JP2001064494A - Polyester composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of giving a polyester raw material exhibiting an excellent tensile strength and elongation by incorporating a polyester and a specific lignophenol in it. SOLUTION: This polyester composition is obtained by incorporating (A) a polyester and (B) 1-50 wt.% lignophenol derivative selected from a lignophenol derivative obtained by adding an acid to a lignophenol-based substance added with a phenol derivative, mixing and separating to the lignophenol derivative and a hydrocarbon, an alkali-treated derivative of the lignophenol derivative and a derivative obtained by blocking hydroxyl group of the lignophenol derivative or the alkali-treated derivative. As the component A, a biodegradable polyester is preferable. As the biodegradable polyester, a homopolymer and/or copolymer of hydroxyalkanoate is preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyester composition. More specifically, the present invention relates to a polyester composition containing a polyester (preferably a biodegradable polyester) and a lignophenol derivative, and a plasticizer for a polyester containing a lignophenol derivative.

[0002]

2. Description of the Related Art In modern society, the use of fossil resources has become indispensable. However, reproduction of fossil resources is impossible, and there is a fear of exhaustion in the near future. Biomass resources are attracting attention as one of the alternatives to fossil resources. Among them, woody biomass is enormous on the earth, can be produced in a short period of time, and is continuously supplied through appropriate maintenance. It is attracting attention because it is a possible resource, and after it is used as a resource, it is degraded in nature and reborn as a new biomass resource. Currently, woody biomass is used in two ways: wood use and pulp use. However, a large amount of waste is discharged in the use as wood, and lignin is hardly used in the use as pulp because the purpose is to use carbohydrate (cellulose).

In order to use lignin effectively in woody (lignocellulosic) biomass,
First, it is necessary to separate the wood into its constituents.
The present inventors have found that, based on previous studies, the combination of swelling of carbohydrates by concentrated acid and the destruction of lignin by the combination of lignin solvation with phenol derivatives suppresses lignin inactivation and reduces A method has been developed for separating polyphenol-based substances and carbohydrates as constituents (JP-A-2-233701).
As a method of utilizing the polyphenol-based substance obtained by this method, for example, it has been reported that a molded article is produced by applying to a molding material such as a cellulose-based fiber (Japanese Patent Application Laid-Open No. 9-278904). However, in order to more fully utilize lignocellulosic resources, it has been desired to develop new uses of this polyphenol-based substance (lignophenol derivative).

On the other hand, polymer materials which can be decomposed in biological systems have been extensively studied with the background of increasing interest in environmental pollution in recent years. One of them is poly3-polyester, which is a polyester in which certain microorganisms accumulate in cells.
Hydroxybutyrate (PHB) has been confirmed to be degraded in the environment, and is attracting attention as a material exhibiting excellent biodegradability and biocompatibility, and is expected to be applied to various fields. However, PHBs produced by microorganisms have low impact resistance, are hard and brittle, and have the problem of physical properties, and have the property of being thermally decomposed even below their melting point, but have poor processability. Was difficult. Attempts to improve the physical properties of PHB include a method of internal plasticization by changing the repeating unit component in the polymer by appropriately selecting a carbon source to be given to the microorganism, and an external plasticizer (for example, 2 ( 3)-
A method of adding t-butyl-4-hydroxyanisole, triacetin, etc.) has been studied. However, there is still a need to develop a new method for providing a biodegradable polyester having sufficiently excellent physical properties, and a demand for an external plasticizer having particularly excellent effects has been high.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art. That is, an object of the present invention is to provide a polyester having excellent physical properties, particularly a biodegradable polyester.
Another object of the present invention is to provide a novel polyester plasticizer capable of sufficiently plasticizing polyester. Another object of the present invention is to develop a new use of a ligphenol derivative separated from a lignocellulosic substance.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, first, an acid was added to a lignocellulosic substance to which a phenol derivative was added and mixed to form the lignocellulose. Lignophenol derivatives obtained by separating the system material into lignophenol derivatives and carbohydrates, and derivatives obtained by acetylating these alkali-treated derivatives were prepared. The present inventors have found that a film obtained by complexing the acetylated derivative with a biodegradable polyester exhibits excellent elongation, and have completed the present invention. That is, according to the present invention, an acid is added to (1) a polyester; and (2) a lignocellulosic material to which a phenol derivative is added, and mixed to separate the lignocellulosic material into a lignophenol derivative and a carbohydrate. Polyester composition comprising: a lignophenol derivative obtained by the method described above, an alkali-treated derivative of the lignophenol derivative, and at least one lignophenol derivative selected from the group consisting of a protected hydroxyl group in the lignophenol derivative or the alkali-treated derivative. Things are provided.

[0007] Preferably, the addition amount of the lignophenol derivative is 1 to 50% by weight based on the total weight of the polyester and the lignophenol derivative. Preferably, the polyester is a biodegradable polyester. Preferably, the polyester is a hydroxyalkanoate homopolymer or copolymer or a mixture thereof. Preferably, the hydroxy alkanoate is a 3-hydroxy alkanoate. Preferably, the hydroxyalkanoate is 3-hydroxypropionate, 3
-Hydroxybutyrate, 3-hydroxyvalerate and at least one selected from the group consisting of 3-hydroxyoctanoate.

