JP2010111707A - Polymer treating agent and dope - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer treating agent including an ionic liquid taking a liquid form at around room temperature, and excellent in handling properties owing to low viscosity. <P>SOLUTION: The polymer treating agent includes an ionic liquid represented by formula (1) and aprotic solvent, e.g. DMSO, and takes a liquid form at 30°C, (wherein R<SP>1</SP>-R<SP>3</SP>may be same or different representing 1-5C alkyl, 3-5C alkenyl, or alkoxyalkyl represented by formula: R<SP>4</SP>-O-(CH<SB>2</SB>)<SB>n</SB>-; R<SP>4</SP>represents methyl or ethyl; n represents a number of 1 or 2; and Y represents a halide ion, carboxylate ion having 1 to 3 carbon atoms in total, perchlorate ion, pseudo-halide ion, cyanamide ion or dicyanamide ion). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polymer treating agent and a dope, and more specifically, comprises an ionic liquid and an aprotic solvent, and includes, for example, a polymer treating agent suitable as a polymer surface treatment, a swelling treatment, and a solubilizer, and an ionic liquid and The present invention relates to a dope obtained by dissolving a polymer in an aprotic solvent.

Conventionally, it is known that polymer substances such as cellulose, silk, and wool dissolve in an ionic liquid (Non-patent Document 1: JACS, 2002, vol.124, p.4274-4275, Non-patent Document 2: JACS, 2004, vol. 126, p. 14350-14351, Non-Patent Document 3: Green Chem., 2005, vol. 7, p. 606-608).
In particular, for cellulose, attempts have been made to regenerate, chemically modify, surface-treat, etc. using an ionic liquid solution of cellulose.

For example, in Patent Document 1 (Japanese Patent Publication No. 2005-506401), a cellulose solution is prepared by dissolving cellulose in an ionic liquid such as 1-butyl-3-methylimidazolium chloride substantially free of water. A method for regenerating cellulose by adding water is disclosed.
Patent Document 2 (International Publication No. 2005/054298) discloses a technique in which cellulose is dissolved in an ionic liquid typified by 1-butyl-3-methylimidazolium chloride, and the hydroxyl group of cellulose is etherified. Yes.
In patent document 3 (Japanese translations of PCT publication No. 2005-530910 gazette), the cellulosic fabric processed with the fabric processing agent containing an ionic liquid shows the functional or aesthetic appearance outstanding, and the fiber reinforcement effect can be exhibited. It is disclosed.

However, since most of ionic liquids having a dissolving ability such as cellulose, silk, wool and the like are solid at room temperature, treatment at room temperature is difficult. For this reason, it is necessary to process at a relatively high temperature at which the ionic liquid melts. However, when the treatment temperature is increased, the molecular weight of the polymer to be treated is remarkably lowered, and as a result, the physical properties of the polymer after treatment are lowered.
In addition, since the ionic liquid has a high viscosity, it is inferior in handleability as a liquid and takes time for contact with the object to be processed and subsequent penetration into the object to be processed.

Recently, when DMSO, DMAc, or dioxane is added to a solution in which cellulose is dissolved in an imidazolium-based ionic liquid (BMIMCl), it is reported that the solution viscosity decreases (Non-patent Document 4: Journal of Cellulose Science and Technology, 2006, 14 (2), 8-12).
However, in Non-Patent Document 4, since the temperature range in which the viscosity characteristics were evaluated is 75 to 100 ° C., the solution of Non-Patent Document 4 may have a high viscosity at room temperature or may be solidified at room temperature. high. Therefore, also in this case, the handleability at room temperature is poor.

It is also known that cellulose dissolves in a system in which DMSO or TMSO (tetramethylene sulfoxide) is added to a tetraalkylammonium halide (Patent Document 4: JP-A-60-144332).
However, in this case as well, there are problems that the tetraalkylammonium halide does not dissolve in DMSO, or because of the high melting point, salt precipitation or solidification of the solution itself occurs at room temperature.
For the reasons described above, a polymer treating agent having a low viscosity and capable of treating a polymer near room temperature is desired.

On the other hand, the preparation of a blend of cellulose and other polymer substances has been attempted.
For example, Patent Document 5 (Japanese Patent Laid-Open No. 4-224838) discloses a cellulose / plastic blend of regenerated cellulose and polyurethane obtained by the viscose method.
However, when blending with a polymer substance, it is necessary to process cellulose in advance and not only the processing solvents for dissolving cellulose are limited, but also those processing solvents are not general-purpose solvents. The possible high molecular substances are also limited, and it has been difficult to obtain a blend polymer with a desired combination.
To solve this problem, the cellulose itself is chemically modified by esterifying or etherifying the hydroxyl group of cellulose, increasing the solubility in general-purpose solvents, and preparing blend polymers with other polymer substances. (Patent Document 6: JP-T-8-510784).
However, in this case, since the cellulose itself is chemically modified, it is difficult to express various physical properties of the unmodified cellulose in the obtained blend polymer, and the fundamental problem has not been solved.

JP 2005-506401 A International Publication No. 2005/054298 Pamphlet JP 2005-530910 A JP 60-144332 A JP-A-4-224838 Japanese translation of PCT publication No. 8-510782 JACS, 2002, vol.124, p.4274-4275 JACS, 2004, vol.126, p.14350-14351 Green Chem., 2005, vol.7, p.606-608 Journal of Cellulose Science and Technology, 2006, 14 (2), 8-12

  The present invention has been made in view of such circumstances, and provides a polymer treatment agent containing an ionic liquid and a dope that is liquid at room temperature and is excellent in handleability because of low viscosity. With the goal.

  As a result of intensive studies to solve the above problems, the present inventors have found that a mixed solvent composed of an ionic liquid and an aprotic solvent is excellent in handleability because of its low viscosity, and does not solidify even at about 30 ° C. It is found that it has a liquid phase and is excellent in dissolving ability of polymers such as cellulose, and at least two kinds of polymers are dissolved in this mixed solvent, and this is regenerated so that it is an unprecedented blend polymer. Was found and the present invention was completed.

That is, the present invention
1. A polymer treating agent comprising an ionic liquid and an aprotic solvent and being liquid at 30 ° C.,
2. 1 polymer processing agent whose content ratio (molar ratio) of the said ionic liquid shown by following formula [1] and an aprotic solvent is 30 to 85%,
3. 1 or 2 polymer processing agents, wherein the aprotic solvent is one or more selected from dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and pyridine,
4). The polymer according to any one of 1 to 3, wherein the ionic liquid comprises a halide ion, a carboxylate ion having 1 to 3 carbon atoms, a perchlorate ion, a pseudohalide ion, a cyanamide ion, or a dicyanamide ion. Processing agent,
5). The polymer treatment agent according to any one of 1 to 4, wherein the ionic liquid is a quaternary ammonium-based ionic liquid represented by the formula (1):
Wherein, R ¹ to R ³ may be the same or different, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or _{^{R 4 -O- (CH 2) n}} , - R ⁴ represents a methyl group or an ethyl group, and n is 1 or 2. Y represents a halide ion, a carboxylate ion having 1 to 3 carbon atoms, a perchlorate ion, a pseudohalide ion, a cyanamide ion, or a dicyanamide ion. ]
6). The ionic liquid is a polymer treating agent of 5 represented by the formula (2):
[Wherein, n and Y represent the same meaning as described above. ]
7). The ionic liquid is a polymer treatment agent of 6 represented by the formula (3):
8). A polymer treating agent according to any one of 1 to 7, which is a treating agent for natural polymer compounds;
9. 8. The polymer treatment agent, wherein the natural polymer compound is cellulose,
10. A polymer treatment agent of any one of 1 to 9 which is a surface treatment agent, a swelling agent or a solubilizer
11. A polymer processing method using the polymer processing agent of any one of 1 to 9,
12 An ionic liquid, an aprotic solvent, and a polymer, the dope in which the polymer is dissolved in the ionic liquid and the aprotic solvent, the ionic liquid and the aprotic solvent represented by the following formula [1] The dope whose content ratio (molar ratio) is 30 to 99%,
13. A dope comprising an ionic liquid, an aprotic solvent, and two or more polymers, wherein the polymers are dissolved in the ionic liquid and the aprotic solvent;
14 13 dopes wherein one of the two or more polymers is cellulose;
15. 14 dopes in which the two or more polymers are cellulose and polylactic acid,
16. The dope according to any one of 12 to 15, wherein the content ratio (molar ratio) of the ionic liquid and the aprotic solvent represented by the following formula [1] is 30 to 99%,
17. The dope according to any one of 12 to 16, wherein the ionic liquid is a quaternary ammonium-based ionic liquid represented by the following formula (1):
Wherein, R ¹ to R ³ may be the same or different, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or _{^{R 4 -O- (CH 2) n}} , - R ⁴ represents a methyl group or an ethyl group, and n is 1 or 2. Y represents a halide ion, a carboxylate ion having 1 to 3 carbon atoms, a perchlorate ion, a pseudohalide ion, a cyanamide ion, or a dicyanamide ion. ]
18. A blend polymer regenerated from 13 dopes,
19. Cellulose-polylactic acid blend polymer regenerated from 15 dopes,
20. A medium compatible with the ionic liquid and the aprotic solvent and having substantially no ability to dissolve the polymer is added to the 13 dope, or the dope is compatible with the ionic liquid and the aprotic solvent. And a method for producing a blend polymer, wherein the polymer is added to a medium substantially not having the ability to dissolve the polymer.

