CN105001082A - Preparation technology of neopentyl polyol laurate - Google Patents
Preparation technology of neopentyl polyol laurate Download PDFInfo
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- CN105001082A CN105001082A CN201510369899.9A CN201510369899A CN105001082A CN 105001082 A CN105001082 A CN 105001082A CN 201510369899 A CN201510369899 A CN 201510369899A CN 105001082 A CN105001082 A CN 105001082A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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Abstract
The invention relates to a preparation technology of neopentyl polyol laurate. The preparation technology comprises 1, determining a theoretical mole ratio of neopentyl polyol to lauric acid as monocarboxylic acid for a complete esterification reaction according to the amount of hydroxyl in the neopentyl polyol molecule, wherein different batches of the lauric acid and the neopentyl polyol are purchased, or 2, carrying out several small tests according to the experiential mole ratio of neopentyl polyol to lauric acid, when the small test sample has an acid value less than or equal to 1.5mg KOH/g and separation properties of the synthetic fluid and water are good, stopping the test, and utilizing raw material batch and a raw material ratio of the last small test as a large scale production raw material ratio for production. The corresponding neopentyl polyol laurate preparation technology fully utilizes raw materials and reduces product aftertreatment trouble.
Description
Technical field
The invention belongs to organic chemistry raw material and manufacture field, particularly a kind of preparation technology of amyl-based polyol 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.
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.In fact, the catalyzer of traditional esterification, as the vitriol oil, tosic acid, thionamic acid and methylsulphonic acid etc., in the carrying out of catalytic esterification, still have very large advantage, speed of response is fast, and esterification is complete.If with tosic acid as catalyzer, it also has a benefit, and the fusing point being exactly it is about 106 DEG C, after reaction end product cools down, its can separate out from product, thus can be filtered in filtration procedure, realizes being separated of catalyzer and product.
Because the source of raw material is different, production technique is also not quite similar, the index such as purity, foreign matter content of different batches raw material also exists trickle fluctuation, so qualified amyl-based polyol fatty acid ester will be produced, also need the feature for different batches raw material to carry out lab scale to grope, the proportioning of Reasonable adjustment raw material.
For the quality fluctuation of raw material between the deficiency of existing production amyl-based polyol fatty acid ester Product Process and different batches, be necessary the harmony considered production control cost and take into account quality product, adopt the tosic acid be easy to get as catalyzer, in conjunction with determining rational proportioning between different batches raw material by lab scale, come economical, reasonably produce amyl-based polyol laurate.
Summary of the invention
The technical problem to be solved in the present invention is to provide and a kind of adopts tosic acid to be catalyzer, economic and preparation technology that is reasonably amyl-based polyol laurate.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of preparation technology of amyl-based polyol laurate, and its innovative point is: for amyl-based polyol and the lauric acid of purchasing the present lot come,
First determine that the monocarboxylic acid such with lauric acid carries out the theoretical molar proportioning completely needed for esterification according to the quantity of hydroxyl in amyl-based polyol molecule used, or selected the mol ratio of current lab scale according to the former experience mol ratio formed for amyl-based polyol 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 adsorption decolouriser, continue heated and stirred 0.5 ~ 2h, then heating is stopped, when being cooled to 50 ~ 70 DEG C in lab scale sample, suction filtration is carried out while hot in the Büchner funnel being covered with middling speed quantitative paper, product in filter flask is transferred in reagent bottle, the method specified according to GB/T 7305-2003, measure the separation property of synthesis liquid and water; After if the result display high-speed stirring recorded terminates within three ten minutes left standstill after, the volume of emulsion layer is less than 3mL, then represent that the separation property of this synthesis liquid and water is good, terminate this lab scale;
Acid number≤1.5mgKOH/g in this lab scale and synthesis liquid and water separation property also satisfactory lab scale mol ratio carry out large-scale production as the proportioning raw materials of present lot raw material.
