CN101417922A - Method for preparing 2,6-di-t-butyl naphthalin - Google Patents
Method for preparing 2,6-di-t-butyl naphthalin Download PDFInfo
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- CN101417922A CN101417922A CNA2007101762712A CN200710176271A CN101417922A CN 101417922 A CN101417922 A CN 101417922A CN A2007101762712 A CNA2007101762712 A CN A2007101762712A CN 200710176271 A CN200710176271 A CN 200710176271A CN 101417922 A CN101417922 A CN 101417922A
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Abstract
The invention relates to a preparation method for 2, 6-di (tert butyl) naphthalene. The invention adopts tert butyl to replace group for carrying out naphthaleneshape selective reaction, thus obtaining a mixture liquid with high content of 2, 6-di (tert butyl) naphthalene. The mixture liquid can be separated and purified in a lower alcohol recrystallation method, thus obtaining high-purity 2, 6-DTBN crystal. The method overcomes the problems of bi-alkyl naphthalene having poor selectivity, the 2, 6-/2, 7-DAN being low and the target production having difficulty in separating when adopting little volume substituent group such as methyl, ethyl and isopropyl to carry out naphthaleneshape selective reaction. As to the Y-type zeolite catalyst with oxalic acidcomplex dealumination modification, the naphthalene conversion rate can reach to 70mol percent, and the 2, 6-/2, 7-DAN approaches to 9.0. The preparation method of 2, 6-di (tert butyl) naphthalene has the advantages of moderate reaction condition, high selectivity of target production and simple and easy for separation.
Description
Technical field
The present invention relates to a kind of naphthalene and select shape tert-butylation preparation and contain 2, the mixed solution of 6-di-t-butyl naphthalin (DTBN) separates to purify obtaining high purity 2,6-DTBN crystalline method by the lower alcohol recrystallization.
Background technology
2,6-dialkyl group naphthalene (DAN) is important Organic Chemicals, its oxidation products 2, and the polyethylene glycol 2 (PEN) that 6-naphthalene dicarboxylic acids and ethylene glycol polymerization obtain is a kind of novel high-performance polyester material.The structural high symmetry of PEN makes it have the characteristic of straight-chain polymer, PET compares with phenyl polymer, more superior at aspects such as gas barrier property, thermotolerance, mechanical property, radiation resistance, chemical stability and dimensional stabilitys, can be used for making Beer Bottle, fresh-keeping packaging material, industrial fiber, magnetic record band and aerospace and nuclear power material etc.At present, global PEN industrial scale is still less than 300,000 tons/year, suppresses the bottleneck problem that PEN comes into the market on a large scale, how to ascribe the Synthetic 2 of highly selective to, and 6-DAN optimizes 2, the isolation technique of 6-DAN, thus reduce the production cost of raw material.
Current research focus concentrates on and improves 2,6-dimethylnaphthalene (DMN) and 2, the synthetic and isolation technique of 6-diisopropylnaphthalene (DIPN).Wherein, 2,6-DMN mainly extracts or makes by the multistep chemical process is synthetic from raw materials such as coal tar and oil refining byproduct heavy arene.Since 2,6-DMN content in these raw materials low (about 0.1-1%), the feed composition complexity, separating step is numerous and diverse, only is suitable for small-scale production.US5396007, US5073670 and CN1192726A, CN1298374A were raw material with o-Xylol and divinyl, p-Xylol and 1-butylene, toluene and amylene respectively once, successively by totally six steps operation Synthetic 2 such as alkylation dehydrocyclization aromizing, 6-DMN.These technology have been built up industrial production device, yet because operational path is longer, are difficult to reduce by 2, the production cost of 6-DMN.Thereby, the decalin base Synthetic 2, the research direction of 6-DAN directly easyly is subjected to common concern gradually with it.But the reaction product of menaphthylization and naphthalene isopropylation is formed complicated, comprises that naphthalene, replaces naphthalene, two replacement naphthalenes, three replace naphthalenes and a small amount of four and replace high boiling material such as naphthalene, purpose product 2, and the 6-DAN selectivity is low.US4795847 has carried out the form selected methylation reaction of methylnaphthalene and methyl alcohol on the HZSM-5 zeolite molecular sieve, react after 0.5 hour, and the methylnaphthalene transformation efficiency only is 7%, 2, and the 6-DMN selectivity is 35%; Thereafter, CN1362392A, CN1762932A and CN1660726A etc. introduce the decalin base reaction with supercritical reaction conditions and ionic liquid catalyst system, but naphthalene transformation efficiency and 2, the 6-DAN selectivity all fails to be significantly improved.In addition, complicated products distribution is given to separate and has also been brought huge difficulty, particularly boiling point is very approaching between two of the naphthalene replacement isomer, easily form eutectic near the fusing point, be difficult to be separated from each other by routine distillation or crystallization method, and also there are not known selective adsorption 2,6-DMN and 2, the material of 6-DIPN at present.CN1183400A, the CN1112539A emulsification crystallization that proposed respectively progressively to heat up carries out the purification that separates of purpose product with three tower batch rectification methods, but product yield is not high, and the operation relative complex has also suppressed the reduction of production cost virtually.
