TW575565B - Production method of isopropyl naphthalene and di-isopropyl naphthalene - Google Patents

Abstract

The invented production method of isopropyl naphthalene and di-isopropyl naphthalene employs propylene as initial reactant and utilizes a trimethylammonium hydrochloride-AlCl3 ionic liquid as alkylation catalyst and solvent to undergo fast isopropylation reaction at normal atmosphere pressure and low temperature; the reaction product can use distillation separation method to obtain isopropyl naphthalene and di-isopropyl naphthalene as final products.

Description

575565 V. Description of the invention (1) The reaction system of the present invention is generally the same as the isopropyl media package 1 C rfj, which is difficult to be activated; the problem is that it should be used until the battery is acidified. A method for producing isopropylnaphthalene and diisopropylnaphthalene, especially a fast isopropylation reaction that can be performed at normal pressure and low temperature. The isopropyl naphthalene and isopropylnaphthalene are separated by distillation. Method for producing diisopropylnaphthalene. Naphthalene should be used to obtain acidic aluminum (A, and acid is annoying; gasification is relatively low, and it must be a large distance from molten salt as it is being used in the current age, solution tank or a strong liquid in the development of isopropyl The production method of naphthyl naphthalene and diisopropylnaphthalene is based on the substance, propylene as the calcining agent, the trans-naphthalene is calcined by using an acidic catalyst, and the diisopropylnaphthalene can be continuously reacted to obtain diisopropylnaphthalene. Commonly used hydrogen chloride Fluoric acid (HF), sulfuric acid (H? S04) 1 3) and acid zeolite. However, the acidity of hydrofluoric acid is too strong, its toxicity, and volatility are more important in terms of safety; sulfur is not high, and the required amount is large. The recovery treatment after the reaction is usually more soluble in organic reaction products than hemp. Although the acid zeolite has the advantage of shape selectivity after recovery, it is operated at a high reaction temperature and has a long service life. The liquid (ionic 1 iquid, or room temperature is Liquid salts, because they can be both solvents and environmentally friendly, are of interest in the chemical industry. The application of ionic liquids can be traced back to the 1940s, and was originally used mainly As an electrolyte for electricity, it has been found in recent years that some ionic liquids have high dissolving power for heavy metal oxides. Therefore, applications in ionic processes and high radioactive nuclear waste treatment have gradually been used in various ionic liquids. Chlorinated 1-ethyl-3

Page 4 575565 V. Description of the invention (2) Methyl-diazacyclopentadiene-chlorine (1 — et hy 1 — 3 — methyl imidazol ium chlorid 6 — A1C13, hereinafter referred to as [emim] Cl — A 1 C 1 3), 1-butyl- 3 -methyl-m-diazapentadiene monochloride (1—butyl— 3—methyl imidazol ium chlor ide— A1C13, hereinafter referred to as [b mim] CI-AICI3), 1-hexyl-1, 3-methyl-m-diazacyclopentadiene dichloride (1 — he xy 1 — 3 — me thyl imidazol ium chloride — A1C13, hereinafter referred to as [hmim] Cl — A1C13), trimethylammonium chloride, aluminum chloride (tr ime t hy 1 ami ne hydrochl or i de — A1C13, hereinafter referred to as TMAC — A 1 C 1 3) and other series are the most widely used in alkylation reactions. It is important to note that the synthesis of these ionic liquids and their applications in alkylation reactions have been mentioned in documents such as world patents WO95 / 21806, WO95 / 2 1 872, and US patent 573 1 1 01. Although the literature has mentioned the application of ionic liquids in alkylation reactions, how to use ionic liquids in the naphthalene and propylene alkylation to synthesize isopropylnaphthalene and diisopropylnaphthalene, including the selection of ionic liquids, and the reaction Conditions and manufacturing procedures have not yet been mentioned in the literature.

The conventional methods for producing isopropylnaphthalene and diisopropylnaphthalene use hydrofluoric acid (HF), sulfuric acid (H 2 S04), aluminum chloride (A 1 C 1 3) or acid mordenite (acid mordeni te ze 0 1 ite), etc. as alkylation catalysts for naphthalene and propylene.