Further, described concrete steps are as follows:
step S1:for amyl-based polyol and the lauric acid of purchasing the present lot come, the quantity calculating hydroxyl in amyl-based polyol molecule used determines that the monocarboxylic acid such with lauric acid carries out the theoretical molar proportioning completely needed for esterification, or carried out lab scale test according to the former experience mol ratio formed for amyl-based polyol and lauric acid, if the hydroxyl value of amyl-based polyol used is n, then lauric acid and the theoretical molar of amyl-based polyol are than being n;
step S2:the mol ratio setting lauric acid and amyl-based polyol in this lab scale is 0.9:n ~ 1.2:n;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into the lauric acid of 0.4 ~ 1.6mol, then the amyl-based polyol of respective amount is dropped into according to the mol ratio set in step S2, open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 ± 4 DEG C, add lauric acid and amyl-based polyol used always feed intake quality 0.5 ~ 2% tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 10 ~ 100mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 120 ~ 250 DEG C, heating 5 ~ 24h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 5 ~ 20 minutes, sampling,
step S4:the acid number of working sample, if the acid number≤1.5mgKOH/g of sample, then leaps to step S9; If the acid number > 1.5mgKOH/g of sample, then enter next step;
step S5:continue reaction 0.5 ~ 2h;
step S6:the reacted acid number of sampling and measuring, if acid number≤1.5mgKOH/g, then jumps to step S9; If acid number > is 1.5mgKOH/g, then enter next step;
step S7:judge the absolute value of acid number and the adjacent last hypo acid value difference measured in above-mentioned steps S6, if this absolute value > is 0.5mgKOH/g, then return step S5; If this absolute value≤0.5mgKOH/g, then enter next step;
step S8:if acid number is > 1.5mgKOH/g still, then terminate this lab scale, and return step S2 and again adjust in the scope of 0.9:n ~ 1.2:n and set once the concrete mol ratio that amyl-based polyol and lauric acid lab scale test; If acid number≤1.5mgKOH/g, then enter next step;
step S9:add in three-necked bottle amyl-based polyol used and lauric acid always feed intake quality 0.5 ~ 5%, particle diameter is the adsorption decolouriser of 65 ~ 80 μm, continue heated and stirred 0.5 ~ 2h, then heating is stopped, when being cooled to 50 ~ 70 DEG C in lab scale sample, in the Büchner funnel being covered with middling speed quantitative paper, carry out suction filtration while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T 7305-2003 specifies, synthesis liquid in mensuration reagent bottle and the separation property of water, if be less than 3mL at the volume of the three ten minutes internal emulsification layers left standstill after the result display high-speed stirring recorded terminates, then represent that the separation property of this synthesis liquid and water is good, terminate this lab scale, write down this batch of lauric acid used and the suitable mol ratio of amyl-based polyol, using the mol ratio of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot; If the separation property of measurement result display synthesis liquid and water is bad, then return step S2, in the test of fine setting lab scale, the concrete mol ratio of lauric acid and amyl-based polyol, then carries out lab scale next time;
step S11:large-scale production;
Further, the step of described large-scale production is specially:
step S111:the present lot obtained with lab scale amyl-based polyol used and lauric mol ratio, at 1M
3reactor in, drop into lauric acid and amyl-based polyol used, the total mass of raw material in still is made to be in the scope of 300 ~ 800kg, open and stir, during beginning, rotating speed maintains 5 ~ 50rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 ± 5 DEG C, add lauric acid and amyl-based polyol used always feed intake quality 0.5 ~ 2% tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 1 ~ 100L/min, the rotating speed of stirring is brought up to 50 ~ 300rpm, timing from now, material in still is warmed up to 120 ~ 250 DEG C, heating 5 ~ 24h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 5 ~ 20 minutes, sampling, the acid number of working sample,
step S112:if the acid number of sample can not reach≤level of 1.5mgKOH/g, then carry out reaction 0.5 ~ 2h, resampling detects acid number, until the acid number≤1.5mgKOH/g of sample;
step S113:add in reactor amyl-based polyol used and lauric acid always feed intake quality 0.1 ~ 2% adsorption decolouriser, continue heated and stirred 0.5 ~ 3h, then heating is stopped, when being cooled to 50 ~ 70 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, order number is adopted to be 250 ~ 300 object filter screens, carry out circulation press filtration, press filtration material out turns back in reactor, the color that circulation press filtration proceeds to the product returned do not seen adsorption decolouriser particle residual till, product after press filtration being decoloured pours in pail pack.