[0008] Preferably, the phenol derivative added to the lignocellulosic material is a phenol which may have one or more substituents. Preferably, the phenol derivative added to the lignocellulosic material is cresol. Preferably, the acid added to the lignocellulosic material is 65% by weight or more concentrated sulfuric acid. Preferably, the lignophenol derivative is an alkali-treated derivative or a derivative in which the hydroxyl group in the alkali-treated derivative is protected. Preferably, the lignophenol derivative is 140
It is a derivative obtained by alkali treatment at a temperature of from 170 ° C. to 170 ° C. or a derivative in which a hydroxyl group in these derivatives is protected. The polyester composition of the present invention is, for example, in the form of a film.

According to another aspect of the present invention, it is obtained by adding an acid to a lignocellulosic material to which a phenol derivative has been added, mixing and separating the lignocellulosic material into a lignophenol derivative and a carbohydrate. A plasticizer for polyester, comprising: a lignophenol derivative, an alkali-treated derivative of the lignophenol derivative, and at least one lignophenol derivative selected from the group consisting of a hydroxyl-protected derivative of the lignophenol derivative and the alkali-treated derivative. Is done.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester composition of the present invention comprises:
It is characterized by comprising a polyester and a lignophenol derivative (or a further derivative thereof) obtained by treating a lignocellulosic substance with a phenol derivative and an acid.

The type of polyester used in the present invention is not particularly limited, but is preferably a biodegradable polyester. The biodegradable polyester is a polyester that can be decomposed in the environment, and its type is not particularly limited. As the biodegradable polyester that can be used in the present invention,
For example, a hydroxyalkanoate homopolymer or copolymer or a mixture thereof. Examples of the hydroxyalkanoate which is a repeating unit in the polyester include a hydroxyalkanoate having 3 to 12 carbon atoms. Examples of the homopolymer of hydroxyalkanoate include poly-3-hydroxypropionate, poly-3-hydroxybutyrate, poly-3-hydroxyvalerate, and poly-3-hydroxyoctanoate such as poly-3-hydroxyoctanoate. Alkanoate,
Examples thereof include poly-4-hydroxyalkanoates such as poly-4-hydroxybutyrate, and particularly preferred is poly-3-hydroxybutyrate.

Examples of the copolymer of hydroxyalkanoate include 3-hydroxybutyrate and C3
And other copolymers with other hydroxyalkanoates, specifically, 3-hydroxybutyrate / 3-hydroxypropionate copolymer, 3-hydroxybutyrate / 3-hydroxypropionate /
4-hydroxybutyrate copolymer, 3-hydroxybutyrate / 3-hydroxyvalerate copolymer, 3
-Hydroxybutyrate / 3-hydroxyvalerate /
3-hydroxyhexanoate / 3-hydroxyheptanoate copolymer, 3-hydroxybutyrate / 3
Hydroxyvalerate / 3-hydroxyhexanoate / 3-hydroxyheptanoate / 3-hydroxyoctanoate copolymer, 3-hydroxybutyrate / 3
-Hydroxyhexanoate / 3-hydroxyoctanoate copolymer, 3-hydroxybutyrate / 3-hydroxyvalerate / 3-hydroxyheptanoate /
3-hydroxyoctanoate copolymer, 3-hydroxybutyrate / 3-hydroxyvalerate / 3-hydroxyhexanoate / 3-hydroxyheptanoate / 3-hydroxyoctanoate / 3-hydroxynonanoate / 3-hydroxy Examples include, but are not limited to, decanoate / 3-hydroxyundecanoate / 3-hydroxylaurate copolymer, 3-hydroxybutyrate / 4-hydroxybutyrate copolymer, and the like.

Furthermore, a mixture of the above-mentioned hydroxyalkanoate homopolymers or copolymers may be used. In addition, the biodegradable polyester as described above is disclosed in JP-A-3-277656,
No. 507214 (the entire contents of these publications are incorporated herein by reference), and the biodegradable polyesters used in the present invention include those described in these publications. Can be used.

The hydroxyalkanoate homopolymer or copolymer used in the present invention may be one produced by various microorganisms or one obtained by chemical synthesis. Microorganisms that produce polyhydroxyalkanoates include, for example, Acinetobactor, Actinomycetos,
etos), Alcaligenes, Aphanothece, Aquaspirillum
m), Azospirillum, Azotobactor, Bacillus, Beggiatoa, Beijerinckia,
Coulobacter, chloroflex (Chl)
orofrexeus), Chlorogloea, Chromatium, Chromobacterium
bacterium), Clostridium, Derxia, Ectothioludspira (Ectoth)
iorhodospira), Echerichia, Ferrobacillus, Gamphosphaeria, Haemophilus,
Halobacterium, Hyphomicrobium, Lamprocytis (Lamp)
rocytis), Lampropedia, Leptospira, Methylobacteria
acterium), Methylocystis,
Micrococcus, Microcolecus (Mic
rocoleus), Microcystis, Moraxella, Mycoplana,
Nitrobacter, Nitrococcus (Nit
rococcus), Nocardia, Oceanospirillum, Paracoccu
s), Photobacterium, Pseudomonas, Rhizobium,
Rhodobacter, Rhodospirillum (Rhodo
spirillum), sphaerotilus (Sphaerotilus), spirillum (Spirillum), sprulina (Spirulina), Streptomyces (Streptomyces), Syntrophomonas (Syntrophomonas), Thiobacillus (Thiobacillus),
Thiocapsa, Thiocystis
tis), Thiodictyon, Thiopedia, Thiosphaera, Vibrio, Xanthobacter,
Examples include various bacteria belonging to bacterial species such as Zoogloea.

