JP2640604B2 - Manufacturing method of chemically modified wood - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a chemically modified wood material having excellent heat fluidity.

[0002]

2. Description of the Related Art Wood materials represented by wood are organic natural resources which are present in the largest amount in the natural world, and have recently attracted attention as reproducible resources. However,
Since these wood materials are insoluble and infusible and do not flow or melt like ordinary thermoplastic resins, it is not easy to process them into an arbitrary shape. Conventionally, wood materials
It is used for building materials and other various applications by taking advantage of its excellent features.Small-diameter trees, thinned timber, and sawdust discharged from timber factories are mostly disposed of by incineration and other methods. Therefore, development of these effective utilization methods is desired.

[0004] Recently, for the purpose of effectively utilizing these promising resources, studies have been made to chemically modify wood to impart thermoplasticity. For example, a method of allylating a wood material using an allyl halide, after a strong alkali treatment of the wood material,
Benzylation of wood with benzyl chloride, acylation of wood with trifluoroacetic anhydride and fatty acids such as acetic acid or lauric acid, wood with epoxy compounds in the presence of potassium salts of fatty acids A method of etherifying a material (Japanese Patent Publication No. 3-33018) and the like have been proposed.

[0005] The present inventors have previously proposed a method for producing modified wood chips (Japanese Patent Application Laid-Open No. 60-83806). In this method, a dibasic acid anhydride and a monoepoxy compound are alternately subjected to an addition esterification reaction with a hydroxyl group in a piece of wood, and the resulting modified piece of wood can be hot-pressed to provide moisture resistance and water resistance. It can be a sheet or board with a good surface.

[0006] However, the chemically modified wood obtained by these methods has thermoplasticity but poor heat fluidity.
It was necessary to perform hot pressing at a high temperature and a high pressure of 0 kg / cm ² or more. Further, when a large amount of the reactive modifier is added to the wood material by the above-described method, the thermal fluidity is slightly improved, but on the contrary, the content of the wood material in the obtained chemically modified wood material is reduced. There was a problem.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for easily producing a chemically modified wood material having a high wood content and excellent heat fluidity.

[0008]

According to the present invention, a wood material is converted into a monoepoxy compound represented by the following formula (1):
Alternatively, there is provided a method for producing a chemically modified wood material, which comprises coexisting a halohydrin compound represented by the following formula 2 when chemically modifying the monoepoxy compound and an organic acid anhydride. There is provided a method for producing a chemically modified wood material, characterized by using styrene oxide as the monoepoxy compound represented by the formula (1), and further comprising a halohydrin compound represented by the formula (2) Uses 2-chloro-2-phenylethanol as a process for producing the chemically modified wood material.

Embedded image (Wherein, Y represents a substituent selected from a halogen atom or an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 5 representing the number of substituents, and n is an integer of 2 to 5) When it represents, the kind of substituent Y may be the same or different.)

Embedded image (Wherein, X represents a halogen atom, Z represents a halogen atom or a substituent selected from an alkyl group having 1 to 4 carbon atoms, m is an integer of 0 to 5 representing the number of substituents, and m When represents an integer of 2 to 5, the types of the substituents Z may be the same or different.)

That is, the inventors of the present invention have proposed a method in which a wood material is mixed with a monoepoxy compound represented by the formula 1 (Chemical Formula 1) or a monoepoxy compound represented by the formula 1 (Chemical Formula 1) in the presence of the halohydrin compound represented by the formula 2 (Formula 2). Chemically modified wood material chemically modified with a monoepoxy compound represented by Chemical Formula 1) and an organic acid anhydride is represented by Formula 1
A monoepoxy compound represented by the following chemical formula 1
The present inventors have found that they have remarkably excellent thermal fluidity as compared with chemically modified wood materials produced in the absence of the halohydrin compound represented by the chemical formula (2), and have completed the present invention.

Hereinafter, a method for producing a chemically modified wood material having excellent heat fluidity according to the present invention will be described in detail. Wood materials used for producing the chemically modified wood material of the present invention include wood flour,
Wood fiber, wood chips, particle boards, fiber chips and other small wood chips such as sander powder discharged during the manufacturing process, and cellulose and lignin such as plant fibers such as straw, rice straw, peach, bagasse, etc. Lignocellulosic materials, holocellulose materials mainly containing cellulose and hemicellulose such as waste paper and pulp, and cellulose materials mainly containing cellulose such as cellulose powder and linter. When the water content in these woody materials is high, it is preferable to use them after drying with a hot air drier or a vacuum drier to remove water to 15% by weight or less. A high water content is not preferred because the rate of side reaction of the organic acid anhydride or monoepoxy compound as a reactant increases.

The monoepoxy compound used in the present invention is a compound represented by the above formula (1), for example, styrene oxide, 1,2-epoxyethyltoluene, 1,2-epoxyethylxylene And the like. In particular, styrene oxide, which is industrially inexpensive and advantageous, is preferable.

