the hydroxyl value of a part ditrimethylolpropane is 4, so 2 ethyl hexanoic acid is 4 with the theoretical molar ratio of ditrimethylolpropane;
step S2:the mol ratio setting ditrimethylolpropane and 2 ethyl hexanoic acid in this lab scale is 0.9:4 ~ 1.3:4;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into the 2 ethyl hexanoic acid of 0.8 ~ 2.0mol, then the ditrimethylolpropane meeting the respective batch that mol ratio requires in step S2 is 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 2 ethyl hexanoic 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 10 ~ 24h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 5 ~ 20 minutes, sampling,
step S4:the acid number of working sample, if the acid number≤1.5mgKOH/g of sample, then leaps to step S9; If the acid number > 1.5mgKOH/g of sample, then enter next step;
step S5:continue reaction 0.5 ~ 2h;
step S6:the reacted acid number of sampling and measuring, if acid number≤1.5mgKOH/g, then jumps to step S9; If acid number > is 1.5mgKOH/g, then enter next step;
step S7:judge the absolute value of acid number and the adjacent last hypo acid value difference measured in above-mentioned steps S6, if this absolute value > is 0.5mgKOH/g, then return step S5; If this absolute value≤0.5mgKOH/g, then enter next step;
step S8:if acid number is > 1.5mgKOH/g still, then terminate this lab scale, and return step S2, again adjust in the scope of 0.9:4 ~ 1.3:4 and set once the concrete mol ratio of 2 ethyl hexanoic acid and ditrimethylolpropane in lab scale test; If acid number≤1.5mgKOH/g, then enter next step;
step S9:add in three-necked bottle ditrimethylolpropane and 2 ethyl hexanoic 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 2 ethyl hexanoic acid, using the mol ratio of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot; If the separation property of measurement result display synthesis liquid and water is bad, then return step S2
,in the test of fine setting lab scale, the concrete mol ratio of 2 ethyl hexanoic acid and ditrimethylolpropane, then carries out lab scale next time;
step S11:large-scale production;
Further, the step of described large-scale production is specially:
step S111:the ditrimethylolpropane for present lot obtained with lab scale and the suitable mol ratio of 2 ethyl hexanoic acid, at 1M
3reactor in, drop into 2 ethyl hexanoic 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 2 ethyl hexanoic 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 140 ~ 200 DEG C, heating 10 ~ 24h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 5 ~ 20 minutes, sampling, the acid number of working sample,
step S112:if the acid number of sample can not reach≤level of 1.5mgKOH/g, then carry out reaction 0.5 ~ 2h, resampling detects acid number, until the acid number≤1.5mgKOH/g of sample;
step S113:add in reactor ditrimethylolpropane and 2 ethyl hexanoic 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) 2 ethyl hexanoic acid ditrimethylolpropane ester of the present invention, for the lurid thick liquid of one, owing to being adopt ditrimethylolpropane and 2 ethyl hexanoic 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 2 ethyl hexanoic acid ditrimethylolpropane ester, and its molecular formula is C
44h
82o
9, this 2 ethyl hexanoic acid ditrimethylolpropane acid esters 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 2 ethyl hexanoic acid ditrimethylolpropane ester, its molecular formula is C
44h
82o
9, there is structural formula as follows:
The corresponding reaction equation of preparation method also disclosing a kind of above-mentioned 2 ethyl hexanoic acid ditrimethylolpropane ester is as follows:
For ditrimethylolpropane and the 2 ethyl hexanoic acid of purchasing the present lot come, first determine the theoretical molar proportioning of carrying out with 2 ethyl hexanoic 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 2 ethyl hexanoic 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 2 ethyl hexanoic acid of purchasing the present lot come, have 4 hydroxyls in a ditrimethylolpropane molecule, then 2 ethyl hexanoic acid is 4 with the theoretical molar ratio of ditrimethylolpropane;