Since the polymer processing agent of the present invention is composed of an ionic liquid and an aprotic solvent, the polymer processing agent does not coagulate near room temperature and can maintain a liquid phase. Therefore, processing near room temperature, which was impossible with conventional ionic liquids, becomes possible. This polymer treating agent is not only excellent in handleability due to its low viscosity, but also excellent in solubility of various polymers including cellulose, and has almost no decrease in molecular weight when cellulose is dissolved.
In addition, since the mixed solvent composed of the ionic liquid and the aprotic solvent of the present invention can dissolve various polymers as described above, a dope containing this mixed solvent and a plurality of types of polymer substances is prepared. By regenerating the polymer, an unprecedented blend polymer can be prepared.

Hereinafter, the present invention will be described in more detail.
The polymer processing agent which concerns on this invention consists of an ionic liquid and an aprotic solvent, and is a liquid state at 30 degreeC. Here, the ionic liquid refers to a liquid which is fluid at 100 ° C. or lower and is completely composed of ions, but is preferably a liquid at 80 ° C. or lower, more preferably a liquid at 70 ° C. or lower. preferable. The polymer treating agent of the present invention exhibits a liquid state at 30 ° C. even when a solid ionic liquid is used at 30 ° C.
The ionic liquid constituting the polymer treating agent of the present invention is arbitrary, and various conventionally known ionic liquids can be used. However, from the viewpoint of the solubility of the polymer, the anion component is a halide ion and the total number of carbon atoms is 1. Preferred are ionic liquids of carboxylic acid ions, perchlorate ions, pseudohalide ions, cyanamide ions, or dicyanamide ions.

Examples of halide ions include Cl ⁻ , Br ⁻ , and I ⁻ , and examples of carboxylate ions having 1 to 3 carbon atoms include C ₂ H ₅ CO ₂ ⁻ , CH ₃ CO ₂ ⁻ , HCO ₂ ^{−, and the} like. Examples of pseudohalide ions include CN ⁻ , SCN ⁻ , OCN ⁻ , ONC ⁻ , N ₃ ^{− and the} like, which are monovalent and have properties similar to halides, but increase the solubility of the polymer. From the viewpoint, a halide ion, a carboxylate ion having 1 to 3 carbon atoms, or a pseudohalide ion is preferable, and Cl ⁻ , Br ⁻ , HCO ₂ ⁻ , and SCN ⁻ are particularly preferable.

On the other hand, as the cation component, either an aliphatic cation or an aromatic cation can be used.
The aliphatic cation is preferably an aliphatic ammonium salt in which at least one of the four substituents is different from the other substituents (asymmetric cation) from the viewpoint of low melting point and compatibility with an aprotic solvent.
In particular, the quaternary ammonium salt ionic liquid represented by the following formula (1) containing an ether group, which is not tetraalkyl, is low in melting point, compatible with an aprotic solvent, and soluble in cellulose (low viscosity). preferable.

Wherein, R ¹ to R ³ may be the same or different, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or _{^{R 4 -O- (CH 2) n}} , - R ⁴ represents a methyl group or an ethyl group, and n is 1 or 2. Y represents a halide ion, a carboxylate ion having 1 to 3 carbon atoms, a perchlorate ion, a pseudohalide ion, a cyanamide ion, or a dicyanamide ion. ]

In the formula (1), examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, 2-methylpropyl group, 1 , 1-dimethylethyl group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, and the like. Examples of the alkenyl group having 3 to 5 carbon atoms include 1-propenyl group, 2-propenyl group (allyl group), isopropenyl group, 1-butenyl group, 2-butenyl group (crotyl group), 3-butenyl group, and isocrotyl group. , 2-methylallyl group (methallyl group) and the like. Examples of the alkoxyalkyl group represented by R ⁴ —O— (CH ₂ ) _n — include a methoxy or ethoxymethyl group and a methoxy or ethoxyethyl group.

Among these, R ¹ to R ³ in Formula (1) may be the same or different, a methyl group, an ethyl group, an allyl group, methallyl group, or _{^{R 4 -O- (CH 2) n}} , - with What is represented is an alkoxyalkyl group (particularly a methoxyethyl group or a methoxymethyl group).
More specifically, an ionic liquid represented by the following formula (2) in which one of the substituents is an alkoxyalkyl group can be suitably used.

[Wherein, n and Y represent the same meaning as described above. ]

In particular, diethylmethylmethoxyethylammonium chloride (DMECl) represented by the following formula (3) in which n = 2 and Y = Cl ⁻ is preferable.

Examples of the aromatic cation include imidazolium cation and pyridinium cation.
Examples of the imidazolium cation include a dialkyl imidazolium cation and a trialkyl imidazolium cation. Specific examples include 1-ethyl-3-methylimidazolium ion, 1-butyl-3-methylimidazolium ion, 1-propyl-3-methylimidazolium ion, 1- (1,2 or 3-hydroxypropyl) -3-methylimidazolium ion, 1,2,3-trimethylimidazolium ion, 1,2-dimethyl-3- Examples include ethyl imidazolium ion, 1,2-dimethyl-3-propyl imidazolium ion, 1-butyl-2,3-dimethyl imidazolium ion, and the like.
As the imidazolium-based ionic liquid, 1-butyl-3-methylimidazolium chloride (BMIMCl) is suitable.

Examples of the pyridinium cation include N-propylpyridinium ion, N-butylpyridinium ion, 3-methyl-N-butylpyridinium ion, 1-butyl-4-methylpyridinium ion, and 1-butyl-2,4-dimethylpyridinium ion. Can be mentioned.
As the pyridinium-based ionic liquid, 3-methyl-N-butylpyridinium chloride (MBPyriCl) is suitable.
In addition, each ionic liquid mentioned above can also be used in combination of 2 or more types.

The aprotic solvent may be any solvent as long as it does not have proton donating properties, but is preferably a solvent having a donor number of 10 or more and an acceptor number of 10 or more, and more preferably a solvent having a dielectric constant of 10 or more. preferable.
Specific examples of the aprotic solvent include dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), acetonitrile, pyridine and the like. These may be used alone or in combination of two or more.
Among these, DMSO is preferable from the viewpoint of dissolution rate, and DMF is preferable from the viewpoint of liquefaction at room temperature.
Table 1 shows the number of donors, the number of acceptors, the melting point, and the dielectric constant of these aprotic solvents.