575565 V. Description of the invention (3) Isopropylnaphthalene and diisopropylnaphthalene were separated as products by distillation [Refer to Chemical Journal 4 3, PP 1 1 9 to 1 2 6 (1 9 9 6)], but these The catalyst has the disadvantages described above, so it is necessary to switch to another more suitable catalyst. For this reason, the present inventors have exhausted their minds, relying on their years of experience in related research. The invention finally came into being. Therefore, the present invention provides a method for producing isopropylnaphthalene and diisopropylnaphthalene, using naphthalene and acrylic as starting reactants, and using trimethylammonium chloride-aluminum chloride ionic liquid as an alkylating catalyst. Solvent and solvent, rapid isopropylation reaction can be carried out at normal pressure and low temperature, and the obtained reaction product can be used as a product or part of isopropylnaphthalene and diisopropylnaphthalene which are gradually separated by distillation. Part of the reflux is reused as a reactant, and naphthalene and triisopropylnaphthalene and above heavy products can be refluxed or distilled after continuing the reaction, while the tris (triammonium chloride) -aluminum chloride ionic liquid is extremely low in volatility Characteristics, low loss rate after reaction, can be reflowed as an alkylating catalyst and solvent. Therefore, the main object of the present invention is to provide a method for producing isopropylnaphthalene and diisopropylnaphthalene, especially a rapid isopropylation reaction which can be performed at normal pressure and low temperature. Isolation of isopropylnaphthalene and diisopropylnaphthalene by distillation. To achieve the above object, the present invention is achieved as follows: a method for producing isopropylnaphthalene and diisopropylnaphthalene, using naphthalene and propylene as starting reactants, and using trimethylammonium chloride-aluminum chloride ionicity The liquid is used as an alkylation catalyst and solvent, and can be rapidly isopropylated at normal pressure and low temperature. The reaction product obtained can be separated by distillation to obtain isopropylnaphthalene and diisopropylnaphthalene. As a product.

575565 V. Description of the invention (4) In order to make your company manufacture by the following method I Lu 16 Bell isopropylammonium-air vaporization-chloride ion and the first product should be isopropyl as the product. 2 Explain in detail the implementation of the review committee, and explain how to understand the purpose, features, and effects of the present invention, as well as the accompanying drawings. Example 1 Please refer to the procedure for the naphthalene ion within 0 ° C. Base naphthyl chloride distillates aluminum liquid reactant 1 while base naphthalene product 14 propyl product 2 1 According to the procedure and the lower of the base liquid 4 of which is used as aluminum ionization method 5 Ion body 7 should produce 1, second 13 15 re-naphthalene and 0, a picture is taken, dilute 1 body 2 at room temperature due to the reversed separable liquid can be separated by the reaction 6 and the first part of the above and the three dioxane, the system is shown as the reaction In order to carry out Cai Yuying, the liquid is separated from the product 7. The product can be distilled in triplicate. The isopropylation can be re-produced. The isopropylation should be alkylated at room temperature. Naphthalene 1 11 should be produced by the method 1 Base naphthalene should be 2 Inventive catalyst reaction of isopropyl naphthalene and diisopropyl naphthalene ~ 8 It will be reversed and re-extraction method 0 Cocoa recyclable 1 stream 1179, plus 2, and 3, CTC should be used as a 9-point chlorine, and then separated by 4, 6 to get the chlorine agent, which is used as the special agent 6 in the reaction. 4 dagger three is alkane ionization. It is a solid at normal pressure time, and through the chlorine point, the catalyst naphthalene is reacted with methyl chloride with ammonium chloride 1 0 flow 1 2 method 1 isopropyl reactant, isopropylpropyl naphthalene 19 can burn trans ammonium, Chamber 12 Therefore, the three distillations of trimethyl-chlorine are dissolved, and the second part is naphthalene 1 The third naphthalene 1 18 is added through the production of a chlorine temperature ~ 0 minutes, and methyl or palladium aluminizing agent is added. Isolate 3 can react 8 and can be used as < Additive 2

