JPH04132737A - Production of lignocellulose-phenolic compound composition specified by water addition - Google Patents

Abstract

PURPOSE:To obtain the subject composition with completing reaction in a short time by making water co-exist in reaction of a lignocellulosic material with a phenolic compound and subjecting to dissolving reaction in heating. CONSTITUTION:A lignocellulosic material (e.g. wood fragment, wood powder, pulp or chaff) and at least a species of phenolic compound (e.g. phenol or catechol) are subjected to dissolving reaction in heating. In said process, the reaction is performed in the co-existence of water (weight ratio of water to phenolic compound is preferably 1:1-3:1) to afford the aimed composition. Besides, an inorganic acid or carboxylic acid, etc., in an amount of 0.1-20wt.% to the lignocellulosic material is preferably added to the system as a dissolving catalyst for accelerating dissolving further.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a lignocellulose-phenol compound composite characterized by the addition of water.

More specifically, the present invention relates to a method for producing a lignocellulose-phenol compound composite that can promote a heating dissolution reaction between a lignocellulose material and a solvent containing at least one type of phenol compound as a main component.

[Conventional technology]

The various sources produced from forests are renewable, and their effective cyclical use is currently strongly desired. For example, in industries that use wood as raw material, such as the pulp industry and the wood industry, there is an urgent need to establish ways to effectively utilize the wood waste generated. There is also a need for urgent development of methods for effectively utilizing agricultural waste containing lignocellulosic materials.

As a method for effectively utilizing lignocellulose materials including wood, for example, Japanese Patent Application Laid-Open No. 57-2360 and Japanese Patent Publication No. 63-1992 disclose that at least one substituent is added to a portion of the hydroxyl group in the lignocellulose molecule. A method is disclosed in which a chemically modified lignocellulose material obtained by introducing a lignocellulose material is dissolved in an organic solvent, and this solution is used as a raw material for various resin materials.

Also, JP-A-60-206883 and JP-A-60-
Japanese Patent No. 104513 discloses a method of using a lignocellulose material as a phenol compound-formaldehyde resin adhesive and a method of making it into fibers.

Furthermore, JP-A-61-215676 and JP-A-61
Publication No. 215675 discloses that a lignocellulose material is dissolved in a solvent consisting of polyhydric alcohol or a bisphenol compound, and this solution is used together with polyurethane, epoxy, or other resin materials to form molded articles, foams, or discloses a method for producing an adhesive.

Furthermore, JP-A No. 61-261358 discloses a method of directly dissolving wood without pretreatment in a solvent consisting of a phenol compound or a bisphenol compound without using a catalyst. Publication No. 79230 discloses a method of directly dissolving wood without pretreatment in a solvent consisting of an alcohol compound, a polyhydric alcohol compound, an oxyether compound, a cyclic ether compound, or a ketone compound without using a catalyst. There is.

Further, Japanese Patent Publication No. 61-2697 discloses a technique in which wood flour is dissolved and reacted in phenol in the presence of a mineral acid.

[Problem to be solved by the invention]

Conventional techniques for dissolving lignocellulosic materials in phenolic compounds have a problem in that the dissolution reaction takes a long time. Therefore, the development of this dissolution promotion technology is
This is an essential and extremely important issue in order to realize the industrial use of lignocellulose material-phenolic compound composites.

The present invention aims to provide a method for producing a lignocellulose-phenol compound composite in which a heating dissolution reaction between a lignocellulose material and a phenol compound can be completed within a short time.

[Means and actions to solve the problem]

The method for producing a lignocellulose-phenolic compound composite of the present invention involves dissolving and reacting a lignocellulose material and a solvent containing at least one type of phenol compound as a main component under heating, by adding an appropriate amount of It is characterized by the coexistence of water.

In the method of the present invention, the amount of water allowed to coexist in the lignocellulose-phenol compound heating dissolution reaction system depends on the mixing ratio of the lignocellulose material and the phenol compound in the reaction system; The weight ratio of the phenolic compound and the phenol compound is preferably within the range of 1:3 to 4:1, more preferably within the range of 1:1 to 3:1.

If the amount of water added is less than 173% of the weight of the phenol compound, the effect of promoting the heating dissolution reaction may be unsatisfactory;
If the amount exceeds twice that, the dissolution reaction promoting effect will be reduced.

Lignocellulosic materials used in the method of the present invention include wood chips, wood flour, wood fibers, wood chips, veneer waste, plywood waste, waste paper, pulp, rice straw, rice husk, kolyang, bagasse, bamboo, wheat straw, etc. Can be selected from vegetable fiber materials.