In the polymer treatment agent of the present invention, as long as the mixed solvent composed of the ionic liquid and the aprotic solvent is in a liquid state at 30 ° C., the ionic liquid and the aprotic solvent can be blended in an arbitrary ratio. 1] The content ratio (molar ratio) of the ionic liquid and the aprotic solvent is preferably 30 to 85%, more preferably 40 to 75%, and more preferably 50 to 70%. Even more preferred.
By setting it as this range, it is liquid at room temperature, and the characteristic as a polymer processing agent can fully be exhibited.

  The preparation of the polymer treatment agent of the present invention is not particularly limited as long as it is a method in which the ionic liquid and the aprotic solvent are not separated and are compatible with each other. For example, an aprotic solvent may be mixed with the ionic liquid, or an ionic liquid may be mixed with the aprotic solvent. In addition, the above preparation method can be applied regardless of whether the ionic liquid is solid or liquid at 30 ° C. However, the polymer treatment agent prepared by the above method may be appropriately heated as necessary.

The polymer treatment agent of the present invention can be suitably used as a polymer surface treatment agent, a solubilizer, a swelling agent and the like.
The viscosity of the polymer treatment agent is preferably as low as possible, but the ease of penetration of the polymer treatment agent into the workpiece, the ease of handling as a liquid, and the mixing of the treatment agent into the cleaning layer in the case of a continuous process are reduced. In view of this, it is preferably 100 Pa · s or less at 25 ° C., more preferably 10 Pa · s or less, and even more preferably 1 Pa · s or less.

In the present invention, dissolution means that the polymer is visually recognized as a uniform phase in the medium. Swelling refers to a state in which the medium has penetrated into the polymer aggregate molecular chain and the interaction between the molecular chains has been relaxed, but the molecular chain aggregation has not been completely solved.
In addition, other components can be added to the polymer treating agent of the present invention as long as the effect is exhibited. Examples of other components include fragrances, dyes, water repellents, oil repellents, antibacterial agents, and fungicides.

The polymer to be treated with the polymer treating agent of the present invention is not particularly limited as long as it dissolves or swells in an ionic liquid, and examples thereof include natural polymer compounds such as sugar chains or proteins, or mixtures thereof. .
Examples of sugar chains include cellulose, chitin, chitosan and the like.
Examples of cellulose include plant-derived cellulose, animal-derived cellulose, bacterial-derived cellulose, and regenerated cellulose. Specific examples include cotton, hemp, bamboo, banana, moon peach, hibiscus rosel, kenaf, hardwood pulp, conifer pulp, squirt cellulose, bacterial cellulose, rayon, cupra, tencel, regenerated cellulose using ionic liquid, etc. Their derivatives are also included as long as they can be dissolved and swelled in the liquid. Examples of the derivatives include derivatives obtained by etherifying or esterifying a hydroxyl group of cellulose, and derivatives obtained by cyanoethylation.
The crystal structure of cellulose is arbitrary, and cellulose having a structure composed of any one of I-type, II-type, III-type, IV-type, and amorphous structure or a combination thereof can be employed. Further, the method of the present invention can be applied regardless of the crystallinity of cellulose.
Examples of proteins include silk, wool, collagen, keratin, sericin, fibroin, and casein.

In addition to the natural polymer compound that dissolves or swells in the ionic liquid described above, the polymer may include other polymer compounds that dissolve or swell in an aprotic solvent.
Examples of other high molecular compounds that dissolve or swell in an aprotic solvent include acrylic resin, polycarbonate resin, ABS resin, polylactic acid, polycaprolactone, polyamide (nylon), polystyrene, and the like.
In addition, although content of another high molecular compound is arbitrary, about 5-95 mass% is suitable with respect to the whole polymer.

Further, the polymer may contain a substance that does not dissolve or swell in either the ionic liquid or the aprotic solvent.
Examples of such a substance include glass fiber, metal fiber, carbon fiber, rock wool, and the like.
In addition, although content of these substances is arbitrary, about 5-95 mass% is suitable with respect to the whole polymer.

  The structure of the polymer is arbitrary, and various structures such as a fiber structure such as a yarn, a woven fabric, a knitted fabric, a non-woven fabric, and paper, a film, a bead, a plate, and a block can be employed.

In the polymer processing method using the polymer processing agent described above, the polymer processing agent is brought into contact with an object to be processed containing the polymer to swell or dissolve the polymer, or to perform surface treatment.
There is no particular limitation on the contact method, and the treatment object is immersed in the polymer treatment agent, the treatment object is passed through a tank containing the polymer treatment agent, or the polymer treatment agent is sprayed on the treatment object. The method of doing is mentioned.

The contact time may be appropriately determined according to the desired effect. For example, the polymer swells or dissolves to the inside due to a long-time contact with the polymer treatment agent, and a short-time contact with the polymer treatment agent. The polymer only swells or dissolves in the vicinity of its surface. In general, it may be appropriately adjusted within a range of about 0.01 seconds to 180 minutes.
The contact temperature may be a temperature range in which the polymer treatment agent is in a liquid state. In the present invention, since it is liquid even at 30 ° C., it is possible to process the object without heating, which is advantageous in terms of energy. Further, since the lower the temperature, the lower the molecular weight of the polymer, so that the physical properties of the object to be processed can be minimized. Specifically, depending on the type of aprotic solvent, it may be −100 ° C. or higher, preferably about 0 to 100 ° C., more preferably about 15 to 60 ° C.

The polymer treatment agent remaining on the object to be treated after the contact treatment can be easily removed by washing with a solution that is compatible with the polymer treatment agent and does not dissolve or swell the polymer.
Examples of such solvents include water, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and dioxane, ketones such as acetone and methyl ethyl ketone, acetonitrile, and chloroform.
After the contact process and the cleaning process performed as necessary, the object to be processed may be dried as appropriate. Any drying method can be used, and various known methods can be used. Specific examples include a heat drum, hot air, infrared rays, and a method using sunlight.

The dope according to the present invention includes an ionic liquid, an aprotic solvent, and a polymer, and the polymer is dissolved in the ionic liquid and the aprotic solvent. In this case, two or more polymers may be used. Examples of the combination of two or more include at least one polymer dissolved in an ionic liquid, at least one polymer dissolved in an ionic liquid, and at least one polymer dissolved in an aprotic solvent.
Examples of the ionic liquid, the aprotic solvent, and the polymer are the same as those described for the polymer treatment agent.

In this dope, the blending amount of the ionic liquid and the aprotic solvent is preferably such that the content ratio (molar ratio) of the ionic liquid and the aprotic solvent represented by the above formula [1] is 30 to 99%. It is more preferable to set it as 40 to 85%, and it is still more preferable to set it as 50 to 75%.
In addition, the polymer content in the dope cannot be defined unconditionally because it depends on the type of polymer used, but in the dope of the present invention, it can be about 0.1 to 50% by mass.

  The method for preparing the dope of the present invention is not particularly limited. Even if the polymer is dissolved in the mixed solvent of the ionic liquid and the aprotic solvent described above, the aprotic solvent is dissolved after the polymer is dissolved in the ionic liquid. The polymer dissolved in the ionic liquid may be dissolved in the ionic liquid, while the polymer dissolved in the aprotic solvent may be dissolved and the respective solutions may be mixed. . As described above, the mixed solvent of the ionic liquid and the aprotic solvent of the present invention is liquid near room temperature and has a low viscosity, can dissolve the polymer at a lower temperature, and hardly causes deterioration of physical properties of the polymer. Therefore, a method of dissolving a polymer in a mixed solvent of an ionic liquid and an aprotic solvent is preferable.