Further, described amyl-based polyol is the one in TriMethylolPropane(TMP), ditrimethylolpropane, dipentaerythritol, neopentyl glycol.
Further, described adsorption decolouriser can be gac, atlapulgite, attapulgite, diatomite.
Further, when described adsorption decolouriser is gac, can use together in conjunction with diatomite, attapulgite, atlapulgite.
The invention has the advantages that:
(1) each batch of raw material owing to buying has trickle fluctuation in purity, so adopt in the theoretical molar proportioning of corresponding raw material or the basis of experience mol ratio, the raw material of each batch is first adjusted to their proportioning by lab scale, until the acid number of amyl-based polyol fatty acid ester that lab scale is synthesized both met the requirements, also after meeting the requirements with the separation property of water, the feed molar proportioning adopting this suitable again goes to carry out large-scale production, raw material can be made to be fully utilized, ensure the quality of product, eliminate the highly energy-consuming that molecule rectifying is such, the lossy post-processing step of product, make production process economy, rationally, product has the market competitiveness.
(2) need not as current some processes, high, the not poisonous organic solvent of the boiling point such as toluene, dimethylbenzene is adopted to go as water entrainer, avoid the Dangerous and Harmful Factors in operating process, there is not the residual of low-boiling-point substance in product, thus ensure that the amyl-based polyol fatty acid ester be synthesized can at high temperature use.
(3) lipid acid owing to not adopting some traditional technologys to adopt is excessive, and then the technique that neutralizes is carried out with alkaline solution, eliminate washing and point equal post-processing step, and reluctant salts substances can not be produced, make that production process seems succinctly, environmental protection, avoid the product that is synthesized in the basic conditions again by the risk of saponification, hydrolysis.
(4) adopt traditional tosic acid as catalyzer, conveniently be easy to get, not exist batch between the discrepant problem of catalytic activity, it also has a benefit, be exactly that its fusing point is about 106 DEG C, after reaction end product cools down, in the process of decolorization filtering, the tosic acid of separating out from system can be filtered out together, realize being separated of catalyzer and product.
(5) when adopting gac as adsorption decolouriser, when gac price is higher, be combined the porousness sorbent material that diatomite, attapulgite, atlapulgite etc. are inexpensive, can the rational thickness of filter bed of heap, both be enough to play good filtration decolorizing effect in suction filtration or circulation pressure-filtering process, and effectively can have reduced again the cost of decolorization.
Embodiment
The following examples can make the present invention of professional and technical personnel's comprehend, but therefore do not limit the present invention among described scope of embodiments.