Summary of the invention
The object of the present invention is to provide a kind of preparation 2, the method for 6-di-t-butyl naphthalin.
For achieving the above object, provided by the invention 2,6-di-t-butyl naphthalin preparation method, step is as follows:
A) with the naphthalene be raw material, the compound that can generate tertiary butyl group is an alkylating reagent, the y-type zeolite molecular sieve is an alkylation catalyst, add in organic inert solvent, in 120-200 ℃, 0.5-4.0MPa reacted 1-5 hour down, obtained containing 2, the mixed solution of 6-di-t-butyl naphthalin component obtains crystallization after this mixed solution distillation concentrates.Wherein:
Raw material: alkylating reagent: inert solvent=1:1:30-1:4:300 mol ratio;
The mass ratio that catalyzer and naphthalene feed intake is 1:1-5:1.
B) crystallization of steps A is carried out recrystallization with lower alcohol and is purified under 20-80 ℃, obtains high purity 2,6-di-t-butyl naphthalin crystal, and wherein the mass ratio of crystallization and lower alcohol is 0.5:1-10:1.
Described method, wherein, the compound that can generate tertiary butyl group is one or more the mixture in the trimethyl carbinol, tert-bromo butane, isopropylcarbinol, iso-butylene, the methyl tertiary butyl ether.
Described method, wherein, organic inert solvent is one or more the mixture in hexanaphthene, normal hexane, sym-trimethylbenzene, the perhydronaphthalene, preferred organic inert solvent is a hexanaphthene.
Described method, wherein, lower alcohol is one or more the mixture in methyl alcohol, ethanol and the propyl alcohol.
Described method, wherein, the condition of B repeats the recrystallization purification set by step.
Method provided by the invention can be easy from naphthalene and trimethyl carbinol preparation 2, the 6-DTBN crystallization, it is higher that the form selected methylation catalyzer has transformation efficiency, selectivity preferably characteristics (the naphthalene transformation efficiency is greater than 70 moles of %, 2,6-/2, the 7-DTBN ratio reaches 9.0.)
Embodiment
The present invention contains 2 for the decalin base reaction provides a new substituting group, naphthalene to select the preparation of shape tert-butylation, and the mixed solution of 6-DTBN separates purification by the lower alcohol recrystallization and obtains high purity 2,6-DTBN crystallization.Method reaction conditions gentleness of the present invention has high reaction activity and high and preferably 2, the 6-DTBN selectivity, and purpose product lock out operation is easy.
The zeolite molecular sieve that the present invention uses is the modified zeolite of Y-type molecular sieve: zeolite is joined in the ammonium oxalate solution with weight ratio 1:2-1:30, under 25-100 ℃ of temperature, added oxalic acid treatment 0.5-10 hour then, keep buffer system pH=3.0~6.0, final drying, roasting.
The present invention selects the catalyzer of shape tertiary butyl reaction as naphthalene with above-mentioned modified zeolite of Y-type molecular sieve catalyst, with the naphthalene is raw material, with the compound that can generate tertiary butyl group is alkylating reagent, in organic inert solvent, synthesize and contain 2, the mixed solution of 6-DTBN, separate promptly obtaining 2, the knot crystallization of 6-DTBN.
Above-mentioned inert solvent does not participate in reaction in reaction process.This inert solvent is hexanaphthene preferably.
Naphthalene transformation efficiency and 2 among the present invention, 6-DTBN selectivity and 2,6-/2,7-DTBN calculates by sampling gas chromatographic analysis result after the mixed solution cooling centrifugation in the reactor.
The present invention obtain 2,6-DTBN carries out recrystallization again and separate to purify: with 2 of gained behind the catalytic alkylation reaction, the 6-DTBN crystallization is recrystallization, washing, drying in 20-80 ℃ of lower alcohol solvent.Above step can repeat repeatedly, obtains high purity white prism-shaped 2, the crystallization of 6-DTBN.