By using the dope of the present invention, a regenerated polymer can be produced. In particular, in the case of a dope containing two or more kinds of polymers, a blend polymer of these polymers can be produced.
In particular, the mixed solvent of the ionic liquid and aprotic solvent of the present invention has been difficult in the past because it can easily dissolve unmodified cellulose and can also dissolve various polymers by appropriately selecting the aprotic solvent. In addition, blend polymers of unmodified cellulose and various polymers can be produced. For example, blend polymers of cellulose and polylactic acid can be easily produced.
In addition, when preparing dope containing polylactic acid, it is preferable to use DMAc and NMP as an aprotic solvent.

  As a specific method for producing a regenerated polymer or a blend polymer, a medium compatible with an ionic liquid and an aprotic solvent and having substantially no ability to dissolve the polymer is added to the dope of the present invention. In addition, a regenerated polymer or a blend polymer can be produced by adding the dope of the present invention to a medium that is compatible with an aprotic solvent and has substantially no ability to dissolve the polymer.

Here, specific examples of the medium that is compatible with the ionic liquid and the aprotic solvent and that does not substantially have the ability to dissolve the polymer include water, alcohols such as methanol and ethanol, tetrahydrofuran, dioxane and the like. Examples include ethers, ketones such as acetone and methyl ethyl ketone, acetonitrile, chloroform, and the like. These may be used alone or in combination of two or more. Among these, water and alcohols are preferable, and water is more preferable in consideration of environmental aspects.
The “medium having substantially no polymer dissolving ability” does not mean a medium that does not dissolve the polymer at all. In addition to the dope of the present invention, the polymer is added when the addition amount is increased to a critical amount or more. Means a medium on which can be deposited.

The use ratio of the dope of the present invention and the above medium is arbitrary as long as the polymer is precipitated, and also varies depending on the medium to be used. In order to precipitate the polymer, the medium / dope liquid ratio is preferably 1 or more, more preferably 2 or more, and even more preferably 5 or more.
In addition, the method of adding a medium in dope and the method of adding dope in a medium are arbitrary.

The form of the recycled polymer or blend polymer is not particularly limited, and may be various shapes such as powder, granule, lump, cotton, short fiber, long fiber, rod, sponge, film, etc. it can.
For example, in the method of adding the dope to the medium, a film-like or long-fiber regenerated polymer or blend polymer can be continuously obtained by extruding the dope into the medium through a T die or the like.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example.

Synthesis Example 1 Synthesis of N, N-diethyl-N-methyl-N-2-methoxyethylammonium chloride

71 parts by mass of diethylamine (manufactured by Kanto Chemical Co., Ltd.) and 88 parts by mass of 2-methoxyethyl chloride (manufactured by Kanto Chemical Co., Ltd.) were mixed and reacted at 120 ° C. for 24 hours in an autoclave. At this time, the maximum ultimate internal pressure was 4.5 kgf / cm ² (0.44 MPa). After 24 hours, the precipitated crystals were washed with tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) and separated by filtration. The filtrate was distilled at atmospheric pressure to obtain 81 parts by mass of a fraction having a boiling point of around 135 ° C. It was confirmed by nuclear magnetic resonance spectrum (hereinafter referred to as NMR) that this compound was 2-methoxyethyldiethylamine.
Subsequently, 9.0 parts by mass of 2-methoxyethyldiethylamine was dissolved in 80 parts by mass of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) in an autoclave, and 15% methyl chloride gas in nitrogen (Nippon Special) Chemical Industry Co., Ltd.) was introduced. Methyl chloride gas was added until the internal pressure reached 4 kgf / cm ² (0.39 MPa), and then the temperature was gradually raised to 60 ° C. over 3 hours. At this time, the maximum internal pressure was 5.4 kgf / cm ² (0.53 MPa). Thereafter, the mixture was allowed to cool while stirring, and the precipitated crystals were separated by filtration. The crystals were dried under reduced pressure to obtain 12 parts by mass of N, N-diethyl-N-methyl-N-2-methoxyethylammonium chloride (hereinafter referred to as DEMECl) which is the target product.

Synthesis Example 2 Synthesis of N, N-diethyl-N-methyl-N-2-methoxyethylammonium thiocyanate

2-Methoxyethyldiethylamine (20 g: 152.4 mmol), which is an intermediate product of Synthesis Example 1, was stirred in tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), and then methyl iodide (Sigma Aldrich Japan Co., Ltd.) was stirred. )) (11.29 ml: 182.9 mmol) was added dropwise. After stirring at room temperature for about 24 hours, the precipitated crystals were separated by filtration. The crystals were dried under reduced pressure to obtain the target N, N-diethyl-N-methyl-N-2-methoxyethylammonium iodide (hereinafter referred to as DEMEI). The structure was confirmed by NMR.
Next, according to the method described in the literature (JM Pringle et al., Journal of Materials Chemistry, 2002, vol. 12, p3475-3480), the I ⁻ ion of DEMEI was substituted with the SCN ⁻ ion, and N, N-diethyl was obtained. -N-methyl-N-2-methoxyethylammonium thiocyanate (hereinafter referred to as DEMESCN) was obtained. The structure was confirmed by NMR.

Synthesis Example 3 Synthesis of N, N-diethyl-N- (2-methoxyethyl) -N- (2-propenyl) ammonium chloride

  2-Methoxyethyldiethylamine (3.43 g: 0.026 mol) which is an intermediate product of Synthesis Example 1 was stirred in acetonitrile, and 3-chloropropene (manufactured by Tokyo Chemical Industry Co., Ltd.) (2.6 ml: 0.031 mol) was added dropwise. After stirring in the dark at room temperature for about 72 hours, the raw materials and solvent were removed with a vacuum pump, and N, N-diethyl-N- (2-methoxyethyl) -N- (2-propenyl) ammonium chloride (hereinafter, Obtained DEMPCl). The structure was confirmed by NMR.

[1] Solid-liquid characteristics [Example 1]
Add 12.0 g of DOMECl (melting point 59-60 ° C.) obtained in Synthesis Example 1 and 4.0 g of DMF (manufactured by Daishin Chemical Co., Ltd.) to a 20 ml sample bottle, and dissolve DEMECl at 70 ° C. A polymer treating agent was prepared.

[Example 2]
A polymer treating agent was prepared in the same manner as in Example 1 except that 10.7 g of DEMECl and 5.3 g of DMF were used.

[Example 3]
A polymer treating agent was prepared in the same manner as in Example 1 except that 8.0 g of DEMECl and 8.0 g of DMF were used.

[Example 4]
A polymer treating agent was prepared in the same manner as in Example 1 except that 5.3 g of DEMECl and 10.7 g of DMF were used.

[Example 5]
A polymer treating agent was prepared in the same manner as in Example 1 except that 4.0 g of DEMECl and 12.0 g of DMF were used.

[Example 6]
A polymer treating agent was prepared in the same manner as in Example 2 except that DMF was changed to DMSO (manufactured by Wako Pure Chemical Industries, Ltd.).

[Example 7]
A polymer treating agent was prepared in the same manner as in Example 3 except that DMF was changed to DMSO.

[Example 8]
A polymer treating agent was prepared in the same manner as in Example 4 except that DMF was changed to DMSO.

[Example 9]
A polymer treating agent was prepared in the same manner as in Example 5 except that DMF was changed to DMSO.

About the polymer processing agent obtained in the said Examples 1-9, the property in 0 degreeC and room temperature (20-25 degreeC) was investigated. Specifically, after each polymer treating agent was allowed to stand at each temperature for 24 hours, the state of the solution was visually observed. The results are shown in Table 2.
In addition, the content ratio in a table | surface shows the content ratio of an ionic liquid and an aprotic solvent, ie, the ratio of the aprotic solvent with respect to a polymer processing agent, and computed using the above-mentioned formula [1].
In the following examples and comparative examples, which will be described later, the content ratio was calculated using the above formula [1].

