JP3140901B2 - Method for producing resin raw material composition obtained by modifying lignocellulosic material such as wood - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the effective use of lignocellulosic substances such as wood such as plants and the like, which are renewable resources. More specifically, the present invention is a method for producing a resin raw material composition by heat-modifying a lignocellulosic substance such as wood with a phenol in the presence of an alkaline additive. The resin raw material composition obtained by the present invention further has a property of becoming a resin by a treatment such as methylolation, epoxidation, or urethane, and therefore, the production method of the present invention is extremely effective for effective use of waste such as wood. It is useful.

[0002]

2. Description of the Related Art At present, in the wood industry and the like, treatment of waste such as bark, sawdust, and board waste discharged at the time of sawing has become a major problem. Forestry managers are also struggling with the use of thinned lumber (young trees that have been thinned out to make thicker, better trees). Therefore, development of effective utilization methods of these woody wastes is urgent. As a method for effectively utilizing a lignocellulosic substance such as wood, there is known a method in which phenols are added to wood and heat-denatured to obtain a wood solution, and the obtained wood solution is used as a resin raw material.

A conventional technique for modifying phenol of wood is proposed in Japanese Patent Application Laid-Open No. 61-261358. This is a method in which 10-1000 parts of wood is added to 100 parts of phenol in a pressure-resistant reaction vessel, and the mixture is reacted at 200-300 ° C. for 15 minutes to several hours to make a lignocellulose substance such as wood into a solution. However, this method has the following problems during manufacturing. (1) As the ratio of lignocellulose / phenol increases, the residue increases. (2) As the ratio of lignocellulose / phenol increases, the viscosity increases, and it becomes difficult to remove the product from the reaction vessel after the reaction.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to improve these disadvantages when reacting lignocelluloses with phenols and to increase the lignocellulose / phenol ratio. An object of the present invention is to provide a method for producing a resin raw material composition having a small residue and a small viscosity.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies with the aim of developing a method for producing a resin raw material composition in which the above-mentioned disadvantages have been improved. As a result, phenols are added to a lignocellulosic substance and heated. It has been found that the above object can be achieved by the presence of an alkaline additive during the modification, and the present invention has been completed. Thus, the present invention provides a method for producing a resin raw material composition by adding a phenol to a lignocellulose material and heat-modifying the lignocellulose material, wherein the lignocellulosic material is heat-denatured in the presence of an alkaline additive. This is a method for producing a resin raw material composition obtained by modifying

[0006] The lignocellulosic substance as a starting material in the method for producing the resin raw material composition of the present invention includes sawdust, wood flour, wood chips, veneer chips, plywood cuttings, bark and other plant fibrils and straw. , Cellulose such as fir, coffee bean refuse, bagasse refuse refuse, beet pulp,
It refers to various plant-derived materials mainly containing lignins and the like. The phenols used in the present invention include phenol, o-, m-, p-cresol, 3,5-, 2,3
-, 2-6-xylenol, o-, m-, p-propylphenol, o-, m-, p-secondary butylphenol, o-, m-, p-tert-butylphenol, hexylphenol, phenylphenol, octylphenol, Monovalent phenols such as naphthol; divalent phenols such as catechol, resorcinol, quinol, bisphenol A, bisphenol B and bisphenol F; There are things.

The alkaline additives used in the present invention include: alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkali metal carbonates such as calcium carbonate Ammonia; and amines such as monoethanolamine. In the present invention, phenols 1
1 lignocellulosic substance such as wood per 0 parts by weight
Parts by weight-1000 parts by weight, preferably 10 parts by weight-10
0 parts by weight and 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight of an alkaline additive are added. In the present invention, phenols are added to lignocellulosic substances such as sawdust and bark, and a runaway reaction due to heat generation is performed by heating at a temperature of about 30 ° C. to 180 ° C. or below the boiling point of phenols at the beginning of the reaction. Prevention, 200-2 in the second half
It is preferable to react at 70 ° C. to obtain a resin raw material composition. In this reaction, in the present invention, the pretreatment step of directly mixing the lignocellulosic substance with the phenol and uniformly mixing the phenol with the lignocellulosic substance can be omitted.

In the production method of the present invention, an organic solvent such as water, acetone or ethyl acetate is added during or during the dissolution for the purpose of lowering the solution viscosity of the lignocellulosic material or promoting the dissolution. It is also possible to make it. In the production of the resin raw material composition of the present invention, the above phenols can be used alone or as a mixture. Furthermore, in order to mitigate the runaway reaction due to the heat generated in the initial stage of the reaction, or to remove a large amount of water from the lignocellulosic material such as wood as the starting material to the outside of the system, an organic solvent azeotropic with water and the generated resin A solvent or the like that dissolves the raw material composition can be added at the beginning of the reaction or during the reaction. It is particularly desirable that the apparatus used in the production method of the present invention is provided with a stirrer to which a large torque can be applied in order to make the reaction uniform in the pressure-resistant reaction vessel. The resin raw material composition produced by the method of the present invention has high reactivity with aldehydes, epoxies, isocyanates and the like regardless of whether or not it contains unreacted phenols. Therefore, the obtained resin raw material composition has a property of becoming a polymer resin substance by an acid, an alkali catalyst, or heating. Therefore, the resin raw material composition obtained by the present invention is a raw material for an adhesive, a molded product, and the like.