embodiment 1
A preparation method for amyl-based polyol laurate, adopt TriMethylolPropane(TMP) and lauric acid to be raw material, concrete steps comprise:
step S1:for TriMethylolPropane(TMP) and the lauric acid of purchasing the present lot come, the quantity calculating hydroxyl in TriMethylolPropane(TMP) molecule used determines that the monocarboxylic acid such with lauric acid carries out the theoretical molar proportioning completely needed for esterification, or carried out lab scale test according to the former experience mol ratio formed for TriMethylolPropane(TMP) and lauric acid, the quantity of the hydroxyl that a part TriMethylolPropane(TMP) contains is 3, then lauric acid is 3 with the theoretical molar ratio of TriMethylolPropane(TMP);
step S2:set the mol ratio of lauric acid and TriMethylolPropane(TMP) in this lab scale, synthesize according to front the experience drawn several times, TriMethylolPropane(TMP) and the proper mol ratio of lauric acid are 1.04:3;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 0.9mol(180.288g) lauric acid, then correspondingly drop into 0.312mol(41.861g) TriMethylolPropane(TMP), open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 DEG C, add lauric acid and TriMethylolPropane(TMP) always to feed intake the 1%(2.22g of quality 222.149g) 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 195 ± 5 DEG C, heating 12h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling, the acid number of working sample, for 0.68mgKOH/g,
step S4:due to the acid number≤1.5mgKOH/g of sample, then leap to step S9;
step S9:in three-necked bottle, adding TriMethylolPropane(TMP) and lauric acid always to feed intake the 2%(4.44g of quality) particle diameter is the atlapulgite of 75 μm, continue heated and stirred 1h, then heating is stopped, when being cooled to 60 DEG C in lab scale sample, in the Büchner funnel being covered with middling speed quantitative paper, carry out suction filtration while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T 7305-2003 specifies, measure the separation property of synthesis liquid and water, the result recorded be high-speed stirring terminate rear leave standstill 15 minutes time, between oil phase and aqueous phase, the volume of emulsion layer is 0mL, represent that the separation property of this synthesis liquid and water is good, so need not adjust this batch of TriMethylolPropane(TMP) again relative to lauric mol ratio;
Terminate this lab scale, write down this batch of lauric acid used and the suitable mol ratio of TriMethylolPropane(TMP), using the mol ratio of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot;
step S11:large-scale production;
Be specially:
Step S111: adopt the TriMethylolPropane(TMP) for present lot and lauric suitable mol ratio 1.04:3 that obtain in above-mentioned steps, at 1M
3reactor in, drop into 600.96kg lauric acid and 139.54kg TriMethylolPropane(TMP), the total mass of raw material in still is made to reach 740.50kg, 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 TriMethylolPropane(TMP) always to feed intake the 1%(7.40kg 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 195 ± 5 DEG C, heating 13h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling, the acid number of working sample, for 0.72mgKOH/g,
Step S112: because the acid number of sample reaches≤the level of 1.5mgKOH/g, so need not proceed reaction again;
Step S113: add TriMethylolPropane(TMP) and lauric acid and always feed intake the 0.5%(3.70kg of quality in reactor) particle diameter is the atlapulgite of 75 μm, continue heated and stirred 1.5h, then heating is stopped, when being cooled to 60 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, employing order number is that the filter screen of 270 μm carries out circulation press filtration, press filtration material out turns back in reactor, after circulation press filtration carries out ten minutes, the color of the product returned has not seen the residual of atlapulgite particle, product after press filtration being decoloured pours in pail pack.
embodiment 2
A preparation method for amyl-based polyol laurate, adopt ditrimethylolpropane and lauric acid to be raw material, concrete steps comprise:
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:the mol ratio setting lauric acid and ditrimethylolpropane in this lab scale is 1:4;
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, the acid number of working sample, for 3.8mgKOH/g,
step S4:the acid number of working sample, 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, if this absolute value > is 0.5mgKOH/g, then return step S5; If this absolute value≤0.5mgKOH/g, then enter next step;
In the present embodiment, the acid number due in the acid number 3.5mgKOH/g(step S6 of one-time detection after sample) and the absolute value of difference of front one-time detection acid number 3.8mgKOH/g result be no more than 0.5mgKOH/g, subsequently enter step S8;
step S8:due to the acid number still > 1.5mgKOH/g of rear primary sample, terminate this lab scale, ditrimethylolpropane and lauric mol ratio are adjusted to 1.05:4, suitable increase ditrimethylolpropane is relative to lauric mol ratio, 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, has reached the requirement of acid number≤1.5mgKOH/g;
step S9:in three-necked bottle, adding ditrimethylolpropane and lauric acid always to feed intake the 1%(2.1g of quality) particle diameter is the gac of 75 μm, continue heated and stirred 1h, then heating is stopped, when being cooled to 60 DEG C in lab scale sample, be carry out suction filtration in the Büchner funnel of the diatomite of 75 μm and middling speed quantitative paper being covered with particle diameter while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T 7305-2003 specifies, measure the separation property of synthesis liquid and water, the result recorded 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; The separation property of synthesizing liquid and water due to the result display recorded is good, so need not adjust this batch of ditrimethylolpropane again relative to lauric mol ratio;
step S11:large-scale production;
Be specially:
Step S111: the ditrimethylolpropane of the present lot obtained with lab scale and lauric suitable mol ratio 1.05:4, at 1M
3reactor in, drop into 320.512kg 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 1.0%(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 need not proceed reaction again;
Step S113: add ditrimethylolpropane and lauric acid and always feed intake the 0.5%(2.13kg of quality in reactor) particle diameter is the gac of 75 μm, 0.2%(0.85kg) 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 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.