As shown in Table 2, by adding DMF or DMSO, which is an aprotic solvent, to DEMECl, the liquid state is maintained not only at room temperature, but also at 0 ° C. depending on the content ratio with DMF. You can see that
In addition, about the polymer processing agent obtained in Examples 1-9, by adding microcrystalline cellulose (manufactured by SIGMA-ALDRICH) to prepare a 5% by mass cellulose dope, each was similarly treated at 0 ° C. and room temperature (20 As a result of examining properties at ˜25 ° C., properties similar to those in Table 2 were confirmed.

[2] Viscosity characteristics [Example 10]
In a 50 ml sample bottle, DEMECl (melting point: 59 to 60 ° C.) obtained in Synthesis Example 1 and DMSO (manufactured by Wako Pure Chemical Industries, Ltd.) were added to DMSO / DEMECl = 0.8 (molar ratio) (content ratio) 44%) and DEMECl was dissolved at 70 ° C. to prepare a polymer treating agent.

[Example 11]
A polymer treating agent was prepared in the same manner as in Example 10 except that DMSO / DEMECl = 1.0 (molar ratio) (content ratio 50%).

[Example 12]
A polymer treating agent was prepared in the same manner as in Example 10 except that DMSO / DEMECl = 1.2 (molar ratio) (content ratio 55%).

[Example 13]
A polymer treating agent was prepared in the same manner as in Example 10 except that DMSO / DEMECl = 1.5 (molar ratio) (content ratio 60%).

[Example 14]
A polymer treating agent was prepared in the same manner as in Example 10 except that DMSO / DEMECl = 2.3 (molar ratio) (content ratio 70%).

The viscosity at room temperature (20 to 25 ° C.) of the polymer treatment agent prepared in Examples 10 to 14 was measured. In addition, a short fibrous cellulose (ARBOCEL B400, manufactured by J. RETTENMAIER & SO EHNE) was added to the polymer treating agent prepared in Examples 10 to 14 to prepare a 5% by mass cellulose dope, respectively, at room temperature (20 to 20 to The viscosity at 25 ° C. was measured. These results are shown in FIG.
The viscosity was measured with a viscometer (VISCOMETER TVB-10, manufactured by Toki Sangyo Co., Ltd.). In measuring the viscosity, the rotor and the number of rotations were appropriately selected according to the viscosity of the liquid.

As shown in FIG. 1, the viscosity of the polymer treating agent at room temperature (20-25 ° C.) is such that the DMSO / DEMECl molar ratio is in the range of 0.8-2.3; When the content ratio of the ionic liquid and the aprotic solvent is in the range of 44 to 70%, it is 1 Pa · s or less, and it can be seen that the viscosity is very low.
In addition, the viscosity of the 5% by mass cellulose dope of these polymer treatment agents indicates 100 Pa · s or less within the above range, which suggests that the polymer treatment agent and the dope can be easily handled. .

[3] Molecular weight of regenerated cellulose [Examples 15 to 17]
To a 50 ml sample bottle, 26.0 g of DEMECl (melting point: 59 to 60 ° C.) obtained in Synthesis Example 1 and 13.0 g of DMSO (manufactured by Wako Pure Chemical Industries, Ltd.) are added (DOMECl / DMSO = 1/1). .2 (molar ratio) (content ratio 55%)), DEMECl was dissolved at 70 ° C. to prepare a polymer treating agent.
To this polymer treatment agent, 2.1 g of microcrystalline cellulose (manufactured by SIGMA-ALDRICH) was added at room temperature (20 to 25 ° C.) (Example 15), 60 ° C. (Example 16), and 100 ° C. (Example 17). This was dissolved to prepare a cellulose dope.
41.1 g of the cellulose dope thus prepared was added in portions to 300 g of water under stirring, and finally the whole amount was added, followed by stirring for 30 minutes to precipitate cellulose.
The aqueous phase was discarded by decantation, and an operation of adding 300 g of water and stirring again was repeated 4 times to wash out DEMECl from the cellulose to obtain regenerated cellulose. The mass of the regenerated cellulose after drying was 2.0 g, 1.9 g, and 2.0 g, respectively.

[Comparative Example 1]
In the same manner as in Example 15, microcrystalline cellulose was dissolved in DEMECl obtained in Synthesis Example 1 at 100 ° C. to prepare a cellulose solution of DEMECl. Using this solution, regenerated cellulose was obtained in the same manner as in Example 15. The mass of the regenerated cellulose after drying was 2.0 g.

[Molecular weight measurement of regenerated cellulose]
The molecular weight of the regenerated cellulose obtained in Examples 15 to 17 and Comparative Example 1 was measured according to TAPPI standard method T238su-63. A specific measurement method is shown below.
To 300 ml of fuming nitric acid (specific gravity 1.52, manufactured by Kanto Chemical Co., Inc.), 50 ml of concentrated nitric acid (specific gravity 1.38, manufactured by Kanto Chemical Co., Ltd.) was added little by little to prepare concentrated nitric acid having a specific gravity of 1.50. Subsequently, 200 g of diphosphorus pentoxide (manufactured by Kokusan Chemical Co., Ltd.) was added to this concentrated nitric acid while cooling with ice water to prepare a mixed acid for nitrification reaction. 1 g of the regenerated cellulose obtained in Examples 15 to 17 and Comparative Example 1 and microcrystalline cellulose (manufactured by SIGMA-ALDRICH) were added and dispersed in 100 ml of this mixed acid under ice water cooling, and the mixture was allowed to disperse for 1 hour. I let you. After completion of the reaction, suction filtration was performed with a glass filter to separate the produced cellulose nitrate from the mixed acid. This cellulose nitrate was dispersed in ice-cold water (300 ml), filtered again with a glass filter, and thoroughly washed with ice-cold water and methanol. Subsequently, it was dried in a dryer at 50 ° C.

The obtained cellulose trinitrate was dissolved in tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) so as to be 0.1% (w / v), and this was analyzed as a sample by gel permeation chromatography (hereinafter referred to as GPC). The molecular weight distribution was measured at
GPC was measured using a 2695 Separatins Module (manufactured by Nippon Waters Co., Ltd.) and three GPC KF-801 columns (manufactured by Showa Denko KK) connected in series at a flow rate of 1 ml / min and a column temperature of 40 ° C. did. This weight average molecular weight (Mw) is a value obtained as a polystyrene conversion value from a calibration curve created using a monodisperse polystyrene standard sample STANDARD SM-105 (manufactured by Showa Denko KK). The results are shown in Table 3.

  As shown in Table 3, when the polymer treatment agent of the present invention is used, the molecular weight reduction of the regenerated cellulose is suppressed, and the molecular weight decreases even when stored for a long time by dissolving the cellulose at a lower temperature. It can be seen that is suppressed more.

[4] Surface treatment of cotton yarn [Example 18]
To a 50 ml sample bottle, 27.97 g of DOMECl (melting point: 59 to 60 ° C.) obtained in Synthesis Example 1 and 12.03 g of DMF (manufactured by Daishin Chemical Co., Ltd.) were added (DOMECl / DMSO = 1/1 (mol). Ratio), (content ratio 50%)), DEMECl was dissolved at 70 ° C. to prepare a polymer treating agent. After the temperature of the polymer treatment agent was gradually cooled to room temperature, 30 cm of 50 count third twisted cotton yarn (Kanebo Katan Yarn) (manufactured by Kanebo Fibers Co., Ltd.) was immersed in this polymer treatment agent at room temperature for 30 seconds. Thereafter, the yarn was washed several times with water and sufficiently dried to obtain the intended yarn. The yarn mass was unchanged before and after treatment.

