CN103980162A - Preparation method of TDI (toluene diisocynate) derived type diamino alkyl formate oil coagulating agent - Google Patents
Preparation method of TDI (toluene diisocynate) derived type diamino alkyl formate oil coagulating agent Download PDFInfo
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- CN103980162A CN103980162A CN201410243584.5A CN201410243584A CN103980162A CN 103980162 A CN103980162 A CN 103980162A CN 201410243584 A CN201410243584 A CN 201410243584A CN 103980162 A CN103980162 A CN 103980162A
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Abstract
The invention discloses a preparation method of a TDI (toluene diisocynate) derived type diamino alkyl formate oil coagulating agent, relating to the preparation method of an oil coagulating agent. The method comprises the steps of (1) adding 0.05mol of TDI and 0.10-0.12mol of C4-C22 fatty alcohol or aromatic alcohol into 100-200mL of organic solvent, and uniformly stirring; (2) performing continuous stirring reaction on a mixture at 50-70 DEG C, wherein the reaction time is 5-48 hours; (3) after completing the reaction, removing the solvent by virtue of distillation to obtain a concentrated solution; (4) pouring the concentrated solution into a glass plate while heating, putting into a vacuum drying box at 120-150 DEG C, and performing vacuum drying for 5-12 hours to obtain the TDI derived type diamino alkyl formate oil coagulating agent. The oil coagulating agent prepared by the preparation method can be used for effectively gelatinizing various oil products and organic solvents such as Russian oil, diesel oil, gasoline, soybean oil, peanut oil, cyclohexane, toluene, carbon tetrachloride and the like overflowing into water, and is less in additive amount of the oil coagulating agent, high in oil coagulating speed, high in oil coagulation block strength and complete in oil coagulation.
Description
Technical field
The present invention relates to a kind of preparation method of fuel thickener, be specifically related to a kind of TDI(tolylene diisocyanate) preparation method of the two alkyl carbamate class fuel thickeners of derivative type.
Background technology
Continually developing of the flourish and offshore petroleum resources of marine traffic transport trade, when bringing tremendous economic interests to the mankind, also produced serious oil spill accident, ocean environment is caused to great threat, and offshore oil oil spill control has at present become a great problem of facing mankind.Extensive oil spill accident generation can cause a large amount of oil moment to enter ocean environment, diffuses to form across the sea the thick oil reservoir of one deck, causes big area ocean anoxic, the hydrobiological existence such as harm fish.In addition, the hydrocarbon compound in oil very easily enters and rests on for a long time in water, long-term the healthy of also final harm humans that accumulate.Have statistics, be poured into every year the oil total amount of ocean at 200～1,000 ten thousand tons, ten thousand tons of above oil tanker oil spill accidents even almost all will occur every year one time, the eco-catastrophe causing is thus difficult to estimate.2013, in Qingdao, just there is oil spilling explosion hazard together, part crude oil overflows into Qingdao sea area.
Through long-term exploration and effort, the treatment process of oil spill accident mainly comprises physics, biological and chemical method at present, physical method mainly comprises asphalt felt, oil skimmer vessel, oil absorber etc., but this method can manage it for the larger oil treatment effect of former wet goods viscosity, but for lightweight oils such as vapour, coal, diesel oil, on sea, velocity of diffusion is fast, and physical method effect is undesirable.Chemical method comprises oil spill dispersant, dispersion agent, fuel thickener etc., wherein fuel thickener can become oil spilling rapid coagulation solid or semi-solid block, floats on the water surface and is convenient to machinery salvaging, has fuel thickener toxicity low, be not subject to the impact of stormy waves, can effectively prevent the advantages such as oil spilling diffusion.Current common fuel thickener comprises sorbyl alcohol type, amino acid pattern, organic salt type etc., but business-like fuel thickener also exist solidifying oil not thoroughly, large, some shortcomings of high in cost of production of consumption, therefore preparing new and effective fuel thickener has huge environmental benefit and social benefit.
In recent years, supramolecule fuel thickener is more and more subject to investigator's extensive attention, and supramolecule jelling agent is again lower molecular weight jelling agent or physics jelling agent.Supramolecule jelling agent (supramolecular mass gelators) has mainly utilized the self-assembly performance between small molecules, between small molecules, can in the one-dimensional square self-assembly that makes progress, form fibrous, banded, tubulose or spirrillum nanostructure by non-covalent interactions such as hydrogen bond, Van der Waals force, electrostatic attractions, more mutually tangle into three-dimensional network structure.On the basis of three-dimensional net structure, utilize surface tension, capillary force etc. by oil spilling equal solvent molecular retention or be fixed in network, and solvent molecule enter the effect that also can play stabilizing network.Different with chemical gel, physical gel can be realized can changing by anti-phase of sol-gel under certain outside stimulus, such as thermal treatment, concussion, mechanical shearing etc., utilize the transformation mutually of this sol-gel can realize supramolecule fuel thickener and solidifying oil recovery recycling.