The invention is characterized in: utilize the duct shape selectivity of bigger steric effect of the tertiary butyl and zeolite molecular sieve, can under relatively mild reaction conditions, carry out alkylated reaction, and the product composition distributes simpler.
Another feature of the present invention is: utilize in the oxalic acid dealuminzation system, there are ionization equilibrium and complexation equilibrium, and the oxalic acid aluminium complex ion volume of three-fold coordination is bigger, stop the complexing of interior brilliant aluminium atom and oxalic ion, shown the effective elimination of outside surface upper skeleton aluminium atom, thereby formed surperficial silicon-rich layer, the zeolite molecular sieve outer surface acidity position is modified, slackened the isomerization reaction of purpose product on the outer surface acidity position, strengthened 2 to reach, 6-DTBN is purpose optionally.
Feature of the present invention also is: utilize 2,6-DTBN and 2,7-DTBN fusing point differ big (being respectively 145-146 ℃ and 82-83 ℃), and 2, the characteristics that 6-DTBN solubleness in lower alcohol is little are effectively isolated purpose product 2,6-DTBN by the method for lower alcohol recrystallization.
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to following examples.
Embodiment 1
Take by weighing aluminum isopropylate 408g, solid sodium hydroxide 800g is dissolved in it in 3.6Kg water, stirs to add the 2.4Kg silicon sol down.Formed initial gel reaction thing is transferred in the seal pot, respectively room temperature crystallization 24 hours, and 60 ℃ of crystallization 48 hours.After the product separating, washing drying, be Y zeolite through the identification of phases of XRD thing.Gained NaY molecular sieve is through NH
4Ion-exchange changes into NH
4Y molecular sieve forms the HY zeolite molecular sieve through roasting again.The resulting HY type zeolite molecular sieve of 20 grams is joined in the 200 gram ammonium oxalate solutions, under 80 ℃ of temperature, add 3.0 gram oxalic acid, handled 3 hours, filter, washing was dried 8 hours for 150 ℃, 550 ℃ of roastings 4 hours promptly obtain the modified Y zeolite molecular sieve catalyst, are numbered OY.
Embodiment 2
With the naphthalene is raw material A, with the trimethyl carbinol is raw material B, with the hexanaphthene is raw material C, and with the mol ratio of A:B:C=2.25:3:200, uses OY that the foregoing description 1 obtains as alkylation catalyst, the mass ratio that catalyzer and naphthalene feed intake is 1.8:1, temperature of reaction is 160 ℃, and reaction pressure is 2.0MPa, and the reaction times is under 2 hours the condition, obtain containing 2, the mixed solution of 6-DTBN component higher concentration.Analytical results shows that the naphthalene transformation efficiency is 70.4 moles of %, 2, and 6-DTBN selectivity in the di-t-butyl naphthalene mixtures is 90.0 moles of %, 2,6-/2,7-DTBN is 9.0.
Embodiment 3
With the naphthalene is raw material A, with the methyl tertiary butyl ether is raw material B, with the sym-trimethylbenzene is raw material C, and with the mol ratio of A:B:C=1.75:3:200, the OY that use the foregoing description 1 obtains is as alkylation catalyst, and the mass ratio that catalyzer and naphthalene feed intake is 3:1, and temperature of reaction is 140 ℃, reaction pressure is 4.0MPa, and the reaction times is 5 hours.Analytical results shows that the naphthalene transformation efficiency is 78.1 moles of %, 2, and 6-DTBN selectivity in the di-t-butyl naphthalene mixtures is 89.3 moles of %, 2,6-/2,7-DTBN is 8.41.
Embodiment 4
With the naphthalene is raw material A, with the iso-butylene is raw material B, with the perhydronaphthalene is raw material C, and with the mol ratio of A:B:C=2.25:5:200, the OY that use the foregoing description 1 obtains is as alkylation catalyst, and the mass ratio that catalyzer and naphthalene feed intake is 5:1, and temperature of reaction is 200 ℃, reaction pressure is 0.5MPa, and the reaction times is 5 hours.Analytical results shows that the naphthalene transformation efficiency is 57.9 moles of %, 2, and 6-DTBN selectivity in the di-t-butyl naphthalene mixtures is 88.7 moles of %, 2,6-/2,7-DTBN is 7.87.