[Example 19]
A target yarn was obtained in the same manner as in Example 18 except that the dipping time was changed from 30 seconds to 60 seconds (1 minute). The yarn mass was unchanged before and after treatment.

[Example 20]
A target yarn was obtained in the same manner as in Example 18 except that the dipping time was changed from 30 seconds to 180 seconds (3 minutes). The yarn mass was unchanged before and after treatment.

[Example 21]
A target yarn was obtained in the same manner as in Example 18 except that the dipping time was changed from 30 seconds to 300 seconds (5 minutes). The yarn mass was unchanged before and after treatment.

[Example 22]
A target yarn was obtained in the same manner as in Example 18 except that the dipping time was changed from 30 seconds to 1200 seconds (20 minutes). The yarn mass was unchanged before and after treatment.

About the cotton yarn obtained in the said Examples 18-22, the tensile strength was measured with the following method. For comparison, the tensile strength of untreated cotton yarn was also measured by the following method.
[Tensile strength]
Using an Instron universal testing machine (model 5582) (manufactured by INSTRON), the distance between the grips was 25 cm and the tensile speed was 30 cm / min, and the test was performed in accordance with JIS L1095-9.5.
These results are shown in Table 4. In addition, the strength ratio was expressed by assuming the strength of the untreated cotton yarn as 1.

As shown in Table 4, by using the polymer treatment agent of the present invention, it is possible to treat cotton yarn at a relatively low temperature of room temperature (20 to 25 ° C.), and in Examples 18 to 21 It can be seen that the surface treatment improves the tensile strength of the cotton yarn.
Note that DEMECl is a solid at room temperature (20 to 25 ° C.), and cotton yarn cannot be treated at this temperature.

[5] Dissolution rate characteristics [Example 23]
To a 20 ml sample bottle, 1.32 g of DOMECl (melting point: 59 to 60 ° C.) obtained in Synthesis Example 1 and 3.96 g of DMF (manufactured by Daishin Chemical Co., Ltd.) are added (DOMECl / DMF = 1/7. 5 (molar ratio), (content ratio 88%)), DEMECl was dissolved at 70 ° C. to prepare a polymer treating agent.
To this polymer treatment agent, 0.05 g (1% by mass) or 0.28 g (5% by mass) of microcrystalline cellulose (manufactured by SIGMA-ALDRICH) was added at room temperature (20 to 25 ° C.), 60 ° C., and 100 ° C. It melt | dissolved at temperature and the time taken until the cellulose melt | dissolved completely about each was observed visually.

[Example 24]
A polymer treating agent was prepared in the same manner as in Example 23 except that 1.65 g of DEMECl and 3.30 g of DMF (DEMECl / DMF = 1/5 (molar ratio), (content ratio 83%)) were used. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.05 g (1% by mass) or 0.26 g (5% by mass) of microcrystalline cellulose was used.

[Example 25]
A polymer treating agent was prepared in the same manner as in Example 23, except that 2.55 g of DEMECl and 2.55 g of DMF (DEMECl / DMF = 1 / 2.5 (molar ratio), (content ratio 71%)) were used. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.05 g (1% by mass) or 0.27 g (5% by mass) of microcrystalline cellulose was used.

[Example 26]
A polymer treating agent was prepared in the same manner as in Example 23 except that 3.07 g of DEMECl and 1.54 g of DMF (DEMECl / DMF = 1 / 1.2 (molar ratio), (content ratio 55%)) were used. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.05 g (1% by mass) or 0.24 g (5% by mass) of microcrystalline cellulose was used.

[Example 27]
A polymer treating agent was prepared in the same manner as in Example 23, except that 3.79 g of DEMECl and 1.26 g of DMF (DEMECl / DMF = 1 / 0.8 (molar ratio), (content ratio 44%)) were used. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.05 g (1% by mass) or 0.27 g (5% by mass) of microcrystalline cellulose was used.

[Example 28]
A polymer treating agent was prepared in the same manner as in Example 23, except that 4.19 g of DOMECl and 0.84 g of DMF (DEMECl / DMF = 1 / 0.5 (molar ratio), (content ratio 33%)) were used. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.05 g (1% by mass) or 0.26 g (5% by mass) of microcrystalline cellulose was used.

[Example 29]
Example 23 except that DEMECl was replaced by 2.04 g and DMF was replaced by DMSO (manufactured by Wako Pure Chemical Industries, Ltd.) 3.41 g (DEMECl / DMSO = 1/7 (molar ratio), (content ratio 88%)). A polymer treating agent was prepared in the same manner as described above. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.06 g (1% by mass) or 0.29 g (5% by mass) of microcrystalline cellulose was used.

[Example 30]
A polymer treating agent was prepared in the same manner as in Example 29 except that 2.53 g of DEMECl and 2.54 g of DMSO (DEMECl / DMSO = 1 / 4.7 (molar ratio), (content ratio 82%)) were used. The dissolution rate of cellulose was observed in the same manner as in Example 29 except that 0.05 g (1% by mass) or 0.27 g (5% by mass) of microcrystalline cellulose was used.

[Example 31]
A polymer treating agent was prepared in the same manner as in Example 29 except that 3.91 g of DEMECl and 1.30 g of DMSO (DEMECl / DMSO = 1 / 2.3 (molar ratio), (content ratio 70%)). The dissolution rate of cellulose was observed in the same manner as in Example 29 except that 0.05 g (1% by mass) or 0.27 g (5% by mass) of microcrystalline cellulose was used.

[Example 32]
A polymer treating agent was prepared in the same manner as in Example 29, except that 2.56 g of DEMECl and 1.28 g of DMSO (DEMECl / DMSO = 1 / 1.2 (molar ratio), (content ratio 55%)) were used. The dissolution rate of cellulose was observed in the same manner as in Example 29 except that 0.04 g (1% by mass) or 0.20 g (5% by mass) of microcrystalline cellulose was used.

[Example 33]
A polymer treating agent was prepared in the same manner as in Example 29, except that it was changed to 3.81 g of DEMECl and 1.27 g of DMSO (DEMECl / DMSO = 1 / 0.8 (molar ratio), (content ratio 44%)). The dissolution rate of cellulose was observed in the same manner as in Example 29 except that 0.05 g (1% by mass) or 0.27 g (5% by mass) of microcrystalline cellulose was used.

[Example 34]
A polymer treating agent was prepared in the same manner as in Example 29 except that 4.25 g of DEMECl and 0.85 g of DMSO (DEMECl / DMSO = 1 / 0.5 (molar ratio), (content ratio 33%)) were used. The dissolution rate of cellulose was observed in the same manner as in Example 29 except that 0.05 g (1% by mass) or 0.27 g (5% by mass) of microcrystalline cellulose was used.

[Example 35]
Example 23 except that DEMECl was changed to 1.59 g of BMIMCl (manufactured by ACROS ORGANICS) and DMF was changed to 3.18 g of DMSO (DEMECl / DMSO = 1 / 4.5 (molar ratio), (content ratio 82%)). Thus, a polymer treatment agent was prepared. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.05 g (1% by mass) or 0.25 g (5% by mass) of microcrystalline cellulose was used.

[Example 36]
A polymer treating agent was prepared in the same manner as in Example 35 except that 2.33 g of BMIMCl and 2.33 g of DMSO (BMIMCl / DMSO = 1 / 2.2 (molar ratio), (content ratio 69%)) were used. The dissolution rate of cellulose was observed in the same manner as in Example 35 except that 0.05 g (1% by mass) or 0.25 g (5% by mass) of microcrystalline cellulose was used.

[Example 37]
A polymer treating agent was prepared in the same manner as in Example 35 except that BMIMCl was 3.00 g and DMSO was 1.50 g (BMIMCl / DMSO = 1 / 1.1 (molar ratio), (content ratio: 52%)). The dissolution rate of cellulose was observed in the same manner as in Example 35 except that 0.05 g (1% by mass) or 0.24 g (5% by mass) of microcrystalline cellulose was used.