[0009]

According to the present invention, a method is employed in which phenols are added to a lignocellulosic substance and heat-denatured in the presence of an alkaline additive to produce various resin raw material compositions. By doing so, the following points are improved. (1) It is possible to produce an efficient resin raw material composition with less reaction residue. (2) The resulting resin raw material composition has a small viscosity and can be easily taken out of the reaction vessel.

Hereinafter, the present invention will be described in more detail with reference to examples. Example 1 120 g of cedar sawdust (water content: 71.4%), 47 g of phenol (wood flour / phenol = 6/4) and 2.35 g of sodium hydroxide were weighed into a 2 L pressure-resistant reaction vessel equipped with a stirrer. In an oil bath, the temperature in the system was reduced to 180 ° C. ± 5 ° C., the temperature was gradually increased to 250 ° C., and the temperature was kept at 250 ° C. for 1 hour to obtain a black substance. This liquid was filtered with a G3 glass filter. When the residue after filtration was washed with dioxane, about 0.4
% Black material was obtained. Next, the filtrate was distilled under reduced pressure to remove water, and the viscosity was measured using an ICI cone plate viscometer (motor speed: 750 rpm, plate temperature: 25 ° C.). The viscosity was 7.6 poise. Example 2 120 g of cedar sawdust (water content: 71.4%), 30 g of phenol (wood flour / phenol = 7/3) and 3 g of sodium hydroxide were weighed into a 2 L pressure-resistant reaction vessel equipped with a stirrer, and the oil bath was used. The temperature inside the system was reduced to 180 ° C ± 5 ° C,
After the temperature was gradually raised to 250 ° C. and kept at 250 ° C. for 1 hour, a black substance was obtained. This liquid was filtered with a G3 glass filter. The residue after filtration was washed with dioxane to obtain about 0.6% of a black substance as a residue on a glass filter. Next, the filtrate was distilled under reduced pressure to remove water and an ICI cone plate viscometer (motor speed 750).
The viscosity was measured using a plate (rpm, plate temperature: 25 ° C.) and found to be 17.6 poise.

Example 3 120 g of cedar sawdust (water content: 71.4%), 47 g of phenol (wood flour / phenol = 6/4) and 2.2 g of calcium hydroxide were weighed into a 2 L pressure-resistant reaction vessel equipped with a stirrer. The heating was weakened at 180 ° C. ± 5 ° C. in an oil bath, the temperature was gradually raised to 250 ° C., and the temperature was kept at 250 ° C. for 1 hour to obtain a black substance. This liquid was filtered with a G3 glass filter. The residue after filtration was washed with dioxane, leaving about 0.3% on the glass filter.
Was obtained. Next, the filtrate was distilled under reduced pressure to remove water, and an ICI cone plate viscometer (motor speed 7) was used.
When the viscosity was measured using 50 rpm and a plate temperature of 25 ° C., it was 14.8 poise. Example 4 120 g of cedar sawdust (water content: 71.4%), 47 g of phenol (wood flour / phenol = 6/4) and 3.6 g of monoethanolamine were weighed into a 2 L pressure-resistant reaction vessel equipped with a stirrer. The heating was weakened at an internal temperature of 180 ° C. ± 5 ° C. in an oil bath, gradually raised to 250 ° C., and kept at 250 ° C. for 1 hour, to obtain a black substance. This liquid was filtered with a G3 glass filter. When the residue after filtration is washed with dioxane, about 1.
0% black material was obtained. Next, the filtrate was distilled under reduced pressure to remove water, and the viscosity was measured using an ICI cone plate viscometer (motor speed: 750 rpm, plate temperature: 25 ° C.). The result was 25.6 poise.

Comparative Example 1 120 g of cedar sawdust (water content: 71.4%) and 47 g of phenol (wood flour / phenol = 6/4) were weighed into a 2 L pressure-resistant reaction vessel equipped with a stirrer, and an alkaline additive was added. And the temperature in the oil bath at 250 ° C.
After a period of time, a black material was obtained. This liquid was filtered with a G3 glass filter. The residue after filtration was washed with dioxane to obtain about 2.8% of a black substance as a residue on a glass filter. Next, the filtrate was distilled under reduced pressure to remove water, and the viscosity was measured using an ICI cone plate viscometer (motor speed: 750 rpm, plate temperature: 25 ° C.).

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Claims (2)

(57) [Claims] 1. A method for producing a resin raw material composition by adding a phenol to a lignocellulose substance and heat-modifying the resin raw material composition, wherein heat denaturation is performed at a temperature higher than 200 ° C. and 270 ° C. or less in the presence of an alkaline additive. A method for producing a resin raw material composition obtained by modifying a lignocellulose substance. 2. The method according to claim 1, wherein the alkaline additive is an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate, ammonia or an amine.