JP2004123666A - Method for producing benzene derivative, aromatic polymer using the same derivative as raw material, and method for producing the same polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a benzene derivative derived from biomass, and to obtain an aromatic polymer using the benzene derivative as a raw material, and to provide a method for producing the aromatic polymer in which all raw materials used are derived from biomass. <P>SOLUTION: Benzene is produced by a catalytic reaction from methane produced from biomass by microbial fermentation, and the benzene derivative containing one or more kinds of ≥2 functional groups selected from amino groups, hydroxy groups and carboxyl groups or the benzene derivative containing ≥2 isocyanate groups is produced from the benzene. The aromatic polymer is produced by using the benzene derivative as a raw material. The aromatic polymer is particularly preferably produced by reacting the benzene derivative with one or more kinds of compounds selected from the group consisting of polyhydroxy compounds, hydroxycarboxylic acid compounds, dicarboxylic acid compounds and amino acids derived from biomass. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a benzene derivative using biomass as a raw material, an aromatic polymer produced using this benzene derivative as a raw material, and a method for producing the aromatic polymer.
[0002]
[Prior art]
Most of polymers (polymers) such as plastics are manufactured using petroleum or the like as a raw material. The produced and consumed polymer is eventually incinerated, generating carbon dioxide and the like, and causing global warming. In addition, it is necessary to develop a polymer raw material that does not depend on petroleum and other resources in preparation for the future depletion of petroleum resources.
[0003]
For example, polylactic acid is known as a plastic manufactured from plant-derived raw materials without using petroleum resources as raw materials. However, polylactic acid is made of an aliphatic main chain and has low heat resistance, so it is used in automobile interiors. It cannot be used in places where high heat resistance is required, such as materials for use and materials around engines.
[0004]
In order to increase the heat resistance of plastic, there is a method of introducing an aromatic ring such as a benzene ring or a naphthalene ring as a polymer structure. As a compound that can be used as a raw material for producing a polymer with an aromatic compound derived from animals and plants, for example, mandelic acid is produced, but the amount produced is extremely small, and it is not obtained in abundance enough to be actually used as a plastic raw material. .
[0005]
Heretofore, as a polymer having an aromatic ring in a molecule (hereinafter, referred to as an “aromatic polymer”) and made of a material derived from animals and plants, for example, polypropylene terephthalate (PTT) is known ( For example, see Non-Patent Document 1.) However, in PTT, a biological process using glucose as a raw material has been developed for the production of 1,3-propanediol, while terephthalic acid is a petroleum raw material as in the past. Regarding other aromatic polymers, there are very few examples in which the aromatic ring portion contained in the polymer is produced from raw materials derived from animals and plants or produced by microbial fermentation.
[0006]
By the way, there is known a method of producing methane from biomass as a raw material by microbial fermentation (for example, see Patent Document 1). Further, a method for producing benzene using methane as a raw material is known (for example, see Patent Document 2). However, there is no known example of using these methods to produce a benzene derivative as a raw material of an aromatic ring portion constituting an aromatic polymer. Furthermore, an aromatic polymer using a raw material in which all materials constituting the aromatic polymer are derived from animals and plants or produced by microbial fermentation, including an aromatic ring portion, that is, a raw material derived from biomass has not been known so far. Was.
[0007]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 2002-154887 [Patent Document 2]
JP-A-11-47606 (page 4)
[Non-patent document 1]
J. A. Miller et al., "Biotechnology and Polymer Chemistry: A Growing Relationship," Macromol. Symp. 174. 7-12 pages (2001)
[0008]
[Problems to be solved by the invention]
The present invention provides a method for producing a benzene derivative from methane produced by microbial fermentation, an aromatic polymer produced using the benzene derivative as a raw material, and a raw material in which all components constituting the aromatic polymer are derived from biomass. The present invention provides a method for producing an aromatic polymer.
[0009]
[Means for Solving the Problems]
The method for producing a benzene derivative of the present invention comprises producing methane from biomass by microbial fermentation, producing benzene from the methane by a catalytic reaction, and further selecting from the benzene an amino group, a hydroxyl group, and a carboxyl group. A benzene derivative containing two or more functional groups or two or more isocyanate groups.