[Example 38]
A polymer treating agent was prepared in the same manner as in Example 35 except that 4.12 g of BMIMCl and 0.82 g of DMSO (BMIMCl / DMSO = 1 / 0.5 (molar ratio), (content ratio 33%)) were used. The dissolution rate of cellulose was observed in the same manner as in Example 35 except that 0.05 g (1% by mass) or 0.26 g (5% by mass) of microcrystalline cellulose was used.

[Example 39]
Example 23, except that DEMECl was replaced with 2.33 g and DMF was replaced with 2.33 g of pyridine (manufactured by Kanto Chemical Co., Ltd.) (DEMECl / pyridine = 1 / 2.3 (molar ratio), (content ratio 70%)). A polymer treating agent was prepared in the same manner as described above. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.05 g (1% by mass) or 0.25 g (5% by mass) of microcrystalline cellulose was used.

[Example 40]
A polymer treating agent was prepared in the same manner as in Example 39 except that 3.00 g of DEMECl and 1.50 g of pyridine (DEMECl / pyridine = 1 / 1.2 (molar ratio), (content ratio 55%)). The dissolution rate of cellulose was observed in the same manner as in Example 39 except that 0.05 g (1% by mass) or 0.24 g (5% by mass) of microcrystalline cellulose was used.

[Example 41]
Example 23 except that DEMECl was changed to 2.33 g and DMF was changed to 2.33 g (DEMECl / NMP = 1 / 1.8 (molar ratio), (content ratio 64%)) of NMP (manufactured by Gordo Solvent Co., Ltd.) A polymer treating agent was prepared in the same manner as described above. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.05 g (1% by mass) or 0.25 g (5% by mass) of microcrystalline cellulose was used.

[Example 42]
A polymer treating agent was prepared in the same manner as in Example 41 except for changing to 3.00 g of DEMECl and 1.50 g of NMP (DEMECl / NMP = 1 / 0.9 (molar ratio), (content ratio 47%)). The dissolution rate of cellulose was observed in the same manner as in Example 41 except that 0.05 g (1% by mass) or 0.24 g (5% by mass) of microcrystalline cellulose was used.

[Example 43]
Example 23, except that DEMECl was changed to 3.00 g and DMF was changed to DMAc (manufactured by Wako Pure Chemical Industries, Ltd.) 1.44 g (DEMECl / DMAc = 1/1 (molar ratio), (content ratio 50%)). A polymer treating agent was prepared in the same manner as described above. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.05 g (1% by mass) or 0.23 g (5% by mass) of microcrystalline cellulose was used.

[Example 44]
Example 23 except that DEMECl was changed to 3.00 g and DMF was changed to 1.50 g of acetonitrile (manufactured by Kanto Chemical Co., Inc.) (DEMECl / acetonitrile = 1 / 2.2 (molar ratio), (content ratio 69%)). A polymer treating agent was prepared in the same manner as described above. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.05 g (1% by mass) or 0.24 g (5% by mass) of microcrystalline cellulose was used.

[Example 45]
A polymer treating agent was prepared in the same manner as in Example 44 except that 3.00 g of DEMECl and 0.68 g of acetonitrile (DEMECl / acetonitrile = 1/1 (molar ratio), (content ratio 50%)) were used. The dissolution rate of cellulose was observed in the same manner as in Example 44 except that 0.04 g (1% by mass) or 0.19 g (5% by mass) of microcrystalline cellulose was used.

[Example 46]
Same as Example 23, except that DEMECl was replaced with 3.00 g of DEMPCl obtained in Synthesis Example 3 and DMF was replaced with 1.50 g of DMSO (DEMPCl / DMSO = 1 / 1.3 (molar ratio), (content ratio 57%)). Thus, a polymer treatment agent was prepared. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.05 g (1% by mass) or 0.24 g (5% by mass) of microcrystalline cellulose was used.

[Example 47]
Same as Example 23, except that DEMEI was changed to 3.00 g of DEMEI obtained in Synthesis Example 2 and DMF was changed to 1.50 g of DMSO (DEMEI / DMSO = 1 / 1.8 (molar ratio), (content ratio 64%)). Thus, a polymer treatment agent was prepared. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.05 g (1% by mass) or 0.24 g (5% by mass) of microcrystalline cellulose was used.

[Example 48]
Same as Example 23, except that DEMECl was changed to 3.00 g of DEMESCN obtained in Synthesis Example 2, and DMF was changed to 1.50 g of DMSO (DEMESCN / DMSO = 1 / 1.3 (molar ratio), (content ratio 57%)). Thus, a polymer treatment agent was prepared. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.05 g (1% by mass) or 0.24 g (5% by mass) of microcrystalline cellulose was used.

[Comparative Example 2]
DEMECl is replaced with tetrabutylammonium chloride (TBACl) (manufactured by Wako Pure Chemical Industries, Ltd.) 3.00 g, DMF is replaced with DMSO 0.84 g (TBACl / DMSO = 1/1 (molar ratio), (content ratio 50%)) A polymer treating agent was prepared in the same manner as in Example 23 except that. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.04 g (1% by mass) or 0.20 g (5% by mass) of microcrystalline cellulose was used.

[Comparative Example 3]
A polymer treating agent was prepared in the same manner as in Comparative Example 2 except that TBACl was changed to 3.00 g and DMSO 1.50 g (TBACl / DMSO = 1 / 1.8 (molar ratio), (content ratio 64%)). The dissolution rate of cellulose was observed in the same manner as in Comparative Example 2 except that 0.05 g (1% by mass) or 0.24 g (5% by mass) of microcrystalline cellulose was used.

[Comparative Example 4]
DEMECl is replaced with 3.00 g of triethylmethylammonium chloride (TEMACl) (manufactured by Wako Pure Chemical Industries, Ltd.), DMF is replaced with 1.55 g of DMSO (TEMACl / DMSO = 1/1 (molar ratio), (content ratio 50%)) A polymer treating agent was prepared in the same manner as in Example 23 except that. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.05 g (1% by mass) or 0.24 g (5% by mass) of microcrystalline cellulose was used.

[Comparative Example 5]
DEMECl to tetraethylammonium chloride (TEACl) (manufactured by Wako Pure Chemical Industries, Ltd.) 3.00 g, DMF to DMSO 1.50 g (TEACl / DMSO = 1 / 1.1 (molar ratio), (content ratio 52%)) A polymer treating agent was prepared in the same manner as in Example 23, except that it was replaced. The dissolution rate of cellulose was observed in the same manner as in Example 23 except that 0.05 g (1% by mass) or 0.24 g (5% by mass) of microcrystalline cellulose was used.

Table 5 shows the properties of the polymer treating agents prepared in Examples 23 to 48 and Comparative Examples 2 to 5 at room temperature (20 to 25 ° C) and 30 ° C, and Table 6 shows the observation results of the dissolution rate of cellulose.
In Table 6, when cellulose was dissolved in the polymer treatment agent, it was defined as “dissolved”, and the time taken for the cellulose to completely dissolve was described. Moreover, when 30 hours passed, the cellulose which remained slightly remained was “partially insoluble”, and the cellulose which was hardly dissolved was “insoluble”. In addition, when the property of the polymer treatment agent is solid, or when the ionic liquid and the aprotic solvent are not completely compatible, the dissolution rate of cellulose is not observed, and is indicated by “−” in the table. It was.

  As shown in Table 6, regardless of the composition of the polymer treatment agent of the present invention, cellulose dissolution occurs when the molar ratio of the ionic liquid / aprotic solvent is 1/1 (content ratio 50%) or close to it. You can see that the speed is the best. In addition, the higher the cellulose dissolution temperature, the better the cellulose dissolution rate, but considering the viewpoint of suppressing the decrease in molecular weight of cellulose, it can be seen that the treatment at 60 ° C. or less is suitable as the polymer treatment method of the present invention.