The number average molecular weight of the polyester (preferably biodegradable polyester) used in the present invention is not particularly limited, but is generally from 10,000 to 3,000,000.
00, preferably 100,000-3,000.
It is about 0000. However, after fermentative synthesis by a microorganism, a material whose molecular weight has been reduced to a number average molecular weight of about 3,000 to 10,000 by post-treatment such as heat treatment or γ-ray treatment may be used.

In the polyester composition of the present invention,
Lignophenol derivatives are used as plasticizers. A lignophenol derivative used in the present invention is a lignophenol derivative obtained by adding an acid to a lignocellulosic material to which a phenol derivative has been added, mixing and separating the lignocellulosic material into a lignophenol derivative and a carbohydrate, It is at least one selected from the group consisting of an alkali-treated derivative of the lignophenol derivative, and a derivative of the lignophenol derivative or the alkali-treated derivative in which a hydroxyl group is protected. Hereinafter, the lignophenol derivative used in the present invention will be described in detail.

As the phenol derivative to be added to the lignocellulosic substance, a monovalent phenol derivative, a divalent phenol derivative, a trivalent phenol derivative, or the like can be used. Specific examples of the monovalent phenol derivative include a phenol that may have one or more substituents, a naphthol that may have one or more substituents, and a phenol that may have one or more substituents. Good anthrol and anthroquinone ol which may have one or more substituents are exemplified. Specific examples of the divalent phenol derivative include catechol optionally having one or more substituents, resorcinol optionally having one or more substituents, and one or more substituents. Good hydroquinone and the like. Specific examples of the trivalent phenol derivative include pyrogallol which may have one or more substituents.

The kind of the substituent which the phenol derivative may have is not particularly limited, and may have any substituent. Preferably, the phenol derivative has a substituent other than an electron-withdrawing group (such as a halogen atom). And an alkyl group (eg, a methyl group, an ethyl group, a propyl group), an alkoxy group (eg, a methoxy group, an ethoxy group, a propoxy group), and an aryl group (eg, a phenyl group). Further, at least one of the two ortho positions of the phenolic hydroxyl group on the phenol derivative is preferably unsubstituted.
A particularly preferred example of a phenol derivative is cresol, especially m-cresol or p-cresol.

The "lignocellulosic substance" used in the present invention includes woody materials, various materials mainly made of wood, for example, wood flour, chips, waste materials, and offcuts. As the wood to be used, any kind of wood, such as conifers and hardwoods, can be used. further,
Various herbaceous plants and samples related thereto, such as agricultural wastes, can also be used.

As the acid to be added to the lignocellulosic substance, an acid having a swelling property with respect to cellulose is preferable. Specific examples of the acid include, for example, sulfuric acid having a concentration of 65% by weight or more (for example, 72% by weight of sulfuric acid), 85% by weight or more of phosphoric acid, 38% by weight or more of hydrochloric acid, p-toluenesulfonic acid, trifluoroacetic acid, Trichloroacetic acid, formic acid and the like can be mentioned.

Next, the method for producing the lignophenol derivative used in the present invention will be described in more detail. In the present invention, the term "lignophenol derivative" means a polymer containing a diphenylpropane unit in which a phenol derivative is introduced by a CC bond at the α-position of the side chain of the phenylpropane unit of lignin. . The amount and molecular weight of the introduced phenol derivative in this polymer vary depending on the lignocellulosic material as the raw material and the reaction conditions.

In order to obtain a lignophenol derivative from a lignocellulosic material, it is necessary to treat the lignin in the lignocellulosic material with a phenol derivative and extract it as a lignophenol derivative from the lignocellulosic material. Currently, there are two types of methods for extracting lignin in lignocellulosic materials as lignophenol derivatives.

