JPS6136341A - Preparation of uniform composition consisting of cellulose and synthetic high polymer - Google Patents

Abstract

PURPOSE:To obtain a composite material moldable into a film or gel, etc. by using a wide range of high polymers, by dissolving cellulose and a synthetic high polymer in an organic solvent containing a tetraalkylammonium halide, and depositing the resultant solution in a regenerating solution. CONSTITUTION:Cellulose and a synthetic high polymer are dissolved in an organic solvent containing a tetraalkylammonium halide expressed by the formula R4NX (R is 1-4C alkyl; X is halogen), and the resultant solution is then deposited in a regenerating solution. A solvent selected from dimethyl sulfoxide, dimethylformamide, tetramethylene sulfone and dimethylacetamide is used as the organic solvent. Tetraethylammonium chloride, etc. is used as the tetraalkylammonium halide, and the amount thereof to be incorporated is 10-80pts.wt. based on 100pts.wt. organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a homogeneous composition consisting of cellulose and a synthetic polymer, and more specifically, to a method for producing a homogeneous composition consisting of cellulose and a synthetic polymer. The present invention relates to an efficient method for producing a homogeneous composition consisting of a polymer.

Conventionally, many techniques including the viscose method have been developed for producing fibers and the like using cellulose as a raw material. However, with these conventional techniques, the performance and properties of the products obtained are basically determined entirely by the cellulose such as the pulp used, and it has been extremely difficult to significantly improve performance or impart new properties.

Therefore, the present inventors focused on the above-mentioned problems with the conventional cellulose utilization technology, and after conducting extensive research, found that an organic solvent such as dimethyl sulfoxide to which a specific tetraalkylammonium halide was added as an auxiliary agent was used. When used,
We have discovered that cellulose and various synthetic polymers can be mixed and dissolved in arbitrary proportions, and that if this is introduced into a regenerating liquid such as water or alcohol, a uniform composition can be precipitated. The present invention was completed based on this knowledge.

That is, the present invention uses cellulose and synthetic polymers as tetraalkylammonium halides represented by the general formula R,NX (wherein, R represents an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom). The present invention provides a method for producing a homogeneous composition consisting of cellulose and a synthetic polymer, which is characterized by dissolving cellulose in an organic solvent containing the cellulose, and then precipitating the resulting solution in a regenerating solution.

There are various types of synthetic polymers that can be used in the method of the present invention, and basically there are no particular restrictions as long as they can be dissolved in an organic solvent containing tetraammonium halide or a liquid containing cellulose. . Usually, an appropriate synthetic polymer is selected depending on the required characteristics of the uniform composition to be manufactured, and specifically polyethylene is selected.

Polyolefins such as polypropylene, polymethacrylic esters such as polymethyl methacrylate and polyethyl methacrylate, polyacrylic esters such as polymethyl acrylate and polyethyl acrylate, vinyl polymers such as polyvinyl acetate, polyvinyl chloride, and polyvinyl pyrrolidone, polydimethylsiloxane Examples include organopolysiloxanes such as polycarbonates, polyamides, polyurethanes, and polyesters. Note that organopolysiloxane such as polydimethylsiloxane is a synthetic polymer that does not dissolve alone in organic solvents such as dimethyl sulfoxide, but it is a synthetic polymer that does not dissolve alone in organic solvents such as dimethyl sulfoxide. It dissolves into a mixed solution that does not cause layer separation.

In this way, the synthetic polymers that can be used in the method of the present invention are very limited, and in reality, all synthetic polymers can be used as long as they are liquid polymers or polymers that can be dissolved in a suitable organic solvent. The molecules can be complexed with cellulose into homogeneous compositions, resulting in new composite materials.

In addition, in the method of the present invention, the mixing ratio of cellulose and synthetic polymer is arbitrary as long as both can be dissolved in the organic solvent used, and can be adjusted as appropriate depending on the use of the homogeneous composition to be produced. Just set it.

Next, in the method of the present invention, the general formula R, NX (wherein R represents an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom) is used as an auxiliary agent for dissolving cellulose or synthetic polymers. ) is used. Here, the amount of tetraalkylammonium halide to be used may be determined as appropriate depending on various conditions, but
Usually, the amount is 10 to 80 parts by weight, preferably 20 to 60 parts by weight, per 100 parts by weight of the organic solvent. Specific examples of the tetraalkylammonium halide include tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium chloride, methyltriethylammonium chloride, propyltriethylammonium chloride, or mixtures thereof.