embodiment 3
A preparation method for amyl-based polyol laurate, adopt dipentaerythritol and lauric acid to be raw material, concrete steps are as follows:
step S1:for dipentaerythritol and the lauric acid of purchasing the present lot come, have 6 hydroxyls in a dipentaerythritol molecule, then lauric acid is 6 with the theoretical molar ratio of dipentaerythritol;
step S2:the mol ratio setting lauric acid and dipentaerythritol in this lab scale is 1:6;
step S3:carry out lab scale, the mol ratio of both employings is that 1:6 carries out lab scale test, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 1.2mol(240.384g) lauric acid, then correspondingly drop into 0.2mol(50.856g) dipentaerythritol, open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 DEG C, add lauric acid and dipentaerythritol always to feed intake the 1%(2.91g of quality 291.24g) tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 30mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 200 ± 5 DEG C, heating 14h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling, the acid number of working sample, for 0.2mgKOH/g,
step S4:because the acid number of sample reaches≤the level of 1.5mgKOH/g, leap to the S9 of conventional steps so subsequent;
step S9:in three-necked bottle, adding dipentaerythritol and lauric acid always to feed intake the 2%(5.82g of quality) particle diameter is the attapulgite of 75 μm, continue heated and stirred 1h, then heating is stopped, when being cooled to 60 DEG C in lab scale sample, in the Büchner funnel being covered with middling speed quantitative paper, carry out suction filtration while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T 7305-2003 specifies, measure the separation property of synthesis liquid and water, the result recorded is that when leaving standstill 30 minutes after high-speed stirring terminates, between oil phase and aqueous phase, the volume of emulsion layer is 6mL, represents that the separation property of this synthesis liquid and water is bad;
The separation property of synthesizing liquid and water due to the result display recorded is bad, so reenter step S2, for this batch of dipentaerythritol of buying and lauric acid, its mol ratio is adjusted to 0.92:6, drop into 1.2mol(240.384g) lauric acid, then correspondingly drop into 0.184mol(46.788g) dipentaerythritol, the rapid S3 of all the other course synchronization of lab scale synthesis, to the product sampling synthesized, recording its acid number is 0.8mgKOH/g, then the decolouring of step S9 is carried out, filter, re-start the separation property measuring synthesis liquid and water, the result recorded is that high-speed stirring terminates rear leaving standstill after 15 minutes, between oil phase and aqueous phase, the volume of emulsion layer is 0mL, represent that the separation property of this synthesis liquid and water can accept, write down the raw material for this batch buied, suitable dipentaerythritol and lauric mol ratio are 0.92:6, using the proportioning raw materials of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot,
step S11:large-scale production;
Be specially:
Step S111: for dipentaerythritol and the lauric suitable mol ratio 0.92:6 of present lot, at 1M
3reactor in, drop into 600.96kg lauric acid and 116.969kg dipentaerythritol, the total mass of raw material in still is made to reach 717.929kg, 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 dipentaerythritol always to feed intake the 1%(7.179kg 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 200 ± 5 DEG C, heating 15h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling, the acid number of working sample, for 0.88mgKOH/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 dipentaerythritol and lauric acid and always feed intake the 0.6%(4.31kg of quality in reactor) particle diameter is the attapulgite of 75 μm, continue heated and stirred 2h, then heating is stopped, when being cooled to 60 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, 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 ten minutes, the color of the product returned has not seen the attapulgite particle residue of brown, product after press filtration being decoloured pours in pail pack.