Summary of the invention
The preparation method who the object of this invention is to provide the two alkyl carbamate class fuel thickeners of a kind of TDI derivative type, utilizes relatively simple single step reaction method successfully to prepare economy, the two alkyl carbamate class fuel thickeners of efficient TDI derivative type.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for the two alkyl carbamate class fuel thickeners of TDI derivative type, concrete operation step is as follows:
(1) by the TDI(2 of 0.05mol, 4/2,6-tolylene diisocyanate) and 0.10 ~ 0.12mol C
4~ C
22fatty alcohol or aromatic alcohol join in suitable organic solvent, the amount of solvent is 100 ~ 200mL approximately, stirs, and transfers in suitable there-necked flask.
In this step, described TDI is Toluene-2,4-diisocyanate, 4-vulcabond (80wt%) and Toluene-2,4-diisocyanate, the mixture of 6-vulcabond (20wt%).
In this step, described fatty alcohol is one or more the mixture in propyl carbinol, n-hexyl alcohol, hexalin, n-Octanol, nonanol-, nonylcarbinol, 1-undecyl alcohol, 1-lauryl alcohol, 2-octyl dodecanol, 1-tetradecyl alcohol, Cetyl OH, 1-stearyl alcohol, 1-behenyl alcohol etc., and described aromatic alcohol is phenylcarbinol etc.
In this step, described organic solvent is chloroform, acetone, tetracol phenixin etc., specifically selects which kind of solvent to be determined by raw materials used solvability, in order to test conveniently, also can mix use.
(2) mixture is placed in to water-bath at 50 ~ 70 ℃ of temperature or oil bath continues stirring reaction, reaction times 5 ~ 48h;
(3) after reaction finishes, by the method for air distillation or rotary distillation, at the temperature higher than solvent boiling point, solvent distillation is removed, obtain concentrated solution;
(4) while hot concentrated solution is poured in glass dish, be placed in the vacuum drying oven vacuum-drying 5 ~ 12h of 120 ~ 150 ℃, to remove unreacted TDI or alcohol, improve the purity of fuel thickener.
(5) take out, room temperature is cooled to whole block, with small-sized general-purpose pulverizer, pulverizes 30 ~ 60s, obtains the two alkyl carbamate class fuel thickeners of TDI derivative type, is designated as nCTDI fuel thickener, the carbon number that n is long chain aliphatic alcohol.
The present invention selects TDI(tolylene diisocyanate) as the small molecule structure unit of fuel thickener, this is because contain the isocyanate group active group that is easy to modify in TDI molecule.TDI and C for the present invention
4~ C
22fatty alcohol or aromatic alcohol be raw material, through simple single step reaction, can prepare the two alkyl carbamate class fuel thickeners of this class TDI derivative type.TDI reacts addition in the isocyanate group of TDI and has generated alkyl carbamate group with long chain aliphatic alcohol, make the carbamate groups that contains oil loving chain alkyl and can carry out intermolecular self-assembly in the two alkyl carbamate class fuel thickener molecules of TDI derivative type of preparation, this be also its can phase selectivity gelation water in the reason place of organic solvent and oil product.
The two alkyl carbamate class fuel thickeners of TDI derivative type prepared by the present invention, its proterties is white powder solid, the small molecule structure of fuel thickener is as follows:
，
。
The present invention has following beneficial effect:
Many advantages such as the two alkyl carbamate class fuel thickeners of TDI derivative type that 1, prepared by the present invention have that preparation is simple, cost is low, easy to use, solidifying oil is effective, the multiple organic solvent of gelling and oil product, formation gel-strength are large, can process easily the leakage of multiple organic solvent or oil product, and can phase selectivity ground gelling leak into the organic pollutant in water, the gel-strength forming is larger, sticky net, does not conveniently salvage recovery, causes that secondary pollution is little.
2, the fuel thickener molecule that prepared by the present invention effectively self-assembly forms tiny fiber, further gathers the fiber that formation is larger, then tangles and forms three-dimensional net structure, and the gel forming with oil product also has sufficient three-dimensional net structure.
3, solidifying oiliness energy test experiments draws, fuel thickener prepared by the present invention effectively gelling spills into oil products and the organic solvents such as Russia's oil in water, diesel oil, gasoline, soybean oil, peanut oil, hexanaphthene, toluene, tetracol phenixin, fast, the solidifying oil clot intensity of few, the solidifying speed oil of fuel thickener addition is high, and solidifying oil thoroughly.