575565 V. Description of the invention (5) 3 can be added to Example 1 by adding 1 body to the alkylation reaction of trimethylammonium, and then carrying out naphthalene, 2 4 · naphthalene. Example 3 A monomer was added to trimethyl chloride in the alkylation reaction, and propyl w t% naphthalene and yl naphthalene were introduced. Example 4 Add 1 sub-liquid at 1 · 7 of chlorine at normal pressure, pass 9 · 5 w t t% diisopropyl. Example 5 add 1 and reflux 2 4 and continue distillation. 0 g naphthalene reactor was reacted with chloroalkylated 5 wt and 2 g of trimethylammonium chloride-aluminum chloride ionic liquid. The reaction shape of this ion should be 1 hour. Chlorine of 1: 2 at 100 ° C under normal pressure. The reaction product contains 7 0 · 9wt% naphthalene and 4.6wt% diisopropyl. 0 g of ammonium in the naphthalene reactor is diluted with 9 · 8. 0 g isomerization of trimethylamine into propylene% naphthalene, ketone, and 2 g of trimethylammonium chloride-aluminum chloride ionic liquid, the ionic chloride is 1% of the anti-calcination reaction. The ratio of 1: 1 _ 7 _ should be formed. At 100 ° C and normal pressure for 1 hour, the reaction product contains 8 7 · 2 propylnaphthalene and 3.0% by weight diisopropylnaphthalene. Alkylation of ammonium with chlorine 5 9 · 3 3 · 3 w 2 g of trisyl chloride monochloride. The ionic liquid is formed by the molar ratio of 1: aluminide reaction at 100 ° C, After 25 minutes of reaction, the reaction product contains wt% isopropylnaphthalene and 27.9 wt% triisopropylnaphthalene. < 〇 g of isopropyl naphthalene and 2 g of trimethyl ammonium chloride-aluminum chloride ion

575565 V. Description of the invention (6) The daughter liquid is introduced with w t% naphthalene, isopropylnaphthalene and the product under a chlorine pressure of 1 · 7. Example 6 An aprotic liquid was added under trichloride of 2 and propylene w t% naphthalene, isopropylnaphthalene, and the product were introduced. Example 7 An aprotic liquid was added under trichloride of 2 and propyl t% naphthalene, 3 propyl naphthalene, and the like were introduced. Example 8 Into an 3 alkylation reactor, the ionic liquid is formed by the reaction of a molar ratio of 1 ·· trimethylammonium ammonium with aluminum chloride, and a calcination reaction is performed at 80 t and propylene for 1 hour. The reaction product is Contains 5 · 5 · 43 · 4wt% of isopropylnaphthalene, 3 · 5wt% of 2 · 15wt% of triisopropylnaphthalene and 0.5wt% of 0 g of isopropyl naphthalene and 2 g of trimethylammonium chloride In the aluminum ionization alkylation reactor, the ionic liquid is formed by a molar ratio of 1: ammonium ammonium and aluminum chloride. The alkylation reaction is performed at 100 ° C and atmospheric olefin for 25 minutes. The reaction product Contains 8 · 7 丨 44 · lwt% isopropyl naphthalene, 36 · 5wt% di 10 · 3wt% triisopropylnaphthalene and 0.4wt% 0 g isopropylnaphthalene and 2 g trimethylammonium chloride- In the aluminum chloride dealkylation reactor, the ionic liquid is formed by the reaction of Molar ratio 1: methyl ammonium and aluminum chloride, and the calcination reaction is carried out at 80 ° C and atmospheric pressure for 1 hour. The reaction product contains 9 1 w 5 〇wt% isopropyl naphthalene, 37 lwt% diisocyanate 7 4wt% triisopropylnaphthalene and 1.4 wt% reproduced 0 g isopropylnaphthalene and 6 g trimethylammonium chloride Aluminum chloride