In the method of the present invention, the phenolic compound forming the dissolved complex with the lignocellulosic material can be selected from the following group of compounds.

(1) -valent phenol compound: for example, phenol, 0
-1m-1 and p-cresol, 3°5-12.3-
1 and 2.6-xylenol, 0-1m-1 and p
-propylphenol, 0, m-1 and p-butylphenol, 0m-1 and p-5ec-butylphenol, 0-m-1 and p-tert-butylphenol, hexylphenol, phenylphenol, octylphenol, and naphthol, etc. (2) Dihydric phenolic compounds such as catechol, resorcinol, quinol, bisphenol A, bisphenol B and bisphenol F (3) Trihydric phenolic compounds such as pyrogallol, chloroglycine, trihydrobenzene, and gallic acid.

The present invention is characterized in that when a lignocellulose material is dissolved and reacted with a phenol compound, the dissolution reaction is promoted even without a dissolution catalyst by using an appropriate amount of water in the reaction system.

However, it is also possible to further promote dissolution by using catalysts.

The dissolving catalyst used in that case is preferably one consisting of at least one member selected from the following compound group.

(1) Inorganic (mineral) acids: such as hydrochloric acid, sulfuric acid, phosphoric acid, and hydrogen bromide (2) Organic acids (a) Carboxylic acids: formic acid, acetic acid, oxalic acid, tartaric acid, and benzoic acid (b) Organic acids Sulfonic acids: e.g. phenolsulfonic acid and P-)luenesulfonic acid, etc. (3) Organic sulfinic acids: e.g. phenolsulfinic acid, etc. (d) Others: e.g. uric acid, etc. (3) Lewis acids: e.g. titanium tetrachloride, aluminum chloride, etc. It is generally preferred that the dissolving solvent be used in a proportion of 0.1 to 20% based on the weight of the lignocellulosic material.

The temperature and pressure of the dissolution reaction in the method of the present invention can be appropriately set depending on the type of phenol compound.

Generally, in the case of normal pressure melting, the melting temperature is 100 to 200°C.
In the case of pressurized dissolution, it is preferably 10 to 40k.
The melting temperature is preferably 200 to 300°C under an applied pressure of g/cj.

Dissolution is generally carried out under stirring for 1 to 10 hours, preferably 2 hours.
It will last for ~5 hours.

〔Example〕

Implementation ■ 10g of wood flour prepared from upper Futani kava chips, 10g of phenol
and 20 g of water were placed in a 50 d capacity stainless steel pressure-resistant container, and sealed at 250°C for 15, 30; 45,
60.

The mixture was allowed to stand for 75 or 90 minutes to carry out a heating dissolution reaction.

The obtained reaction product was dissolved in dioxane, and the undissolved residue was filtered off using a glass filter paper to determine the undissolved residue rate.

On the other hand, the amount of free phenol in the reaction product was determined by liquid chromatography, and the amount of bound phenol chemically bonded to the low-molecular wood component after liquefaction [relative to wood weight (%)] was determined.

The above test results are shown in Table 1.

After sealing the first surface, 30, 45, 60, 75 at 250℃
, 90, or 120 minutes and heated and dissolved.

Thereafter, the obtained reaction products were treated in the same manner as in Examples 1 to 6, and the percentage of insoluble residue and the amount of bound phenol were determined, and the results shown in Table 2 were obtained.

Table 2 10g of wood flour prepared from birch chips and 10g of phenol
g in a 301 d capacity stainless steel pressure container, water was added to a reaction mixture system consisting of 10 g of wood flour prepared from birch chips and 10 g of phenol, and the water/wood weight ratio was 0.5.
1.2.2.5.3 or 3.5,
This reaction system was charged into a 30 to 50 d capacity stainless steel pressure-resistant container, and after the container was tightly stoppered, the container was allowed to stand at 250° C. for 30 minutes to perform a heating dissolution reaction treatment. The obtained reaction product was dissolved in dioxane, and the undissolved residue was filtered using glass filter paper.
The residue rate was determined. The values obtained are shown in Table 3.

It has become possible to perform third shrinkage, thereby enabling the practical production and supply of lignocellulose-phenolic compound composites.

Claims (1)

[Claims] 1. When dissolving and reacting a lignocellulose material with at least one phenolic compound under heating, an appropriate amount of water is allowed to coexist in the reaction system,
A method for producing a lignocellulose-phenol compound composite.