Embodiment 5
With the naphthalene is raw material A, is raw material B with tert-bromo butane and isopropylcarbinol by weight the mixture of=1:1, with normal hexane and sym-trimethylbenzene by volume=mixing solutions of 0.6:1 is raw material C, and with the mol ratio of A:B:C=2.25:3:200, the OY that use the foregoing description 1 obtains is as alkylation catalyst, and the mass ratio that catalyzer and naphthalene feed intake is 1:1, and temperature of reaction is 120 ℃, reaction pressure is 0.8MPa, and the reaction times is 1 hour.Analytical results shows that the naphthalene transformation efficiency is 85.6 moles of %, 2, and 6-DTBN selectivity in the di-t-butyl naphthalene mixtures is 85.9 moles of %, 2,6-/2,7-DTBN is 6.11.
Embodiment 6
Contain 2 with what obtain in the foregoing description, the distillation of 6-DTBN mixed solution concentrates post crystallization, with the ratio of solid-liquid mass ratio 5:1, in resulting coarse-grain mixture, add hot ethanol and carry out recrystallization, can obtain white prism-shaped 2,6-DTBN, its fusing point is at 142-144 ℃, and is smart 2, and 6-DTBN purity is 97.05%, essence 2, the 6-DTBN yield is 92.35%.
Embodiment 7
Contain 2 with what obtain in the foregoing description, the distillation of 6-DTBN mixed solution concentrates post crystallization, with the ratio of solid-liquid mass ratio 3:1, in resulting coarse-grain mixture, add hot ethanol and carry out recrystallization, can obtain white prism-shaped 2,6-DTBN, its fusing point is at 142-144 ℃, and is smart 2, and 6-DTBN purity is 98.11%, essence 2, the 6-DTBN yield is 85.26%.
Claims (6)
1, a kind of preparation 2, the method for 6-di-t-butyl naphthalin, step is as follows:
A) with the naphthalene be raw material, the compound that can generate tertiary butyl group is an alkylating reagent, the modified Y zeolite molecular sieve is a catalyzer, add in organic inert solvent, in 120-200 ℃, 0.5-4.0MPa reacted 1-5 hour down, obtained containing 2, the mixed solution of 6-di-t-butyl naphthalin component obtains crystallization after this mixed solution distillation concentrates; Wherein:
Raw material: alkylating reagent: inert solvent=1:1:30-1:4:300 mol ratio;
The mass ratio that catalyzer and naphthalene feed intake is 1:1-5:1;
B) crystallization that obtains of steps A is carried out recrystallization with lower alcohol and is purified under 20-80 ℃, obtains 2,6-di-t-butyl naphthalin crystal, and wherein the mass ratio of crystallization and lower alcohol is 0.5:1-10:1.
2, the method for claim 1, wherein alkylating reagent is one or more a mixture in the trimethyl carbinol, tert-bromo butane, isopropylcarbinol, iso-butylene, the methyl tertiary butyl ether.
3, the method for claim 1, wherein organic inert solvent is one or more the mixture in hexanaphthene, normal hexane, sym-trimethylbenzene, the perhydronaphthalene.
4, as claim 1 or 3 described methods, wherein, organic inert solvent is a hexanaphthene.
5, the method for claim 1, wherein lower alcohol is one or more a mixture in methyl alcohol, ethanol and the propyl alcohol.
6, the method for claim 1, wherein set by step the condition of B repeat recrystallization and purify.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105601459A (en) * | 2015-12-01 | 2016-05-25 | 中国科学院大连化学物理研究所 | Method for preparing 2-methyl-6-tert-butylnaphthalene from 2-methylnaphthalene through alkylation |
CN109433253A (en) * | 2018-11-30 | 2019-03-08 | 中国科学院大连化学物理研究所 | The catalyst and its preparation method and application of 2,6- di-t-butyl naphthalin is prepared for naphthalene form selected methylation |
-
2007
- 2007-10-24 CN CNA2007101762712A patent/CN101417922A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105601459A (en) * | 2015-12-01 | 2016-05-25 | 中国科学院大连化学物理研究所 | Method for preparing 2-methyl-6-tert-butylnaphthalene from 2-methylnaphthalene through alkylation |
CN109433253A (en) * | 2018-11-30 | 2019-03-08 | 中国科学院大连化学物理研究所 | The catalyst and its preparation method and application of 2,6- di-t-butyl naphthalin is prepared for naphthalene form selected methylation |
CN109433253B (en) * | 2018-11-30 | 2020-11-27 | 中国科学院大连化学物理研究所 | Catalyst for preparing 2, 6-di-tert-butyl naphthalene by naphthalene shape-selective alkylation and preparation method and application thereof |
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