Page 9 575565 V. Description of the invention (7) The ionic liquid is in an alkylation reactor. The ionic liquid is formed by the reaction of trimethyl ammonium chloride and aluminum chloride at a molar ratio of 1: 2. At 0 ° C and normal pressure, propylene was passed through for calcination reaction: After 5 minutes, the reaction product contained 10 · 7 wt% naphthalene, 65 · 6 wt% isopropylnaphthalene, 21 · 9wt% diisopropylnaphthalene, 1 · 4w, t% triisopropylnaphthalene and 0.4% by weight of heavy product; after 25 minutes, the reaction product contains 10.6% by weight of naphthalene, 46.6% by weight of isopropylnaphthalene, 34.2% by weight of diisopropylnaphthalene, 6 · 7 wt% triisopropylnaphthalene and 1.9 wt% heavy product; after 1 hour, the reaction product contains 7.8 wt% naphthalene, 36 · 9 wt% isopropylnaphthalene, and 40 · 7wt% diisopropyl Naphthalene, 1 · 4 w_t% triisopropylnaphthalene, and 3 · 2wt% weight product; Example 9 was added 10g of isopropylcae and 2g of trimethylchloro chloride gasification ionic liquid in alkane In an ionization reactor, the ionic liquid is formed by reacting trimethylammonium chloride with aluminum chloride at a molar ratio of 1: 2. At room temperature of 2 8 ° C and normal pressure, it is passed through propylene for calcination reaction1 Hours, the reaction product contains 0 · 2 wt% naphthalene, 73.7 wt% isopropyl , 20 · 2wt% diisopropylnaphthalene, 4 · 5wt% triisopropyl-naphthalene and 1 · 4wt% weight product. Example 10 10 g of isopropylnaphthalene and 1 g of trimethylammonium chloride-aluminum chloride were added to an alkylation reactor. The ionic liquid was chlorine with a molar ratio of 1: 2. It is formed by the reaction of triammonium ammonium with aluminum chloride, at room temperature 100 ° C,

Page 10 575565 V. Description of the invention (8) Under normal pressure, pass propylene into the alkylation reaction for 1 hour. The reaction product contains 0.4 wt% naphthalene, 73.2 wt% isopropyl naphthalene, and 23 lwt% diisopropyl. Naphthalene, 2.8 wt% triisopropylnaphthalene, and 0.4 wt% heavy product. Example 11 1 The final reaction product of Example 8 was subjected to vacuum distillation under the conditions of 150 × 50, 7 300 mm H gvac. After all the reaction products were distilled out, about 5. 8 g of chlorine remained at the bottom of the column. Trimethylammonium monoaluminum chloride ionic liquid showed no significant loss of ionic liquid. Because the boiling points of the components in the reaction product are significantly different, they can be separated one by one by any steaming method, and the separated components can be used as products or refluxed. _ The weight ratio of trimethylammonium chloride-aluminum chloride ionic liquid to the reactant naphthalene or isopropylnaphthalene is preferably between 1: 1 to 20, and trimethylammonium chloride monochloride The aluminum ionic liquid is formed by reacting triammonium chloride with aluminum chloride at a molar ratio of 1: 1. 5 to 2. 2. The following examples of two ionic liquids are given below for comparison with the present invention: Example 1 2 10 g of isopropylnaphthalene and 2 g of 1-butyl-3-methyl-methylene chloride are added. Azapentadiene-aluminum chloride ionic liquid in an alkylation reactor, the ionic liquid is 1-butyl-3-methyl-m-diazacyclopentane chloride with a molar ratio of 1: 2 Diene is formed by reaction with aluminum chloride. At 100 ° C under normal pressure, propylene is passed through for alkylation reaction. After 1 hour and 4 hours, the reaction product contains only less than 0.5% Isopropylnaphthalene and polyisopropylnaphthalene.

575565 V. Description of the invention (9) Example 1 3 Add 10 g of isopropylnaphthalene and 2 g of 1-hexyl-3 -methyl-m-diazacyclopentadiene-aluminum chloride ionic liquid in alkane In an ionization reactor, the ionic liquid is formed by the reaction of 1-hexyl chloride 3-hexyl-diazacyclopentadiene and aluminum chloride at a molar ratio of 1: 2, at 100 ° C, Under normal pressure, propylene was passed into the alkylation reaction. After 1 hour, the reaction product also contained less than 0.5% diisopropylnaphthalene and polyisopropylnaphthalene, and continued to raise the reaction temperature to 140. ° C, and then pass in propylene for 1 hour, the reaction product still contains less than 0. 5% of diisopropyl and polyisopropyl Cai. Based on the above examples, the method for producing isopropylnaphthalene and diisopropylnaphthalene of the present invention has the following advantages: -1. The reaction operation is easy, can be performed at low temperature and normal pressure, and the reaction rate is fast. 2 · The product separated by distillation can be repeatedly refluxed as a reactant, which is economical. 3 · Isopropyl naphthalene can be used as a coke scavenger, synthetic naphthol or dialkylated to diisopropyl tsai; and the diisopropyl naphthalene isomer mixture can be used as a non-carbon carbon paper solvent, which is highly commercial value. 4 · Trimethylammonium chloride-aluminum chloride ionic liquid used as a catalyst has no conventional drawbacks, and has low volatility and is not easy to lose. It can be used as a catalyst and a solvent at the same time, which is good for environmental protection and has a wide range of uses. Therefore, the present invention does have excellent industrial applicability and advancement, which complies with the requirements of the invention patent application. However, the invention patent application is submitted in accordance with the law.