[0010]
Further, the aromatic polymer of the present invention is produced by using the above-mentioned benzene derivative for a part or all of the raw material.
[0011]
Further, the method for producing an aromatic polymer containing a benzene ring of the present invention comprises the following process:
Producing methane from biomass by microbial fermentation;
Producing an aromatic compound containing benzene from the methane by a catalytic reaction;
Producing a benzene derivative containing two or more functional groups selected from an amino group, a hydroxyl group, and a carboxyl group or two or more isocyanate groups from the aromatic compound;
One or more of the benzene derivatives and one or more compounds selected from the group consisting of polyhydroxy compounds, hydroxycarboxylic acid compounds, polycarboxylic acid compounds, and amino acids obtained by microbial fermentation and / or from animals and plants. Reacting or reacting the one or more benzene derivatives with each other.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present specification, a polymer refers to a polymer in which a number of monomers are bonded by a covalent bond, and includes not only a polymer having a large molecular weight but also an oligomer having a relatively small molecular weight.
[0013]
The production of the aromatic polymer having a benzene ring of the present invention (hereinafter, referred to as “benzene-based aromatic polymer”) is performed as follows. First, methane is produced from biomass by microbial fermentation, and benzene is produced by a catalytic reaction using the produced methane as a raw material. Using the obtained benzene as a raw material, a benzene derivative containing at least two functional groups selected from the group consisting of an amino group, a hydroxyl group, and a carboxyl group, or a benzene derivative containing two or more isocyanate groups is produced by chemical synthesis. . The one or more benzene derivatives are reacted with one or more compounds selected from the group consisting of polyhydroxy compounds, polyamines, hydroxycarboxylic acid compounds, polycarboxylic acid compounds, and amino acids. Alternatively, if the benzene derivatives can form a polymer by a condensation reaction or the like, the benzene derivatives can be reacted with each other. One or more compounds selected from the group consisting of the polyhydroxy compounds, hydroxycarboxylic acid compounds, polycarboxylic acid compounds, and amino acids may be biomass-derived compounds obtained by microbial fermentation and / or from animals and plants. Particularly preferred.
[0014]
Known methods can be used for the production of methane by microbial fermentation of biomass. For example, the method described in Patent Document 1 described above can be exemplified, but is not limited thereto. Methane gas can be recovered by performing the above-described microbial fermentation in an appropriate reaction vessel.
[0015]
Next, benzene is produced using methane obtained by microbial fermentation as a raw material. The production of benzene from methane can be exemplified by the method described in Patent Document 2 described above. In this method, for example, an aromatic compound can be synthesized with a conversion of methane of about 9 to 10% and a selectivity of about 70% using a catalyst in which molybdenum and iron are supported on zeolite HZSM-5. Is benzene. The produced benzene can be purified by distillation.
[0016]
The benzene compound as a raw material of the aromatic polymer of the present invention is a benzene derivative containing at least two functional groups selected from an amino group, a hydroxyl group and a carboxyl group, or a benzene derivative containing two or more isocyanate groups. Is preferred. In addition, these amino group, hydroxyl group, carboxyl group, and isocyanate group may not be directly substituted on the benzene ring, but may be bonded to the benzene ring via an alkyl group. Specific benzene compounds include phthalic acids including phthalic acid, isophthalic acid, and terephthalic acid, trimellitic acid, pyromellitic acid, and phenylenediamines (including orthophenylenediamine, metaphenylenediamine, and paraphenylenediamine. ), Hydroquinones (including orthohydroquinone, metahydroquinone, and parahydroquinone), hydroxybenzenecarboxylic acid, aminobenzenecarboxylic acid, phenylenediisocyanates (including orthophenylenediisocyanate, metaphenylenediisocyanate, and paraphenylenediisocyanate), Dihydroxybenzene (including o-, m- and p-isomers), xylylenediamine (including o-, m- and p-isomers) and xylylenediisocyanate are preferred. Properly (o-, m-, and a p- isomers.), Phthalates, phenylenediamines, hydroquinones, and phenylene diisocyanates are particularly preferred.