[6] Preparation of blend polymer [Example 49] L polylactic acid / cellulose (1/5: mass ratio) blend polymer A DEMECl / NMP mixed solvent having a molar ratio of 1/1 (content ratio 50%) was reduced to 0.76 g. 0.10 g of fibrous cellulose (ARBOCEL B400, manufactured by J. RETTENMAIER & SO EHNE) was added and dissolved at 60 ° C., and further 25 ml of NMP was added thereto to prepare a cellulose-containing solution.
On the other hand, 0.02 g of L polylactic acid (manufactured by Mitsui Chemicals) was dissolved in 20 ml of NMP at 160 ° C. to prepare a polylactic acid-containing solution.
Each of these solutions was gradually cooled to room temperature and then mixed with stirring at room temperature to prepare a dope. After filtering this dope, 300 ml of methanol was added and the resulting precipitate was collected by filtration through a membrane filter and dried at 40 ° C. to obtain 0.10 g of a blend polymer.
The electron micrograph which image | photographed the obtained blend polymer in SEM (S-4800, product made from Hitachi, Ltd.) is shown in FIG.
Moreover, the electron micrograph after this blend polymer is immersed in chloroform for 6 hours is shown in FIG.

[Example 50] L polylactic acid / cellulose (1/1: mass ratio) blend polymer Blend polymer in the same manner as in Example 49 except that 0.05 g of short fibrous cellulose and 0.05 g of L polylactic acid were used. Got.

[Example 51] L-polylactic acid / cellulose (5/1: mass ratio) blend polymer A blend polymer in the same manner as in Example 49 except that 0.02 g of short fibrous cellulose and 0.10 g of L-polylactic acid were used. Got.

[Example 52] L-polylactic acid / cellulose (10/1: mass ratio) blend polymer A blend polymer in the same manner as in Example 49 except that 0.05 g of short fibrous cellulose and 0.5 g of L-polylactic acid were used. Got. An electron micrograph of the obtained blend polymer is shown in FIG.

[Comparative Example 6] NMP dissolution and regenerated L polylactic acid 0.10 g of L polylactic acid (manufactured by Mitsui Chemicals, Inc.) was dissolved in 20 ml of NMP at 160 ° C to prepare a polylactic acid-containing solution.
After filtering this solution, 300 ml of methanol was added and the resulting precipitate was collected by filtration through a membrane filter and dried at 40 ° C. to obtain 0.10 g of regenerated L polylactic acid.

[Comparative Example 7] DEMECl dissolution, regenerated cellulose 0.10 g of short fibrous cellulose was dissolved in 2.00 g of DEMECl at 160 ° C to prepare a cellulose-containing solution.
A precipitate formed by adding 20 ml of methanol to this solution was collected by filtration through a membrane filter and dried at 40 ° C. to obtain 0.09 g of regenerated cellulose.

About the blend polymer obtained in the said Examples 49-51, by a TG / DTA analysis (differential thermogravimetric simultaneous measuring device TG / DTA6200, Seiko Instruments Co., Ltd. product), a thermal decomposition point (10% mass reduction temperature) and The final mass loss rate (600 ° C.) was measured. The results are shown in Table 7.
The same measurement was performed on the L polylactic acid and the short fibrous cellulose obtained in Comparative Examples 6 and 7. The results are also shown in Table 7.

As shown in Table 7, the thermal decomposition point of the blend polymer is located between the thermal decomposition points indicated by each of L polylactic acid and short fibrous cellulose, and shows the result reflecting the thermal characteristics of a large amount of components. I understand that.
Moreover, as FIG. 2-4 shows, the obtained blend polymer shows that polylactic acid is uniformly blended in cellulose.

It is a graph which shows the viscosity change at the room temperature (20-25 degreeC) of the polymer processing agent prepared in Examples 10-14 and a 5 mass% cellulose dope. FIG. 4 is an electron micrograph of the blend polymer obtained in Example 49. It is a figure which shows the electron micrograph after the blend polymer obtained in Example 49 was immersed in chloroform for 6 hours. FIG. 4 is an electron micrograph of the blend polymer obtained in Example 52.

Claims (20)

  A polymer treating agent comprising an ionic liquid and an aprotic solvent and liquid at 30 ° C. The polymer treatment agent according to claim 1, wherein the content ratio (molar ratio) of the ionic liquid and the aprotic solvent represented by the following formula [1] is 30 to 85%.
  The polymer processing agent according to claim 1 or 2, wherein the aprotic solvent is one or more selected from dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and pyridine. .   The ionic liquid according to any one of claims 1 to 3, wherein the ionic liquid comprises a halide ion, a carboxylate ion having 1 to 3 carbon atoms, a perchlorate ion, a pseudohalide ion, a cyanamide ion, or a dicyanamide ion. The polymer treating agent according to 1. The polymer treatment agent according to any one of claims 1 to 4, wherein the ionic liquid is a quaternary ammonium-based ionic liquid represented by the formula (1).
Wherein, R ¹ to R ³ may be the same or different, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or _{^{R 4 -O- (CH 2) n}} , - R ⁴ represents a methyl group or an ethyl group, and n is 1 or 2. Y represents a halide ion, a carboxylate ion having 1 to 3 carbon atoms, a perchlorate ion, a pseudohalide ion, a cyanamide ion, or a dicyanamide ion. ] The polymer processing agent according to claim 5, wherein the ionic liquid is represented by the formula (2).
[Wherein, n and Y represent the same meaning as described above. ] The polymer processing agent according to claim 6, wherein the ionic liquid is represented by the formula (3).
  It is a processing agent of a natural high molecular compound, The polymer processing agent of any one of Claims 1-7.   The polymer treatment agent according to claim 8, wherein the natural polymer compound is cellulose.   The polymer treatment agent according to claim 1, which is a surface treatment agent, a swelling agent, or a solubilizing agent.   The polymer processing method using the polymer processing agent in any one of Claims 1-9. A dope comprising an ionic liquid, an aprotic solvent, and a polymer, wherein the polymer is dissolved in the ionic liquid and the aprotic solvent,
Dope whose content ratio (molar ratio) of the said ionic liquid and aprotic solvent shown by following formula [1] is 30 to 99%.
  A dope comprising an ionic liquid, an aprotic solvent, and two or more polymers, wherein the polymers are dissolved in the ionic liquid and the aprotic solvent.   The dope according to claim 13, wherein one of the two or more polymers is cellulose.   The dope according to claim 14, wherein the two or more kinds of polymers are cellulose and polylactic acid. The dope according to any one of claims 13 to 15, wherein a content ratio (molar ratio) of the ionic liquid and the aprotic solvent represented by the following formula [1] is 30 to 99%.
The dope according to any one of claims 12 to 16, wherein the ionic liquid is a quaternary ammonium-based ionic liquid represented by the following formula (1).
Wherein, R ¹ to R ³ may be the same or different, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or _{^{R 4 -O- (CH 2) n}} , - R ⁴ represents a methyl group or an ethyl group, and n is 1 or 2. Y represents a halide ion, a carboxylate ion having 1 to 3 carbon atoms, a perchlorate ion, a pseudohalide ion, a cyanamide ion, or a dicyanamide ion. ]   A blend polymer reclaimed from the dope of claim 13.   A cellulose-polylactic acid blend polymer regenerated from the dope according to claim 15.   A dope according to claim 13, added with a medium that is compatible with the ionic liquid and an aprotic solvent and has substantially no ability to dissolve the polymer, or the dope according to claim 13 with the ionic liquid and A method for producing a blend polymer, which is added to a medium that is compatible with an aprotic solvent and has substantially no ability to dissolve the polymer.