Accompanying drawing explanation
Fig. 1 is the SEM figure that the two alkyl carbamate class fuel thickeners of 12CTDI derivative type and hexanaphthene form gel;
Fig. 2 is the SEM figure that the two alkyl carbamate class fuel thickeners of 12CTDI derivative type and gasoline form gel;
Fig. 3 is the FT-IR test spectrogram of 12CTDI derivative type fuel thickener sample;
Fig. 4 is that 12CTDI carries out the experiment photo of the solidifying oil test of phase selectivity by method 1;
Fig. 5 is that 12CTDI carries out the experiment photo of the solidifying oil test of phase selectivity by method 2;
Fig. 6 is that 12CTDI carries out the experiment photo of the solidifying oil test of phase selectivity by method 3.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but do not limit to so; every technical solution of the present invention is modified or is equal to replacement, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment one: present embodiment is prepared the two alkyl carbamate class fuel thickeners of 12CTDI derivative type in accordance with the following steps:
(1) by the TDI(2 of 0.05mol, 4/2,6-tolylene diisocyanate) and 0.10mol lauryl alcohol join in the chloroform of 100mL, stir, and transfer in the there-necked flask of 250mL.
(2) mixture is continued in the water-bath of 55 ℃ to stirring reaction 24h;
(3) after reaction finishes, temperature is risen to 85 ℃, adopt air distillation that solvent chloroform distillation is removed, obtain concentrated solution;
(4) while hot concentrated solution is poured in the glass dish of d=9.5cm, be placed in the vacuum drying oven vacuum-drying 8h of 138 ℃, to remove unreacted TDI, improve the purity of fuel thickener.
(5) take out, it is whole block that room temperature is cooled to white, with small-sized general-purpose pulverizer, pulverizes 30s, obtains the two alkyl carbamate class fuel thickeners of 12CTDI derivative type of white powder.
The two alkyl carbamate class fuel thickeners of 12CTDI derivative type and partial gel thereof prepared by present embodiment have carried out Microstructure characterization, and SEM test result as shown in Figure 1 and 2.By Fig. 1 ~ 2, can be found out, fuel thickener prepared by the present invention and gel self-assembly thereof have formed relatively elongated fiber and have mutually tangled and formed fibrous-network structure, can analyze by effectively catching oil spilling, so gelling property is better.By technology such as infrared, LC-MS, nuclear-magnetisms, the molecular structure of fuel thickener is characterized, the infrared spectrum of 12CTDI fuel thickener of take is briefly described as example simultaneously, and FT-IR schemes as shown in Figure 3.Be analyzed as follows: the characteristic peak analysis of carbamate structural unit: 3292cm
-1strong fignal center is the N-H stretching vibration absorption peak of hydrogen bond association, illustrates and between adjacent molecule, has intermolecular hydrogen bonding effect; 1700cm
-1having occurred very sharp-pointed peak, is the stretching vibration absorption peak of C=O in carbamate; 1537cm
-1for-NH is out of shape absorption peak; 1077cm
-1place in-COO--C-O stretching vibration absorption peak; The characteristic absorbance peak intensity of several carboxylamine ester structures is all very large above, illustrates that reaction has generated the material with carboxylamine ester structure really.In addition 1602cm,
-1near there is the charateristic avsorption band of phenyl ring, corresponding to lower wave number district 722cm with it
-1~ 873cm
-1between occurred 1,2,4-and 1,2,3-position substituted benzene ring=C-H out-of-plane deformation vibration frequency, the two alkyl carbamate class fuel thickener molecules of TDI derivative type that simultaneously have 2,4-and 2,6-are described.
Embodiment two: present embodiment is prepared the two alkyl carbamate class fuel thickeners of 14CTDI derivative type in accordance with the following steps:
(1) by slightly excessive in 0.05mol(reality) TDI(2,4/2,6-tolylene diisocyanate) and the 1-tetradecyl alcohol of 0.10mol join in the acetone of 100mL, stir, and transfer in the there-necked flask of 250mL.
(2) mixture is continued in the water-bath of 50 ℃ to stirring reaction 24h;
(3) after reaction finishes, temperature is risen to 75 ℃, adopt air distillation that solvent acetone distillation is removed, obtain concentrated solution;
(4) while hot concentrated solution is poured in the glass dish of d=9.5cm, be placed in the vacuum drying oven vacuum-drying 8h of 135 ℃, to remove unreacted TDI, improve the purity of fuel thickener.
(5) take out, it is whole block that room temperature is cooled to white, with small-sized general-purpose pulverizer, pulverizes 40s, obtains the two alkyl carbamate class fuel thickeners of 14CTDI derivative type of white powder.
The two alkyl carbamate class fuel thickeners of TDI type of preparation are oil products and the organic solvent such as gelling Russia oil, diesel oil, gasoline, soybean oil, peanut oil, sweet oil, ethyl acetate, normal hexane, hexanaphthene, tetracol phenixin effectively, what performance was best is 12CTDI fuel thickener, and 14CTDI fuel thickener and 10CTDI fuel thickener performance are taken second place.The gel-strength forming after gelling is large, with skimming ladle, directly salvages not sticky net, and solidifying oil clot can be in water time stable existence several months, along with the increase of time, the intensity of gel also can further increase.