embodiment 4
A preparation method for amyl-based polyol laurate, adopt neopentyl glycol and lauric acid to be raw material, concrete steps are as follows:
step S1:have 2 hydroxyls in a neopentyl glycol molecule, then lauric acid and the theoretical molar of neopentyl glycol are than being 2:1;
step S2:set the mol ratio of lauric acid and neopentyl glycol in this lab scale, synthesize according to front the experience drawn several times, neopentyl glycol and the proper mol ratio of lauric acid are 1.01:2;
step S3:in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 1mol(200.32g) lauric acid, then correspondingly drop into 0.505mol(52.596g) neopentyl glycol, open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 DEG C, add lauric acid and neopentyl glycol always to feed intake the 1%(2.53g of quality 252.916g) 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 3h, 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 2.5mgKOH/g,
step S4:the acid number of working sample, because the acid number of sample does not reach≤the level of 1.5mgKOH/g, therefore enters next step;
step S5:continue reaction 1h;
step S6:the reacted acid number of sampling and measuring, it is 1.7mgKOH/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, then return step S5; If this absolute value≤0.5mgKOH/g, then enter next step;
In the present embodiment, acid number due in the acid number 1.7mgKOH/g(step S6 of one-time detection after sample) and the absolute value of difference of front one-time detection acid number 2.5mgKOH/g result more than 0.5mgKOH/g, therefore step S5 is returned, carry out reaction 1h again, and then sampling detects acid number, the acid number of sample is 1.3mgKOH/g, reaches≤the level of 1.5mgKOH/g, and the absolute value of difference of acid number result that adjacent two sub-samplings detect is no more than 0.5mgKOH/g, subsequently enter step S8;
step S8:due to third time, the acid number of sample reaches≤the level of 1.5mgKOH/g, subsequently enters step S9;
step S9:in three-necked bottle, add neopentyl glycol and lauric acid always to feed intake the 2%(5.06g of quality) particle diameter be the diatomite of 75 μm, continue heated and stirred 1h, then heating is stopped, when being cooled to 60 DEG C in lab scale sample, in the Büchner funnel being covered with middling speed quantitative paper, carry out suction filtration while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T 7305-2003 specifies, measure the separation property of synthesis liquid and water, the result recorded be high-speed stirring terminate rear leave standstill 15 minutes time, between oil phase and aqueous phase, the volume of emulsion layer is 1mL, represent that the separation property of this synthesis liquid and water is good, writing down this batch of neopentyl glycol and the suitable mol ratio of lauric acid, is 1.01:2, using the proportioning raw materials of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot; The separation property of synthesizing liquid and water due to the result display recorded is good, so need not adjust this batch of neopentyl glycol again relative to lauric mol ratio;
step S11:large-scale production;
Be specially:
Step S111: for neopentyl glycol and the lauric suitable mol ratio 1.01:2 of present lot, at 1M
3reactor in, drop into 600.96kg lauric acid and 82.036kg neopentyl glycol, the total mass of raw material in still is made to reach 682.996kg, 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 neopentyl glycol always to feed intake the 0.8%(5.464kg of quality) tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 10L/min, the rotating speed of stirring is brought up to 160rpm, timing from now, material in still is warmed up to 180 ± 5 DEG C, heating 5.5h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling, the acid number of working sample, for 1.36mgKOH/g,
Step S112: because the acid number of sample reaches≤the level of 1.5mgKOH/g, so need not proceed reaction again;
Step S113: add neopentyl glycol and lauric acid and always feed intake the 0.6%(4.10kg of quality in reactor) particle diameter is the diatomite of 75 μm, continue heated and stirred 1.5h, then heating is stopped, when being cooled to 60 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, employing order number is that the filter screen of 270 μm carries out circulation press filtration, press filtration material out turns back in reactor, after circulation press filtration carries out six minutes, the color of the product returned has not seen the residual of diatomite particle, product after press filtration being decoloured pours in pail pack.