step S2:set the mol ratio of 2 ethyl hexanoic acid and ditrimethylolpropane in this lab scale, the theoretical molar proportioning 1:4 of both employings carries out lab scale test;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 1.2mol(173.052g) 2 ethyl hexanoic acid, then correspondingly drop into 0.3mol(75.099g) 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 2 ethyl hexanoic acid and ditrimethylolpropane always to feed intake the 1%(2.35g of quality 235.07g) tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 30mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 190 ± 5 DEG C, heating 21h, 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 2.8mgKOH/g, because the acid number of sample does not reach≤the level of 1.5mgKOH/g, enters next step;
step S5:continue reaction 1h;
step S6:the reacted acid number of sampling and measuring is 2.4mgKOH/g, due to acid number still > 1.5mgKOH/g, enters 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, due to this absolute value≤0.5mgKOH/g, enter next step;
step S8:due to acid number still > 1.5mgKOH/g, terminate this lab scale, and return step S2, the mol ratio of ditrimethylolpropane and 2 ethyl hexanoic acid is adjusted to 1.04:4, drop into 1.2mol(173.052g) 2 ethyl hexanoic acid, then correspondingly drop into 0.312mol(78.103g) ditrimethylolpropane, all the other process repeats step S3, reaction 21h, sampling, the sample acid number recorded is 1.2mgKOH/g, has reached the requirement of acid number≤1.5mgKOH/g;
step S9:in three-necked bottle, adding ditrimethylolpropane and 2 ethyl hexanoic acid always to feed intake the 1%(2.51g of quality) particle diameter is the gac of 75 μm, continue heated and stirred 1h, then heating is stopped, when being cooled to 60 DEG C in lab scale sample, be carry out suction filtration in the Büchner funnel of the diatomite of 75 μm and middling speed quantitative paper being covered with particle diameter while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T7305-2003 specify, measure the separation property of synthesis liquid and water, the result recorded is when leaving standstill ten minutes after high-speed stirring terminates, namely the emulsion layer mediated is can't see between oil phase and aqueous phase, namely the volume of emulsion layer is 0mL, 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 2 ethyl hexanoic acid again; Terminate this lab scale, write down this batch of ditrimethylolpropane used and the suitable mol ratio 1.04:4 of 2 ethyl hexanoic acid;
step S11:large-scale production;
Be specially:
Step S111: the suitable mol ratio 1.04:4 adopting the ditrimethylolpropane for present lot and the 2 ethyl hexanoic acid obtained in above-mentioned steps, at 1M
3reactor in, drop into 346.104kg2-thylhexoic acid and 156.206kg ditrimethylolpropane, the total mass of raw material in still is made to reach 502.31kg, 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 2 ethyl hexanoic acid and ditrimethylolpropane always to feed intake the 1.0%(5.02kg 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 190 ± 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, the acid number of working sample, for 0.95mgKOH/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 2 ethyl hexanoic acid and always feed intake the 0.5%(2.51kg of quality in reactor) particle diameter is the gac of 75 μm, 0.2%(1.00kg) particle diameter is the diatomite of 75 μm, continue heated and stirred 1.5h, then heating is stopped, when being cooled to 60 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, order number is adopted to be 270 object filter screens, carry out circulation press filtration, press filtration material out turns back in reactor, after circulation press filtration carries out five 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 2 ethyl hexanoic 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 2 ethyl hexanoic acid ditrimethylolpropane ester.
Getting the sample of the 2 ethyl hexanoic acid ditrimethylolpropane ester product that above-described embodiment obtains, be placed in reagent bottle, observe under natural light, is lurid thick liquid.Detect above-mentioned sample, recording its kinematic viscosity 40 DEG C time is 158.57mm
2/ s, kinematic viscosity when 100 DEG C is 12.79mm
2/ s, pour point is-17 DEG C, and flash-point is 258 DEG C.