[0017]
The benzene derivative can be produced from benzene by a known method in organic synthesis. For example, as a method for producing terephthalic acid from benzene, benzene is reacted with methyl chloride in the presence of aluminum chloride, methylated to toluene, and the resulting toluene is reacted with paraformaldehyde and hydrochloric acid in the presence of aluminum chloride. how Te by chloromethylation to synthesize p- chloromethyl toluene, or a method of oxidizing this, the toluene and carbon monoxide and p- tolyl aldehyde were reacted HF-BF ₃ catalyst presence, oxidizes this Are known, but not limited to these.
[0018]
A method for producing phenylenediamine from benzene is, for example, a method of dinitrating benzene with nitric acid-sulfuric acid and catalytically reducing it with nickel, or a method of mononitrating benzene and reducing it with Fe-HCl to produce aniline. A method of further nitrating and then reducing again is known, but is not limited thereto.
[0019]
As a method of producing hydroquinone from benzene, for example, a method of oxidizing the above aniline with manganese dioxide or sodium dichromate in the presence of sulfuric acid to form parabenzoquinone and then reducing the aniline is known, but not limited thereto.
[0020]
It is known that phenylene diisocyanate can be produced by reacting the above-mentioned phenylene diamine with phosgene, and known methods and reaction conditions can be used.
[0021]
Benzene derivatives, such as phthalic acid, phenylenediamine, hydroquinone, and phenylenediisocyanate, produced by the above-mentioned method are polyhydroxy compounds such as ethylene glycol, propylene glycol, 1,3-propanediol, and 1,4-butanediol. 1,6-hexanediol, cyclohexanedimethanol, polypropylene glycol, and polyethylene glycol; polyamines, such as ethylenediamine, 1,4-tetramethylenediamine, and 1,6-hexamethylenediamine; polycarboxylic acids, such as succinic acid Aromatic polymers can be produced by a condensation reaction or an addition reaction with a polyfunctional compound selected from the group consisting of, adipic acid and azelaic acid, and such condensation reaction or addition method is known. A. The polyhydroxy compound, the polyamine, and the polycarboxylic acid may be used as a mixture of one or more compounds. The specific examples of the polyhydroxy compound, polyamine, and polycarboxylic acid are only examples, and the present invention is not limited thereto.
[0022]
For example, an aromatic polyester can be produced by dehydrating and condensing diol and terephthalic acid among polyhydroxy compounds. By using ethylene glycol, 1,3-propanediol, and 1,4-butanediol as the diol, polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate can be produced, respectively. These aromatic polyesters can be produced by previously converting phthalic acid into an ester derivative such as a methyl ester, and subjecting the ester derivative to a transesterification reaction with a polyhydroxy compound. Also, aromatic polyester can be produced by converting phthalic acid into acid chloride in advance and reacting the acid chloride with a polyhydroxy compound.
[0023]
An aromatic polyester can be produced by subjecting hydroquinone produced by the method of the present invention to a polycarboxylic acid, for example, succinic acid, adipic acid, and azelaic acid by a dehydration condensation reaction. Also in this case, the polycarboxylic acid can be converted into an ester derivative such as a methyl ester or an acid chloride in advance and reacted with hydroquinone.
[0024]
Aromatic polyester can also be obtained by condensing a benzene derivative having a hydroxy group and a carboxyl group such as salicylic acid derived from benzene or parahydroxybenzoic acid with a derivative having a hydroxy group and a carboxyl group such as lactic acid. Can be manufactured.
[0025]
An aromatic polyamide can be produced by reacting the phenylenediamine produced by the method of the present invention with a polycarboxylic acid, for example, succinic acid, adipic acid, and / or azelaic acid. An aromatic polyamide can also be produced by reacting phthalic acid produced by the method of the present invention and a polyamine, for example, ethylenediamine, 1,4-tetramethylenediamine, and / or 1,6-hexamethylenediamine. . Further, the phenylenediamine and phthalic acid can be reacted to produce a wholly aromatic polyamide. For the production method of these polyamides, known methods can be used.For example, a direct dehydration condensation reaction between a carboxyl group and an amino group, or a carboxyl group previously converted to an ester group such as a methyl ester or an acid chloride, A wholly aromatic polyamide can also be produced by reacting an ester group or acid chloride with an amino group.