Page 12 575565 V. Description of the Invention Although the present invention has been disclosed above with the preferred embodiments, it is not intended to limit the scope of implementation of the present invention; anyone skilled in the art will not depart from the spirit and scope of the present invention. It should be possible to make some changes and retouches, that is, all equal changes and modifications made in accordance with the present invention should be covered by the patent scope of the present invention, and the definition should be based on the scope of the patent application. _

Page 13 575565 Brief description of the drawings Figure 1 Figure 1.

Jan .............. No .... 01234567890 ISjjf 1 ± 0〇4- -Ιο OD 00 Qw- IX 1 ± 1 ± IX 1 ± IX 1 ± IX CVI is the manufacturing process flow description of isopropylnaphthalene and diisopropylnaphthalene according to the present invention: • naphthalene and propylene • tris (fluorenyl ammonium chloride) -aluminum chloride ionic liquid • firing reaction • iso Propylnaphthalene • Distillation or vacuum distillation method • First reaction product • Trimethylammonium chloride monochloride ionic liquid • Reflux • Distillation method • Naphthalene • Second reaction product • Distillation method • Isopropylnaphthalene • Third reaction product • Product • Reflux • Distillation method • Diisopropylnaphthalene • Triisopropylnaphthalene and above heavy products • Product

Page 14 575565 Brief description of the diagram 2 1 · · · Naphthalene 2 2 · · • Transalkylation reaction 2 3 · · • Transalkylation reaction product 2 4 · · • Reflux

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III

Claims (1)

575565 Thai six! _u ^ _ VI. Application scope 1 · A method for producing isopropylnaphthalene and diisopropylnaphthalene, using naphthalene and propylene as starting reactants, and using trimethylammonium chloride-aluminum chloride ionic liquid As an alkylation catalyst and solvent, a fast isopropylation reaction can be performed at normal pressure and low temperature. The obtained reaction product is separated by distillation to obtain isopropylnaphthalene and diisopropylnaphthalene. 2. The manufacturing method according to item 1 of the scope of patent application, wherein the trimethylammonium chloride-aluminum chloride ionic liquid system is made of trimethyl chloride with a molar ratio of 1: 1. 5 to 2. 2 Ammonium is formed by reaction with aluminum chloride. 3. The manufacturing method as described in item 1 of the scope of patent application, wherein the weight ratio of trimethylammonium chloride-aluminum gasified ionic liquid to naphthalene is between 1: 1 and 20. _ 4 · The manufacturing method according to item 1 of the scope of patent application, wherein isopropylnaphthalene is added as a reactant. 5 · The manufacturing method as described in item 1 of the scope of patent application, wherein the normal pressure means one atmosphere pressure or close to one atmosphere pressure. 6 · The manufacturing method according to item 1 of the scope of patent application, wherein low temperature means between room temperature and 160 t. 7. The manufacturing method as described in item 1 of the scope of patent application, wherein after the reaction product is distilled, the residual trimethylammonium chloride-aluminum chloride ionic liquid is refluxed and reused as an alkylation catalyst and a solvent. 8. The manufacturing method according to item 1 of the scope of patent application, wherein the naphthalene obtained by separating the reaction product by distillation is reused under reflux as a reaction product. 9 · The manufacturing method described in item 1 of the scope of patent application, wherein the reaction Page 16 575565 VI. Scope of patent application Triisopropylnaphthalene and heavy products obtained by distillation of the product are separated by distillation. After adding naphthalene, it is used for refining isopropylnaphthalene and diisopropylnaphthalene through transalkylation reaction. 1 0 · The manufacturing method described in item 1 of the scope of patent application, wherein the isopropyl naphthalene obtained by the distillation method is separated, and a part of the reflux is used as a reactant. 0 1 · As described in the scope of patent application 7, 8, 9, or 1 The manufacturing method described in item 0, wherein the distillation method refers to atmospheric distillation or vacuum distillation. _ _ Page 17