The first method is a method described in JP-A-2-233701. In this method, for example, as shown in FIG. 1, a phenol derivative in a liquid state is added to a lignocellulose-based material such as wood flour (as described above,
For example, cresol or the like is infiltrated, lignin is solvated with a phenol derivative, and then the lignocellulosic material is added with a concentrated acid (as described above, for example, 72% sulfuric acid) and mixed to form a cellulose component. Dissolve. According to this method, a phenol derivative solvated with lignin and a concentrated acid in which a cellulose component is dissolved form a two-phase separation system. The lignin solvated by the phenol derivative is contacted with the acid only at the interface where the phenol derivative phase comes into contact with the concentrated acid phase, and the side chain α-position which is a high reaction site of the lignin basic structural unit generated by the contact with the acid. The cation at the (benzyl position) is attacked by the phenol derivative. As a result, a phenol derivative is CC at the α-position.
It is introduced by a bond, and the molecular weight is reduced by the cleavage of the benzyl aryl ether bond. As a result, lignin is reduced in molecular weight, and at the same time, a lignophenol derivative in which a phenol derivative is introduced at the benzyl position of the basic structural unit is formed in the phenol derivative phase (see FIG. 3). From this phenol derivative phase, a lignophenol derivative is extracted. The lignophenol derivative is obtained as a part of an aggregate of a low molecular weight lignin in which the benzyl aryl ether bond in the lignin is cleaved and reduced. It is known that some phenol derivatives are introduced at the benzyl position via the phenolic hydroxyl group.

The extraction of the lignophenol derivative from the phenol derivative phase can be performed, for example, by the following method. That is, the precipitate obtained by adding the phenol derivative phase to a large excess of ethyl ether is collected and dissolved in acetone. The acetone-insoluble portion is removed by centrifugation, and the acetone-soluble portion is concentrated. The acetone-soluble portion is added dropwise to a large excess of ethyl ether, and the precipitate is collected. After distilling off the solvent from this precipitation section, the precipitate is dried in a desiccator containing phosphorus pentoxide to obtain a lignophenol derivative as a dried product. The crude lignophenol derivative can be obtained by simply removing the phenol derivative phase by distillation under reduced pressure. The acetone-soluble part is directly converted into a lignophenol derivative solution and derivatized (alkali treatment).
Can also be used.

In the second method, as shown in FIG. 2, a solvent (for example, ethanol or acetone) in which a solid or liquid phenol derivative is dissolved is penetrated into a lignocellulosic material, and the solvent is distilled off. (Phenol derivative sorption step). Next, a concentrated acid is added to the lignocellulosic material to dissolve the cellulose component. As a result, as in the first method, the lignin solvated with the phenol derivative causes the cation at the high reaction site (α side position of the side chain) of the lignin generated by contact with the concentrated acid to be attacked by the phenol derivative, and Derivatives are introduced.
Further, the benzyl aryl ether bond is cleaved to lower the molecular weight of lignin. The properties of the obtained lignophenol derivative are the same as those obtained by the first method. Then, similarly to the first method, the phenol-derivatized lignophenol derivative is extracted with the liquid phenol derivative. The extraction of the lignophenol derivative from the liquid phenol derivative phase can be performed in the same manner as in the first method. Alternatively, the entire reaction solution after the concentrated acid treatment is poured into excess water, the insoluble fraction is collected by centrifugation, and after deoxidation,
dry. Acetone or alcohol is added to the dried product to extract a lignophenol derivative. Further, similarly to the first method, the soluble fraction is dropped into excess ethyl ether or the like to obtain the lignophenol derivative as an insoluble fraction. In this method, similarly, the acetone-soluble portion can be used as a lignophenol derivative solution for derivatization treatment (alkali treatment).

Of these two methods, the second method is particularly the latter, that is, the method of extracting and separating the lignophenol derivative with acetone or alcohol requires a small amount of the phenol derivative. Is economical. Further, this method can treat many lignocellulosic materials with a small amount of a phenol derivative, and thus is suitable for mass synthesis of a lignophenol derivative. The lignophenol derivative obtained by the above method is also referred to herein as an original lignophenol derivative. In the present specification, when referred to as “lignophenol derivative”, unless otherwise specified, it includes, in addition to the above-mentioned original lignophenol derivative, those derivatives described below in the present specification (specifications). More specifically, all of an alkali-treated derivative or a derivative in which a hydroxyl group is protected are included.

The original lignophenol derivative obtained by the above method generally has the following characteristics. However, the characteristics of the lignophenol derivative used in the present invention are not limited to the following. (1) The weight average molecular weight is about 3000 to 5000. (2) It has almost no conjugated system in the molecule and its color tone is extremely light. (3) It has a melting point of about 170 ° C derived from softwood and about 130 ° C derived from hardwood. (4) As a result of selective grafting of the phenol derivative to the α-position of the side chain, the lignin derivative has an extremely large amount of phenolic hydroxyl groups and is imparted with high phenol properties. (5) The aromatic nucleus of the lignin structural unit and the aromatic nucleus of the phenol derivative grafted at the α-position of the side chain form a diphenylmethane type structure, and self-condensation is suppressed. (6) methanol, ethanol, acetone, dioxane, pyridine, THF (tetrahydrofuran), DMF
Easily soluble in various solvents such as (dimethylformamide).

The original lignophenol derivative obtained by the above-described method can be used as it is in the polyester composition of the present invention, but can also be used after further derivatization. As a treatment for obtaining such a derivative, alkali treatment of the original lignophenol derivative can be mentioned.

