CN102617531B

CN102617531B - Method for using mixed C5 to produce methyl nadic anhydride

Info

Publication number: CN102617531B
Application number: CN201210063204.0A
Authority: CN
Inventors: 王中锋; 杨振强; 马伟英; 陈淑敏; 杨瑞娜; 吕海宽; 韩兆海; 冯培培; 杨素青
Original assignee: PUYANG HUICHENG ELECTRONIC MATERIAL CO Ltd
Current assignee: PUYANG HUICHENG ELECTRONIC MATERIAL CO Ltd
Priority date: 2012-03-12
Filing date: 2012-03-12
Publication date: 2014-04-16
Anticipated expiration: 2032-03-12
Also published as: CN102617531A

Abstract

The invention discloses a method for using mixed C5 to produce methyl nadic anhydride, which belongs to the field of organic synthesis. According to the method, the mixed C5 is used as a starting raw material, the main component of the mixed C5, i.e. cyclopentadiene, is subjected to reaction with a methylation agent to synthesize methyl cyclopentadiene under the effect of an alkaline catalyst, and methyl nadic anhydride is synthesized by Diels-Alder reaction of maleic anhydride and low-temperature distillate obtained via distillation of methyl cyclopentadiene. Thermal polymerization and separation of the cyclopentadiene in the raw material mixed C5 are not required in the reaction process, thus the production cost, energy consumption and environmental pollution are reduced, and the method is suitable for the industrial production and has better application prospects. The solidification point of the product produced by the method is lower than minus 15 DEG C, the anhydride content is more than or equal to 40 percent, and the methyl nadic anhydride can maintain stability for a long time.

Description

A kind of utilization mixed the method that carbon five is produced methyl carbic anhydride

Technical field

The present invention relates to a kind of production method of Chemicals, relate in particular to the production method of methyl carbic anhydride, belong to organic synthesis field.

Background technology

Methyl carbic anhydride (Methyl nadic anhydride, be called for short MNA) claim again MNA, it is a kind of organic acid anhydride based epoxy resin curing agent of excellent property, be widely used in electrical apparatus insulation material, especially the insulating material of large electric appliances, it has following characteristics: under room temperature, viscosity is lower, can construct at a lower temperature and long-term storage; Long working life with epoxy resin composition, curing speed is slow, and heat release is little, and this is very favourable for preparing lamination, winding material, cast material; , ageing resistance high temperature resistant with the cured article of epoxy resin and chemical resistance excellence; Under hot conditions, solidify for a long time, can make its epoxy resin-cured product have good thermotolerance and hardness, cure shrinkage is little.

At present, the methyl carbic anhydride production method of bibliographical information, is take methyl cycle pentadiene dimer as starting raw material, and after cracking, monomer whose and MALEIC ANHYDRIDE are synthesized through Diels-Alder addition.Because raw material methyl cycle pentadiene dimer source is limited, cause methyl carbic anhydride production cost higher, in addition, its output also cannot meet industrial demand.Solve raw material sources, the substitute of finding methyl cycle pentadiene dimer raw material becomes current methyl carbic anhydride actual industrialization and produces urgent problem.

Summary of the invention

The object of the invention is to provide a kind of production cost low, and environmental pollution is little, and product purity, yield are high, to mix carbon five, produces the novel method of the applicable suitability for industrialized production of methyl carbic anhydride as starting raw material.

In order to realize the object of the invention, the present invention from solve raw material sources, directly use mixing carbon five be starting raw material, its main component cyclopentadiene under basic catalyst effect with methylating reagent CH ₃x reaction synthesizing methyl cyclopentadiene, after simple distillation, low temperature fraction (main component is methyl cyclopentadiene, m-pentadiene and isoprene etc.) reacts synthesizing methyl carbic anhydride with MALEIC ANHYDRIDE through Diels-Alder under certain condition.

Concrete synthetic route is as follows:

Concrete reactions steps is as follows:

In reactor, add successively and mix carbon five and basic catalyst, at 10-20 ℃ of stirring reaction, add methylating reagent CH ₃x, stirring reaction, when gas-chromatography (GC) detects without cyclopentadiene, stopped reaction.Distill to such an extent that 80 ℃ of following cuts are methyl cyclopentadiene mixture, control temperature of reaction between 0-20 ℃, this mixture is splashed in the reaction flask that MALEIC ANHYDRIDE is housed, dropwise, stirring reaction 4-6 h, GC detection reaction system is during without MALEIC ANHYDRIDE, be warming up to 80 ℃ of reclaim under reduced pressure decylization carbon five (main component m-pentadiene and isoprene), then add an acidic catalyst, continue to be warming up to 160-200 ℃ of reaction, underpressure distillation obtains methyl carbic anhydride, and yield is greater than 90%(and calculates according to MALEIC ANHYDRIDE).

Described mixing carbon five main components are cyclopentadiene, m-pentadiene and isoprene.

Basic catalyst is sodium hydroxide, potassium hydroxide, sodium tert-butoxide etc., and the molar ratio of its consumption and cyclopentadiene is 1.05-1.2: 1.

An acidic catalyst is polyphosphoric acid, p-methyl benzenesulfonic acid etc., and the mass ratio of its consumption and cyclopentadiene is 0.04-0.05: 1.

Methylating reagent CH ₃x is monobromethane, methyl iodide etc., and the molar ratio of cyclopentadiene and methylating reagent is 1: 1.1-1.4.