As the organic acid anhydride, maleic anhydride,
Examples thereof include phthalic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3.6-dichlorophthalic anhydride, itaconic anhydride, heptic anhydride, and acetic anhydride. In particular, industrially inexpensive and advantageous maleic anhydride, phthalic anhydride, succinic anhydride and the like are preferable.

Examples of the halohydrin compound represented by the formula (2) include 2-chloro-2-phenylethanol, 2-bromo-2-phenylethanol, 2-bromo-2-m-tolylethanol and the like. .

The amount of the halohydrin compound represented by the above formula (2) is preferably 1.0 to 50 parts by weight based on 100 parts by weight of the wood material. When the addition amount is less than 1.0 part by weight, the obtained chemically modified wood material has poor thermal fluidity, and for example, it is impossible to measure a melt index (MI) which is one index of thermal fluidity, which is preferable. Absent. On the other hand, if the addition amount of the halohydrin compound exceeds 50 parts by weight, the content of the halohydrin compound in the product after the completion of the reaction becomes too large, which is not preferable.

In the production method of the present invention, the wooden material is represented by the formula 1
The case of chemical modification with a monoepoxy compound represented by In the reaction, the wood material, the monoepoxy compound and the halohydrin compound are charged into the reaction vessel at once,
The reaction is carried out at a reaction temperature of 60 ° C. or higher, preferably 90 ° C. to 200 ° C., and the chemically modified wood material of the present invention is obtained in a reaction time of 10 minutes to 20 hours. Although the reaction product can be washed to remove unreacted products and by-products, the reaction product can be used as it is as a chemically modified wood material. This reaction proceeds sufficiently without using a catalyst, but a general etherification catalyst such as potassium acetate, dimethylbenzylamine, imidazoles or the like can be used to promote the reaction.

The amount of the monoepoxy compound used is as follows.
It is preferable to use 15 to 250 parts by weight based on 00 parts by weight. If the used amount is less than 15 parts by weight, the obtained thermoplastic chemically modified wood material has poor thermal fluidity, and it is impossible to measure MI. Conversely, if the amount used exceeds 250 parts by weight, a chemically modified wood material excellent in heat fluidity can be obtained, but the content of the wood material is too low, which is not only contrary to the object of the present invention, but also economical. Is also not preferred.

Next, the case where the wood material is chemically modified with a monoepoxy compound and an organic acid anhydride in the production method of the present invention will be described. The total amount of the monoepoxy compound and the organic acid anhydride is 15 to 100 parts by weight of the wood material.
It is preferred to use 250 parts by weight. If the used amount is less than 15 parts by weight, the obtained chemically modified wood material has poor thermal fluidity, so that MI cannot be measured. Conversely, the amount used is 2
When the amount exceeds 50 parts by weight, although a chemically modified wood material excellent in heat fluidity is obtained, the wood material content is too low,
This is not only contrary to the object of the present invention but also economically undesirable.

The proportion of the organic acid anhydride to the monoepoxy compound is preferably not more than 1.5 equivalents to 1 equivalent of the epoxy group. When the number of the anhydride groups is larger than this, the amount of the half-ester of the organic acid anhydride having a carboxyl group added to the hydroxyl group in the wood material at the terminal increases, and the water resistance of the obtained chemically modified wood material decreases. Is not preferred.

The reaction of wood material with the monoepoxy compound and the organic acid anhydride in the presence of the halohydrin compound represented by the above formula (2) generally proceeds easily at a reaction temperature of 60 ° C. or higher. , Preferably at 90 ° C to 200 ° C. The reaction method is wood,
The monoepoxy compound, the organic acid anhydride and the halohydrin compound represented by the above formula (Chemical Formula 2) are put into a reaction vessel at one time and reacted, or a wood material and the monoepoxy compound and the compound of the above formula (Chemical Formula 2) are reacted. The halohydrin compound represented by the formula is heated and stirred in advance for 10 minutes to 5 hours, and then an acid anhydride is added thereto and reacted, or the wood material and the acid anhydride and the halohydrin compound represented by the above formula (Chemical Formula 2) are added for 10 minutes in advance. After heating and stirring for up to 5 hours, a method of adding the monoepoxy compound and causing a reaction may be used, but any of these methods may be used. Thus, the chemically modified wood material of the present invention can be obtained. The reaction product can be washed to remove unreacted products and by-products, but the reaction product can be used as it is as a chemical modifying material.

The chemically modified wood material obtained by the production method of the present invention has good heat fluidity, so that a usual thermoplastic resin is molded and processed by extrusion molding, injection molding and the like as well as general press molding. It can be molded under processing conditions, used as a modifier for thermoplastic resins, or as a raw material for foamed plastics, and is suitable as an industrial component material, building material, or the like in many fields.

[0021]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, wood flour (trade name:
LIGNOCEL S150TR; Retten
marier &Soehne; fiber length: 30-
60μ) was used. The wood flour percentage of the obtained chemically modified wood was determined by the following equation from the weight (M) of the wood and the weight (N) of the compound charged in addition to the wood. Wood quality (%) = 100M / (M + N)

The acetone-soluble portion means a chemically modified wood material that has become soluble in acetone, and by-products not bound to the wood material component. The acetone-soluble part was determined from the weight (X) of a sample sampled from the obtained chemically modified wood material and the weight (Y) of the acetone-soluble part when this sample was subjected to Soxhlet extraction by the following formula. Acetone soluble part (% by weight) = 100Y / X The larger the acetone soluble part, the better the thermal fluidity of the chemically modified wood material.

The heat fluidity of the obtained chemically modified wood material is M
I was evaluated. MI is 1 according to JIS K7210.
It was determined from values measured at 50 ° C. and a sample load of 10 kgf, or at 190 ° C. and a sample load of 10 kgf. The unit is g
/ 10 min. It is.

Example 1 18.8 g of dry wood flour, 13.27 of styrene oxide
g and 2-chloro-2-phenylethanol 5.64
g into a 500 ml separable flask,
After stirring at 2 ° C. for 2 hours, 5.53 g of succinic anhydride was added, and the mixture was further reacted under stirring at 150 ° C. for 5 hours to obtain a chemically modified wood material (1A). Further, a part of the chemically modified wood material (1A) is taken, washed with a large amount of 2-propanol to remove by-products not bound to the wood material component, and then dried to obtain a chemically modified wood material. (1B) was obtained. Table 1 shows the weight percent of the acetone-soluble part and the MI of these chemically modified wood materials by Soxhlet extraction.

Example 2 20.0 g of dry wood flour, 8.57 g of styrene oxide,
5.5 g of 2-chloro-2-phenylethanol and
Charge into a 00 ml separable flask,
The mixture was reacted under stirring for a time to obtain a chemically modified wood material. The weight percent of the acetone-soluble part by the Soxhlet extraction, and MI
Are shown in Table 1.

Comparative Example 1 15.0 g of dry wood flour, 11.17 of styrene oxide
g, and 6.16 g of butyl-3-chloro-2-hydroxypropyl ether were charged into a 500 ml separable flask, and stirred at 150 ° C. for 2 hours.
62 g was added, and the mixture was further reacted under stirring at 150 ° C. for 5 hours to obtain a chemically modified wood material. Table 1 shows the weight% of the acetone-soluble part and the value of MI obtained by the Soxhlet extraction.

Comparative Example 2 18.8 g of dry wood flour, phenylglycidyl ether 1
4.10 g and 2.64 g of 2-chloro-2-phenylethanol were charged into a 500 ml separable flask, stirred at 150 ° C. for 2 hours, and then 4.71 g of succinic anhydride.
And further reacted under stirring at 150 ° C. for 5 hours to obtain a chemically modified wood material. Table 1 shows the weight% of the acetone-soluble part and the value of MI obtained by the Soxhlet extraction.

[0028]

[Table 1]

As shown in Example 1 or 2 of Table 1, SO was used as the monoepoxy compound represented by the above formula 1 (Chemical formula 1), and CPE was used as the halohydrin compound represented by the above formula 2 (Chemical formula 2). The manufactured chemically-modified wood material exhibited thermal fluidity such that MI could be measured. On the other hand, when the halohydrin compound represented by Formula 2 was not used as shown in Comparative Example 1 or when the monoepoxy compound represented by Formula 1 was not used as shown in Comparative Example 2, , MI could not be measured. From this, it can be seen that in order to obtain a chemically modified wood material having good thermal fluidity, it is essential to use the monoepoxy compound represented by Formula 1 and the halohydrin compound represented by Formula 2 in combination. .

[0030]

Industrial Applicability The chemically modified wood obtained by the production method of the present invention has a high wood content, and has extremely excellent heat fluidity as compared with the chemically modified wood obtained by the conventional production method.
By heating, it can be discharged from an orifice tube having a diameter of 2.095 mm, and can be molded and processed in the same manner as a normal thermoplastic resin. Can be easily manufactured by a simple method.

Claims (3)

(57) [Claims] When a wood material is chemically modified with a monoepoxy compound represented by the following formula 1 (Chemical formula 1) or the monoepoxy compound and an organic acid anhydride, a halohydrin compound represented by the following formula 2 (Chemical formula 2) A method for producing a chemically modified wood material, characterized by coexistence of Embedded image (Wherein, Y represents a substituent selected from a halogen atom or an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 5 representing the number of substituents, and n is an integer of 2 to 5) When it represents, the kind of substituent Y may be the same or different.) Wherein X represents a halogen atom, Z represents a halogen atom or a substituent selected from an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 5 representing the number of substituents. And when m represents an integer of 2 to 5, the types of the substituents Z may be the same or different.) 2. The method for producing a chemically modified wood material according to claim 1, wherein the monoepoxy compound represented by the formula 1 is a styrene oxide. 3. The method for producing a chemically modified wood material according to claim 1, wherein the halohydrin compound represented by the formula (2) is 2-chloro-2-phenylethanol.