The original lignophenol derivative obtained by a phase separation process from natural lignin has its active Cα blocked by the phenol derivative.
Overall stable. However, under alkaline conditions, the phenolic hydroxyl group is easily dissociated and the resulting phenoxide ion attacks the adjacent Cβ position where sterically possible. As a result, the aryl ether bond at the Cβ position is cleaved, the lignophenol derivative is reduced in molecular weight, and the phenolic hydroxyl group in the introduced phenol nucleus is transferred to the lignin parent. Therefore, it is expected that the alkali-treated derivative will have higher hydrophobicity than the original derivative. At this time, the alkoxide ion or carbanion of the lignin aromatic nucleus existing at the Cγ position is
It is also expected to attack the β-position, but this requires much higher energy than the phenoxide ion.
Therefore, under mild alkaline conditions, the adjacent group effect of the phenolic hydroxyl group of the introduced phenol nucleus preferentially appears,
Under more severe conditions, a further reaction occurs, and the phenolic hydroxyl group of the once-etherified cresol nucleus is regenerated, whereby the lignophenol derivative is further reduced in molecular weight and the number of hydroxyl groups increases, and the hydrophilicity may increase. Be expected.

Further, the original lignophenol derivative and the lignophenol derivative obtained by alkali-treating the original lignophenol derivative exhibit various properties due to the presence of phenolic and alcoholic hydroxyl groups. By protecting this hydroxyl group, derivatives having different different properties can be obtained. As a method for protecting the hydroxyl group, for example, an acyl group (for example, an acetyl group, a propionyl group, a benzyl group, etc., preferably an acyl group)
And protecting the hydroxyl group with a protecting group such as In the polyester composition of the present invention, a derivative whose hydroxyl group is protected as described above can be used.

The addition amount of the lignophenol derivative in the polyester composition of the present invention is preferably 1 based on the total weight of the polyester and the lignophenol derivative.
-50% by weight, more preferably 5-50% by weight, particularly preferably 5-30% by weight, for example, 5% by weight,
0%, 20% or 30% by weight, most preferably 10-20% by weight.

The polyester composition of the present invention is characterized by containing a polyester and a lignophenol derivative, but may contain other optional components. As an optional component, (A) a plasticizer other than the lignophenol derivative (for example,
Alkylphenol compounds, high-boiling esters of polybasic acids, polyhydric alcohols, aromatic sulfonamides, etc.), (B) stabilizers against thermal decomposition or oxidative decomposition, (C) inorganic fillers (eg, glass fiber, carbon fiber, plate-like) Or foil-like particles, silica, clay, magnesium silicate, etc.) (D) Organic filler (eg, cellulose fibers or particles, protein fibers, synthetic polymer particles or fibers, wood flour) (E) Polymers other than polyester (F) Pigment (G) Nucleating agent (preferably 0.2 to 2.0 phr of boron nitride, talc, ammonium chloride or DZB / Zn
Stearates) (H) Volatile solvents for polyesters and lignophenol derivatives, but are not limited thereto.

The polyester composition of the present invention can be processed into any form. For example, the polyester composition of the present invention can be processed into a film form.
When processing into a film, a predetermined amount of a polyester and a predetermined amount of a lignophenol derivative are completely dissolved in a volatile solvent for polyester (for example, a halogenated hydrocarbon solvent such as chloroform), and then a stainless steel square is used. A film can be prepared by casting in a vat, leaving it on a horizontal place for one day, and distilling off the solvent. Alternatively, the polyester composition of the present invention can be molded into a desired shape by using a mold, passing through a die, or the like to produce a molded article. Examples of the molding method include injection molding, compression molding, fiber or film extrusion, profile extrusion, gas flow spinning, adhesive spinning, and substrate coating. The polyester composition of the present invention can be used in any form such as a melt, particles, or a solution in a volatile solvent. Although the use of the polyester composition of the present invention is not particularly limited, examples of molded products include films for packaging, coated products (such as paper, cardboard and nonwoven fabric), fibers, nonwoven fabrics, extruded nets,
Personal hygiene articles, bottles and drinking containers, agricultural and horticultural films and containers, sustained release devices and the like. Alternatively, the polyester composition of the present invention can be used as an adhesive.

According to the present invention, there is provided a polyester plasticizer comprising the lignophenol derivative used in the present invention. The kind of the polyester referred to here is not particularly limited, and examples thereof include the biodegradable polyester described above in this specification. As used herein, a plasticizer refers to a substance that, when added to a polyester, increases its flowability, flexibility or extensibility. The plasticizer of the present invention, when used in combination with polyester, not only increases the extensibility of the film, but also has the advantage that the decrease in the tensile strength of the film is smaller than when a conventional plasticizer is used. Having. Some of the lignophenol derivatives used in the present invention increase the tensile strength of the polyester film. In such a case, the lignophenol derivative can be used as a polyester reinforcing agent.

It has now been found that when the lignophenol derivative used in the present invention is blended with polyester to form a film, the film exhibits excellent physical properties (ie, excellent elongation). Thus, it was shown that a lignophenol derivative isolated from a lignocellulosic material, which is a wood resource, is useful as a plasticizer for polyester. The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples.