Above content shows and describes ultimate principle of the present invention and principal character.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (8)
1.
a kind ofthe preparation technology of amyl-based polyol laurate, it is characterized in that: described preparation technology is amyl-based polyol and lauric acid for purchasing the present lot come, first determine that the monocarboxylic acid such with lauric acid carries out the theoretical molar proportioning completely needed for esterification according to the quantity of hydroxyl in amyl-based polyol molecule used, or selected the mol ratio of current lab scale according to the former experience mol ratio formed for amyl-based polyol 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 adsorption decolouriser, continue heated and stirred 0.5 ~ 2h, then heating is stopped, when being cooled to 50 ~ 70 DEG C in lab scale sample, suction filtration is carried out while hot in the Büchner funnel being covered with middling speed quantitative paper, product in filter flask is transferred in reagent bottle, the method specified according to GB/T 7305-2003, measure the separation property of synthesis liquid and water; After if the result display high-speed stirring recorded terminates within three ten minutes left standstill after, the volume of emulsion layer is less than 3mL, then represent that the separation property of this synthesis liquid and water is good, terminate this lab scale;
Acid number≤1.5mgKOH/g in this lab scale and synthesis liquid and water separation property also satisfactory lab scale mol ratio carry out large-scale production as the proportioning raw materials of present lot raw material.
2. the preparation technology of amyl-based polyol laurate according to claim 1, is characterized in that described concrete steps are as follows:
step S1:for amyl-based polyol and the lauric acid of purchasing the present lot come, the quantity calculating hydroxyl in amyl-based polyol molecule used determines that the monocarboxylic acid such with lauric acid carries out the theoretical molar proportioning completely needed for esterification, or carried out lab scale test according to the former experience mol ratio formed for amyl-based polyol and lauric acid, if the hydroxyl value of amyl-based polyol used is n, then lauric acid and the theoretical molar of amyl-based polyol are than being n;
step S2:the mol ratio setting lauric acid and amyl-based polyol in this lab scale is 0.9:n ~ 1.2:n;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into the lauric acid of 0.4 ~ 1.6mol, then the amyl-based polyol of respective amount is dropped into according to the mol ratio set in step S2, open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 ± 4 DEG C, add lauric acid and amyl-based polyol used always feed intake quality 0.5 ~ 2% tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 10 ~ 100mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 120 ~ 250 DEG C, heating 5 ~ 24h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 5 ~ 20 minutes, sampling,
step S4:the acid number of working sample, if the acid number≤1.5mgKOH/g of sample, then leaps to step S9; If the acid number > 1.5mgKOH/g of sample, then enter next step;
step S5:continue reaction 0.5 ~ 2h;
step S6:the reacted acid number of sampling and measuring, if acid number≤1.5mgKOH/g, then jumps to step S9; If acid number > is 1.5mgKOH/g, then enter next step;
step S7:judge the absolute value of acid number and the adjacent last hypo acid value difference measured in above-mentioned steps S6, if this absolute value > is 0.5mgKOH/g, then return step S5; If this absolute value≤0.5mgKOH/g, then enter next step;
step S8:if acid number is > 1.5mgKOH/g still, then terminate this lab scale, and return step S2 and again adjust in the scope of 0.9:n ~ 1.2:n and set once the concrete mol ratio that amyl-based polyol and lauric acid lab scale test; If acid number≤1.5mgKOH/g, then enter next step;
step S9:add in three-necked bottle amyl-based polyol used and lauric acid always feed intake quality 0.5 ~ 5%, particle diameter is the adsorption decolouriser of 65 ~ 80 μm, continue heated and stirred 0.5 ~ 2h, then heating is stopped, when being cooled to 50 ~ 70 DEG C in lab scale sample, in the Büchner funnel being covered with middling speed quantitative paper, carry out suction filtration while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T 7305-2003 specifies, synthesis liquid in mensuration reagent bottle and the separation property of water, if be less than 3mL at the volume of the three ten minutes internal emulsification layers left standstill after the result display high-speed stirring recorded terminates, then represent that the separation property of this synthesis liquid and water is good, terminate this lab scale, write down this batch of lauric acid used and the suitable mol ratio of amyl-based polyol, using the mol ratio of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot; If the separation property of measurement result display synthesis liquid and water is bad, then return step S2, finely tune the concrete mol ratio of lauric acid and amyl-based polyol in lab scale test next time, then carry out lab scale next time;
step S11:large-scale production.