In addition, in the method of the present invention, various organic solvents can be used, but in addition to the above-mentioned tetraalkylammonium halide, cellulose and synthetic polymers are dissolved. Specifically, dimethyl sulfoxide (D
MSO), dimethylformamide (DMF), tetramethylene sulfoxide and dimethylacetamide. Among them, DMSO is particularly preferably used.

In the method of the present invention, as described above, cellulose and a desired synthetic polymer are first dissolved in a melt containing a tetraalkylammonium halide, but the order of operations is not particularly limited. First, an organic solvent such as DMSO is infiltrated into finely cut cellulose such as bulbs, and while heating this, tetraalkylammonium halide is added and stirred to dissolve the cellulose.
Thereafter, a synthetic polymer is added and stirred under heating to prepare a solution in which cellulose and synthetic polymer are dissolved. Alternatively, a solution in which cellulose and synthetic polymer are dissolved can also be prepared by first dissolving the synthetic polymer in an organic solvent, then adding cellulose, and then adding tetraalkylammonium halide under heating and stirring. . Furthermore, a solution in which cellulose and a synthetic polymer are dissolved can also be prepared by adding a synthetic polymer and a tetraalkylammonium halide to an organic solvent, dissolving the mixture under heating, and then adding cellulose and stirring.

In the method of the present invention, a solution in which cellulose and a synthetic polymer prepared by the above-described procedure are dissolved is allowed to precipitate in a regenerating liquid. The regenerating liquid used here dissolves and removes the organic solvent and tetraalkylammonium halide from the above solution to precipitate a mixture of cellulose and synthetic polymer. Specifically, examples include water, methanol, ethanol, ethylene glycol, or mixtures thereof, and mixtures of these with DMSO and DMF, depending on the type of synthetic polymer and the required characteristics of the intended composition. It may be determined as appropriate.

In the method of the present invention, when the obtained solution is precipitated in a regenerating liquid, by spinning this solution into the regenerating liquid from a spinning nozzle, fibers or filaments of a uniform composition of cellulose and a synthetic polymer are produced. can get. Furthermore, if the solution is applied to a glass plate or the like and then introduced into a regenerating solution, a film or sheet of a uniform composition can be obtained. In addition, a molded article of a uniform composition molded into a predetermined shape can be obtained by various methods.

The composition obtained by the method of the present invention is a homogeneous composition in which cellulose and synthetic polymer are completely and uniformly mixed, and there is no decrease in the degree of polymerization or deterioration of the cellulose or synthetic polymer in this composition. can not see. Moreover, in the method of the present invention, since no chemical reaction is performed on cellulose, the cellulose molecules in the regenerated composition retain the same chemical structure as natural cellulose. It has the characteristic that the degree of polymerization does not decrease. The properties of the homogeneous composition produced by the method of the present invention can be freely adjusted by adjusting the type and amount of the synthetic polymer used.

In addition, the method of the present invention does not require the use of harmful substances in the entire process from solution preparation to regeneration, and can be said to be an excellent method for pollution control specialists. After precipitation, the organic solvent and tetraalkylammonium halide can be easily separated and recovered from the regenerated solution, and the recovered organic solvent and tetraalkylammonium halide can be repeatedly reused, which is advantageous from an economical point of view and saving. It is also preferable from the viewpoint of resources.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 A DP900 viscose sulfide valve that had been cut into pieces was dried under reduced pressure at 90°C for 3 hours.
After sufficiently infiltrating 0 g with 59 g of DMSO, it was heated to 90°C and tetraethylammonium chloride (TEAC
) and stirred for 2 hours to dissolve cellulose in DMSO.
A liquid I was obtained. Next, add 50g, 30g, 10g of this solution.
and 5 g, each containing 0.26 g of polymethyl methacrylate (MMA) and 1.8 g of DMSO.
solution dissolved in.

0.5 g MMA in 4.5 g DMSO, 2 g MMA in 188 DMSO, 4
A solution of g of MMA dissolved in 36 g of DMSO and a solution of 4.5 g of MMA dissolved in 40.5 g of DMSO were added, and the mixture was further stirred at 90°C for 1 hour to form a DMSO solution in which cellulose and MMA were dissolved. I got 4 types. When each of the obtained solutions was observed under a microscope (100x magnification), no undissolved substances were detected in any of the solutions. The concentrations of each component in the obtained solution are shown in Table 1.

Example 2 DP was added to a solution of MMA1g dissolved in 838 DMSO.
After adding 10 g of dried and cut 900 viscose sulfide pulp and allowing the solution to fully penetrate,
After heating to 0°C, add 31 g of TEAC and stir for 2 hours to obtain 3 wt% cellulose and 8 wt% MMAo.