Beneficial effect of the present invention is: mixing carbon five is the by products in a kind of cracking ethylene process of cheapness, the present invention directly prepares methyl carbic anhydride take it as raw material, substitute methyl cycle pentadiene dimer, has reduced production cost, reduce environmental pollution, be applicable to suitability for industrialized production; The product zero pour <-15 ℃ making by the method, boiling point >250 ℃, viscosity 130 ~ 250 mPas (25 ℃), acid anhydride base content >=40%, colourity is lower than 160(platinum-cobalt look number), and can keep for a long time stable; The present invention contributes to promote the market competitiveness of methyl carbic anhydride, and the decylization carbon five reclaiming can recycle, and has deepened the resources effective utilization of mixing carbon five.

Tool present embodiment

For the present invention is described in detail better, give an actual example as follows:

embodiment 1

In the reaction flask that electric stirring is housed, add successively 1000 g mixing carbon five (main component cyclopentadiene, m-pentadiene and isoprene, wherein cyclopentadiene accounts for total mass per-cent 17%) and 123.4 g(3.1 mol) sodium hydroxide, after 20 ℃ of stirring reaction 4 h, slowly add 349.6 g(3.7 mol) monobromethane, add and at this temperature, continue stirring reaction 3 h, when GC detects without cyclopentadiene, distill, obtain 80 ℃ following cuts of distillation are equipped with 226.9 g(2.3 mol keeping temperature of reaction slowly to splash between 0-20 ℃) in the reaction flask of MALEIC ANHYDRIDE, drip Bi Jixu stirring reaction 4 h, GC detection reaction system is during without MALEIC ANHYDRIDE, reclaim under reduced pressure 835 g decylization carbon five at 80 ℃, add 8.5g polyphosphoric acid, reaction system continues to be warming up to 180 ℃ of reaction 5 h, stopped reaction, underpressure distillation obtains 373.3 g methyl carbic anhydrides, yield 90.5%.

embodiment 2

In the reaction flask that electric stirring is housed, add successively 2000 g mixing carbon five (main component cyclopentadiene, m-pentadiene and isoprene, wherein cyclopentadiene accounts for total mass per-cent 17%) and 387.2 g(5.7 mol) potassium hydroxide, after 15 ℃ of stirring reaction 2 h of temperature of reaction, slowly add 586.1 g(6.2 mol) monobromethane, then at this temperature, continue stirring reaction 4 h, when GC detects without cyclopentadiene, distill, obtain 80 ℃ following cuts of distillation slowly splash into 454.2 g(4.6 mol are housed between temperature of reaction 0-20 ℃) in the reaction flask of MALEIC ANHYDRIDE, drip complete stirring reaction 5 h, GC detection reaction system is during without MALEIC ANHYDRIDE, reclaim under reduced pressure 1680 g decylization carbon five at 80 ℃, add 15g polyphosphoric acid, reaction system continue to be warming up to 160 ℃ reaction 8 h after stopped reaction, underpressure distillation obtains 759 g methyl carbic anhydrides, yield 92%.

embodiment 3

In the reaction flask that electric stirring is housed, add successively 1500 g mixing carbon five (main component cyclopentadiene, m-pentadiene and isoprene, wherein cyclopentadiene accounts for total mass per-cent 17%), 393.6 g(4.1 mol) sodium tert-butoxide, after 10 ℃ of stirring reaction 3 h of temperature of reaction, add gradually 602.4 g(4.3 mol) methyl iodide, after adding, at this temperature, continue stirring reaction 4 h, when GC detects without cyclopentadiene, distill, obtain 80 ℃ following cuts of distillation slowly splash into 340.6 g(3.5 mol are housed at temperature of reaction 0-20 ℃) in the reaction flask of MALEIC ANHYDRIDE, drip after complete stirring reaction 6 h, GC detection reaction system is during without MALEIC ANHYDRIDE, reclaim under reduced pressure 1256 g decylization carbon five at 80 ℃, add 10.2 g p-methyl benzenesulfonic acids, reaction system continues to be warming up to after 200 ℃ of reaction 7 h, stopped reaction, underpressure distillation obtains 581.5 g methyl carbic anhydrides, yield 94%.

Claims

1. a method of producing methyl carbic anhydride, is characterized in that, to mix carbon five as starting raw material, at temperature of reaction 10-20 ℃, in reactor, adds successively mixing carbon five, basic catalyst, and stirring reaction, adds methylating reagent CH ₃x, then continues stirring reaction, when gas-chromatography (GC) detects without cyclopentadiene, distills, and distills to such an extent that 80 ℃ of following cuts are methyl cyclopentadiene mixture; Control temperature of reaction between 0-20 ℃, this mixture is splashed in the reaction flask that MALEIC ANHYDRIDE is housed, drip and finish, stirring reaction, GC detection reaction system is during without MALEIC ANHYDRIDE, and reclaim under reduced pressure decylization carbon five at 80 ℃, then adds an acidic catalyst, reaction system continues to be warming up to 160-200 ℃ of reaction, and underpressure distillation obtains methyl carbic anhydride; Described mixing carbon five main components are cyclopentadiene, m-pentadiene and isoprene;

The basic catalyst adopting is that following compounds is wherein a kind of: sodium tert-butoxide, and sodium hydroxide, potassium hydroxide, its consumption and cyclopentadiene molar ratio are 1.05-1.2:1;

An acidic catalyst is polyphosphoric acid or p-methyl benzenesulfonic acid, and the mass ratio of its consumption and cyclopentadiene is 0.04-0.05: 1;

Methylating reagent CH ₃x is monobromethane or methyl iodide, cyclopentadiene and CH ₃the molar ratio of X is 1: 1.1-1.4.