[0036]

EXAMPLES Example 1: Production of lignophenol derivatives (1) Sorption of cresol 20 mesh pass wood flour (beech) with a dry weight of 2 kg
Was placed in a 25 L stainless steel tank. Lignin C ₉
An acetone solution (about 8 L) containing 3 mol times of p-cresol (784 g) per unit is quickly added, and the mixture is stirred until no bubbles are formed. Left for 2 days.
After 2 days, open the lid, distill off excess acetone in the fume hood, and then transfer to a stainless steel vat and stir well with a stainless steel scoop until the wood flour dries to avoid uneven sorption, eliminating the acetone odor Until distilled off.

(2) Concentrated Acid Treatment The sorbed wood flour was aliquoted into 3 L beakers (250 g was divided into 8 equal parts). 72% sulfuric acid (about 0.8 L) was added in 5 or 6 portions each time with good stirring with a glass rod. Initially, the wood flour was vigorously agitated so that there was no portion where it did not come into contact with the sulfuric acid. Approximately 10 minutes after the addition of sulfuric acid, a stirrer was used (a vinyl sheet was applied to prevent scattering of the sulfuric acid). One hour after the addition of sulfuric acid, the stirring was stopped, and the reaction was stopped by charging the mixture into a 20-L poly container containing purified water in half. Then add purified water until the 8th minute of the container, stop stirring,
Left for 2 days.

(3) Deoxidation treatment Two days later, the supernatant was decanted as much as possible without sucking the sediment in the container, and purified water was added again until the 8th minute, followed by stirring for 15 minutes. This was repeated daily to remove the acid and excess p-cresol. This operation was repeated six times until the supernatant reached pH 6-7. (4) Drying of the acid-treated precipitate After the supernatant in the container became neutral, the supernatant was decanted. Spread the precipitate on a stainless steel vat and
The mixture was dried in a dryer set at 0 ° C until excess water was evaporated, and further dried at 60 ° C overnight. At this time, the mixture was taken out of the dryer every day and stirred while finely pulverizing the particles so as to be easily dried. Thereafter, drying was performed under reduced pressure until complete drying was confirmed on P ₂ O ₅ .

(5) Extraction with Acetone The dry solid obtained in (4) was put into two 5 L Erlenmeyer flasks, and 4 L of acetone was added to each of them.
After leaving for days, lignocresol was extracted. The extraction mixture is centrifuged, and the supernatant is filtered through a glass fiber filter (Whatman GF /
It filtered in A). Acetone was added to the extraction residue again, and extraction and filtration were performed in the same procedure. (6) Distilling off acetone 10 g of lignocresol in a 1000 mL eggplant-shaped flask
Of acetone was added thereto, and acetone was distilled off with a rotary evaporator. The solid on the wall of the eggplant flask was taken out with a spatula, pulverized in a mortar, and dried under reduced pressure until the acetone odor was eliminated. This was repeated to obtain lignocresol used for secondary function conversion (alkali treatment). The original sample was purified by dropping the acetone extract into diethyl ether. An acetone extract prepared to be 20 times the amount of lignin was put into a separating funnel, and added dropwise to vigorously stirred diethyl ether of 20 times the amount of the acetone extract. Thereafter, the mixture was left for 30 minutes, the supernatant was decanted, and the precipitate was collected by centrifugation and washed twice with diethyl ether. After drying in the draft for 2 days,
It was dried under reduced pressure on P ₂ O ₅ to obtain powdered lignocresol (hereinafter also referred to as original lignocresol).

Example 2 Preparation of Derivative by Lignocresol Secondary Function Conversion (Alkali Treatment) 8 g of the lignocresol obtained in Example 1 was placed in a 300 mL beaker, and 160 mL of 0.5N NaOH was added.
After confirming complete dissolution, it was transferred to two 100 mL stainless steel autoclaves. 140 ° C or 1 in advance
The autoclave was charged into an oil bath whose temperature was set to 70 ° C., and after the temperature reached a predetermined temperature again, the reaction was performed for 1 hour (20 minutes).
Minutes and after 40 minutes). Then, it was cooled with water. After cooling sufficiently, the contents were transferred to a 500 mL beaker. While measuring the pH meter with 1N HCl, p
Acidified to H2. The deposited precipitate is collected by centrifugation (3000 rpm, 10 minutes, normal temperature),
Washed with deionized water until 5. After lyophilization, it was dried over P ₂ O ₅ to obtain a derivative treated at 140 ° C. and a derivative treated at 170 ° C. An alkali-treated derivative was prepared by repeating the above operation.

Example 3 Acetylation of Original Lignocresol, Derivatives Treated at 140 ° C. and Derivatives Treated at 170 ° C. Since the lignocresol obtained in Examples 1 and 2 has phenolic and alcoholic hydroxyl groups, It is sparingly soluble in chloroform as a preparation solvent.
The hydroxyl group was acetylated to make it non-polar, facilitating complexation with the biodegradable polyester. Lignin sample (original lignocresol obtained in Example 1,
10 g of the derivative treated at 140 ° C. or the derivative treated at 170 ° C. obtained in Example 2 was placed in a 300 mL Erlenmeyer flask, and 100 mL of pyridine was added to completely dissolve lignin.
This solution was centrifuged and filtered to remove the insoluble fraction.