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 2 ethyl hexanoic acid ditrimethylolpropane ester, is characterized in that: its molecular formula is C
44h
82o
9, there is structural formula as follows:
.
2. a preparation method for 2 ethyl hexanoic acid ditrimethylolpropane ester according to claim 1, is characterized in that: the corresponding reaction equation of described preparation technology is as follows:
For ditrimethylolpropane and the 2 ethyl hexanoic acid of purchasing the present lot come, first determine the theoretical molar proportioning of carrying out with 2 ethyl hexanoic 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 2 ethyl hexanoic 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 method for production 2 ethyl hexanoic acid ditrimethylolpropane ester according to claim 2, is characterized in that described concrete steps are as follows:
step S1: for ditrimethylolpropane and the 2 ethyl hexanoic acid of purchasing the present lot come, the quantity calculating hydroxyl in ditrimethylolpropane molecule used determines the theoretical molar proportioning of carrying out with 2 ethyl hexanoic acid completely needed for esterification, or the mol ratio of current lab scale was selected according to the former experience mol ratio formed for ditrimethylolpropane and 2 ethyl hexanoic acid, the hydroxyl value of a part ditrimethylolpropane is 4, so 2 ethyl hexanoic acid is 4 with the theoretical molar ratio of ditrimethylolpropane;
step S2:the mol ratio setting ditrimethylolpropane and 2 ethyl hexanoic acid in this lab scale is 0.9:4 ~ 1.3:4;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into the 2 ethyl hexanoic acid of 0.8 ~ 2.0mol, then the ditrimethylolpropane meeting the respective batch that mol ratio requires in step S2 is 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 2 ethyl hexanoic 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 10 ~ 24h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 5 ~ 20 minutes, sampling,
step S4:the acid number of working sample, if the acid number≤1.5mgKOH/g of sample, then leaps to step S9; If the acid number > 1.5mgKOH/g of sample, then enter next step;
step S5:continue reaction 0.5 ~ 2h;
step S6:the reacted acid number of sampling and measuring, if acid number≤1.5mgKOH/g, then jumps to step S9; If acid number > is 1.5mgKOH/g, then enter next step;
step S7:judge the absolute value of acid number and the adjacent last hypo acid value difference measured in above-mentioned steps S6, if this absolute value > is 0.5mgKOH/g, then return step S5; If this absolute value≤0.5mgKOH/g, then enter next step;
step S8:if acid number is > 1.5mgKOH/g still, then terminate this lab scale, and return step S2, again adjust in the scope of 0.9:4 ~ 1.3:4 and set once the concrete mol ratio of 2 ethyl hexanoic acid and ditrimethylolpropane in lab scale test; If acid number≤1.5mgKOH/g, then enter next step;
step S9:add in three-necked bottle ditrimethylolpropane and 2 ethyl hexanoic 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 2 ethyl hexanoic acid, using the mol ratio of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot; If the separation property of measurement result display synthesis liquid and water is bad, then return step S2
,in the test of fine setting lab scale, the concrete mol ratio of 2 ethyl hexanoic acid and ditrimethylolpropane, then carries out lab scale next time;
step S11:large-scale production.
4. the method for production 2 ethyl hexanoic acid ditrimethylolpropane ester according to claim 3, is characterized in that the step of described large-scale production is specially:
step S111:the ditrimethylolpropane for present lot obtained with lab scale and the suitable mol ratio of 2 ethyl hexanoic acid, at 1M
3reactor in, drop into 2 ethyl hexanoic 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 2 ethyl hexanoic 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 140 ~ 200 DEG C, heating 10 ~ 24h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 5 ~ 20 minutes, sampling, the acid number of working sample,
step S112:if the acid number of sample can not reach≤level of 1.5mgKOH/g, then carry out reaction 0.5 ~ 2h, resampling detects acid number, until the acid number≤1.5mgKOH/g of sample;
step S113:add in reactor ditrimethylolpropane and 2 ethyl hexanoic 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.
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