TEA C25wt%, cellulose/MMA=10
(weight ratio) solution was obtained. When this solution was also observed under a microscope (100x magnification), no undissolved matter was detected.

Example 3 Dried and cut DP900 viscose sulfide valve Log, DMS059g and TEAC32g
DM of cellulose was performed in the same manner as in Example 1 using
A SO solution was prepared. Next, divide the resulting solution into four equal parts,
In each of these solutions, 2.5 g of polyvinyl acetate was dissolved in 023 g of DMS.

A solution in which 2.5 g of polyvinyl chloride was dissolved in 023 g of DMS, a solution in which 2.58 g of polycarbonate was dissolved in 023 g of DMS, and 2.58 g of polyvinylpyrrolidone was dissolved in DMS.
A solution dissolved in 0.023 g was added thereto, and the mixture was stirred at 90°C for 1 hour. The composition of the obtained solution was 5 wt % cellulose, 1 synthetic polymer (polyvinyl acetate).

Polyvinyl chloride, polycarbonate, polyvinylpyrrolidone) 5 wt%, TEAC 16 wt%.

Cellulose/synthetic polymer-1 (weight ratio), and no undissolved matter was detected in either solution.

Next, for these synthetic polymers using the above method, the total concentration of cellulose and synthetic polymer was fixed at 10 wt%, and the composition of cellulose and each synthetic polymer was varied within this range,
We observed the presence or absence of cellulose precipitation and N separation, and found that all materials were stable, with no solid matter precipitation or layer formation when the cellulose/synthetic polymer weight ratio ranged from a minimum value of 0.5 to a maximum value of 9.5. No separation was detected.

Example 4 83gf7) After adding 1g of polyvinyl acetate and 31g of TEAC in DMSO and dissolving at 90°C,
To this was added 10 g of dried and cut DP900 sulfide bulb for viscose and stirred for 1.5 hours to obtain a DMSO solution in which cellulose and polyvinyl acetate were dissolved.

Furthermore, a DMSO solution in which cellulose and polyvinyl chloride, polycarbonate, or polyvinylpyrrolidone were dissolved was obtained in the same manner as above.

The composition of the solution obtained in this way was 8 wt% cellulose.
1 synthetic polymer (polyvinyl acetate, polyvinyl chloride, polycarbonate) 0.8 wt%,
TEAC 25wt%, cellulose/synthetic polymer = 10 (
(weight ratio), and it was a good solution with no undissolved matter or layer separation observed.

Example 5 In the same manner as in Example 1, 10 g of sulfide pulp for viscose was dissolved in 32 g of TEAC and 068 g of DMS to obtain a DMSO solution of cellulose.

Next, divide this solution into four equal parts and add 0.25 g, 1 g, and 2.5 g of polydimethylsiloxane to each solution.
.

5g was added and further stirred at 90°C for 1 hour. Although there was no precipitation of solid matter in any of the solutions obtained in this manner, in the solution to which 5 g of dimethylsiloxane was added, slight layer separation of dimethylsiloxane was found when observed under a microscope (100x magnification).

Table 2 shows the composition and dissolution status of each solution.

Example 6 DMSO solutions of the cellulose obtained in Examples 1 and 3.4 and each synthetic polymer of polymethyl methacrylate (MMA), polyvinyl acetate polyvinyl chloride, polycarbonate, and polydimethylsiloxane were each
After filtering through polyester felt at 0℃, the caliber is 0.0.
Wet spinning was performed through a 100-hole spinneret. Table 4 shows the polymer mixing ratio and physical properties of cellulose fibers obtained by two-bath wet spinning using the two types shown in Table 3.

Table 3 (Regeneration liquid composition) Example 7 By the same operation as in Example 1, 411 t% of cellulose was obtained.

MMAl, 5 wt%, TEAC 12 wt% DMSO
A solution was prepared. Next, this solution was applied to a thickness of about 0.3 nm+m on a clean glass plate and left to stand in the air for 10 minutes, after which a regenerating solution consisting of a 2:1 mixture of methanol and water was gently added. As a result, a composite film of cellulose and MMA could be formed.

Claims (2)

[Claims] (1) Cellulose and synthetic polymers have the general formula R_4N
A tetraalkylammonium halide represented by 1. A method for producing a homogeneous composition comprising cellulose and a synthetic polymer, the method comprising precipitating cellulose and a synthetic polymer. (2) The method according to claim 1, wherein the organic solvent is one or more compounds selected from the group consisting of dimethyl sulfoxide, dimethylformamide, tetramethylene sulfoxide, and dimethylacetamide.