The 12CTDI fuel thickener of best performance of take is introduced the concrete using method of the two alkyl carbamate class fuel thickeners of TDI type of preparation as example:
Method 1: fuel thickener is dissolved in tetrahydrofuran (THF), is mixed with the highly concentrated solution (> 80wt%) of fuel thickener, after thoroughly dissolving, will obtain clear liquor.Then it is evenly sprayed onto in the mixture of oil spilling or organic solvent and water, 5min left and right oil reservoir gets final product complete gelation, and water layer does not have impact substantially, and experiment effect figure as shown in Figure 4.
Method 2: add the two alkyl carbamate class fuel thickeners of 12CTDI derivative type that account for oil or organic solvent amount 30wt% in the mixture of oil or organic solvent and water, at 80 ℃ of left and right temperature, heat, until solid fuel thickener dissolves completely, then take out under room temperature standing, about 15 ~ 30min, oil reservoir or organic solvent layer get final product complete gelation, and Fig. 5 is shown in by experiment test photo.
Method 3: under 80 ~ 90 ℃ of left and right heated conditions, fuel thickener is dissolved in hot gasoline, the hot gasoline solution of the fuel thickener of compounding high concentration, is also clear liquor.Then it is evenly sprayed onto in the mixture of oil spilling or organic solvent and water, 2min gets final product complete gelation with interior oil reservoir, and solidifying oil clot intensity is larger.Because fuel thickener is gelling solvent-gasoline used effectively, also effective other multiple oil spilling and organic solvents of gelling, so the secondary pollution that this using method causes reduces greatly.Fig. 6 is shown in by experiment effect photo.
The minimum gelling concentration of 12CTDI fuel thickener gelling oil and organic solvent is between 8 ~ 19wt%, and the gelling difficulty of oil product is greater than pure organic solvent, because its composition is relatively complicated.
Claims (6)
1. a preparation method for the two alkyl carbamate class fuel thickeners of TDI derivative type, is characterized in that described method concrete operation step is as follows:
(1) by the TDI of 0.05mol and 0.10 ~ 0.12mol C
4~ C
22fatty alcohol or aromatic alcohol join in 100 ~ 200mL organic solvent and stir;
(2) mixture is continued at 50 ~ 70 ℃ of temperature to stirring reaction, reaction times 5 ~ 48h;
(3) after reaction finishes, solvent distillation is removed, obtain concentrated solution;
(4) while hot concentrated solution is poured in glass dish, be placed in the vacuum drying oven vacuum-drying 5 ~ 12h of 120 ~ 150 ℃, obtain the two alkyl carbamate class fuel thickeners of TDI derivative type.
2. the preparation method of the two alkyl carbamate class fuel thickeners of TDI derivative type according to claim 1, is characterized in that described TDI is 80wt% Toluene-2,4-diisocyanate, 4-vulcabond and 20wt% Toluene-2,4-diisocyanate, the mixture of 6-vulcabond.
3. the preparation method of the two alkyl carbamate class fuel thickeners of TDI derivative type according to claim 1, is characterized in that described fatty alcohol is one or more the mixture in propyl carbinol, n-hexyl alcohol, hexalin, n-Octanol, nonanol-, nonylcarbinol, 1-undecyl alcohol, 1-lauryl alcohol, 2-octyl dodecanol, 1-tetradecyl alcohol, Cetyl OH, 1-stearyl alcohol, 1-behenyl alcohol.
4. the preparation method of the two alkyl carbamate class fuel thickeners of TDI derivative type according to claim 1, is characterized in that described aromatic alcohol is phenylcarbinol.
5. the preparation method of the two alkyl carbamate class fuel thickeners of TDI derivative type according to claim 1, is characterized in that described organic solvent is one or more the mixing in chloroform, acetone, tetracol phenixin.
6. the preparation method of the two alkyl carbamate class fuel thickeners of TDI derivative type according to claim 1, is characterized in that solvent distillation being removed at the temperature higher than solvent boiling point by the method for air distillation or rotary distillation.
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Cited By (3)
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| CN105131907A (en) * | 2015-08-12 | 2015-12-09 | 哈尔滨工业大学 | Supramolecular oil gelling agent, preparation method and recovery method thereof |
| CN115322115A (en) * | 2022-08-30 | 2022-11-11 | 中国海洋大学 | Amphiphilic low-molecular-weight organic oil gelling agent for offshore oil spill treatment and preparation method thereof |
| CN116162044A (en) * | 2023-03-06 | 2023-05-26 | 湖北航天化学技术研究所 | Organogel factor and organogel material, and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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