3. the preparation technology of amyl-based polyol laurate according to claim 1 and 2, is characterized in that the step of described large-scale production is specially:
step S111:the present lot obtained with lab scale amyl-based polyol used and lauric mol ratio, at 1M
3reactor in, drop into lauric acid and amyl-based polyol used, the total mass of raw material in still is made to be in the scope of 300 ~ 800kg, open and stir, during beginning, rotating speed maintains 5 ~ 50rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 ± 5 DEG C, add lauric acid and amyl-based polyol used always feed intake quality 0.5 ~ 2% tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 1 ~ 100L/min, the rotating speed of stirring is brought up to 50 ~ 300rpm, timing from now, material in still is warmed up to 120 ~ 250 DEG C, heating 5 ~ 24h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 5 ~ 20 minutes, sampling, the acid number of working sample,
step S112:if the acid number of sample can not reach≤level of 1.5mgKOH/g, then carry out reaction 0.5 ~ 2h, resampling detects acid number, until the acid number≤1.5mgKOH/g of sample;
step S113:add in reactor amyl-based polyol used and lauric acid always feed intake quality 0.1 ~ 2% adsorption decolouriser, continue heated and stirred 0.5 ~ 3h, then heating is stopped, when being cooled to 50 ~ 70 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, order number is adopted to be 250 ~ 300 object filter screens, carry out circulation press filtration, press filtration material out turns back in reactor, the color that circulation press filtration proceeds to the product returned do not seen adsorption decolouriser particle residual till, product after press filtration being decoloured pours in pail pack.
4. the preparation technology of amyl-based polyol laurate according to claim 1 and 2, is characterized in that: described amyl-based polyol is the one in TriMethylolPropane(TMP), ditrimethylolpropane, dipentaerythritol, neopentyl glycol.
5. the preparation technology of amyl-based polyol laurate according to claim 3, is characterized in that: described amyl-based polyol is the one in TriMethylolPropane(TMP), ditrimethylolpropane, dipentaerythritol, neopentyl glycol.
6. the preparation technology of amyl-based polyol laurate according to claim 2, is characterized in that: described adsorption decolouriser can be gac, atlapulgite, attapulgite, diatomite.
7. the preparation technology of amyl-based polyol laurate according to claim 3, is characterized in that: described adsorption decolouriser can be gac, atlapulgite, attapulgite, diatomite.
8. the preparation technology of the amyl-based polyol laurate according to claim 6 or 7, is characterized in that: when described adsorption decolouriser is gac, can use together in conjunction with diatomite, attapulgite, atlapulgite.
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| 邢凤兰等: ""三羟甲基丙烷酯的合成及其抗乳化性能研究"", 《化工进展》 * |
| 顾信鸽: ""三羟甲基丙烷羧酸酯的合成与性能研究"", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
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