Next, 100 mL of acetic anhydride was added, sealed (parafilm was put on aluminum foil, and further sealed with cellophane tape) and left at room temperature for 48 hours. 48 hours later,
Centrifugation and filtration were performed again, and the reaction product was added dropwise to 4 L of cold water. The precipitate is centrifuged (3000 rpm, 10 minutes,
5 ° C.) and washed only once with cold water. After freeze-drying the precipitate, a wrapping paper was placed in a petri dish, the precipitate was spread thereon, and dried under reduced pressure on P ₂ O ₅ until the odor of pyridine and acetic acid disappeared to prepare an acetylated derivative.

Example 4 Preparation of Composite Film of Lignophenol Derivative (Aceylated Derivative) and Biodegradable Polyester and Measurement of Its Physical Properties (1) Preparation of Composite Film Biopol (D400) was used as a biodegradable polyester material.
P, HV8%, Monsanto). As a plasticizer,
The three lignocresol derivatives (acetylated derivatives) obtained in Example 3 were used, and BHA (2 (3) -t-butyl-4-hydroxyanisole, SIGMA) and a plasticizer for comparison were used. Triacetin (Nacalai Tesque, Inc.) was used. In a 100 mL Erlenmeyer flask, add Biopol and a predetermined amount (5
-30% by weight) of a lignocresol derivative, BHA or triacetin, and weighed to a total amount of 2 g.
mL of chloroform was added and dissolved on a 50 ° C. water bath with stirring. After confirming that it was completely dissolved, cast it on a stainless steel square bat, leave it on a horizontal place for one day,
Chloroform was distilled off to prepare a film having a thickness of 0.10 to 0.15 mm. As a control, a film containing only BioPol was prepared in the same manner.

When dissolved in chloroform, each sample was completely dissolved in 20 to 30 minutes. However, in the case of a sample in which original lignocresol was combined, 30
After a minute, a white mass remained and it took 2 hours to completely dissolve. In addition, the feel of the film became more flexible as the amount of the plasticizer was increased, regardless of the use of any plasticizer. The flexibility decreased in the order of the derivative treated with lignocresol at 170 ° C., the derivative treated with lignocresol at 140 ° C., and the original lignocresol.

(2) Measurement of Physical Properties of Composite Film The film prepared in the above (1) was cut with a dumbbell (Dumbbell Company, SDK-500-D, JISK-6251), and was cut with a tensile tester (Shimazu Seisakusho EZ Test). A tensile test was performed at a speed of 5 mm / min, and the maximum load, elongation, and elastic modulus were measured. The value obtained by dividing the maximum load by the cross-sectional area of the film was defined as tensile strength (N / mm ² ), and the elongation was divided by the span (33 mm) and multiplied by 100 to obtain the elongation (%). The obtained results are shown in FIGS.

FIGS. 4 to 6 show the original lignocresol (acetylated form) (FIG. 4), the derivative (acetylated form) treated at 140 ° C. (FIG. 5), and the derivative (acetylated form) treated at 170 ° C. The elongation and tensile strength of the film composited in 6) were shown. In the original lignocresol (acetylated product) composite film, the elongation decreased as the amount of addition increased with respect to the control film containing only Biopol. Since the tensile strength was increased, it was found that it was possible to add strength to the film with a small amount of addition.

In the case of the derivative (acetylated) composite film treated at 140 ° C., the elongation increased up to an addition amount of 20%, and a good plasticizing effect was exhibited. In addition, at the addition amount of 5%, the same tensile strength as the control was exhibited. In the case of the derivative (acetylated product) composite film treated at 170 ° C., the tensile strength decreased as the amount of addition increased, but the elongation was 8.2 times, 19.8 times, 23.8 times, and 23 times that of the control. A good plasticizing effect of 0.6 times was exhibited. From the above results, it was found that a lower molecular weight lignocresol derivative exhibited a better plasticizing effect.

FIGS. 7 to 9 show the elongation and the elongation of a film composited with a 170 ° C.-treated derivative (acetylated product) showing the best plasticizing effect or BHA and triacetin, which are known bioplastic plasticizers. The tensile strength was shown for each of the added amounts of 10% by weight (FIG. 7), 20% by weight (FIG. 8) and 30% by weight (FIG. 9). At 10% by weight, 1
The derivative (acetylated product) composite film treated at 70 ° C. and the BHA composite film showed high elongation, but triacetin showed almost no plasticizing effect. 170
In the case of the derivative (acetylated product) treated with ° C and the BHA composite film, the tensile strength was also good.