[0026]
The phenylene diisocyanate produced by the method of the present invention is used as a polyhydroxy compound, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, cyclohexanedimethanol, polypropylene Polyurethane resins can be produced by an addition reaction with one or more compounds selected from glycols and polyethylene glycols. The production of a urethane resin by an addition reaction between a polyisocyanate and a polyhydroxy compound is known, and known raw materials including a catalyst for producing a urethane resin, known methods and conditions, and the like can be used.
[0027]
A polyurea resin can be produced by reacting the phenylene diisocyanate produced by the method of the present invention with a polyamine such as ethylenediamine, 1,4-tetramethylenediamine, and 1,6-hexamethylenediamine. The production of a urea resin by an addition reaction between a polyisocyanate and a polyamine is known, and known methods and conditions can be used.
[0028]
Further, a polyurethane urea resin can also be produced by reacting the phenylenediisocyanate produced by the method of the present invention with a polyhydroxy compound and a polyamine. A method for producing a polyurethane urea resin by reacting a polyisocyanate with a polyhydroxy compound and a polyamine is known, and known raw materials, methods and conditions can be used.
[0029]
The polyhydroxy compound, hydroxycarboxylic acid compound, dicarboxylic acid compound, and one or more kinds selected from the group consisting of amino acids used for producing an aromatic polymer by reacting with the benzene derivative produced by the method of the present invention. The compound (hereinafter, referred to as “polyhydroxy compound, etc.”) is particularly preferably a biomass-derived compound obtained by microbial fermentation and / or from animals and plants. By using these materials, all the raw materials constituting the aromatic polymer can be composed of a biomass-derived compound together with the benzene derivative of the present invention.
[0030]
Examples of the biomass-derived polyhydroxy compound include 1,3-propanediol, succinic acid, lactic acid, and various amino acids, but are not limited thereto.
[0031]
Aromatic polymer produced by the method of the present invention, as a polymer produced using a raw material derived from biomass, a polymer having higher heat resistance than conventionally known polylactic acid and the like, and also having a high mechanical strength can be obtained, It can be used as a material for automobile interiors or a material around an engine.
[0032]
【The invention's effect】
According to the production method of the present invention, a benzene derivative derived from biomass, which has been difficult so far, can be produced. Aromatic polymers manufactured using this benzene derivative as a raw material, especially aromatic polymers manufactured using raw materials in which all the constituents of the aromatic polymer are derived from biomass, should have extremely low dependence on petroleum raw materials. Can be. The aromatic polymer of the present invention has better heat resistance than a polymer produced using a conventionally known raw material derived from biomass such as polylactic acid, and can be used for automotive interior materials, or around engines. .

Claims (3)

Methane is produced from biomass by microbial fermentation, benzene is produced from the methane by a catalytic reaction, and from the benzene, two or more functional groups of one or more selected from the group consisting of an amino group, a hydroxyl group, and a carboxyl group or A method for producing a benzene derivative, comprising producing a benzene derivative containing two or more isocyanate groups. An aromatic polymer produced using the benzene derivative according to claim 1 as a part or all of a raw material. A process for producing an aromatic polymer containing a benzene ring, comprising the following process:
Producing methane from biomass by microbial fermentation;
Producing an aromatic compound containing benzene from the methane by a catalytic reaction;
Producing a benzene derivative containing two or more functional groups selected from an amino group, a hydroxyl group, and a carboxyl group or two or more isocyanate groups from the aromatic compound;
One or more of the benzene derivatives and one or more compounds selected from the group consisting of polyhydroxy compounds, hydroxycarboxylic acid compounds, polycarboxylic acid compounds, and amino acids obtained by microbial fermentation and / or from animals and plants. Reacting or reacting one or more benzene derivatives with each other. A method for producing an aromatic polymer containing a benzene ring, comprising: