JPH0128130B2 - - Google Patents

Description

[Detailed Description of the Invention] (a) Industrial Application Field The present invention relates to a method for producing a plasticized wood filament, and more specifically, to a method for producing a plasticized wood filament. , relates to a method for producing a filamentous body by discharging it into the air from a spinneret.

(b) Prior Art There is currently a great desire to develop more effective methods of using forest resources, which are renewable resources. Furthermore, in industries that use wood as raw materials, such as the wood industry and the pulp industry, there is an urgent need to establish methods for effectively utilizing wood-based waste. Under these circumstances, attempts have been made to make more advanced use of wood-based raw materials, including wood, by imparting plastic properties to wood through simple chemical reactions such as esterification or etherification. Proposed.

For example, JP-A-57-103804 and JP-A-56-103804
No. 135552 discloses a technology to esterify or etherify wood (powder) by introducing organic groups into some of the hydroxyl groups, and the plasticized wood thus obtained can be used as is or with various synthetic polymers. It is described that the mixture is used as a molding raw material. Furthermore, in JP-A No. 57-2360, a solution is prepared by dissolving plasticized wood obtained by esterifying or etherifying wood (powder) by introducing organic groups into some of the hydroxyl groups in an organic solvent. The technique is disclosed, and it is also stated that the prepared solution can be formed into a film by itself or in co-dissolution with various synthetic polymers. However, no technology has been developed for converting plasticized wood obtained by esterification or etherification into filaments or fibers as is (ie, without mixing with synthetic polymers).

(c) Purpose of the Invention The purpose of the present invention is to provide a method for converting plasticized wood obtained by treating wood with a plasticizing modifier into filaments or fibers as is (i.e., without mixing with synthetic polymers). is to provide.

(d) Structure of the Invention The method for producing a plasticized wood filament according to the present invention involves adding an organic solvent to wood that has been made into plastic by introducing at least one substituent to some or all of the hydroxyl groups, and then adding a spinning solution to the wood. The spinning solution is discharged into the air from a spinneret, and the discharged yarn is drawn by 10% to 100% of the original fiber length at room temperature to heating.

(e) Preferred embodiment The raw material for producing plasticized wood is wood flour or mechanical pulp. Further, there is no restriction on the type of wood used as a raw material, and the method of the present invention can be applied to any type of wood. The plasticization modification reaction of the present invention, which introduces substituents into wood raw materials,
This is a reaction in which aliphatic acyl substituents are introduced into at least some of the hydroxyl groups of cellulose, hemicellulose, or lignin present in wood raw materials to esterify them.

Modifiers used for esterification include acids and their derivatives, such as free acids, acid halides, and acid anhydrides. Preferred examples of substituents introduced by the plastic modification reaction include acetyl group, propionyl group, butyryl group,
Examples include aliphatic acyl groups such as valeroyl group. It is also possible to introduce two or more of these substituents.

The introduction ratio of substituents varies depending on the type of substituent, but in general, in order to obtain modified wood having good organic solvent solubility, the substitution ratio expressed as substituent morality is 7.5 or more. Here, "substituent morality" refers to the number of moles of substituents introduced by substitution per 1000 g of wood.

Plastic modification treatment can be carried out according to known techniques. Generally, powdered wood may be treated with a modifier in the presence of an organic solvent or a swelling agent at room temperature to elevated temperatures. Thoroughly wash the wood to be modified. For example, it is poured into methanol, filtered, and washed with water or methanol. Then dry.

Plasticized wood has a good affinity for some organic solvents and either gels or dissolves. The organic solvent used for preparing the spinning solution is selected from chloroform, dichloromethane, acetone, and dimethylformamide.
Two or more of these solvents can be used in combination, if necessary.

The spinning solution can be prepared by stirring a mixture of modified wood and an organic solvent at room temperature or high temperature, if necessary, in a pressure container. The concentration of modified wood in the spinning solution is preferably 3 to 25% by weight.

The spinning solution is discharged into air or other atmosphere through a spinning orifice at around room temperature. The discharged filament is made to travel through a drying tube and then wound up. In the drying tube, most of the organic solvent evaporates and evaporates within a few seconds, and the discharged filament solidifies almost completely.

The modified wood that has become a filament is stretched at temperatures ranging from room temperature to 350°C in order to improve its tensile strength and other mechanical properties. Stretching ratio is 1.1 to 2.0 times,
That is, the fibers are stretched by 10 to 100% relative to the original fiber length.
Stretching at high magnifications, such as in the stretching of many synthetic polymer filaments, is difficult. Stretching temperature is approximately 100℃~
About 300°C is preferred. The drawing technique may be the same as that commonly used for drawing many filaments or fibers, for example between rolls having different speeds.

The plasticized wood filament obtained by the method of the present invention has a tensile strength of about 7 to 12 kg/mm ² and an elongation of 1.0 to 4.0%. The filament obtained by the method of the present invention can be carbonized to produce ion-exchange carbon fibers, or esterified with phosphoric acid ester to be used as flame-spinning fibers or cation-exchange fibers.

(c) Examples Hereinafter, the method of the present invention will be specifically explained using examples.

Example 1 After drying, 3 g of radiata pine refined ground pulp (RGP) was weighed and placed in a reactor.
A mixed solution of 114 mmol of anhydrous trifluoroacetic acid and 120 mmol of acetic acid, which had been aged in advance at 50°C for 30 minutes, was put into the above reactor, the temperature was set at 50°C, and the mixture was allowed to react for 2 hours. After the reaction is completed, the reaction solution is dispersed in 1.5 methanol to decompose excess acylating reagent, and then dried. The substituent morality of the obtained modified wood was 12.6.

25 ml of chloroform is added to 2 g of the modified wood thus obtained and stirred to obtain a spinning solution. Put the spinning solution into a glass syringe and use a circular spinneret (pore size
0.6mm) and is discharged into air at room temperature using piston pressure. The discharged yarn is dried by running through a 20 cm long drying tube located 10 cm below the spinneret. Thereafter, the filamentous body was heated under hot air at 190°C.
Stretch 35% of the original length (stretch ratio 1.35). This filament had a diameter of 0.16 mm, a tensile strength of 8.6 Kg/mm ² , and an elongation of 3.5%. Note that the tensile strength and elongation were measured in accordance with JISL-1069.

Example 2 After adding 25 ml of chloroform to 2 g of the modified wood prepared in Example 1, it was placed in a pressure vessel and heated to 130°C.
Heat for 30 minutes to dissolve. Thereafter, it is cooled to around room temperature to obtain a spinning solution. The spinning solution is put into a glass syringe and discharged into air at room temperature through a circular spinneret (pore diameter: 0.3 mm) by piston pressure. The discharged yarn was dried in the same manner as in Example 1, and then stretched to 40% of its original length under hot air at 160°C.

This filament has a diameter of 0.099 mm and a tensile strength of 11.0
Kg/mm ² and elongation was 1.6%.

Example 3 After adding 25 ml of chloroform to 2 g of the modified wood prepared in Example 1, it was placed in a pressure vessel and heated to 180°C.
The spinning solution is prepared by heating for 30 minutes and then cooling to around room temperature. The spinning solution is put into a glass syringe and expelled from a circular spinneret (pore diameter: 0.3 mm) into air at room temperature by piston pressure to obtain a filamentous body. This discharged yarn is stretched to 50% of its original length at 285°C under a nitrogen stream.

This filament has a diameter of 0.100 mm and a tensile strength of 11.0
Kg/mm ² and elongation was 7.0%.

Example 4 18.5 ml of dichloromethane is added to 2 g of the modified wood prepared in Example 1 and stirred to obtain a spinning solution. Spinning and drawing were performed in the same manner as in Example 1 to obtain a drawn filament.

This filament has a diameter of 0.15mm and a tensile strength of 8.0Kg/
mm ² and elongation was 3.8%.

Example 5 3 g of dried Pine radiata RGP was weighed out and placed in a reaction vessel. A mixture of 114 mmol of trifluoroacetic anhydride, 85 mmol of propionic acid, and 35 mmol of acetic acid, which had been aged in advance at 50°C for 30 minutes, is added, the reaction temperature is set at 50°C, and the mixture is allowed to react for 2 hours. After the reaction was completed, the reaction solution was dispersed in 1.5 methanol to decompose the excess acylating reagent, and then
After filtering and washing with water or methanol, dry. The substituent morality of the obtained modified wood is 11.8
It was hot.

Add 25 ml of chloroform to 2 g of the modified wood thus obtained and stir at room temperature to obtain a spinning solution. The spinning solution is put into a glass syringe and discharged into air at room temperature by piston pressure from a circular spinneret (hole diameter 0.6 mm). As in Example 1, after drying, the filamentous body is stretched to 40% of its original length under hot air at 145°C.

This filament has a diameter of 0.16 mm and a tensile strength of 7.8 Kg/mm ² .
The elongation was 3.8%.

Example 6 3 g of dried Pine radiata RGP and 4.0 ml of acetic acid are placed in a reaction vessel and left at room temperature for 2 hours with occasional stirring. After this pretreatment is completed, mix 18 ml of acetic acid, 8.4 ml of acetic anhydride, and 0.15 ml of sulfuric acid, add the above mixture to the ice-cooled acetic acid mixture, and react with shaking in a constant temperature bath at 50°C for 2 hours. . After the reaction is completed, 8.0 ml of water is added and the saponification reaction is carried out at 70°C for 3 hours. After the saponification reaction is completed, 1 is added to stop the reaction.
Pour the product into 300 ml of % magnesium acetate aqueous solution, stir, collect in a glass filter,
Wash with 0.1% magnesium acetate aqueous solution 2, water, and dry. The substituent morality of the obtained modified wood was 8.0. 18.5 ml of dichloromethane is added to 2 g of the modified wood thus prepared, placed in a pressure vessel, and heated at 150° C. for 30 minutes to dissolve.
Thereafter, it is cooled to around room temperature to obtain a spinning solution. The spinning solution is put into a glass syringe and discharged into air at room temperature through a circular spinneret (pore diameter: 0.3 mm) by piston pressure. The discharged yarn was dried in the same manner as in Example 1, and then 45% of its original length was dried at 270°C under a nitrogen stream.
Stretch.

This filament has a diameter of 0.180mm and a tensile strength of 9.0Kg/
mm ² and elongation of 3.5%.

Claims (1)

[Claims] 1. Chloroform, dichloromethane, An organic solvent selected from acetone and dimethylformamide is added to form a spinning solution, the spinning solution is discharged into the air from a spinneret, and the discharged yarn is heated to 10% of the original fiber length at room temperature to heating.
A method for producing a plastic wood filament characterized by ~100% stretching.