When the amount of addition was 20% by weight, the elongation decreased sharply in the BHA composite film, but increased in the 170 ° C.-treated derivative (acetylated product) composite film, showing a good plasticizing effect. Furthermore, in terms of tensile strength,
While the BHA composite film decreased, the 170 ° C.-treated derivative (acetylated product) composite film retained high tensile strength. Even at an addition amount of 30% by weight, the derivative (acetylated) composite film treated at 170 ° C. showed a high elongation. The triacetin composite film also showed a relatively high elongation, but was about 60% of the elongation of the derivative (acetylated) composite film treated at 170 ° C. From the above, it was shown that the biopolyester composition of the present invention has high plasticity.

[0050]

According to the present invention, it has become possible to provide a novel polyester material having excellent physical properties, specifically, excellent tensile strength and elongation. Further, the present invention provides a novel plasticizer for polyester. Furthermore, the present invention provides a new use of a lignophenol derivative separated from a lignocellulosic material, and further promotes effective use of wood resources.

[Brief description of the drawings]

FIG. 1 is a diagram showing a first method for producing a lignophenol derivative.

FIG. 2 is a diagram showing a second method for producing a lignophenol derivative.

FIG. 3 is a diagram showing a reaction between lignin and a phenol derivative through contact with a concentrated acid at an interface of the phenol derivative phase in a two-phase separation system of a phenol derivative phase and a concentrated acid phase. .

FIG. 4 is a diagram showing the elongation and the tensile strength of a film composited with an original lignocresol (acetylated product).

FIG. 5 is a derivative (acetylated product) treated at 140 ° C.
FIG. 3 is a view showing the elongation and the tensile strength of the film composited in FIG.

FIG. 6 shows a derivative treated at 170 ° C. (acetylated product).
FIG. 3 is a view showing the elongation and the tensile strength of the film composited in FIG.

FIG. 7 shows the elongation and the tensile strength of a film composited with a derivative (acetylated product) treated at 170 ° C., BHA or triacetin with an addition amount of 10%.

FIG. 8 shows the elongation and the tensile strength of a film composited with a derivative (acetylated product) treated at 170 ° C., BHA or triacetin with an addition amount of 20%.

FIG. 9 shows the elongation and the tensile strength of a film conjugated with a derivative (acetylated product) treated at 170 ° C., BHA or triacetin with an addition amount of 30%.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yoshiyo Shibahara 845-2 Nakanotsubo, Osato Kubota-cho, Tsu-shi, Mie Prefecture F-term (reference) 4F071 AA43 AA73 AA78 AB23 AC11 AE04 AF52 BA02 BB02 BC01 4J002 AH002 CE002 CF181 EJ016 FD010 FD020

Claims (13)

[Claims] An acid is added to (1) a polyester; and (2) a lignocellulosic material to which a phenol derivative is added, and the mixture is mixed to separate the lignocellulosic material into a lignophenol derivative and a carbohydrate. At least one selected from the group consisting of a lignophenol derivative obtained, an alkali-treated derivative of the lignophenol derivative, and a hydroxyl-protected derivative of the lignophenol derivative or the alkali-treated derivative.
A polyester composition comprising: a species of lignophenol derivative. 2. The polyester composition according to claim 1, wherein the amount of the lignophenol derivative is 1 to 50% by weight based on the total weight of the polyester and the lignophenol derivative. 3. The polyester composition according to claim 1, wherein the polyester is a biodegradable polyester. 4. The polyester composition according to claim 1, wherein the polyester is a hydroxyalkanoate homopolymer or copolymer or a mixture thereof. 5. The method according to claim 1, wherein the hydroxyalkanoate is 3-hydroxyalkanoate.
Item 10. The polyester composition according to item 8. 6. The method of claim 1, wherein the hydroxyalkanoate is 3-hydroxypropionate, 3-hydroxybutyrate, 3
At least one selected from the group consisting of -hydroxyvalerate and 3-hydroxyoctanoate,
The polyester composition according to claim 5. 7. The polyester composition according to claim 1, wherein the phenol derivative added to the lignocellulosic substance is a phenol which may have one or more substituents. 8. The polyester composition according to claim 7, wherein the phenol derivative added to the lignocellulosic substance is cresol. 9. The polyester composition according to claim 1, wherein the acid added to the lignocellulosic material is 65% by weight or more of concentrated sulfuric acid. 10. The polyester composition according to claim 1, wherein the lignophenol derivative is an alkali-treated derivative or a derivative of the alkali-treated derivative in which a hydroxyl group is protected. 11. A lignophenol derivative at 140 ° C.
The polyester composition according to any one of claims 1 to 10, which is a derivative obtained by an alkali treatment at a temperature of from 170 to 170 ° C or a derivative in which a hydroxyl group is protected in these derivatives. 12. The polyester composition according to claim 1, which is in the form of a film. 13. A lignophenol derivative obtained by adding and mixing an acid to a lignocellulosic material to which a phenol derivative is added, and separating the lignocellulosic material into a lignophenol derivative and a carbohydrate; A plasticizer for polyester comprising: an alkali-treated derivative of the above; and at least one lignophenol derivative selected from the group consisting of the above-mentioned lignophenol derivative or a derivative in which a hydroxyl group is protected in the alkali-treated derivative.